JP3436736B2 - Civil and architectural materials, their production and their use - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a roadbed material, a roadbed material,
The present invention relates to materials for civil engineering and construction that can be used as caisson filling materials, landfill materials, embankment materials, or aggregates used for concrete, mortar, etc., a method for manufacturing the same, and a method for using the same.

[0002]

2. Description of the Related Art Conventionally, it has been considered to use a sulfur solidified product produced by mixing sulfur and an inorganic material as a material for civil engineering / construction such as landfill material. For example, an appropriate molding die is mixed and filled with a sulfur melt and an inorganic material, cooled and solidified to obtain a molded product, and then crushed to an appropriate particle size to obtain a sulfur solidified product for civil engineering and construction. It has been proposed to use it for the materials. However, the sulfur solidified product obtained by crushing has a large amount of inorganic material exposed on the surface, so the granularity is not stable, and since it has sharp edges due to crushing, it lacks fluidity and It is hard to say that it is suitable for civil engineering and construction materials.

[0003]

By the way, there are various conceivable requirements for civil engineering and construction materials, depending on their specific uses. For example, the following requirements (1) to (3) can be used for civil engineering and construction materials such as roadbed materials, roadbed materials, caisson filling materials, landfill materials, embankment materials, and aggregates.
I think that the performance such as is necessary. (1) It has strength and fluidity such that it can be used as an aggregate, etc. (2) The strength of the material surface is average, and strength control when used as a civil engineering material is easy,
(3) The water absorption rate on the surface of the material is average, and it is easy to control the water absorption rate. Conventionally, it is hard to say that the solidified product using sulfur, which has been proposed as a civil engineering / construction material, sufficiently satisfies the above requirements (1) to (3). On the other hand, in order to detoxify and dispose of municipal waste and industrial waste containing harmful substances such as heavy metals, various technologies using activated sulfur, sodium silicate, sodium sulfide, chelating agents, etc. have been proposed. For example, a method for detoxifying harmful heavy metals contained in fly ash by rolling granulation of fly ash and active sulfa (JP-A-7-100545 and JP-A-7-251142) is known. There is. The solidified product obtained for the purpose of reacting with such an active sulfur or a chelating agent has a low compressive strength and the like.
It cannot be used as a building material and is not intended for such use. Further, when the purpose is to react a metal with an active sulfur or a chelating agent, the use of an aqueous solution is essential, so that a waste liquid treatment thereof is also required, and there is a problem that the production becomes complicated.

Therefore, an object of the present invention is to provide civil engineering / construction which has both strength and fluidity and can be used as roadbed materials, roadbed materials, caisson filling materials, landfill materials, embankment materials, aggregates, etc. The purpose is to provide a material and a manufacturing method thereof. Another object of the present invention is to provide a civil engineering / construction material that can block outflow of harmful substances such as heavy metals and can effectively use municipal waste, industrial waste, and the like, and a manufacturing method thereof.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an inorganic material is coated with a sulfur melt to have a specific particle size.
The present invention has been completed by finding that it has strength and fluidity as a material for civil engineering and construction. That is, according to the present invention, 10 to 30% by mass of sulfur and 70 to 90 % by mass of the inorganic material
% , The particle size is 44.4 mm or less specified by the JIS standard sieve, and each of the secondary particles of the inorganic material is coated with sulfur.
A coated material in which the coated secondary particles are further coated with sulfur.
Have an internal structure in which
However, there is provided a civil engineering / construction material characterized in that the inorganic material is substantially covered with sulfur. Further, according to the present invention, a mixture containing an inorganic material and a sulfur-containing melt of 120 to 170 ° C. is granulated while being cooled to a temperature below the solidification temperature of sulfur, and the inorganic material is coated with sulfur. A method for manufacturing the above-mentioned civil engineering / construction material is provided. Furthermore, according to the present invention, the above-mentioned civil engineering / construction material is used as a roadbed material, a roadbed material, a caisson filling material, a landfill material, an embankment material, or an aggregate. Instructions for use are provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The civil / building material of the present invention contains sulfur and an inorganic material, has a specific particle size, and
Each of the secondary particles of the inorganic material is coated with sulfur,
The secondary particles coated with sulfur are further coated with sulfur.
The inside of a state in which the covered coating is aggregated and integrally configured
A structure having an inorganic material substantially coated with sulfur, for example, an acute angle that inhibits fluidity, which is found in a crushed product obtained by crushing a conventional sulfur molded solidified product. It is a material that has substantially no parts. Such civil engineering / construction materials of the present invention are preferably used as, for example, roadbed materials, roadbed materials, caisson filling materials, landfill materials, embankment materials, or various aggregates used for concrete, mortar, etc. You can

