CN113912131B - Zinc ferrite treatment method - Google Patents
Zinc ferrite treatment method Download PDFInfo
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- CN113912131B CN113912131B CN202111181630.XA CN202111181630A CN113912131B CN 113912131 B CN113912131 B CN 113912131B CN 202111181630 A CN202111181630 A CN 202111181630A CN 113912131 B CN113912131 B CN 113912131B
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- zinc ferrite
- zinc
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- oxalic acid
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 114
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 104
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 238000005580 one pot reaction Methods 0.000 claims abstract description 29
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000009466 transformation Effects 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229940062993 ferrous oxalate Drugs 0.000 claims abstract description 11
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 36
- 229960005070 ascorbic acid Drugs 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 49
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 46
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000011787 zinc oxide Substances 0.000 abstract description 23
- 238000009854 hydrometallurgy Methods 0.000 abstract description 8
- 239000012084 conversion product Substances 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 20
- 229910052725 zinc Inorganic materials 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000000197 pyrolysis Methods 0.000 description 16
- 238000002386 leaching Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the technical field of comprehensive recovery of solid waste generated by hydrometallurgy, and particularly discloses a zinc ferrite treatment method which comprises the following steps: carrying out one-pot transformation on the slurry containing zinc ferrite, oxalic acid and a reducing agent, and then carrying out solid-liquid separation to obtain transformation products of zinc oxalate and ferrous oxalate; wherein the weight ratio of the oxalic acid to the zinc ferrite is more than or equal to 0.5; the weight ratio of the reducing agent to the zinc ferrite is greater than or equal to 0.25. The research of the invention finds that the cooperation can be realized unexpectedly under the combined control of the components and the proportion, namely the mild one-pot conversion of the zinc ferrite is realized, and the conversion product is further pyrolyzed at low temperature in inert atmosphere, so that the ferroferric oxide and the zinc oxide can be obtained, and the mild resource utilization of the zinc ferrite is realized. The method can realize large-scale high-value utilization of the zinc ferrite, is simple and convenient to operate, short in process flow, mild in reaction condition, high in conversion efficiency, clean and low in energy consumption, and has an excellent industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy slag comprehensive recovery, and particularly relates to a zinc ferrite recycling method.
Background
The zinc hydrometallurgy is a smelting process selected by most zinc smelting enterprises in China, and the main steps of the zinc hydrometallurgy are processes such as roasting, leaching, purifying and electrodepositing. Roasting the zinc concentrate to obtain zinc calcine, wherein the main component of the zinc calcine comprises zinc ferrite (ZnFe)2O4) And ZnO is easily dissolved in acid and can be leached out under the condition of lower acid concentration, so that the existence of zinc ferrite is the main reason for low leaching rate of zinc in the process of zinc hydrometallurgy. The zinc ferrite is of a spinel structure, has stable properties and is insoluble in dilute acid and alkali. Research shows that the concentration of sulfuric acid is 120g/L, the leaching time is 150-180 min, zinc ferrite starts to be dissolved when the leaching temperature reaches 75 ℃, but iron is leached into the solution under high acid concentration, impurities are introduced, and the steps of subsequent zinc extraction are increased. While Fe in solution3+The increase in (b) results in an increase in the potential of the solution, which in turn inhibits the decomposition of zinc ferrite. In the zinc hydrometallurgy process, the leaching residue in zinc obtained after zinc calcine is leached is subjected to hot acid leaching to obtain a pickling solution, and the pre-neutralization solution obtained after the pickling solution is subjected to pre-neutralization is subjected to iron removal by an iron-vanadium method to obtain a dangerous waste, namely iron-vanadium residue. The ferrovanadium slag not only contains a large amount of valuable metals such as Ga, Ge, In, Ag and Fe, but also has serious threat to the environment because zinc calcine is not effectively treated, zinc ferrite is a phase which is difficult to be recycled and separated from the ferrovanadium slag, and In addition, the ferrovanadium slag has large slag deposition amount, thereby not only wasting a large amount of valuable metal resources such as Ga, Ge, In, Ag and Fe, but also occupying a large amount of land.
