CN106241883A - The preparation method of ferrite - Google Patents
The preparation method of ferrite Download PDFInfo
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- CN106241883A CN106241883A CN201610833728.1A CN201610833728A CN106241883A CN 106241883 A CN106241883 A CN 106241883A CN 201610833728 A CN201610833728 A CN 201610833728A CN 106241883 A CN106241883 A CN 106241883A
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- C—CHEMISTRY; METALLURGY
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- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
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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
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C01G49/0036—Mixed oxides or hydroxides containing one alkaline earth metal, magnesium or lead
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The present invention relates to the preparation method of ferrite, belong to the technical field of comprehensive utilization of titanium dioxide side-product ferrous sulfate.Present invention solves the technical problem that the preparation method being to provide ferrite.Ferrous sulfate, metal inorganic salt and reducing agent are mixed by the method, under protective atmosphere, and 400～900 DEG C of reactions 10～120min, cooling, obtain ferrite.The inventive method can prepare the ferrite solid that purity is higher, and technological process is simple, and cost is relatively low, and reaction temperature is low, saves the energy, it is adaptable to industrialized great production.And the ferrous sulfate of the present invention can derive from the by-product of titanium white production, metal inorganic salt also can derive from Industrial Solid Waste, thus reaches the purpose of the treatment of wastes with processes of wastes against one another; protection environment; and greatly reduce cost, and to turn waste into wealth, the development for society's recycling economy is played a positive role.
Description
Technical field
The present invention relates to the preparation method of ferrite, belong to the comprehensive utilization technique neck of titanium dioxide side-product ferrous sulfate
Territory.
Background technology
Ferrite is that a class is with iron oxides and other metallic element composite oxides as main component, ferrite nanometer
Granule has outstanding thermo-chemical stability, photocatalysis property, bioaffinity and magnetic, and therefore ferrite material is by extensively
Be applied to chemosynthesis research, catalyst development, the field such as pharmaceutical carrier and electromagnetic technique, additionally due to synthesis ferrite
The low in raw material price of material, synthetic method is simple, and reaction condition is gentle, therefore can develop industrialization production system.
The synthetic method of ferrite is segmented into Physical and chemical method, and in the lab, what we were commonly used is chemical method,
I.e. liquid phase facture.It includes hydro-thermal method, sol-gal process and coprecipitation, but these methods are longer for reaction time, instead
Answer condition harsh, be unfavorable for industrialized production.The preparation method of existing ferrite material be mainly sol-gel process, hydro-thermal method,
Coprecipitation, microemulsion method, high-energy ball milling method, self-propagating high-temperature synthesis, nanolithographic synthetic method etc..
Sol-gel synthesis method is that divalent metal saline solution and ferric salt solution are stoichiometrically mixed water
Solution, adds a certain amount of organic acid and makees part, regulates the pH value of solution with mineral acid or alkali, and slow evaporation prepares gel forerunner
Thing, thermally treated organic remains of going out, more at high temperature calcine to obtain required product.The particle size that the method produces is little, point
Dissipate uniformly, there is higher magnetic performance, but, its process conditions are wayward, and mostly raw materials used be organic compound, cost
Height, processes the time long, it is impossible to be applicable to industrialized great production.Such as Application No. CN201110326087.8, the Chinese Academy of Sciences
Entitled " the water-soluble ferrite nanoclusters that a kind of polyacrylic acid is modified of the application such as physiochemical techniques institute Zhang Tierui, Zhang Donghui
Bunch preparation method " patent, disclose the preparation method of water-soluble ferrite nanocluster that a kind of polyacrylic acid is modified, belong to
In the preparation field of nano material, relate to FeCl3·6H2O、CoCl2·6H2O etc. are presoma, with hydrophilic group
Polyacrylic acid is surfactant, utilizes alkali metal or the pH of the regulation reaction solution such as the hydroxide of alkaline-earth metal and acetate
Value, then carries out solvent heat treatment to this system, can obtain and have water miscible superparamagnetic MFe2O4(M=Fe, Co, Ni, Cu,
Mn, Zn) nanocluster.By changing the preparation parameters such as reaction density, response time and temperature, can be at 33.7～1909.8nm models
Enclose the interior particle diameter to gained nanocluster and carry out modulation.MFe prepared by this invention2O4(M=Fe, Co, Ni, Cu, Mn, Zn) receives
Rice cluster has stable dispersibility, and the feature of easily enrichment under outside magnetic field in aqueous.This invention solves water solublity
Magnetic Nano cluster preparation process is loaded down with trivial details, high in cost of production problem, transport at targeted drug, the field such as magnetic thermotherapy have wide should
Use prospect.Shortcoming is the more difficult control of technological operation, and mostly raw materials used be organic compound, and cost is high, processes the time long, should not use
Make industrialized production.
