JP6776210B2 - Molded body for refining or smelting addition - Google Patents

Description

The present invention relates to a smelting or smelting addition molded body containing a leavening agent.

In the refining or smelting process, various additions such as deoxidizing material, heating material, heat insulating material, slag-making material or carbonizing material are added to the reaction system in order to obtain the desired metal, metal compound or refined product thereof. Add the agent.

For example, the deoxidizing material is used to remove oxygen in molten steel in the steelmaking process, and mainly contains an aluminum-based material typified by aluminum dross as an active ingredient. Further, in the field of steelmaking, carbon materials such as coke and graphite are used as an active ingredient of a heating material or a heat insulating material, and are also used as an active ingredient of a charcoal material for adjusting the carbon content of steel.

It is desired that the active ingredient of these additives is easily diffused in the system and the effect is exhibited quickly. On the other hand, the above-mentioned additives improve convenience such as transportation and transportation; facilitate workability when they are put into the system; increase sedimentation after being put into the system; and in the system. It is said that it is necessary to have a certain level of strength or higher in order to prevent dust generation at the time of charging.

On the other hand, in the field of casting unrelated to these refining or smelting processes, expanded graphite, which is a typical example of a component exhibiting an expansion effect as described in Patent Document 1, is used as a core (basket). It is known to be. Further, it is known that vermiculite, which is a component exhibiting the same effect, is also used in the field of a mold as described in Patent Document 2.

Japanese Unexamined Patent Publication No. 2010-036252 JP 2009-161409

As described above, the additive (molded body) used in the refining or smelting process is disk-shaped or formed by using a tableting machine or a briquette machine in order to improve convenience such as transportation and transportation. It is molded into a shape having a certain degree of strength, such as a columnar tablet, a massec type, an egg type, or a pillow type.

On the other hand, when the molded product having the above-mentioned strength is added to the system, the active ingredient contained therein is not sufficiently diffused into the system, and as a result, it becomes difficult to exert the effect.

The present invention provides a molded product added in a refining or smelting process, which exhibits sufficient diffusivity when added into a system and has sufficient strength to the extent that it does not affect operability or the like. That is the issue.

As a result of diligent studies by the present inventors in order to solve the above-mentioned problems, by adopting an expansion material that has not been used in the field of refining or smelting process so far, while having sufficient strength, Moreover, it has been found that it is possible to provide a molded product having a high diffusivity after addition.

The present invention has been made based on the above findings, and broadly includes the inventions of the following aspects.

Item 1 A molded product for refining or smelting addition containing at least one expanding material selected from the group consisting of expanded graphite, vermiculite and pearlite.

Item 2 The refining or smelting addition according to Item 1, further comprising at least one selected from the group consisting of carbons, iron, lime, non-ferrous metals, slags and resins. Molded body.

Item 3 The refining or smelting addition molding according to Item 2, wherein the carbons are at least one selected from the group consisting of coal, coke and graphite.

Item 4 The refining or smelting addition according to Item 2, wherein the nonferrous metal is at least one selected from the group consisting of nickel, chromium, silicon, manganese, molybdenum, titanium, phosphorus, sulfur, copper and vanadium. Molded body.

Item 5 The smelting or smelting addition molding according to Item 2, wherein the mineral slag is steel slag and / or aluminum dross.

Item 6 The smelting or smelting addition molding according to Item 2, wherein the resins described above are hydrocarbons and / or plastics.

Item 7 The refining or smelting addition molding according to Item 6, wherein the hydrocarbon is selected from the group consisting of paraffin, pitch and tar.

Item 8 The refining or refining according to Item 6, wherein the plastics are selected from the group consisting of phenol, epoxy, melamine, polyester, polyurethane, polyimide, polyethylene, polypropylene, polystyrene, nylon, polycarbonate, acrylic and polyethylene terephthalate resin. Molded body for smelting addition.

Item 9 The refining or smelting addition molding according to any one of Items 1 to 8, wherein 0.1 to 45 parts by weight of the expanding material is contained with respect to 100 parts by mass of the molded body. ..

Item 10. The smelting or smelting addition molding according to any one of Items 1 to 9, wherein the crushing strength of the molded product is 30 to 100 kgf.