In the pyrometallurgical zinc smelting process, the zinc ferrite can be C, SO at high temperature2And reduction of CO or the like to Fe3O4And ZnO, but the process is susceptible to over-reduction to ZnO andFeO or ZnO and Fe. Chinese patent CN103276197A discloses a method for flash reduction roasting of zinc calcine, which improves the problem of high energy efficiency, can realize rapid and thorough decomposition and reduction (1-3 s) of zinc ferrite in the zinc calcine, but still has the problem of over-reduction, and how to develop a new method for controllable and efficient resource separation of the zinc ferrite becomes the problem to be urgently solved for treating zinc hydrometallurgy iron-precipitation slag.
Disclosure of Invention
In order to solve the problems of zinc ferrite property temperature and great resource utilization difficulty, the invention aims to provide mild zinc ferrite transformation and resource co-production of Fe3O4And a ZnO treatment method.
A zinc ferrite treatment method comprises the steps of carrying out one-pot conversion (also called one-pot reaction) on slurry containing zinc ferrite, oxalic acid and a reducing agent, and then carrying out solid-liquid separation to obtain conversion products of zinc oxalate and ferrous oxalate;
wherein the weight ratio of oxalic acid to zinc ferrite is greater than or equal to 0.5; the weight ratio of the reducing agent to the zinc ferrite is greater than or equal to 0.25.
The zinc ferrite has a spinel structure, is stable in property, is difficult to transform and convert, and has high acid leaching difficulty and low leaching rate, for example, basically has no leaching effect in an oxalic acid system. In order to solve the industrial problem, the invention tries to convert the raw materials into liquid phase in one pot in the prior art, but the prior effect is not ideal, mainly the conversion effect is not ideal, and the converted solid phase product is loaded on the surface of the raw materials to block a reaction channel, thereby further influencing the conversion treatment effect. Aiming at the technical problem, the invention innovatively discovers that the coordination can be realized by putting the zinc ferrite into a system containing oxalic acid and a reducing agent under the synchronous treatment of the oxalic acid and the reducing agent, and the zinc oxalate and the ferrous oxalate can be formed by one-pot mild liquid phase transformation; thus, the method is beneficial to realizing the resource treatment of the zinc ferrite.
The research finds that the one-pot synchronization (initial synchronization) of the oxalic acid and the reducing agent and the combined control of the conditions are the key for realizing the one-pot temperature and transformation of the zinc ferrite synergistically.
In the invention, in order to realize the synergy of the oxalic acid and the reducing agent and improve the one-pot transformation effect, a mixed solution in which the oxalic acid and the reducing agent are dissolved can be added into zinc ferrite and a turbid solution (slurry) thereof, or the zinc ferrite and a solution (slurry) thereof are added into a base solution in which the oxalic acid and the reducing agent are dissolved, and the zinc ferrite and the solution (slurry) thereof are mixed to obtain the slurry. Thus being more beneficial to realizing one-pot synchronous synergistic treatment of the zinc ferrite, the oxalic acid and the reducing agent.
In the invention, the solvent of the ore pulp is water.
Preferably, in the slurry, the amount of the solvent is not particularly required, for example, the mass ratio of the solvent to the zinc ferrite is 30: 1-50: 1.
preferably, the reducing agent is a water-soluble reducing compound, preferably ascorbic acid and water-soluble salts thereof. The reducing agent may be used in the form of a solid or an aqueous solution.
According to the invention, under the one-pot cooperation of the oxalic acid and the reducing agent, the control of the component proportion is further matched, so that the cooperation is further improved, and the mild transformation effect of the zinc ferrite is improved.
Preferably, the mass ratio of oxalic acid to zinc ferrite (dry weight basis) is greater than or equal to 0.7; preferably 0.7-1.5: 1, more preferably 1-1.5: 1.
preferably, the mass ratio of the reducing agent to the zinc ferrite (dry weight basis) is greater than or equal to 0.25; preferably 0.25-2: 1; more preferably 1 to 1.5: 1.
in the invention, a one-pot reaction is carried out under an open condition;
preferably, the one-pot reaction is carried out under stirring, and the preferred stirring speed is 100-300 r/min.
In the invention, the transformation of zinc ferrite can be realized under mild conditions by virtue of the synergy of the oxalic acid and the reducing agent in proportion. The treatment temperature is not particularly required, and for the sake of simplicity of operation, the temperature of the one-pot reaction may be, for example, 10 ℃ or higher, and more preferably 40 to 60 ℃.
