JP2002060491A - Method for manufacturing sulfur binder, sulfur binder, and method for manufacturing sulfur composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a sulfur binder which makes the reaction control easy and can produce, with good workability, a sulfur binder capable of improving mechanical strength, water barrier properties, ignitability, resistance to sulfur oxidizing bacteria and the like, and reconverting wastes into resources, to obtain a sulfur binder, and to provide a method for manufacturing a sulfur composition by using this binder. SOLUTION: The method for manufacturing a sulfur binder comprises a step of subjecting sulfur, dicyclopentadiene, and a hydroaromatic compound to heat treatment, and the method for manufacturing a sulfur composition comprises a step of melt-mixing the sulfur binder and an aggregate and a step of cooling the molten mixture or a step of subjecting sulfur, dicyclopentadiene, a hydroaromatic compound, and an aggregate to heat treatment and a step of cooling the heat-treated mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a sulfur binder, a sulfur binder, and a method for producing a sulfur composition using the sulfur binder. More specifically, a method for producing a sulfur binder, which can be used when preparing civil engineering and construction materials, etc. by effectively utilizing general and industrial wastes, a sulfur binder obtained by the method, The present invention relates to a method for producing a sulfur composition that can be used for civil engineering and construction materials.

[0002]

2. Description of the Related Art Attempts have been made to use sulfur as one of materials for civil engineering, construction and the like by utilizing its property that it dissolves at temperatures exceeding 119 ° C. and is solid at room temperature. For example, use as a binding material such as a pavement material (U.S. Pat. No. 4,290,816), a building material (Japanese Patent Publication No. 55-49024), or a waste sealing material (Japanese Patent Publication No. 62-15274). Are being considered. However, in the case of a binder containing only sulfur, since the outer surface of the obtained molded product is sulfur,
The molded article has many problems such as ignitability, poor mechanical strength, and poor resistance to sulfur-oxidizing bacteria, and its use is not necessarily expanding. Therefore, in order to improve such properties, many additive compounds have been studied. In particular, dicyclopentadiene as a compound for addition is inexpensive and economical, and has a new use of sulfur.
-II, 1978, pp. 68-77, it is known to have a good effect on mechanical strength and the like. Also,
Examples of improving the properties of sulfur by adding vinyltoluene, dipentene, and other olefin oligomers and using them as paving materials, adhesives, sealants, and the like (Japanese Patent Publication No. 25929/1990 and Japanese Patent Publication No. 28529/1990) are also available. Are known. As a pavement material, a mixture of asphalt and sulfur has been put to practical use.

[0003]

Heretofore, one of the uses of sulfur is as a binder, and it has been used as a civil engineering construction material by producing a molded product by mixing with various aggregates. However, in the case of sulfur alone, molded articles have many problems in physical properties, and their use is limited. For example, regarding flammability, sulfur has a flash point of 207 ° C. and a spontaneous ignition temperature of 245 ° C.
Ignitable, and the sulfur exposed on the surface is easy to burn. Regarding mechanical strength, sulfur shows high strength in a stable solid state if there are no defects, but in actuality, when solidified by cooling from a liquid state, it is orthorhombic, monoclinic, amorphous sulfur Are mixed, and their ratio changes depending on cooling conditions, and also changes depending on elapsed time. Therefore, there is a problem that defects are easily generated and brittleness occurs. The most stable sulfur in the solid state is orthorhombic sulfur. Since orthorhombic sulfur has the highest density among the three types, gaps open over time, reducing mechanical strength or in extreme cases. When sulfur is used to block harmful substances, water penetrates into the gaps and dissolves the sulfur-coated internal blocker, and is present in soil or water There is a problem that the sulfur-oxidizing bacteria enter and corrode the surface, and the mechanical strength and the sealing property decrease. Therefore, a method of adding dicyclopentadiene has been studied as one of the improvement methods. The reaction between dicyclopentadiene and sulfur is said to be a kind of polymerization reaction. First, dicyclopentadiene reacts with sulfur, and then sulfur is polymerized by a radical chain reaction. Therefore, the reaction between dicyclopentadiene and sulfur causes a sudden rise in temperature with a large amount of heat generated, and a sudden rise in viscosity, so that the reaction cannot be controlled and the solidification occurs rapidly, resulting in a state in which molding cannot be performed. There is a point. When the dicyclopentadiene-containing sulfur binder once cooled and solidified is reheated, the reaction starts again and the viscosity increases. Suitable properties of such a dicyclopentadiene-containing sulfur binder, production conditions for mixing with an aggregate, and the like have not been established. Therefore, development of a reaction inhibitor or a viscosity modifier for solving these problems and improving the operability of production conditions is desired. Furthermore, it is not known that dicyclopentadiene-containing sulfur binders can be used as binders for sequestering general and industrial wastes, and their production conditions have not been established. At present, general and industrial wastes are disposed of by landfill, incineration, and the like. However, disposal sites for such disposal are becoming smaller and smaller, and reuse of the waste is required as much as possible. For example, when the aggregate is waste such as iron and steel slag, coal ash, incineration ash, etc., in order to make the molded product into civil engineering landfill material, construction material, etc., mechanical properties such as compression / bending / tensile strength and impact resistance are required. It is required to have strength, water-blocking properties to prevent the elution of heavy metal compounds contained in industrial waste, flame resistance that does not ignite with open flames, durability against sulfur oxidizing bacteria that corrode surface sulfur in soil and sea, etc. You. In particular, incinerated ash contains harmful substances such as heavy metals and dioxins, and when used for landfill, it is necessary to suppress elution thereof. Steel slag discharged from the steel industry is used for aggregates for pavement materials and civil engineering materials. When wet with water, it generates yellow water due to polysulfides, which has an adverse effect on the environment. Accordingly, there is also a need for a binder that can completely block these industrial wastes and that can be recycled as civil engineering construction materials.

