CN107662909B - Preparation method of phosphate - Google Patents
Preparation method of phosphate Download PDFInfo
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- CN107662909B CN107662909B CN201711051788.9A CN201711051788A CN107662909B CN 107662909 B CN107662909 B CN 107662909B CN 201711051788 A CN201711051788 A CN 201711051788A CN 107662909 B CN107662909 B CN 107662909B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/265—General methods for obtaining phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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Abstract
The invention provides a preparation method of phosphate, which comprises the following steps: 1) dissolving a raw material capable of dissolving out metal ions by acid, and separating to obtain a clear solution; the acid comprises nitric acid, and the raw material capable of dissolving out metal ions by the acid is selected from one or a mixture of more of metal, metal oxide, metal hydroxide, metal carbonate and metal basic carbonate; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; the phosphorus-containing reducing agent is a phosphorus-containing substance with a valence lower than a positive pentavalent state. The method has the advantages of less impurities introduced into the system, less washing times, low cost, high purity of the prepared product and small granularity, and provides an effective and feasible method for preparing the phosphate.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a preparation method of phosphate.
background
Phosphates are important phosphate compounds, and their use varies depending on the purity, and they are widely used in the chemical industry, coating industry, new energy, agriculture, medicine, food, and the like.
The existing preparation method of phosphate mainly adopts a precipitation method, generally, soluble metal salt solution is firstly prepared, then phosphoric acid or soluble phosphate is added and mixed, the pH value is regulated to form phosphate, and then the phosphate is obtained by washing and filtering.
Because phosphate is generally difficult to wash, especially nano-sized and micron-sized powder, the washing is more difficult, and for high-purity phosphate, the water consumption is larger to reduce the impurity content. At present, a large amount of impurities are introduced in two links in the mainstream process, firstly, anion impurities are often introduced when a soluble metal salt solution is prepared, and secondly, ammonia water or sodium hydroxide is generally added and cation impurities are introduced when the pH value is adjusted, so that the washing in the preparation process of phosphate becomes particularly difficult, and a large amount of chemical wastewater which is difficult to treat is formed.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the main object of the present invention is to provide a method for preparing phosphate, which has the advantages of less impurities introduced into the system, less washing times and water amount, low cost, high purity of the prepared product, and small particle size.
in order to achieve the purpose, the invention adopts the following technical scheme: a method for the preparation of phosphate, said method comprising the steps of:
1) dissolving a raw material capable of dissolving out metal ions by acid, and separating to obtain a clear solution; the acid comprises nitric acid, and the raw material capable of dissolving out metal ions by the acid is selected from one or a mixture of more of metal, metal oxide, metal hydroxide, metal carbonate and metal basic carbonate;
2) Adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; the phosphorus-containing reducing agent is a phosphorus-containing substance with a valence lower than a positive pentavalent state.
As a further preference, in the step 1), the metal is selected from iron, aluminum, copper, nickel, cobalt, manganese and zinc.
Further preferably, in the step 1), the acid is selected from the group consisting of nitric acid, a mixed acid of nitric acid and phosphoric acid, a mixed acid of nitric acid and hydrochloric acid, a mixed acid of nitric acid and sulfuric acid, and a mixed acid of nitric acid and oxalic acid.
As a further preference, in the step 2), the phosphorus-containing substance with the valence lower than the positive pentavalent state is selected from one or a mixture of several of elementary phosphorus, phosphorous acid, hypophosphorous acid, ferrophosphorus, phosphine hydrogen and diphosphine.
As a further preference, in the step 2), when the yield of the phosphate in the reaction system reaches a suitable degree, the following are: the phosphate yield is greater than 0.1% and less than 100%.
as a further preference, in step 2), the particle size of the phosphate solids is less than 10 microns.
Preferably, in the step 2), the purity of the washed phosphate solid after being dried at 800 ℃ is 98.0-99.999%.
As a further preference, further comprising step 3): oxidizing the nitrogen oxide gas generated in the step 2) by using oxygen, and absorbing by using water or all or part of mother liquor in the step 2) to obtain nitric acid.