In the invention, the time of the one-pot reaction can be adjusted according to the conversion condition, for example, the time of the one-pot reaction is more than or equal to 1 h; more preferably 1 to 2 hours.
In the invention, after one-pot reaction, solid-liquid separation is carried out, and then water washing, alcohol washing and drying treatment are carried out to obtain transformation products of zinc oxalate and ferrous oxalate.
In the invention, the rotary product is roasted under protective atmosphere to obtain Fe3O4And ZnO;
preferably, the protective atmosphere is at least one of nitrogen and inert gas;
preferably, the baking temperature is 400-600 ℃, and more preferably 400-500 ℃.
The research of the invention finds that the transformation product can realize the synergistic transformation of the composite oxalate obtained by the transformation in the protective atmosphere and at the temperature unexpectedly and successfully, and is beneficial to controllably obtaining Fe3O4And ZnO phase products.
Preferably, the roasted product is subjected to magnetic separation to obtain Fe3O4And ZnO.
In the invention, the zinc ferrite is derived from at least one of pure substances, minerals and slag.
The invention relates to a preferable zinc ferrite treatment method, which comprises the steps of slurrying zinc ferrite, oxalic acid and a reducing agent with water to obtain slurry; the slurry was subjected to one-pot conversion treatment, followed by separation to obtain a conversion product containing zinc oxalate and ferrous oxalate. Preferably, the transformation product is roasted at 400-600 ℃ in a protective atmosphere to obtain a roasted product containing ferroferric oxide and zinc oxide.
The invention takes zinc ferrite as raw material to prepare ferroferric oxide and zinc oxide, has simple preparation process and high purity of the produced product, can fully utilize the zinc ferrite and realize the low-cost industrial production of the zinc oxide and the ferroferric oxide.
A more preferred method of the invention comprises the steps of:
(1): adding a zinc ferrite material into water, wherein the mass ratio of a solvent to the zinc ferrite is 30: 1-50: 1; stirring for 5-10 min;
(2): synchronously adding a reducing agent and a leaching agent into a zinc ferrite-solvent system, wherein the mass ratio of the reducing agent (ascorbic acid) to the leaching agent to the zinc ferrite is 0.25-1.5: 0.7-1.5: 1; uniformly mixing and stirring the mixed system, and reacting at the temperature of 40-60 ℃ for 1-2 hours to obtain a reaction product; the reaction conditions are all normal-pressure air atmosphere.
(3): washing the product obtained after the reaction in the step (2) for 3-5 times by using distilled water or absolute ethyl alcohol, and drying the washed product in a freezing vacuum manner or in a vacuum oven to obtain a dried product, namely a mixture of zinc oxalate and ferrous oxalate;
(4): and (4) carrying out pyrolysis reaction (pyrolysis temperature is raised to 400-600 ℃) on the mixture of zinc oxalate and ferrous oxalate obtained in the step (3) in an inert atmosphere (such as nitrogen or argon), so as to obtain ferroferric oxide and zinc oxide, and separating the ferroferric oxide and the zinc oxide through magnetic separation.
The method can also be extended to the preparation application of other similar materials. For example, other iron slag materials containing zinc ferrite may be used in place of the zinc ferrite.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
in order to solve the problem that the zinc ferrite is difficult to be controllably and efficiently separated and utilized as resources, the invention can cause the zinc ferrite to be mildly transformed into an oxalate mixture by one-pot synchronous cooperation of oxalic acid and a reducing agent and further by the combined control of reaction temperature and material proportion; further converting the converted product into magnetic Fe directionally under inert atmosphere and low-temperature pyrolysis3O4And ZnO, and finally Fe can be respectively obtained by a magnetic separation mode3O4And ZnO. Through the combination of the above measures, the invention can realize the mild conversion and the resource controllable high-efficiency separation of the zinc ferrite.
The method has mild reaction conditions and simple operation, realizes the controllable and efficient resource treatment and value-added utilization of the zinc ferrite, provides a method and a technical reference for fundamentally solving the problem of iron slag deposition in the zinc hydrometallurgy process, and has wide industrial application prospect.
