阅读说明：本技术 一种氧化铁红及其制备方法 (Iron oxide red and preparation method thereof ) 是由 陈丽娟 牛利 张保华 韩冬雪 于 2021-09-23 设计创作，主要内容包括：本发明公开了一种氧化铁红及其制备方法。本发明提供的氧化铁红纯度和色度高,氧化铁红的粒径小,色泽鲜红。本发明利用含铁废弃物,并通过液相法和高压均质机进行均质,得到产物氧化铁红,该制备方法成本低,消除工业废弃物,有利于环境治理。本发明公开的氧化铁红制备方法可广泛应用于含铁废弃资源回收领域。(The invention discloses iron oxide red and a preparation method thereof. The iron oxide red provided by the invention has high purity and chroma, small particle size and bright red color. The invention utilizes the waste containing iron and homogenizes the waste by a liquid phase method and a high-pressure homogenizer to obtain the product of the iron oxide red. The preparation method of the iron oxide red disclosed by the invention can be widely applied to the field of iron-containing waste resource recovery.)

1. An iron oxide red is characterized in that: the iron oxide red has at least one of the following characteristics:

the content of iron element is 68.0 wt% -69.7 wt%;

the volatile matter at 105 ℃ is 0.6 to 1.0 weight percent;

the average particle diameter is 0.15 μm to 0.5. mu.m.

2. A method for producing the iron oxide red according to claim 1, characterized in that: the method comprises the following steps:

1) mixing iron-containing waste with acid, and reacting to obtain an iron source solution;

2) carrying out ion exchange on the iron source solution to obtain a purified iron-containing solution;

3) mixing the purified iron-containing solution with alkali, and reacting to obtain iron hydroxide;

4) heating hydroxide of iron to obtain a crude iron oxide red product;

5) and mixing the crude iron oxide red with an organic solvent, and homogenizing by using a homogenizer to obtain the iron oxide red.

3. The method of claim 2, wherein: the iron-containing waste in the step 1) comprises at least one of copper-nickel slag, fly ash, pyrite cinder, blast furnace slag, steel slag, coal slag and sulfuric acid slag.

4. The method of claim 2, wherein: the organic solvent in the step 5) comprises at least one of an ester solvent, an alkane solvent, a sulfone solvent and an alcohol solvent.

5. The method of claim 4, wherein: and step 5), the mass ratio of the organic solvent to the crude iron oxide red product is 1: (4-15).

6. The method of claim 2, wherein: and 5) homogenizing for 5-20 times.

7. The method of claim 2, wherein: and 5) homogenizing by the homogenizer at the pressure of 100-1000 bar.

8. The method of claim 2, wherein: and 5) homogenizing by the homogenizer with the power of 4kW-7 kW.

9. The method of claim 2, wherein: and 5) homogenizing by the homogenizer with the treatment capacity of 10L/h-40L/h.

10. Use of the process for the preparation of iron oxide red according to any one of claims 2 to 9 in the recovery of iron-containing waste resources.

Technical Field

The invention belongs to the field of materials, and particularly relates to iron oxide red and a preparation method thereof.

Background

Iron oxide red, also known as iron oxide red or iron oxide red, is dark red or red powder, is the most used inorganic dyeing pigment in the world at present, and has a chemical formula of alpha-Fe₂O₃Its melting point is 1565 deg.C, and it is non-toxic and insoluble in water. At present, the traditional preparation method of the iron oxide red comprises a dry process and a wet process, wherein the dry process comprises a copperas calcining method, an iron oxide yellow calcining method, an iron oxide black calcining method and a ferrous sulfate-sodium carbonate calcining method, and the wet process comprises a sulfate method, a nitrate method and a mixed acid salt method. However, these methods have the disadvantages of high cost, long production period, high energy consumption and environmental pollution caused by wastesAnd the like. Aiming at the problems of the existing process method, the process improvement mainly comprises the following steps: catalysis, hydrothermal, and core-coating. The improved method has the advantages of short reaction time, low temperature and high yield. However, the particle size of the red iron oxide is not fine enough to be controlled.

