JP2006306634A - Porous modified sulfur solidified body composed mainly of shell pulverized product and civil engineering/building structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous modified sulfur solidified body composed mainly of a shell pulverized product, which is expected to utilize a large quantity of waste shells, provides workability and strength equivalent to concrete, and can be utilized as a civil engineering/building structure excellent in gathering and adhesion effect of underwater creatures, a material for the same and the like. <P>SOLUTION: The porous modified sulfur solidified body comprises >20 mass% and ≤33 mass% of a modified sulfur material comprising 100 pts.mass of a fine aggregate having a particle size of 5 mm or less and 30-400 pts.mass of a modified sulfur, and ≥67 mass% and <80 mass% of a pulverized shell product having a particle size of 3-10 mm. The porous modified sulfur solidified body has continuous voids exhibiting water permeability and a percentage of void of 10-40 vol%. The civil engineering/building structure comprises the above porous modified sulfur solidified body. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention can be highly blended with shells that are often treated as waste, and can be expected to be used in large quantities, and is excellent in the collection and settlement of aquatic organisms. Various blocks, fishing reefs, algae reefs, structures for revetment The present invention relates to a porous modified sulfur solidified body mainly composed of a ground shell material that can be used as a civil engineering / construction structure, etc., and a material of the structure.

In recent years, shellfish have been actively cultivated mainly in oysters and scallops, and the treatment of shells generated with this has become serious. For example, some of the discarded shells are used for soil fertilizers, feeds, etc., but most of them are piled up in the vicinity in the fishing area, and there are concerns about the impact on the surrounding environment such as the generation of odors. In particular, oyster shells and scallop shells are generated more than tens of thousands of tons per year, and their effective use is desired.
Recently, various studies have been made on the effective use of such discarded shells. For example, Patent Documents 1 to 4 include civil engineering / cement improvement materials such as ground improvement materials for breakwater foundations, fishing reefs, algae reefs, and various blocks. Many techniques have been proposed for blending waste shells into building structures.
However, when waste shells are used for various civil engineering and building structures using cement, the odor removal operation of the shells becomes complicated, and when cement is used, it is difficult to remove sufficient shell odors. Also, in order to maintain a certain level of strength for use as a civil engineering / building structure, it is necessary to reduce the blending ratio when mixing shellfish, which contains a large amount of salt and itself has low strength, with cement. At most, only about 30% by mass of the total amount of the structure is expected. Therefore, the utilization rate is not sufficient from the viewpoint of large-scale use of discarded shells, and there are still problems in measures against odors of shells.

Therefore, Patent Document 5 uses a material having no water permeability obtained by kneading a crushed shell having a particle size of 5 mm or more and a crushed shell having a particle size of less than 5 mm with a modified sulfur in a molten state and solidifying. Civil engineering / architectural structures have been proposed. In such a structure, it is possible to obtain high strength even when a high amount of waste shells is blended, but it cannot be said that the collection and settlement of aquatic organisms are necessarily sufficient.
On the other hand, Patent Document 6 proposes a porous sulfur material that includes a sulfur material and an aggregate, has continuous voids that show water permeability, and has a porosity of 5 to 40% by volume.
However, in this document, when using a shell pulverized product as an aggregate, it is necessary to use a mixture of a specific fine aggregate and modified sulfur as a sulfur material. However, there is no teaching about a structure that can obtain a structure excellent in collecting and setting up underwater organisms.
JP 11-246277 A JP 2002-136242 A JP 2002-241165 A JP 2002-238398 A JP 2004-323314 A JP 2004-189538 A

  The subject of the present invention is a civil engineering / construction that can contain a high amount of shells that are discarded in large quantities, is expected to be used in large quantities, and has the same workability and strength as concrete, and is excellent in collecting and setting up underwater organisms. Another object of the present invention is to provide a porous modified sulfur solidified body mainly composed of a crushed shell and can be used as a material for the structure and a material for the structure.