Item 11 The refining or smelting according to any one of Items 1 to 10, wherein the shape is a disk type, a cylindrical type, a Masek type, an egg type, a pillow type, a lens type or an almond type. Molded body for addition.

The refined or smelting-added molded product of the present invention exerts an action of easily diffusing when administered into the system. Based on this action, the active ingredient contained in the refining or smelting addition molding of the present invention does not remain undissolved in the system, and the effect of the active ingredient can be exhibited at an early stage.

Since the smelting or smelting addition forming body of the present invention has sufficient strength, it is advantageous in terms of convenience such as transportation and transportation. Further, it can be expected to have effects such as improvement of workability when the product is charged into the system, improvement of sedimentation property after the product is charged into the system, and prevention of dust generation when the product is charged into the system.

A photographic image showing the results of Example 1. The results of a disintegration test at 1000 ° C. of a molded product containing expanded graphite having a concentration of 0% by weight, 0.1% by weight or 0.3% by weight are shown. In the figure, the elapsed time from the installation of these in the electric furnace for heating the molded body is shown. A photographic image showing the results of Example 1. The results of a disintegration test at 1000 ° C. of a molded product containing expanded graphite having a concentration of 0.5% by weight or 1% by weight are shown. In the figure, the elapsed time from the installation of these in the electric furnace for heating the molded body is shown. A photographic image showing the results of Example 1. The results of a disintegration test at 1400 ° C. of a molded product containing expanded graphite having a concentration of 0% by weight, 0.1% by weight or 0.3% by weight are shown. In the figure, in an electric furnace to heat the molded body. The elapsed time since these were installed is recorded. A photographic image showing the results of Example 1. In the figure showing the results of the decay test at 1400 ° C. of the molded product containing 0.5% by weight or 1% by weight of expanded graphite, these were installed in an electric furnace to heat the molded product. Record the elapsed time from. A photographic image showing the results of Example 2. The results of the disintegration test of the molded product containing various concentrations of vermiculite are shown. Each photographic image shows the state before the molded body is installed in the electric furnace at 1000 ° C., after the installation for 3 minutes and after the installation for 5 minutes. A photographic image showing the results of Example 2. The results of the disintegration test of the molded product containing 0.5% by weight and 1% expanded graphite are shown. Each photographic image shows the state before the molded product is installed in the electric furnace at 1200 ° C., after the installation for 3 minutes and after the installation for 5 minutes. A photographic image showing the results of Example 2. The results of the disintegration experiment of the molded product containing various concentrations of vermiculite and 0.5% by weight of graphite are shown. Each photographic image shows the state before the molded product is installed in the electric furnace at 1200 ° C., after the installation for 3 minutes and after the installation for 5 minutes. A photographic image showing the results of Example 3. The result of the collapse test of the molded body which does not contain various expansion materials is shown. Each photographic image shows the state before installing the molded body in an electric furnace at 1200 ° C (corresponding to "before charging" in the figure), after installing for 5 minutes, 10 minutes, and 20 minutes. The numerical value shown in the photographic image "before loading" indicates the pressure at which the molded body was produced, and the position of the molded body shown in each of the other photographic images is the same as this. A photographic image showing the results of Example 3. The state before and after installing the molded body containing vermiculite having a concentration of 1% by weight and 5% by weight in an electric furnace at 1400 ° C., which was produced by molding with various molding pressures, is shown. In addition, the numerical values described in the photographic images shown in "1%" and "before charging" indicate the pressure at which the molded body was produced, and these and the molded body at the same position as the photographic images shown in "5%" and "before charging" are It is shown that they are molded bodies obtained by molding at the same pressure. In addition, both "1%" and "5%" have the same position of the molded body of the photographic image before and after 5 minutes of injection. A photographic image showing the results of Example 3. The appearances of the molded product containing 1% by weight of expanded graphite of the F product and the N product, which were molded by various molding pressures, before and after being installed in the electric furnace at 1400 ° C. for 5 minutes are shown. The numerical values shown in the photographic images shown in "F product: 1%" and "before charging" indicate the pressure at which the molded body was produced, and are the same as these and the photographic images shown in "N product: 1%" and "before charging". The molded bodies at the positions indicate that they are molded bodies obtained by molding at the same pressure. In addition, both "F product: 1%" and "N product: 1%" have the same position of the molded body of the photographic image before and 5 minutes after the injection.