In the civil engineering and construction material of the present invention and the method for producing the same, sulfur is, for example, normal sulfur alone,
Examples include sulfur that is naturally produced or produced by desulfurization of petroleum or natural gas; modified sulfur of sulfur and other materials such as a chelating agent; and a sulfur-containing melt. However, it does not include active sulfur that is dissolved in an alkaline aqueous solution and reacts with an inorganic material described later to form a sulfide. The mixing ratio of sulfur is
The amount may be a desired granulated product when mixed and solidified with an inorganic material, and is usually 5 mass% or more, preferably 10 to 70 mass% with respect to the total amount of sulfur and the inorganic material. ,
Particularly preferably, it is 10 to 30% by mass. When the blending ratio of sulfur is less than 5% by mass, it may not be possible to sufficiently wet and coat the inorganic material or the like. Further, the granular sulfur solidified product obtained by the present invention is characterized in that it is substantially coated with sulfur, which is formed by agglomeration of the inorganic material coated with sulfur. When the blending ratio of sulfur exceeds the above range, when the molten mixture solidifies,
Since it is mechanically cut by vibration or rolling, or adheres to the device, the granularity of the sulfur solidified product is not stable, and the fluidity is poor, and a desired material cannot be obtained.

Examples of the inorganic material in the civil engineering / construction material of the present invention include inorganic oxides, clay minerals, activated carbon, carbon fiber, glass fiber, sand, gravel, municipal waste incineration ash / incineration fly ash, urban Waste fly ash generated from high-temperature refuse melting furnace, coal ash discharged from electric power industry and general industry, fluid sand used in fluidized bed incinerator, soil contaminated with heavy metals, grinding dust, steel slag / dust, ferro As by-products and the like that are by-produced during the production of various metals such as nickel slag, aluminum dross, and copper slag, it is particularly preferable to use municipal waste incineration ash / incineration fly ash and steel slag / dust. These may be used alone or as a mixture upon use. If a material having high strength (for example, coal ash) is used as the inorganic material, the mechanical strength of the material for civil engineering and construction of the present invention can be further improved. The mixing ratio of the inorganic material may be any amount as long as it becomes a desired granulated product when mixed and solidified with sulfur, and usually,
With respect to the total amount of sulfur and inorganic materials, 95 mass% or less, preferably 30 to 90 mass%, particularly preferably 70.
Is about 90% by mass.

The civil engineering / construction material of the present invention may contain other materials in addition to the above-mentioned sulfur and inorganic materials as long as the object of the present invention is not impaired. Other materials include sodium silicate, sodium sulfide, heavy metal sequestering stabilizers such as chelating agents, asphalt, and various polymers. Further, in order to change the properties of the sulfur, for example,
Examples thereof also include olefin hydrocarbons having 4 to 20 carbon atoms, diolefin hydrocarbons, and the like. Specifically, cyclic olefinic hydrocarbons such as limonene; aromatic hydrocarbons such as styrene, vinyltoluene, and methylstyrene; dicyclopentadiene and its oligomers (hereinafter simply referred to as "dicyclopentadiene"), dienes such as cyclopentadiene. It may contain a system hydrocarbon and the like. These olefinic hydrocarbons, diolefinic hydrocarbons, etc. that change the properties of sulfur can be added to sulfur in advance, and the addition amount is 30% by mass or less based on the total amount with sulfur. Preferably. The present invention also includes an embodiment in which sulfur modified in advance to such properties is used. For modification of sulfur, modification with a diene hydrocarbon such as dicyclopentadiene is preferable. The modified sulfur, with respect to sulfur,
Usually, 2 to 30% by mass, preferably 2 to 20% by mass of diene hydrocarbon is melt-mixed at 135 to 155 ° C., and 14
It can be obtained by a method of performing a polymerization reaction such that the viscosity at 0 ° C. is 0.05 to 1.2 Pa · s and then cooling to 135 ° C. or less. By modifying sulfur in this way, it is possible to improve the properties of the civil engineering and construction material of the present invention, such as flame retardancy, resistance to sulfur bacteria, water impermeability, and compressive strength.