[0004] An object of the present invention is to improve the mechanical strength, water shielding, ignitability, resistance to sulfur oxidation bacteria, etc., which are the problems of the above-mentioned sulfur binder, and to recycle waste. An object of the present invention is to provide a method for producing a sulfur binding material capable of easily producing a dicyclopentadiene-containing sulfur binding material with good workability, and a sulfur binding material obtained by the production method. Another object of the present invention is to improve the mechanical strength, water shielding, ignitability, resistance to sulfur oxidation bacteria, etc., which are problems of civil engineering and building materials using the above-mentioned sulfur binder, sealing materials, etc. It is an object of the present invention to provide a method for producing a sulfur composition which can produce a sulfur composition using a dicyclopentadiene-containing sulfur binder capable of recycling a product with good workability.

[0005]

Means for Solving the Problems The present inventors have studied diligently to solve the above-mentioned problems. First, in order to solve these problems, it is effective to add dicyclopentadiene to sulfur and make it react. I found something. However, since this reaction is difficult to control and it is difficult to obtain a desired binder, an additive having a reaction suppressing function and a viscosity adjusting function was further studied for the purpose of improving workability during the reaction. As a result, they found that a hydroaromatic compound is effective as such an additive, and that by appropriately setting the conditions, a reaction suppressing effect and a viscosity adjusting effect can be obtained in the reaction between sulfur and dicyclopentadiene. The present invention has been completed.

That is, according to the present invention, there is provided a method for producing a sulfur binder, which comprises subjecting sulfur, dicyclopentadiene and a hydroaromatic compound to heat treatment. Further, according to the present invention, there is provided a method for producing a sulfur composition, wherein the sulfur binder obtained by the above production method and the aggregate are melt-mixed and cooled. Further, according to the present invention, there is provided a sulfur binder obtained by the above production method. Further, according to the present invention, sulfur, dicyclopentadiene,
There is provided a method for producing a sulfur composition, which comprises subjecting a hydroaromatic compound and an aggregate to heat treatment and cooling.
Further, according to the present invention, there is provided a method for producing a sulfur composition, which comprises melting and mixing the sulfur binder-containing material containing the sulfur binder and the aggregate, followed by cooling.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a sulfur binder according to the present invention includes a step of heat-treating sulfur, dicyclopentadiene and a hydroaromatic compound. Examples of the sulfur used in the present invention include ordinary sulfur, which is naturally produced or produced by desulfurization of petroleum or natural gas. Examples of the dicyclopentadiene used in the present invention include a simple substance of cyclopentadiene, a mixture mainly composed of a dimer to a tetramer, and the like. The content of dicyclopentadiene in the mixture is usually at least 70 mass%, preferably at least 85 mass%. Therefore, many commercially available products called so-called dicyclopentadiene can be used.

The sulfur and dicyclopentadiene are used in a ratio by mass of sulfur: dicyclopentadiene of 5:
0 to 98: 2 to 50 is preferred. The amount of dicyclopentadiene used, in addition to the controllability of the production and the reaction time,
It can be determined appropriately from the performance of the product. The reaction between sulfur and dicyclopentadiene is considered to be a polymerization reaction, and the rate of increase in viscosity due to the reaction is also related to the concentration of dicyclopentadiene. The higher the concentration, the faster the rate of increase in viscosity. Therefore, from the viewpoint of controllability in production, it is easier to use dicyclopentadiene at a lower concentration, but the production time is shorter in a higher concentration of dicyclopentadiene. From the viewpoint of the performance of the product, in order to develop elastic strength, the concentration of dicyclopentadiene is preferably low, and is preferably 2 to 10% by mass based on the total amount of sulfur and dicyclopentadiene. Where 2
If the amount is less than mass%, the strength is not sufficiently improved, which is not preferable. In order to maximize the elastic strength of the obtained sulfur binder, the use ratio of sulfur: dicyclopentadiene can be, for example, 90 to 95: 5 to 10, and in this case,
The reaction can be performed in a short time by setting the heat treatment temperature described below to 150 ° C., and the operability can be improved by immediately stopping the reaction and reducing the viscosity. The flame retardancy, water shielding, and sulfur-oxidizing bacterial resistance of the resulting sulfur binder are
All are related to the amount of dicyclopentadiene used. Generally, the larger the amount used, the better the performance of each is. However, the performance can be appropriately selected from the preferable range according to the application such as other performance. For example, if the amount of dicyclopentadiene exceeds 10% by mass with respect to the total amount of sulfur and dicyclopentadiene, viscous properties are added in addition to elasticity, so that the product becomes a viscoelastic body, easily deformed, and easily increases in stickiness. It does not break down. Dicyclopentadiene is 20
If the content is more than mass%, the viscous property tends to appear remarkably. Therefore, in applications where such properties are not preferred, the amount of dicyclopentadiene used may be limited within the above preferred range.

