CN107662909A - A kind of method for production of phosphate salt - Google Patents
A kind of method for production of phosphate salt Download PDFInfo
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- CN107662909A CN107662909A CN201711051788.9A CN201711051788A CN107662909A CN 107662909 A CN107662909 A CN 107662909A CN 201711051788 A CN201711051788 A CN 201711051788A CN 107662909 A CN107662909 A CN 107662909A
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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
Abstract
The invention provides a kind of method for production of phosphate salt, methods described comprises the following steps：1) raw material of theobromine dissolution metal ion is dissolved using acid, settled solution is obtained after separation；The acid includes nitric acid, the one or more of mixtures of the raw material of the theobromine dissolution metal ion in metal, metal oxide, metal hydroxides, metal carbonate and basic metal carbonates；2) reaction system is formed after phosphorous reducing agent being added in the settled solution, reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree in reaction system, phosphate solid and mother liquor are obtained after separation of solid and liquid, washing removes the impurity in the phosphate solid；The phosphorous reducing agent is the phosphorus containg substances that valent state is less than positive pentavalent.The impurity that system in methods described introduces is few, and washing times are few, and cost is low and the purity of obtained product is high, granularity is small, and effective and feasible method is provided for phosphatic prepare.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, more particularly to a kind of method for production of phosphate salt.
Background technology
Phosphate is important phosphate compounds, and purposes is different with purity, and it is in chemical industry, coatings industry, new energy
Source, agricultural, medicine, food etc. have been widely used.
Method for production of phosphate salt mainly uses the precipitation method at present, usually prepares the metal salt solution of solubility first,
Then phosphoric acid or soluble phosphate mixing are added, regulation pH value forms phosphate, is washed out filtering to obtain phosphate.
Because phosphate is typically difficult to wash, especially nanometer and micron-sized powder, washing is more difficult, for high purity phosphorus
For hydrochlorate for reduction impurity content, the water consumed is even more big.Prevailing technology all introduces a large amount of impurity in two links at present,
First is when preparing the metal salt solution of solubility, often introduces anionic impurity, second is when adjusting pH value, typically to add ammonia
Water or sodium hydroxide, introduce cation impurity again so that washing becomes particularly difficult in phosphatic preparation process, and is formed
A large amount of reluctant wastewater from chemical industry.
The content of the invention
For drawbacks described above of the prior art, it is a primary object of the present invention to provide a kind of phosphatic preparation side
Method, the impurity that the system in methods described introduces is few, and washing times and water are few, and cost is low and the purity of obtained product is high, grain
Spend small.
In order to achieve the above object, the present invention adopts the following technical scheme that：A kind of method for production of phosphate salt, methods described
Comprise the following steps：
1) raw material of theobromine dissolution metal ion is dissolved using acid, settled solution is obtained after separation；The acid includes nitre
Acid, the raw material of the theobromine dissolution metal ion are selected from metal, metal oxide, metal hydroxides, metal carbonate and gold
Belong to one or more of mixtures in subcarbonate；
2) reaction system, reaction generation phosphate and nitrogen oxidation are formed after phosphorous reducing agent is added in the settled solution
Thing gas, when phosphate yield reaches appropriate degree in reaction system, phosphate solid and mother liquor are obtained after separation of solid and liquid, washed
Remove the impurity in the phosphate solid；The phosphorous reducing agent is the phosphorus containg substances that valent state is less than positive pentavalent.
As further preferably, in the step 1), the metal is selected from iron, aluminium, copper, nickel, cobalt, manganese and zinc.
As further preferably, in the step 1), the acid is selected from nitric acid, the mixed acid of nitric acid and phosphoric acid, nitric acid
Mixed acid, nitric acid and the mixed acid and nitric acid of sulfuric acid and the mixed acid of oxalic acid with hydrochloric acid.
As further preferably, in the step 2), the valent state is selected from single less than the phosphorus containg substances of positive pentavalent
Matter phosphorus, phosphorous acid, ortho phosphorous acid, ferrophosphorus, phosphine hydrogen, the one or more of mixtures for joining phosphine.
As it is further preferably, it is described to work as phosphate yield in reaction system and reach appropriate degree in the step 2)
For：Phosphate yield is more than 0.1% and less than 100%.