In other words, according to the present invention, the modified sulfur material including 20 parts by mass of fine aggregate having a particle size of 5 mm or less and 100 parts by mass of modified sulfur and 30 to 400 parts by mass of modified sulfur exceeds 33% by mass, and the particle diameter of 3 to 10 mm. The main component is a crushed shell material characterized in that it contains 67 mass% or more and less than 80 mass% of the crushed shell material, has continuous voids showing water permeability, and has a porosity of 10 to 40% by volume. A porous modified sulfur solidified body is provided.
Moreover, according to this invention, the structure for civil engineering and building provided with the said porous modified sulfur solidified body is provided.

  The porous modified sulfur solidified body of the present invention is a modified sulfur material containing a specific fine aggregate and modified sulfur in a specific ratio, and a shell pulverized product having a specific particle size range. Therefore, it is possible to expect a large amount of waste shells to be used, and it is possible to obtain workability and strength similar to concrete, and to excel the aquatic organism collection and settlement. Therefore, the porous modified sulfur solidified body of the present invention is useful for civil engineering and construction structures such as various blocks, fishing reefs, algae reefs, and revetment structures.

Hereinafter, the present invention will be described in more detail.
The porous modified sulfur solidified body of the present invention contains a fine aggregate having a particle diameter of 5 mm or less and a modified sulfur material containing modified sulfur in a specific ratio and a shell pulverized product having a specific particle diameter range in a specific ratio. Here, it is satisfied that the modified sulfur material is preferably a non-hazardous material that is verified by a small gas flame ignition test.
The modified sulfur is obtained by polymerizing normal sulfur, for example, sulfur produced naturally or by desulfurization of petroleum or natural gas with a sulfur modifier, and is a reaction product of sulfur and the sulfur modifier. .
Examples of the sulfur modifier include olefin compounds such as dicyclopentadiene (DCPD), tetrahydroindene (THI), or DCPD and cyclopentadiene oligomer (2 to 5 mer mixture), dipentene, vinyltoluene, and dicyclopentene. The mixture with 1 type, or 2 or more types of a kind is mentioned.
As the DCPD, in addition to the simple substance of DCPD, a mixture mainly composed of 2-5 pentamers of cyclopentadiene can be used. Examples of the mixture include those having a content of DCPD of 70% by mass or more, preferably 85% by mass or more, and many commercially available products called dicyclopentadiene can be used.
As the THI, in addition to THI alone, one or more selected from the group consisting of THI, DCPD alone, a polymer of cyclopentadiene and butanediene, and a cyclopentadiene dimer to pentamer. It is also possible to use a mixture of those composed mainly of The THI content in the mixture is usually 50% by mass or more, preferably 65% by mass or more. As the mixture, many commercially available products called tetrahydroindene and by-product oil discharged from an ethyl norbornene production plant can be used.

The modified sulfur can be obtained by melt-mixing sulfur and a sulfur modifier. Under the present circumstances, the usage-amount of a sulfur modifier is 0.1-30 mass% normally with respect to the total amount of sulfur and a sulfur modifier, and the ratio of 1.0-20 mass% is especially preferable.
The melt mixing can be performed using, for example, an internal mixer, a roll mill, a drum mixer, a pony mixer, a ribbon mixer, a homomixer, a static mixer, or the like.
In preparing the modified sulfur, the melt mixing conditions are, for example, a range of 120 to 160 ° C. for sulfur and a sulfur modifier, preferably 130 to 155 ° C., more preferably 140 to 155 so that sulfur is efficiently modified. Desirable is a condition in which the mixture is melt-mixed in the range of ° C and retained until the viscosity at 140 ° C becomes 0.05 to 3.0 Pa · s.

  In the modified sulfur material, the content ratio of the modified sulfur is usually 30 to 400 parts by mass, preferably 30 to 300 parts by mass with respect to 100 parts by mass of the fine aggregate described later. If it is less than 30 parts by mass, uniform kneading with the fine aggregate is not sufficient, and if it exceeds 400 parts by mass, the modified sulfur and the fine aggregate may be separated and it may be difficult to obtain a uniform modified sulfur material. .

The fine aggregate is a fine aggregate having a particle size of 5 mm or less, preferably 1 mm or less. When the particle size of the fine aggregate exceeds 5 mm, remelting cannot be performed quickly. A known technique can be used to adjust the particle size of such fine aggregate, and for example, it can be adjusted with a sieve or the like. The particle size can be defined using a JIS standard sieve.
The fine aggregate is not particularly limited as long as it has the above-mentioned specific particle size, for example, coal ash, silica sand, silica fume, One type or two or more types selected from the group consisting of quartz powder, sand, glass powder, and electrostatic dust ash are preferred.