Drawings
FIGS. 1 and 2 are XRD and SEM images, respectively, of zinc ferrite;
FIGS. 3 and 4 are XRD and SEM images, respectively, of the product obtained in example 1;
FIG. 5 is an XRD pattern of inert pyrolysis products of the product obtained in example 1;
FIG. 6 is an XRD and SEM images for the group a case of example 2 (7: 10 by weight);
FIG. 7 is an XRD and SEM image for group b case of example 2 (1.5: 1 by weight);
FIGS. 8 and 9 are SEM and XRD patterns, respectively, obtained from example 3;
FIGS. 10 and 11 are the SEM and XRD patterns, respectively, of the product obtained in example 4 (at 60 deg.C);
FIG. 12 is an XRD pattern of the product obtained in comparative example 1;
FIGS. 13 and 14 are a SEM photograph and a XRD photograph, respectively, of the product obtained in comparative example 1 (with 0.1g of ascorbic acid added) and a thermogravimetric product;
FIGS. 15 and 16 are SEM and XRD patterns, respectively, of the product obtained in comparative example 2;
FIG. 17 is an XRD pattern of the product obtained in comparative example 3;
FIG. 18 is an XRD pattern of the product obtained in comparative example 4;
FIGS. 19 and 20 are SEM and XRD patterns, respectively, of the product obtained in comparative example 5;
FIG. 21 is an XRD pattern of a product obtained by pyrolysis in an air atmosphere of comparative example 6;
FIG. 22 is an XRD pattern of the product obtained by pyrolysis of comparative example 7;
FIG. 23 is an XRD pattern of the product of pyrolysis of comparative example 8;
Detailed Description
The present invention will be described in further detail with reference to examples.
The zinc ferrite in the embodiment of the invention is mainly obtained by leaching reagent grade and jarosite slag at one time.
Example 1
In the embodiment, reagent-grade zinc ferrite (analytically pure, XRD is shown in fig. 1, and SEM is shown in fig. 2) is used to reduce, dissolve and recrystallize zinc ferrite through cooperation of oxalic acid and ascorbic acid to obtain zinc oxalate and ferrous oxalate, and then zinc oxide and ferroferric oxide are obtained through inert atmosphere pyrolysis, and finally iron-zinc separation can be realized through a magnetic separation method, and the specific operation procedure is performed according to the following steps:
(1) adding 2.75g of zinc ferrite into solvent water, and uniformly stirring to obtain slurry, wherein the mass ratio of the solvent water to the zinc ferrite is 30: 1;
(2) synchronously adding a leaching agent oxalic acid and a reducing agent ascorbic acid (adding a mixed solution of oxalic acid and ascorbic acid) into the slurry obtained in the step (1); the mass ratio of the leaching agent to the reducing agent to the zinc ferrite is 1: 1: 1, uniformly mixing to obtain a precursor system;
(3) the precursor system is stirred at 40 ℃ (the stirring speed is 250r/min) for reaction, the reaction process is carried out in an open container, the reaction time is 2h, after the reaction, distilled water or absolute ethyl alcohol is adopted for washing, the supernatant is poured out, the reaction is repeated for 3 times, reaction products are obtained, XRD and SEM spectrums of the reaction products are shown in attached figures 3 and 4, and the attached figures 3 and 4 show that: the XRD spectrum of the zinc ferrite dissolved recrystallization product shows that the XRD diffraction peak of the zinc ferrite phase disappears, and the appearance and the phase structure of the zinc ferrite are obviously transformed.
(4) And (4) under an inert atmosphere (argon atmosphere), heating the powder product obtained in the step (3) to 600 ℃, and preserving heat for 2 hours to obtain a pyrolysis product. The XRD pattern of the pyrolysis product is shown in figure 5. Researches find that zinc ferrite dissolution recrystallization products can be converted into ferroferric oxide and zinc oxide through inert atmosphere pyrolysis, so that separation and recycling of iron and zinc in the zinc ferrite are realized, and the scheme of the invention has excellent industrial application value.
Example 2
Compared with the example 1, the difference is only that the ratio of oxalic acid is changed, wherein the weight ratio of the oxalic acid to the zinc ferrite is (a) 7: 10; (b) 1.5: 1; the other conditions were the same as in example 1.