As further preferably, in the step 2), the particle diameter of the phosphate solid is less than 10 microns.
As further preferably, in the step 2), phosphate solid is after drying under the conditions of 800 DEG C after the washing
Purity be 98.0~99.999%.
As further preferably, in addition to step 3)：Caused oxides of nitrogen gas in the step 2) is used into oxygen
After gas oxidation, absorb to obtain nitric acid using all or part of mother liquor in water or step 2).
As further preferably, in addition to step 4)：The nitric acid for absorbing to obtain described in step 3) is back to step
1) raw material of dissolving theobromine dissolution metal ion in.
As further preferably, in addition to step 5)：Supplement and be less than into the nitric acid for absorbing to obtain described in step 3)
The nitric acid that 2 times of metal molar amount, and for the raw material of dissolving theobromine dissolution metal ion in step 1).
As further preferably, in addition to step 6)：Supplement and be less than into the nitric acid for absorbing to obtain described in step 3)
The phosphoric acid that 5 times of metal molar amount, and for the raw material of dissolving theobromine dissolution metal ion in step 1).
The beneficial effects of the invention are as follows：The present invention is obtained the dissolution of raw material of theobromine dissolution metal ion using the acid containing nitric acid
To solution, phosphorus containg substances of the valent state less than positive pentavalent are added by reducing nitrate radical, while valent state is less than positive pentavalent
Phosphorus containg substances in phosphorus oxygen chemical conversion phosphate radical, react to obtain calcium phosphate precipitation with metal ion, reaction is not only not introduced into other
Impurity, the cost of materials consumed is also greatlyd save, it is phosphatic prepared by the present invention on the premise of same purity is reached
Washing times greatly reduce, and caused wastewater from chemical industry also greatly reduces, and reducing agent used at the same time does not contain organic carbon, makes waste water
In COD (COD) content greatly reduce, waste water is easily handled.
Brief description of the drawings
Fig. 1 is the process chart of the method for production of phosphate salt of the embodiment of the present invention 1.
Fig. 2 is the process chart of the method for production of phosphate salt of the embodiment of the present invention 2.
Fig. 3 is the process chart of the method for production of phosphate salt of the embodiment of the present invention 3.
Fig. 4 is the size distribution curve of aluminum phosphate made from preparation method of the embodiment of the present invention.
Embodiment
The present invention is solved during prior art prepares phosphate, production by providing a kind of method for production of phosphate salt
The defects of product impurity content is high, and washing water is big, and waste water COD content is high and cost is too high.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
Method for production of phosphate salt of the embodiment of the present invention, methods described comprise the following steps：
1) raw material of theobromine dissolution metal ion is dissolved using acid, settled solution is obtained after separation；The acid includes nitre
Acid, the raw material of the theobromine dissolution metal ion are selected from metal, metal oxide, metal hydroxides, metal carbonate and gold
Belong to one or more of mixtures in subcarbonate；
2) reaction system, reaction generation phosphate and nitrogen oxidation are formed after phosphorous reducing agent is added in the settled solution
Thing gas, when phosphate yield reaches appropriate degree in reaction system, phosphate solid and mother liquor are obtained after separation of solid and liquid, washed
Remove the impurity in the phosphate solid；The phosphorous reducing agent is the phosphorus containg substances that valent state is less than positive pentavalent.
Above-mentioned steps 1) in, above-mentioned metal may be selected from iron, aluminium, copper, nickel, cobalt, manganese and zinc.
Above-mentioned steps 1) in, mixed acid, the nitre of the acid selected from nitric acid, the mixed acid of nitric acid and phosphoric acid, nitric acid and hydrochloric acid
The mixed acid and the mixed acid of nitric acid and oxalic acid of acid and sulfuric acid.
Above-mentioned steps 2) in, above-mentioned valent state may be selected from elemental phosphorous, phosphorous acid, secondary Asia less than the phosphorus containg substances of positive pentavalent
Phosphoric acid, ferrophosphorus, phosphine hydrogen, the one or more of mixtures for joining phosphine.
The temperature of above-mentioned reaction system is 20-150 DEG C, more preferably 90-150 DEG C.
In order to which above and other purpose, feature and the advantage of the present invention can be become apparent, number cited below particularly is implemented
Example, to illustrate method for production of phosphate salt of the present invention.