The particle size of the granular sulfur solidified material which constitutes the civil engineering and construction material of the present invention is 4 specified by the JIS standard sieve.
It is 4.4 mm or less, preferably 31.7 mm or less, and particularly preferably 22.2 mm or less. The sulfur solidified substance is in the form of particles having substantially no sharp protrusions on the outer periphery that obstruct the fluidity. The particle size can be adjusted by the particle size and blending ratio of the inorganic material used, and can also be adjusted by the granulating conditions such as cooling speed, rotation speed, and vibration speed during production. Preferably, as shown in FIGS. 1 and 2, for example, the internal structure is dispersed with a large particle size of an inorganic material, and the periphery thereof is covered with a fine inorganic material and a sulfur solidified material. In addition, a structure having few cavities and excellent mechanical strength is desirable. For example, use of a granular sulfur solidified product using an inorganic material having high strength is preferable from the viewpoint of improving mechanical strength. With such a structure, sufficient compressive strength can be expected as a civil engineering / construction material. The civil engineering / construction material of the present invention is usually 10 to 100 MPa, preferably 20.
It has a compressive strength of ˜100 Mpa, particularly preferably 30-100 Mpa.

In the granular sulfur solidified product, since the inorganic material is substantially covered with sulfur, even if the inorganic material contains harmful substances such as heavy metals, Almost all outflow of harmful substances is suppressed, and it has mechanical strength equivalent to or higher than that of a solidified product by a conventional molding die. When the inorganic material is substantially covered with sulfur, it means that the covering state in both the covering state of the inorganic material on the outer peripheral surface of the granular sulfur solidified product and the covering state of the inorganic material in the internal structure is sulfur. It is meant to be substantially covered. The coating state on the outer peripheral surface is
It is preferable that the inorganic material is coated so that it is not completely exposed on the outer peripheral surface. However, the present invention is not limited to this, and for example, desired mechanical strength and fluidity can be ensured, and harmful substances such as heavy metals contained in inorganic materials may be eluted beyond environmental standards. If it can be prevented, a part of the inorganic material (for example, about 20 to 30% at maximum with respect to the total outer peripheral area) may be exposed on the outer peripheral surface. On the other hand, the coating state of the internal structure of the granular sulfur solidified material means, for example, the state in which the individual inorganic materials are substantially coated with sulfur as shown in FIGS. 1 and 2. Coating on the internal, the method of manufacturing its, for example, due to tumbling granulation method or oscillating granulator method, unevenness of particulate or powder form secondary particles (primary particles of the inorganic material surface and that aggregate at van der Waals forces, etc.), each being coated with sulfur, Oh in the state of being integrally formed by aggregation which they are further coated with sulfur
It Conditions such as this, for example, the conventional sulfur concrete product crushed and melt mixture of sulfur concrete product solidified by using a mold is mechanically cut by vibration or rolling when solidified, The solidified state is different as a thing. However, the obtained compressive strength of the granular sulfur solidified product in the present invention is the same as or higher than that of the sulfur solidified product solidified by using the conventional molding die. The above-mentioned covering state is preferably using the civil engineering / construction material of the present invention, and Environment Agency Notification No. 13
(February 16, 1973) The assay solution prepared by the method described in "Testing methods for metals contained in waste" is prescribed in Prime Minister's Ordinance Article 5 (February 17, 1973) "For landfill disposal" It is preferable that the coated state has a value lower than the standard shown in the “determination standard relating to the above” or the “determination standard relating to disposal at sea”. Furthermore, Environmental Agency Notification No. 46 (August 2, 1991)
It is preferable that the coated state shows a value below the “environmental standard for soil pollution” of 3 days).

The method for manufacturing a civil engineering / construction material of the present invention is
It can be obtained by granulating a mixture containing an inorganic material and a sulfur-containing melt at 120 to 170 ° C. while cooling to below the solidification temperature of sulfur, and coating the inorganic material with sulfur. For example, sulfur is melted at 120 to 170 ° C., inorganic material that has been dried in advance and other materials are added to the melted sulfur and kneaded, and granulated while cooling to below the solidification temperature of sulfur. Method, sulfur and a pre-dried inorganic material, and if necessary, other materials are mixed first, and then at least 120 to 170 ° C. is melted and mixed at a temperature of 120 to 170 ° C., and cooled to a temperature below the solidification temperature of sulfur. While granulating, or by melting sulfur and, if necessary, other materials at 120 to 170 ° C. in advance, and mixing the melted material with a previously dried inorganic material to a temperature not higher than the solidification temperature of sulfur. Examples of the method include granulating while cooling. Preferred examples of sulfur, inorganic materials and other materials include the specific examples listed above. The cooling temperature is not particularly limited as long as it is lower than 120 ° C at which sulfur solidifies.