The products after treatment were found to have similar structural morphology to those of example 1 by measurement. The SEM image and XRD image are shown in FIGS. 6 and 7 respectively (FIG. 6 is a case of group a; FIG. 7 is a case of group b).
Example 3
Compared with the example 1, the difference is only that the ratio of the ascorbic acid is changed, wherein the weight ratio of the ascorbic acid to the zinc ferrite is respectively as follows: (a) 1: 4; (b) 1.5: 1; other conditions were the same as in example 1;
the products after treatment were found to have similar structural morphology to those of example 1 by measurement. For example, the XRD and SEM images of the product obtained in the example are shown in figures 8 and 9 respectively, and it can be seen that the zinc ferrite phase disappears and the morphology and structure of the product are changed significantly after the reaction compared with the zinc ferrite material.
Example 4
Compared with example 1, the difference is only that the reaction temperature of step (3) (one-pot reaction temperature) is changed to 15 ℃, 50 ℃, 60 ℃; the other conditions were the same as in example 1.
The products after treatment were found by measurement to have a morphology similar to that of example 1. For example, the SEM and XRD patterns of the 60 ℃ product are shown in figures 10 and 11 respectively (the 15 ℃ reaction product is shown in the right figure), and compared with the original zinc ferrite material, the phase of the zinc ferrite disappears, and the appearance and the structure of the zinc ferrite obviously change.
Comparative example 1
The difference from example 1 is only that the ascorbic acid content is reduced, that is, the ascorbic acid is added in an amount of 0.1, 0.3 and 0.5g, respectively; the other conditions were the same as in example 1.
In contrast to the results of 0.7g of ascorbic acid added, the XRD pattern of this case is shown in FIG. 12, and the SEM pattern of the product at the addition of 0.1g of ascorbic acid is shown in FIG. 13. The results show that when the addition amount of the ascorbic acid is less, the main products of the reaction are zinc ferrite and zinc oxalate, which indicates that the addition amount of the reducing agent is less and the structural transformation of the zinc ferrite is difficult to promote, and the XRD (figure 14) results of the thermogravimetric products show that the pyrolysis products are zinc oxide and zinc ferrite under the inert atmosphere. It can be seen that zinc ferrite cannot be converted and pyrolyzed and separated to obtain ferroferric oxide and zinc oxide without being controlled within the range required by the invention.
Comparative example 2
The difference compared to example 1 is only that the oxalic acid content is reduced, i.e. the ratio of oxalic acid to zinc ferrite is controlled to be 1: 5; the other conditions were the same as in example 1.
The SEM image and XRD of the case are respectively shown in figures 15 and 16, and the analysis result shows that the oxalic acid is less and does not generate the synergistic effect of promoting the dissolution and recrystallization of the zinc ferrite with the ascorbic acid, and the XRD spectrum result shows that the zinc ferrite conversion product is ZnFe2O4And Zn (C)2O4)2H2And (O). It can be seen that, without being controlled within the range required by the invention, the zinc ferrite conversion product cannot be pyrolyzed in an inert atmosphere to obtain ferroferric oxide and zinc oxide.
Comparative example 3
The only difference from example 1 is that in step (2), ascorbic acid alone was added in amounts of 0.5, 1.0, 1.5 and 2.5g, respectively, and oxalic acid was not added.
The XRD of the product obtained in this case is shown in FIG. 17, in comparison with the XRD pattern of zinc ferrite, the main phase of which is still ZnFe2O4Therefore, it is known that the zinc ferrite structure is hardly destroyed in the presence of ascorbic acid alone.
Comparative example 4
The only difference from example 1 is that in step (2), oxalic acid alone was added in amounts of 0.5, 1.0, 1.5 and 2.5g, respectively, and ascorbic acid was not added.
The XRD of the product obtained in this case is shown in FIG. 18, in comparison with the XRD pattern of zinc ferrite, and its main phase is ZnFe2O4And Zn (C)2O4)2H2O, therefore, only partial conversion of zinc ferrite can be realized under the condition of singly existing oxalic acid.