Embodiment 1
As shown in figure 1, the method for production of phosphate salt of the embodiment of the present invention 1, including：1) by the original of theobromine dissolution metal ion
Material is dissolved using nitric acid first, and settled solution is obtained after separation；2) formed after phosphorous reducing agent being added in the settled solution
Reaction system, reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree, solid-liquid in reaction system
Phosphate solid and mother liquor are obtained after separation, washing removes the impurity in the phosphate solid.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from aluminium hydroxide；
Phosphate yield reaches appropriate degree and reaches 98% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is elemental phosphorous.
The temperature of above-mentioned reaction system is 120 DEG C.
The implementation result of the embodiment of the present invention 1：
The embodiment of the present invention 1 can obtain high-purity phosphoric acid aluminium with the water washing with 3 times of quality of aluminum phosphate, and washing water is few, production
Product epigranular, particle mean size is in 70nm or so, product purity 99%, and COD contents are 20ppm in waste water, and use is elemental phosphorous
Phosphoric acid and the member of formic acid raw material aluminum phosphate per ton more than cheap 400 are used for reducing agent production cost ratio.
Embodiment 2
As shown in Fig. 2 the method for production of phosphate salt of the embodiment of the present invention 2, including：
1) raw material of theobromine dissolution metal ion is obtained clear first using nitric acid and the mixed-acid dissolution of phosphoric acid after separation
Clear solution；
2) reaction system, reaction generation phosphate and nitrogen oxidation are formed after phosphorous reducing agent is added in the settled solution
Thing gas, when phosphate yield reaches appropriate degree in reaction system, phosphate solid and mother liquor are obtained after separation of solid and liquid, washed
Remove the impurity in the phosphate solid；
3) after caused oxides of nitrogen gas in step 2) being used into dioxygen oxidation, absorbed using water or above-mentioned mother liquor into nitre
Acid, and for the raw material of dissolving theobromine dissolution metal ion in step 1).
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metal carbonate and basic metal carbonates
In mixture, metal carbonate and basic metal carbonates mol ratio are 1：1；The metal is selected from copper.
Phosphate yield reaches appropriate degree and reaches 0.1% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is selected from the mixture of phosphorous acid and ortho phosphorous acid, phosphorous acid and time Asia
The mol ratio of phosphoric acid is 5：1.
The temperature of above-mentioned reaction system is 140 DEG C.
The implementation result of the embodiment of the present invention 2：
The embodiment of the present invention 2 can obtain high-purity phosphoric acid copper with the water washing with 3 times of quality of cupric phosphate, and washing water is few, production
Product epigranular, particle mean size is in 70nm or so.
Embodiment 3
The method for production of phosphate salt of the embodiment of the present invention 3, including：1) raw material of theobromine dissolution metal ion is used first
The mixed-acid dissolution of nitric acid and sulfuric acid, settled solution is obtained after separation；2) after phosphorous reducing agent being added in the settled solution
Form reaction system, reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree in reaction system,
Phosphate solid and mother liquor are obtained after separation of solid and liquid, washing removes the impurity in the phosphate solid；3) will be produced in step 2)
After raw oxides of nitrogen gas uses dioxygen oxidation, absorbed using water into nitric acid, into the water after absorption, supplement accounts for metal molar
The nitric acid of amount 200%, and it is used for the raw material of dissolving theobromine dissolution metal ion in step 1) together.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metallic zinc.
Phosphate yield reaches appropriate degree and reaches 0.1% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is selected from mole of phosphine hydrogen and the mixture phosphine hydrogen for joining phosphine and connection phosphine
Than for 2：1.
The temperature of above-mentioned reaction system is 90 DEG C.
The embodiment of the present invention 3 can obtain high-purity zinc phosphate with the water washing with 2.8 times of quality of trbasic zinc phosphate, and washing water is few,
Product granularity is uniform, and particle mean size is in 80nm or so.
