The present invention relates to a method for producing valuable hydrocomposites from iron and steel slag.
In response to the growing global demand, production volume of steel has been increasing every year. In the production process of steel, iron and steel slag such as blast furnace slag and steel slag is produced as a by-product. Although the iron and steel slag has been used as resources for wide applications such as road-paving material, concrete additives, and soil conditioner, so as to completely process the iron and steel slag of which amount is increasing every year, it is necessary to develop new usage.
The iron and steel slag includes many components such as oxide of e.g. Ca, Si, Al, Fe, and Mg. It is assumed that various functional substances can be produced by controlling these components. Examples of the functional substances obtained from the above components include: composite oxides such as zeolite, hydrogarnet, and hydrocalumite; hydroxide; and carbonate. These can be suitably used for, for example, ion-exchange material, immobilizing material for refractory substances, and absorbent. These functional substances can be produced by various methods (for example, see Patent documents 1 to 4.); there is a possibility for synthesis and production with iron and steel slag as a starting material (there may be referred to as “raw material”.). However, there are few examples actually attempting synthesis of the above functional substances with iron and steel slag. Therefore, in this situation, processing of the increasing iron and steel slag cannot catch up with its production. This is because it has been presumably thought that solubility and reactivity, for example, of the above components contained in the iron and steel slag are different per component, in view of necessary removal of some components and addition of other components, it is quite wasteful to use the iron and steel slag as the starting material.
For example, Patent documents 5 and 6 propose methods for producing zeolite A with iron and steel slag as a starting material. The methods include the steps of: preparing the components in the iron and steel slag into a predetermined composition; dissolving the composition in an alkaline solution; and carrying out hydrothermal treatment.
Patent documents 1 to 4 do not specifically study the iron and steel slag as a starting material. In addition, in the Patent document 5, to obtain zeolite A from iron and steel slag, an iron and steel slag is processed by acid treatment in advance for removing Ca and Mg to adjust a composition. Then, the acid-treated iron and steel slag is dissolved in an alkaline solution and the dissolved components only are hydrothermally treated. Accordingly, this method requires the step of removing Ca and Mg components before synthesis reaction, which makes the process complicated; moreover, it is necessary to add other components to supplement components poorly-soluble in the solution. The Patent document 6 also discloses the method including the steps of: adjusting the composition of the iron and steel slag in advance; then carrying out hydrothermal treatment for components only dissolved in the alkaline solution. This method requires addition of deficient components before the synthesis reaction and removal of excessive components, which make the process complicated. In other words, in the conventional technique for synthesizing the functional substances from the iron and steel slag, there is no idea to effectively utilize the entire components in the iron and steel slag.
Accordingly, an object of the present invention is to provide a novel method for producing functional substances (particularly hydrocomposite) from the iron and steel slag, which simplifies the process and which provides a new recycling idea for iron and steel slag with a mode which is capable of effectively utilizing the entire slag including the poorly-soluble portion as well as the readily-soluble portion of the components. Another object of the invention is to provide a characteristic hydrocomposite obtained by the method.
As a result of intensive study by the inventors, they discovered that the entire iron and steel slag is readily-dissolved and powderized, which provides a favorable mode to effectively use the entire components contained in the slag when producing hydrocomposites by carrying out alkaline treatment (alkaline melting treatment) for iron and steel slag and discovered that the obtained hydrocomposites are characteristic ones. Then, they completed the present invention.
The first aspect of the present invention solves the above problems by providing a hydrocomposite produced from an iron and steel slag, which comprises hydrogarnet and calcite, a ratio (α1/β1) of strength in X-ray diffraction (α1) of (420) crystal face of the hydrogarnet to strength in X-ray diffraction (β1) of (104) crystal face of the calcite respectively obtained by X-ray diffraction measurement being 0.05-200.
