CN113582238A - Preparation method of iron source for manganese-zinc ferrite - Google Patents
Preparation method of iron source for manganese-zinc ferrite Download PDFInfo
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- CN113582238A CN113582238A CN202110924558.9A CN202110924558A CN113582238A CN 113582238 A CN113582238 A CN 113582238A CN 202110924558 A CN202110924558 A CN 202110924558A CN 113582238 A CN113582238 A CN 113582238A
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- manganese
- zinc ferrite
- ferrous sulfate
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- ammonium bicarbonate
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 73
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 69
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 53
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 53
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 53
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 53
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 47
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 47
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000004277 Ferrous carbonate Substances 0.000 claims abstract description 30
- 235000019268 ferrous carbonate Nutrition 0.000 claims abstract description 30
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229960004652 ferrous carbonate Drugs 0.000 claims abstract description 30
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 69
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- 230000035699 permeability Effects 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000001704 evaporation Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 3
- 235000014413 iron hydroxide Nutrition 0.000 abstract 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical group [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 15
- 238000005406 washing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
Abstract
According to the preparation method of the iron source for the manganese-zinc ferrite, impurities of ferrous sulfate serving as a titanium dioxide byproduct are removed to obtain a pure ferrous sulfate solution, a certain amount of defoaming agent such as an alcohol defoaming agent or a polyether defoaming agent is added into a system containing the pure ferrous sulfate solution, then an ammonium bicarbonate solution or particles are added, a reactant is filtered and washed after a certain reaction time to obtain a ferrous carbonate precursor and a filtrate, the filtrate can be subjected to flash evaporation to obtain agricultural ammonium sulfate powder, the ferrous carbonate precursor is dried in an air atmosphere, and the iron source for the manganese-zinc ferrite can be obtained after the reaction is dried for a certain time, wherein the main component of the iron source for the manganese-zinc ferrite is iron hydroxide, and the potential crystallization hazard in the subsequent process of preparing the manganese-zinc ferrite from the iron source for the manganese-zinc ferrite can be avoided by using a silicon-free phosphorus defoaming agent; and the defoaming agent can greatly improve the production efficiency, and the precursor with larger specific surface area can be obtained due to higher reaction speed, so that the performance of the manganese-zinc ferrite is improved.
Description
Technical Field
The application relates to the technical field of ferrite materials, in particular to a preparation method of an iron source for manganese-zinc ferrite.
Background
The manganese-zinc ferrite is a soft magnetic material with a spinel structure, and is widely applied to the industries of communication, sensing, televisions and the like due to the physical and chemical properties of high magnetic conductivity, low loss and the like; along with the higher requirements of people on energy conservation and emission reduction, the requirements on the performance of the manganese-zinc-depleted ferrite are more urgent, such as high magnetic permeability, low loss and the like.
Iron sources such as iron oxide and the like are one of the main raw materials for preparing the manganese-zinc ferrite, and the price of the iron sources is increased along with the increase of the demand of the manganese-zinc ferrite; other ways of preparing iron sources are sought by those skilled in the art.
The existing process for preparing iron oxide based on ferric sulfate is relatively mature and generally comprises the following steps: dissolving, adjusting pH, adding complexing agent to remove impurities, adding precipitant, filtering, washing, drying, calcining, detecting and packaging, but the method needs calcining, so the cost is higher in the production process and the environment is polluted to a certain extent. Meanwhile, the existing method is mainly used for preparing dye-grade iron oxide red, and because the calcination temperature of the iron oxide is higher, the calcined activity is uneven, and the activity requirement on preparing the high-performance manganese-zinc ferrite material is difficult to meet.
Disclosure of Invention
The application provides a preparation method of an iron source for manganese-zinc ferrite, and aims to provide a mode for preparing the iron source for manganese-zinc ferrite.
The application provides a preparation method of an iron source for manganese-zinc ferrite, which comprises the following steps:
dissolving ferrous sulfate as a titanium dioxide byproduct and removing impurities to obtain a pure ferrous sulfate solution;
adding a silicon-free phosphorus defoaming agent into the pure ferrous sulfate solution, then adding an ammonium bicarbonate solution or ammonium bicarbonate particles, and precipitating to obtain a ferrous carbonate precursor, wherein the silicon-free phosphorus defoaming agent comprises polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents;
stirring, crushing and drying the ferrous carbonate precursor in an air atmosphere at 50-90 ℃ without presintering to obtain the iron source for the manganese-zinc ferrite.