Hydro-thermal method is by autoclave in enclosed system, with water as solvent, under self pressure of uniform temperature and water
Carry out chemical reaction, it is achieved construct and crystal growth from the microgranule of atom, molecular level.It is high that the method has advantages of good crystallization, purity
Advantage, but its material purity required is high, relatively costly, and need the container of high-voltage-resistant anti-corrosion, the working cycle is long, to work
Industry brings certain difficulty.Such as Application No. CN201310419811.0, North China Electric Power University Qin Wu, Li Qu, Wang Lei etc.
The patent of entitled " a kind of microwave-hydrothermal method prepares the method for nano-copper ferrite composite oxygen carrier ", disclose and belong to chemical chain combustion
The method that a kind of microwave-hydrothermal method in burning technology field prepares nano-copper ferrite composite oxygen carrier, the method for this invention is by copper nitrate
It is dissolved in deionized water with ferric nitrate, then carries out supersound process, and drip excess of ammonia water/urea liquid, regulate pH, from
The heart separates and cleans precipitation to neutral, and precipitation is put into reactor afterwards, adds dispersant, and adds deionized water to reaction
At the 2/3～3/4 of still volume, reactor is placed in heating in the microwave oven of water cooled reflux device, heats at 150～220 DEG C
10～20h, then it is cooled to room temperature, after being dried, i.e. obtains nano ferrous acid copper.Use coppe ferrite prepared by hydrothermal synthesis method not
Only even particle size, grain development be complete, soilless sticking, and the response time is short, reaction temperature is low, applies this invention to prepare
Coppe ferrite has good application prospect at burning chemistry chains.But its material purity required is high, relatively costly, and needs resistance to
The container of high-pressure anticorrosion, the working cycle is long, brings certain difficulty to industrialization.
Coprecipitation refers to add in the soluble salt solutions of above metal ion suitable precipitation in comprising 2 kinds or 2
Agent, by metal ion homogeneous precipitation or crystallization treatment, then obtains process obtain ferrite through filtration, washing, drying and calcining.The party
Method can obtain the product that purity is high, but there is washing, filtration difficulty.And precipitant is easily mixed into as impurity, response speed is not
The defect such as easy to control, should not be used as industrialized production.Such as Application No. CN200710156685.9, Zhejiang University Ye Ying etc.
The patent of entitled " preparation method of a kind of nano ferrite ", discloses the preparation method of a kind of nano ferrite, and it is to use
The sedimentation method obtain the presoma of ferrite, and the carrier with agricultural wastes, wood flour or sawdust as presoma, become through high-temperature calcination
Type, prepares nano ferrite, the preparation method of this invention nano ferrite, overcomes the one of existing nano ferrite technology of preparing
A little not enough, the phase caused such as the difference of pH condition when different elements precipitate in aqueous is irregular, chemical uniformity is poor
And granular size such as is difficult to control at the shortcoming, but exist washing, filtration difficulty, and precipitant be easily mixed into as impurity, response speed
The defect such as wayward, should not be used as industrialized production.
Microemulsion method refers to that 2 kinds of immiscible solvents form emulsion, i.e. parents' molecule under the effect of surfactant
Continuous media is divided into short space form microreactor, and reactant reacts generation solid phase wherein, due to nucleation, crystal
Grow, coalesce, the process such as reunion is limited by microreactor, thus is formed and be enclosed with layer of surface activating agent, and had one
Determine the nanoparticle of condensed state structure and form.The advantage of microemulsion method is that experimental provision is simple, and energy consumption is low, processing ease, institute
Nano particle diameter narrowly distributing, and monodispersity, interface characteristics and good stability, particle diameter is easily controllable simultaneously, adapts to wide etc..
Shortcoming is the more difficult control of technological operation.
Visible, there is cost of material height, process time length, production stage complexity and production technology in the production of current ferrite
The defect such as wayward, production cost is expensive so that it is is widely applied to industrial circle and is extremely restricted.How to simplify ferrite
Production technology, reduce production cost so that it is industrialized great production can be applied to, become this area scientific research personnel research heat
Point.
Titanium dioxide is one of important industrial chemicals, is widely used in coating industry as high-grade Chinese white, the widest
General being applied to the aspects such as modern industry, agricultural, national defence, social required quantity rises year by year.Titanium dioxide be widely used in coating, plastics,
The industries such as rubber, ink, paper, chemical fibre, pottery, daily use chemicals, medicine, food.The domestic titanium powder plant overwhelming majority uses sulphuric acid
Method technique.Titanium dioxide ferrous sulfate by-product is the principal by product during sulfate process titanium dioxide produces, different according to mineral resources, titanium white per ton
Powder wants ferrous sulfate by-product 3.5～4t.The sulfuric acid method titanium pigment factory of China all uses ilmenite to be raw material, titanium dioxide per ton
Want by-product about 3t ferrous sulfate.The composition of byproduct ferrous sulfate of titanium dioxide is shown in Table 1.