In the first and the following aspects of the invention, the term “X-ray diffraction measurement” means a powder X-ray diffraction measurement employing CuKα (wavelength 0.154 nm) as a radiation source. The term “(420) crystal face of the hydrogarnet” means, in the above powder X-ray diffraction measurement, a crystal face related to diffraction peak(s) at around 32-33°. The term “(104) crystal face of the calcite” means, in the above powder X-ray diffraction measurement, a crystal face related to diffraction peak(s) at around 29-30°. In the present invention, “RAD-C” manufactured by Rigaku Corporation is used as an X-ray diffraction measurement equipment; then, the powder X-ray diffraction measurement is carried out in accordance with a step operation method (Angle range: 2θ=5-50°, Step width: 0.2°, Holding time: 300 seconds) to obtain data related to the diffraction peak.
In the first aspect of the invention, the ratio (α1/β1) is preferably 0.05-10. Particularly, it is preferably 0.1-9.5, more preferably 0.3-4. Within the above ranges, hydrogarnet can be easily obtained from iron and steel slag.
In the second aspect of the invention solves the above problems by providing a hydrocomposite produced from an iron and steel slag, which comprises hydrocalumite and calcite, a ratio (α2/β2) of strength in X-ray diffraction (α2) of (102) crystal face of the hydrocalumite to strength in X-ray diffraction (β2) of (104) crystal face of the calcite respectively obtained by X-ray diffraction measurement being 0.05-200.
In the second aspect of the invention, the term “hydrocalumite” means a concept including calcium-based hydrocalumite itself and magnesium-based hydrotalcite having a crystal structure equivalent to that of hydrocalumite. The term “(102) crystal face of the hydrocalumite” means, in the above X-ray diffraction measurement, a crystal face related to diffraction peak(s) at around 11-12°.
In the second aspect of the invention, the ratio (α2/β2) is preferably 0.05-10. Particularly, it is preferably 0.1-6, more preferably 0.2-3. Within the above ranges, hydrocalumite can be easily obtained from iron and steel slag.
The third aspect of the invention solves the above problems by providing a hydrocomposite produced from an iron and steel slag, which at least comprises: zeolite X, zeolite A, calcite, and hydroxysodalite.
In the third aspect of the invention, a ratio (α3/β3) of strength in X-ray diffraction (α3) of (111) crystal face of the zeolite X to strength in X-ray diffraction (β3) of (104) crystal face of the calcite; a ratio (α4/β3) of strength in X-ray diffraction (α4) of (200) crystal face of the zeolite A to strength in X-ray diffraction (β3) of (104) crystal face of the calcite; or a ratio (α5/β3) of strength in X-ray diffraction (α5) of (211) crystal face of the hydroxysodalite to strength in X-ray diffraction (β3) of (104) crystal face of the calcite, respectively obtained by X-ray diffraction measurement, is preferably 0.5-200.
In the third aspect of the invention, the term “(111) crystal face of the zeolite X” means, in the above powder X-ray diffraction measurement, a crystal face related to diffraction peak(s) at around 6-7°. The term “(200) crystal face of the zeolite A” means, in the above powder X-ray diffraction measurement, a crystal face related to diffraction peak(s) at around 7-8°. The term “(211) crystal face of the hydroxysodalite” means, in the above powder X-ray diffraction measurement, a crystal face related to diffraction peaks) at around 24-25°.
In the third aspect of the invention, the ratio (α3/β3, α4/β3, or α5/β3) is preferably 0.5-1.
The first to third aspects of the present invention are preferably produced by the entire components contained in the iron and steel slag.
The fourth aspect of the present invention solves the above problems by providing a method for producing hydrocomposite, which comprises: a mixture producing step by adding solid base to an iron and steel slag-containing starting material and mixing them to produce a mixture; a molten chips producing step by melting the mixture obtained in the mixture producing step at a temperature within the range of 100-1000° C. to produce molten chips; a hydrocomposite producing step by adding the molten chips obtained in the molten chips producing step to a solvent to produce a solution and then producing a hydrocomposite from the solution.