<Explanation of terms>
The terms "include" and "contain" as used herein include both the meanings of "included as essential" and "consisting of only" unless otherwise noted.

As used herein, the term "refining" refers to a purification step that increases the purity of crude metals. For example, the step of melting a crude metal and oxidizing or reducing it corresponds to this.

As used herein, the term "smelting" means the process of manufacturing a metal or alloy by separating or extracting the contained metal from an ore or other raw material. For example, in the steel field, this is a process of melting iron ore in a melting furnace or the like to produce pig iron.

Molded body for refining or smelting addition The molded body for refining or smelting addition of the present invention is various types of molded body for addition used in the field of refining or smelting, and is composed of expanded graphite, vermiculite and pearlite. Contains at least one expansive material of choice.

That is, the smelting or smelting additive molding of the present invention contains at least one expanding material selected from the group consisting of expanded graphite, vermiculite and pearlite in the additive used in the field of smelting or smelting. , It can be said that this is a molded body.

The above-mentioned expanded graphite is not particularly limited as long as the effect of the present invention is exhibited. Specifically, it is possible to select a material that usually causes a volume change at about 150 to 500 ° C. and has a characteristic that the expansion coefficient after the volume change is usually about 200% or more, preferably about 400% or more.

By making the expansion material contained in the smelting or smelting addition molding of the present invention exhibit a volume change, that is, an expansion effect at about 150 ° C. or higher, the expansion material expands before being put into the system. It is possible to prevent it from exerting its effect.

Further, the temperature in the system into which the smelting or smelting addition molding of the present invention is put is usually about 1000 ° C. or higher, but it is better to exert the expansion effect at about 500 ° C., which is a lower temperature. The active ingredient described later contained in the molded body together with the expander can be diffused more quickly.

Further, by setting the expansion coefficient of the expanding material contained in the refining or smelting addition molding body of the present invention to about 200% or more, the amount of the expanding material contained in the molded body can be reduced, which will be described later. It is possible to blend more active ingredients.

The above-mentioned vermiculite is not particularly limited as long as the effect of the present invention is exhibited. Specifically _{(Mg 1-x (Mg,} Fe, Fe 3+, Al) 3 (Si, Al) 4 O 10 (OH) 2 · 4H 2 O) has a chemical composition of, soil improvement, construction materials , A component used for applications such as gasket materials or sealing materials. Further, similarly to the above-mentioned expanded graphite, one having a characteristic that a volume change usually occurs at about 150 to 500 ° C. and an expansion rate after the volume change is usually about 200% or more, preferably about 400% or more is selected. be able to.

The above-mentioned pearlite is not particularly limited as long as the effect of the present invention is exhibited. Specifically, it is a component used for horticultural culture, soil improvement, filter media, cold insulation material, cold insulation material, etc., and like the above-mentioned expanded graphite and vermiculite, it usually has a volume of about 150 to 500 ° C. It is possible to select a medium that causes a change and has a characteristic that the expansion rate after the volume change is usually about 200% or more, preferably about 400% or more.

The additives used in the above-mentioned refining or smelting fields are not particularly limited as long as the effects of the present invention are exhibited. Specific examples thereof include a carbonizing material, a heating material, a deoxidizing material, a desulfurizing material, a dephosphorizing material, a sedative material, and a non-ferrous metal additive material.

The above-mentioned carbonized material is a material that exerts an effect of adjusting the carbon concentration in the system to be input, and contains carbons typified by coal, coke, graphite, etc. as an active ingredient.

The above-mentioned heating material is a material that exerts an effect of raising the temperature in the system to be charged by a combustion reaction, and is mainly carbons typified by coal, coke, graphite, etc .; silicon; aluminum or magnesium. It contains non-ferrous metals such as iron or iron as an active ingredient.

The deoxidizing material described above is a material that exerts an effect of lowering the oxygen concentration in the system to be charged, and contains aluminum, aluminum dross, or the like as an active ingredient.