Embodiment 4
The method for production of phosphate salt of the embodiment of the present invention 4, including：1) raw material of theobromine dissolution metal ion is used first
The mixed-acid dissolution of nitric acid and hydrochloric acid, settled solution is obtained after separation；2) after phosphorous reducing agent being added in the settled solution
Form reaction system, reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree in reaction system,
Phosphate solid and mother liquor are obtained after separation of solid and liquid, washing removes the impurity in the phosphate solid；3) will be produced in step 2)
After raw oxides of nitrogen gas uses dioxygen oxidation, absorbed using 50% mother liquor in step 2) into nitric acid, to after absorption
Supplement accounts for the nitric acid of metal molar amount 10% in mother liquor, and supplement accounts for the phosphoric acid of metal molar amount 10%, and is used to walk together
The raw material of rapid 1) middle dissolving theobromine dissolution metal ion.
The temperature of above-mentioned reaction system is 150 DEG C.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metal and metal oxide mixture, gold
Category and metal oxide mol ratio are 99：1；The metal is selected from iron.
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 3：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 0.9：1.
Phosphate yield reaches appropriate degree and reaches 60% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is selected from phosphine hydrogen.
The embodiment of the present invention 4 can obtain high-purity phosphoric acid iron with the water washing with 5 times of quality of ferric phosphate, and washing water is few, production
Product epigranular, particle mean size is in 5 microns.
Embodiment 5
The method for production of phosphate salt of the embodiment of the present invention 5, including：1) raw material of theobromine dissolution metal ion is used first
The mixed-acid dissolution of nitric acid and oxalic acid, settled solution is obtained after separation；2) after phosphorous reducing agent being added in the settled solution
Form reaction system, reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree in reaction system,
Phosphate solid and mother liquor are obtained after separation of solid and liquid, washing removes the impurity in the phosphate solid；3) will be produced in step 2)
After raw oxides of nitrogen gas uses dioxygen oxidation, absorbed using 80% mother liquor in step 2) into nitric acid, to after absorption
Supplement accounts for the phosphoric acid of metal molar amount 0.01% in mother liquor, and is used for the original of dissolving theobromine dissolution metal ion in step 1) together
Material.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metallic cobalt.
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 3：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 1：1.
Phosphate yield reaches appropriate degree and reaches 40% for yield in reaction system in the step 2)
In the step 2), the phosphorous reducing agent is selected from phosphorous acid.
The temperature of above-mentioned reaction system is 110 DEG C.
The embodiment of the present invention 5 can obtain high-purity phosphoric acid cobalt with the water washing with 2.6 times of quality of cobalt phosphate, and washing water is few,
Product granularity is uniform, and particle mean size is in 65nm or so.
Embodiment 6
As shown in figure 3, the method for production of phosphate salt of the embodiment of the present invention 6, including：
1) raw material of theobromine dissolution metal ion is dissolved using nitric acid first, settled solution is obtained after separation；2) institute
State and form reaction system, reaction generation phosphate and oxides of nitrogen gas after phosphorous reducing agent is added in settled solution, work as reaction
Phosphate yield reaches appropriate degree in system, and phosphate solid and mother liquor are obtained after separation of solid and liquid, and washing removes the phosphoric acid
Impurity in salt solid；3) after caused oxides of nitrogen gas in step 2) being used into dioxygen oxidation, using in step 2)
100% mother liquor is absorbed into nitric acid, and into the mother liquor after absorption, supplement accounts for 0.1% nitric acid of metal molar amount, and supplement
The phosphoric acid of metal molar amount 0.1% is accounted for, and is used for the raw material of dissolving theobromine dissolution metal ion in step 1) together.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from aluminium hydroxide；
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 2：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 0.9：1.
Phosphate yield reaches appropriate degree and reaches 98% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is elemental phosphorous.
The temperature of above-mentioned reaction system is 120 DEG C.
The implementation result of the embodiment of the present invention 6：
The embodiment of the present invention 6 can obtain high-purity phosphoric acid aluminium with the water washing with 3 times of quality of aluminum phosphate, and washing water is few, production
Product epigranular, particle mean size is in 70nm or so, product purity 99%, and COD contents are 20ppm in waste water, and use is elemental phosphorous
It is that reducing agent production cost ratio is divided using phosphoric acid and the member of formic acid raw material aluminum phosphate per ton more than cheap 400, accompanying drawing for 4 phosphoric acid aluminium particle sizes
Cloth curve.