The hydroaromatic compound used in the present invention has, for example, an action of suppressing the reaction between sulfur and dicyclopentadiene;
Any material may be used as long as the resulting sulfur binder has a high viscosity suppressing effect, a hardening preventing effect, a viscosity lowering effect, and the like. The action of such a hydroaromatic compound is due to a chemical action that causes the hydroaromatic compound to donate hydrogen to the polymerization reaction between sulfur and dicyclopentadiene. It is considered that the result of the effect of the compound having excellent compatibility with the binder is the result of the combined effect.

Examples of the above-mentioned hydroaromatic compound include dihydronaphthalene, trihydronaphthalene, tetrahydronaphthalene (hereinafter referred to as “tetralin”), methyltetralin, ethyltetralin, propyltetralin, butyltetralin, methyldihydronaphthalene, ethyldihydronaphthalene, Propyldihydronaphthalene, butyldihydronaphthalene, dihydroacenaphthene, trihydroacenaphthene, tetrahydroacenaphthene, methyltetrahydrofluorene, ethylhydrofluorene, propylhydrofluorene, butylhydrofluorene, octahydrophenanthrene, tetrahydrophenanthrene, dihydrophenanthrene, octahydroanthran One or more selected from the group consisting of sene and the like are preferred. Further, compositions containing these compounds, for example, hydrides of decrystallized anthracene oil obtained from coal-based tar, hydrides of coal tar oil, and other mixtures may be used as the hydroaromatic compound used in the present invention. it can.

In the method for producing a sulfur binder according to the present invention,
The addition ratio of the hydroaromatic compound is usually 1 to 500 parts by mass with respect to 100 parts by mass of dicyclopentadiene,
Preferably it is 10 to 100 parts by mass. When the addition amount is less than 1 part by mass, the reaction suppressing effect and the viscosity increasing suppressing effect in the reaction between sulfur and dicyclopentadiene, the viscosity lowering effect and the like are not effectively exhibited, and when it exceeds 500 parts by mass, the production cost is high. In addition, the strength of the obtained sulfur binder is not further improved, which is not preferable.

In the method for producing a sulfur binder according to the present invention,
In heating the sulfur, dicyclopentadiene and hydroaromatic compound, the order of mixing the respective components is not particularly limited. However, in consideration of good workability, the following methods, particularly methods 1) and 2), are preferred. Are preferred. 1) A method of producing a sulfur binder by adding a hydroaromatic compound after heat-reacting dicyclopentadiene with sulfur to form modified sulfur. 2) A method in which sulfur is added to a mixture of dicyclopentadiene and a hydroaromatic compound, followed by heat treatment to produce a sulfur binder. 3) A method in which dicyclopentadiene is added to a mixture of sulfur and a hydroaromatic compound, followed by heat treatment to produce a sulfur binder. In the method for producing a sulfur binder according to the present invention, the heat treatment is a heat treatment under conditions in which sulfur reacts with dicyclopentadiene to generate modified sulfur, and the heat reaction involves a chemical reaction of the hydroaromatic compound. And any process of melt mixing without accompanying. The temperature of this heat treatment is usually 135
１５155 ° C. If the temperature is 135 ° C. or higher, sulfur can be favorably converted into modified sulfur by reaction with dicyclopentadiene. However, if the temperature exceeds about 160 ° C., there is a possibility that a problem of simultaneous polymerization of pure sulfur may occur. Therefore, the upper limit temperature is preferably set to about 155 ° C.

In the method 1), the reaction between sulfur and dicyclopentadiene can be suppressed by adding a hydroaromatic compound, and the viscosity of the system can be adjusted to a desired value.
This is preferable because workability is improved by lowering the viscosity. In the above method 1), the timing for adding the hydroaromatic compound is preferably when the viscosity of the modified sulfur is 50 to 1000 mPa · s. Hereinafter, a specific example of the method for producing a sulfur binder by the method 1) will be described in detail.