The desulfurization material described above is a material that exerts an effect of lowering the sulfur concentration in the system to be charged, and contains lime, aluminum dross, or the like as an active ingredient.

The above-mentioned dephosphorizing material is a material that exerts an effect of lowering the phosphorus concentration in the system to be charged, and contains lime or the like as an active ingredient.

The above-mentioned sedative material is a material that exerts an effect of preventing or suppressing sloping and forming in the system to be charged, and contains resins as an active ingredient.

The non-ferrous metal additive material described above is a material that exerts the effect of imparting a non-ferrous metal component in the system to be input into the system, and is nickel, chromium, silicon, manganese, molybdenum, titanium, phosphorus, sulfur, copper. Alternatively, it contains non-ferrous metals such as vanadium as an active ingredient.

Therefore, the molded body for refining or smelting addition of the present invention is represented by the above-mentioned expansion material and carbons such as coal, coke and graphite, iron, lime, non-ferrous metals, steel slag and aluminum dross. It can be an embodiment containing the slag and an active ingredient such as a hydrocarbon or a plastic resin.

The above-mentioned hydrocarbon is not particularly limited as long as the effect of the present invention is exhibited. For example, paraffin, pitch, tar and the like can be mentioned. Further, the above-mentioned plastics are not particularly limited as long as the effects of the present invention are exhibited. For example, phenol, epoxy, melamine, polyester, polyurethane, polyimide, polyethylene, polypropylene, polystyrene, nylon, polycarbonate, acrylic or polyethylene terephthalate resin can be mentioned.

The above-mentioned epoxy, melamine and acrylic resin are not particularly limited as long as the effects of the present invention are exhibited. For example, a known resin can be appropriately selected.

The content of the above-mentioned expansion material in the refining or smelting addition molding of the present invention is not particularly limited as long as the effect of the present invention is exhibited. Specifically, it is usually about 0.1 to 45 parts by weight, preferably about 0.3 to 30 parts by weight, and more preferably about 0.5 to 10 parts by weight with respect to 100 parts by weight of the molded body for refining or smelting addition.

By containing about 0.1 part by weight or more of the expanding material with respect to 100 parts by weight of the refining or smelting additive molding body of the present invention, the additive charged into the system is likely to disintegrate, and the effective content contained in the molded body It tends to exert the effect of sufficiently diffusing the components.

Further, by setting the content of the expanding material to about 45 parts by weight or less with respect to 100 parts by weight of the molded body for refining or smelting addition, the effect of the active ingredient contained in the above-mentioned molded body tends to be sufficiently exhibited. Become.

The crushing strength of the smelting or smelting addition molding of the present invention is not particularly limited as long as the effect of the present invention is exhibited. Specifically, as a numerical value measured by the crushing strength test method of JIS Z 8841 "Granulated product-strength test method", it is usually about 30 to 100 kgf, preferably about 50 to 500 kgf, and more preferably about 100 to 200 kgf. Can be mentioned.

By setting the crushing strength of the smelting or smelting addition molding of the present invention to about 30 kgf or more, the molding tends to suppress dust generation and improve the handling property. .. Further, by setting the crushing strength of the smelting or smelting addition molding of the present invention to about 1000 kgf or less, the molded body is quickly disintegrated and dispersed after being put into the system, and the effect of the active ingredient is exhibited. It tends to be easy to demonstrate.

The shape of the molded body for refining or smelting addition of the present invention is not particularly limited as long as the effect of the present invention is exhibited. For example, a disk type, a cylindrical type, a Masek type, an egg type, a pillow type, a lens type, an almond type and the like can be mentioned.

The above-mentioned molded body for refining or smelting addition can be obtained by blending the above-mentioned expansion material with various additives used in the field of refining or smelting together with a binder, if necessary.

The specific size of the refined or smelting-added molded product of the present invention is not particularly limited as long as the effect of the present invention is exhibited. For example, the length of the three sides can usually be about 20 to 90 mm. In addition, the diameter can usually be about 20 to 90 mm.

