CN108793261A - It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material - Google Patents

It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material Download PDF

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CN108793261A
CN108793261A CN201810963730.XA CN201810963730A CN108793261A CN 108793261 A CN108793261 A CN 108793261A CN 201810963730 A CN201810963730 A CN 201810963730A CN 108793261 A CN108793261 A CN 108793261A
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ball mill
monheimite
powder
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CN108793261B (en
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彭志勤
刘珉琦
池贺海
万军民
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Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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    • C01G49/00—Compounds of iron
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    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
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Abstract

The present invention relates to gas sensor field, disclose it is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, including：1）By monheimite ball mill grinding under dry air atmosphere, the mixed-powder of smithsonite and limonite is obtained；2）Dilute sulfuric acid is slowly dropped in mixed-powder, impurity is removed and uses ball grinding stirring, obtains the aqueous solution of ferric sulfate and zinc sulfate；3) dilute sodium hydroxide is slowly dropped in acquired solution, ball grinding stirring obtains colloidal precipitation liquid；4）Absolute ethyl alcohol is poured into, ball grinding stirring washs under dry air atmosphere, by colloidal precipitation liquid filtering screening, drying, obtains nanometer powder；5）Powder is put into calcining in Muffle furnace and obtains zinc ferrite nanoparticle.Can nanoscale ferrous acid Zinc material quickly being prepared environmentally friendlyly through the invention, material being provided for Metal Oxide Semiconductor Gas Sensing sensor, there is very important realistic meaning to the development of China's gas sensor industry.

Description

It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material
Technical field
The present invention relates to gas sensor fields more particularly to a kind of using monheimite as the system of the nanometer zinc ferrite of raw material Preparation Method.
Background technology
Smithsonite is most common Zinc oxide minerals, and main component is zinc carbonate, zinc oxide and a small amount of carbon dioxide.Water chestnut Usually there are two types of types for zinc ore, i.e., iron-containing and nonferrous.Wherein, the Main Morphology of iron is ferric carbonate in monheimite.It removes Except this, generally there are lead salt, calcium salt, ferrous salt, mantoquita, cadmium salt, aluminium salt, magnesium salts and silica etc. miscellaneous in monheimite Matter.When aoxidizing, monheimite can gradually resolve into the mixture of smithsonite and limonite.
Social people increasingly pay attention to air quality now, in order to improve the detection performance of gas sensor, new air-sensitive Element material is constantly developed.Wherein, metal oxide semiconductor nano-material is due to its high sensitive to gas And high stability, become the new lover in gas sensor field.Nanometer zinc ferrite with hierarchical structure, which is even more PARA FORMALDEHYDE PRILLS(91,95), to be had Outstanding selectivity becomes the research emphasis of gas sensitive.
But the preparation method of nano-metal-oxide semi-conducting material at this stage, such as hydro-thermal method, coprecipitation, molten Glue-gel method etc. can not prepare the product haveing excellent performance if it were not for finished product is inferior, otherwise be exactly step complexity, can only test It is made on a small quantity in room, lacks industrialized condition.Therefore, how quickly big under the premise of reducing the pollution to environment as far as possible Preparing the nano-metal-oxide semi-conducting material haveing excellent performance to amount becomes important directions to gas sensor field.
Invention content
In order to solve the above technical problem, the present invention provides a kind of using monheimite as the system of the nanometer zinc ferrite of raw material Preparation Method.The present invention is decomposed into smithsonite and limonite by monheimite under oxygen effect, instills dilute sulfuric acid and forms Zn2+ And Fe3+Mixed solution, then by sodium hydroxide adjust pH value, under mechanical force formed zinc/iron colloid, it is anti-by hydro-thermal Metal oxide precursor should be formed, nanometer zinc ferrite particle is prepared finally by calcining.Zinc ferrite prepared by this method is micro- Grain particle diameter distribution is uniform, and structure is unified, and air-sensitive performance is outstanding, and nearly all process can be completed in ball mill and whole process Almost without there is toxic harmfulness exhaust gas, operating process is simple, nontoxic, harmless, environmentally protective.