The granulation is carried out, for example, in the above-mentioned FIG. 1 and FIG.
In order to add the structure shown in
It is preferable to use a rolling granulator or a vibrating granulator equipped with a horizontal or inclined plate and to carry out the rolling granulation method or the vibrating granulation method. By adopting such a method, the internal structure of the obtained granular sulfur solidified product, the above-mentioned, each of the secondary particles of the particulate or powdery inorganic material is coated with sulfur, these are further sulfur It is possible to obtain a state in which those coated with are aggregated and integrally configured. In these methods, specific conditions are appropriately selected and determined in accordance with the types and blending ratios of sulfur and inorganic materials so that the obtained particulate sulfur solidified product has the above-mentioned particle size. In the case of the tumbling granulation method, the particle size of the granular sulfur solidified product can be adjusted by the inclination angle of the rotating plate or the drum, the rotation speed, and the like. However, it is not particularly necessary to select the size of the rotating plate or the drum in consideration of the desired particle size, and for example, particles having an arbitrary size of 2 to 44.4 mm can be produced on the same rotating plate. The tilt angle is generally adjusted in the range of 0 to 70 °. In the case of the vibration granulation method, the particle size of the granular sulfur solidified product can be adjusted by the frequency, the amplitude, and the tilt angle. For example, the frequency is about 3000 times / minute, the amplitude is 0.3 mm or more, and the sulfur solidified material in the molten state is selected within a range that does not scatter. The tilt angle is usually adjusted in the range of 0 to 60 °. The vibration method may be a reciprocating method, a rotating method, or a mixed method thereof. It is also possible to use a rotating drum or the like to substantially vibrate for granulation.
As another granulation method, there is also a method of dropping molten sulfur into water, but in some cases the coating of the inorganic material is not perfect because heavy metals are eluted in the water and rust occurs on the surface of the granulated material. It is not preferable.

The proportion of the inorganic material and the sulfur-containing melt at the time of granulation is 100% by mass based on the total amount of these materials.
Inorganic material 95 mass% or less, preferably 30 to 95 mass%, more preferably 72 to 95 mass%, particularly preferably 72 to 90 mass%, sulfur-containing melt 5 mass% or more, preferably 5 to 70 mass% , More preferably 5 to 28% by mass, particularly preferably 10 to 28% by mass. If the proportion of the sulfur-containing melt charged exceeds this range, the granularity of the sulfur solidified product is stable because the molten mixture is mechanically cut by vibration or rolling when it solidifies, or adheres to the equipment. Moreover, the desired material cannot be obtained because of lack of fluidity.

The civil engineering / construction material of the present invention has a specific grain size without an acute angle portion which hinders fluidity on the outer periphery, has a sufficient mechanical strength in its structure, and is made of a heavy metal or the like. Outflow of harmful substances is also inhibited, and since metal components such as iron that easily rust are coated, deterioration of the granular sulfur solidified product due to rust is unlikely to occur. Therefore, it can be used as a roadbed material, a roadbed material, a caisson filling material, a landfill material, an embankment material, or various aggregates used for concrete, mortar and the like. Such use, depending on the application, adjust the particle size and mechanical strength of the granular sulfur solidified product, ordinary roadbed material, roadbed material, caisson filling material, landfill material,
It can be used similarly to the embankment material or various aggregates.

[0016]

The civil engineering / construction material of the present invention is a granular sulfur solidified product having a specific particle size, which has substantially no sharp corners,
Since the inorganic material is substantially covered with sulfur, it has both strength and fluidity, and is useful for roadbed materials, roadbed materials, caisson filling materials, landfill materials, embankment materials, aggregates, etc. is there.
Moreover, the outflow of harmful substances such as heavy metals can be prevented, and it is also useful for the effective use of municipal waste, industrial waste, and the like. In the production method of the present invention, the above-mentioned civil engineering / construction material can be easily obtained by a simple method such as granulation. In particular, since a material such as active sulfur producing waste water is not an essential component, no complicated operation is required.