Table 1
Visible, because byproduct ferrous sulfate of titanium dioxide is containing plurality of impurities, it is impossible to directly utilize.The whole nation is annual produces titanium white pair
Product ferrous sulfate about 3,000,000 t.Along with titanium dioxide yield constantly increases, FeSO4Problem of complex utilization more and more prominent.Sulfur
The channel of the ferrous comprehensive utilization of acid is a lot, in China, is mainly used in iron pigment, fertilizer and feed additive, catalyst, on a small quantity
As water purification agent, the overwhelming majority is abandoned as garbage, piles up placement everywhere；Not only waste sulfur and iron resource, and seriously dirty
Dye environment.Along with the development of titanium dioxide industry, production-scale continuous expansion, solve the comprehensive of titanium dioxide side-product ferrous sulfate
Utilizing question is extremely the most urgent, not only complies fully with national sustainable development policy, and for economic growth and environmental conservation
It is of great immediate significance.
Summary of the invention
For the problems referred to above, the present invention proposes a kind of employing metal inorganic salt and the byproduct ferrous sulfate of titanium dioxide system of reacting
The thinking of standby ferrite, can reduce the production cost of ferrite, titanium dioxide side-product ferrous sulfate can be carried out comprehensive utilization again
With, turn waste into wealth.
Present invention solves the technical problem that be to provide ferrous sulfate couples the method preparing ferrite with metal inorganic salt.
The preparation method of ferrite of the present invention, comprises the steps:
A, by ferrous sulfate, metal inorganic salt and reducing agent mix, under protective atmosphere, be warming up to 400～900 DEG C, instead
Answer 10～120min, be cooled to room temperature, obtain the solid product including ferrite and tail gas；In molar ratio, metal inorganic
Salt: ferrous sulfate: reducing agent=0.1～1:1:0.1～1；
B, from solid product extract obtain ferrite；
Wherein, described metal inorganic salt is the sulfate of metal than iron, sulphite, disulfate, bisulfite
Salt, chlorate, phosphate, hydrophosphate, nitrate, nitrite, carbonate, bicarbonate, silicate, fluoride salt, boric acid
Salt or aluminate；
Described reducing agent be ferrous disulfide, ferrum, hydrogen, carbon monoxide, hydrogen sulfide, carbon, sulfur, phosphorus, Carbon bisulfide or
Ammonia.
Further, described metal inorganic salt is sulfate, and the most described metal inorganic salt is magnesium sulfate, potassium sulfate, sulfur
At least one in acid sodium, copper sulfate, zinc sulfate.
Preferably, described reducing agent is ferrous disulfide, and in molar ratio, sulfate: ferrous sulfate: curing
Ferrous=3.1～4:5～6:1, the most in molar ratio, sulfate: ferrous sulfate: ferrous disulfide=3.5:5:1.
As another preferred version, described reducing agent is carbon, and in molar ratio, sulfate: ferrous sulfate: carbon=1.1～
2:2～4:1, the most in molar ratio, sulfate: ferrous sulfate: carbon=1.5:3:1.
It is furthermore preferred that described metal inorganic salt is magnesium sulfate, described reducing agent is ferrous disulfide, in molar ratio, sulphuric acid
Magnesium: ferrous sulfate: ferrous disulfide=3.5:5:1；
Or described metal inorganic salt is magnesium sulfate, zinc sulfate, copper sulfate or sodium sulfate, described reducing agent is carbon, massage
That ratio, metal inorganic salt: ferrous sulfate: carbon=1.5:3:1；
Or described metal inorganic salt is magnesium sulfate, described reducing agent is carbon monoxide, in molar ratio, magnesium sulfate: sulphuric acid
Ferrous: carbon monoxide=1:2.5:2；
Or described metal inorganic salt is magnesium sulfate, described reducing agent is hydrogen sulfide, in molar ratio, magnesium sulfate: sulphuric acid is sub-
Ferrum: hydrogen sulfide=1:2.5:1；
Or described metal inorganic salt is magnesium sulfate, described reducing agent is phosphorus, in molar ratio, magnesium sulfate: ferrous sulfate: phosphorus
=1:3:1.
Wherein, described protective atmosphere is inert atmosphere or weak oxide atmosphere, and described inert atmosphere is nitrogen, titanium dioxide
At least one in carbon, helium, neon, argon；Described weak oxide atmosphere is the atmosphere of oxygen content≤5%.
Further, the water content of metal inorganic salt, reducing agent and ferrous sulfate is preferably respectively less than 10wt%.