Further, dissolving the titanium dioxide byproduct ferrous sulfate and removing impurities to obtain a pure ferrous sulfate solution, comprising:
dissolving ferrous sulfate as a titanium dioxide byproduct into water at the temperature of 50-60 ℃ to obtain a mixed solution;
adding alkali liquor into the mixed solution to adjust the pH value to 2.5-4.5, then adding polyacrylamide, performing precipitation reaction, and filtering to obtain a pure ferrous sulfate solution and titanium-containing filter residue;
the titanium-containing filter residue is used for preparing titanium dioxide.
Further, adding a defoaming agent to the pure ferrous sulfate solution, and then adding an ammonium bicarbonate solution or granules, comprising:
and adding a certain amount of silicon-free phosphorus defoaming agent into the pure ferrous sulfate solution, and simultaneously quickly adding ammonium bicarbonate solution or particles.
Further, the ferrous carbonate precursor is crushed and dried in the air atmosphere at the temperature of 50-90 ℃, and then is rapidly heated to the temperature of 280-380 ℃ for heating decomposition, and the iron source for the manganese-zinc ferrite is ferric oxide or ferric hydroxide.
Further, adding a certain amount of defoaming agent into the pure ferrous sulfate solution, simultaneously adding ammonium bicarbonate solution or ammonium bicarbonate particles, precipitating to obtain a ferrous carbonate precursor and a filtrate, wherein the filtrate is subjected to flash evaporation to obtain agricultural ammonium sulfate powder.
Further, adding a defoaming agent into the pure ferrous sulfate solution, and simultaneously adding an ammonium bicarbonate solution or ammonium bicarbonate particles, wherein the temperature of the ammonium bicarbonate solution is 30-45 ℃, and the concentration of the ammonium bicarbonate solution is 15-25%.
Further, the molar ratio of the ferrous sulfate to the added ammonium bicarbonate in the solution is 1: 1.5-2.5.
And further, after filtering and washing the ferrous carbonate precursor, if the ionic conductivity in the filtrate is required to be controlled below 800uS, the filtering and washing is qualified.
Furthermore, the manganese-zinc ferrite can be directly prepared by using an iron source for the manganese-zinc ferrite without pre-sintering at a temperature of more than 500 ℃, and the manganese-zinc ferrite is high in magnetic permeability and low in power consumption.
Has the advantages that: the application provides a preparation method of an iron source for manganese-zinc ferrite, which comprises the following steps: dissolving ferrous sulfate serving as a titanium dioxide byproduct and removing impurities to obtain a pure ferrous sulfate solution and titanium-containing filter residue, wherein the titanium-containing filter residue can be used for preparing titanium dioxide, adding a large amount of silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents into a system containing the pure ferrous sulfate solution, then adding an ammonium bicarbonate solution or even adding ammonium bicarbonate particles, filtering and washing reactants after reacting for a certain time to obtain a ferrous carbonate precursor and a filtrate, wherein the filtrate can be subjected to flash evaporation to obtain agricultural ammonium sulfate powder, drying the ferrous carbonate precursor in an air atmosphere, and drying for a certain time to obtain an iron source for manganese-zinc ferrite, wherein the iron source for the manganese-zinc ferrite is ferric oxide.
In the process, on one hand, a ferrous sulfate solution and an ammonium bicarbonate solution can generate a large amount of bubbles in the hydrolysis reaction process, Si in the traditional organic silicon defoaming agent is easy to cause crystallization hidden trouble in the subsequent process of preparing the manganese-zinc ferrite by the iron source for the manganese-zinc ferrite, and the product performance is influenced.
On the other hand, after a large amount of silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents are added into a system containing pure ferrous sulfate solution, ammonium bicarbonate solution or ammonium bicarbonate particles can be rapidly added, the reaction rate is accelerated, the production efficiency is improved, the organic defoaming agents can play a role in electrostatic repulsion in the reaction process, so that a ferrous carbonate precursor with a large specific surface area can be obtained, iron source particles prepared from the ferrous carbonate precursor with the large specific surface area are fine, and the iron source with the fine particles can have high reaction activity in the subsequent production of manganese-zinc ferrite, so that the performance of the manganese-zinc ferrite can be improved, and the manganese-zinc ferrite with high magnetic conductivity and low power consumption is obtained. Wherein, the ammonium bicarbonate particles can be rapidly added, and the waste of water is reduced.
On the other hand, the process for preparing the iron source does not need traditional calcination, saves energy, reduces emission, meets the requirement of carbon neutralization, has higher reaction activity because the ferrous carbonate is not calcined, and further improves the performance of the manganese-zinc ferrite.
The application provides an iron source for manganese zinc ferrite need not process through 500 and need not above temperature and handle, can directly be used for preparing manganese zinc ferrite, manganese zinc ferrite is high magnetic conductivity and low-power consumption manganese zinc ferrite.