A homogenizer is a widely used homogenizing apparatus, and the acting force of the homogenizer mainly includes two kinds of shearing force and pressure. During the homogenizing process of the substance, a flow layer effect is generated, and particles or liquid drops of the dispersed phase are broken up by shearing force and extension; under the influence of turbulence effect, the particles or liquid drops deform under the fluctuation of pressure, small bubbles are rapidly broken under higher pressure, the capacity is released, local oscillation is caused, and under the combined action of the forces, the materials are well dispersed. The high-pressure homogenizer utilizes the energy released by the high-speed impact action and the cavitation phenomenon and strong high-frequency vibration to crush the particles, thereby achieving the effects of homogenizing and crushing, and enabling the substances to have more uniform and smaller particle sizes.

The fly ash is a common iron-containing waste, is industrial waste residue in a flue of the coal-fired power generation industry, mainly comprises silicon dioxide, aluminum oxide, iron oxide and calcium oxide, and causes huge environmental pollution and economic loss because the fly ash generated in the power generation industry every year cannot be treated. If the iron oxide in the iron-containing waste can be recycled, the problem of environmental pollution can be solved, and benefits and income can be brought to enterprises, so that a process method for preparing the iron oxide red by using the iron-containing waste is needed to be developed.

Disclosure of Invention

In order to overcome the problems of the prior art, an object of the present invention is to provide an iron oxide red; the second purpose of the invention is to provide a preparation method of the iron oxide red; the invention also aims to provide the application of the preparation method of the iron oxide red.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

in a first aspect, the present invention provides an iron oxide red, which has at least one of the following characteristics:

the content of iron element is 68.0 wt% -69.7 wt%;

the volatile matter at 105 ℃ is 0.6 to 1.0 weight percent;

the average particle diameter is 0.15 μm to 0.5. mu.m.

Further preferably, the content of the iron oxide red iron element is 68.0 wt% -69.7 wt%; still further preferably, the content of the iron oxide red iron element is 68.4 wt% -69.5 wt%; more preferably, the content of the iron oxide red iron element is 68.7 wt% to 69.3 wt%.

Further preferably, the volatile matter of the iron oxide red at 105 ℃ is 0.6-1.0 wt%; still further preferably, the volatile matter of the iron oxide red at 105 ℃ is 0.7-0.9 wt%; more preferably, the volatile matter of the iron oxide red at 105 ℃ is 0.8-0.9 wt%.

More preferably, the average grain diameter of the iron oxide red is 0.15-0.5 μm; still more preferably, the average particle size of the iron oxide red is 0.15 to 0.4 μm; more preferably, the average particle size of the iron oxide red is 0.20 to 0.4 μm.

In a second aspect, the present invention provides a method for preparing iron oxide red according to the first aspect of the present invention, comprising the steps of:

1) mixing iron-containing waste with acid, and reacting to obtain an iron source solution;

2) carrying out ion exchange on the iron source solution to obtain a purified iron-containing solution;

3) mixing the purified iron-containing solution with alkali, and reacting to obtain iron hydroxide;

4) heating hydroxide of iron to obtain a crude iron oxide red product;

5) and mixing the crude iron oxide red with an organic solvent, and homogenizing by using a homogenizer to obtain the iron oxide red.

Preferably, the iron-containing waste in the step 1) comprises at least one of copper-nickel slag, fly ash, pyrite cinder, blast furnace slag, steel slag, coal slag and sulfuric acid slag; further preferably, the iron-containing waste in the step 1) comprises at least one of copper-nickel slag, fly ash, pyrite cinder, blast furnace slag and steel slag; still further preferably, the iron-containing waste in the step 1) comprises at least one of copper-nickel slag and fly ash; still more preferably, the iron-containing waste in step 1) is fly ash.

Preferably, the acid in step 1) comprises at least one of hydrochloric acid, sulfuric acid and nitric acid; further preferably, the acid in step 1) includes at least one of hydrochloric acid and sulfuric acid.