In the fourth aspect of the invention, the starting material to be mixed with the solid base may contain 20-80 mass % of calcium component equivalent to CaO. In the invention, even if the starting material contains a large amount of components such as components conventionally removed and components poorly-soluble in the solution, it is possible to readily dissolve these components. Accordingly, with the mode which enables to effectively utilize calcium components also, it is possible to produce various hydrocomposites. In general, iron and steel slag contains a large amount of calcium components, the invention can use the iron and steel slag only itself as the starting material without removing the calcium components or adding other components.
In the mixture producing step of the fourth aspect of the invention, 40-200 parts by mass of the solid base is preferably added and mixed to 100 parts by mass of the starting material. By setting the ratio of the starting material and the solid base as above, in the molten chips producing step, the molten chips can be readily dissolved and powderized, effectively.
Moreover, in the fourth aspect of the invention, the solid base is preferably sodium hydroxide or lithium hydroxide, which enables to lower the production cost, enables to carry out the melting treatment easily, and enables to obtain a suitable form of the molten chips.
Further, in the hydrocomposite producing step of the fourth aspect of the invention, the solution in which the molten chips are dissolved may be aged for 3 hours or more to obtain hydrocalumite. In the invention, since the poorly-soluble components in the iron and steel slag-containing components is made readily-soluble and dissolved in the solution, it is possible to cause reaction in the solution by only aging the solution; thereby possible to obtain hydrocalumite easily.
Still further, in the hydrocomposite producing step of the fourth aspect of the invention, the solution in which the molten chips are dissolved may be heated at a temperature within the range of 80-200° C. to obtain hydrogarnet. In the invention, since the poorly-soluble components in the iron and steel slag-containing components is made readily-soluble and dissolved in the solution, it is possible to obtain hydrogarnet easily by only heating the solution, without adding other components.
Still further, in the hydrocomposite producing step of the fourth aspect of the invention, a chelator may be added to the solution in which the molten chips are dissolved and then the mixture is heated at a temperature within the range of 20-200° C. to obtain zeolite. With the form of molten chips, the components which are conventionally treated as pooly-soluble components can be ionized. So, the chelator can adequately function and easily trap a particular components compared with the case of removing the components from solids or air; thereby it is possible to obtain zeolite easily. In addition, the components trapped by the chelator can be collected easily by adjusting pH.
Still further, in the fourth aspect of the invention to obtain zeolite in the hydrocomposite producing step, the chelator is preferably ethylenediamine tetraacetate (EDTA). This is because zeolite can be produced more easily by trapping the calcium components.
With the production method of the present invention, by alkaline melting treatment of iron and steel slag to form molten chips, the iron and steel slag can be made readily-soluble and be powderized and the entire iron and steel slag-containing components can be used when producing the hydrocomposites; thereby it is possible to produce hydrocomposites such as zeolite and hydrogarnet with easy processes. Moreover, since a solid base is used, the solution can be alkalified without adding thereto other components and the hydrocomposite can be produced with simplified processes. Further, by recycling the whole slag, the method can contribute to a recycling-intensive society with zero emissions. Still further, with the production method of the invention, characteristic hydrocomposites having functions such as ion-exchange property can be obtained; so, the iron and steel slag can be effectively used.
In this mode of the invention, a material including iron and steel slag is used as a starting material (it may also be called “raw material”.) of the molten chips. In the raw material, iron and steel slag is preferably contained as the main component. The term “main component” in this context means a component accounting for 80 mass % or more based on the total mass of the raw material. The raw material may consist of the iron and steel slag only. The raw material may also contain components other than iron and steel slag.
