JP4920893B2 - Method for increasing the content of ferric oxide in limonite and method for producing limonite with an increased content of ferric oxide - Google Patents

Description

  The present invention relates to limonite, limonite-containing materials, and limonite-containing concrete.

  Conventionally, it is known that limonite containing goethite (goethite) as a main component has a deodorizing action. By using this limonite to form a fired molded article, it is possible to form a fired molded article having a deodorizing action. (For example, refer to Patent Document 1).

  As such a limonite mining site, the area around Mt. Aso is known, and the mined limonite has little deodorizing effect immediately after mining, and usually has a desired deodorizing effect by exposure to the field for about 2 to 3 years. It is known to have.

  In other words, about 70% of limonite is composed of iron, and when it is buried in the ground, the chemical properties are relatively unstable due to the presence of ferrous oxide due to the lack of oxygen. It is thought to have become.

  Therefore, immediately after mining, various unexplained reactions occur in limonite at the same time, resulting in a relatively low deodorizing effect. By oxidizing limonite by field exposure, ferrous oxide becomes ferric oxide. It is believed that the limonite is stabilized and deodorizing occurs.

Moreover, as ferrous oxide is oxidized to ferric oxide, limonite turns from brown immediately after mining to ocher and is judged to be shippable when it becomes a predetermined ocher with field exposure. And shipped as a product.
JP 2004-010473 A

  In recent years, it has been found that the above-described limonite has not only a deodorizing action but also a water quality improving action that seems to be an effect caused by ferric oxide and a meat quality improving action by using it as an additive for livestock animal feed. In particular, when limonite is used as a kind of aggregate in concrete, it has been found that by using such concrete for revetment work, it can be made concrete with a water quality improvement function, Although the demand for limonite is increasing, it is impossible to supply in a timely manner because it is necessary to oxidize ferric oxide by field exposure for 2-3 years and to stabilize the chemical properties. There is a problem that it is difficult to supply limonite that meets market demands.

  In particular, in order to determine how much ferrous oxide in field-exposed limonite has become ferric oxide, it has been difficult to make a clear determination, and it can be shipped. It has become extremely difficult to determine the quality, and there has been a problem that the oxidation treatment period by field exposure becomes long in order to secure a required margin.

  In view of the current situation, the present inventor conducted research to develop a determination method that can reliably determine the degree of oxidation from ferrous oxide to ferric oxide while shortening the oxidation treatment period. The present invention has been achieved.

In method of increasing the content of ferric oxide in the limonite of the present invention, by drying while irradiating ultraviolet rays you were increased reflection intensity of the surface exponent (110) in X-ray diffraction. Further, the reflection intensity at the surface index (110) in X-ray diffraction is characterized by being larger than the reflection intensity of the surface index (111), and also characterized by heating and drying in an ozone atmosphere. Is.

In addition, in the method for producing limonite in which the content ratio of ferric oxide is increased, a raw material having a reflection intensity with a surface index (111) larger than that with a surface index (110) in X-ray diffraction is irradiated with ultraviolet rays. However, the raw material is dried to make the reflection intensity at the surface index (110) higher than the reflection intensity at the surface index (111) . Further, when the reflection intensity of a plane index (110) was 100, the reflection intensity at the plane index (111) is characterized in that as a 85 or less, and the casing, within the casing A conveyor that conveys limonite; an inlet that is provided upstream of the conveyor in the conveying direction; and that is used to introduce limonite into the casing; The treatment is carried out in an oxidation treatment apparatus comprising an ultraviolet irradiation lamp for irradiating the limonite on the conveyor with ultraviolet rays and a hot air insufflator for supplying warm air at a predetermined temperature containing ozone in the casing. It also has a feature.

Further , the reflection intensity at the plane index (110) in the X-ray diffraction of limonite is compared with the reflection intensity at the plane index (111), and the reflection intensity at the plane index (110) is compared with the plane index (111). ) To determine the degree of oxidation from ferrous oxide to ferric oxide in limonite that is determined to have produced a predetermined content of ferric oxide in the limonite. for a shall which have a feature also. Further, in the production of limonite having an increased content of ferric oxide, the reflection intensity at the plane index (110) in X-ray diffraction was compared with the reflection intensity at the plane index (111) to oxidize limonite. There is also a feature in the use of data in which the ratio of at least the reflection intensity at the surface index (110) and the reflection intensity at the surface index (111) can be determined to determine the degree of progression of.