[0017]

EXAMPLES The present invention will be described in more detail with reference to Comparative Examples and Examples, but the present invention is not limited thereto. Example 1 200 g of sulfur was melted at 150 ° C., and 560 g of previously dried blast furnace slag and 240 g of coal ash were kneaded. 1000 g of the obtained molten mixture was poured into a table-type vibrator (manufactured by Murata Seiko Co., Ltd., 2 HV-type vibrators were used, and a 500 × 500 mm iron plate was fixed as a vibration table), and the vibration frequency was 3000 times / min. It was solidified while applying reciprocating vibration for 1 minute with an amplitude of 1 mm. As a result, a granular sulfur solidified material whose entire circumference was covered with the sulfur solidified material having a particle size of 10 mm or less and having no sharp corners that hinder the fluidity was obtained. When the compressive strength of the obtained granular sulfur solidified product was measured, it was 55 M.
It was pa. Further, a cross-sectional structure of a part of the obtained granular sulfur solidified product was observed using a scanning electron microscope (Pt vapor deposition, applied voltage 15 keV). 50 x 1.4
A photocopy of a double secondary electron image is shown in FIG. 1, and a photocopy of a 50 × 1.4-fold backscattered electron image (BEI) in the same field of view as in FIG. 1 is shown in FIG. In addition, the enlarged photograph of FIG. 1 (1000 × 1.4
3 is a copy of FIG. 3 and an enlarged photograph (1000 × 1.
FIG. 4 shows a copy of the same field of view as in FIG.
Further, with respect to FIG. 3, FIG. 5 shows a copy of a photograph in the same field of view as FIG. 3 in which the existence range of sulfur was confirmed by Kα ray. In addition, in FIGS. 1 and 2, it seems that the inorganic material is exposed on the outer peripheral surface. This is because a part of the sulfur solidified material covering the outer periphery is peeled off when the cross section is polished. . Further, the coating thickness of sulfur of the granulated product was 1 to 30 μm.

Comparative Example 1 In Example 1, the molten solidified product was solidified without vibration during solidification. As a result, the molten and solidified material injected into the table-type vibrator was solidified not as a granular material but as a single lump. The cross section of the obtained solidified product was observed in the same manner as in Example 1. A copy of the 50 × 1.4 × secondary electron image is shown in FIG. 6, and a 50 × 1.4 × reflected electron image (B
A copy of the photograph of EI) is shown in FIG. 8 is a magnified photograph (1000 × 1.4 times) of FIG. 6, and FIG. 9 is a magnified photograph (1000 × 1.4 times) of FIG. . Further, the compression strength of the obtained solidified product was measured and found to be 55 Mpa.

From FIGS. 1 to 5, the granular material obtained in Example 1 has a structure in which the inorganic material is confined inside. Particularly, as is clear from FIG. 5, the periphery of each inorganic material particle is It can be seen that even inside the sulfur stream, the structure is covered with sulfur (white part in FIG. 5). In addition, there are almost no cracks or cavities inside the granular material that reduce the mechanical strength. The porosity on the cross-sectional photograph was 10% or less (however, the pores of the inorganic material itself are excluded).
The compressive strength of the granular sulfur solidified product prepared in Example 1 was the same as the compressive strength of the solidified solid product prepared in Comparative Example 1, which is the mass obtained in Comparative Example 1 from FIGS. It is considered that the solidified product of is basically similar to the structure of the granular material obtained in Example 1. Since the granular sulfur solidified product prepared in Example 1 had a compressive strength of 55 Mpa, for example, when considering that the aggregate for concrete can be used as long as it has a compressive strength of about 30 Mpa, It is understood that the granular sulfur solidified product of Example 1 is suitable as various civil engineering / construction materials. In particular, there are no sharp edges that hinder fluidity on the outer circumference, and because it has excellent mechanical strength, it is a roadbed material, a roadbed material, a caisson filling material, landfill material,
It proves to be useful as a fill material or an aggregate.

