WO2003072522A1 - Method for producing modified sulfur containing binding agent and method for producing modified sulfur containing material - Google Patents

Abstract

A method for producing a modified sulfur containing material which comprises a step (A) of melting and mixing sulfur and cyclopentadiene at 135 to 155°C, a step (B) of cooling the resultant molten product having a viscosity of 0.05 to 1.2 Pa · s at 140°C to a temperature of 135°C or lower, to produce a modified sulfur containing binding agent, a step (C) of mixing and melting the binding agent and an aggregate at a temperature of 135 to 155°C, while maintaining a viscosity of the binding agent at 140°C within the range of 0.05 to 1.2 Pa · s, and a step (D) of cooling the product to 135°C or lower. A modified sulfur containing material produced by the above method is good in mechanical strength, water-intercepting property, ignition resistance and the resistance to sulfur oxidizing bacteria, and thus can be used as a civil engineering or building material, even when a domestic or industrial waste is used as a law material aggregate, and the method allows the modified sulfur containing material and the binding agent to be produced by the use of a simple and easy control.

Description

 Specification

 Method for producing modified sulfur-containing binder and method for producing modified sulfur-containing material

 The present invention relates to a method for producing a modified sulfur-containing binder modified with dicyclopentadiene, and a method for producing a modified sulfur-containing material that enables general and industrial waste to be reused as civil engineering or construction materials. Related to manufacturing method.

Background art

 Sulfur dissolves above 119 ° C and is a solid at room temperature, and its use as civil engineering and construction materials has been attempted. For example, use as a pavement material (U.S. Pat.No. 4,290,816), a building material (Japanese Patent Publication No. 55-49024), or a binder for sealing waste (Japanese Patent Publication No. 62-15274) has been considered. I have.

 However, a binder made of sulfur alone has ignitability because the outer surface of the obtained molded product is sulfur, and further has poor mechanical strength and resistance to sulfur-oxidizing bacteria. And its use is not necessarily expanding.

 Therefore, many additive compounds have been studied to improve such problems. Dicyclopentadiene as an additive for incorporation is inexpensive and economical, and has a good effect on mechanical strength as shown in New Uses of Sulfur-II, 1978, p68-77. Are known. In addition, there is also an example in which Biertoluene, dipentene, and other olefin oligomers are added to improve the properties of sulfur and used in paving materials, adhesives, and sealing materials (Japanese Patent Publication Nos. 2-25929 and 2-28529). Are known. Pavement materials using a mixture of asphalt and sulfur have been put to practical use.

 Until now, sulfur has been known for its use as a binder, and it has been mixed with various types of aggregate to produce molded products and used as civil engineering construction materials. However, moldings using a sulfur-only binder have many problems in physical properties and their use is limited.

 Sulfur has an ignition point of 207 ° C and a spontaneous ignition temperature of 245 ° C, so it is ignitable, and the sulfur exposed on the surface is flammable and has a problem in flammability. Sulfur exhibits high strength in a stable solid state if there are no defects, but when solidified by cooling from a liquid state, three types of orthorhombic, monoclinic, and amorphous sulfur are mixed, and cooling conditions However, these ratios change with the passage of time, and because they change with the passage of time, there is a problem that defects are likely to occur in practice and are brittle.

The most stable sulfur in the solid state is orthorhombic sulfur, which is among the three Due to the highest density, gaps occur over time and the mechanical strength decreases, and in extreme cases cracks occur. In addition, water penetrates into the gaps and dissolves the sealed substances inside, reducing the sealing ability of harmful substances.In addition, there is a problem that sulfuric acid bacteria existing in soil or water enter and corrode the surface. .

 Therefore, a method of adding dicyclopentadiene is being studied. The reaction between dicyclopentadiene and sulfur is said to be a kind of polymerization reaction. Dicyclopentadiene and sulfur first react, and then the sulfur is polymerized by a radical chain reaction. Therefore, the reaction between dicyclopentadiene and sulfur rapidly increases in temperature with a large amount of heat, and a sharp increase in viscosity occurs. As a result, the reaction cannot be controlled and rapidly solidifies to a state where molding cannot be performed. In order to prevent this, a method of adding an olefin oligomer has been studied (Japanese Patent Publication No. 2-28529). However, the production conditions when dicyclopentadiene is added have not been sufficiently studied, and the relationship between the reaction conditions such as the concentration of dicyclopentene and the temperature and the desired properties of the binder to be produced have been investigated. Is not fully understood.