In addition, the non-target products obtained in the steps in the embodiment of the application can be used for other purposes, so that the waste of resources is avoided.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing an iron source for manganese-zinc ferrite according to an embodiment of the present disclosure.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Iron sources such as iron oxide and the like are one of the main raw materials for preparing the manganese-zinc ferrite, and the price of the iron sources is increased along with the increase of the demand of the manganese-zinc ferrite; other ways of preparing iron sources are sought by those skilled in the art.
The following describes a method for producing an iron source for manganese-zinc ferrite provided by the present application with reference to fig. 1.
The application provides a preparation method of an iron source for manganese-zinc ferrite, which comprises the following steps:
s110: dissolving ferrous sulfate as a titanium dioxide byproduct and removing impurities to obtain a pure ferrous sulfate solution.
Impurities in the titanium dioxide byproduct ferrous sulfate are mainly titanium, so that the titanium is removed to purify the ferrous sulfate; titanium is not removed by adding phosphoric acid, and because the introduction of the P element can easily cause crystallization hidden trouble in the subsequent process of preparing the manganese-zinc ferrite by using an iron source for the manganese-zinc ferrite, the product performance is influenced; therefore, in the method for removing titanium in the examples of the present application, phosphoric acid was not added, but the following method was used.
Specifically, dissolving the titanium dioxide byproduct ferrous sulfate and removing impurities to obtain a pure ferrous sulfate solution, which comprises the following steps:
dissolving ferrous sulfate as a titanium dioxide byproduct into water at the temperature of 50-60 ℃ to obtain a mixed solution;
adjusting the pH value of the mixed solution to 2.5-4.5, then adding polyacrylamide, performing precipitation reaction, and filtering to obtain a pure ferrous sulfate solution and titanium-containing filter residue; the method specifically comprises the following steps: and adding alkali liquor into the mixed solution to adjust the pH value to 2.5-4.5, then adding polyacrylamide, performing precipitation reaction, and filtering to obtain a pure ferrous sulfate solution and titanium-containing filter residue.
The titanium-containing filter residue can be used for preparing titanium dioxide.
Wherein, polyacrylamide is complexed with titanium ions to form precipitates so as to remove titanium impurities.
S120: and adding a silicon-free phosphorus defoaming agent into the pure ferrous sulfate solution, then adding an ammonium bicarbonate solution or ammonium bicarbonate particles, and precipitating to obtain a ferrous carbonate precursor, wherein the silicon-free phosphorus defoaming agent comprises polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents.
The amount of the silicon-free phosphorus defoaming agent, such as polyether defoaming agent, alcohol defoaming agent and polyalkyl defoaming agent is large, and the ammonium bicarbonate solution or particles can be rapidly added on the premise of the existence of a large amount of silicon-free phosphorus defoaming agent; and obtaining a filtrate while obtaining the ferrous carbonate precursor, wherein the filtrate is subjected to flash evaporation to obtain agricultural ammonium sulfate powder.
Specifically, the molar ratio of ferrous sulfate to the added ammonium bicarbonate in the solution is 1: 1.5-2.5.
Wherein the temperature of the ammonium bicarbonate solution is 30-45 ℃, and the concentration is 15-25%.
In the application, silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents are adopted, so that the generation of bubbles can be inhibited, and the silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents can be decomposed at high temperature in the sintering step in the process of preparing manganese-zinc ferrite through an iron source for manganese-zinc ferrite, so that the crystallization hidden danger is avoided.
On the other hand, after a large amount of silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents are added into a system containing pure ferrous sulfate solution, ammonium bicarbonate solution or ammonium bicarbonate particles can be rapidly added to accelerate the reaction rate, and the silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents can play a role in electrostatic repulsion in the reaction process, so that a ferrous carbonate precursor with a large specific surface area can be obtained, iron source particles prepared from the ferrous carbonate precursor with the large specific surface area are fine, and the iron source with the fine particles can have high reaction activity in the subsequent production of manganese-zinc ferrite, so that the performance of the manganese-zinc ferrite can be improved, and the manganese-zinc ferrite with high magnetic conductivity and low power consumption can be obtained.
In the embodiment of the present application, after the polyether defoamer, the alcohol defoamer, and the polyalkyl defoamer are added, the ammonium bicarbonate particles can be rapidly added, and the ammonium bicarbonate solution is replaced by the ammonium bicarbonate particles, so that the use of water can be reduced.