Preferably, the method further comprises the step of standing the mixed solution for 6 to 30 hours after the reaction in the step 1); further preferably, the reaction of step 1) further comprises a step of standing the mixed solution for 12 to 24 hours.

Preferably, the ion exchange in step 2) is performed by ion exchange of the iron source solution with an iron removal resin.

Preferably, the alkali in step 3) comprises at least one of sodium hydroxide and potassium hydroxide.

Preferably, the heating mode in the step 4) comprises at least one of calcination, sand bath and silicon oil bath; more preferably, the heating mode in step 4) is calcination.

Preferably, the heating temperature in the step 4) is 260-340 ℃; further preferably, the heating temperature in the step 4) is 290-310 ℃.

Preferably, the organic solvent in step 5) includes at least one of an ester solvent, an alkane solvent, a sulfone solvent and an alcohol solvent; further preferably, the organic solvent in step 5) comprises ethyl acetate, ethanol, n-butanol, thionyl chloride and heptane; still more preferably, the organic solvent in step 5) is ethyl acetate.

Preferably, the mass ratio of the organic solvent to the crude iron oxide red in the step 5) is 1: (4-15); further preferably, the mass ratio of the organic solvent in the step 5) to the crude iron oxide red is 1: (5-13); still further preferably, the mass ratio of the organic solvent in the step 5) to the crude iron oxide red is 1: (6-11).

Preferably, the homogenizing pressure of the homogenizer in the step 5) is 100bar-1000 bar; further preferably, the pressure for homogenizing in the homogenizer in the step 5) is 400bar-1000 bar.

Preferably, the homogenizing power of the homogenizer in the step 5) is 4kW-7 kW; further preferably, the power for homogenizing by the homogenizer in the step 5) is 5kW-6 kW.

Preferably, the homogenizing treatment amount of the homogenizer in the step 5) is 10L/h-40L/h; more preferably, the homogenizing treatment amount of the homogenizer in the step 5) is 10L/h-30L/h; more preferably, the homogenizing treatment amount of the homogenizer in the step 5) is 10L/h-20L/h.

Preferably, the homogenization time of the homogenization step in the step 5) is 5-20 times; further preferably, the homogenization time of the homogenization step in the step 5) is 5 to 15; still more preferably, the number of homogenization in the homogenization step in the step 5) is 5 to 10.

Preferably, the step of drying is further included after the mixed material in the step 5) is homogenized.

Preferably, the drying temperature is 50-100 ℃; further preferably, the drying temperature is 60-90 ℃.

In a third aspect, the invention provides the application of the preparation method of the iron oxide red in the second aspect in the recovery of iron-containing waste resources.

The invention has the beneficial effects that:

the iron oxide red provided by the invention has high purity and chroma, small particle size and bright red color. The invention utilizes the waste containing iron and homogenizes the waste by a liquid phase method and a high-pressure homogenizer to obtain the product of the iron oxide red. The preparation method of the iron oxide red disclosed by the invention can be widely applied to the field of iron-containing waste resource recovery.

Specifically, the invention has the following advantages:

1) the iron-containing waste is utilized, the liquid phase method and the high-pressure homogenizer are adopted to prepare the iron oxide red, and the preparation conditions disclosed by the invention are mild, safe, nontoxic, efficient and quick;

2) the nano-scale iron oxide red prepared by the method has high purity and chroma, fine crystal nucleus fineness, small particle size of the iron oxide red and bright red color;

3) the iron oxide red is prepared by using the iron-containing industrial waste as an iron source, the cost is low, the environment is friendly, the iron-containing waste can be consumed by preparing the iron oxide red by adopting the method, and the iron oxide red preparation method disclosed by the invention can be widely applied to the field of iron-containing waste resource recovery.

Drawings

FIG. 1 is a flow chart of the preparation of iron oxide red in example 1.

FIG. 2 is a bar graph of the particle diameter versus volume fraction of the red iron oxide particles prepared in example 1.

Fig. 3 is a bar graph of the diameter of the iron oxide red particles versus the volume fraction prepared in example 3 and comparative example 1.