First, as the solid sulfur is heated, 119
At C, a phase change from solid to liquid begins. After liquefaction, the temperature is raised to about 130 ° C. while measuring the viscosity with a suitable viscometer, for example, a B-type viscometer while stirring the whole. A predetermined amount of dicyclopentadiene is added little by little thereto and mixed. If the temperature is lower than 135 ° C., the reaction rate of sulfur by dicyclopentadiene is slow, no sudden heat generation and no increase in viscosity occur, and only slight temperature increase and viscosity increase are observed.
Maintain an almost constant viscosity. After confirming that no heat is generated by the mixing, preferably 135 to 155 ° C.
Temperature rises to The viscosity increase rate is related to the reaction temperature, and the higher the temperature is, the faster it is. For example, for 95 parts by mass of sulfur and 5 parts by mass of dicyclopentadiene, about 15 hours at 135 ° C., about 5 hours at 140 ° C., and 145 ° C. About 2 hours,
At 150 ° C for about 0.5 hours, the viscosity is 100mPa
s. If the temperature exceeds 155 ° C., the modification of sulfur proceeds rapidly, and the viscosity rises rapidly and reaches a desired viscosity in a short time. Therefore, before or immediately after the viscosity increase, a hydroaromatic compound having a reaction suppressing effect is required. It is preferable to add a fixed amount to reduce the rate of increase in viscosity and improve operability. The temperature at which the hydroaromatic compound is added is usually 120 to 155C, preferably 135 to 150C. The viscosity of the reaction product of sulfur and dicyclopentadiene when adding the hydroaromatic compound is 50 to 10
The range of 00 mPa · s is preferable. The end of the reaction is preferably determined by the viscosity of the resulting sulfur binder.
Usually measured at 140 ° C., 15 to 1000 mPa · s
Is preferred, but from the viewpoint of the strength of the molded product manufactured from the dicyclopentadiene-containing sulfur binder and the workability of the manufacturing process, 20 to 500 mPa · s is most generally preferable.

When sulfur and dicyclopentadiene are reacted by heat treatment at a high temperature, particularly at a temperature of 150 ° C. or more, a sharp increase in viscosity accompanies. However, in the above method 2), the hydroaromatic compound is added to dicyclopentadiene in advance, so that the above-mentioned rapid increase in viscosity is suppressed and a mild reaction is performed to facilitate handling during operation. Can be. Hereinafter, a specific example of the method 2) will be described in detail.

In the above method 2), when sulfur is added to a mixture of dicyclopentadiene and a hydroaromatic compound and the mixture is heated, for example, the dicyclopentadiene and the hydroaromatic compound are added to 95 parts by mass of sulfur. When 5 parts by mass of each was used, at 150 ° C., 1.
The viscosity reaches 100 mPa · s in 5 hours, and it takes a slightly longer time to increase the viscosity than when the hydroaromatic compound is used later as in the method 1). Even at 150 ° C., even if dicyclopentadiene and hydroaromatic compound are added to each of 10 parts by mass with respect to 90 parts by mass of sulfur, the viscosity reaches 100 mPa · s.
It takes minutes, and the reaction can be performed mildly, and the time required to increase the viscosity can be easily controlled, so that the handling during the production of the sulfur binder is facilitated.

The sulfur binder of the present invention is not particularly limited as long as it is a sulfur binder obtained by the above-mentioned method of heat-treating sulfur, dicyclopentadiene and a hydroaromatic compound. The sulfur binder of the present invention is distinguished from conventionally known modified sulfur in that it contains a hydroaromatic compound or a reactant thereof. The sulfur binder of the present invention can also be called a sulfur cement or a sulfur binder, and can be used as civil engineering or construction materials. For example, it can be used as a pavement material, a building material, or a waste sealing material by mixing with various aggregates.

In the method for producing a sulfur composition according to the present invention, in the method for producing a sulfur binder, a heat treatment is performed in the presence of an aggregate, and the mixture is cooled, that is, sulfur, dicyclopentadiene, and hydroaromatic. Heat-treating and cooling the aromatic compound and the aggregate, or melt-mixing the sulfur binder containing the sulfur binder obtained by the above-described production method, the aggregate, and the hydroaromatic compound if necessary. And cooling. Each method is a method of cooling the mixture of the above-mentioned melt of the sulfur binder and the aggregate.In the following description, in each of the methods, the method before cooling is simply referred to as the sulfur binder and the bone. There is a method called melt mixing with a material. The sulfur, dicyclopentadiene, hydroaromatic compound, and the heat treatment conditions and the mixing ratio thereof used in the method for producing the sulfur composition of the present invention are the same as those described in the above-described method for producing the sulfur binder of the present invention. Is the same as

The aggregate used in the method for producing the sulfur composition of the present invention is not particularly limited as long as it can be used as an aggregate. Industrial wastes and the like are preferred because they can be rendered harmless and can reuse industrial wastes. Examples of industrial waste include incinerated ash and incinerated fly ash, melt fly ash generated from municipal solid waste high-temperature melting furnaces, coal ash discharged from the power business and general industries, fluidized sand used in fluidized bed incinerators, heavy metals Soil contaminated with, polishing debris, by-products by-products during the production of various metals (for example, steel slag dust, ferronickel slag, aluminum dross,
One or more selected from steel slag and the like). In particular, waste such as steel slag, incineration ash, and coal ash can be usefully reused while making them harmless as the aggregate of the present invention.

