CN110371944B - Method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate - Google Patents
Method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate Download PDFInfo
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- CN110371944B CN110371944B CN201910684701.4A CN201910684701A CN110371944B CN 110371944 B CN110371944 B CN 110371944B CN 201910684701 A CN201910684701 A CN 201910684701A CN 110371944 B CN110371944 B CN 110371944B
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
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Abstract
The invention relates to a method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate. The technical scheme is as follows: adding water into the phosphoric acid raffinate acid according to the mass ratio of 1: 0.1-0.3, and stirring for 0.5-1 h at normal temperature to obtain diluted phosphoric acid raffinate acid; adding urea into the diluted phosphoric acid raffinate acid according to the mass ratio of urea to the diluted phosphoric acid raffinate acid of (0.5-2) to 1, stirring at 70-100 ℃ until the pH value is 5-6, cooling, carrying out solid-liquid separation, and washing to obtain iron-removed aluminum liquid and iron-containing aluminum slag; and then stirring the iron-removed aluminum liquid at 70-100 ℃ until the pH value is 6-7, cooling, carrying out solid-liquid separation, and washing to obtain phosphoric acid raffinate acid purified liquid and magnesium ammonium phosphate hexahydrate. The method has the characteristics of short process flow, small phosphorus loss and easy recycling of metal ions.
Description
Technical Field
The invention belongs to the technical field of phosphoric acid extraction spent acid. In particular to a method for purifying phosphoric acid raffinate and recovering magnesium ammonium phosphate hexahydrate.
Background
Phosphoric acid is an important intermediate product in the phosphorus chemical industry, and is widely applied to the fields of fertilizers, foods, medicines and other chemical industries. The production of phosphoric acid is mainly divided into a thermal method and a wet method. The energy consumption for producing phosphoric acid by a thermal method is high, and the method is mainly used for producing high-purity and high-added-value products; while the energy consumption for producing phosphoric acid by a wet method is low, a large amount of impurities such as Fe, Al, Mg and the like enter a leaching solution along with phosphorus in the production process, so that the subsequent separation of phosphorus and impurity ions is difficult. Although the wet phosphoric acid solvent extraction process has significant economic benefits, there are two major problems: firstly, phosphorus is extracted in the extraction process, impurity ions are enriched, the viscosity of raffinate acid is very high, a large amount of colloidal precipitates appear, direct filtration is very difficult, and a plate-and-frame filter press is commonly adopted in the industry for filtration, but the efficiency is low; secondly, the raffinate acid still contains phosphorus with a certain concentration, and is commonly used for producing agricultural monoammonium phosphate or diammonium phosphate, but the content of impurity ions such as Fe, Al, Mg and the like is very high, so that the purity of subsequent phosphorus products does not reach the standard, and certain difficulty is brought to the recovery of phosphorus in the raffinate acid.
"method for preparing industrial grade monoammonium phosphate by twice-neutralization raffinate" (CN 103896232A) patent technology and kui et al adopt ammonia gas twice-neutralization method to treat phosphoric acid raffinate (kui et al. process optimization for preparing industrial grade monoammonium phosphate by raffinate [ J ], chemical and biological engineering, 2015, 32(08), 63-66), and finally adopt crystallization method to prepare industrial grade monoammonium phosphate: firstly, diluting high-viscosity raffinate acid; then, carrying out primary ammonia neutralization on the diluted raffinate acid, wherein the final pH value of the primary neutralization is 3.4-3.6, and filtering after curing; then ammonia gas neutralization for the second time is carried out, the end point pH of the neutralization for the second time is 4.4-4.6, and the mixture is filtered after curing; finally, preparing the monoammonium phosphate by adopting a concentration crystallization method. The process adopts the conventional neutralizer-ammonia gas to treat the raffinate phosphoric acid, and although the impurity removal effect is better, the process still has the following three problems: firstly, a large amount of colloidal precipitates are generated in the impurity removal process, the phosphorus loss is large and generally reaches 25-30%; secondly, the purity of the precipitation slag obtained by twice neutralization is not high, so that magnesium ions in the raffinate phosphoric acid are difficult to comprehensively utilize; thirdly, ammonia is adopted for impurity removal, the ammonia is difficult to avoid escaping from the reactor in the operation process, and the operation environment of a laboratory and an industrial field is poor.