 In addition, when the cooled and solidified binder is reheated to be mixed with the aggregate, the polymerization reaction with the redicyclic pentagen starts and the hardening proceeds. In this case, the proper properties of the binder and the manufacturing conditions for mixing with the aggregate have not been established.

Further, it has not been known to use a binder improved by disposable pentagen as a binder for sequestering general and industrial wastes, and its production conditions have not been established. Generally, general and industrial wastes are disposed of by landfill or incineration. However, the number of disposal sites for them is becoming smaller and smaller, and their reuse is required as much as possible. For example, in the case of wastes such as steel slag, coal ash, and incinerated ash, the molded products can be used for civil engineering landfills, construction materials, etc., using compressive strength, bending strength, tensile strength, impact resistance, etc. Requires mechanical strength. In addition, water barriers to prevent the elution of heavy metal compounds contained in industrial waste, flame retardancy that does not ignite over open flames, and durability against sulfur oxidizing bacteria that corrode surface sulfur in soil and in the sea are required. You. In particular, incinerated ash contains harmful substances such as heavy metals and dioxins, and when used for landfill, it is necessary to suppress its elution. Steel slag discharged from the steel industry is used for pavement aggregates and civil engineering materials. 1 When wet with water, it produces yellow water due to polysulfides, which has an adverse effect on the environment. Therefore, there is a need for a binder that satisfies the above-mentioned requirements for using these industrial wastes as civil engineering construction materials and that enables recycling. Disclosure of the invention

 An object of the present invention is to prepare civil engineering and construction materials by using general and industrial wastes as raw material aggregates, and to provide the materials with mechanical strength, water barrier, ignition resistance, and sulfur oxidation resistance. It is an object of the present invention to provide a production method capable of efficiently obtaining a modified sulfur-containing binder that can impart bacterial properties and can be used for sealing general and industrial wastes by easy reaction control.

 Another object of the present invention is that even when general and industrial wastes are used as raw material aggregates, they have good mechanical strength, water-blocking properties, resistance to ignition, and resistance to sulfur-oxidizing bacteria. An object of the present invention is to provide a production method capable of obtaining a modified sulfur-containing material that sufficiently satisfies the required performance as a material by simple control.

 According to the present invention, a step (A) of melting and mixing 100 parts by weight of sulfur and 2 to 20 parts by weight of dicyclopentadiene at 135 to 155 ° C, and a step of 140 ° C of the melt obtained in step (A) (B) obtaining a modified sulfur-containing binder by cooling to 135 ° C. or lower after the viscosity at 0.05 to 1.2 Pa-s in step (B), to provide a method for producing a modified sulfur-containing binder.

 Further, according to the present invention, the modified sulfur-containing binder and the aggregate obtained in the step (A), the step (B), and the step (B) are in a weight ratio; Melt mixing at a temperature of 135 to 155 ° C at a temperature of 135 to 155 ° C while maintaining the viscosity of the modified sulfur-containing binder at 140 ° C within a range of 0.05 to 1.2 Pa's (C); (C) cooling the molten mixture to 135 ° C. or lower.

 Further, according to the present invention, a step (X) of melt-mixing sulfur, dicyclopentadiene and aggregate at 135 to 155 ° C for 0.5 to 5 hours, and a step of reducing the molten mixture of the step (X) to 135 ° C or less. Cooling (Y).

Preferred embodiments of the invention

 The method for producing a modified sulfur-containing binder according to the present invention includes a step (A) of melt-mixing a specific ratio of sulfur and a dicyclopentene under specific conditions, and cooling the melt obtained in step (A) under specific conditions. (B).

 The sulfur used in the production method of the present invention is ordinary sulfur alone, and for example, natural sulfur, sulfur generated by desulfurization of petroleum or natural gas can be used.