Further, the granularity of metal inorganic salt, reducing agent and ferrous sulfate is preferably all 100～400 mesh.
Wherein, described tail gas preferably enters acid making system for preparing sulphuric acid.
Further, described ferrous sulfate derives from ferrous sulfate sterling or the ore deposit of ferrous sulfate content >=20wt% or work
Industry waste residue；Preferably sulfuric acid ferrous iron derives from ore deposit or the industrial residue of ferrous sulfate content >=80wt%；More preferably ferrous sulfate comes
Come from the side-product in sulphuric acid legal system titanium white.
Compared with prior art, there is advantages that
1) present invention uses in the presence of a reducing agent, and metal inorganic salt and ferrous sulfate carry out solid-solid reaction, one-step method
Preparing ferrite, technological process is simple, and cost is relatively low, and reaction temperature is low, saves the energy, it is adaptable to industrialized great production.
2) using the inventive method, ferrous sulfate resolution ratio is high, can prepare the ferrite solid that purity is higher, gas
SO2Can be used for preparing sulphuric acid, the utilization rate of raw material is high.
3) ferrous sulfate of the present invention can derive from the by-product of titanium white production, and metal inorganic salt also can derive from industry
Solid waste, thus reach the purpose of the treatment of wastes with processes of wastes against one another, not only contribute to solve the problem of current titanium dioxide waste residue bulk deposition, protection ring
Border, and greatly reduce cost, to turn waste into wealth, the development for society's recycling economy is played a positive role.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the magnesium ferrite prepared of the present invention and standard magnesium ferrite.
Fig. 2 is zinc ferrite and the XRD figure spectrum of standard zinc ferrite of the embodiment of the present invention 2 preparation.
Fig. 3 is coppe ferrite and the XRD figure spectrum of standard coppe ferrite of the embodiment of the present invention 3 preparation.
Fig. 4 is sodium ferrite and the XRD figure spectrum of standard sodium ferrite of the embodiment of the present invention 4 preparation.
Detailed description of the invention
The preparation method of ferrite of the present invention, comprises the steps:
A, by ferrous sulfate, metal inorganic salt and reducing agent mix, under protective atmosphere, be warming up to 400～900 DEG C, instead
Answer 10～120min, be cooled to room temperature, obtain the solid product including ferrite and tail gas；In molar ratio, metal inorganic
Salt: ferrous sulfate: reducing agent=0.1～1:1:0.1～1；
B, from solid product extract obtain ferrite；
Wherein, described metal inorganic salt is the sulfate in addition to iron salt, sulphite, disulfate, bisulfites, chlorine
Change salt, phosphate, hydrophosphate, nitrate, nitrite, carbonate, bicarbonate, silicate, fluoride salt, borate or aluminum
Hydrochlorate.
Reducing agent commonly used in the art is all applicable to the present invention.Further, described reducing agent be preferably ferrous disulfide,
Ferrum, hydrogen, carbon monoxide, hydrogen sulfide, carbon, sulfur, phosphorus (yellow phosphorus, white phosphorus or red phosphorus), Carbon bisulfide or ammonia.
The reaction temperature of the present invention is too low, then react and do not occur, and temperature is too high, not only wastes energy, is also easy to it
Its side reaction, therefore, the temperature of the present invention is 400～800 DEG C and is advisable.
Further, described metal inorganic salt is sulfate, and the most described metal inorganic salt is magnesium sulfate, potassium sulfate, sulfur
At least one in acid sodium, copper sulfate, zinc sulfate.
Preferably, described reducing agent is ferrous disulfide.It has been investigated that, sulfate and ferrous sulfate are at two sulfur
Change and following reaction will occur under ferrous reduction:
3MSO4+5FeSO4+FeS2=3MFe2O4+10SO2(g)
Wherein, MSO4For sulfate, preferably magnesium sulfate, potassium sulfate, sodium sulfate, copper sulfate or zinc sulfate.
Further, in molar ratio, preferably sulfuric acid salt: ferrous sulfate: ferrous disulfide=3.1～4:5～6:1, preferably
In molar ratio, sulfate: ferrous sulfate: ferrous disulfide=3.5:5:1.
As another preferred version, described reducing agent is carbon.Sulfate and ferrous sulfate will occur such as under the reduction of carbon
Lower reaction:
MSO4+2FeSO4+ C=MFe2O4+3SO2(g)+CO2(g)
Wherein, MSO4For sulfate, preferably magnesium sulfate, potassium sulfate, sodium sulfate, copper sulfate or zinc sulfate.
Further, in molar ratio, sulfate: ferrous sulfate: carbon=1.1～2:2～4:1, the most in molar ratio, sulphuric acid
Salt: ferrous sulfate: carbon=1.5:2:1.