The patent technology of 'a method for preparing disodium hydrogen phosphate by purifying phosphoric acid raffinate acid by using melamine' (CN 105584998A) adopts melamine as a precipitator, removes impurities from wet-process phosphoric acid raffinate acid, generates complex salt of melamine in the impurity removal process, and recovers the complex salt of the melamine by using sodium carbonate, so that the disodium hydrogen phosphate is finally prepared, but the added melamine in the process has high price and large consumption, and magnesium ions in a solution cannot be recovered.
The 'process for removing magnesium from raffinate phosphoric acid' (CN 102583302A) patent technology and the Nippon super-grade technology respectively adopt a solvent extraction method and an ion exchange method to remove magnesium ions in phosphoric acid raffinate acid (the Nippon super-grade technology purifies magnesium ions [ J ] in wet-process phosphoric acid, journal of Guizhou university, 2008, 37(1), 36-39), and good effects are obtained. However, the existing solvent extraction and ion exchange process can only treat one kind of ions in the phosphoric acid raffinate, and the sectional treatment of different impurities is feasible in the process, but the process flow is long, the generated phosphorus-containing intermediate products are more, and the total recovery rate of phosphorus is reduced.
In conclusion, the existing phosphoric acid extraction spent acid purification technology mainly has the defects of long process flow, large phosphorus loss, difficult recovery of metal ions and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate, which has the advantages of short process flow, small phosphorus loss and easy recovery of metal ions.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step one, dilution
Adding water into the phosphoric acid raffinate according to the mass ratio of 1: 0.1-0.3, and stirring for 0.5-1 h at normal temperature to obtain diluted phosphoric acid raffinate.
Step two, removing iron and aluminum
Adding urea into the diluted phosphoric acid raffinate acid according to the mass ratio of (0.5-2): 1, stirring at 70-100 ℃ until the pH value is 5-6, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain iron-aluminum-removed liquid and iron-aluminum-containing slag.
Step three, recycling magnesium
Stirring the iron-removed aluminum liquid at 70-100 ℃ until the pH value is 6-7, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain phosphoric acid raffinate acid purified liquid and magnesium ammonium phosphate hexahydrate.
The phosphoric acid raffinate acid: p 2 O 5 Content (wt.)>35 wt%, MgO 2-8 wt%, Al 2 O 3 4-8 wt% of Fe 2 O 3 0.5-3 wt% of CaO, and<0.05wt％，K 2 content of O<0.1wt％，Na 2 Content of O<1.5 wt%, the solid content is 4-8 wt%, and the pH value is less than-0.8; the density of the phosphoric acid raffinate acid clear liquid is more than 1.6g/cm 3 。
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
(1) the urea is added at one time and decomposed in two stages, iron and aluminum impurities are removed in the first stage, and the removal rate of the iron and aluminum impurities can reach more than 98%; the second stage is to recover magnesium ions, magnesium exists in the second stage precipitate in the form of magnesium ammonium phosphate heptahydrate, the purity of magnesium ammonium phosphate heptahydrate reaches more than 98%, the recovery rate of magnesium reaches more than 90%, and the magnesium ammonium phosphate heptahydrate can be directly and comprehensively utilized or further purified to prepare a product with higher purity.