In order to explain the present invention in more detail, the experimental results for confirming the temperature responsiveness of various molded bodies, which are typical examples of the molded bodies for refining or smelting addition of the present invention, are shown below. Needless to say, the present invention is not construed as being limited to the inventions shown in the following examples.

Example 1
Molded product obtained by adding expanded graphite to coal powder and iron powder-containing additive for coal and temperature rise. Coal addition and temperature rise by blending expanded graphite (made in China) at the ratio shown in Table 1 below. Additives (coal powder: graphite powder = 4: 1) were kneaded together with a binder, and then molded into a massec mold using a roll molding machine; in-house. The crushing strength (kgf) in the table is the average value (10 pieces) of the values measured using a press machine; in-house manufactured. The measuring means was carried out according to the crush strength test method described in JIS Z 8841 “Granulated product-strength test method”. Also. The apparent specific gravity (g / mL) in the table is the average value of the five molded bodies.

The molded product thus produced was put into an electric furnace heated to 1000 ° C. or 1400 ° C., and the state of its collapse was observed by a photographic image (an image of the inside of the furnace taken through a light-shielding plate). The results are shown in FIGS. 1 to 4.

From FIGS. 1 and 3, the conventionally blended molded product containing no expanded graphite does not collapse within 4 minutes after charging, regardless of the temperature condition of 1000 ° C. or 1400 ° C. There wasn't. On the other hand, it was clarified that the molded product containing expanded graphite collapsed according to its content ratio.

For example, under the temperature conditions of 1000 ° C from FIGS. 1 and 2, the molded product containing 0.1% by weight of expanded graphite collapsed in 3 minutes and 50 seconds, 0.3% by weight was 2 minutes and 42 seconds, and 0.5% by weight was 2 minutes and 25 seconds. And at 1% by weight, it collapsed in 2 minutes and 4 seconds.

In addition, under the temperature condition of 1400 ° C, it collapses faster than the temperature condition of 1000 ° C, and from FIGS. 3 and 4, the molded product containing 0.1% by weight of expanded graphite collapses in 3 minutes and 14 seconds, and at 0.3% by weight, it collapses at 1 minute 27. It collapsed in 1 minute and 12 seconds at 0.5% by weight and 1 minute and 5 seconds at 1% by weight.

As shown in Table 1 above, the crushing strength of these molded bodies exceeds 100 kgf, and it can be said that there is generally no inconvenience in the operation during transportation and loading of the molded bodies.

Example 2
Vermiculite and expanded graphite, which are expansion materials, are contained in a predetermined concentration with respect to aluminum dross used in the field of molded steelmaking obtained by adding various expansion materials in various blending amounts to the deoxidizing additive. A molded body was produced.

Vermiculite was kneaded with a binder so as to be 5% by weight or 10% by weight with respect to aluminum dross, and these were molded into a massec mold by adopting the means shown in Example 1 above. The molded body containing 5% by weight of vermiculite was molded so as to have a crushing strength of 150 kgf or 500 kgf, respectively, while adopting the means for which the strength was confirmed in Example 1 above. Similarly to this, a molded product containing expanded graphite in an amount of 0.5% by weight or 1% by weight with respect to aluminum dross was also produced.

The molded product thus produced was put into an electric furnace at 1000 ° C. or 1400 ° C., and the state of its collapse was observed by a photographic image (an image taken outside the furnace). The results are shown in Figures 5-7.

As shown in FIG. 5, when the crushing strength of the molded product containing 5% by weight of vermiculite was 150 kgf, the degree of collapse progressed as the crushing strength increased to 3 minutes and 5 minutes after the injection. On the other hand, when the crushing strength was 500 kgf, it became clear that neither collapsed 3 minutes or 5 minutes after the injection.

The degree of disintegration of the molded product (the crushing strength at this time was 320 kgf) in the case of containing 10% by mass of vermiculite progressed as a long time of 3 minutes and 5 minutes.

Example 3
Addition moldings containing various expansion materials molded at various pressures For aluminum dross used in the field of steelmaking, moldings containing vermiculite and expansion graphite, which are expansion materials, in a predetermined amount were prepared.

A cylindrical molded body was prepared with a predetermined pressure of 2t, 4t, 6t, 8t and 10t of aluminum ross. Specifically, the molded body was produced by adopting the means produced in Example 1 described above (the difference is that a hydraulic press was used).