As a further preference, further comprising step 4): recycling the nitric acid obtained by the absorption in the step 3) to the raw material for dissolving the acid-dissociable metal ions in the step 1).
As a further preference, further comprising step 5): supplementing nitric acid with a molar amount of less than 2 times of the metal molar amount to the nitric acid obtained by the absorption in the step 3), and dissolving the raw material capable of dissolving the metal ions dissolved by the acid in the step 1).
As a further preference, further comprising step 6): phosphoric acid, the molar amount of which is 5 times less than the metal molar amount, is supplemented to the nitric acid obtained by the absorption in the step 3), and is used for dissolving the raw material capable of dissolving the metal ions capable of being dissolved by the acid in the step 1).
The invention has the beneficial effects that: the invention adopts nitric acid-containing acid to dissolve the raw material which can dissolve out metal ions by acid to obtain solution, then adds in phosphorus-containing substance with the valence lower than the positive pentavalent to reduce nitrate radical, and at the same time, the phosphorus in the phosphorus-containing substance with the valence lower than the positive pentavalent is oxidized into phosphate radical, and reacts with metal ions to obtain phosphate precipitate, and the reaction does not introduce other impurities, and greatly saves the raw material consumption cost.
Drawings
FIG. 1 is a process flow diagram of the process for the preparation of phosphate according to example 1 of the present invention.
FIG. 2 is a process flow diagram of the phosphate production process of example 2 of the present invention.
FIG. 3 is a process flow diagram of a method for preparing phosphate according to example 3 of the present invention.
FIG. 4 is a graph showing the particle size distribution of aluminum phosphate produced by the method of the present invention.
Detailed Description
The invention provides a preparation method of phosphate, which solves the defects of high impurity content, large washing water amount, high COD content in wastewater and overhigh cost of the product in the process of preparing the phosphate in the prior art.
In order to solve the above-mentioned defects, the main idea of the embodiment of the present invention is:
The preparation method of the phosphate provided by the embodiment of the invention comprises the following steps:
1) Dissolving a raw material capable of dissolving out metal ions by acid, and separating to obtain a clear solution; the acid comprises nitric acid, and the raw material capable of dissolving out metal ions by the acid is selected from one or a mixture of more of metal, metal oxide, metal hydroxide, metal carbonate and metal basic carbonate;
2) Adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; the phosphorus-containing reducing agent is a phosphorus-containing substance with a valence lower than a positive pentavalent state.
In the step 1), the metal may be selected from iron, aluminum, copper, nickel, cobalt, manganese and zinc.
In the step 1), the acid is selected from nitric acid, a mixed acid of nitric acid and phosphoric acid, a mixed acid of nitric acid and hydrochloric acid, a mixed acid of nitric acid and sulfuric acid, and a mixed acid of nitric acid and oxalic acid.
In the step 2), the phosphorus-containing substance with a valence lower than the positive pentavalent state can be selected from one or a mixture of several of simple substance phosphorus, phosphorous acid, hypophosphorous acid, ferrophosphorus, phosphine hydride and diphosphine.
The temperature of the reaction system is 20 to 150 ℃ and more preferably 90 to 150 ℃.
In order to make the aforementioned and other objects, features, and advantages of the present invention more comprehensible, several embodiments accompanied with figures are described below to illustrate the method of the present invention for preparing phosphate.
example 1
as shown in fig. 1, a method for preparing phosphate according to example 1 of the present invention includes: 1) dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) and adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, separating solid from liquid when the yield of phosphate in the reaction system reaches a proper degree to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid.
In the step 1), the raw material capable of dissolving metal ions in acid is selected from aluminum hydroxide;
the yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 98 percent.
In the step 2), the phosphorus-containing reducing agent is elemental phosphorus.
the temperature of the above reaction system was 120 ℃.
The embodiment 1 of the invention has the following implementation effects:
In the embodiment 1 of the invention, high-purity aluminum phosphate can be obtained by washing with water which is 3 times of the aluminum phosphate in mass, the washing water amount is small, the product granularity is uniform, the average granularity is about 70nm, the product purity is 99%, the COD content in wastewater is 20ppm, and the production cost is more than 400 yuan less than that of phosphoric acid and formic acid raw materials used per ton of aluminum phosphate by using elemental phosphorus as a reducing agent.