Detailed Description

The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available through commercial purchase.

Unless otherwise specified, the iron-removing resin used in the examples of the present application was a 001 × 7 type iron-removing resin produced by rui-friendly chemical limited, large city county.

Example 1

FIG. 1 is a flow chart of the preparation of iron oxide red in example 1. The following is further described with reference to fig. 1, with specific steps.

The preparation method of the iron oxide red comprises the following specific steps:

1) 50g of fly ash waste after boiler combustion is recovered, at room temperature, 50mL of sulfuric acid solution with the pH value of 2 is used for dissolving the fly ash, standing is carried out for 12 hours, and a clear solution of the fly ash is collected;

2) and (3) carrying out ion exchange on the collected clear solution by adopting iron-removing resin, wherein the using amount of the iron-removing resin is 50% of the solid mass of the fly ash, so as to obtain a solution containing ferric sulfate. And then adding sodium hydroxide solid into the ferric sulfate solution, wherein the mass of the added sodium hydroxide is 0.03 percent of the mass of the ferric sulfate solution. Iron ions are changed into insoluble ferric hydroxide to be separated out when meeting sodium hydroxide to form a precipitate phase, and the precipitate is obtained by separation after standing for 3 hours;

3) calcining the obtained insoluble compound ferric hydroxide at 300 ℃ for 3h to obtain a compound iron oxide red crude product;

4) and adding the crude iron oxide red into an organic solvent ethyl acetate for dissolving, wherein the mass of the ethyl acetate is 10% of that of the mixture. And adding the mixed solution into a high-pressure homogenizer, wherein the homogenizing pressure in the homogenizing process of the high-pressure homogenizer is 100bar, the homogenizing power is 5.5kW, the homogenizing treatment capacity is 40 liters/hour, circulating for 5 times, taking out the mixed solution, and drying at 60 ℃ to obtain the final product of the iron oxide red.

Example 2

The preparation method of the iron oxide red comprises the following specific steps:

1) recycling 80g of fly ash waste after boiler combustion, dissolving the fly ash with 150mL of sulfuric acid solution with the pH value of 2.5 at room temperature, standing for 14h, and collecting a clear solution;

2) and (3) carrying out ion exchange on the collected clear solution by adopting an iron-removing resin, wherein the using amount of the iron-removing resin is 50% of the solid mass of the fly ash, so as to obtain a solution containing ferric chloride. And then adding sodium hydroxide into the ferric chloride solution, wherein the addition amount of the sodium hydroxide is 0.04 percent of the mass of the ferric chloride solution. The iron ions become insoluble ferric hydroxide when meeting sodium hydroxide and are separated out to form a precipitate phase, and the precipitate is obtained after standing for 3.5 hours and separation;

3) calcining the obtained insoluble compound ferric hydroxide at 300 ℃ for 3h to obtain a compound iron oxide red crude product;

4) and adding the crude iron oxide red into an organic solvent ethyl acetate for dissolving, wherein the amount of the ethyl acetate accounts for 12% of the mass of the mixture. And adding the mixed solution into a high-pressure homogenizer, wherein the homogenizing pressure in the homogenizing process of the high-pressure homogenizer is 300bar, the homogenizing power is 5.5kW, the homogenizing treatment capacity is 35 liters/hour, circulating for 5 times, taking out the mixed solution, and drying at 65 ℃ to obtain the final product of the iron oxide red in the embodiment.

Example 3

The preparation method of the iron oxide red comprises the following specific steps:

1) recycling 100g of fly ash waste after boiler combustion, dissolving fly ash with 200mL of sulfuric acid solution with pH of 3 at room temperature, standing for 16h, and collecting clear solution;

2) and (3) carrying out ion exchange on the collected clear solution by adopting iron-removing resin, wherein the using amount of the iron-removing resin is 50% of the solid mass of the fly ash, so as to obtain a solution containing ferric sulfate. And then adding sodium hydroxide into the ferric sulfate solution, wherein the addition amount of the sodium hydroxide is 0.05 percent of the mass of the ferric sulfate solution. The iron ions become insoluble ferric hydroxide when meeting sodium hydroxide and are separated out to form a precipitate phase, and the precipitate is obtained by separation after standing for 4 hours;