According to the first aspect of the invention, by drying while irradiating with ultraviolet rays, it is possible to carry out the oxidation treatment from ferrous oxide to ferric oxide in a much shorter time than before, and to perform X-ray diffraction. the reflection intensity of a plane index (110) in the by greatly can increase the existence ratio of ferric oxide in the limonite, it generates a limonite which reliably stabilize the chemical properties.

Moreover, by making the reflection intensity at the surface index (110) in X-ray diffraction larger than the reflection intensity of the surface index (111), the chemical properties are stabilized at a high level, and the limonite in which quality variation is suppressed. Can be generated.

According to the invention described in claim 2 , by heating and drying in an ozone atmosphere, the oxidation of ferrous oxide can be further promoted, and limonite having stable chemical properties can be generated in a shorter time.

According to the invention of claim 3, by drying the raw material while irradiating ultraviolet rays to the raw material having a reflection intensity of the surface index (111) larger than the reflection intensity of the surface index (110) in X-ray diffraction, Limonite having desired characteristics can be obtained in an extremely short time compared to the prior art, and the reflection intensity at the surface index (110) in X-ray diffraction is made larger than the reflection intensity of the surface index (111), thereby allowing limonite. By increasing the abundance ratio of the ferric oxide therein, it is possible to obtain a limonite having a stable chemical property.

According to the invention described in claim 4 , when the reflection intensity at the surface index (110) is 100, the reflection intensity at the surface index (111) is 85 or less, so that the chemical properties of limonite are obtained. Can be stabilized at a high level and quality variation can be suppressed, so that the quality of the limonite-containing material can be further improved.

According to the invention of claim 5 , a casing, a conveyor that conveys limonite in the casing, an inlet that is provided upstream in the conveyance direction of the conveyor, and injects limonite into the casing, and conveyance of the conveyor An outlet for taking out limonite in the casing, an ultraviolet irradiation lamp for irradiating the limonite on the conveyor with ultraviolet rays, and a temperature for sending hot air at a predetermined temperature containing ozone in the casing. By performing the treatment in an oxidation treatment apparatus including an air blower, limonite having desired characteristics can be generated in a short time by further promoting the oxidation of limonite.

According to the sixth aspect of the present invention, the reflection intensity at the plane index in the X-ray diffraction of the Li Monaito (110), it is compared with the reflection intensity of a plane index (111), in the plane index (110) When the reflection intensity of the surface index (111) is greater than the reflection intensity of the surface index (111), it is determined that ferric oxide having a predetermined content is generated in the limonite. Since the method for determining the degree of oxidation to ferrous iron is used, an objective determination can be made, and the degree of progress of oxidation can be determined more accurately. In addition, according to the invention described in claim 7, in the production of limonite having an increased content of ferric oxide, the reflection intensity at the surface index (110) in the X-ray diffraction and the surface index (111) Use of data that shows the ratio of at least the reflection index at the plane index (110) and the reflection intensity at the plane index (111) to determine the degree of oxidation of limonite by comparing the reflection intensity of Thus, an objective determination can be made, and the progress of oxidation can be determined more accurately.

  In the limonite, the limonite-containing material and the limonite-containing concrete of the present invention, the limonite excavated from the required mining site is dried while being irradiated with ultraviolet rays, so that the reflection intensity at the surface index (110) in the X-ray diffraction of limonite is obtained. Is larger than the reflection intensity of the plane index (111).

  The inventor has found that the reflection intensity at each surface index in the X-ray diffraction reflects the oxidation state of iron in the limonite, and uses this reflection intensity to determine the end of the oxidation process of limonite. It has come.

  That is, limonite immediately after being excavated from the mining site has a high content of ferrous oxide, and the reflection intensity at the plane index (111) in X-ray diffraction is higher than the reflection intensity at the plane index (110). However, as the ferrous oxide is oxidized to ferric oxide and the content of this ferric oxide increases, the reflection intensity at the plane index (110) becomes the reflection intensity at the plane index (111). It is determined that ferric oxide having a predetermined content is generated when the reflection intensity at the plane index (110) becomes larger than the reflection intensity at the plane index (111).

  FIG. 1 is a peak search diagram showing X-ray diffraction results of limonite immediately after mining. Here, assuming that the reflection intensity at the surface index (111) is “100”, the reflection intensity at the surface index (110) is about “80”.

  By oxidizing this limonite as described later, the reflection intensity at the surface index (110) becomes larger than the reflection intensity at the surface index (111) as shown in the peak search diagram of FIG. By comparing the reflection intensities, the degree of progress of oxidation in limonite can be determined. In FIG. 2, when the reflection intensity at the surface index (110) is “100”, the reflection intensity at the surface index (111) is about “80”.