Example 2
as shown in fig. 2, a method for preparing phosphate according to example 2 of the present invention includes:
1) Dissolving a raw material capable of dissolving metal ions by acid by using a mixed acid of nitric acid and phosphoric acid, and separating to obtain a clear solution;
2) Adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid;
3) the nitrogen oxide gas generated in step 2) is oxidized with oxygen, and then absorbed into nitric acid using water or the above-mentioned mother liquor, and used for dissolving the raw material from which the metal ions can be eluted with acid in step 1).
in the step 1), the raw material capable of acid-dissolving out metal ions is selected from a mixture of metal carbonate and metal basic carbonate, and the molar ratio of the metal carbonate to the metal basic carbonate is 1: 1; the metal is selected from copper.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 0.1%.
In the step 2), the phosphorus-containing reducing agent is selected from a mixture of phosphorous acid and hypophosphorous acid, and the molar ratio of the phosphorous acid to the hypophosphorous acid is 5: 1.
The temperature of the above reaction system was 140 ℃.
the embodiment 2 of the invention has the following implementation effects:
In the embodiment 2 of the invention, high-purity copper phosphate can be obtained by washing with water which is 3 times of the weight of the copper phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 70 nm.
example 3
Embodiment 3 of the present invention is a method for preparing phosphate, comprising: 1) dissolving a raw material capable of dissolving metal ions by acid by using a mixed acid of nitric acid and sulfuric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas with water to form nitric acid, supplementing the absorbed water with nitric acid accounting for 200% of the metal molar weight, and using the nitric acid and the nitric acid together in the step 1) to dissolve the raw materials capable of dissolving metal ions by acid.
in the step 1), the raw material capable of acid-dissolving out metal ions is selected from metallic zinc.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 0.1%.
In the step 2), the molar ratio of phosphine hydride to diphosphine selected from the mixture of phosphine hydride and diphosphine is 2: 1.
the temperature of the above reaction system was 90 ℃.
In the embodiment 3 of the invention, the high-purity zinc phosphate can be obtained by washing with water 2.8 times of the mass of the zinc phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 80 nm.
Example 4
Embodiment 4 of the present invention is a method for preparing phosphate, comprising: 1) dissolving a raw material capable of dissolving metal ions by acid by using a mixed acid of nitric acid and hydrochloric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 50% of the mother liquor in step 2), supplementing the nitric acid accounting for 10% of the metal molar quantity and supplementing phosphoric acid accounting for 10% of the metal molar quantity into the absorbed mother liquor, and using the nitric acid and the phosphoric acid together for dissolving the raw material capable of dissolving metal ions by acid in step 1).
The temperature of the above reaction system was 150 ℃.
in the step 1), the raw material capable of dissolving out metal ions by acid is selected from a mixture of metal and metal oxide, and the molar ratio of the metal to the metal oxide is 99: 1; the metal is selected from iron.
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 3: 1.
in the steps 1) and 3), the molar ratio of the metal element to the total amount of phosphoric acid is 0.9: 1.
the yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 60 percent.
In the step 2), the phosphorus-containing reducing agent is selected from phosphine.
In the embodiment 4 of the invention, the high-purity ferric phosphate can be obtained by washing with water 5 times the weight of ferric phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 5 micrometers.
Example 5
Embodiment 5 of the present invention provides a method for preparing phosphate, comprising: 1) dissolving a raw material capable of dissolving metal ions by acid by using a mixed acid of nitric acid and oxalic acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 80% of the mother liquor in step 2), supplementing phosphoric acid accounting for 0.01% of the molar amount of the metal into the absorbed mother liquor, and using the nitric acid and the phosphoric acid together as a raw material for dissolving metal ions which can be dissolved out by acid in step 1).
In the step 1), the raw material capable of acid-dissolving out metal ions is selected from metallic cobalt.
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 3: 1.