3) calcining the obtained insoluble compound ferric hydroxide at 300 ℃ for 3h to obtain a compound iron oxide red crude product;

4) and adding the crude iron oxide red into an organic solvent ethyl acetate for dissolving, wherein the amount of the ethyl acetate accounts for 13% of the mass of the mixture. And adding the mixed solution into a high-pressure homogenizer, wherein the homogenizing pressure in the homogenizing process of the high-pressure homogenizer is 450bar, the homogenizing power is 5.5kW, the homogenizing treatment capacity is 32 liters/hour, circulating for 6 times, taking out the mixed solution, and drying at 70 ℃ to obtain the final product of the iron oxide red.

Example 4

The preparation method of the iron oxide red comprises the following specific steps:

1) recycling 60g of fly ash waste after boiler combustion, dissolving the fly ash with 100mL of hydrochloric acid solution with the pH value of 3.5 at room temperature, standing for 18h, and collecting a clear solution;

2) and (3) carrying out ion exchange on the collected clear solution by adopting an iron-removing resin, wherein the using amount of the iron-removing resin is 50% of the solid mass of the fly ash, so as to obtain a solution containing ferric chloride. And adding potassium hydroxide into the ferric chloride solution, wherein the addition amount of the potassium hydroxide is 0.06 percent of the mass of the ferric ion solution. Iron ions are changed into insoluble ferric hydroxide to be separated out when meeting potassium hydroxide to form a precipitate phase, and the precipitate is obtained by separation after standing for 4.5 hours;

3) calcining the obtained insoluble compound ferric hydroxide at 300 ℃ for 3h to obtain a compound iron oxide red crude product;

4) and (3) adding the crude iron oxide red into an organic solvent ethyl acetate for dissolving, wherein the amount of the ethyl acetate is 14% of the mass of the mixture. And adding the mixed solution into a high-pressure homogenizer, wherein the homogenizing pressure in the homogenizing process of the high-pressure homogenizer is 700bar, the homogenizing power is 5.5kW, the homogenizing treatment capacity is 15 liters/hour, circulating for 7 times, taking out the mixed solution, and drying at 80 ℃ to obtain the final product of the iron oxide red.

Example 5

The preparation method of the iron oxide red comprises the following specific steps:

1) recycling 80g of fly ash waste after boiler combustion, dissolving fly ash with 150mL of hydrochloric acid solution with pH of 4 at room temperature, standing for 24h, and collecting a clear solution;

2) and (3) carrying out ion exchange on the collected clear solution by adopting an iron-removing resin, wherein the using amount of the iron-removing resin is 50% of the solid mass of the fly ash, so as to obtain a solution containing ferric chloride. And adding potassium hydroxide into the ferric chloride solution, wherein the addition amount of the potassium hydroxide is 0.07 percent of the mass of the ferric chloride solution. Iron ions are changed into insoluble ferric hydroxide to be separated out when meeting potassium hydroxide to form a precipitate phase, and the precipitate is obtained by separation after standing for 5 hours;

3) calcining the obtained insoluble compound ferric hydroxide at 300 ℃ for 3h to obtain a compound iron oxide red crude product;

4) and (3) adding the crude iron oxide red into an organic solvent ethyl acetate for dissolving, wherein the amount of the ethyl acetate is 15% of the mass of the mixture. And adding the mixed solution into a high-pressure homogenizer, wherein the homogenizing pressure in the homogenizing process of the high-pressure homogenizer is 1000bar, the homogenizing power is 5.5kW, the homogenizing treatment capacity is 10 liters/hour, circulating for 8 times, taking out the mixed solution, and drying at 90 ℃ to obtain the final product of the iron oxide red.

