CN116534820B - Method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate - Google Patents
Method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate Download PDFInfo
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- CN116534820B CN116534820B CN202310347061.4A CN202310347061A CN116534820B CN 116534820 B CN116534820 B CN 116534820B CN 202310347061 A CN202310347061 A CN 202310347061A CN 116534820 B CN116534820 B CN 116534820B
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 98
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 89
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 89
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 89
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 61
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 61
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 61
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 61
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 title claims abstract description 49
- 235000019837 monoammonium phosphate Nutrition 0.000 title claims abstract description 49
- 239000006012 monoammonium phosphate Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000005056 compaction Methods 0.000 title claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000007670 refining Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000003337 fertilizer Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000001038 titanium pigment Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- -1 iron ions Chemical class 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 229910000398 iron phosphate Inorganic materials 0.000 description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01B25/375—Phosphates of heavy metals of iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of electrode materials, in particular to a method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate. The method comprises the following steps: dissolving and refining ferrous sulfate; (2) oxidation of ferrous sulfate; (3) preparation of ferric phosphate; (4) primary filtration slurrying; (5) multistage filtration; (6) drying-calcining-pulverizing. The invention adopts a reaction route of oxidation and then double decomposition, and a small amount of monoammonium phosphate in the early stage rapidly reacts with iron ions to form small-particle ferric phosphate and aggregate to grow, so that the reaction is thorough; the method has the advantages that the particle size distribution of the ferric phosphate particles is more uniform by slowly adding monoammonium phosphate, the closest packing effect of the ferric phosphate can be realized by matching with the ageing and calcining links, the tap density of the finally obtained ferric phosphate product is high, and the volume specific capacity of the battery anode material prepared by the method is high and the energy density of the battery is high.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate.
Background
The lithium ion battery has the advantages of small volume, light weight, large capacity and high energy, and is representative of modern high-performance batteries. Among lithium ion batteries, a material containing lithium elements is generally used as an electrode, and lithium iron phosphate batteries are one that uses lithium iron phosphate as a positive electrode material and carbon as a negative electrode material. Lithium iron phosphate is the safest positive electrode material of lithium ion batteries, and has the advantages of high energy density and high charging performance.
In the production process of lithium iron phosphate, the ferric phosphate has unique catalytic property, ion exchange capacity and electrochemical performance, and is an excellent raw material for preparing the lithium iron phosphate. In the prior art, the production process of ferric phosphate mainly comprises 6 processes of a sodium method, an ammonium method, iron powder, fertilizer phosphoric acid, ferric oxide red and calcium hydrophosphate, wherein the ammonium method is that ferrous sulfate solution reacts with monoammonium phosphate, and ferric phosphate finished products are obtained by neutralizing excessive acid after precipitation and filtration, and ferrous sulfate in raw materials can be ferrous sulfate solid byproducts of titanium pigment production by using a sulfuric acid method. Because the ammonium method has lower raw material cost, relatively balanced product performance, relatively balanced compaction and capacity, relatively better winter low-temperature performance, the ammonium method is mainly used for producing the ferric phosphate in the prior art.
In the lithium battery industry, iron phosphate is limited by the existing production process, and the tap density of the produced finished product is low and is only 0.7-0.8g/cm 3 The lithium iron phosphate electrode prepared by using the low tap density ferric phosphate as a raw material has low volume specific capacity, and the energy density in practical application is limited, so that the capacity of the lithium iron phosphate battery is not ideal. Therefore, the improvement of tap density of the ferric phosphate product and the improvement of volume specific capacity of the lithium iron phosphate electrode are of great significance to the practical application of the lithium iron phosphate battery.
Disclosure of Invention
Aiming at the technical problems of low tap density, low volume specific capacity of prepared electrode chips and limited energy density of iron phosphate obtained by the existing industrial production process, the invention provides a method for preparing high-compaction iron phosphate by industrial monoammonium phosphate and ferrous sulfate, which adopts a reaction route of first oxidation and then double decomposition, and a small amount of monoammonium phosphate in the early stage rapidly reacts with iron ions to form small-particle iron phosphate and is aggregated to grow, so that the reaction is thorough; the method has the advantages that the particle size distribution of the ferric phosphate particles is more uniform by slowly adding monoammonium phosphate, the closest packing effect of the ferric phosphate can be realized by matching with the ageing and calcining links, the tap density of the finally obtained ferric phosphate product is high, and the volume specific capacity of the battery anode material prepared by the method is high and the energy density of the battery is high.