Additionally, sulfate and ferrous sulfate can also be in ferrum, hydrogen, carbon monoxide, hydrogen sulfide, sulfur, phosphorus, curing
React under the reduction of carbon, ammonia etc..
Here sulfate (other Sulfates is seemingly) as a example by magnesium sulfate, enumerates magnesium sulfate from ferrous sulfate in different reduction
Reaction equation under agent:
FeSO4+MgSO4+ Fe=MgFe2O4+2SO2(g)
In molar ratio, magnesium sulfate: ferrous sulfate: ferrum=1～2:1～2:1, the most in molar ratio, magnesium sulfate: sulphuric acid is sub-
Ferrum: ferrum=1:1.5:1.
2FeSO4+MgSO4+2H2=MgFe2O4+3SO2(g)+2H2O(g)
In molar ratio, magnesium sulfate: ferrous sulfate: hydrogen=1～2:2～4:1～2, the most in molar ratio, magnesium sulfate: sulfur
Acid is ferrous: hydrogen=1:2.5:2.
2FeSO4+MgSO4+ 2CO=MgFe2O4+3SO2(g)+2CO2(g)
In molar ratio, magnesium sulfate: ferrous sulfate: carbon monoxide=1～2:2～4:2～4, the most in molar ratio, sulphuric acid
Magnesium: ferrous sulfate: carbon monoxide=1:2.5:2.
3FeSO4+1.5MgSO4+H2S=1.5MgFe2O4+5.5SO2(g)+H2O(g)
In molar ratio, magnesium sulfate: ferrous sulfate: hydrogen sulfide=1～2:2～4:1～2, the most in molar ratio, magnesium sulfate:
Ferrous sulfate: hydrogen sulfide=1:2.5:1.
2FeSO4+MgSO4+ S=MgFe2O4+4SO2(g)
In molar ratio, magnesium sulfate: ferrous sulfate: sulfur=1～2:2～4:1～2, the most in molar ratio, magnesium sulfate: sulfur
Acid is ferrous: sulfur=1:2.5:1.
5FeSO4+2.5MgSO4+ 2P=2.5MgFe2O4+7.5SO2(g)+P2O5
In molar ratio, magnesium sulfate: ferrous sulfate: phosphorus=1～2:2～4:1～2, the most in molar ratio, magnesium sulfate: sulphuric acid
Ferrous: phosphorus=1:3:1.
6FeSO4+3MgSO4+CS2=3MgFe2O4+11SO2(g)+CO2(g)
In molar ratio, magnesium sulfate: ferrous sulfate: Carbon bisulfide=1～2:2～4:0.1～1, the most in molar ratio, sulphuric acid
Magnesium: ferrous sulfate: Carbon bisulfide=1:2.5:0.5.
3.5FeSO4+1.75MgSO4+NH3=1.75MgFe2O4+5.25SO2(g)+1.5H2O(g)+NO2(g)
In molar ratio, magnesium sulfate: ferrous sulfate: ammonia=1～2:2～4:0.5～1.5, the most in molar ratio, sulphuric acid
Magnesium: ferrous sulfate: ammonia=1:2.5:0.8.
Further, described protective atmosphere is preferably inert atmosphere or weak oxide atmosphere, and described inert atmosphere is preferably
At least one in nitrogen, carbon dioxide, helium, neon, argon；Described weak oxide atmosphere is preferably oxygen content (volume basis
Number)≤the atmosphere of 5%.
Metal inorganic salt of the present invention and reducing agent can first be dried before the reaction, preferably, and metal inorganic salt, also
Former dose is respectively less than 10wt% with the water content of ferrous sulfate.
For increasing reaction contact area, the granularity of metal inorganic salt, reducing agent and ferrous sulfate is both preferably 100～400
Mesh.
For saving the energy, can first preheat before reaction heating.
Described ferrous sulfate derives from the side-product in sulphuric acid legal system titanium white,
Ferrous sulfate catabolic process of the present invention is single step reaction, and the ferrite product generated after reaction can do adsorbing material
With, the utilization of reaction end gas sulfur dioxide is divided into two parts, and a part is used for sulfur for preheated mixture material, another part
The ferrous raw material dehydration of acid, the reaction end gas after preheating enters acid making system after dehydration, and sulphuric acid can return system for titanium
The acidolysis reaction of iron mine, it is achieved thereby that the recycling of Sulphur ressource.
Further, described ferrous sulfate derives from ferrous sulfate sterling or the ore deposit of ferrous sulfate content >=20wt% or work
Industry waste residue；Preferably sulfuric acid ferrous iron derives from ore deposit or the industrial residue of ferrous sulfate content >=80wt%；More preferably ferrous sulfate comes
Come from the side-product in sulphuric acid legal system titanium white.If the ferrous sulfate content in industrial residue is relatively low, those skilled in the art
After can being enriched with by various methods, the method that the present invention can be used.
