KR20200083002A - Bur-like feooh·fe2o3 and method for preparing the same - Google Patents

Abstract

The present invention relates to: a method for manufacturing iron hydroxide and iron oxide, which can control a shape according to reaction time and molar concentration and change particle size by using a Fe precursor compound; and iron hydroxide and iron oxide having a chestnut bur shape manufactured by using the same. According to the present invention, the present invention has an advantage of being applied to various purposes by controlling the shape and size according to the concentration and reaction time of the precursor while reacting at a relatively lower temperature than a conventional method for manufacturing iron hydroxide and iron oxide, and since the present invention has a simple manufacturing method, manufacturing cost can be reduced to improve productivity efficiency when applying the same.

Description

Iron hydroxide and iron oxide having a chestnut shape and a manufacturing method therefor{BUR-LIKE FEOOH·FE2O3 AND METHOD FOR PREPARING THE SAME}

The present invention relates to a method for producing iron hydroxide and iron oxide having a chestnut shape, and a method for producing iron hydroxide and iron oxide having a shape and size controllable according to reaction conditions using a Fe precursor compound that can be obtained relatively easily and manufactured using the same It relates to iron hydroxide and iron oxide.

Iron hydroxide and iron oxide are produced in various forms in nature, and they are attracting much attention due to their non-toxic and psychedelic properties. In particular, it has been used in the steel and steel industries, but has excellent physical, chemical, optical, and electrical properties, and has been used in various fields such as pigments, catalysts, gas sensors, and magnetic recording media.

Iron hydroxide and iron oxide can be adjusted in various forms from rod shape to spindle shape, and are classified into α, β, and γ depending on the number of oxides and structure, and each has its own characteristics. As it is being applied, the manufacturing process is most important.

Accordingly, there is a need for a manufacturing method capable of providing iron hydroxide and iron oxide used for various purposes in a simpler process, controlling shape and size, and giving diversity to surface area characteristics.

[Patent Document 1] Republic of Korea Patent Publication No. 10-2009-0004374

An object of the present invention is to provide a method for producing iron hydroxide and iron oxide having a chestnut shape that can control shape and particle size, and can give diversity to surface area characteristics.

In addition, it is an object of the present invention to provide iron hydroxide and iron oxide in the form of chestnut.

In order to achieve the above object, the method for producing iron hydroxide according to the present invention may include the following steps:

1) dissolving the pH adjusting agent in a solvent;

2) adding a Fe precursor compound to the solution obtained in step 1);

3) reacting by heating the product of step 2);

4) Drying the reactant obtained in step 3) to obtain iron hydroxide powder.

In the method for producing iron hydroxide of the present invention,

In step 3), a step of adding a structure derivative solution to react with a hydroxyl group to control the size of particles may be further added to the result of step 2) prior to the temperature increase reaction.

The pH adjusting agent may be one or more selected from the group consisting of KOH, NaOH strong base, NH ₄ OH, and carbonyl diamide (CH ₄ N ₂ O).

The solvent may be at least one selected from distilled water and alcohol.

The alcohol may be one or more selected from methanol, ethanol, propanol and alcohol.

The Fe precursor compound is Fe(NO ₃ ) ₃ , FeCl ₃ , FeC ₂ O ₄ , FeCl ₂ , FeBr ₂ , FeBr ₃ , FeI ₂ , FeI ₃ , Fe(NO ₃ ) ₂ and one or more Fe precursor compounds selected from the group consisting of hydrates thereof.

In step 2), the molar concentration ratio of the pH adjusting agent:Fe precursor compound may be 1:1 to 5 (however, the Fe precursor molar concentration ranges from 2M or more to less than 10M).

The heating reaction can be carried out at 70 to 150°C for 10 minutes to 48 hours.

The drying may be performed at 25 to 150°C for 10 minutes to 48 hours.

The structural derivatives are cetyltrimethyl ammonium bromide ('CTAB'), octadecyltrimethyl ammonium bromide ('OTAB'), dodecyltrimethyl ammonium bromide ('DTAB') Bromine-based compounds such as; Imine polymer compounds such as polyetherimide ('PEI'); Pyrolidonone polymer compounds such as polyvinylpyrrolidone ('PVP'); Chloride-based compounds such as cetyltrimethyl ammonium chloride ('CTAC'); And amine-based polymer compounds such as trimethylamine ('TEA'), isopropylamine ('IPA'), dipropylamine ('DPA'), and diethylamine ('DEA'). It may be one or more structural derivatives selected from the group consisting of.