The invention provides a method for preparing high-compaction ferric phosphate by industrial monoammonium phosphate and ferrous sulfate, which comprises the following steps:
(1) Dissolving and refining ferrous sulfate, dissolving impurity-containing ferrous sulfate solid in water, adding iron powder for full reaction, filtering, collecting filtrate to obtain refined ferrous sulfate solution, adding iron powder to remove metal ions such as titanium and zinc and improve the content of iron element in the refined ferrous sulfate;
(2) Oxidizing ferrous sulfate, adding hydrogen peroxide into the refined ferrous sulfate solution for full reaction to obtain an oxidized solution, wherein the main reaction equation of the step (2) is as follows: 2FeSO 4 +H 2 O 2 +H 2 SO 4 ＝Fe 2 (SO 4 ) 3 +2H 2 O；
(3) Preparing ferric phosphate, namely adding monoammonium phosphate solution into the oxidation solution, heating and fully reacting to obtain ferric phosphate slurry, wherein the main reaction equation of the step (3) is as follows: fe (Fe) 2 (SO 4 ) 3 +2NH 4 H 2 PO 4 ＝2FePO 4 +(NH 4 ) 2 SO 4 +2H 2 SO 4 ；
(4) Primary filtering and pulping, namely primary filtering the ferric phosphate slurry, collecting a solid part, washing to obtain a primary filter cake, adding pure water into the washed primary filter cake, stirring, and aging in a conversion kettle to obtain aged ferric phosphate slurry;
(5) Performing multistage filtration, namely performing secondary filtration on the aged ferric phosphate slurry, collecting a solid part, washing to obtain a secondary filter cake, adding pure water into the washed secondary filter cake, stirring, performing tertiary filtration, and collecting the solid part to obtain a tertiary filter cake;
(6) Drying, calcining and crushing, drying the three-stage filter cake to obtain ferric phosphate containing crystal water, calcining the ferric phosphate containing crystal water to remove crystal water, crushing in a crushing device, and pulse collecting the crushed tail gasThe dust collector is discharged from high altitude after reaching the standard, and the crushed materials are uniformly mixed to obtain high-compaction ferric phosphate, and the tap density of the high-compaction ferric phosphate is more than or equal to 0.9g/cm 3 。
Further, the impurity ferrous sulfate solid in the step (1) is a ferrous sulfate solid byproduct of titanium pigment production by a sulfuric acid method.
Further, the reaction temperature of the step (1) is 40-60 ℃, and the mass percentage concentration of iron element in the prepared refined ferrous sulfate solution is 6-8%.
Further, H in the hydrogen peroxide added in the step (2) 2 O 2 The molar ratio of the iron element in the refined ferrous sulfate solution is 0.5-1: 1. the reaction temperature is 40-60 ℃ and the reaction time is 15min-2h.
Further, the monoammonium phosphate solution in the step (3) is industrial monoammonium phosphate solution, NH 4 H 2 PO 4 The mass percentage concentration is 25% -28%.
Further, NH in monoammonium phosphate solution added in step (3) 4 H 2 PO 4 The molar ratio of the iron element to the iron element in the oxidizing solution is 0.9-1.1:1, heating by steam in the reaction process, wherein the temperature is 80-90 ℃ and the reaction time is 2-4h.
Further, the filtrate part is collected after the first-stage filtration in the step (4) and is used in the production link of fertilizer, and the filtrate contains (NH) 4 ) 2 SO 4 And NH 4 H 2 PO 4 Can be used for producing nitrogenous fertilizer and phosphate fertilizer.
Further, the solid part collected by the first-stage filtration is washed in the step (4), and the washing end point is that the conductivity of the effluent is less than or equal to 4000 mu s/cm.
And (3) washing the solid part collected by the secondary filtration in the step (5), wherein the washing end point is that the conductivity of the effluent is less than or equal to 1500 mu s/cm.
Further, in the step (6), the ferric phosphate containing crystal water is calcined through a rotary kiln, the calcining temperature is 500-800 ℃, and the calcining time is 2-4 hours.