Additionally, metal inorganic salt also can derive from the Industrial Solid Waste containing this metal inorganic salt.Inventor passes through numerous studies,
Find that the impurity in by-product of white titanium pigment and in metal inorganic salt has no effect on the carrying out of present invention reaction.Therefore, the present invention
Raw material all can use solid waste, to reach the purpose of the treatment of wastes with processes of wastes against one another.
B step of the present invention is extracted from solid product and is obtained ferrite prior art can be used to extract, as used magnetic
Choosing or the method such as acidleach, washing are extracted.
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described, the most therefore the present invention is limited
System is among described scope of embodiments.
Magnesium ferrite is prepared in embodiment 1 magnesium sulfate and titanium white by product ferrous sulfate coupling
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration be less than 10%, reducing agent two
Iron sulfuret. raw material is dried after broken and removes moisture, and ferrous disulfide granularity crosses 200 mesh sieves, and water content is less than 10%, sulfur
Acid magnesium raw material is dried after broken and removes moisture, and magnesium sulfate granularity was 200 mesh sieves, and water content is less than 10%, by magnesium sulfate:
Ferrous sulfate: the mol ratio of ferrous disulfide=3.5:5:1 feeds intake, at N2Under atmosphere, dried magnesium sulfate, ferrous disulfide
After the ferrous sulfate monohydrate batch mixing after dehydration, preheated process, it is then sent in reacting furnace reaction, reaction temperature is 650 DEG C,
Response time is 30min, and reaction terminates reactor cooled and stops being passed through of corresponding gas shield gas to room temperature, is washed by product
After, obtaining magnesium ferrite, its XRD figure spectrum is shown in Fig. 1.After measured, the purity of magnesium ferrite is 98.13%, and chemical analysis measures sulphuric acid
Ferrous resolution ratio is 98.55%.
Zinc ferrite is prepared in embodiment 2 zinc sulfate and titanium white by product ferrous sulfate coupling
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration be less than 10%, reducing agent carbon
Raw material is dried after broken and removes moisture, and carbon granules spends 200 mesh sieves, and water content is less than 10%, and zinc sulfate raw material is through broken
Rear being dried removes moisture, and magnesium sulfate granularity was 200 mesh sieves, and water content is less than 10%, zinc sulfate: ferrous sulfate: carbon=1.5:
The mol ratio of 3:1 feeds intake, at N2Under atmosphere, the ferrous sulfate monohydrate after dried potassium sulfate, ferrous disulfide and dehydration mixes
After material, preheated process, it is then sent in reacting furnace reaction, reaction temperature is about 650 DEG C, and the response time is 30min, reaction knot
Bundle reactor stops being passed through of corresponding gas shield gas after being cooled to room temperature, after being washed by product, obtain zinc ferrite, its XRD figure
Spectrum is shown in Fig. 2.After measured, the purity of zinc ferrite is 98.24%, and it is 98.61% that chemical analysis measures the resolution ratio of ferrous sulfate.
Coppe ferrite is prepared in embodiment 3 copper sulfate and titanium white by product ferrous sulfate coupling
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration be less than 10%, reducing agent carbon
Raw material is dried after broken and removes moisture, and carbon granules spends 200 mesh sieves, and water content is less than 10%, and copper sulfate raw material is through broken
Rear being dried removes moisture, and magnesium sulfate granularity was 200 mesh sieves, and water content is less than 10%, copper sulfate: ferrous sulfate: carbon=1.5:
The mol ratio of 3:1 feeds intake, at N2Under atmosphere, the ferrous sulfate monohydrate after dried potassium sulfate, ferrous disulfide and dehydration mixes
After material, preheated process, it is then sent in reacting furnace reaction, reaction temperature is about 800 DEG C, and the response time is 10min, reaction knot
Bundle reactor stops being passed through of corresponding gas shield gas after being cooled to room temperature, after being washed by product, obtain coppe ferrite, its XRD figure
Spectrum is shown in Fig. 3.After measured, the purity of coppe ferrite is 97.86%, and it is 98.33% that chemical analysis measures the resolution ratio of ferrous sulfate.
Sodium ferrite is prepared in embodiment 4 sodium sulfate and titanium white by product ferrous sulfate coupling
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration be less than 10%, reducing agent carbon
Raw material is dried after broken and removes moisture, and carbon granules spends 200 mesh sieves, and water content is less than 10%, and sodium sulfate raw material is through broken
Rear being dried removes moisture, and magnesium sulfate granularity was 200 mesh sieves, and water content is less than 10%, sodium sulfate: ferrous sulfate: carbon=1.5:
The mol ratio of 3:1 feeds intake, at N2Under atmosphere, the ferrous sulfate monohydrate after dried potassium sulfate, ferrous disulfide and dehydration mixes
After material, preheated process, it is then sent in reacting furnace reaction, reaction temperature is about 800 DEG C, and the response time is 20min, reaction knot
Bundle reactor stops being passed through of corresponding gas shield gas after being cooled to room temperature, after being washed by product, obtain sodium ferrite, its XRD figure
Spectrum is shown in Fig. 4.After measured, the purity of sodium ferrite is 97.35%, and it is 98.14% that chemical analysis measures the resolution ratio of ferrous sulfate.