With respect to the iron and steel slag, an iron and steel slag which is produced in the steel production process may be used without any limitation: such as blast furnace slag obtained by separating and recovering components of iron ore melted in the blast furnace for producing pig, together with ash portion in limestone and coke as auxiliary material; and steel slag produced in the steel-making process to process a molten iron in the blast furnace into steel. The iron and steel slag has various compositions depending on the types of slag; it contains components such as: lime (CaO), silica (SiO2), and alumina (Al2O3); but also sulfur portion (S, etc.), phosphorus portion (P2O5, etc.), manganese portion (MnO), magnesia (MgO), and T-Fe (Total Fe: FeO and Fe). Particularly, the proportion of CaO is large. In this mode of the invention, to utilize the above contained components as a whole, the iron and steel slag is mixed with the below-described solid base to make it readily-soluble and to be powderized. It should be noted that so as to accelerate the reaction, specific surface of the iron and steel slag may be enlarged by pulverization and so on. For pulverization, conventional equipment for pulverization such as pulverizer and ball mill can be used without any limitation. To adjust the composition of the iron and steel slag, other components may be added or contained components may be removed. However, since this mode of the invention can effectively utilize the whole components contained in the iron and steel slag, it is presumably possible to produce hydrocomposites without adding other components. That is, in this mode of the invention, although an iron and steel slag in which a particular component is removed or added to may be mixed with the solid base to produce the below-described molten chips in a conventional manner, it is also possible to produce molten chips by mixing the iron and steel slag only with the solid base. It should be noted that by combining: a conventional step of removing a particular component from the iron and steel slag or adding a particular component to the iron and steel slag; and the production method of the present invention, hydrocomposites can be produced more efficiently. As the starting material to be mixed with the solid base, a material containing 20-80 mass % of CaO based on the total mass of the starting material may be acceptable.
The solid base can be used without any limitation as long as it is a substance which can suitably carry out alkaline melting treatment for iron and steel slag to make the iron and steel slag readily-soluble. Specific examples of the solid base include: preferably alkali metal hydroxide such as sodium hydroxide and alkali metal carbonate such as sodium carbonate; more preferably alkali metal hydroxide; and particularly preferably sodium hydroxide. In view of uniformly mixing the solid base in the iron and steel slag, the solid base is preferably sufficiently finely pulverized and mixed, then, heated at a temperature within the range of 200-600° C. with melting treatment. The method of pulverizing and mixing the solid base may be known methods without any limitation.
The molten chips are a powdery solid produced by the steps of: mixing a starting material containing the above iron and steel slag with a solid base; pulverizing the mixture; and processing by melting treatment. The molten chips is produced by adding a solid base at an amount of preferably 40-200 parts by mass, more preferably 80-200 parts by mass, and particularly preferably 120-160 parts by mass based on 100 parts by mass of the above iron and steel slag (starting material). By setting the proportion of the starting material and the solid base, it is possible to obtain sufficiently readily-soluble molten chips; thereby possible to obtain the molten chips without causing unintended side reaction.
When dissolving the molten chips in a solvent (solution), various functional substances can be obtained from the solution. The hydrocomposite thus obtained in accordance with the production method of this mode of the invention contains hydrocalumite, hydrogarnet, or zeolite. These are made from components derived from the iron and steel slag; so, it is different from the conventional ones in that the iron and steel slag as a whole is utilized. Specific conditions and the like for synthesizing each hydrocomposite will be described as follows.
Hereinafter, each step of the method for producing the hydrocomposite of this mode of the invention will be described in detail.
In the mixture producing step S1, a solid base and a material containing the above iron and steel slag are mixed at a predetermined proportion to produce a mixture. The iron and steel slag is preferably pulverized. The mixing method is not particularly limited as long as it is capable of mixing a solid with other solids. The mixture is kneaded by, for example, ball mill to be additionally finely pulverized and then supplied to the molten chips producing step.
In the molten chips producing step S2, the mixture obtained in the above step S1 is processed by melting treatment to produce powdery molten chips. The pressure of the melting treatment is not specifically limited. The temperature of the melting treatment is not specifically limited either, as long as the temperature is sufficient for the melting treatment. In view of shortening the reaction time and inhibiting side reaction, the temperature is within the range of 100-1000° C., preferably 200-800° C., more preferably 500-700° C., and further more preferably 600° C. It should be noted that by adequately changing the heating time and heating temperature in the melting treatment, the composition and yield of the hydrocomposites obtained in the below-described hydrocomposite producing step S3 can be changed. After the melting treatment, by cooling the heated mixture, powdery molten chips in which components contained in the iron and steel slag has been made readily-soluble can be obtained.