The steel slag refers to slag by-produced from the steelmaking industry, and includes blast furnace slag discharged from a blast furnace, open hearth slag discharged from an open hearth and a converter, converter slag, and the like. The main components of the steel slag include oxides such as silica, alumina, calcium oxide and iron oxide and other inorganic sulfides.
The incineration ash is discharged from various combustion furnaces such as municipal waste incinerators and industrial waste incinerators, and the main components are also silica, alumina, calcium oxide, oxides such as iron oxide,
The content of harmful metals such as lead, cadmium and arsenic is also high. Such incinerated ash is often landfilled at a final disposal site that does not emit sewage, but in the present invention, such incinerated ash can also be used as aggregate. The coal ash is discharged from various types of coal-fired combustion furnaces for power generation, heating, and the like, and those conventionally used as a concrete or civil engineering material mixture can be used. In the method for producing a sulfur composition of the present invention, in addition to the above-described aggregate, for example, a clay mineral,
Activated carbon, carbon fiber, glass fiber, vinylon fiber, aramid fiber, sand, gravel, and inorganic and organic materials containing no equivalent harmful substances can also be used as aggregates.

In the method for producing a sulfur composition of the present invention,
As a method of melting and mixing the above-mentioned sulfur binder and the aggregate, for example, the following methods are preferable from the viewpoint of workability and the like, and among them, the methods (a) and (b) are preferable. (a) a method of melt-mixing the aggregate with the above-mentioned sulfur binder, (b) heat-treating the modified sulfur of sulfur and dicyclopentadiene, the aggregate, and if necessary, the hydroaromatic compound, and then hydroaromatic A method of adding a compound, (c) a method of melt-mixing sulfur and modified sulfur of dicyclopentadiene with a mixture of an aggregate and a hydroaromatic compound and, if necessary, melting and mixing a hydroaromatic compound, wherein sulfur and dicyclopentadiene are added. Is preferably obtained by heating and reacting 50 to 98 parts by mass of sulfur and 2 to 50 parts by mass of dicyclopentadiene, and has a viscosity of 15 to 1000 mPa at 140 ° C.
・ S is preferred.

In the method for producing a sulfur composition according to the present invention,
Usually, the addition ratio of the hydroaromatic compound is preferably from 1 to 500 parts by mass based on 100 parts by mass of the modified sulfur or the dicyclopentadiene used for the sulfur binder of the present invention. Here, when using the sulfur binder of the present invention,
It is also necessary to consider the amount of hydroaromatic compound used in making this sulfur binder.

The temperature at the time of melt mixing in the method of melt mixing the sulfur binder and the aggregate is usually 120 to 155 ° C, preferably 135 to 155 ° C. This temperature is 120 ° C
If it is less than 155 ° C., the viscosity of the system becomes high, and if it exceeds 155 ° C., a polymerization reaction between pure sulfur (unreacted sulfur) may occur at the same time, which is not preferable. When the mixing temperature is 155 ° C. or less and the temperature is higher, the fluidity of the binder is higher, the mixing efficiency is higher, and the mixing is completed in a shorter time. At high temperatures, the curing reaction due to the progress of denaturation is rapid, causing problems in operability.However, by adding a hydroaromatic compound, improving the flowability and slowing the progress of the curing reaction to improve the operation. Can be. In the case where the hydroaromatic compound is not used, the mixing time is usually 5 to 30 minutes. However, the addition of the hydroaromatic compound suppresses the modification of sulfur and increases the fluidity and mixing efficiency. Since the mixing time can be adjusted at a high temperature and the viscosity can be adjusted, the range of production conditions can be widened.

Prior to the above mixing, the mixer was set at 135-1.
It can be preheated to 55 ° C, sulfur, dicyclopentadiene, hydroaromatic compounds, each component of aggregate, modified sulfur,
One or more of the sulfur binder or the mixture of the aggregate and the hydroaromatic compound can be preheated to 120 to 155 ° C and mixed with the remaining other components. The mixing time is desirably as long as possible, as long as the properties of the product allow, but the mixing time can be set to an optimum condition in accordance with the production cost. The optimum conditions can be determined by the amount of the hydroaromatic compound used. If the mixing is not sufficient, the modified sulfur and the aggregate will not be sufficiently mixed, and the molded product will not be a continuous phase, and a gap will be opened or the surface will not be smooth. If the mixing is sufficient and the viscosity is low, the molded product becomes a complete continuous phase and the surface can be smoothed. Therefore, it is desirable to appropriately select such mixing conditions. The kneading machine and the mixing method may be known ones, and for example, an internal mixer, a roll mill, a ball mill, a drum mixer, a screw extruder, a bag mill, a Bonnie mixer, a ribbon mixer and the like can be used.