The dicyclopentene used in the production method of the present invention may be a simple substance of dicyclopentene or a mixture mainly composed of a cyclopentadiene 1 to tetramer. The mixture contains pentagen at the outlet of the nozzle generally at least 70 mass%, preferably at least 85 mass%. Including. Therefore, many commercially available products called so-called dicyclopentadiene can be used. In step (A), the proportion of dicyclopentadiene used is 2 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of sulfur. The properties of the resulting binder and the modified sulfur-containing material to be mixed with the aggregate, which will be described later, mixed with the aggregate, such as flame retardancy, water barrier properties, and resistance to sulfur oxidation bacteria, depend on the amount of dicyclopentadiene used. Relatedly, the higher the usage, the better each performance. However, the improvement effect is saturated when the amount of dicyclopentadiene used is about 10 parts by weight with respect to 100 parts by weight of sulfur.

 The amount of dicyclopentadiene used can be determined not only from the controllability of the reaction and the reaction time but also from the performance of the product. The viscosity of the molten sulfur increases as the modification of the sulfur with dicyclopentadiene proceeds. The rate of increase in viscosity is also related to the amount of dicyclopentadiene, and the higher the amount of dicyclopentadiene added, the faster. For example, at 140 ° C, if the amount of dicyclopentadiene is less than 2 parts by weight with respect to 100 parts by weight of sulfur, the viscosity does not reach O.lPa's even after 10 hours or more. On the other hand, when the amount of dicyclopentadiene is 10 parts by weight or more, the viscosity reaches O.lPa's in 0.5 to 3 hours. It is preferable that dicyclopentadiene be added in a small amount because the handling during the production is easy. However, in order to produce efficiently and in a short time, the addition amount may not be too small. In order to exhibit elastic strength from the viewpoint of the performance of the product, the ratio of dicyclopentadiene is preferably 2 to 10 parts by weight based on 100 parts by weight of sulfur. If the amount of dicyclopentadiene is less than 2 parts by weight, the strength is not sufficiently improved. The strength of the obtained elastic body becomes highest when dicyclopentadiene is 5 to 10 parts by weight with respect to 100 parts by weight of sulfur. If the amount of dicyclopentadiene exceeds 10 parts by weight, viscous properties are added in addition to elasticity, so that the product becomes a viscoelastic body, easily deformed, and increases in stickiness and is not easily broken. On the other hand, if the amount of dicyclopentene exceeds 20 parts by weight, viscous properties are remarkably exhibited, and the rate of increase in viscosity during production is so large that reaction control becomes difficult. Therefore, the amount of dicyclopentene used is determined in consideration of these properties.

In the step (A), the melt mixing of the sulfur with the dicyclopentene is carried out in a range of 135 to 155 ° C until the viscosity of the melt at 140 ° C becomes 0.05 to: 1.2 Pa's. Specifically, first, sulfur is heated and melted. When the solid sulfur is calo-heated, a phase change from solid to liquid starts at 119 ° C, so the sulfur is liquefied and the whole is stirred, and the temperature is raised to about 130 ° C while measuring the viscosity with a B-type viscometer, for example. To rise. Next, a predetermined amount of dicyclopentadiene is added little by little. Below 135 ° C, sulfur does not readily denature. Ie 120 ~: 135 ° C temperature In the temperature range, the polymerization reaction between sulfur and dicyclopentene is slow, no sudden heat generation and no increase in viscosity occurs, but a slight increase in temperature and increase in viscosity occurs to maintain almost constant viscosity. After confirming that no heat is generated, gradually raise the temperature to 135 to 155 ° C. If the temperature exceeds 155 ° C, the viscosity rises rapidly and control becomes difficult. The viscosity rise rate is related to the reaction temperature, and the higher the temperature, the faster. From the above points, the melting and mixing temperature of sulfur and dicyclopentadiene needs to be 135 to 155 ° C in order to efficiently modify sulfur.

 The time for melt mixing varies depending on the amount of dicyclopentadiene used and the melting temperature. For example, 100 parts by weight of sulfur and 5 parts by weight of pentagen with dicyclopentine require about 15 hours at 135 ° C, about 5 hours at 140 ° C, about 2 hours at 145 ° C, and about 0.5 hours at 150 ° C. Each viscosity reaches O.lPa's. A particularly preferred temperature range from the viewpoint of temperature control and production time is 140 to 5 ° C. The end of the reaction by melt mixing can be determined by the viscosity of the melt. The viscosity is in the range of 0.05 to 1.2 Pa's at 140 ° C., but the optimum viscosity is 0.08 to 0.5 Pa's from the viewpoint of the strength of the molded product produced from the obtained binder and the workability of the production process. It is. When the viscosity is less than 0.05 Pa's, the strength of the civil engineering construction material using the obtained binder becomes low, and the modifying effect by dicyclopentadiene becomes insufficient. As the viscosity increases, denaturation progresses, and the strength of the obtained binder also increases. However, when the viscosity exceeds 1.2 Pa-s, stirring and mixing become difficult, workability is remarkably deteriorated, and the modification effect is saturated.