The invention has the beneficial effects that:
1. the method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate adopts a reaction route of firstly oxidizing and then double decomposing, firstly using hydrogen peroxide to completely oxidize a refined ferrous sulfate solution, then slowly adding monoammonium phosphate, leading the initial iron element concentration of the reaction solution to be high, leading a small amount of added monoammonium phosphate to quickly react with high-concentration iron ions to form small-particle ferric phosphate, and taking the small-particle ferric phosphate as a core to be aggregated and grown in the subsequent reaction, so that the reaction is thorough.
2. The method continuously reacts in a mode of slowly adding monoammonium phosphate, the growth degree of the ferric phosphate particles formed by the reaction in different time periods is different at the end of the reaction, so that the particle size distribution of the ferric phosphate particles generated by the reaction is more uniform, small-particle ferric phosphate can be fully interstitial between large-particle ferric phosphate by matching with the subsequent aging and calcining links, the closest packing effect is realized, and the tap density of the finally obtained ferric phosphate product is high and can reach 0.9g/cm 3 The battery anode material prepared by the method has high volume specific capacity and high energy density.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a production flow chart of example 1.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
A method for preparing high-compaction ferric phosphate by industrial monoammonium phosphate and ferrous sulfate, comprising the following steps:
(1) Dissolving and refining ferrous sulfate, adding water into a ferrous sulfate solid byproduct produced in the production of titanium pigment by a sulfuric acid method, adding iron powder, controlling the reaction temperature to be 45 ℃, fully reacting, filtering, and collecting filtrate to obtain a refined ferrous sulfate solution 1t with the mass percentage concentration of iron element of 6.90%;
(2) Oxidizing ferrous sulfate, adding hydrogen peroxide into refined ferrous sulfate solution for full reaction, and adding H into the hydrogen peroxide 2 O 2 The molar ratio of the iron element in the refined ferrous sulfate solution is 0.7: 1. the reaction temperature is 45 ℃ and the reaction is carried out for 30min to obtain an oxidation solution;
(3) Preparation of ferric phosphate, adding monoammonium phosphate solution with mass percent concentration of 25% into the oxidation solution, and adding NH into the monoammonium phosphate solution 4 H 2 PO 4 The molar ratio of the iron element in the oxidizing solution is 1:1, adding monoammonium phosphate solution at a constant speed, and heating by steam to react at 80-90 ℃, wherein the feeding time of the monoammonium phosphate solution is 90min, and the total reaction time is 2.5h, so as to obtain ferric phosphate slurry;
(4) Primary filtering and pulping, performing primary filtering on the ferric phosphate slurry, and collecting a filtrate part for use in a fertilizer production link; collecting and washing the solid part, wherein the washing end point is that the conductivity of the effluent is less than or equal to 4000 mu s/cm, so as to obtain a first-stage filter cake; adding pure water into the washed primary filter cake, stirring, and transferring to a conversion kettle for ageing to obtain aged ferric phosphate slurry;
(5) Performing multistage filtration, namely performing secondary filtration on the aged ferric phosphate slurry, collecting a solid part, washing, and obtaining a secondary filter cake at the washing end point that the conductivity of the effluent is less than or equal to 1500 mu s/cm; adding pure water into the washed secondary filter cake, stirring, performing tertiary filtration, and collecting a solid part to obtain a tertiary filter cake;
(6) Drying, calcining and crushing, namely drying the three-stage filter cake to obtain ferric phosphate containing crystal water, calcining the ferric phosphate containing crystal water through a rotary kiln at the calcining temperature of 600 ℃ for 2.5 hours, conveying the calcined ferric phosphate into a crushing device for crushing, discharging the crushed tail gas up to the standard through a pulse dust collector, and uniformly mixing the crushed materials to obtain the high-compaction ferric phosphate.