(2) The urea adopted by the invention is used as the slow-release precipitator, the occurrence of coprecipitation can be effectively prevented, iron and aluminum impurities in phosphoric acid raffinate are removed in a targeted manner, magnesium ions are recovered, the inclusion of phosphorus is prevented, the generated precipitate is powdery, the generation of colloidal precipitate in the conventional ammonia water purification process is avoided, and the loss rate of phosphorus can be reduced to below 5%. The mechanism of removing impurity ions and inhibiting phosphorus loss by adopting urea is as follows:
urea slowly releases ammonia when heated above 60 ℃ and has the following reaction formula:
CO(NH 2 ) 2 +H 2 O→CO 2 ↑+2NH 3
NH 3 +H 2 O→NH 4 + +OH -
NH product obtained by urea hydrothermal decomposition 4 + Is a reactant for the subsequent preparation of ammonium phosphate salt products, and OH is generated by the reaction - It helps to raise the pH of the solution and eventually reaches the optimum pH range for precipitation of impurities in the phosphoric acid raffinate. In addition, the condition is controlled to slowly decompose the urea and uniformly release OH in the solution - The method can prevent the coiling of phosphor caused by the local strong hydrolysis of Fe and Al due to the local over-high pH value in the conventional ammonia water pH adjusting method.
Comparing the surface appearance of the iron-containing aluminum slag with the surface appearance of the ammonia water impurity-removing slag in the prior art: compared with the ammonia water impurity removal product in the prior art, the urea impurity removal product has more complete and uniform appearance and larger crystal size. In the process of Fe and Al precipitation, useful elements of phosphorus and magnesium are not easy to be rolled up, so that the loss of phosphorus is reduced, and conditions are created for recycling magnesium.
(3) The method has the advantages that the turbid phosphoric acid raffinate is taken as a treatment object, impurities are directly removed from the turbid phosphoric acid raffinate, the phosphoric acid raffinate can be purified without filtering colloidal precipitates in the phosphoric acid raffinate, the precipitates generated on a microscopic level have high crystallinity and large grain sizes, particles are in a fine powder state on a macroscopic level, impurity removal slag obtained in the impurity removal mode in the prior art is in a colloid state, and the turbid matters in the phosphoric acid raffinate react with a precipitator in the impurity removal process, so that the filtering process is easier to carry out, and the process flow is shortened.
Therefore, the method has the characteristics of short process flow, small phosphorus loss and easy recycling of magnesium ions.
Drawings
FIG. 1 is an SEM image of the surface topography of an iron-containing aluminum slag of the invention;
FIG. 2 is an SEM image of the surface topography of the ammonia water impurity removal product of the prior art.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
In this embodiment:
the phosphoric acid raffinate acid: p 2 O 5 Content (wt.)>35 wt%, MgO content of 2-8 wt%, Al 2 O 3 4-8 wt% of Fe 2 O 3 0.5-3 wt% of CaO, and<0.05wt％，K 2 content of O<0.1wt％，Na 2 Content of O<1.5 wt%, the solid content is 4-8 wt%, and the pH value is less than-0.8; the density of the phosphoric acid raffinate acid clear liquid is more than 1.6g/cm 3 。
The detailed description is omitted in the embodiments.
Example 1
A method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate. The method of the embodiment comprises the following specific steps:
step one, dilution
Adding water into the phosphoric acid raffinate according to the mass ratio of 1: 0.1-0.15, and stirring for 0.5-0.7 h at normal temperature to obtain diluted phosphoric acid raffinate.
Step two, removing iron and aluminum
Adding urea into the diluted phosphoric acid raffinate acid according to the mass ratio of (0.5-1): 1, stirring at 70-80 ℃ until the pH value is 5-5.4, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain the molten iron-aluminum removing liquid and the iron-aluminum containing slag.
Step three, recycling magnesium
And stirring the iron-removed aluminum liquid at 70-80 ℃ until the pH value is 6-6.4, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain phosphoric acid raffinate acid purified liquid and magnesium ammonium phosphate hexahydrate.
Example 2
A method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate. The method of the embodiment comprises the following specific steps:
step one, dilution
Adding water into the phosphoric acid raffinate according to the mass ratio of 1: 0.15-0.2, and stirring for 0.6-0.8 h at normal temperature to obtain diluted phosphoric acid raffinate.
Step two, removing iron and aluminum
Adding urea into the diluted phosphoric acid raffinate acid according to the mass ratio of urea to the diluted phosphoric acid raffinate acid of (1-1.5): 1, stirring at 80-90 ℃ until the pH value is 5.2-5.6, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain the molten iron-removed aluminum and the iron-containing aluminum slag.