Embodiment 5
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration less than 10%, and reducing agent is adopted
With carbon monoxide (i.e. yellow phosphoric tail gas), magnesium sulfate raw material is dried after broken and removes moisture, and magnesium sulfate granularity was 200 mesh
Sieve, water content is less than 10%, by magnesium sulfate: ferrous sulfate: the mol ratio of carbon monoxide=1:2.5:2 feeds intake, at N2Under atmosphere,
After ferrous sulfate monohydrate batch mixing after dried magnesium sulfate and dehydration, deliver to reacting furnace reacts, be passed through carbon monoxide, reaction
Temperature is 800 DEG C, and the response time is 60min, and reaction terminates reactor cooled and stops the logical of corresponding gas shield gas to room temperature
Entering, after being washed by product, obtain magnesium ferrite, its XRD figure spectrum is shown in Fig. 1.After measured, the purity of magnesium ferrite is 98.33%, chemistry point
It is 98.87% that analysis method measures the resolution ratio of ferrous sulfate.
Embodiment 6
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration less than 10%, and reducing agent is adopted
With hydrogen sulfide, magnesium sulfate raw material is dried after broken and removes moisture, and magnesium sulfate granularity was 200 mesh sieves, and water content is less than
10%, by magnesium sulfate: ferrous sulfate: the mol ratio of hydrogen sulfide=1:2.5:1 feeds intake, at N2Under atmosphere, dried magnesium sulfate
After the ferrous sulfate monohydrate batch mixing after dehydration, delivering to react in reacting furnace, be passed through hydrogen sulfide gas, reaction temperature is 700 DEG C,
Response time is 80min, and reaction terminates reactor cooled and stops being passed through of corresponding gas shield gas to room temperature, is washed by product
After, obtaining magnesium ferrite, its XRD figure spectrum is shown in Fig. 1.After measured, the purity of magnesium ferrite is 97.45%, and chemical analysis measures sulphuric acid
Ferrous resolution ratio is 98.12%.
Embodiment 7
Titanium white by product ferrous sulfate carries out processed, makes the ferrous sulfate monohydrate after dehydration less than 10%, and reducing agent is adopted
With yellow phosphorus, being dried and remove moisture after yellow phosphorus is broken, granularity was 200 mesh sieves, and water content is less than 10%, and magnesium sulfate raw material is through broken
Being dried after broken and remove moisture, magnesium sulfate granularity was 200 mesh sieves, and water content is less than 10%, by magnesium sulfate: ferrous sulfate: phosphorus=
The mol ratio of 1:3:1 feeds intake, at N2Under atmosphere, after the ferrous sulfate monohydrate batch mixing after dried magnesium sulfate, yellow phosphorus and dehydration,
Delivering to react in reacting furnace, reaction temperature is 650 DEG C, and the response time is 60min, and reaction terminates reactor cooled and stops to room temperature
Stopping being passed through of corresponding gas shield gas, after being washed by product, obtain magnesium ferrite, its XRD figure spectrum is shown in Fig. 1.After measured, magnesium ferrite
Purity is 98.63%, and it is 99.21% that chemical analysis measures the resolution ratio of ferrous sulfate.
Claims (10)
1. the preparation method of ferrite, it is characterised in that comprise the steps:
A, by ferrous sulfate, metal inorganic salt and reducing agent mix, under protective atmosphere, be warming up to 400～900 DEG C, react 10
～120min, it is cooled to room temperature, obtains the solid product including ferrite and tail gas；In molar ratio, metal inorganic salt: sulfur
Acid is ferrous: reducing agent=0.1～1:1:0.1～1；
B, from solid product extract obtain ferrite；
Wherein, described metal inorganic salt is the sulfate of metal than iron, sulphite, disulfate, bisulfites, chlorine
Change salt, phosphate, hydrophosphate, nitrate, nitrite, carbonate, bicarbonate, silicate, fluoride salt, borate or aluminum
Hydrochlorate；
Described reducing agent is ferrous disulfide, ferrum, hydrogen, carbon monoxide, hydrogen sulfide, carbon, sulfur, phosphorus, Carbon bisulfide or ammonia.