The viscosity of the sulfur binder constituting the sulfur composition at the end of mixing before cooling is measured at 140 ° C.
The range of 1000 mPa · s is preferable, but from the viewpoint of the strength of the molded product manufactured from the sulfur binder and the workability of the manufacturing process, 20 to 500 mPa · s is the overall optimum viscosity.

In the method for producing a sulfur composition of the present invention,
Cooling may be either natural cooling or forced cooling,
The temperature can be appropriately set to a temperature at which the sulfur composition cures. In cooling, the mixture of the molten sulfur binder and the aggregate may be poured into a desired mold to form a desired shape. Further, in order to obtain a granular sulfur composition, the above-mentioned molten mixture of the sulfur binder and the aggregate,
The sulfur binder can be obtained by using a granulator in a molten state and cooling while granulating. Although the granulation method is not particularly limited, for example, the granulation method can be performed using a device of a rolling type equipped with a drum or an inclined plate, or a vibration type equipped with a horizontal or inclined plate. Further, the sulfur composition obtained by the production method of the present invention may be obtained by crushing a lump produced by cooling the above-mentioned molten mixture into an irregular shape.

[0027] For example, a granular sulfur composition obtained by the method for producing a sulfur composition of the present invention has high strength of individual particles and can adjust the particle size thereof, so that it is suitable as a construction material and , Quarries and the like. Further, since the contact with the surrounding water is basically blocked by sulfur, the mixed inorganic material is less likely to be directly exposed to the outside, and the elution of the contained harmful substances can be suppressed. The sulfur composition obtained in the present invention should be further noted, cement-based materials, for example, when mixing with cement, concrete, gypsum, etc.
It does not affect its curing or the optimal water content.

Conventionally, when a cured product is obtained using a cement-based material and incinerated ash, it can be cured by a pozzolan reaction or a sulfopozolan reaction, but it is important to adjust the water content to an optimum value. is there. In particular, when mixing incinerated ash from municipal waste with high water absorption, it is very difficult to adjust the water content. For example, when incinerated ash from municipal solid waste is dried and mixed, the incinerated ash absorbs more moisture than the cementitious mixture and thus lacks moisture. The mixture becomes excessive in moisture, and in any case, the performance as a construction material may be impaired. In addition, the aggregate containing the harmful substance expands when it absorbs water, so that it cannot be used as an aggregate. In the sulfur binder and the sulfur composition of the present invention,
By making such aggregates containing harmful substances harmless using sulfur, it is possible to greatly open the way to recycling of the aggregates.

The sulfur composition obtained by the production method of the present invention can be used as a landfill material, a roadbed material, an embankment material and the like if it is granular, and can be used as a panel material and the like as a molded body.

[0030]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 950 g of solid sulfur was put into a stirring and mixing tank, dissolved at 120 ° C., and then kept at 140 ° C. The viscosity at that time was 18 mPa · s when measured with a B-type viscometer. Next, about 9
50 g of dicyclopentadiene heated and dissolved at 0 ° C. was slowly added, and the mixture was stirred gently for about 5 minutes and then heated to 145 ° C. After the start of the reaction, the reaction temperature and viscosity gradually increased, and after confirming that the temperature increase was completed, the reaction temperature was controlled at 150 ° C. After the viscosity reaches 100 mPa · s in about 1 hour, 90
50 g of tetralin preheated to <RTIgt; At this time, the viscosity of the system became 20 mPa · s, and after 30 minutes, the viscosity became 3 mPa · s.
It was 0 mPa · s. After adjusting the temperature of the system to 130 ° C,
The mixture was poured into a container and cooled to obtain a sulfur binder A. Then
Aggregate in which 670 g of blast furnace slag and 130 g of coal ash were preheated at 140 ° C., and a melt obtained by reheating 200 g of the binder A by reheating to 130 ° C. were simultaneously put into a kneader kept at 140 ° C. Subsequently, the mixture was kneaded for 20 minutes, poured into a cylindrical shape having a diameter of 5 cm and a height of 10 cm, and cooled to prepare two specimen molded products. The obtained molded products are referred to as molded products A and A ′. The surfaces of the molded products A and A ′ were smooth. For each of the obtained cured products,
The compressive strength was measured using a Tensilon apparatus. as a result,
Compressive strength of the binder A is 31.6MN / m ^2, the compressive strength of the molded product A is 52.0MN / m ^2, the compressive strength of the molded article A 'was 50.0MN / m ^2. The difference in compressive strength between the molded products A and A ′ was small, and the addition of tetralin made the surface of the molded product smooth and eliminated the variation in compressive strength.

Example 2 The amount of sulfur was 900 g and the amount of dicyclopentadiene was 10
Except that the amount was set to 0 g, all operations were performed in the same manner as in Example 1 to prepare a corresponding binder B and a molded product B, and each compressive strength was measured. As a result, the compressive strength of binder B was 21.5 MN /
m ² , the compression strength of molded product B is 54.5 MN / m ² ,
Both had sufficient compressive strength.