In the hydrocomposite producing step S3, the molten chips obtained in the above step S2 is dissolved in a solvent (solution) until the entire components derived from the iron and steel slag are dissolved; then, the hydrocomposite is obtained. The solvent (solution) for dissolving the molten chips is not particularly limited as long as it can adequately dissolve the molten chips; water is preferably used. Water includes: not only distilled water and deionized water; but also highly adulterated water such as industrial water, sea water, river water, and hot-spring water. The specific production process of each hydrocomposite in the step S3 (steps S13, S23, and S33) will be described as follows.
When synthesizing the hydrocomposite, by aging the solution in which the molten chips are dissolved for 3 hours or more, preferably 24-48 hours, hydrocalumite can be obtained. The concentration of the solution is not specifically limited; the molten chips are preferably contained at an amount of about 1-3 g to 10 mL solvent. In this mode of the invention, since the iron and steel slag component is made readily-soluble and dissolved in the solution, it is possible to obtain the hydrocalumite easily by only aging the solution without adding any other components; thus, the process can be simplified. In addition, since the solution is alkalified by the solid base contained in the molten chips, it is capable of adequately adjusting the pH of the solution without adding other basic components. The hydrocalumite contains calcium and aluminum as the main components; these have high anion exchange performance, so that these can be suitably used as anion trapping materials for, for instance, preventing corrosion.
When obtaining the hydrocomposite, by heating the solution in which the molten chips are dissolved at a temperature within the range of 80-200° C., preferably 80-120° C. and then starting the reaction, hydrogarnet can also be obtained. The concentration of the solution is not specifically limited; the molten chips are preferably contained at an amount of about 1-3 g to 10 mL solvent. Garnet is a silicate which may contain, for example, calcium, aluminum, magnesium, and iron; so, the components contained in the iron and steel slag can be fully used. In the same manner as step S13, in the step S23, iron and steel slag components as a whole are made readily-soluble and dissolved in the solution; so, the components of the iron and steel slag can be fully used and it is possible to obtain the hydrogarnet without adding other components. Hydrogarnet has properties of absorbing and fixing high-temperature acid gas, therefore it can be suitably used as absorbent or capture agent for toxic exhaust gas of incinerator or the like.
When obtaining the hydrocomposite, by adding a chelator to the solution in which the molten chips are dissolved and then making the mixture react at a temperature within the range of 20-200° C., preferably 60-120° C., zeolite can be obtained. The concentration of the solution is not particularly limited; the molten chips are preferably contained at an amount of about 0.5-2 g to 10 mL solvent. The chelator is preferably added at an amount of about 100-250 parts by mass to 100 parts by mass of the molten chips. Zeolite is synthesized by using mainly aluminum component and silicon component both contained in the iron and steel slag. Due to this, a chelator is added so as to prevent other components such as calcium from contributing to the reaction. In this mode of the invention, since the molten chips are made readily-soluble, the whole components of the iron and steel slag are dissolved and ionized in the solution. Therefore, compared with a case of removing a particular component from solid component or gas component, the particular components can be easily captured by using chelator and thereby the process will not be complicated. Chelator is not particularly limited as long as it can capture ions of components other than aluminum components and silicon components; it is particularly preferably ethylenediamine tetraacetate (EDTA). With the chelator, it is possible to capture particularly calcium component and prevent it from contributing to the reaction. The calcium component captured by the chelator can be easily recovered by adjusting pH of the solution after the reaction.
By the above-described steps S1 to S3, each of the hydrocomposites are produced from the iron and steel slag. In this mode of the invention, iron and steel slag is made into a form of molten chips and the components contained in the iron and steel slag are made readily-soluble; thereby it is possible to effectively utilize the iron and steel slag as a whole in the synthetic reaction without adding other components. Hereinafter, the production method of the invention and the hydrocomposites obtained by the production method will be described in further detail with reference to the Examples.