The specific technical solution of the present invention is：It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, with g It counts, includes the following steps with ml：
1) preliminary crushing process：50-60g monheimites are put into ball mill, 30-40min is crushed under the conditions of noting oxygen, are turned Speed is 180-190r/min, obtains the mixed-powder of smithsonite and limonite.
The present invention is ground into particle and with O in step 1) using monheimite2Oxidation forms smithsonite and limonite, ball The mechanical force of grinding machine makes metal oxide and metal salt activate, and is conducive to next reaction.Monheimite exists It is rich in mineral resources, it is of low cost, and Zn elements and Fe elements, production efficiency higher can be obtained simultaneously in reaction.
2) dedoping step：In the ball mill, by drum's speed of rotation at the uniform velocity promoted arrive 190-200r/min, by mixed-powder into One step crushes, the removal of impurities then followed the steps below：
1. under the conditions of noting oxygen, it is poured slowly into dilute sulfuric acid 160-175ml, it is ferric sulfate and zinc sulfate to obtain main component Aqueous solution, lead, calcium ion in solution form hardly soluble sulfate precipitation, and the ferrous ion in solution is aoxidized At ferric ion, the carbon dioxide that simultaneous reactions generate is taken away by oxygen, filtering removal impurity；
2. under the conditions of noting oxygen, it is poured slowly into and is slowly added to iron powder 5-6g, copper, cadmium, the lead ion in solution is displaced It is precipitated to be formed, the ferrous ion in solution is oxidized to ferric ion, filtering removal impurity；
3. under the conditions of noting oxygen, sodium hydroxide, which is added, makes pH=4.8-5, and the ferric ion and aluminium ion in solution are formed Hydroxide precipitates, and filtering, precipitation retains；
4. injecting carbon dioxide, the magnesium ion in solution forms the carbonate deposition of indissoluble, filtering removal impurity；
5. under the conditions of noting oxygen, by step 3. in the ferric ion that filters out and aluminium ion hydroxide precipitation place back in In solution, dilute sulfuric acid, which is added, makes precipitation dissolve, and 5-10g flocculants are added, aluminium element and element silicon in solution and other can not Molten impurity, which is drawn into flocculant, forms precipitation, and filtering removal impurity finally obtains the pure water-soluble of ferric sulfate and zinc sulfate Liquid.
The present invention reacts to form Zn using smithsonite and limonite in step 2) with dilute sulfuric acid2+And Fe3+Ion, simultaneously The degree of purity of zinc/water solution is promoted by a series of removal of impurities means, including：
①Pb2++SO4 2-→PbSO4↓；Ca2++5O4 2-→CaSO4↓；Fe2++O2→Fe3+；
②Fe+Cu2+→Fe2++Cu；Fe+Cd2+→Fe2++Cd；Fe+Pb2+→Fe2++pb；Fe2++O2→Fe3+；
③Fe3++OH-→FeOH3↓；Al3++OH-→AlOH3↓；
④Mg2++CO4 2-→MgCO4↓；
⑤SiO2, Al3+, other insoluble material+flocculant → complex compound sediments.
Due to the mechanical force activating of ball mill, the step reaction is rapid, and efficiency is higher, and the CO generated2Nothing Poison is harmless, can be taken away by air, and driving a reaction is moved to positive reaction direction.
3) colloid forming process：In the ball mill, the sodium hydroxide solution of 100-120ml is slowly dropped to step 2) institute In the aqueous solution obtained, with 100-120 DEG C of stirring 12-14h, wherein drum's speed of rotation is promoted to 220-250r/ in 0-6h Drum's speed of rotation is promoted to 250-300r/min by min, 6-10h, and drum's speed of rotation is promoted to 300-350r/ by remaining time Min obtains colloidal precipitation liquid.
Metal ion mixed liquor is reacted to form metal ion colloid by the present invention in step 3) with sodium hydroxide, is led to simultaneously The automatic reaction for crossing multistage changeup mill activated metal ion, finally makes colloidal solid be refined into the particle of Nano grade.Ball milling The mechanism of machine accelerates the rate of hydro-thermal reaction, while but also the particle size of particle is more uniform.
