CN102863030B - Method for preparing nanometer ferroferric oxide through acid-regenerating desilicated mud cake - Google Patents
Method for preparing nanometer ferroferric oxide through acid-regenerating desilicated mud cake Download PDFInfo
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- CN102863030B CN102863030B CN201210359893.XA CN201210359893A CN102863030B CN 102863030 B CN102863030 B CN 102863030B CN 201210359893 A CN201210359893 A CN 201210359893A CN 102863030 B CN102863030 B CN 102863030B
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- desiliconization mud
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Abstract
The invention discloses a method for preparing nanometer ferroferric oxide through acid-regenerating desilicated mud cake. The method comprises the steps as follows: adding water to desilicated mud cake, heating and pulping to obtain desilicated slurry which has good dispersibility; and then adding acid for regeneration to the obtained desilicated slurry; heating and uniformly agitating; then adding thin iron rim charge after reacting for 2 hours; heating to 80 to 90 DEG C so as to achieve acid dissolution and reduction to the desilicated mud cake; filtering, washing with water, and adjusting pH to 4 through ammonia water to obtain filtrate which is ferrous chloride turbid solution; further adding fatty acid to carry out oxidization; centrifuging, washing and drying to obtain nanometer ferroferric oxide rough product; finally ultrasonically dispersing the nanometer ferroferric oxide rough product into the water; magnetically attracting and separating; and then drying in a vacuum drying box at 60 to 90 DEG C so as to obtain nanometer ferroferric oxide. According to the method for preparing nanometer ferroferric oxide through acid-regenerating desilicated mud cake disclosed by the invention, the recycling and reusing of industrial waste desilicated mud cake is achieved, and the environmental pollution can be reduced.
Description
Technical field
The present invention relates to a kind of preparation method of soft magnetic material, the trade waste desiliconization mud cake obtaining after the cold rolling mill spent acid of specifically take recycling is prepared the method for nano ferriferrous oxide as raw material.
Background technology
Nano ferriferrous oxide is a kind of important spinel type ferrite, when its particle diameter is less than certain critical dimension, can produce superparamagnetism.This material is very easily magnetization under external magnetic field, when external magnetic field is cancelled, very easily demagnetizes, and be a kind of soft magnetic materials that can be not permanently magnetized.Due to its special magnetics and electric property, it is had a wide range of applications in fields such as magnetic fluid, magnetic recording, medical targets.
At present, the method for the preparation of nano ferriferrous oxide has coprecipitation, high-temperature decomposition, mini-emulsion process and sol-gel process etc.Wherein chemical coprecipitation is to study method the most widely, need to use original Fe
3+and Fe
2+the alkaline solution of solution, complex steps, condition is difficult to control, and particle is difficult to control and is easy to reunite; High-temperature decomposition be mainly the metallo-organic compound of the iron such as ferrocene as raw material, raw material is expensive; The technical process of sol-gel process and mini-emulsion process all needs to consider temperature, pH value and adds the impact of emulsifying agent on nano ferriferrous oxide, and source of iron is also mainly pure Fe
2+and Fe
3+, cost is higher.Therefore, finding a kind of source of iron with low cost is to prepare nano ferriferrous oxide problem demanding prompt solution.
The desiliconization mud cake of cold rolling mill output, as a kind of trade waste, after filter press compacting, it is block that desiliconization mud cake is, yellowish red color, after being dried, total iron content is in 60-70% left and right.Because mud cake is that flocculation by ferric hydroxide colloid generates, its fluffy degree is high, and grain fineness is good, and good uniformity is a kind of very good material of preparing nano material.Meanwhile, the desiliconization mud cake that the annual output of Yi Ge large-scale cold rolling steel mill is ten thousand tons, desiliconization mud cake is all used as discarded object and fills out sea processing conventionally, how to develop and to utilize desiliconization mud cake to become an important topic of steel mill's comprehensive utilization of resources.
Summary of the invention
The object of this invention is to provide a kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide, usingd acid regeneration desiliconization mud cake as source of iron, molten by acid, reduction, oxidation, prepare nano ferriferrous oxide.This utilizes acid regeneration desiliconization mud cake to prepare the method for nano ferriferrous oxide, reaches the object of the environmental pollution comprehensive regulation, the problem of solution resource recycling.