In the steps 1) and 3), the molar ratio of the metal element to the total amount of phosphoric acid is 1: 1.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 40 percent
in the step 2), the phosphorous-containing reducing agent is selected from phosphorous acid.
The temperature of the above reaction system was 110 ℃.
In the embodiment 5 of the invention, the high-purity cobalt phosphate can be obtained by washing with water 2.6 times of the weight of the cobalt phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 65 nm.
Example 6
As shown in fig. 3, a method for preparing phosphate according to example 6 of the present invention includes:
1) Dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 100% of the mother liquor in step 2), supplementing nitric acid accounting for 0.1% of the metal molar quantity and phosphoric acid accounting for 0.1% of the metal molar quantity into the absorbed mother liquor, and using the nitric acid and the phosphoric acid together for dissolving the raw material capable of dissolving metal ions by acid in step 1).
In the step 1), the raw material capable of dissolving metal ions in acid is selected from aluminum hydroxide;
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 2: 1.
In the steps 1) and 3), the molar ratio of the metal element to the total amount of phosphoric acid is 0.9: 1.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 98 percent.
In the step 2), the phosphorus-containing reducing agent is elemental phosphorus.
The temperature of the above reaction system was 120 ℃.
embodiment 6 of the present invention has the following effects:
In the embodiment 6 of the invention, high-purity aluminum phosphate can be obtained by washing with water which is 3 times of aluminum phosphate in mass, the washing water amount is small, the product granularity is uniform, the average granularity is about 70nm, the product purity is 99%, the COD content in wastewater is 20ppm, the production cost is more than 400 yuan less than that of phosphoric acid and formic acid raw materials used per ton of aluminum phosphate by using elemental phosphorus as a reducing agent, and the attached figure is a 4-aluminum phosphate granularity distribution curve.
Example 7
The preparation method of the phosphate of the embodiment 7 of the invention comprises the following steps: 1) dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid using 10.0% of the mother liquor in step 2), supplementing the nitric acid, which accounts for 200% of the molar amount of the metal, into the absorbed mother liquor, and using the nitric acid and the nitric acid together as a raw material for dissolving the acid-dissociable metal ions in step 1).
in the step 1), the raw material capable of acid-dissolving out metal ions is selected from a mixture of metal carbonate and metal basic carbonate, and the molar ratio of the metal carbonate to the metal basic carbonate is 1: 1; the metal is selected from copper.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 0.1%.
in the step 2), the phosphorus-containing reducing agent is selected from a mixture of phosphorous acid and hypophosphorous acid, and the molar ratio of the phosphorous acid to the hypophosphorous acid is 5: 1.
Embodiment 7 of the present invention has the following effects:
In the embodiment 7 of the invention, high-purity copper phosphate can be obtained by washing with water which is 3 times of the weight of the copper phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 70 nm.
example 8
The preparation method of the phosphate of the embodiment 8 of the invention comprises the following steps: 1) dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas with water to form nitric acid, supplementing the absorbed water with phosphoric acid accounting for 500% of the metal molar weight, and using the phosphoric acid and the phosphoric acid together in the step 1) to dissolve the raw materials capable of dissolving metal ions in acid.
In the step 1), the raw material capable of dissolving out metal ions by acid is selected from metal zinc
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 0.01: 1.
In the steps 1) and 3), the molar ratio of the metal element to the total amount of phosphoric acid is 0.01: 1.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 0.1 percent
In the step 2), the molar ratio of phosphine hydride to diphosphine selected from the mixture of phosphine hydride and diphosphine is 2: 1.
In the embodiment 8 of the invention, the high-purity zinc phosphate can be obtained by washing with water 2.8 times of the mass of the zinc phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 80 nm.
Example 9
The preparation method of the phosphate of the embodiment 9 of the invention comprises the following steps: 1) dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 50% of the mother liquor in step 2), supplementing the nitric acid accounting for 10% of the metal molar quantity and supplementing phosphoric acid accounting for 10% of the metal molar quantity into the absorbed mother liquor, and using the nitric acid and the phosphoric acid together for dissolving the raw material capable of dissolving metal ions by acid in step 1).
in the step 1), the raw material capable of dissolving out metal ions by acid is selected from a mixture of metal and metal oxide, and the molar ratio of the metal to the metal oxide is 99: 1; the metal is selected from iron.