Example 3 Octahydrophenanthrene 25 instead of tetralin
g, the same procedure as in Example 1 was carried out except that the viscosity of the system poured into the container for obtaining the binder was 25 mPa · s, and the corresponding binder C was produced, followed by preparation of the molded product C. Then, each compressive strength was measured. As a result, the compressive strength of the binder C was 32.0 MN / m ² and the compressive strength of the molded product C was 5
It was 1.5 MN / m ² and had sufficient compressive strength.

Comparative Example 1 A corresponding binder D and molded article D were prepared in the same manner as in Example 1 except that the amount of sulfur was 1000 g and no dicyclopentadiene was added, and the respective compressive strengths were measured. did. As a result, the compressive strength of the bonding material D was 7.4 MN /
m ² , the compression strength of the molded product D was 45.0 MN / m ² , and the compression strength was not sufficient.

Comparative Example 2 1900 g of solid sulfur was placed in a stirring and mixing tank,
, And kept at 140 ° C. The viscosity at that time was measured by a B-type viscometer, and the result was 18 mPa · s. Then
100 g of dicyclopentadiene heated and melted at about 90 ° C
Was slowly added, and the mixture was gently stirred for about 5 minutes.
The temperature was raised to 5 ° C. After the start of the reaction, the reaction temperature and viscosity gradually increased, and after confirming that the temperature increase was completed, the reaction temperature was controlled at 150 ° C. In about 1 hour, the viscosity reached 100 mPa · s, and a sulfur-dicyclopentadiene-based sulfur binder E having a viscosity of 100 mPa · s was obtained. Then, 670 g of blast furnace slag and 130 g of coal ash
Was preheated at 140 ° C., and 200 g of the binder E was reheated to 130 ° C., and the molten material was almost simultaneously introduced into a kneader kept at 140 ° C. 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 obtain molded products E and E ′. Molded product E '
Is partially rough, and it is estimated that the fluidity is worse than that of the example in which tetralin is added. When the compressive strength of each of the obtained cured products was measured in the same manner as in Example 1, the compressive strength of the binder E was 31.0 MN / m ² , the compressive strength of the molded product E was 52.0 MN / m ² , The compressive strength of thing E 'is 46.
It was 0 MN / m ² , and there was variation in compressive strength between the molded products E and E ′. It is considered that this variation caused the load to concentrate on a roughened portion due to the surface roughness of the molded product E ′, and the strength of this portion of the molded product E ′ was lowered.

Example 4 950 g of solid sulfur was placed in a stirring and mixing tank and heated.
After the sulfur was dissolved at 0 ° C, it was further heated and kept at 140 ° C. The viscosity at that time was measured by a B-type viscometer.
mPa · s. Next, a mixture of 40 g of dicyclopentadiene and 10 g of tetralin, which were heated and dissolved at about 90 ° C., was added. After gentle stirring for about 5 minutes, the temperature was raised to 145 ° C. After the start of the reaction, the reaction temperature and viscosity gradually increased, and after confirming that the temperature increase was completed, the reaction temperature was controlled at 150 ° C. In the method of Example 1, the time to reach the viscosity of 100 mPa · s was 1 hour, but in the present example, the viscosity was 1 hour and 40 minutes later and the viscosity reached 1 mPa · s.
The viscosity reached 00 mPa · s, and the subsequent increase in viscosity was moderate, and the production operation was easy. Then, set the temperature of the system to 1
After the temperature was raised to 30 ° C., the mixture was charged into a container and cooled to obtain a binder F. Next, 670 g of blast furnace slag and 130 g of coal ash were preheated at 140 ° C., and 200 g of the binder F 200 g.
The re-melted material that had been reheated to 30 ° C. and dissolved was introduced almost simultaneously into a kneader kept at 140 ° C. Subsequently, the mixture was kneaded for 20 minutes. However, the viscosity was not increased due to the progress of the polymerization of sulfur, and the stirring torque was small, so that the step of pouring into the next mold was easy. The size of the mold was a cylinder having a diameter of 5 cm and a height of 10 cm. The mold was poured into the mold and cooled to obtain a molded product F. The surface of the molded product F was smooth and good. When the compressive strength of each cured product was measured in the same manner as in Example 1,
The compressive strength of the binder F was 31.0 MN / m ² , and the compressive strength of the molded product F was 53.0 MN / m ² .