 As the mixer used for the melt mixing, a known mixer can be used as long as sufficient mixing is possible, and a mixer mainly used for liquid stirring is preferably used. For example, internal mixers, roll mixers, drum mixers, bonnie mixers, ripon mixers, homomixers, and static mixers can be mentioned.

 The cooling in the step (B) can be performed at a temperature of 135 ° C. or lower, which is lower than the reaction temperature, so that the melt-mixing is completed when the above-mentioned specific viscosity is reached, so as not to cause high viscosity. The lower limit of the cooling temperature is not particularly limited, and may be about room temperature.

 The binder obtained by the production method of the present invention contains modified sulfur obtained by reacting sulfur with dicyclopentadiene and may contain pure sulfur, and is also referred to as sulfur cement. The binder is useful as a civil engineering and construction material. For example, it can be used as a pavement material, a building material, or a material for sealing waste by mixing with various aggregates.

The method for producing the modified sulfur-containing material of the present invention comprises the steps of: (a) combining the binder obtained in step (A) and step (b) with the aggregate at a specific ratio of 135 to 155 ° C. Viscosity of binder at 140 ° C (C) in which the melt mixture is maintained while maintaining the temperature within the range of 0.05 to 1.2 Pa's, and a step (D) in which the melt mixture in the step (C) is cooled to 135 ° C or lower (hereinafter referred to as `` No. Method 1), the step of melting and mixing sulfur, dicyclopentadiene and aggregate under specific conditions (X), and the step of cooling the molten mixture of step (X) to 135 ° C or lower (Y) (Hereinafter referred to as “second method”).

 The aggregate used in the first and second methods is not particularly limited as long as it can be used as the aggregate, but it is preferable to use reusable industrial waste. Examples of industrial waste include incinerated ash, incinerated fly ash, molten fly ash generated from municipal solid waste high-temperature melting furnaces, coal ash discharged from the electric power business and general industry, fluidized sand used in fluidized bed incinerators, Examples include soil contaminated with heavy metals, grinding waste, by-products from the production of various metals, or mixtures thereof. Examples of the by-products at the time of producing the various metals include steel slag, steel dust, ferro-nickel slag, aluminum dross, steel slag, and a mixture thereof. In the production method of the present invention, waste such as iron slag, incinerated ash, and coal ash can be reused while being harmless as aggregate. Iron and steel slag is slag by-produced from the steelmaking industry, and includes blast furnace slag, open hearth slag, converter slag, and the like. The main components of steel slag include acids such as silica, alumina, calcium oxide and iron oxide, and other inorganic sulfur.

 Incinerated ash is discharged from various types of combustion furnaces such as municipal solid waste incinerators or industrial waste incinerators, and its main component is oxides such as silica, alumina, calcium calcium oxide, and iron oxide, and lead, cadmium, and arsenic. Content of harmful metals such as The incinerated ash is landfilled at a final disposal site that does not emit sewage. In the present invention, the incinerated ash can also be used as aggregate.

 Coal ash is discharged from various types of coal-fired combustion furnaces for power generation, heating, etc., and can be used as concrete or as a mixture of civil engineering materials.

 The aggregate used in the present invention includes other aggregates other than those described above, for example, clay minerals, activated carbon, carbon fiber, glass firer, vinyl acetate, aramide, sand, gravel, and equivalent harmful substances. Various inorganic and organic materials can be used.