Embodiment 7
The method for production of phosphate salt of the embodiment of the present invention 7, including：1) raw material of theobromine dissolution metal ion is used first
Nitric acid is dissolved, and settled solution is obtained after separation；2) reaction system is formed after phosphorous reducing agent is added in the settled solution, instead
Phosphate and oxides of nitrogen gas should be generated, when phosphate yield reaches appropriate degree in reaction system, is obtained after separation of solid and liquid
Phosphate solid and mother liquor, washing remove the impurity in the phosphate solid；3) by caused nitrogen oxides gas in step 2)
After body uses dioxygen oxidation, absorbed using 10.0% mother liquor in step 2) into nitric acid, supplement and account for into the mother liquor after absorption
200% nitric acid of metal molar amount, and it is used for the raw material of dissolving theobromine dissolution metal ion in step 1) together.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metal carbonate and basic metal carbonates
In mixture, metal carbonate and basic metal carbonates mol ratio are 1：1；The metal is selected from copper.
Phosphate yield reaches appropriate degree and reaches 0.1% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is selected from the mixture of phosphorous acid and ortho phosphorous acid, phosphorous acid and time Asia
The mol ratio of phosphoric acid is 5：1.
The implementation result of the embodiment of the present invention 7：
The embodiment of the present invention 7 can obtain high-purity phosphoric acid copper with the water washing with 3 times of quality of cupric phosphate, and washing water is few, production
Product epigranular, particle mean size is in 70nm or so.
Embodiment 8
The method for production of phosphate salt of the embodiment of the present invention 8, including：1) raw material of theobromine dissolution metal ion is used first
Nitric acid is dissolved, and settled solution is obtained after separation；2) reaction system is formed after phosphorous reducing agent is added in the settled solution, instead
Phosphate and oxides of nitrogen gas should be generated, when phosphate yield reaches appropriate degree in reaction system, is obtained after separation of solid and liquid
Phosphate solid and mother liquor, washing remove the impurity in the phosphate solid；3) by caused nitrogen oxides gas in step 2)
After body uses dioxygen oxidation, absorbed using water into nitric acid, into the water after absorption, supplement accounts for the phosphoric acid of metal molar amount 500%,
And it is used for the raw material of dissolving theobromine dissolution metal ion in step 1) together.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metallic zinc
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 0.01：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 0.01：1.
Phosphate yield reaches appropriate degree and reaches 0.1% for yield in reaction system in the step 2)
In the step 2), the phosphorous reducing agent is selected from mole of phosphine hydrogen and the mixture phosphine hydrogen for joining phosphine and connection phosphine
Than for 2：1.
The embodiment of the present invention 8 can obtain high-purity zinc phosphate with the water washing with 2.8 times of quality of trbasic zinc phosphate, and washing water is few,
Product granularity is uniform, and particle mean size is in 80nm or so.
Embodiment 9
The method for production of phosphate salt of the embodiment of the present invention 9, including：1) raw material of theobromine dissolution metal ion is used first
Nitric acid is dissolved, and settled solution is obtained after separation；2) reaction system is formed after phosphorous reducing agent is added in the settled solution, instead
Phosphate and oxides of nitrogen gas should be generated, when phosphate yield reaches appropriate degree in reaction system, is obtained after separation of solid and liquid
Phosphate solid and mother liquor, washing remove the impurity in the phosphate solid；3) by caused nitrogen oxides gas in step 2)
After body uses dioxygen oxidation, absorbed using 50% mother liquor in step 2) into nitric acid, into the mother liquor after absorption, supplement accounts for gold
Belong to the nitric acid of mole 10%, and supplement accounts for the phosphoric acid of metal molar amount 10%, and it is used for dissolving theobromine in step 1) together
The raw material of dissolution metal ion.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metal and metal oxide mixture, gold
Category and metal oxide mol ratio are 99：1；The metal is selected from iron.
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 3：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 0.9：1.
Phosphate yield reaches appropriate degree and reaches 60% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is selected from phosphine hydrogen.
The embodiment of the present invention 4 can obtain high-purity phosphoric acid iron with the water washing with 5 times of quality of ferric phosphate, and washing water is few, production
Product epigranular, particle mean size is in 5 microns.