Wherein ammonium bicarbonate powder can be adopted to ammonium bicarbonate solution, can use the granularity to be less than 20 mesh ammonium bicarbonate directly to drop into ferrous sulfate solution and carry out precipitation reaction specifically, need produce more moisture when having reduced the adoption solution on the one hand, cause the energy waste of follow-up flash distillation process, on the other hand has also improved production efficiency, has reduced the granule granularity.
S130: stirring, crushing and drying the ferrous carbonate precursor in an air atmosphere at 50-90 ℃ without presintering to obtain the iron source for the manganese-zinc ferrite.
Specifically, the iron source for manganese-zinc ferrite can be obtained by stirring, crushing and drying the ferrous carbonate precursor in the air atmosphere of 50-90.
A large amount of air must be introduced during the drying process to ensure that the powder is completely oxidized into reddish brown, wherein the obtained iron source for the manganese-zinc ferrite is iron oxide, namely the drying process in the embodiment of the application comprises an oxidation process.
It should be noted that in the embodiment of the application, the ferrous acid precursor is stirred, crushed and dried in an air atmosphere at 50-90 ℃, and the iron source for manganese-zinc ferrite can be obtained without pre-sintering, so that pre-sintering is not required, energy is saved, emission is reduced, and the carbon neutralization requirement is met.
The iron source for the manganese-zinc ferrite provided by the application does not need to be subjected to pre-sintering treatment at a temperature of more than 500 ℃, and can be directly used for preparing the manganese-zinc ferrite, wherein the manganese-zinc ferrite is high in magnetic permeability and low in power consumption.
The following specific examples are provided below based on the above-described method:
20000kg of ferrous sulfate is added into water with the temperature of 55 ferrous to prepare a ferrous sulfate solution with the concentration of 40%. Adding ammonia water into the prepared solution while stirring to adjust the pH value to 3.5, stirring for 20 minutes, adding 340kg of polyacrylamide solution with the concentration of 5 per mill, stirring for 30 minutes, filtering and washing, returning filter residues to a titanium dioxide manufacturer, or adding sulfuric acid to dissolve, and then adopting a recrystallization method to produce titanium dioxide, wherein the filtrate is a purified ferrous sulfate solution.
Adding 32kg of alcohol defoaming agent into the filtrate, then keeping the temperature of the solution at 40 alcohol, slowly adding 40-mesh ammonium bicarbonate particles, wherein the adding amount is 12000kg, preserving the temperature and stirring for 20 minutes after the adding is finished, and then filtering and washing.
And (3) carrying out flash evaporation on the filtered and washed solution to prepare an ammonium sulfate fertilizer, conveying filter residues into a drying chamber through a belt conveyor, and drying for 1 day under the condition of 60-time washing and blowing air to obtain a ferrous carbonate precursor for manganese-zinc ferrite.
The weight percentage of Fe element of the dried ferrous carbonate is measured by adopting a fluorescence method or a potassium dichromate method, and then the weight percentage of the element is Fe: mn: adding manganese oxide and zinc oxide into Zn at a ratio of 68.8:16.3:14.9, presintering the product in a 900-oxygen rotary kiln for 1 hour, adding a certain amount of trace elements, carrying out wet grinding, carrying out spray granulation to obtain manganese-zinc ferrite granules with high magnetic conductivity, carrying out compression molding on the granules, and sintering to obtain the manganese-zinc ferrite with the magnetic conductivity of more than 15000.
As can be seen from the above description, the present application provides a method for preparing an iron source for manganese-zinc ferrite, comprising: dissolving ferrous sulfate serving as a titanium dioxide byproduct and removing impurities to obtain a pure ferrous sulfate solution and titanium-containing filter residue, wherein the titanium-containing filter residue can be used for preparing titanium dioxide, adding a large amount of silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents into a system containing the pure ferrous sulfate solution, then adding ammonium bicarbonate solution or ammonium bicarbonate particles, filtering and washing reactants after reacting for a certain time to obtain a ferrous carbonate precursor and a filtrate, wherein the filtrate can be subjected to flash evaporation to obtain agricultural-grade ammonium sulfate powder, drying the ferrous carbonate precursor in an air atmosphere, and drying for a certain time to obtain an iron source for manganese-zinc ferrite, wherein the iron source for the manganese-zinc ferrite is ferric oxide.
In the process, on one hand, a ferrous sulfate solution and an ammonium bicarbonate solution can generate a large amount of bubbles in the hydrolysis reaction process, Si in the traditional organic silicon defoaming agent is easy to cause crystallization hidden trouble in the subsequent process of preparing the manganese-zinc ferrite by the iron source for the manganese-zinc ferrite, and the product performance is influenced.