The tap density of the iron phosphate obtained in example 1 was 0.93g/cm 3 。
Example 2
A method for preparing high-compaction ferric phosphate by industrial monoammonium phosphate and ferrous sulfate, comprising the following steps:
(1) Dissolving and refining ferrous sulfate, adding water into a ferrous sulfate solid byproduct produced in the production of titanium pigment by a sulfuric acid method, adding iron powder, controlling the reaction temperature to be 55 ℃, fully reacting, filtering, and collecting filtrate to obtain a refined ferrous sulfate solution 1t with the mass percentage concentration of iron element of 7.32%;
(2) Oxidizing ferrous sulfate, adding hydrogen peroxide into refined ferrous sulfate solution for full reaction, and adding H into the hydrogen peroxide 2 O 2 The molar ratio of the iron element in the refined ferrous sulfate solution is 0.9: 1. the reaction temperature is 55 ℃ and the reaction is carried out for 1h to obtain an oxidation solution;
(3) Preparation of ferric phosphate, adding monoammonium phosphate solution with mass percent concentration of 25% into the oxidation solution, and adding NH into the monoammonium phosphate solution 4 H 2 PO 4 The molar ratio of the iron element in the oxidizing solution is 1:1, adding monoammonium phosphate solution at a constant speed, and heating by steam to react at 80-90 ℃, wherein the feeding time of the monoammonium phosphate solution is 85min, and the total reaction time is 3h, so as to obtain ferric phosphate slurry;
(4) Primary filtering and pulping, performing primary filtering on the ferric phosphate slurry, and collecting a filtrate part for use in a fertilizer production link; collecting and washing the solid part, wherein the washing end point is that the conductivity of the effluent is less than or equal to 4000 mu s/cm, so as to obtain a first-stage filter cake; adding pure water into the washed primary filter cake, stirring, and transferring to a conversion kettle for ageing to obtain aged ferric phosphate slurry;
(5) Performing multistage filtration, namely performing secondary filtration on the aged ferric phosphate slurry, collecting a solid part, washing, and obtaining a secondary filter cake at the washing end point that the conductivity of the effluent is less than or equal to 1500 mu s/cm; adding pure water into the washed secondary filter cake, stirring, performing tertiary filtration, and collecting a solid part to obtain a tertiary filter cake;
(6) Drying, calcining and crushing, namely drying the three-stage filter cake to obtain ferric phosphate containing crystal water, calcining the ferric phosphate containing crystal water through a rotary kiln at the calcining temperature of 650 ℃ for 3.5 hours, conveying the calcined ferric phosphate into a crushing device for crushing, discharging the crushed tail gas up to the standard through a pulse dust collector, and uniformly mixing the crushed materials to obtain the high-compaction ferric phosphate.
The tap density of the iron phosphate obtained in example 1 was 0.98g/cm 3 。
Comparative example 1
The preparation method of ferric phosphate comprises the steps of directly mixing ferrous sulfate with monoammonium phosphate solution and hydrogen peroxide, heating and reacting to obtain ferric phosphate slurry, and carrying out multistage filtration pulping on the ferric phosphate slurry to obtain a ferric phosphate finished product, wherein the specific steps comprise:
(1) Dissolving and refining ferrous sulfate, adding water into a ferrous sulfate solid byproduct produced in the production of titanium pigment by a sulfuric acid method, adding iron powder, controlling the reaction temperature to be 50 ℃, fully reacting, filtering, and collecting filtrate to obtain a refined ferrous sulfate solution 1t with the mass percentage concentration of iron element of 6.82%;
(2) Preparing ferric phosphate, namely adding hydrogen peroxide and monoammonium phosphate solution into the refined ferrous sulfate solution at the same time, wherein the adding time of the hydrogen peroxide and monoammonium phosphate solution is 60min, and H in the hydrogen peroxide 2 O 2 NH in monoammonium phosphate solution 4 H 2 PO 4 The molar ratio of the iron element in the refined ferrous sulfate solution is 1:1:1, reacting for 2 hours at the reaction temperature of 80 ℃ to obtain ferric phosphate slurry;
(3) Primary filtering and pulping, performing primary filtering on the ferric phosphate slurry, and collecting a filtrate part for use in a fertilizer production link; collecting and washing the solid part, wherein the washing end point is that the conductivity of the effluent is less than or equal to 4000 mu s/cm, so as to obtain a first-stage filter cake; adding pure water into the washed primary filter cake, stirring, and transferring to a conversion kettle for ageing to obtain aged ferric phosphate slurry;
(4) Performing multistage filtration, namely performing secondary filtration on the aged ferric phosphate slurry, collecting a solid part, washing, and obtaining a secondary filter cake at the washing end point that the conductivity of the effluent is less than or equal to 1500 mu s/cm; adding pure water into the washed secondary filter cake, stirring, performing tertiary filtration, and collecting a solid part to obtain a tertiary filter cake;
(5) Drying, calcining and crushing, namely drying the three-stage filter cake to obtain ferric phosphate containing crystal water, calcining the ferric phosphate containing crystal water through a rotary kiln at the calcining temperature of 600 ℃ for 2.5 hours, conveying the calcined ferric phosphate into a crushing device for crushing, discharging the crushed tail gas up to the standard through a pulse dust collector, and uniformly mixing the crushed materials to obtain a ferric phosphate product.