Example 5 950 g of solid sulfur was placed in a stirring and mixing vessel, dissolved at 120 ° C., and further heated to 140 ° C. When the viscosity at that time was measured by a B-type viscometer, it was 18 mPa · s. 50 g of dicyclopentadiene heated and dissolved at about 90 ° C. was slowly added thereto, and the mixture was stirred gently for about 5 minutes, and then heated to 145 ° C. After confirming that the polymerization reaction of sulfur started, the reaction temperature and the viscosity gradually increased, and then the temperature increase was completed, the temperature was controlled at 150 ° C. Since the viscosity reached 100 mPa · s in about 1 hour, the mixture was cooled to produce a sulfur-dicyclolopentadiene-based binder G. Then, 670 g of blast furnace slag and 130 g of coal ash
Was preliminarily heated at 140 ° C., and a dissolved material obtained by reheating 200 g of the binder G at 130 ° C. were introduced almost simultaneously into a kneader maintained at 140 ° C. Subsequently, 10 g of tetralin was added, followed by kneading for 20 minutes. The addition of tetralin allowed the kneading to be carried out smoothly without increasing the stirring torque of the kneading machine. This was poured into a cylindrical shape having a diameter of 5 cm and a height of 10 cm and cooled to produce molded products G and G ′. The surfaces of the molded products G and G ′ were smooth and the fluidity was better than that of the tetralin-free system.
When the compressive strength of each cured product was measured in the same manner as in Example 1, the compressive strength of binder G was 29.5 MN / m ² , the compressive strength of molded product G was 51.0 MN / m ² , and molded product G 'Had a compressive strength of 50.3 MN / m ² , and there was almost no variation in the compressive strength between the molded products G and G', indicating that it was good.

[0037]

The method for producing a sulfur binder of the present invention includes a step of heat-treating sulfur, dicyclopentadiene, and a hydroaromatic compound. Can be expected to significantly improve the strength, waterproofness, flame retardancy, resistance to sulfur oxidizing bacteria, etc. of the sulfur binder used, as well as easy control of the production conditions during production, in a shorter time and with better operability. Can be manufactured. Further, in the method for producing a sulfur composition of the present invention, since the sulfur binder or the method for producing the same is used, the sulfur binder and the aggregate are sufficiently mixed, and the molded product is likely to be a uniform continuous phase, and the Therefore, it is possible to easily produce a material suitable as a material for civil engineering and construction, which is smooth and has little variation in compressive strength and the like. Furthermore, even when general and industrial waste is used as aggregate, the production method is easy, and the obtained sulfur composition is used for civil engineering and industrial waste.
As it can maintain the performance as building materials etc., it can also suppress or prevent the risk of contamination by harmful substances etc.
This is an effective method for recycling these wastes.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshio Tajima 8 Chidoricho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Central Research Laboratory, Nisseki Mitsubishi Co., Ltd. (72) Inventor Hiroshi Hashimoto 8 Chidoricho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Address F-term in Nisseki Mitsui Co., Ltd. Central Research Laboratory (reference) 4D004 AA36 AA43 BA02 CA15 CA29 CA32 CA34 CC11 4J030 BA05 BA47 BB18 BC02 BE04 BF01 BG34

Claims (12)

[Claims] 1. A method for producing a sulfur binder, comprising heat-treating sulfur, dicyclopentadiene and a hydroaromatic compound. 2. The method for producing a sulfur binder according to claim 1, wherein after the sulfur is reacted with dicyclopentadiene by heating to form modified sulfur, a hydroaromatic compound is added and heat treatment is performed. 3. The method for producing a sulfur binder according to claim 2, wherein the viscosity of the modified sulfur at the time of adding the hydroaromatic compound is 50 to 1000 mPa · s. 4. The method for producing a sulfur binder according to claim 1, wherein, after mixing dicyclopentadiene and the hydroaromatic compound, sulfur is added and mixed, followed by heat treatment. 5. The use ratio of sulfur to dicyclopentadiene is from 50 to 98: 2 to 50 by mass ratio, and the use amount of hydroaromatic compound is dicyclopentadiene 10
The method for producing a sulfur binder according to any one of claims 1 to 4, wherein the amount is 1 to 500 parts by mass with respect to 0 parts by mass. 6. The method for producing a sulfur binder according to claim 1, wherein the temperature during the heat treatment is 135 to 155 ° C. 7. The final viscosity of the resulting sulfur binder is 140.
The method for producing a sulfur binder according to any one of claims 1 to 6, wherein the heat treatment is performed so that the temperature is 15 to 1000 mPa · s at ° C. 8. A sulfur binder obtained by the method according to any one of claims 1 to 7. 9. A method for producing a sulfur composition, comprising heat-treating sulfur, dicyclopentadiene, a hydroaromatic compound, and an aggregate, followed by cooling. 10. A method for producing a sulfur composition, comprising melt-mixing a sulfur binder-containing material containing the sulfur binder according to claim 8 and an aggregate, followed by cooling. 11. The temperature at the time of melt mixing is 120 to 155 ° C.
The method for producing a sulfur composition according to claim 10, wherein 12. The final viscosity of the sulfur binder constituting the sulfur composition after melt mixing at 140 ° C. is 15 to 1000.
The method for producing a sulfur composition according to any one of claims 9 to 11, wherein the pressure is mPa · s.