A granulated slag was pulverized down to 1 mm or less by pulverizer. Ten gram each of the powder thus obtained was charged in crucibles made of nickel; as solid base, 16 g each of sodium hydroxide, potassium hydroxide, and lithium hydroxide were respectively added to each of the crucible and then the granulated slag powder and the solid base were pulverized and mixed. The obtained mixture was heated and melted at 600° C. for 6 hours by electric furnace to produce respective molten chips. To 20 mL distilled water, 2 g of the obtained molten chips was added and stirred at 700 rpm for 24 hours. Then, each of the products were analyzed by XRD (that means powdery X-ray diffraction measurement using CuKα as a radiation source. As described above, RAD-C manufactured by Rigaku Corporation was used as an X-ray diffraction measurement; by carrying out powdery X-ray diffraction measurement in accordance with the step operation method (angle range: 2θ=5-50°, step width: 0.2°, holding time: 300 seconds), data relating to the diffraction peaks was obtained. Hereinafter, it is the same.). The results are shown in
Further, product obtained under the same conditions was sealed in a pressure tight case and then synthetic reaction was carried out at 80° C. for 6 hours by electric furnace; after that, each of the products was analyzed by XRD. The results are shown in
A granulated slag was pulverized down to 1 mm or less by pulverizer. Ten gram of the powder thus obtained was charged in a crucible made of nickel; 16 g each of sodium hydroxide was added to the crucible and then the granulated slag powder and the solid base were pulverized and mixed. The obtained mixture was heated and melted at 600° C. for 6 hours by electric furnace to produce molten chips. To 0M, 0.1M, 0.25M, 0.5M concentration of 20 mL ethylenediamine tetraacetate (EDTA) solutions, 2 g each of molten chips was respectively added and stirred at 700 rpm for 24 hours. Then, each of the products were analyzed by XRD. The results are shown in
Further, product obtained under the same conditions was sealed in a pressure tight case and then synthetic reaction was carried out at 100° C. for 6 hours by electric furnace; after that, each of the products was analyzed by XRD. The results are shown in
The results shown in
With respect to the products after 24 hour stirring (before heating) and the products after heating at 100° C. for 6 hours (after heating), the amount of calcium extracted in the solution was determined by ICP emission spectroscopy. The results are shown in Table 1. Calcium is one of the interfering elements in zeolite synthesis. The amount of calcium extracted in the solution increases by addition of EDTA as a chelator; it is understood that the amount increases furthermore by heating. In addition, it is also understood that masking effect is even maintained or facilitated by heating.
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of each powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 200° C., 400° C., 600° C., and 800° C. for 6 hours by electric furnace. The molten chips after melting was added to 80 mL distilled water and then aged with stirring at 700 rpm at room temperature for 24 hours. Each of the products derived from respective slag was analyzed by XRD. The results are shown in
The results shown in
Further, molten chips melted under the same conditions as above was added to a solution in the same manner as above and then stirred for 24 hours. After that, it was sealed in a pressure tight case and then heated at 80° C. for 6 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 5 g of each powder thus obtained, 2 g, 4 g, 5 g, 8 g, and 10 g of sodium hydroxide were respectively added; then, the powder and sodium hydroxide were pulverized and mixed. Each of the obtained mixtures was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 40 mL distilled water and then stirred at 700 rpm at room temperature for 24 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
Further, each of the molten chips melted under the same conditions as above was added to each of solutions in the same manner as above and then stirred for 24 hours. After that, it was sealed in a pressure tight case and then heated at 80° C. for 6 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of each powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 40 mL, 80 mL, and 160 mL distilled water (i.e. 4, 8, 16 mL/g-mixture.) and then respectively stirred at 700 rpm at room temperature for 24 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
Further, each of the molten chips melted under the same conditions as above was added to each of solutions in the same manner as above and then stirred for 24 hours. After that, it was sealed in a pressure tight case and then heated at 80° C. for 6 hours. Each of the products was analyzed by XRD. The results are shown in
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of each powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 80 mL distilled water and then stirred at room temperature for 24 hours. The stirring speed was 0 rpm, 350 rpm, 700 rpm, and 1400 rpm. Each of the products was analyzed by XRD. The results are shown in
The results of