  The modified sulfur material can be obtained by mixing a melt of modified sulfur and fine aggregate. When the modified sulfur is in a molten state, it can be mixed and solidified with the shell crushed material described later. When the modified sulfur material is solidified, it can be re-melted and then mixed and solidified with the crushed shell.

The shell pulverized product is not particularly limited, and is expected to be consumed in large quantities. For example, one or more kinds selected from the group consisting of scallop shell pulverized product, oyster shell pulverized product, and oyster shell crushed product etc. Use of ground shells is preferred.
The particle size of the crushed shell is in the range of 1 to 20 mm, preferably 3 to 10 mm. Although crushed shells with a particle size of less than 3 mm may be included, if the ratio increases, the desired porosity in the resulting porous modified sulfur solidified product may not be obtained, so crushed shells with a particle size of less than 3 mm It is preferable that a thing is not included as much as possible. On the other hand, crushed shells with a particle size of more than 10 mm may be included, but crushed shells with a particle size of more than 10 mm because the compressive strength of the resulting porous modified sulfur solidified product may decrease if the ratio increases. Is preferably not contained as much as possible. In this case, the bulk density of the shell ground product, in order to increase the strength of the desired material obtained, typically 0.8~1.80g / cm ^3, in particular 1.0~1.80g / cm ³ preferred.

Preparation of the shell pulverized product is, for example, waste shells are washed, coarsely pulverized, dried, etc. if desired, and then pulverized to a predetermined particle size by a pulverization method such as a hammer crusher method, a stone mortar method, a jaw crusher, etc. It can obtain by the method of doing.
In addition to the above-mentioned preparation of the shell pulverized product, it may be carried out at the time of kneading with a modified sulfur material, which will be described later, after washing, roughly pulverizing, drying, etc., if desired.

  The porous modified sulfur solidified body of the present invention contains other aggregates and the like as necessary as long as the desired effects of the present invention are not impaired, in addition to the modified sulfur material and shell pulverized material which are the essential components. May be.

In the porous modified sulfur solidified body of the present invention, the blending ratio of the modified sulfur material and the shell pulverized product is more than 20 mass% and not more than 33 mass%, preferably 25 to 30 mass%. Yes, the crushed shell is 67 mass% or more and less than 80 mass%, preferably 70 to 75 mass%.
When the blending ratio of the modified sulfur material is 20% by mass or less, that is, when the blending ratio of the shell shell pulverized product is 80% by mass or more, there is a possibility that the compressive strength of the resulting porous modified sulfur solidified material varies. On the other hand, when the blending ratio of the modified sulfur material exceeds 33% by mass, that is, when the blending ratio of the shell pulverized product is less than 67% by mass, a desired porosity in the obtained porous modified sulfur solidified product cannot be obtained. There is a risk that the effect of collecting algae and collecting fish will decrease.

The porous modified sulfur solidified body of the present invention has continuous voids exhibiting water permeability and has a porosity of 10 to 40% by volume, preferably 25 to 35% by volume. Here, the presence or absence of continuous voids indicating water permeability is determined by whether or not water passes. The porosity is a value calculated on the basis of the density of the molded body and the material (modified sulfur, fine aggregate, etc.) of each individual.
When there is no continuous void showing the water permeability, or when the porosity is less than 10% by volume, there is a possibility that the collection and settlement action of aquatic organisms may be reduced. On the other hand, when the porosity exceeds 40% by volume, a desired compressive strength may not be obtained.
The porous modified sulfur solidified body of the present invention can usually exhibit an average compressive strength of 20 N / mm ² or more.
The porous modified sulfur concrete substance of the present invention is usually, 1.5 g / cm ³ or higher, preferably have a specific gravity of 1.7~1.8g / cm ^3. When the specific gravity is less than 1.5 g / cm ³ , for example, when a civil engineering / architectural structure is installed in the sea, the structure may move due to waves or the like.