Technical scheme of the present invention
A kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide, first, desiliconization mud cake is added to water and add hot breakdown, form dispersed desiliconization mud preferably, described desiliconization mud cake is that steel mill utilizes the desiliconization mud cake producing in acid regeneration silica removal process, and its water content is 44～62%;
Then, in the desiliconization mud of gained, add regenerated acid, heating stirs and reacts after 2h, add again thin iron rim charge, continue to be heated to the molten and reduction of 80-90 ℃ of acid that realizes desiliconization mud cake, filter, washing, with ammoniacal liquor, regulate pH=4, the filtrate obtaining is the turbid liquid of frerrous chloride;
The consumption of above-mentioned desiliconization mud, regenerated acid and Bao Tie rim charge, by desiliconization mud cake contained in desiliconization mud: regenerated acid: thin iron rim charge is that 1g:2ml:0.5-1g calculates;
Further, add fatty amine to carry out after oxidation reaction, through centrifugal, with the washing of acetone and ethanol, vacuum drying, obtain the thick product of nano ferriferrous oxide;
Described fatty amine is triethylamine, n-butylamine, lauryl amine or octadecyl amine etc., and the amount of the fatty amine adding is by the mass ratio of desiliconization mud cake used in itself and the turbid liquid of frerrous chloride, i.e. fatty amine: desiliconization mud cake is 1.5-4.5:1;
Finally, by ultrasonic being dispersed in water of the thick product of nano ferriferrous oxide, after magnetic attraction separation, obtain nano ferriferrous oxide.
A kind of above-mentioned method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide, specifically comprises the steps:
(1) will in block desiliconization mud cake, add water, and pull an oar under 80-90 ℃ of heating state, finally form dispersed desiliconization mud preferably;
Control the mass ratio of desiliconization mud cake and water, i.e. desiliconization mud cake: water is 1-3:5;
(2) regenerated acid is joined in the desiliconization mud that step (1) obtains, and drop into thin iron rim charge, be heated to 80-90 ℃, realize the molten and reduction of the acid of desiliconization mud cake, filter, wash with water, with ammoniacal liquor, regulate pH=4, the filtrate obtaining is the turbid liquid of frerrous chloride;
(3) the turbid liquid of frerrous chloride that step (2) obtains, add former desiliconization mud cake quality 1.5-4.5 fatty amine doubly, at 85 ℃, keep after 12h, after centrifugal, acetone and ethanol washing, after the vacuum drying chamber inner drying 12h of 60-90 ℃, obtain the thick product of nano ferriferrous oxide;
(4) step (3) is obtained to the thick product of nano ferriferrous oxide, ultrasonic being dispersed in water, is further purified tri-iron tetroxide by magnetic attraction separation, finally obtains soft magnetism nano ferriferrous oxide.
beneficial effect of the present invention
The present invention proposes a kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide, owing to having adopted solubilizing reaction and oxidize water thermal response, utilize trade waste desiliconization mud cake to prepare nano ferriferrous oxide soft magnetic material, granularity is evenly dispersed, be easy to magnetize, be also easy to demagnetization; Can from mud cake, separate preferably.Meanwhile, realize the recycling of trade waste desiliconization mud cake, reduced environmental pollution.
Accompanying drawing explanation
The XRD of the nano ferriferrous oxide of gained figure in Fig. 1, the embodiment of the present invention 1;
The magnetic hysteresis tropic of the nano ferriferrous oxide of gained in Fig. 2, the embodiment of the present invention 1.
The specific embodiment
Below by specific embodiment, also by reference to the accompanying drawings the present invention is further set forth, but do not limit the present invention.
Main equipment used and model and the manufacturer of instrument in various embodiments of the present invention
X-ray powder diffraction instrument (XRD), model D8 advance, Brooker company produces;
Field emission scanning electron microscope (SEM), model S-4800, Hitachi, Ltd produces;
Numerical control ultrasonic cleaner, model KQ-100DB type, Kunshan Ultrasonic Instruments Co., Ltd. produces;
Hysteresis curve tester, model SMT-600, U.S. MI/KJS company produces.
embodiment 1
Utilize acid regeneration desiliconization mud cake to prepare a method for nano ferriferrous oxide, specifically comprise the steps:
(1), will in block desiliconization mud cake 200g, add 500mL water, and pull an oar under 80 ℃ of heating states, finally form dispersed desiliconization mud preferably;
(2) according to the mass volume ratio of desiliconization mud cake and regenerated acid, be, desiliconization mud cake: the ratio that regenerated acid is 1g:2ml, regenerated acid is joined in step (1) in resulting desiliconization mud, continuing 80 ℃ adds after thermal agitation 2h, throw the thin iron rim charge of 100g, be heated to the molten and reduction of 80 ℃ of acid that realizes desiliconization mud cake, then after filtering, washing, with ammoniacal liquor, regulate pH=4, be settled to 1L, obtain the turbid liquid of frerrous chloride;
(3), get the turbid liquid of the resulting frerrous chloride of step (2), add 600g lauryl amine, at 85 ℃, keep after 12h, after suction filtration, with after acetone and ethanol washing 3 times, after the vacuum drying chamber inner drying 12 of 60 ℃, obtain nano ferriferrous oxide crude product;
(4), ultrasonic being dispersed in water of nano ferriferrous oxide crude product that step (3) is obtained, by attraction, carry out magnetic attraction separation and be further purified tri-iron tetroxide, finally obtain soft magnetism nano ferriferrous oxide.