Embodiment 10
The method for production of phosphate salt of the embodiment of the present invention 10, including：1) raw material of theobromine dissolution metal ion is adopted first
Dissolved with nitric acid, settled solution is obtained after separation；2) reaction system is formed after phosphorous reducing agent being added in the settled solution,
Reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree in reaction system, after separation of solid and liquid
To phosphate solid and mother liquor, washing removes the impurity in the phosphate solid；3) by caused nitrogen oxides in step 2)
After gas uses dioxygen oxidation, absorbed using 80% mother liquor in step 2) into nitric acid, supplement and account for into the mother liquor after absorption
The nitric acid of metal molar amount 0.01%, and supplement account for the phosphoric acid of metal molar amount 0.1%, and are used for dissolving step 1 together) in
The raw material of theobromine dissolution metal ion.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metallic cobalt.
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 3：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 1：1.
Phosphate yield reaches appropriate degree and reaches 40% for yield in reaction system in the step 2)
In the step 2), the phosphorous reducing agent is selected from phosphorous acid.
The embodiment of the present invention 5 can obtain high-purity phosphoric acid cobalt with the water washing with 2.6 times of quality of cobalt phosphate, and washing water is few,
Product granularity is uniform, and particle mean size is in 65nm or so.
Embodiment 11
The method for production of phosphate salt of the embodiment of the present invention 11, including：1) raw material of theobromine dissolution metal ion is adopted first
Dissolved with nitric acid, settled solution is obtained after separation；2) reaction system is formed after phosphorous reducing agent being added in the settled solution,
Reaction generation phosphate and oxides of nitrogen gas, when phosphate yield reaches appropriate degree in reaction system, after separation of solid and liquid
To phosphate solid and mother liquor, washing removes the impurity in the phosphate solid；3) by caused nitrogen oxides in step 2)
After gas uses dioxygen oxidation, absorbed using 100% mother liquor in step 2) into nitric acid, then supplemented into the mother liquor after absorption
Account for the nitric acid of metal molar amount 0.1%, and be used for dissolving step 1) in theobromine dissolution metal ion raw material.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metal oxide；The metal is selected from nickel.
Phosphate yield reaches appropriate degree and reaches 33% for yield in reaction system in the step 2).
In the step 2), the phosphorous reducing agent is selected from connection phosphine.
The embodiment of the present invention 11 can obtain high-purity phosphoric acid nickel with the water washing with 5 times of quality of nickel phosphate, and washing water is few, production
Product epigranular, particle mean size is in 3 microns.
Embodiment 12
The method for production of phosphate salt of the embodiment of the present invention 12, including：1) raw material of theobromine dissolution metal ion is adopted first
Dissolved with the acid containing nitric acid, settled solution is obtained after separation；2) formed instead after phosphorous reducing agent is added in the settled solution
System, reaction generation phosphate and oxides of nitrogen gas are answered, when phosphate yield reaches appropriate degree, solid-liquid point in reaction system
Phosphate solid and mother liquor are obtained from after, washing removes the impurity in the phosphate solid；3) by caused nitrogen in step 2)
After oxide gas use dioxygen oxidation, absorbed using 70% mother liquor in step 2) into nitric acid, into the mother liquor after absorption
Supplement accounts for the nitric acid of metal molar amount 50%, and supplement accounts for the phosphoric acid of metal molar amount 300%, and is used for together in step 1)
Dissolve the raw material of theobromine dissolution metal ion.
In the step 1), the raw material of the theobromine dissolution metal ion is selected from metal oxide；The metal is selected from manganese.
In the step 3), the mol ratio of the nitric acid total amount and phosphoric acid total amount is 40：1.
The step 1) and 3) in, the mol ratio of metallic element and the phosphoric acid total amount is 60：1.
Phosphate yield reaches appropriate degree and reaches 70% for yield in reaction system in the step 2)
In the step 2), the phosphorous reducing agent is selected from ferrophosphorus.
The embodiment of the present invention 12 can obtain high-purity phosphoric acid ferromanganese with the water washing with 4 times of quality of iron manganese phosphate, wash water
Few, product granularity is uniform, and particle mean size is in 1 microns.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
The dissolution of raw material of theobromine dissolution metal ion is obtained solution by the present invention using the acid containing nitric acid, adds chemical valence
State is less than the phosphorus containg substances of positive pentavalent by reducing nitrate radical, while valent state is less than the phosphorus oxidation in the phosphorus containg substances of positive pentavalent
Into phosphate radical, react to obtain calcium phosphate precipitation with metal ion, reaction is not only not introduced into other impurities, also greatlys save former material
Expect consuming cost, on the premise of same purity is reached, the phosphatic washing times prepared by the present invention greatly reduce, and produce
Wastewater from chemical industry also greatly reduce, reducing agent used at the same time does not contain organic carbon, contains the COD (COD) in waste water
Amount greatly reduces, and waste water is easily handled.