Example 2 280 g of sulfur was melted at 150 ° C., 320 g of previously dried steel slag (2 mm or less) and 400 g of incineration fly ash generated from an incinerator were kneaded. 1000 g of the obtained molten mixture was used as a table-type vibrator (Murata Seiko Co., Ltd.).
Made by 2 HV type vibrators, 500 x as a vibrating table
500mm iron plate is fixed) and the vibration frequency is 3000 times /
Min. And an amplitude of 1 mm, the material was solidified while applying reciprocating vibration for 1 minute. As a result, a granular sulfur solidified substance having a particle size of 2 mm or less and having no sharp corners which hinders fluidity was obtained, which was entirely covered with the sulfur solidified substance. The obtained granular sulfur solidified product was used as it was without crushing, and an elution test was carried out by the method described in Environmental Agency Notification No. 46, "Environmental Standards Concerning Soil Contamination". As a result, the amount of lead eluted in the eluate is below the detection limit (0.005 mg / l), which satisfies the soil environmental standard, and can be used as a civil engineering / construction material. Furthermore, when the obtained granular sulfur solidified product was subjected to a CBR test (Pavement Test Method Handbook "Road bearing capacity test"), the CBR value was 155%.
This material proves to be particularly suitable as a roadbed material, a roadbed material or an embankment material.

Comparative Example 2 In Example 2, the molten solidified product was solidified without vibration during solidification. As a result, the molten and solidified material injected into the table-type vibrator was solidified not as a granular material but as a single lump. The obtained solidified product was crushed to a particle size of 2 mm or less by a crusher, and the dissolution test was conducted in the same manner as in Example 2. As a result, the elution amount of lead was 0.03 mg / l. This is a much larger amount of detection than in Example 2, and it does not meet the soil environmental standards, so it can be seen that it cannot be used as a civil engineering / construction material.

Example 3 190 g of sulfur was put in a stirring and mixing tank, heated and sufficiently melted, and then dicyclopentadiene was added to sulfur at 5 mas.
s% (9.5 g) was added. After the addition of dicyclopentadiene, the reaction was started by heating to 150 ° C, so the temperature was kept at 150 ° C. After about 1 hour, the viscosity of the melt at 140 ° C. reached 100 mPa · s. The obtained sulfur polymer was melted at 140 ° C., and 360 g of previously dried steel slag (2 mm or less) and 450 g of incineration fly ash generated from an incinerator were kneaded. Next, 1000 g of the obtained molten mixture was used as a vibrating table by using two table-type vibrators (Murata Seiko Co., Ltd., HV-type vibrators).
(Steel plate of 00 × 500mm is fixed) and the vibration frequency is 300
Solidification was performed by applying reciprocating vibration for 1 minute under conditions of 0 times / minute and an amplitude of 1 mm. As a result, a granular sulfur solidified substance having a particle size of 2 mm or less and having no sharp corners which hinders fluidity was obtained, which was entirely covered with the sulfur solidified substance. Using the obtained particulate sulfur solidified product as it was, a small gas flame ignition test was carried out in accordance with the small gas flame ignition test specified in the Hazardous Materials Class 2 (flammable solids) test method of the Fire Service Agency. In this test, the test article weighed 3 cm ³ is brought into contact with the flame of the ignition device for 10 seconds, and the operation of observing the time until ignition and whether or not the combustion can be continued is repeated 10 times to make the determination. If the ignition time is 3 seconds or less and combustion continues, "Type 1 combustible solid", if the combustion continues for more than 3 seconds and within 10 seconds, "Type 2 combustible solid", and 10 measurements In case of non-ignition or if combustion did not continue, there is no danger
Is determined. The results are shown in Table 1. Those that ignited within 10 seconds were marked with ◯, and those that were not loaded after 10 seconds were marked with x, and judgment was made from the test results of 10 times. Further, in order to evaluate the resistance to sulfur-oxidizing bacteria, 100 g of the obtained granular sulfur solidified product was separately immersed in a bottle containing 700 ml of seawater containing sulfur-oxidizing bacteria.
It was allowed to stand for a day and the change in pH was measured. The results are shown in Fig. 10.

Comparative Example 3 190 g of sulfur was melted at 150 ° C., and 360 g of previously dried steel slag (2 mm or less) and 450 g of incinerated fly ash generated from an incinerator were kneaded. Next, 1000 g of the obtained molten mixture was solidified without applying vibration.
As a result, the molten solidified product was solidified as one lump rather than as a granular material. The obtained solidified product was pulverized with a pulverizer to have a particle size of 2 mm or less, and the pulverized product was used to prepare Example 3
Small gas flame ignition test and evaluation of resistance to sulfur-oxidizing bacteria were conducted in the same manner as in. The results are shown in Table 1 and FIG. 10, respectively.