4) metal oxide precursor forming process：In the ball mill, it is stirred with 120-150 DEG C under dry air atmosphere 3-5h, rotating speed 40-50r/min, and pour into 100-120ml absolute ethyl alcohols respectively in three times, by colloidal precipitation liquid in step 3) Filtering screening, drying, dry air is by the H in solution2O takes away, and obtains the powder of 70nm or less grain sizes.
The present invention is in step 4), under the stirring action of ball mill, is got rid of in colloidal solution by ethyl alcohol washing Impurity.Under high temperature action, the ethyl alcohol of evaporation takes away impurity, while taking away the moisture in ball mill, obtains dry receive Rice precursor powder.
5) forming process is calcined：Powder in step 4) is put into Muffle furnace, with 500-750 DEG C of calcining 2-3h, heating speed 2-2.25 DEG C/min is spent, 3-3.5h is persistently kept the temperature, until Temperature fall, final to obtain zinc ferrite nanoparticle.
The present invention is in step 5), and under the action of high temperature, the hydrogen-oxygen and carbon in powder are with H2O and CO2Form go It removes, forms zinc ferrite nanoparticle.
Preferably, a concentration of 50wt% of the dilute sulfuric acid, a concentration of 10wt% of the sodium hydroxide solution, described A concentration of 99.5wt% of absolute ethyl alcohol.
Preferably, step 1), 2), 3), 4) in, material whole process in the ball mill and in flowing drying gas Under, the effect of gas be participate in step 1), 2) in oxidation reaction, and take away step 1), 2), 3), 4) in the gas that volatilizees.
Preferably, flocculant used is polyaluminium sulfate and polyacrylamide in step 2).
Preferably, in step 3), the aqueous solution pH is 8-10.5 after sodium hydroxide solution is added dropwise.
Preferably, the ball mill is the high temperature resistant ball mill with setting heating temperature, the calcining molding of step 5) Process carries out in the ball mill.Reaction rate is further improved while reducing operating procedure.
It is compared with the prior art, the beneficial effects of the invention are as follows：
1, all operations step in addition to calcining has all been put into ball mill by the present invention and Muffle furnace together can be with A production line is constituted, realizes that extensive consecutive production, production efficiency greatly promote in factory.
2, the step of will produce escaping gas in preparation process of the present invention all in the ball mill being fully sealed in, both Ensure that the gas of generation does not pollute the environment can also stop influence of the outside air to production process.
3, the exhaust gas main composition that generates is carbon dioxide and vapor in the present invention, pollution-free to air；In the present invention Liquid environment to open be initially acidic liquid, become akaline liquid to below, be exhausted to last OH- as neutral liquid, Common vapor is formed with drying steps, it is environmentally safe, meet the thinking of green preparation.
4, it is reacted using ball mill in the present invention, the activation of uniform stirring makes the production efficiency of finished product greatly greatly Soon, the particle diameter distribution of nano-particle is more uniform, and air-sensitive performance is more superior.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1：
It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, include the following steps：
1) preliminary crushing process：50g monheimites are put into ball mill, crush 30min under the conditions of noting oxygen, rotating speed is 180r/min obtains the mixed-powder of smithsonite and limonite；
2) dedoping step：In the ball mill, drum's speed of rotation is at the uniform velocity promoted and arrives 190r/min, mineral dust is further It crushes, prepares for next removal of impurities：
1. under the conditions of noting oxygen, 50wt% dilute sulfuric acid 160ml are poured slowly into, it is ferric sulfate and zinc sulfate to obtain main component Aqueous solution, lead, calcium ion in solution forms hardly soluble sulfate precipitation, and the ferrous ion in solution is by oxygen It is melted into ferric ion, the carbon dioxide that simultaneous reactions generate is taken away by oxygen, filtering removal impurity；
2. under the conditions of noting oxygen, it is poured slowly into and is slowly added to iron powder 5g, copper, cadmium, the lead ion in solution is replaced out Precipitation is formed, the ferrous ion in solution is oxidized to ferric ion, filtering removal impurity；
3. under the conditions of noting oxygen, sodium hydroxide, which is added, makes pH=4.8, and the ferric ion and aluminium ion in solution form hydrogen Oxide precipitation, filtering, precipitation retain；
4. injecting carbon dioxide, the magnesium ion in solution forms the carbonate deposition of indissoluble, filtering removal impurity；