The tap density of the iron phosphate prepared in comparative example 1 was 0.72g/cm 3 。
It can be seen that the high compaction iron phosphate product made in examples 1-2 has a tap density significantly higher than the iron phosphate product made in comparative example 1.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A method for preparing high-compaction ferric phosphate by industrial monoammonium phosphate and ferrous sulfate, which is characterized by comprising the following steps:
(1) Dissolving and refining ferrous sulfate, dissolving impurity-containing ferrous sulfate solid in water, adding iron powder for full reaction, filtering, and collecting filtrate to obtain refined ferrous sulfate solution;
(2) Oxidizing ferrous sulfate, adding hydrogen peroxide into the refined ferrous sulfate solution for full reaction to obtain an oxidized solution;
(3) Preparation of ferric phosphate, slowly adding monoammonium phosphate solution into the oxidation solution, addingNH in monoammonium phosphate solution 4 H 2 PO 4 The molar ratio of the iron element to the iron element in the oxidizing solution is 0.9-1.1:1, adding monoammonium phosphate solution at a constant speed, heating by steam at 80-90 ℃ for reaction, wherein the adding time of the monoammonium phosphate solution is 75-90min, the total reaction time is 2-4h, and fully reacting to obtain ferric phosphate slurry;
(4) Primary filtering and pulping, namely primary filtering the ferric phosphate slurry, collecting a solid part, washing to obtain a primary filter cake, adding pure water into the washed primary filter cake, stirring, and aging in a conversion kettle to obtain aged ferric phosphate slurry;
(5) Performing multistage filtration, namely performing secondary filtration on the aged ferric phosphate slurry, collecting a solid part, washing to obtain a secondary filter cake, adding pure water into the washed secondary filter cake, stirring, performing tertiary filtration, and collecting the solid part to obtain a tertiary filter cake;
(6) Drying, calcining and crushing, namely drying the three-stage filter cake to obtain ferric phosphate containing crystal water, calcining the ferric phosphate containing crystal water, conveying the ferric phosphate containing crystal water into a crushing device for crushing, and uniformly mixing the crushed materials to obtain the high-compaction ferric phosphate.
2. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the impurity-containing ferrous sulfate solid in step (1) is a ferrous sulfate solid byproduct of sulfuric acid process titanium pigment production.
3. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the reaction temperature of the step (1) is 40-60 ℃, and the mass percentage concentration of iron element in the prepared refined ferrous sulfate solution is 6-8%.
4. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein H in the hydrogen peroxide added in the step (2) 2 O 2 The molar ratio of the iron element in the refined ferrous sulfate solution is 0.5-1: 1. the reaction temperature is 40-60 ℃ and the reaction time is 15min-2h.
5. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the monoammonium phosphate solution in the step (3) is an industrial monoammonium phosphate solution, and the mass percentage concentration of monoammonium phosphate is 25% -28%.
6. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the filtrate fraction is collected after the primary filtration in step (4) and used in the fertilizer production process.
7. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the solid part collected by the primary filtration is washed in the step (4) at the end point of water outlet conductivity of 4000 μs/cm or less.
8. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the solid part collected by the secondary filtration is washed in the step (5) at the end point of the washing, wherein the conductivity of the effluent is less than or equal to 1500 mu s/cm.
9. The method for preparing high-compaction ferric phosphate from industrial monoammonium phosphate and ferrous sulfate according to claim 1, wherein the step (6) is to calcine the ferric phosphate containing crystal water through a rotary kiln at a calcination temperature of 500-800 ℃ for 2-4 hours.
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