By the nano ferriferrous oxide of above-mentioned gained, carry out XRD test, obtain the XRD figure of nano ferriferrous oxide as shown in Figure 1, as can be seen from Figure 1 diffraction maximum is consistent with the standard diagram of tri-iron tetroxide, and the product that preparation method's gained of the present invention is described is tri-iron tetroxide; There is obvious broadening in diffraction maximum, illustrates that what obtain is nano ferriferrous oxide.
By the nano ferriferrous oxide of above-mentioned gained, with the test of hysteresis curve tester, obtain the magnetic hysteresis tropic of nano ferriferrous oxide as shown in Figure 2, magnetic coercive force and remanence intensity are less as can be seen from Figure 2, are easy to magnetization and demagnetization, are a kind of soft magnetic materials.
embodiment 2
Utilize acid regeneration desiliconization mud cake to prepare a method for nano ferriferrous oxide, specifically comprise the steps:
(1), will in block desiliconization mud cake 200g, add 400ml water, and pull an oar under 80 ℃ of heating states, finally form dispersed desiliconization mud preferably;
(2) according to the mass volume ratio of desiliconization mud cake and regenerated acid, be, desiliconization mud cake: the ratio that regenerated acid is 1g:2ml, regenerated acid is joined in the desiliconization mud obtaining in step (1), continuing 80 ℃ adds after thermal agitation 2h, drop into the thin iron rim charge of 200g, be heated to the molten and reduction of 85 ℃ of acid that realizes desiliconization mud cake, then after filtering, washing, with ammoniacal liquor, regulate pH=4, be settled to 500ml, obtain the turbid liquid of frerrous chloride;
(3), get the turbid liquid of the resulting frerrous chloride of step (2), add 400g n-butylamine, at 85 ℃, keep after 12h, after suction filtration, acetone and ethanol washing 3 times, after the vacuum drying chamber inner drying 12h of 70 ℃, obtain nano ferriferrous oxide crude product;
(4), step (3) is obtained to nano ferriferrous oxide crude product, ultrasonic being dispersed in water, is further purified tri-iron tetroxide by magnetic attraction separation, finally obtains soft magnetism nano ferriferrous oxide.
embodiment 3
Utilize acid regeneration desiliconization mud cake to prepare a method for nano ferriferrous oxide, specifically comprise the steps:
(1), will in block desiliconization mud cake 200g, add 400mL water, and pull an oar under 80 ℃ of heating states, finally form dispersed desiliconization mud preferably;
(2) according to the mass volume ratio of desiliconization mud cake and regenerated acid, be, desiliconization mud cake: the ratio that regenerated acid is 1g:2ml, regenerated acid is joined in the desiliconization mud obtaining in above-mentioned (a) step, continuing 80 ℃ adds after thermal agitation 2h, drop into the thin iron rim charge of 160g, be heated to the molten and reduction of 85 ℃ of acid that realizes desiliconization mud cake, after then filtering, washing with water.With ammoniacal liquor, regulate pH=4, be settled to 500ml, obtain the turbid liquid of frerrous chloride;
(3), get the turbid liquid of the resulting frerrous chloride of step (2) and add 840g octadecyl amine, at 85 ℃, keep after 12h, suction filtration, after acetone and ethanol washing 3 times, after the vacuum drying chamber inner drying 12h of 60 ℃, obtains nano ferriferrous oxide crude product;
(4), step (3) is obtained to nano ferriferrous oxide crude product, ultrasonic being dispersed in water, is further purified tri-iron tetroxide by magnetic attraction separation, finally obtains soft magnetism nano ferriferrous oxide.