5. under the conditions of noting oxygen, by step 3. in the ferric ion that filters out and aluminium ion hydroxide precipitation place back in In solution, appropriate dilute sulfuric acid, which is added, makes precipitation dissolve, addition 5g flocculants (polyaluminium sulfate and polyacrylamide), in solution Aluminium element and element silicon and other insoluble impurity, which are drawn into flocculant, forms precipitation, and filtering removal impurity finally obtains The pure aqueous solution of ferric sulfate and zinc sulfate；
3) colloid forming process：In the ball mill, the 10wt% sodium hydroxides of 100ml are slowly dropped to obtained by step 2) Aqueous solution in, with 100 DEG C of stirring 12-14h, wherein drum's speed of rotation is promoted to 220r/min in 0-6h, 10h is by ball Mill speed is promoted to 250r/min, and drum's speed of rotation is promoted to 300r/min by remaining time, obtains colloidal precipitation liquid；
4) metal oxide precursor forming process：In the ball mill, 3h are stirred with 120 DEG C under dry air atmosphere, Rotating speed is 40r/min, and pours into 100ml absolute ethyl alcohols respectively in three times, by colloidal precipitation liquid filtering screening, baking in step 3) Dry, dry air is by the H in solution2O takes away, and obtains the powder of 70nm or less grain sizes；
5) forming process is calcined：Powder in step 4) is put into Muffle furnace, with 500 DEG C calcining 2h, 2 DEG C of heating rate/ Min persistently keeps the temperature 3h, until Temperature fall, final to obtain zinc ferrite nanoparticle.
Wherein, step 1), 2), 3), 4) in, material whole process in the ball mill and in flowing drying gas under, gas The effect of body be participate in step 1), 2) in oxidation reaction, and take away step 1), 2), 3), 4) in volatilize gas.
Embodiment 2：
It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, include the following steps：
1) preliminary crushing process：50g monheimites are put into ball mill, crush 30min under the conditions of noting oxygen, rotating speed is 180r/min obtains the mixed-powder of smithsonite and limonite；
2) dedoping step：In the ball mill, drum's speed of rotation is at the uniform velocity promoted and arrives 190r/min, mineral dust is further It crushes, prepares for next removal of impurities：
1. under the conditions of noting oxygen, 50wt% dilute sulfuric acid 160ml are poured slowly into, it is ferric sulfate and zinc sulfate to obtain main component Aqueous solution, lead, calcium ion in solution forms hardly soluble sulfate precipitation, and the ferrous ion in solution is by oxygen It is melted into ferric ion, the carbon dioxide that simultaneous reactions generate is taken away by oxygen, filtering removal impurity；
2. under the conditions of noting oxygen, it is poured slowly into and is slowly added to iron powder 5g, copper, cadmium, the lead ion in solution is replaced out Precipitation is formed, the ferrous ion in solution is oxidized to ferric ion, filtering removal impurity；
3. under the conditions of noting oxygen, sodium hydroxide, which is added, makes pH=4.8, and the ferric ion and aluminium ion in solution form hydrogen Oxide precipitation, filtering, precipitation retain；
4. injecting carbon dioxide, the magnesium ion in solution forms the carbonate deposition of indissoluble, filtering removal impurity；
5. under the conditions of noting oxygen, by step 3. in the ferric ion that filters out and aluminium ion hydroxide precipitation place back in In solution, appropriate dilute sulfuric acid, which is added, makes precipitation dissolve, addition 5g flocculants (polyaluminium sulfate and polyacrylamide), in solution Aluminium element and element silicon and other insoluble impurity, which are drawn into flocculant, forms precipitation, and filtering removal impurity finally obtains The pure aqueous solution of ferric sulfate and zinc sulfate；
3) colloid forming process：In the ball mill, the 10wt% sodium hydroxides of 100ml are slowly dropped to obtained by step 2) Aqueous solution in, with 120 DEG C of stirring 14h, wherein drum's speed of rotation is promoted to 250r/min in 0-6h, 6-10h is by ball milling Machine rotating speed is promoted to 300r/min, and drum's speed of rotation is promoted to 350r/min by remaining time, obtains colloidal precipitation liquid；
4) metal oxide precursor forming process：In the ball mill, 3h are stirred with 150 DEG C under dry air atmosphere, Rotating speed is 50r/min, and pours into 120ml absolute ethyl alcohols respectively in three times, by colloidal precipitation liquid filtering screening, baking in step 3) Dry, dry air is by the H in solution2O takes away, and obtains the powder of 70nm or less grain sizes；
5) forming process is calcined：Powder in step 4) is put into Muffle furnace, with 750 DEG C of calcining 3h, heating rate 2.25 DEG C/min, 3.5h is persistently kept the temperature, until Temperature fall, final to obtain zinc ferrite nanoparticle.