Although preferred embodiments of the present invention have been described, but those skilled in the art once know basic creation
Property concept, then can make other change and modification to these embodiments.So appended claims be intended to be construed to include it is excellent
Select embodiment and fall into having altered and changing for the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various changes and modification without departing from the spirit and scope of the present invention.So, if these modifications and variations of the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these changes and modification
It is interior.
Claims (10)
- A kind of 1. method for production of phosphate salt, it is characterised in that：Methods described comprises the following steps：1) raw material of theobromine dissolution metal ion is dissolved using acid, settled solution is obtained after separation；The acid includes nitric acid, institute The raw material for stating theobromine dissolution metal ion is selected from metal, metal oxide, metal hydroxides, metal carbonate and basic metal One or more of mixtures in carbonate；2) reaction system, reaction generation phosphate and nitrogen oxides gas are formed after phosphorous reducing agent is added in the settled solution Body, when phosphate yield reaches appropriate degree in reaction system, phosphate solid and mother liquor are obtained after separation of solid and liquid, washing removes Impurity in the phosphate solid；The phosphorous reducing agent is the phosphorus containg substances that valent state is less than positive pentavalent.
- 2. method for production of phosphate salt according to claim 1, it is characterised in that：In the step 1), the metal is selected from Iron, aluminium, copper, nickel, cobalt, manganese and zinc.
- 3. method for production of phosphate salt according to claim 1, it is characterised in that：In the step 1), the acid is selected from nitre Acid, nitric acid and the mixed acid of phosphoric acid, the mixed acid of nitric acid and hydrochloric acid, nitric acid and the mixed acid and nitric acid of sulfuric acid and mixing for oxalic acid Close acid.
- 4. method for production of phosphate salt according to claim 1, it is characterised in that：In the step 2), the valent state Mixed less than one or more of the phosphorus containg substances of positive pentavalent selected from elemental phosphorous, phosphorous acid, ortho phosphorous acid, ferrophosphorus, phosphine hydrogen, connection phosphine Compound.
- 5. method for production of phosphate salt according to claim 1, it is characterised in that：It is described to work as reactant in the step 2) Phosphate yield reaches appropriate degree and is in system：Phosphate yield is more than 0.1% and less than 100%.
- 6. method for production of phosphate salt according to claim 1, it is characterised in that：In the step 2), phosphorus after the washing Hydrochlorate solid dried purity under the conditions of 800 DEG C is 98.0~99.999%.
- 7. method for production of phosphate salt according to claim 1, it is characterised in that：Also include step 3)：By the step 2) In caused oxides of nitrogen gas use dioxygen oxidation after, absorb to obtain using all or part of mother liquor in water or step 2) Nitric acid.
- 8. method for production of phosphate salt according to claim 7, it is characterised in that：Also include step 4)：By institute in step 3) State and absorb the raw material that obtained nitric acid is back to dissolving theobromine dissolution metal ion in step 1).
- 9. method for production of phosphate salt according to claim 1, it is characterised in that：Also include step 5)：The institute into step 3) The nitric acid that supplement in the nitric acid for absorbing and obtaining is less than 2 times of metal molar amount is stated, and for dissolving theobromine dissolution metal in step 1) The raw material of ion.
- 10. method for production of phosphate salt according to claim 1, it is characterised in that：Also include step 6)：The institute into step 3) The phosphoric acid that supplement in the nitric acid for absorbing and obtaining is less than 5 times of metal molar amount is stated, and for dissolving theobromine dissolution metal in step 1) The raw material of ion.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113880061A (en) * | 2021-10-14 | 2022-01-04 | 太仓沪试试剂有限公司 | Preparation method of high-purity phosphate |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113880061A (en) * | 2021-10-14 | 2022-01-04 | 太仓沪试试剂有限公司 | Preparation method of high-purity phosphate |
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