On the other hand, after a large amount of silicon-free phosphorus defoaming agents such as polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents are added into a system containing pure ferrous sulfate solution, ammonium bicarbonate solution or ammonium bicarbonate particles can be quickly added to accelerate the reaction rate, the alcohol defoaming agents can play a role in electrostatic repulsion in the reaction process, so that a ferrous carbonate precursor with a large specific surface area can be obtained, iron source particles prepared from the ferrous carbonate precursor with the large specific surface area are fine, and an iron source with the fine particles can have high reaction activity in the subsequent production of manganese-zinc ferrite, so that the performance of the manganese-zinc ferrite can be improved, and the manganese-zinc ferrite with high magnetic conductivity and low power consumption can be obtained.
On the other hand, the process for preparing the iron source does not need to be subjected to traditional calcination, and the ferrous carbonate is not subjected to calcination, so that the reaction activity is higher, and the performance of the manganese-zinc ferrite is further improved.
The application provides an iron source for manganese zinc ferrite need not handle through the temperature more than 500 ℃, can directly be used for preparing manganese zinc ferrite, manganese zinc ferrite is high magnetic conductivity and low-power consumption manganese zinc ferrite.
In addition, the non-target products obtained in the steps in the embodiment of the application can be used for other purposes, so that the waste of resources is avoided.
Since the above embodiments are all described by referring to and combining with other embodiments, the same portions are provided between different embodiments, and the same and similar portions between the various embodiments in this specification may be referred to each other. And will not be described in detail herein.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
The above-described embodiments of the present application do not limit the scope of the present application.
Claims (9)
1. A method for preparing an iron source for manganese-zinc ferrite, comprising:
dissolving ferrous sulfate as a titanium dioxide byproduct and removing impurities to obtain a pure ferrous sulfate solution;
adding a silicon-free phosphorus defoaming agent into the pure ferrous sulfate solution, then adding an ammonium bicarbonate solution or ammonium bicarbonate particles, and precipitating to obtain a ferrous carbonate precursor, wherein the silicon-free phosphorus defoaming agent comprises polyether defoaming agents, alcohol defoaming agents and polyalkyl defoaming agents;
stirring, crushing and drying the ferrous carbonate precursor in an air atmosphere at 50-90 ℃ without presintering to obtain the iron source for the manganese-zinc ferrite.
2. The method of claim 1, wherein dissolving the titanium dioxide byproduct ferrous sulfate and removing impurities to obtain a pure ferrous sulfate solution comprises:
dissolving ferrous sulfate as a titanium dioxide byproduct into water at the temperature of 50-60 ℃ to obtain a mixed solution;
adding alkali liquor into the mixed solution to adjust the pH value to 2.5-4.5, then adding polyacrylamide, performing precipitation reaction, and filtering to obtain a pure ferrous sulfate solution and titanium-containing filter residue;
the titanium-containing filter residue is used for preparing titanium dioxide.
3. The method of claim 1, wherein adding an alcohol defoamer to the purified ferrous sulfate solution along with an ammonium bicarbonate solution or granules comprises:
and adding a certain amount of silicon-free phosphorus defoaming agent into the pure ferrous sulfate solution, and simultaneously quickly adding ammonium bicarbonate solution or particles.
4. The method as claimed in claim 1, wherein the iron source for manganese-zinc ferrite is obtained by crushing and drying the ferrous carbonate precursor in an air atmosphere at 50-90 ℃, and then rapidly heating to 280-380 ℃ for thermal decomposition.
5. The method of claim 1, wherein an amount of antifoaming agent is added to the pure ferrous sulfate solution, and ammonium bicarbonate solution or ammonium bicarbonate particles are added simultaneously, and precipitation is performed to obtain a ferrous carbonate precursor and a filtrate, wherein the filtrate is flashed to obtain agricultural grade ammonium sulfate powder.
6. The method of claim 1, wherein an antifoaming agent is added to the pure ferrous sulfate solution, and an ammonium bicarbonate solution or ammonium bicarbonate particles is added, wherein the ammonium bicarbonate solution has a temperature of 30 ℃ to 45 ℃ and a concentration of 15% to 25%.
7. The method of claim 1 wherein the molar ratio of ferrous sulfate to added ammonium bicarbonate in said solution is from 1: 1.5-2.5.
8. The method of claim 1, wherein the iron source for manganese-zinc ferrite is acceptable when the ionic conductivity of the filtrate is controlled to be 800uS or less after the ferrous carbonate precursor is filtered.
9. The method of claim 1, wherein the source of Mn-Zn ferrite can be used directly to produce Mn-Zn ferrite without pre-sintering at a temperature of 500 ℃ or higher, and the Mn-Zn ferrite has high magnetic permeability and low power consumption.
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Application publication date: 20211102 |