Wherein, step 1), 2), 3), 4) in, material whole process in the ball mill and in flowing drying gas under, gas The effect of body be participate in step 1), 2) in oxidation reaction, and take away step 1), 2), 3), 4) in volatilize gas.
Embodiment 3：
It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, include the following steps：
1) preliminary crushing process：60g monheimites are put into ball mill, crush 40min under the conditions of noting oxygen, rotating speed is 190r/min obtains the mixed-powder of smithsonite and limonite；
2) dedoping step：In the ball mill, drum's speed of rotation is at the uniform velocity promoted and arrives 200r/min, mineral dust is further It crushes, prepares for next removal of impurities：
1. under the conditions of noting oxygen, 50wt% dilute sulfuric acid 175ml are poured slowly into, it is ferric sulfate and zinc sulfate to obtain main component Aqueous solution, lead, calcium ion in solution forms hardly soluble sulfate precipitation, and the ferrous ion in solution is by oxygen It is melted into ferric ion, the carbon dioxide that simultaneous reactions generate is taken away by oxygen, filtering removal impurity；
2. under the conditions of noting oxygen, it is poured slowly into and is slowly added to iron powder 6g, copper, cadmium, the lead ion in solution is replaced out Precipitation is formed, the ferrous ion in solution is oxidized to ferric ion, filtering removal impurity；
3. under the conditions of noting oxygen, sodium hydroxide, which is added, makes pH=5, and the ferric ion and aluminium ion in solution form hydrogen-oxygen Compound precipitates, and filtering, precipitation retains；
4. injecting carbon dioxide, the magnesium ion in solution forms the carbonate deposition of indissoluble, filtering removal impurity；
5. under the conditions of noting oxygen, by step 3. in the ferric ion that filters out and aluminium ion hydroxide precipitation place back in In solution, appropriate dilute sulfuric acid, which is added, makes precipitation dissolve, addition 7g flocculants (polyaluminium sulfate and polyacrylamide), in solution Aluminium element and element silicon and other insoluble impurity, which are drawn into flocculant, forms precipitation, and filtering removal impurity finally obtains The pure aqueous solution of ferric sulfate and zinc sulfate；
3) colloid forming process：In the ball mill, the 10wt% sodium hydroxides of 120ml are slowly dropped to obtained by step 2) Aqueous solution in, with 120 DEG C of stirring 13h, wherein drum's speed of rotation is promoted to 250r/min in 0-6h, 6-10h is by ball milling Machine rotating speed is promoted to 300r/min, and drum's speed of rotation is promoted to 350r/min by remaining time, obtains colloidal precipitation liquid；
4) metal oxide precursor forming process：In the ball mill, 5h are stirred with 150 DEG C under dry air atmosphere, Rotating speed is 50r/min, and pours into 110ml absolute ethyl alcohols respectively in three times, by colloidal precipitation liquid filtering screening, baking in step 3) Dry, dry air is by the H in solution2O takes away, and obtains the powder of 70nm or less grain sizes；
5) forming process is calcined：Powder in step 4) is put into Muffle furnace, with 600 DEG C of calcining 2.5h, heating rate 2 DEG C/min, 3h is persistently kept the temperature, until Temperature fall, final to obtain zinc ferrite nanoparticle.
Wherein, step 1), 2), 3), 4) in, material whole process in the ball mill and in flowing drying gas under, gas The effect of body be participate in step 1), 2) in oxidation reaction, and take away step 1), 2), 3), 4) in volatilize gas.