In order to prepare the porous modified sulfur solidified body of the present invention, for example, the modified sulfur material in which the modified sulfur is in a molten state is usually crushed at a temperature of 120 to 160 ° C., preferably 130 to 140 ° C. If necessary, it can be obtained by kneading with other aggregates and solidifying to a desired shape.
In the kneading, it is preferable to preheat crushed shells and the like to about 120 to 155 ° C. and to preheat the mixer to a temperature of 120 to 155 ° C. in order to avoid temperature drop during kneading.
The kneading time is preferably as short as possible within the range allowed by the properties of the product in order to increase the viscosity by polymerization of the modified sulfur and to avoid curing.
However, if the mixing time is too short, the mixture is not sufficiently mixed, and the resulting porous modified sulfur solidified body may not be a continuous phase and may not be in a uniform porous shape. Therefore, it is preferable to appropriately determine the mixing time so that the obtained porous modified sulfur solidified body is preferably a complete continuous phase and has a uniform porous shape.
The mixer used for the kneading is not particularly limited as long as kneading can be sufficiently performed, and preferably used for solid-liquid stirring. For example, an internal mixer, roll mill, ball mill, drum mixer, screw extruder, pug mill, pony mixer, ribbon mixer, kneader and the like can be used.
The solidification can be performed by introducing the kneaded material into a desired formwork or the like and cooling and solidifying. The molding at the time of cooling and solidification may be performed while appropriately applying vibration or irradiating ultrasonic waves.

The civil engineering / architecture structure of the present invention may be provided with the porous modified sulfur solidified body of the present invention, and a part or all of the structure is composed of the porous modified sulfur solidified body of the present invention. The
The civil engineering / architecture structure of the present invention preferably includes, for example, various types of blocks such as rooting blocks, wave-dissipating blocks, covering blocks, artificial reefs, fishing reefs, algae reefs, structures for revetment, etc. It may be a tubular molded product such as a fume tube or a manhole, a box culvert, a panel material, or a tile.

Hereinafter, although an example and a comparative example explain concretely, the present invention is not limited to these examples.
Examples 1-2 and Comparative Examples 1-3
95 kg of solid sulfur was placed in a closed stirring and mixing vessel, heated at 120 ° C. and dissolved, and then maintained at 130 ° C. Subsequently, 5 kg of dicyclopentadiene heated and dissolved at about 50 ° C. was slowly added and stirred gently for about 10 minutes. After confirming that the temperature increase due to the initial reaction had converged, the temperature was raised to 140 ° C. . The reaction starts, the viscosity gradually increases, and when the viscosity reaches 0.1 Pa · s in about 1 hour, the heating is stopped immediately, poured into an appropriate mold or container and cooled at room temperature to obtain modified sulfur. It was.
Next, 20 kg of coal ash having a particle diameter of 1 mm or less preheated to 140 ° C. and a melt obtained by reheating 40 kg of the modified sulfur to 130 ° C. in a kneader (Pro-Sharer mixer) maintained at 140 ° C. Almost simultaneously. Subsequently, the mixture was kneaded for 10 minutes, cooled, and crushed to 100 mm or less to prepare a modified sulfur material.
On the other hand, the scallop shell was washed, coarsely pulverized with a jaw crusher, and dried for 4 hours with a thermostatic chamber. Next, crushed shellfish with a particle size of 3 to 10 mm, which was pulverized with a hammer crusher and adjusted in particle size using a JIS sieve, was prepared.
The modified sulfur material was introduced into the batch type stirring and mixing tank so as to have the ratio shown in Table 1, heated at 120 ° C and dissolved, and then maintained at 130 ° C. Subsequently, the prepared shell crushed material was introduced so as to have the ratio shown in Table 1 in a state preheated to 130 ° C., and kneaded at 130 ° C. for 10 minutes.
The obtained kneaded material was put into a predetermined mold and naturally cooled for 1 hour to obtain a cylindrical test body having a diameter of 5 cm and a height of 10 cm.
With respect to the obtained specimen, the porosity was calculated based on the density of the specimen and the material (modified sulfur, fine aggregate, and crushed shell), respectively. Moreover, the presence or absence of the continuous space | gap which has water permeability was judged by whether water passed a test body. Further, the compressive strength of the specimen was measured according to JIS A1108, and the specific gravity was measured according to JIS A1161. The results are shown in Table 1.