The preparation method of ferrite the most according to claim 1, it is characterised in that: described metal inorganic salt is sulfate,
The most described metal inorganic salt is at least one in magnesium sulfate, potassium sulfate, sodium sulfate, copper sulfate, zinc sulfate.
The preparation method of ferrite the most according to claim 2, it is characterised in that: described reducing agent is ferrous disulfide,
And in molar ratio, sulfate: ferrous sulfate: ferrous disulfide=3.1～4:5～6:1, the most in molar ratio, sulfate: sulphuric acid
Ferrous: ferrous disulfide=3.5:5:1.
The preparation method of ferrite the most according to claim 2, it is characterised in that: described reducing agent is carbon, and by mole
Ratio, sulfate: ferrous sulfate: carbon=1.1～2:2～4:1, the most in molar ratio, sulfate: ferrous sulfate: carbon=1.5:3:
1。
The preparation method of ferrite the most according to claim 2, it is characterised in that:
Described metal inorganic salt is magnesium sulfate, and described reducing agent is ferrous disulfide, in molar ratio, magnesium sulfate: ferrous sulfate: two
Iron sulfuret .=3.5:5:1；
Or described metal inorganic salt is magnesium sulfate, zinc sulfate, copper sulfate or sodium sulfate, described reducing agent is carbon, in molar ratio,
Metal inorganic salt: ferrous sulfate: carbon=1.5:3:1；
Or described metal inorganic salt is magnesium sulfate, described reducing agent is carbon monoxide, in molar ratio, magnesium sulfate: ferrous sulfate:
Carbon monoxide=1:2.5:2；
Or described metal inorganic salt is magnesium sulfate, described reducing agent is hydrogen sulfide, in molar ratio, magnesium sulfate: ferrous sulfate: sulfur
Change hydrogen=1:2.5:1；
Or described metal inorganic salt is magnesium sulfate, described reducing agent is phosphorus, in molar ratio, magnesium sulfate: ferrous sulfate: phosphorus=1:
3:1。
6. according to the preparation method of the ferrite described in any one of Claims 1 to 5, it is characterised in that: described protective atmosphere is
Inert atmosphere or weak oxide atmosphere, described inert atmosphere is at least in nitrogen, carbon dioxide, helium, neon, argon
Kind；Described weak oxide atmosphere is the atmosphere of oxygen content≤5%.
7. according to the preparation method of the ferrite described in any one of claim 1～6, it is characterised in that: metal inorganic salt, reduction
The water content of agent and ferrous sulfate is respectively less than 10wt%.
8. according to the preparation method of the ferrite described in any one of claim 1～7, it is characterised in that: metal inorganic salt, reduction
The granularity of agent and ferrous sulfate is 100～400 mesh.
9. according to the preparation method of the ferrite described in any one of claim 1～8, it is characterised in that: described tail gas enters system
Acid system is used for preparing sulphuric acid.
10. according to the preparation method of the ferrite described in any one of claim 1～9, it is characterised in that: described ferrous sulfate comes
Come from ferrous sulfate sterling or the ore deposit of ferrous sulfate content >=20wt% or industrial residue；It is sub-that preferably sulfuric acid ferrous iron derives from sulphuric acid
The ore deposit of iron content >=80wt% or industrial residue；Side-product during more preferably ferrous sulfate derives from sulphuric acid legal system titanium white.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565330A (en) * | 1979-06-20 | 1981-01-20 | Seitetsu Kagaku Co Ltd | Preparation of zinc ferrite |
| US4469669A (en) * | 1982-04-14 | 1984-09-04 | Basf Aktiengesellschaft | Preparation of ferrites from iron (II) sulfate |
| CN1843940A (en) * | 2006-03-24 | 2006-10-11 | 昆明理工大学 | Method for preparing pigment of zinc ferrite |
| CN103864150A (en) * | 2014-04-04 | 2014-06-18 | 四川大学 | Preparation method of calcium ferrite |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565330A (en) * | 1979-06-20 | 1981-01-20 | Seitetsu Kagaku Co Ltd | Preparation of zinc ferrite |
| US4469669A (en) * | 1982-04-14 | 1984-09-04 | Basf Aktiengesellschaft | Preparation of ferrites from iron (II) sulfate |
| CN1843940A (en) * | 2006-03-24 | 2006-10-11 | 昆明理工大学 | Method for preparing pigment of zinc ferrite |
| CN103864150A (en) * | 2014-04-04 | 2014-06-18 | 四川大学 | Preparation method of calcium ferrite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116588941A (en) * | 2023-05-18 | 2023-08-15 | 昆明理工大学 | Method for comprehensively utilizing yellow phosphorus slag |
| CN116588941B (en) * | 2023-05-18 | 2024-04-30 | 昆明理工大学 | Method for comprehensively utilizing yellow phosphorus slag |
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