embodiment 4
Utilize acid regeneration desiliconization mud cake to prepare a method for nano ferriferrous oxide, specifically comprise the steps:
(1), will in block desiliconization mud cake 150g, add 300mL water, and pull an oar under 80 ℃ of heating states, finally form dispersed desiliconization mud preferably;
(2) according to the mass volume ratio of desiliconization mud cake and regenerated acid, be, desiliconization mud cake: the ratio that regenerated acid is 1g:2ml, regenerated acid is joined in the desiliconization mud of gained in step (1), continuing 80 ℃ adds after thermal agitation 2h, drop into the thin iron rim charge of 90g, be heated to the molten and reduction of 85 ℃ of acid that realizes desiliconization mud cake, after then filtering, being washed with water to, with ammoniacal liquor, regulate pH=4, be settled to 500ml, obtain the turbid liquid of frerrous chloride;
(3), get the turbid liquid of frerrous chloride of step (2) gained, add 240g triethylamine, at 85 ℃, keep after 12h, suction filtration, with after acetone and ethanol washing 3 times, after the vacuum drying chamber inner drying 12h of 80 ℃, obtains nano ferriferrous oxide crude product;
(4), nano ferriferrous oxide crude product that step (3) is obtained, ultrasonic being dispersed in water, is further purified tri-iron tetroxide by magnetic attraction separation, finally obtains soft magnetism nano ferriferrous oxide.
As can be seen from the above embodiments, a kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide of the present invention, owing to having adopted the oxidation reaction of fatty amine, makes to produce that ferriferrous oxide particles degree is even, size is little, has the performance of softwood.
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (4)
1. utilize acid regeneration desiliconization mud cake to prepare a method for nano ferriferrous oxide, it is characterized in that:
First, desiliconization mud cake is added to water and add hot breakdown, form dispersed desiliconization mud preferably;
Then, in the desiliconization mud of gained, add regenerated acid, heating stirs and reacts after 2h, add again thin iron rim charge, continue to be heated to 80-90 ℃, realize the molten and reduction of the acid of desiliconization mud cake, filter, wash, with ammoniacal liquor, regulate pH=4, the filtrate obtaining is the turbid liquid of frerrous chloride;
The consumption of above-mentioned desiliconization mud, regenerated acid and Bao Tie rim charge, by desiliconization mud cake contained in desiliconization mud: regenerated acid: thin iron rim charge is that 1g:2ml:0.5-1g calculates;
Further, in the turbid liquid of frerrous chloride, add fatty amine, control temperature and be 85 ℃ and carry out after oxidation reaction 12h, through suction filtration, with acetone and ethanol wash, vacuum drying obtains the thick product of nano ferriferrous oxide;
Finally, by ultrasonic being dispersed in water of the thick product of nano ferriferrous oxide, after magnetic attraction separation, obtain nano ferriferrous oxide.
2. a kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide as claimed in claim 1, is characterized in that described desiliconization mud cake is that steel mill utilizes the desiliconization mud cake producing in acid regeneration silica removal process, and its water content is 44～62%;
Described fatty amine is triethylamine, n-butylamine, lauryl amine or octadecyl amine.
3. a kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide as claimed in claim 2, it is characterized in that described desiliconization mud cake is added to water add hot breakdown, form dispersed desiliconization mud preferably, control the mass ratio of desiliconization mud cake and water, be desiliconization mud cake: water is 1-3:5, in block desiliconization mud cake, add water, and pull an oar under 80-90 ℃ of heating state, the desiliconization mud finally forming.
4. a kind of method of utilizing acid regeneration desiliconization mud cake to prepare nano ferriferrous oxide as claimed in claim 3, the amount that it is characterized in that added fatty amine is by the mass ratio of desiliconization mud cake used in itself and the turbid liquid of frerrous chloride, i.e. fatty amine: desiliconization mud cake is 1.5-4.5:1.
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| CN106475098B (en) * | 2015-08-31 | 2019-04-23 | 宝山钢铁股份有限公司 | A method of magnetic photocatalyst is prepared by acid regeneration desiliconization mud cake |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6302952B1 (en) * | 1998-01-26 | 2001-10-16 | Laporte Industries Limited | Process for the production of black iron oxide pigments |
| CN1807263A (en) * | 2006-02-21 | 2006-07-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black using desilicified mud cake |
| CN101560336A (en) * | 2008-04-18 | 2009-10-21 | 上海宝齐氧化铁有限公司 | Spherical iron oxide black and preparation technology thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6302952B1 (en) * | 1998-01-26 | 2001-10-16 | Laporte Industries Limited | Process for the production of black iron oxide pigments |
| CN1807263A (en) * | 2006-02-21 | 2006-07-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black using desilicified mud cake |
| CN101560336A (en) * | 2008-04-18 | 2009-10-21 | 上海宝齐氧化铁有限公司 | Spherical iron oxide black and preparation technology thereof |
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