The present invention provides iron hydroxide having a chestnut blossom shape produced by the method for manufacturing iron hydroxide according to the present invention.

The method for manufacturing iron oxide according to the present invention may include the step of preparing iron hydroxide by the method for manufacturing iron hydroxide, and then firing the prepared iron hydroxide.

The firing may be performed at 100 to 700°C for 1 to 10 hours.

The present invention provides iron oxide having a chestnut shape produced by the method for manufacturing iron oxide according to the present invention.

According to the method of manufacturing iron hydroxide and iron oxide powder according to the present invention, the process is simple by using a hydrothermal synthesis method at a relatively low temperature, unlike the conventional production method, and thus can contribute to productivity efficiency.

In addition, iron hydroxide and iron oxide produced by the manufacturing method of the present invention have a chestnut shape, and since the particle size is controlled, diversity in surface area characteristics is given, and thus it can be applied to many fields.

1 shows a flow chart of an example of a method for producing iron hydroxide and iron oxide particles by a hydrothermal synthesis method according to the present invention, respectively.
Figure 2 shows the FE-SEM image of the iron hydroxide particles of Example 1 and Comparative Example 1 prepared by the hydrothermal synthesis method of the present invention.
Figure 3 shows the XRD results of the iron hydroxide particles of Examples 1, 2, and Comparative Example 1 and iron oxide particles of Examples 6 and 7 prepared by the hydrothermal synthesis method of the present invention.
Figure 4 shows the BET results to find out the surface properties of the iron hydroxide particles of Examples 1, 2 and Comparative Example 1 prepared by the hydrothermal synthesis method of the present invention.

Advantages and features of the present invention, and a method of achieving them will be clarified with reference to embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the specific embodiments disclosed below, but may be implemented in various different forms, and only specific embodiments of the present invention allow the disclosure of the present invention to be complete, and in the technical field to which the present invention pertains. It is provided to completely inform the person of ordinary skill in the scope of the invention, and the present invention is only defined by the scope of the claims.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used as meanings commonly understood by those skilled in the art to which the present invention pertains. In addition, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively, unless specifically defined.

Hereinafter, a method of manufacturing iron hydroxide and iron oxide according to the present invention and iron hydroxide and iron oxide produced using the same will be described in detail.

The method for manufacturing iron hydroxide according to the present invention may include the following steps:

1) dissolving the pH adjusting agent in a solvent;

2) adding a Fe precursor compound to the solution obtained in step 1);

3) reacting by heating the product of step 2);

4) Drying the reactant obtained in step 3) to obtain iron hydroxide powder.

In addition, the method for producing iron hydroxide of the present invention may further include a 3') step of adding a bromine compound solution to the product of step 2) before the temperature-raising reaction in step 3).

The pH adjusting agent used in step 1) may be at least one selected from the group consisting of KOH, NaOH strong base, NH ₄ OH, and carbonyl diamide (CH ₄ N ₂ O), but is not limited thereto.

The solvent used in step 1) is not particularly limited as long as it is an OH ^- group-rich solvent, and may be, for example, one or more selected from distilled water and alcohol, but is not limited thereto.

The alcohol may be one or more selected from methanol, ethanol, propanol, and all alcohols, but is not limited thereto.

The Fe precursor compound used in step 2) is a bivalent or trivalent iron salt, and is not limited as long as it is a material that can be dissolved in water and ionized, for example, the Fe precursor compound is Fe(NO ₃ ) ₃ , FeCl ₃ , FeC ₂ O ₄ , FeCl ₂ , FeBr ₂ , FeBr ₃ , FeI ₂ , FeI ₃ , Fe(NO ₃ ) ₂ and one or more Fe precursor compounds selected from the group consisting of hydrates thereof, but may be It is not limited.

In the step 2), the amount of the Fe precursor compound used is preferably an amount such that the molar ratio of the pH adjusting agent:Fe precursor compound is 1:1 to 5 (however, the Fe precursor molar concentration has a range of 2M or more to less than 10M). .), the molar concentration ratio is more preferably 1: 1 to 3, but outside the above range, the more the amount of the precursor compound enters, the higher the production cost and the lower the yield, so it is not preferable.