Step three, recycling magnesium
Stirring the iron-removed aluminum liquid at the temperature of 80-90 ℃ until the pH value is 6.2-6.6, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain phosphoric acid raffinate acid purified liquid and magnesium ammonium phosphate hexahydrate.
Example 3
A method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate. The method of the embodiment comprises the following specific steps:
step one, dilution
Adding water into the phosphoric acid raffinate acid according to the mass ratio of 1: 0.2-0.3, and stirring for 0.8-1 h at normal temperature to obtain diluted phosphoric acid raffinate acid.
Step two, removing iron and aluminum
Adding urea into the diluted phosphoric acid raffinate acid according to the mass ratio of urea to the diluted phosphoric acid raffinate acid of (1.5-2): 1, stirring at 90-100 ℃ until the pH value is 5.6-6, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain the molten iron-aluminum removing liquid and the iron-aluminum containing slag.
Step three, recycling magnesium
Stirring the iron-removed aluminum liquid at 90-100 ℃ until the pH value is 6.6-7, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain phosphoric acid raffinate acid purified liquid and magnesium ammonium phosphate hexahydrate.
Compared with the prior art, the specific implementation mode has the following positive effects:
(1) in the specific embodiment, the urea is added at one time and decomposed in two stages, wherein iron and aluminum impurities are removed in the first stage, and the removal rate of the iron and aluminum impurities can reach more than 98%; the second stage is to recover magnesium ions, magnesium exists in the second stage precipitate in the form of magnesium ammonium phosphate heptahydrate, the purity of magnesium ammonium phosphate heptahydrate reaches more than 98%, the recovery rate of magnesium reaches more than 90%, and the magnesium ammonium phosphate heptahydrate can be directly and comprehensively utilized or further purified to prepare a product with higher purity.
(2) The urea adopted by the specific embodiment is used as the slow-release precipitator, so that the occurrence of coprecipitation can be effectively prevented, iron and aluminum impurities in phosphoric acid raffinate can be removed in a targeted manner, magnesium ions are recovered, the inclusion of phosphorus is prevented, the generated precipitate is powdery, the generation of colloidal precipitate in the conventional ammonia water purification process is avoided, and the loss rate of phosphorus can be reduced to below 5%. The mechanism of precipitating impurity ions and inhibiting phosphorus loss by using urea in the embodiment is as follows:
urea slowly releases ammonia when heated above 60 ℃ and has the following reaction formula:
CO(NH 2 ) 2 +H 2 O→CO 2 ↑+2NH 3
NH 3 +H 2 O→NH 4 + +OH -
NH product obtained by urea hydrothermal decomposition 4 + Is a reactant for the subsequent preparation of ammonium phosphate salt products, and OH is generated by the reaction - It helps to raise the pH of the solution and eventually reaches the optimum pH range for precipitation of impurities in the phosphoric acid raffinate. In addition, the condition is controlled to slowly decompose the urea and uniformly release OH in the solution - The method can prevent the coiling of phosphor caused by the local strong hydrolysis of Fe and Al due to the local over-high pH value in the conventional ammonia water pH adjusting method.
Comparing the surface appearance of the iron-containing aluminum slag of the embodiment with the surface appearance of the ammonia water impurity-removing slag in the prior art, the results are shown in fig. 1 and fig. 2: FIG. 1 is an SEM image of the surface topography of an iron-containing aluminum slag of example 1; FIG. 2 is a SEM image of the surface morphology of the product of ammonia water impurity removal in the prior art. As can be seen from FIG. 1, the impurity-removed product of the present embodiment is stacked in a flake form, and the structure is complete and consistent, which proves that the urea precipitation product has high crystallinity. As can be seen from FIG. 2, the ammonia water impurity removal product in the prior art has small flake-shaped particle size and irregular shape, and is easy to form large particle agglomeration. As can be seen from the comparison between fig. 1 and fig. 2, the urea impurity removal product of the present embodiment has a more complete and uniform morphology and a larger crystal size than the ammonia water impurity removal product of the prior art. In the process of Fe and Al precipitation, useful elements of phosphorus and magnesium are not easy to be rolled up, so that the loss of phosphorus is reduced, and conditions are created for recycling magnesium.