Embodiment 4：
It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, include the following steps：
1) preliminary crushing process：55g monheimites are put into ball mill, crush 35min under the conditions of noting oxygen, rotating speed is 185r/min obtains the mixed-powder of smithsonite and limonite；
2) dedoping step：In the ball mill, drum's speed of rotation is at the uniform velocity promoted and arrives 195r/min, mineral dust is further It crushes, prepares for next removal of impurities：
1. under the conditions of noting oxygen, 50wt% dilute sulfuric acid 170ml are poured slowly into, it is ferric sulfate and zinc sulfate to obtain main component Aqueous solution, lead, calcium ion in solution forms hardly soluble sulfate precipitation, and the ferrous ion in solution is by oxygen It is melted into ferric ion, the carbon dioxide that simultaneous reactions generate is taken away by oxygen, filtering removal impurity；
2. under the conditions of noting oxygen, it is poured slowly into and is slowly added to iron powder 5.5g, copper, cadmium, the lead ion in solution is displaced It is precipitated to be formed, the ferrous ion in solution is oxidized to ferric ion, filtering removal impurity；
3. under the conditions of noting oxygen, sodium hydroxide, which is added, makes pH=4.9, and the ferric ion and aluminium ion in solution form hydrogen Oxide precipitation, filtering, precipitation retain；
4. injecting carbon dioxide, the magnesium ion in solution forms the carbonate deposition of indissoluble, filtering removal impurity；
5. under the conditions of noting oxygen, by step 3. in the ferric ion that filters out and aluminium ion hydroxide precipitation place back in In solution, appropriate dilute sulfuric acid, which is added, makes precipitation dissolve, addition 7g flocculants (polyaluminium sulfate and polyacrylamide), in solution Aluminium element and element silicon and other insoluble impurity, which are drawn into flocculant, forms precipitation, and filtering removal impurity finally obtains The pure aqueous solution of ferric sulfate and zinc sulfate；
3) colloid forming process：In the ball mill, the 10wt% sodium hydroxides of 110ml are slowly dropped to obtained by step 2) Aqueous solution in, with 105 DEG C of stirring 13h, wherein drum's speed of rotation is promoted to 230r/min in 0-6h, 6-10h is by ball milling Machine rotating speed is promoted to 275r/min, and drum's speed of rotation is promoted to 325r/min by remaining time, obtains colloidal precipitation liquid；
4) metal oxide precursor forming process：In the ball mill, 4h are stirred with 140 DEG C under dry air atmosphere, Rotating speed is 45r/min, and pours into 110ml absolute ethyl alcohols respectively in three times, by colloidal precipitation liquid filtering screening, baking in step 3) Dry, dry air is by the H in solution2O takes away, and obtains the powder of 70nm or less grain sizes；
5) forming process is calcined：Powder in step 4) is calcined, with 550 DEG C calcining 2.5h, 2.1 DEG C of heating rate/ Min persistently keeps the temperature 3.25h, until Temperature fall, final to obtain zinc ferrite nanoparticle.
In the present embodiment, the ball mill is the high temperature resistant ball mill with setting heating temperature, and step 5) is sintered into Type process carries out in the ball mill.
Wherein, step 1), 2), 3), 4) in, material whole process in the ball mill and in flowing drying gas under, gas The effect of body be participate in step 1), 2) in oxidation reaction, and take away step 1), 2), 3), 4) in volatilize gas.
Here is that the air-sensitive performance between four kinds of case study on implementation and ferrous acid zinc nanoparticles that conventional hydrothermal method is prepared is examined Survey result.It can be evident that from table, the ferrous acid zinc nanoparticles prepared by such method, grain size smaller And evenly, to bring more superior air-sensitive performance, not only sensitivity rises, and respond and recovery time also It reduces, from table as can be seen that this preparation method can actually more quickly prepare the zinc ferrite largely haveing excellent performance Nano particle, this result have reached our expection.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example The protection domain of case.