In addition, about 80 to 120 kgf for 2t, about 180 to 220kgf for 4t, about 280 to 320kgf for 6t, about 380 to 420kgf for 8t, and about 480 to 520kgf for 10t. The crushing strength is about the same.

Further, a molded body in which vermiculite was kneaded and included in an amount of 1% by weight with respect to aluminum dross was also produced in the same manner. At this time, the molded body produced by applying a pressure of 2t is about 70 to 120kgf, 4t is about 160 to 210kgf, 6t is about 250 to 300kgf, and 8t is about 350 to 400kgf. And in the case of 10t, the crushing strength is about 450 to 500kgf.

Then, a molded body containing vermiculite in an amount of 5% by weight based on aluminum dross was also produced in the same manner. At this time, the molded body manufactured by applying a pressure of 2t is about 50 to 100kgf, 4t is about 160 to 210kgf, 6t is about 230 to 280kgf, and 8t is about 320 to 370kgf. And in the case of 10t, the crushing strength is about 420 to 470kgf.

On the other hand, molding in which two types of expanded graphite called F product (expansion rate: about 900%) and N product (N product: expansion rate: about 3600%) are included in aluminum dross so as to be 1% by weight. The body was made. Similar to the above-mentioned vermiculite-containing molded body, a columnar molded body was prepared at a predetermined pressure of 2t, 4t, 6t, 8t and 10t.

Here, 2t of F product is about 80 to 120kgf, 4t is about 180 to 220kgf, 6t is about 280 to 320kgf, 8t is about 380 to 420kgf, and 10t. Has a crushing strength of about 480 to 520 kgf.

And, in the case of N product 2t, it is about 80 to 120kgf, in the case of 4t, it is about 180 to 220kgf, in the case of 6t, it is about 280 to 320kgf, in the case of 8t, it is about 380 to 420kgf, and in the case of 10t. The crush strength is about 480 to 520 kgf.

The various molded bodies thus produced were put into an electric furnace at 1200 ° C., and the state of the molded bodies after a lapse of a predetermined time was observed. The results are shown in Figures 8-10.

FIG. 8 shows the state of the molded product of aluminum dross alone before, 5 minutes, 10 minutes, and 20 minutes after the injection into the electric furnace at 1200 ° C. In the case of 2t, it started to collapse after 5 minutes, but the molded product prepared under other pressure did not collapse even if it was continuously charged for 20 minutes. From the above, it has been clarified that the higher the pressure at the time of producing the molded body, the lower the disintegration property tends to be, even if the molded body does not contain the expansion component.

FIG. 9 shows a state of a molded product containing 1% by weight or 5% by weight of vermiculite in aluminum dross before and 5 minutes after the injection into an electric furnace at 1200 ° C. In both cases, it was found that the degree of collapse of the molded body after 5 minutes tended to decrease as the pressure during the production of the molded body increased, and it became clear that both of them hardly collapsed at a pressure of 10 tons. ..

FIG. 10 shows a state of an aluminum dross molded product containing 1% F product or N product expanded graphite before and 5 minutes after being charged into an electric furnace at 1200 ° C. It was clarified that the molded bodies produced at all pressures collapsed after 5 minutes for both F and N products.

From the above results, it was clarified that the disintegration property was higher when expanded graphite having a high expansion coefficient was used.

Claims (4)

A molded product for refining or smelting addition that does not contain vermiculite or pearlite but contains expanded graphite, and contains 0.1 to 10 parts by weight of expanded graphite with respect to 100 parts by mass of the molded product. A molded body for refining or smelting addition, which comprises. The refining or smelting addition according to claim 1, further comprising at least one selected from the group consisting of carbons, iron, lime, non-ferrous metals, slags and resins. Molded body. The smelting or smelting addition molding according to claim 1 or 2, wherein the crushing strength of the molded body is 30 to 100,000 kgf. The refining or smelting addition according to any one of claims 1 to 3, wherein the shape is a disk type, a cylindrical type, a massec type, an egg type, a pillow type, a lens type or an almond type. Molded body.