(3) The processing object of the specific embodiment is turbid phosphoric acid raffinate, the turbid phosphoric acid raffinate is directly subjected to impurity removal, colloidal precipitates in the phosphoric acid raffinate do not need to be filtered, purification of the phosphoric acid raffinate can be achieved, the precipitates generated on the microscopic level are high in crystallinity, the grain size is large, particles on the macroscopic level are fine powder, impurity removal slag obtained by the impurity removal mode in the prior art is colloidal, and turbid substances in the phosphoric acid raffinate react with a precipitator in the impurity removal process, so that the filtering process is easier to carry out, and the process flow is shortened.
Therefore, the specific implementation mode has the characteristics of short process flow, small phosphorus loss and easiness in recycling magnesium ions.
Claims (2)
1. A method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate is characterized by comprising the following specific steps:
step one, dilution
Adding water into the phosphoric acid raffinate acid according to the mass ratio of 1: 0.1-0.3 of the phosphoric acid raffinate acid to the water, and stirring for 0.5-1 h at normal temperature to obtain diluted phosphoric acid raffinate acid;
step two, removing iron and aluminum
Adding urea into the diluted phosphoric acid raffinate acid according to the mass ratio of urea to the diluted phosphoric acid raffinate acid of (0.5-2): 1, stirring at 70-100 ℃ until the pH value is 5-6, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain iron-aluminum-removed liquid and iron-aluminum-containing slag;
step three, recycling magnesium
Stirring the iron-removed aluminum liquid at 70-100 ℃ until the pH value is 6-7, cooling to normal temperature, carrying out solid-liquid separation, and washing to obtain phosphoric acid raffinate acid purified liquid and magnesium ammonium phosphate hexahydrate.
2. The method of purifying phosphoric acid raffinate and recovering magnesium ammonium phosphate hexahydrate according to claim 1, wherein the phosphoric acid raffinate: p 2 O 5 Content (wt.)>35 wt%, MgO content of 2-8 wt%, Al 2 O 3 4-8 wt% of Fe 2 O 3 0.5-3 wt% of CaO, and<0.05wt％，K 2 content of O<0.1wt％，Na 2 Content of O<1.5 wt%, the solid content is 4-8 wt%, and the pH value is less than-0.8; the density of the phosphoric acid raffinate acid clear liquid is more than 1.6g/cm 3 。
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| CN104058378A (en) * | 2014-07-09 | 2014-09-24 | 昆明隆祥化工有限公司 | Method for producing monoammonium phosphate and magnesium ammonium phosphate by using wet concentrated phosphoric acid residues |
| CN105600763A (en) * | 2016-01-22 | 2016-05-25 | 金正大诺泰尔化学有限公司 | Method for producing industrial monoammonium phosphate through fluoride salt purification method |
| CA2977986A1 (en) * | 2017-08-30 | 2019-02-28 | Boost Environmental systems Inc. | Process for removal or recovery of ammonium nitrogen from wastewater streams |
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- 2019-07-26 CN CN201910684701.4A patent/CN110371944B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1654317A (en) * | 2004-12-24 | 2005-08-17 | 贵州宏福实业开发有限总公司 | Purified wet-process technique for producing phosphoric acid and equipment thereof |
| CN101891504A (en) * | 2010-07-26 | 2010-11-24 | 瓮福（集团）有限责任公司 | Method for producing granular monoammonium phosphate with raffinate |
| CN102815685A (en) * | 2012-08-10 | 2012-12-12 | 清华大学 | Wet-method phosphoric acid staged extraction and purification process |
| CN104058378A (en) * | 2014-07-09 | 2014-09-24 | 昆明隆祥化工有限公司 | Method for producing monoammonium phosphate and magnesium ammonium phosphate by using wet concentrated phosphoric acid residues |
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