Claims (6)

1. it is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, in terms of g and ml, it is characterised in that including following Step：
1）Preliminary crushing process：50-60g monheimites are put into ball mill, crush 30-40min under the conditions of noting oxygen, rotating speed is 180-190r/min obtains the mixed-powder of smithsonite and limonite；
2）Dedoping step：In the ball mill, drum's speed of rotation is at the uniform velocity promoted and arrives 190-200r/min, mixed-powder is further It crushes, the removal of impurities then followed the steps below：
Under the conditions of noting oxygen, it is poured slowly into dilute sulfuric acid 160-175ml, it is the water-soluble of ferric sulfate and zinc sulfate to obtain main component Liquid, lead, calcium ion in solution form hardly soluble sulfate precipitation, and the ferrous ion in solution is oxidized to three Valence iron ion, the carbon dioxide that simultaneous reactions generate are taken away by oxygen, filtering removal impurity；
It under the conditions of noting oxygen, is poured slowly into and is slowly added to iron powder 5-6g, copper, cadmium, the lead ion in solution, which are replaced out, to be formed It precipitates, the ferrous ion in solution is oxidized to ferric ion, filtering removal impurity；
Under the conditions of noting oxygen, sodium hydroxide, which is added, makes pH=4.8-5, and the ferric ion and aluminium ion in solution form hydroxide Object precipitates, and filtering, precipitation retains；
Carbon dioxide is injected, the magnesium ion in solution forms the carbonate deposition of indissoluble, filtering removal impurity；
Under the conditions of noting oxygen, the ferric ion filtered out and aluminium ion hydroxide precipitation are placed back in solution, are added dilute Sulfuric acid makes precipitation dissolve, and 5-10g flocculants are added, and the aluminium element and element silicon and other insoluble impurity in solution are drawn into Precipitation is formed in flocculant, filtering removal impurity finally obtains the pure aqueous solution of ferric sulfate and zinc sulfate；
3）Colloid forming process：In the ball mill, the sodium hydroxide solution of 100-120ml is slowly dropped to step 2）Gained In aqueous solution, with 100-120 DEG C of stirring 12-14h, wherein drum's speed of rotation is promoted to 220-250r/min, 6- in 0-6h Drum's speed of rotation is promoted to 250-300r/min by 10h, and drum's speed of rotation is promoted to 300-350r/min by remaining time, is obtained Colloidal precipitation liquid；
4）Metal oxide precursor forming process：In the ball mill, with 120-150 DEG C of stirring 3- under dry air atmosphere 5h, rotating speed 40-50r/min, and pour into 100-120ml absolute ethyl alcohols respectively in three times, by step 3）Middle colloidal precipitation liquid mistake Screen choosing, drying, dry air is by the H in solution2O takes away, and obtains the powder of 70nm or less grain sizes；
5）Calcine forming process：By step 4）Middle powder is held with 500-750 DEG C of calcining 2-3h, 2-2.25 DEG C of heating rate/min Continue insurance temperature 3-3.5h, until Temperature fall, finally obtains nanometer zinc ferrite.
2. as described in claim 1 a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, which is characterized in that A concentration of 50wt% of the dilute sulfuric acid, a concentration of 10wt% of the sodium hydroxide solution, the absolute ethyl alcohol it is a concentration of 99.5wt%。
3. as described in claim 1 a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, which is characterized in that Step 1）,2）,3）,4）In, for material whole process in the ball mill and under the gas of the drying in flowing, the effect of gas is to participate in Step 1）,2）In oxidation reaction, and take away step 1）,2）,3）,4）The gas of middle volatilization.
4. as described in claim 1 a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, which is characterized in that Step 2）In flocculant used be polyaluminium sulfate and polyacrylamide.
5. as described in claim 1 a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, which is characterized in that Step 3）In, the aqueous solution pH is 8-10.5 after sodium hydroxide solution is added dropwise.
6. as described in claim 1 a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material, which is characterized in that The ball mill is the high temperature resistant ball mill with setting heating temperature, step 5）Calcining forming process in the ball mill into Row.
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CN104787803A (en) * 2015-04-04 2015-07-22 天津大学 Method for preparing nano-sized zinc ferrite from zinc-contained steel pickling waste liquid
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CN104787803A (en) * 2015-04-04 2015-07-22 天津大学 Method for preparing nano-sized zinc ferrite from zinc-contained steel pickling waste liquid
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* Cited by examiner, † Cited by third party
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CN116022835A (en) * 2023-02-21 2023-04-28 贵州师范大学 Recycling treatment method of aluminum electrolysis carbon-containing hazardous waste

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