In the step (C) of the first method, the mixing ratio of the binder and the aggregate is 1 to 5: 5 to 9 by weight. The strength of the material obtained is highest when the proportion of binder is such that it fills the voids of the aggregate in a close-packed structure. If the ratio of the binder is less than 10% by weight, that is, if the aggregate exceeds 90% by weight, the surface of the inorganic material as the aggregate cannot be sufficiently wetted, and the aggregate is exposed and the strength is sufficient. It does not develop and water barrier cannot be maintained. On the other hand, if the ratio of binder exceeds 50% by weight, that is, if the aggregate is less than 50% by weight, the strength will decrease. The mixing ratio of the binder and the aggregate varies depending on the type of the aggregate, and can be appropriately selected from the above range according to the type of the aggregate. For example, when steel slag is used as the aggregate, the mixing ratio of the aggregate is preferably about 15 to 25% by weight.

 In the step (C), the viscosity at the time of melt-mixing the binder and the aggregate increases with time, so that it is necessary to set the viscosity in the optimum viscosity range in which the handling is easy. The viscosity is such that the viscosity at 140 ° C is in the range of 0.05 to 1.2 Pa's. If the viscosity is less than 0.05 Pa's, the strength of the resulting modified sulfur-containing material decreases, and the modifying effect is insufficient. As the viscosity increases, the strength of the obtained material also increases. However, when the viscosity exceeds 1.2 Pa's, stirring during production becomes difficult, and workability is markedly impaired.

 In the step (C), it is preferable that in the melt mixing, both materials of the binder and the aggregate are preheated in order to avoid a temperature drop during mixing. Aggregate should be preheated to 120-: L55 ° C, binder should be preheated to 120-155 ° C as short as possible to avoid the progress of the reaction, and the mixer should also be preheated to 120-155 ° C. Is preferred. The preheated components are introduced into the mixer almost simultaneously, and can be mixed at 135 to 155 ° C, preferably for 5 to 30 minutes. At 155 ° C or lower, higher temperatures have higher fluidity and mixing efficiency of the binder, and the melting and mixing are completed in a short time. However, at higher temperatures, the hardening reaction proceeds. At a low temperature, the progress of the curing reaction is slow instead of a decrease in fluidity. Thus, the preferred temperature range is 140-: L45 ° C. In this case, the preheating range of the aggregate is preferably 140 to 145 ° C, and the preheating range of the binder is preferably 135 to 140 ° C.

 The mixing time is desirably as short as possible within the range permitted by the properties of the product in order to avoid increasing the viscosity and avoiding hardening due to the polymerization of sulfur with the dicyclopentene pentadiene. On the other hand, if the mixing time is too short, the binder and the aggregate are not sufficiently mixed, and the resulting material does not form a continuous phase, resulting in a gap or a smooth surface. If the mixing is sufficient, the material becomes a perfect continuous phase and the surface is smooth, so the mixing must be determined appropriately in consideration of the performance of the obtained material. In the first method, other components can be mixed as desired in addition to the binder and the aggregate. In this case, a method of re-melting the binder and mixing other components, or a method of mixing other components before cooling in the step (B) may be used.

The mixer used in the first and second methods is not particularly limited as long as sufficient mixing is possible, and preferably a mixer for solid-liquid stirring can be used. For example, internal mixer, mouth mill, pole mill, drum mixer, screw extruder, pug mill, poemi A mixer, Ripon mixer, kneader, etc. can be used.

 In step (X) of the second method, the melt mixing of sulfur, dicyclopentadiene and aggregate is carried out by simultaneously mixing the aggregate and modifying sulfur, or by melting and mixing sulfur and dicyclopentadiene. (A) and a step (X2) of mixing the aggregate with the molten mixture of the step (XI) and melt-mixing under specific conditions. As the sulfur, dicyclopentadiene and aggregate that can be used in these methods, those similar to those described above are preferably mentioned. It is also preferable that the amount of each material used is appropriately selected from the above-mentioned range. In short, the charge ratio of the dicazene pentagen is usually 2 to 20 parts by weight, preferably 5 to 10 parts by weight, per 100 parts by weight of sulfur. It is desirable that the mixing ratio of the aggregate is appropriately selected so that the weight ratio of the total amount of sulfur and dicyclopentadiene to the amount of the aggregate is 1 to 5: 5 to 9. In the second method, in the case where sulfur, dicyclopentene and aggregate are simultaneously melt-mixed, unlike the first production method in which a modified sulfur-containing binder is produced in advance, the modified sulfur-containing material is produced in one step. it can. Therefore, in the second method, the production process can be simplified, and the modified sulfur-containing material can be obtained in a short time as a whole even if the melting and mixing time is lengthened.