  As described above, the limonite is dried while being irradiated with ultraviolet rays until the reflection intensity at the surface index (110) in the X-ray diffraction becomes larger than the reflection intensity of the surface index (111). By containing diiron, limonite with stabilized chemical properties can be produced.

  In particular, when the reflection intensity at the surface index (110) is 100, when the reflection intensity at the surface index (111) is 85 or less, the chemical characteristics are stabilized at a high level, Limonite with suppressed quality variation can be produced.

  In addition, the degree of progress of oxidation is not determined by the color of limonite that is colored ocher by oxidation from ferrous oxide to ferric oxide, but the degree of progress of oxidation is determined using the measurement results in X-ray diffraction. By determining, an objective determination can be made, and the degree of progress of oxidation can be determined more accurately.

  FIG. 3 (a) is a TG-DTA curve of limonite immediately after mining, and FIG. 3 (b) is a TG-DTA curve diagram showing a TG-DTA curve of limonite after the oxidation treatment described later, after the oxidation treatment. It can be seen that the limonite produced as a product is sufficiently dried.

  FIG. 4 is a graph showing the adsorption test results of limonite immediately after mining and the hydrogen sulfide gas of limonite subjected to the oxidation treatment described later. The concentration of the gas leaked from this filter is shown by using each limonite as a filter. This is what we are comparing. It can be seen that the limonite subjected to the oxidation treatment has less leakage and shows a high adsorption power.

  The oxidation treatment of limonite is performed using the oxidation treatment apparatus shown in the schematic diagram of FIG. The oxidation treatment apparatus includes a first rectangular conveyor 11, a second conveyor 12, a third conveyor 13, a fourth conveyor 14, a fifth conveyor 15, and a sixth conveyor in order from above in a casing 10 having a substantially rectangular shape. 16 and the seventh conveyor 17 are arranged one above the other, and the limonite is placed on the first conveyor 11 → the second conveyor 12 → the third conveyor 13 → the fourth conveyor 14 → the fifth conveyor 15 → the sixth conveyor 16 → the seventh. The inside of the oxidation processing apparatus is conveyed in the order of the conveyor 17.

  The first to seventh conveyors 11 to 17 are configured by suspending a conveyor belt between a driving roller and a driven roller provided at a predetermined interval, and each conveyor 11 to 17 is on the downstream side in the conveying direction. Is arranged in a twisted state as a downward gradient state by lowering than the upstream side in the transport direction.

  Limonite is fed to the uppermost first conveyor 11 by a charging conveyor 22 inserted in a charging port 21 provided in the upper part of the casing 10.

  On the other hand, the limonite conveyed by the lowermost seventh conveyor 17 is delivered to the discharge conveyor 24 inserted into the discharge port 23 provided in the lower part of the casing 10 and is taken out from the oxidation processing apparatus by the discharge conveyor 24. Then, it is conveyed to the subsequent process.

  In the present embodiment, the casing 10 is provided with seven conveyors 11 to 17 and continuously performs the oxidation treatment described later. However, the number of conveyors is not limited to seven, and more Or less. Further, the oxidation treatment may be performed by batch treatment instead of continuous oxidation treatment.

  On the inner surface of the casing 10, an ultraviolet irradiation lamp 25 is disposed at a predetermined position. In particular, the ultraviolet irradiation lamp 25 is provided slightly above the conveyors 11 to 17 so as to irradiate the limonite mounted on the upper surfaces of the conveyors 11 to 17 having a downward slope. In addition, since the conveyors 11 to 17 are inclined downward, the ultraviolet rays irradiated from the ultraviolet irradiation lamp 25 can be reliably applied to the limonite on the upper surfaces of the conveyors 11 to 17.

  Further, a hot air insufflator 26 is connected to the lower side of the inner side surface of the casing 10, and hot air at a predetermined temperature is supplied into the casing 10 from the hot air insufflator 26, thereby Is heated to a predetermined temperature. The heating in the casing 10 is not limited to the case where the heating is performed by warm air feeding by the warm air feeding device 26, and a heater may be provided in the casing 10 or around the casing 10 for heating. Good.

  Moreover, in the hot air insufflator 26 of the present embodiment, ozone is generated and air containing ozone can be supplied into the casing 10. Accordingly, the ozone concentration in the casing 10 can be increased, and the limonite having desired characteristics can be generated in a short time by further promoting the oxidation of limonite.

  Further, the warm air insufflator 26 adjusts the dew point of the air to be supplied into the casing 10 so that the air can be supplied, and a predetermined amount of water is present inside the casing 10 to oxidize limonite. It is easy to promote.