[0024]

[Table 1]

From the results shown in Table 1, the granular sulfur solidified product of Example 3 showed no flammability and could be judged as "no risk". In addition, from the result of FIG. 10, the pH on the 80th day
Was 6.17 in the case of the pulverized product of Comparative Example 3 and was affected by the sulfur-oxidizing bacteria, whereas the solidified product of Example 3 was 7.56 and was hardly affected by the sulfur-oxidizing bacteria. I understood. Therefore, the solidified product using the sulfur polymer modified with dicyclopentadiene prepared in Example 3 was
It has been found that it can be widely used as a building material.

[Brief description of drawings]

FIG. 1 is a photograph of a secondary electron image by a scanning electron microscope of a cross-sectional structure of a granular sulfur solidified product prepared in Example 1.

FIG. 2 is a photograph (same field of view as in FIG. 1) of a backscattered electron image (BEI) of a cross-sectional structure of the granular sulfur solidified product prepared in Example 1 by a scanning electron microscope.

FIG. 3 is an enlarged photograph of FIG.

4 is an enlarged photograph of FIG. 2 (same field of view as FIG. 3).

5 is a photograph based on FIG. 3, in which the existence range of sulfur was confirmed by Kα rays (the same field of view as in FIG. 3).

FIG. 6 is a photograph of a secondary electron image of a cross-sectional structure of the solidified product prepared in Comparative Example 1 by a scanning electron microscope.

FIG. 7 is a photograph of the backscattered electron image (BEI) of the cross-sectional structure of the solidified product prepared in Comparative Example 1 taken by a scanning electron microscope (the same field of view as in FIG. 6).

8 is an enlarged photograph of FIG.

9 is an enlarged photograph of FIG. 7 (same field of view as FIG. 8).

FIG. 10 is a graph showing evaluation results of sulfur-oxidizing bacterium resistance of each sulfur solidified product prepared in Example 3 and Comparative Example 3.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Kawada 3-390 Koyasu-dori, Kanagawa-ku, Yokohama, Kanagawa Prefecture Nisseki Mitsubishi Refining Co., Ltd.Yokohama Refinery (72) Inventor, Hiroshi Isobe, Shirattoridai, Aoba-ku, Yokohama-shi, Kanagawa 12-304 (72) Inventor Takuya Yamato 2-12--4-306 Shiba, Minato-ku, Tokyo (72) Inventor Hiroshi Hashimoto 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Hishishi Mitsubishi Central Research Institute ( 56) References JP-A-62-292659 (JP, A) JP-A-62-246850 (JP, A) JP-A-58-181756 (JP, A) JP-A-2000-327399 (JP, A) Japanese Patent Publication 2-28529 (JP, B2) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C04B 28/36 C04B 12/00 C04B 14/02 C04B 14/36 C04B 20/10 C08G 75/00

Claims (6)

(57) [Claims] 1. An inorganic material 70 containing 10 to 30% by mass of sulfur.
Of 90% by mass or more, and the particle size is 44.4 mm or less defined by the JIS standard sieve, and each of the secondary particles of the inorganic material is coated with sulfur.
The secondary particles coated with the sulfur are further coated with sulfur.
In the state that the coated coating is aggregated and integrally configured
A civil engineering / construction material having an internal structure, in which an inorganic material is substantially covered with sulfur. 2. The civil / building material according to claim 1, wherein the sulfur is sulfur modified with dicyclopentadiene. 3. A mixture containing an inorganic material and a sulfur-containing melt at 120 to 170 ° C. is granulated while being cooled to a temperature below the solidification temperature of sulfur, and the inorganic material is coated with sulfur. The method for manufacturing a civil engineering / construction material according to claim 1. 4. The method according to claim 3 , wherein the granulation is performed by a rolling granulation method or a vibration granulation method. 5. The proportion of the inorganic material and the sulfur-containing melt during granulation is 72 to 95% by mass of the inorganic material and 5 to 28% by mass of the sulfur-containing melt with respect to 100% by mass in total. The manufacturing method according to claim 3 or 4 , wherein 6. A civil engineering / construction material using the civil engineering / construction material according to claim 1 as a roadbed material, a roadbed material, a caisson filling material, a landfill material, an embankment material or an aggregate. How to use.