 In the step (X), the melt mixing is preferably sufficiently stirred or kneaded so that the entire melt becomes a uniform temperature, the melting temperature is 135 to 155 ° C, and the mixing time is 0.5 to 5 hours. If the mixing time is less than 0.5 hours, the pentadene, the sulfur mouth and the aggregate are not sufficiently mixed, and the resulting material does not form a continuous phase, and a gap is formed or the surface is not smooth. If the melt-mixing is sufficient, the material becomes a perfect continuous phase and the surface is smooth. On the other hand, if the mixing time exceeds 5 hours, the modification of sulfur progresses, the viscosity of the modified sulfur increases, and furthermore, it hardens and the workability decreases.

 In the step (X), if the aggregate is present when the sulfur is modified with the dicyclopentene, it is very difficult to directly measure the progress of the reaction between the sulfur and the dicyclopentene by the viscosity. However, the reaction between sulfur and dicyclopentadiene is essentially as described above. To control the reaction, the temperature, mixing method and mixing time must be strictly determined while predicting the progress of sulfur modification. It can be achieved by controlling. For example, the melt mixing temperature and time are 3-5 hours at 140 ° C, 150. C for 45-90 minutes.

Specific examples of the melt-mixing in the step (X) include, for example, a method in which the sulfur heated at 125 to 135 ° C [I-heated sulfur, and the dicyclopentadiene melted at 40 to 50 ° C are mixed at 135 to 155 ° C. Almost at the same time, put the mixture into a preheated mixer, and then put the pre-ripened aggregate to about 125 to 155 ° C. A method of melting and mixing at a temperature of 155 ° C. for 0.5 to 5 hours is exemplified. As a more preferable melt mixing method, a kneader is used in an amount of 140 to 150. Preheating at C and melt-mixing at a temperature of 145 to 155 ° C. The reason why sulfur and dicyclopentadiene are first mixed is that the presence of the aggregate does not hinder the sulfur polymerization reaction.

 In step (D) or step (Y) of the first or second method, the molten mixture of step (C) or step (X) is cooled to 135 ° C or less. The lower limit of the cooling temperature is not particularly limited, and may be about room temperature. In the step (D) or the step (Y), the modified sulfur-containing material obtained by cooling using a desired mold, a granulating device, or a molding device is converted into a molded product, a pellet, a crushed product, or the like having a desired shape. It can be granular. In the step (D) and the step (Y), the cooling is carried out at a predetermined flow state by lowering the temperature and mixing at 120 to 135 ° C. in order to avoid an excessive increase in the viscosity of the modified sulfur. You may go after continuing for a while.

 The granulating device is not particularly limited, and for example, a rolling type device equipped with a drum or an inclined plate, and a vibration type device equipped with a horizontal plate or an inclined plate can be used.

 When the materials obtained by the first and second methods are used as granules, the strength of each granule is high and the grain size of these granules can be adjusted, so it is suitable as a construction material and can be used in the same way as quarrying . In addition, the materials obtained by the first and second methods must be directly exposed to the outside, because the modified aggregate basically blocks the aggregate from coming into contact with the surrounding water. And the elution of contained harmful substances can be suppressed to some extent. Therefore, this material does not affect its hardening and optimum moisture content when mixed with cementitious materials such as cement, concrete, gypsum and the like.

Conventionally, when a hardened product is obtained using a cement-based material and incinerated ash, it is important to adjust the water content to an optimum value by the pozzolan reaction and the sulfopozolan reaction. In particular, when mixing incinerated ash from municipal solid waste with high water absorption, it is very difficult to adjust the water content. For example, when drying and mixing incinerated ash from municipal solid waste, the incinerated ash absorbs more moisture than the cementitious mixture, resulting in a shortage of water. However, the water content of the cementitious mixture becomes excessive and in any case, the performance as a construction material may be impaired. When the aggregate containing harmful substances absorbs moisture, it expands and becomes impossible to use as aggregate. The material obtained by the production method of the present invention can be detoxified by using modified sulfur even for an aggregate containing a harmful substance, and thus is extremely useful for recycling the aggregate. The material obtained by the present invention can be used as a panel material, a floor material, a wall material, a roof tile, an underwater structure, for example, if it is a granular material, by taking advantage of a characteristic that can be manufactured into an arbitrary structure if it is a molded body. It can be used as landfill material, roadbed material, embankment material or aggregate for concrete.