  A suction device 27 is connected to the upper side surface of the casing 10, and the air in the casing 10 leaks from the inlet 21 and the outlet 23 by sucking and exhausting the air in the casing 10 by the suction device 27. It is possible to prevent the leakage of ozone generated by the warm air insufflator 26. The aspirator 27 is provided with an ozone decomposition function so that the sucked ozone can be decomposed.

  In addition, the hot air insufflator 26 is connected to the casing 10 so as to supply warm air to a position above the outlet 23, so that air in the casing 10 leaks from the outlet 23. It can be reliably prevented.

  In this oxidation treatment apparatus, limonite is fed into the oxidation treatment apparatus by the charging conveyor 22 while the temperature in the casing 10 is about 40 to 70 ° C., and the fed limonite is fed by the first to seventh conveyors 11 to 17. It is transported sequentially downward, transferred from the lowermost seventh conveyor 17 to the discharge conveyor 24 and discharged from the oxidation treatment apparatus. During the transport of limonite by the first to seventh conveyors 11-17, limonite is transferred. While irradiating ultraviolet rays while heating, the oxidation of limonite is promoted, and ozone is supplied to further promote the oxidation of limonite.

  The transport of limonite by the first to seventh conveyors 11 to 17 may be performed at a very low speed, and in particular, the first to seventh conveyors 11 to 17 may be operated intermittently rather than continuously. In the present embodiment, the first to seventh conveyors 11 to 17 are intermittently movable by moving the conveyor belt by 5 cm every 5 minutes.

  The hot air insufflator 26 does not supply ozone with a predetermined concentration, but supplies oxygen with an oxygen concentration higher than that of the atmosphere. You may make it make it.

  In the oxidation treatment apparatus of this embodiment, the oxidation treatment is performed for about 14 hours, and the reflection intensity at the surface index (110) is determined by analyzing the limonite oxidized after the oxidation treatment by X-ray diffraction. When the reflection intensity at the surface index (111) is 85 or less when 100 is set, the oxidized limonite is conveyed to the subsequent process.

  On the other hand, when the reflection intensity at the surface index (111) is not 85 or less, the oxidation treatment is performed again by the oxidation treatment apparatus.

  Limonite oxidized by the above-described oxidation treatment apparatus is adjusted to have a moisture content of 12 to 18% using a separate drying apparatus, and then stored in a storage warehouse. Thus, by adjusting the water content to be 12 to 18%, it is possible to suppress the occurrence of alteration during storage.

  After crushing limonite stored in a storage warehouse with a hammer mill, the limonite dispensed by a 4.5 mm sieve is clay, deodorant, soil conditioner, brick, tile, tile, water purification agent, agglomeration for earthenware. It can be used as a raw material for a VOC gas removing agent, a fermentation accelerator, a sludge decomposing agent, etc., in an agent, a house, and the like.

  Alternatively, limonite is pulverized with a hammer mill, dispensed with a 3 mm sieve, and further sterilized by ultraviolet irradiation. Livestock feed, soil conditioner, clay or glaze for earthenware, desulfurization It can be used as a raw material for a hydrogen agent, a water purification agent, a flocculant, a VOC gas removal agent in a house, a fermentation accelerator, a sludge decomposer, etc., and the quality of these limonite-containing materials can be improved.

  Furthermore, limonite is pulverized with a hammer mill, then dispensed with a 3 mm sieve, heat-sterilized with a far-infrared heater at a temperature of about 250 ° C. to adjust the water content to 5% or less, and then pulverized with an atomizer. The limonite sieved to 50 mesh or less can be used as a raw material for cultured fish bait, pet food, clay for ceramics, glazes, etc., and to improve the quality of these limonite-containing materials. be able to.

  As mentioned above, the concrete which mixes the oxidized limonite as a kind of aggregate has the effect of improving the water quality, and by using this limonite-containing concrete when forming the revetment structure, it is expected to improve the water quality. be able to.

  In particular, limonite has a phosphorus adsorbing action for adsorbing phosphorus, so that it has an effect of suppressing the generation of blue-green algae and algae, and can suppress the growth of moss on the concrete structure surface.

  In addition, by exposing the surface of the concrete structure, the exposed area of the limonite, which is an aggregate, can be expanded, and the phosphorus adsorption action and the accompanying water quality improvement effect can be significantly improved.

  Specific examples of the exposure process include a wash-out finishing process, a sharpening finishing process, a blast finishing process by shot blasting or sand blasting, a small hitting finishing process, a Vishan finishing process, a flea finishing process, and a lifting finishing process.