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 3: 1.
In the steps 1) and 3), the molar ratio of the metal element to the total amount of phosphoric acid is 0.9: 1.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 60 percent.
in the step 2), the phosphorus-containing reducing agent is selected from phosphine.
In the embodiment 4 of the invention, the high-purity ferric phosphate can be obtained by washing with water 5 times the weight of ferric phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 5 micrometers.
Example 10
The preparation method of the phosphate of the embodiment 10 of the invention comprises the following steps: 1) dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 80% of the mother liquor in step 2), supplementing nitric acid accounting for 0.01% of the metal molar quantity and phosphoric acid accounting for 0.1% of the metal molar quantity into the absorbed mother liquor, and dissolving the raw materials capable of dissolving metal ions in step 1) together.
In the step 1), the raw material capable of acid-dissolving out metal ions is selected from metallic cobalt.
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 3: 1.
In the steps 1) and 3), the molar ratio of the metal element to the total amount of phosphoric acid is 1: 1.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 40 percent
In the step 2), the phosphorous-containing reducing agent is selected from phosphorous acid.
In the embodiment 5 of the invention, the high-purity cobalt phosphate can be obtained by washing with water 2.6 times of the weight of the cobalt phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 65 nm.
example 11
The preparation method of the phosphate of the embodiment 11 of the invention comprises the following steps: 1) dissolving a raw material capable of dissolving metal ions out by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 100% of the mother liquor in step 2), supplementing the nitric acid accounting for 0.1% of the molar amount of the metal into the absorbed mother liquor, and dissolving the raw material capable of dissolving out the metal ions in step 1).
In the step 1), the raw material capable of acid-dissolving out metal ions is selected from metal oxides; the metal is selected from nickel.
the yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 33 percent.
In the step 2), the phosphorus-containing reducing agent is selected from diphosphine.
in the embodiment 11 of the invention, high-purity nickel phosphate can be obtained by washing with water which is 5 times of the mass of nickel phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 3 microns.
Example 12
The preparation method of the phosphate provided by the embodiment 12 comprises the following steps: 1) dissolving a raw material capable of dissolving metal ions by acid by using nitric acid, and separating to obtain a clear solution; 2) adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; 3) oxidizing the nitrogen oxide gas generated in step 2) with oxygen, absorbing the nitrogen oxide gas into nitric acid by using 70% of the mother liquor in step 2), supplementing the nitric acid accounting for 50% of the metal molar quantity and supplementing phosphoric acid accounting for 300% of the metal molar quantity into the absorbed mother liquor, and using the nitric acid and the phosphoric acid together for dissolving the raw material capable of dissolving metal ions by acid in step 1).
In the step 1), the raw material capable of acid-dissolving out metal ions is selected from metal oxides; the metal is selected from manganese.
In the step 3), the molar ratio of the total amount of the nitric acid to the total amount of the phosphoric acid is 40: 1.
In the steps 1) and 3), the molar ratio of the total amount of the metal element to the total amount of the phosphoric acid is 60: 1.
The yield of the phosphate in the reaction system in the step 2) reaches a proper degree, namely the yield reaches 70 percent
In the step 2), the phosphorus-containing reducing agent is selected from ferrophosphorus.
In the embodiment 12 of the invention, high-purity ferromanganese phosphate can be obtained by washing with water 4 times of the mass of ferromanganese phosphate, the washing water amount is small, the product granularity is uniform, and the average granularity is about 1 micron.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
the invention adopts nitric acid-containing acid to dissolve the raw material which can dissolve out metal ions by acid to obtain solution, then adds in phosphorus-containing substance with the valence lower than the positive pentavalent to reduce nitrate radical, and at the same time, the phosphorus in the phosphorus-containing substance with the valence lower than the positive pentavalent is oxidized into phosphate radical, and reacts with metal ions to obtain phosphate precipitate, and the reaction does not introduce other impurities, and greatly saves the raw material consumption cost.
while preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. a method for preparing phosphate is characterized in that: the method comprises the following steps:
1) dissolving a raw material capable of dissolving out metal ions by acid, and separating to obtain a clear solution; the acid comprises nitric acid, and the raw material capable of dissolving out metal ions by the acid is selected from one or a mixture of more of metal, metal oxide, metal hydroxide, metal carbonate and metal basic carbonate;
2) Adding a phosphorus-containing reducing agent into the clarified solution to form a reaction system, reacting to generate phosphate and nitrogen oxide gas, when the yield of phosphate in the reaction system reaches a proper degree, performing solid-liquid separation to obtain phosphate solid and mother liquor, and washing to remove impurities in the phosphate solid; the phosphorus-containing reducing agent is selected from one or a mixture of more of simple substance phosphorus, phosphorous acid, hypophosphorous acid, ferrophosphorus, phosphine hydride and diphosphine.
2. the method for preparing phosphate according to claim 1, wherein: in the step 1), the metal is selected from iron, aluminum, copper, nickel, cobalt, manganese and zinc.
3. The method for preparing phosphate according to claim 1, wherein: in the step 1), the acid is selected from nitric acid, a mixed acid of nitric acid and phosphoric acid, a mixed acid of nitric acid and hydrochloric acid, a mixed acid of nitric acid and sulfuric acid, and a mixed acid of nitric acid and oxalic acid.
4. The method for preparing phosphate according to claim 1, wherein: in the step 2), when the yield of the phosphate in the reaction system reaches a proper degree, the following steps are carried out: the phosphate yield is greater than 0.1% and less than 100%.
5. The method for preparing phosphate according to claim 1, wherein: in the step 2), the purity of the washed phosphate solid after drying at 800 ℃ is 98.0-99.999%.
6. The method for preparing phosphate according to claim 1, wherein: further comprising step 3): oxidizing the nitrogen oxide gas generated in the step 2) by using oxygen, and absorbing by using water or all or part of mother liquor in the step 2) to obtain nitric acid.
7. The method for preparing phosphate according to claim 6, wherein: further comprising step 4): recycling the nitric acid obtained by the absorption in the step 3) to the raw material for dissolving the acid-dissociable metal ions in the step 1).
8. The method for preparing phosphate according to claim 6, wherein: further comprising step 5): supplementing nitric acid with a molar amount of less than 2 times of the metal molar amount to the nitric acid obtained by the absorption in the step 3), and dissolving the raw material capable of dissolving the metal ions dissolved by the acid in the step 1).
9. The method for preparing phosphate according to claim 6, wherein: further comprising step 6): phosphoric acid, the molar amount of which is 5 times less than the metal molar amount, is supplemented to the nitric acid obtained by the absorption in the step 3), and is used for dissolving the raw material capable of dissolving the metal ions capable of being dissolved by the acid in the step 1).
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| CN103094571A (en) * | 2013-01-31 | 2013-05-08 | 贵州省开阳安达磷化工有限公司 | Method for preparing ferric pyrophosphate for lithium battery and ferric pyrophosphate prepared by method |
| CN104098074A (en) * | 2014-05-09 | 2014-10-15 | 浙江悦瑞环保工程有限公司 | Process for preparing disodium hydrogen phosphate from phosphonomethyl aminodiacetic acid wastewater |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN106829901A (en) * | 2017-01-24 | 2017-06-13 | 武汉工程大学 | A kind of water insoluble method for production of phosphate salt |
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| CN103094571A (en) * | 2013-01-31 | 2013-05-08 | 贵州省开阳安达磷化工有限公司 | Method for preparing ferric pyrophosphate for lithium battery and ferric pyrophosphate prepared by method |
| CN104098074A (en) * | 2014-05-09 | 2014-10-15 | 浙江悦瑞环保工程有限公司 | Process for preparing disodium hydrogen phosphate from phosphonomethyl aminodiacetic acid wastewater |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN106829901A (en) * | 2017-01-24 | 2017-06-13 | 武汉工程大学 | A kind of water insoluble method for production of phosphate salt |
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