Comparative example 5
Compared with example 1, the difference is only that in step (3), the one-pot reaction time is shortened to 0.5 h. Compared with SEM and XRD patterns of the one-pot reaction product of example 1, the SEM and XRD patterns of the product obtained in this case are shown in figures 19 and 20 respectively, and its main phase is ZnFe2O4、Zn(C2O4)2H2O。
Comparative example 6
The only difference compared to example 1 is that in step (4), the atmosphere for pyrolysis is air. The analysis result of the XRD pattern (figure 21) of the pyrolysis product shows that the phase composition of the pyrolysis product is mainly zinc ferrite and zinc oxide.
Comparative example 7
The difference compared to example 1 is essentially that a sample of slag containing zinc ferrite (containing a mixture phase of iron oxalate, zinc oxalate, lead oxalate) is pyrolysed for 2h at 800 ℃ under Ar. As a result, it was found (FIG. 22) that the ferrous oxalate was converted to ferrous oxide and no ferriferrous oxide phase product was obtained.
Comparative example 8
The difference compared to example 1 is mainly that a sample of zinc ferrite-containing slag (containing a mixture phase of ferrous oxalate, zinc oxalate, lead oxalate) was pyrolysed for 2h at 300 ℃ under Ar atmosphere. As a result (FIG. 23), the oxalate mixture was found to lose only crystalline water and did not convert to ferroferric oxide and zinc oxide. Pyrolysis under such temperature conditions does not allow for the separate conversion thereof.
Claims (17)
1. A zinc ferrite treatment method is characterized in that slurry containing zinc ferrite, oxalic acid and a reducing agent is subjected to one-pot transformation, and then solid-liquid separation is carried out to obtain transformation products of zinc oxalate and ferrous oxalate;
wherein the weight ratio of the oxalic acid to the zinc ferrite is 0.7-1.5: 1; the weight ratio of the reducing agent to the zinc ferrite is 0.25-2: 1;
the temperature of the one-pot reaction is 40-60 ℃; the one-pot reaction time is 1-2 h.
2. The zinc ferrite treatment method according to claim 1, wherein the mass ratio of oxalic acid to zinc ferrite is 1 to 1.5: 1.
3. the zinc ferrite treatment method of claim 1, wherein said reducing agent is a water-soluble reducing compound.
4. The zinc ferrite treatment method of claim 1, wherein said reducing agent is ascorbic acid and its water-soluble salts.
5. The zinc ferrite treatment method according to claim 1, wherein the mass ratio of the reducing agent to the zinc ferrite is 1 to 1.5: 1.
6. the zinc ferrite treatment method according to claim 1, wherein said slurry is obtained by adding a mixed solution of the zinc ferrite and the solution thereof in which oxalic acid and the reducing agent are dissolved, or by adding the zinc ferrite and the solution thereof to a base solution in which oxalic acid and the reducing agent are dissolved.
7. The zinc ferrite treatment method of claim 1, wherein the solvent of said slurry is water.
8. The zinc ferrite treatment method according to claim 1, wherein the one-pot reaction is carried out under open conditions.
9. The zinc ferrite treatment method of claim 1, wherein the one-pot reaction is carried out under stirring.
10. The zinc ferrite treatment method according to claim 9, wherein the stirring speed of the one-pot reaction is 100 to 300 r/min.
11. The zinc ferrite treatment method according to claim 1, wherein after the one-pot reaction, solid-liquid separation is performed, followed by washing with water, alcohol washing, and drying treatment to obtain a transformation product of iron oxalate and zinc oxalate.
12. The zinc ferrite treatment method according to claim 1, wherein the transformation product is subjected to a roasting treatment under a protective atmosphere to obtain Fe3O4And ZnO.
13. The zinc ferrite treatment method of claim 12, wherein the roasting temperature is 400-600 ℃.
14. The zinc ferrite treatment method of claim 12, wherein the roasting temperature is 400 to 500 ℃.
15. The zinc ferrite treatment method of claim 12, wherein said protective atmosphere is at least one of nitrogen and an inert gas.
16. The zinc ferrite treatment method of claim 12, wherein the roasted product is subjected to magnetic separation to obtain Fe3O4And ZnO.
17. The method of treating zinc ferrite of claim 1, wherein said zinc ferrite is derived from at least one of a pure substance, a mineral and slag.
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