Similar to the specimen prepared above, 1 m × 1 m × 0.45 m blocks were prepared and each was installed in the sea. A block prepared in the same way with cement concrete was also installed in the sea.
After 60 days, the area ratio of algae grown on the block surface was measured, and the effect of collecting fish was observed. The fish collection effect was visually observed, with 3 being good, 2 being normal, and 1 being bad. Furthermore, the movement from the installation position by the wave of the block was observed, and 3 points were not moved, 2 points were slightly moved, and 1 point was fast moving. The results are shown in Table 2.

表１より、改質硫黄資材の割合が２０質量％である比較例１では、透水性及び空隙率は十分であったが、圧縮強度にばらつきが見られ、平均圧縮率も低いものであった。改質硫黄資材の割合が３５質量％である比較例２では、圧縮強度はばらつきが見られず、平均圧縮率も高いものであったが、透水性及び空隙率が十分でなかった。一方、改質硫黄資材の割合が２５質量％及び３０質量％である実施例１及び２では、透水性、空隙率及び圧縮強度のいずれも十分なものであった。

From Table 1, in Comparative Example 1 in which the ratio of the modified sulfur material was 20% by mass, the water permeability and the porosity were sufficient, but the compressive strength was uneven and the average compressibility was low. . In Comparative Example 2 in which the proportion of the modified sulfur material was 35% by mass, the compressive strength did not vary and the average compressibility was high, but the water permeability and porosity were not sufficient. On the other hand, in Examples 1 and 2 in which the ratio of the modified sulfur material was 25% by mass and 30% by mass, all of water permeability, porosity and compressive strength were sufficient.

表２より、改質硫黄資材の割合が２０質量％である比較例１及び２５質量％である実施例１では、藻類の着生及び魚の蝟集効果は良好であった。また、波による移動も若干なものであった。改質硫黄資材の割合が３５質量％である比較例２及びセメントコンクリートを用いた比較例３では、波による移動は認められなかったが、藻類の着生及び魚の蝟集効果は実施例１及び２に比較して劣るものであった。改質硫黄資材の割合が３０質量％である実施例２では、波による移動が認められず、藻類の着生及び魚の蝟集効果も十分なものであった。

From Table 2, in Comparative Example 1 in which the ratio of the modified sulfur material is 20% by mass and Example 1 in which it is 25% by mass, the algae settlement and the fish collection effect were good. In addition, the movement by waves was slight. In Comparative Example 2 where the proportion of the modified sulfur material is 35% by mass and Comparative Example 3 using cement concrete, no movement due to waves was observed, but the effects of algae growth and fish collection were the same as in Examples 1 and 2. It was inferior to In Example 2 in which the proportion of the modified sulfur material was 30% by mass, no movement due to waves was observed, and the effects of algae growth and fish collection were sufficient.

Claims (6)

  More than 20% by mass of the modified sulfur material including 100 parts by mass of fine aggregate having a particle size of 5 mm or less and 30 to 400 parts by mass of modified sulfur, and 33% by mass or less, and 67% by mass of crushed shells having a particle size of 3 to 10 mm. The porous modified sulfur-solidified product comprising a crushed shell as a main component, characterized in that it has continuous voids that show water permeability and has a porosity of 10 to 40% by volume. .   The fine aggregate is one or more selected from the group consisting of coal ash, silica sand, silica fume, quartz powder, sand, glass powder and electrostatic dust ash, and the shell pulverized product is scallop The porous modified sulfur solidified material according to claim 1, which is one or more kinds of crushed shells selected from the group consisting of crushed shells, oyster shells and crushed shellfish shells. The porous modified sulfur solidified body according to claim 1 or 2, having an average compressive strength of 20 N / mm ² or more. The porous solidified solid body according to any one of claims 1 to ^{3, wherein the} specific gravity is 1.5 g / cm ³ or more.   A civil engineering / building structure comprising the porous modified sulfur solidified body according to any one of claims 1 to 4. The civil engineering / architecture structure according to claim 5, wherein the civil engineering / architecture structure is a block, fishing reef, algae reef, or a revetment structure.