In step 3), the temperature increase reaction is preferably performed at 70 to 150°C for 10 minutes to 48 hours, and more preferably at 80 to 100°C for 30 minutes to 24 hours. Outside the above range, there are limitations in controlling the shape and size, which is not preferable because the desired iron hydroxide is not produced.

In step 4), drying is preferably performed at 25 to 100°C for 1 to 24 hours, and more preferably at 50 to 70°C for 7 to 10 hours, wherein the drying temperature and time are outside the above range. It is not preferable because cotton hydroxide is oxidized to iron oxide, which is difficult to produce iron hydroxide.

The structure derivative compound used in step 3') is not particularly limited, and for example, the structure derivative is a bromine-based compound such as cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide; Imine polymer compounds such as polyetherimide; Pyridone-based polymer compounds such as polyvinylpyrrolidone; Chloride-based compounds such as cetyltrimethyl ammonium chloride; And it may be one or more selected from the group consisting of amine-based polymer compounds such as triethylamine, isopropylamine, dipropylamine, diethylamine, but is not limited thereto.

The iron hydroxide according to the present invention manufactured by the method for producing iron hydroxide according to the present invention can impart diversity to the surface area properties by having a chestnut shape, and thus can be used for various applications.

The method for manufacturing iron oxide according to the present invention may include the step of firing iron hydroxide produced by the method for manufacturing iron hydroxide according to the present invention.

The firing is preferably performed at 100 to 700°C for 1 to 10 hours, more preferably 300 to 500°C for 2 to 5 hours, and when the firing temperature and time are outside the above range, the chestnut shape is It does not appear, and there is a limit in size control, which is not preferable.

The iron oxide according to the present invention, manufactured by the method for manufacturing iron oxide according to the present invention, may have a chestnut shape to impart diversity to surface area properties, and thus may be used in various applications.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are only intended to illustrate the present invention and the scope of the present invention is not limited to the following examples.

<Physical property evaluation>

The physical properties of the iron hydroxide and iron oxide particles were evaluated by drying in the form of a powder, and the powder was dried in a vacuum oven for 24 hours at 60°C.

1. To confirm the surface area characteristics of the iron hydroxide particles of Example 1 and Comparative Example 1, it was confirmed by BET analysis.

2. The shapes of the particles of Examples 1, 2, 6, and 7 and Comparative Example 1 were confirmed by measuring dry powder with FE-SEM.

Example 1

After adding carbonyl diamide (CH ₄ N ₂ O) 3M to 100 ml of distilled water, the mixture was stirred for 20 minutes until completely dissolved. Then FeCl ₃ ·6H ₂ O 3M was added and stirred for 30 minutes until completely dissolved. After adding 0.002 mol of cetyl trimethylammonium bromide, the temperature was raised to 90° C., followed by reaction for 24 hours. When the reaction was completed, it was sufficiently cooled at room temperature, and then filtered and washed using a vacuum pump. Iron hydroxide powder was prepared by drying at 60° C. for 8 hours in a hot air dryer, and the measurement results of the properties are shown in Tables 1, 2, 3 and 4 below.

Example 2

In the process of manufacturing the iron hydroxide powder of Example 1, except that the reaction time was changed to 30 minutes, it was performed in the same manner as in Example 1, and the measurement results of the properties are shown in Tables 1, 3 and 4 below. Did.

Example 3

In the process of manufacturing the iron hydroxide powder of Example 1, except that the reaction time was changed to 1 hour, it was performed in the same manner as in Example 1, and the results of measurement of its properties are shown in Table 1 below.

Example 4

The method of Example 1 was performed except that the reaction time was changed to 6 hours in the process of preparing the iron hydroxide powder of Example 1, and the results of the measurement of its properties are shown in Table 1 below.

Example 5

In the process of manufacturing the iron hydroxide powder of Example 1, except that the reaction time was changed to 12 hours, it was performed in the same manner as in Example 1, and the results of measurement of its properties are shown in Table 1 below.

Example 6

After preparing the iron hydroxide powder according to Example 1, the prepared iron hydroxide powder was calcined at 300° C. for 3 hours to prepare iron oxide powder, and the results of measurement of the physical properties thereof are shown in Table 1 and FIG. 3.