Example

 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The present invention is not limited thereto. The respective binders and molded products produced in the examples were measured and evaluated according to the following methods. Tables 1 to 3 show these results.

 Compressive strength: A cylindrical specimen of φ2.5 X 6.25 cm was prepared, and measured on the 7th day after preparation using a 30-ton pressurized tensile strength measuring instrument. The rate at which the sample shrunk before crushing was defined as the strain rate. Water absorption: を Prepare a 2.5 x 6.25 cm cylindrical specimen, immerse it in water at room temperature for a certain period of time, remove it, and wipe off the surface moisture. After that, the weight change was measured and the weight increase was calculated as the water content.

Resistance to sulfur-oxidizing bacteria _{of: NH 4 C12.0g, KH 2 P0} 4 4.0g, MgCl 2 - 6H 2 O 0.3 g, CaCl 2 - 2H 2 0 0.3g, FeCl 2 -4H 2 0 O.Olg及Pi ion exchange A 100-mL culture solution prepared by adjusting a solution consisting of 1.0 L of water to pH 3.0 with hydrochloric acid and a prism sample of 2 cm X 2 cm X 4 cm are placed in a 500-mL baffle flask and inoculated with an inoculum (sulfur-oxidizing bacteria: Thiobacillus thiooxidans IFO 12544). After the inoculation, the cells were subjected to rotary shaking culture (170 rpm) in a 28 ° C constant temperature room, and the pH change and the state of the material after the inoculation were examined. At this time, a decrease in the pH means that sulfur was oxidized by the sulfur oxidizing bacterium to generate sulfate ions.

 Flame retardancy: Evaluated in accordance with the ignitability test for the evaluation of flammable solids 0 Class 2) in the Fire Service Law. Class 1 flammable solids that ignite within 3 seconds and continue burning for 10 seconds or more, and Class 2 flammable solids that ignite within 3 seconds and exceed 3 seconds and continue burning Was determined to be "ignitable", and those that ignited for more than 10 seconds and those that did not continue burning were rated "no danger".

 Example 1

950 g of solid sulfur was put in a stirring and mixing tank, dissolved at 120 ° C, and kept at 130 ° C. The viscosity at that time was measured by a B-type viscometer and was found to be 0.002 Pa's. Subsequently, 50 g of dicyclopentadiene heated and dissolved at about 50 ° C was slowly added, and the mixture was gently stirred for about 5 minutes to confirm that the temperature did not rise, and then the temperature was raised to 140 ° C. The reaction was started and the viscosity gradually increased.When the viscosity reached O.lPa's in about 5 hours, the heating was stopped immediately and an appropriate The mixture was poured into a mold or a container and cooled at room temperature to obtain a binder A.

 Next, kneading the aggregate containing 670 g of blast furnace slag and 130 g of coal ash preheated at 140 ° C, and the melt obtained by reheating 200 g of the binder A described above at 130 ° C and dissolving it at 140 ° C. They were put into the cabin almost simultaneously. Subsequently, the mixture was kneaded for 20 minutes, poured into a column having a diameter of 5 cm and a height of 10 cm, and cooled to prepare a specimen. This specimen is referred to as molded article A.

 Example 2

 All operations were performed in the same manner as in Example 1 except that the amount of sulfur was set to 900 g and the amount of dicyclopentene was set to 100 g, to prepare a binder B and a molded product B corresponding to the binder A and the molded product A.

 Example 3

 Except that the amount of sulfur was set to 800 g and the amount of di-entrance pentadiene was set to 200 g, the same operation as in Example 1 was carried out to prepare a binder C and a binder C and a molded product C corresponding to the molded product A.

 Comparative Example 1

 A binder D containing no dicyclopentadiene and a molded article D were prepared in the same manner as in Example 1 except that the amount of sulfur was 1000 g and no dicyclopentane was used.