Further, each of the molten chips melted under the same conditions as above was added to each of the solutions in the same manner as above and then stirred for 24 hours. After that, it was sealed in a pressure tight case and then heated at 80° C. for 6 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of the powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 80 mL distilled water and then stirred at 700 rpm at room temperature for each stirring time. The stirring times were respectively 5 minutes (shown as 0 hour in
The results of
Further, each of the molten chips melted under the same conditions as above was added to each of the solutions in the same manner as above and then stirred for each stirring time. After that, it was sealed in a pressure tight case and then heated at 80° C. for 6 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of each powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 80 mL distilled water and then stirred at 700 rpm at room temperature for 24 hours. After that, it was sealed in a pressure tight case and then heated at 80° C., 100° C., 120° C., 150° C., and 180° C., for 6 hours. Each of the products was analyzed by XRD. The results are shown in
The results of
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of the powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 80 mL, distilled water and then stirred at 700 rpm at room temperature for 24 hours. After that, it was sealed in a pressure tight case and then heated at 80° C. and 180° C. for 0 hour, 0.5 hour, 1.2 hours, and 4 hours to obtain the products. Each of the products was analyzed by XRD. The results at 80° C. heating temperature are shown in
The results of
The results of
A granulated slag, a slowly-cooled slag, and a converter slag were respectively pulverized down to 1 mm or less by pulverizer. To 10 g of the powder thus obtained, 16 g of sodium hydroxide was added; then, the powder and sodium hydroxide were pulverized and mixed. The obtained mixture was charged in a crucible made of nickel and then melted with heating at 600° C. for 6 hours by electric furnace. The molten chips after melting was added to 80 mL distilled water and then stirred at 700 rpm at room temperature for 24 hours. Untreated slags, molten chips, and each of the products was respectively analyzed by XRD and those surfaces were observed by SEM. The results are shown in
The results of
As described above, with the production method of the present invention, it is possible to convert the iron and steel slag into valuable hydrocomposites. Hereinafter, an example of performance and applications of the hydrocomposites of the invention will be described.
Performance of iron and steel slag and hydrocomposites of the present invention obtained from the iron and steel slag was evaluated. Specifically, adsorption test of a predetermined anion was carried out with various iron and steel slag used as the raw material and the hydrocalumites (products) obtained from the iron and steel slag; then, the performance was evaluated. The hydrocalumites used in the adsorption test were the ones obtained in the same manner as Example 10. In other words, comparison between a granulated slag and a hydrocalumite obtained from the granulated slag and comparison between a slowly-cooled slag and a hydrocalumite obtained from the slowly-cooled slag were carried out.
The evaluation test was carried out in accordance with the following procedures. That is, 0.1 g of samples for adsorption test were prepared; then, 10 mL of 1 mM anionic solution was added to each of the prepared samples and shaped for 12 hours; finally, anionic adsorption performance of each mixture was evaluated.
The results of anionic adsorption performance are shown in
As shown in
Zeolite and hydrogarnet both obtained from iron and steel slag are much the same. Zeolite can be used for, for example, detergent for water and soil conditioner; hydrogarnet can be used for, for example, immobilizing material for hydrochloric gas.
The above has described the present invention associated with the most practical and preferred embodiments thereof. However, the invention is not limited to the embodiments disclosed in the specification. Thus, the invention can be appropriately varied as long as the variation is not contrary to the subject substance and conception of the invention which can be read out from the claims and the whole contents of the specification. It should be understood that a method for producing the hydrocomposites with such an alternation are included in the technical scope of the invention.
By the present invention, it is possible to produce hydrocomposites such as zeolite and hydrogarnet from iron and steel slag without adding other components and requiring complex treatment process. Therefore, the method is useful for the new application of iron and steel slag and is useful as the new processing method. In addition, by recycling of the whole slag, zero emissions can be achieved thereby it is possible to contribute to a recycling-intensive society.
Number | Date | Country | Kind |
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2009-013406 | Jan 2009 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP2010/050817 | 1/22/2010 | WO | 00 | 7/22/2011 |