Example 7

After preparing the iron hydroxide powder according to Example 2, the prepared iron hydroxide powder was calcined at 300° C. for 3 hours to prepare iron oxide powder, and the results of measurement of the physical properties thereof are shown in Table 1 and FIG. 3.

Comparative Example 1

In the process of preparing the iron hydroxide powder of Example 1, it was carried out in the same manner as in Example 1, except that the concentrations of cetyltrimethylammonium bromide (CH ₄ N ₂ O) and FeCl ₃ ·6H ₂ O were changed to 1M. The results of the measurement of the properties are shown in Tables 1, 2, 3 and 4 below.

Comparative Example 2

After preparing the iron hydroxide powder according to Example 1, the prepared iron hydroxide powder was calcined at 500° C. for 3 hours to prepare iron oxide powder, and the measurement results of the properties are shown in Table 1 and FIG. 3.

Particle size shape BET Example 1 13㎛ sticker 12.3㎡/g Example 2 3㎛ sticker 21.5㎡/g Example 3 6㎛ sticker 7.9㎡/g Example 4 8㎛ sticker 6.9㎡/g Example 5 10㎛ sticker 6.1㎡/g Example 6 5~6㎛ sticker 9.7㎡/g Example 7 2~3㎛ sticker 15.4㎡/g Comparative Example 1 1~2㎛ couch 6.5㎡/g Comparative Example 2 1~2㎛ Octahedron 18.1㎡/g

As shown in Table 1, it can be seen that Examples 1 to 7 by the manufacturing method according to the present invention produced iron oxide and iron hydroxide having a chestnut shape having a particle size of 2 to 13 μm.

Claims (14)

Method for manufacturing iron hydroxide comprising the following steps:
1) dissolving the pH adjusting agent in a solvent;
2) adding a Fe precursor compound to the solution obtained in step 1);
3) reacting by heating the product of step 2);
4) Drying the reactant obtained in step 3) to obtain iron hydroxide powder. According to claim 1,
Method of producing iron hydroxide further comprising the step of adding a structure derivative solution to control the size of the particles by reacting with a hydroxyl group to the result of the step 2) before the temperature-raising reaction in step 3). According to claim 1,
The pH adjusting agent is a method of producing at least one iron hydroxide selected from the group consisting of KOH, NaOH, NH ₄ OH, and carbonyl diamide (CH ₄ N ₂ O). According to claim 1,
The solvent is a method of producing at least one iron hydroxide selected from distilled water and alcohol. According to claim 4,
The alcohol is a method of producing at least one iron hydroxide selected from methanol, ethanol, and propanol. According to claim 1,
The Fe precursor compound is Fe(NO ₃ ) ₃ , FeCl ₃ , FeC ₂ O ₄ , FeCl ₂ , FeBr ₂ , FeBr ₃ , FeI ₂ , FeI ₃ , Fe(NO ₃ ) ₂ and one or more Fe precursor compounds selected from the group consisting of hydrates of iron hydroxide . According to claim 1,
In the step 2), the molar concentration of the Fe precursor has a range of 2M or more and less than 10M, and the molar concentration ratio of the pH adjusting agent:Fe precursor compound is 1:1 to 5. According to claim 1,
The heating reaction is a method of producing iron hydroxide is performed for 10 minutes to 48 hours at 70 to 150 ℃. According to claim 1,
The drying method of iron hydroxide is carried out for 1 to 24 hours at 25 ~ 100 ℃. According to claim 2,
The structural derivatives include cetyltrimethyl ammonium bromide, octadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, polyetherimide, polyvinylpyrrolidone, cetyltrimethyl ammonium chloride, triethylamine, isopropylamine, dipropylamine and Method for producing at least one iron hydroxide selected from the group consisting of diethylamine. An iron hydroxide produced by the method for producing iron hydroxide according to any one of claims 1 to 10 and having a chestnut shape. A method for producing iron oxide comprising producing iron hydroxide by the method for producing iron hydroxide according to any one of claims 1 to 10, and then firing the prepared iron hydroxide. The method of claim 12,
The firing method of iron oxide is carried out for 1 to 10 hours at 100 ~ 700 ℃. An iron oxide produced by the method for manufacturing iron oxide according to claim 12 and having a chestnut shape.

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