Comparative example 1

The preparation method of the iron oxide red comprises the following specific steps:

1) recycling 80g of fly ash waste after boiler combustion, dissolving the fly ash with 150mL of sulfuric acid solution with the pH value of 2.5 at room temperature, standing for 14h, and collecting a clear solution;

2) and (3) carrying out ion exchange on the collected clear solution by adopting iron-removing resin, wherein the using amount of the iron-removing resin is 50% of the solid mass of the fly ash, so as to obtain a solution only containing ferric sulfate. And then adding sodium hydroxide into the ferric sulfate solution, wherein the mass of the added sodium hydroxide is 0.03 percent of that of the ferric sulfate solution. Iron ions are changed into insoluble ferric hydroxide to be separated out when meeting sodium hydroxide to form a precipitate phase, and the precipitate is obtained by separation after standing for 3 hours;

3) the insoluble compound iron hydroxide obtained was calcined at 300 ℃ for 3 hours to obtain crude iron oxide red, which is the final product of this example.

4) And crushing, grinding and sieving the obtained crude iron oxide red by a high-speed crusher to obtain the final product iron oxide red of the comparative example.

Performance testing

The iron oxide red prepared in examples 1 to 5 and comparative example 1 was subjected to a performance test, and the test results are shown in table 1.

Table 1: results of performance test of iron oxide red prepared in examples 1 to 5 and comparative example 1

Note: the detection of the iron content follows the standard GB/T1863-2008; the detection of volatiles follows the standard GB/T5211.3-1985; the average particle size is detected according to the standard GB/T15445.2-2006; the quality standard is 190# iron oxide red.

As can be seen from Table 1, the iron contents of the iron oxide red prepared in the examples of the present application are 98.13% -99.05%, which is higher than 96.6% of the standard value, and the iron contents of the iron oxide red are 68.7% -69.3%. The volatile matter of the iron oxide red prepared by the embodiment of the application is 0.80-0.89% at 105 ℃ and is lower than 1.0% of the standard value. In addition, it can be seen from table 1 that the grain sizes of the iron oxide red prepared in examples 1 to 5 were all smaller than 0.5 μm of the standard value, and the grain sizes of the iron oxide red prepared therefrom were gradually decreased from 0.39 μm to 0.20 μm as the number of homogenization with the high-pressure homogenizer was gradually increased from 5 to 8, and it was seen that the grain sizes of the iron oxide red prepared were gradually decreased as the number of homogenization with the high-pressure homogenizer was increased. In contrast, comparative example 1, in which the grain size of the iron oxide red prepared by pulverizing, grinding and sieving was 0.58 μm, which was greater than 0.5 μm of the standard value, only by a conventional high-speed pulverizer, shows that the high-pressure homogenizer was effective in reducing the grain size of the iron oxide red. The iron oxide prepared by the embodiment of the application is reddish brown in appearance and free of agglomeration, and meets the quality standard of iron oxide red.

FIG. 2 is a bar graph of the particle diameter versus volume fraction of the red iron oxide particles prepared in example 2. As can be seen from FIG. 2, the average particle size of the iron oxide red particles prepared in example 2 was 0.30 μm, and the particle size was concentrated in the range of 0.28 μm to 0.34. mu.m. It can be seen that the iron oxide red particles homogenized by the high-pressure homogenizer have a narrow particle size distribution range.

Fig. 3 is a bar graph of the diameter of the iron oxide red particles versus the volume fraction prepared in example 3 and comparative example 1. As can be seen from FIG. 3, the iron oxide red particles prepared in example 3 had an average particle size of 0.25 μm and a particle size distribution in the range of 0.18 μm to 0.36. mu.m. The iron oxide red particles prepared in comparative example 1 had an average particle size of 0.58 μm and a particle size distribution in the range of 0.45 μm to 0.71. mu.m. As can be seen from the comparison of the particle sizes of example 3 and comparative example 1, the iron oxide red homogenized by the high-pressure homogenizer has a smaller particle diameter.

According to the analysis, the nano-scale iron oxide red prepared by the method has higher purity and chroma, finer crystal nucleus fineness, smaller particle size of the iron oxide red and more bright red color, and can be widely applied to the field of preparing the iron oxide red.

The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.