 Example 4

 Aggregate consisting of 190 g of sulfur dissolved by heating to 120 ° C, 10 g of dicyclopentadiene heated and melted at about 50 ° C, and 670 g of blast furnace slag and 130 g of coal ash preheated at 140 ° C. Was charged almost simultaneously into a kneader maintained at 140 ° C. After kneading for about 5 minutes, the temperature was raised to 150 ° C, and after reaching 150 ° C, kneading was continued for 60 minutes. The obtained kneaded material was poured into a cylindrical shape having a diameter of 2.5 cm and a height of 10 cm, and cooled to prepare a molded product E as a specimen. The time required for production was 65 minutes.

 Example 5

 A molding F corresponding to the molding E was prepared in the same manner as in Example 4 except that the amount of sulfur was changed to 180 g and the amount of dicyclopentadiene was changed to 20 g. The time required for production was 65 minutes.

 Example 6

A molded product G corresponding to the molded product E was prepared in the same manner as in Example 4, except that the amount of sulfur was 160 g and the amount of pentacene having a disc-opening was 40 g. The time required for production was 65 minutes.

表 1より、 実施例 1〜6で得られた結合材及ぴ成型物は、 比較例 1の結合材及ぴ成 型物より圧縮強度が高いか、 或いは歪み率が大きく良好であった。 また吸水率も非常 に小さく良好であった。

Table 1 shows that the binders and molded products obtained in Examples 1 to 6 were higher in compressive strength or larger in strain rate than the binders and molded products of Comparative Example 1 and were good. The water absorption was also very small and good.

 Table 2

From Table 2, it was found that the binder and the molded product obtained in Example 1 and Example 4 had a smaller pH drop and higher sulfur-resistant bacteria than the binder and the molded product of Comparative Example 1.

Table 3

 X: No ignition, 〇: Ignition

 From Table 3, it was found that all of the sulfur molded products obtained in Examples 1 to 6 had good ignitability, unlike the sulfur molded product of Comparative Example 1 in which ignitability was recognized.

 Further, the molded articles A to G of the above Examples and Comparative Examples were immersed in beakers, and a change in color was observed after 30 days. As a result, only the solution of the molded product D of Comparative Example 1 was colored yellow, and generation of turbid water was observed. Each molded product of the example was colorless and transparent, and no change was observed.

Claims

The scope of the claims  1. Step (A) of melting and mixing 100 parts by weight of sulfur and 2 to 20 parts by weight of dicyclopentene at 155 ° C, and the viscosity at 140 ° C of the melt obtained in step (A) is 140 ° C. 0.05 to: a method for producing a modified sulfur-containing binder comprising a step (B) of cooling to 135 ° C. or less after reaching 1.2 Pa's to obtain a modified sulfur-containing binder. 2. Step (A) of melt-mixing 100 parts by weight of sulfur and 2 to 20 parts by weight of dicyclopentene at 135 to 155 ° C, and the viscosity of the melt obtained in step (A) at 140 ° C of 0.05 ~: Step (B) of obtaining a modified sulfur-containing binder by cooling to 135 ° C or less after reaching 1.2 Pa 's, and weighing the modified sulfur-containing binder and aggregate obtained in step (B). The viscosity at 140 ° C of the modified sulfur-containing binder at a temperature of 135 to 155 ° C at a ratio of 1 to 5: 5 to 9 at a temperature of 135 to 155 ° C; while maintaining the viscosity within a range of L. ² Pa's. A method for producing a modified sulfur-containing material, comprising: a step (C) of melt-mixing; and a step (D) of cooling the molten mixture of the step (C) to 135 ° C or lower.  3. Step (X) of melt-mixing sulfur, dicyclopentadiene and aggregate at 135-155 ° C for 0.5-5 hours, and step of cooling the molten mixture of step (X) to 135 ° C or less (Y ) Containing the modified sulfur-containing material.  4. In step (X), the charged ratio of dicyclopentadiene is 2 to 20 parts by weight with respect to 100 parts by weight of sulfur, and the charged ratio of the aggregate is determined by the total weight of sulfur and 4. The method according to claim 3, wherein the weight ratio to the material amount is 1 to 5: 5 to 9.  5. Step (X) is a step (XI) in which sulfur and dicyclopentadiene are melt-mixed, and an aggregate is mixed with the molten mixture in step (XI) and melted at 135 to 155 ° C for 0.5 to 5 hours. 5. The production method according to claim 4, comprising a mixing step (X2).