  Wash-out finishing is to wash the surface with water so that the concrete surface is not completely hardened by applying a delay effect to the concrete surface or by applying surface concrete to the concrete surface. This exposes the aggregate.

  The sharpening finish process is a process in which the aggregate is exposed by peeling the surface of the hardened concrete with disc paper.

  Blasting treatment is to blow the surface concrete by spraying particles such as iron balls in the case of shot blasting and powder such as sand in the case of sandblasting to the surface of the hardened concrete. This exposes the aggregate.

  The small hitting finish process is to expose the aggregate by hitting the surface of the hardened concrete with a hammer and breaking the concrete on the surface. A small hammer for hammering is used.

  Bishan finishing is a process in which aggregate is exposed by hitting the surface of hardened concrete with a hammer and scratching the surface of the concrete. It uses a Vishan hammer with many bodies.

  The flea finishing process is to expose the aggregate by scraping the surface of the hardened concrete with a flea.

  The hull finish processing exposes the aggregate by peeling off the surface of the hardened concrete with a chisel or electric pick.

  Here, the concrete is not limited to ordinary concrete, and may be special concrete such as porous concrete, and it is desirable that 1 to 50% of the total amount of aggregate blended as aggregate is limonite.

  In addition, when limonite is mix | blended with concrete, since the neutralization effect | action of alkaline concrete arises by the acidity of limonite, it is desirable to adjust the compounding quantity of limonite to such an extent that a predetermined pH value can be maintained. Thus, it can be set as the eco-friendly concrete also by the neutralization effect | action of concrete being produced by limonite.

It is a peak search figure which shows the X-ray-diffraction result of the limonite just after mining. It is a peak search figure which shows the X-ray-diffraction result of the limonite after an oxidation process. (A) is a TG-DTA curve diagram showing a TG-DTA curve of limonite immediately after mining, and (b) is an oxidation treatment. It is a graph which shows the adsorption test result of the limonite immediately after mining and the hydrogen sulfide gas of the limonite oxidized. It is a schematic diagram of the oxidation treatment apparatus used for the oxidation treatment of limonite.

Explanation of symbols

10 Casing
11 First conveyor
12 Second conveyor
13 Third conveyor
14 4th conveyor
15 5th conveyor
16 6th conveyor
17 7th conveyor
21 slot
22 Loading conveyor
23 Discharge port
24 Discharge conveyor
25 UV irradiation lamp
26 Hot air ventilator
27 Aspirator

Claims (7)

A method of increasing the content ratio of ferric oxide in limonite by making the reflection intensity at the plane index (110) in X-ray diffraction larger than the reflection intensity at the plane index (111) by drying while irradiating with ultraviolet rays. . The method for increasing the content ratio of ferric oxide in limonite according to claim 1, wherein the method is heat-dried in an ozone atmosphere.   The raw material is dried while irradiating the raw material having a surface index (111) having a higher reflection intensity than the surface index (110) in X-ray diffraction, and the reflection intensity at the surface index (110) is increased. The manufacturing method of the limonite which increased the content rate of the ferric oxide made larger than the reflective intensity of an index (111). The ferric oxide according to claim 3 , wherein the reflection intensity at the surface index (111) is 85 or less when the reflection intensity at the surface index (110) is 100. A method for producing limonite having an increased content. A casing,
A conveyor for transporting limonite in the casing;
Provided upstream in the conveying direction of the conveyor, and an inlet for charging limonite into the casing,
A discharge port provided downstream in the conveying direction of the conveyor, and for taking out limonite in the casing;
An ultraviolet irradiation lamp for irradiating the limonite on the conveyor with ultraviolet rays;
According to claim 3 or claim 4, characterized in that performing the processing in the oxidation processing apparatus and a hot air insufflator for air warm air having a predetermined temperature containing ozone in the casing A method for producing limonite having an increased content of ferric oxide.   The reflection intensity at the surface index (110) in X-ray diffraction of limonite is compared with the reflection intensity at the surface index (111), and the reflection intensity at the surface index (110) is A method for determining the degree of oxidation from ferrous oxide to ferric oxide in limonite that determines that ferric oxide having a predetermined content has been generated in the limonite due to an increase in reflection intensity.   During the production of limonite with an increased content of ferric oxide, the progress of oxidation of limonite by comparing the reflection intensity at the plane index (110) and the reflection intensity at the plane index (111) in X-ray diffraction. Use of data to determine the ratio of at least the reflection intensity at the surface index (110) and the reflection intensity at the surface index (111) to determine the degree.

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