JP2000264714A - Production of sulfur composition hardened body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material suitable for obtaining a tough and dense large- sized molding by injecting a fluid prepared by mixing sulfur and fly ash in a specified weight ratio under heating in a specified temperature range into a molding formed by mixing sulfur and fly ash in a specified weight ratio at a specified temperature or below and molding the mixture and carrying out integration and solidification by cooling. SOLUTION: A fluid prepared by mixing sulfur and fly ash in a weight ratio of 1:(0.1-1.5) under heating at 120-160 deg.C is molded at ordinary temperature or after heating to <160 deg.C, preferably 120-160 deg.C to form a primary molding. Sulfur and fly ash are mixed in a weight ratio of 1:(1-4) at <=160 deg.C and the mixture is injected as an injection into the primary molding while it is in a fluid state. When a secondary molding to be finally obtained is similar in shape to the primary molding and the primary molding is formed by molding in a metallic mold, the injection is directly poured into the mold without releasing the primary molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cured sulfur composition comprising sulfur and fly ash. More specifically, the present invention relates to a production method for obtaining a high-strength cured product of a sulfur composition composed of sulfur and fly ash that can be used for a relatively large molded product.

[0002]

2. Description of the Related Art There is known a sulfur mortar or a sulfur concrete in which an aggregate is mixed with sulfur, kneaded at a temperature at which the sulfur melts, and then cooled and solidified. When producing sulfur mortar or concrete, in order to prevent the separation of sulfur from the aggregate and to reduce shrinkage and void formation during cooling and solidification, a fly that is inert to sulfur at or below its melting temperature is used. BACKGROUND ART Fillers made of fine powders of mineral substances such as ash, silica, and clay minerals have been used. The effect can be enhanced by increasing the amount of the filler.

[0003] However, when the compounding amount of the filler is large, since the filler itself is a substance having almost no curability, the strength of the obtained sulfur concrete or the like decreases, and the fluidity of the kneaded material decreases. When poured into a mold, there is a problem that many voids tend to remain and a concrete molded product having sufficient strength cannot be obtained. Although such a problem can be solved by applying a considerable amount of pressure during molding, on the other hand, a pressure molding machine capable of generating a high pressure of at least about 1000 N / cm ² is required. In addition to the remarkable increase in cost, the pressure molding machine itself was huge and easily hindered in terms of installation location and operation efficiency. Further, it is extremely difficult to cope with a complicated shaped product by such a method.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems found in conventional sulfur concrete and the like from the viewpoint of production, and is particularly advantageous in that it is strong and dense without the need for a large-scale press forming apparatus. An object of the present invention is to provide a method for producing a cured sulfur composition suitable for obtaining a large-sized molded product.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted various studies to achieve the above object, and as a result, have used fly ash produced as an industrial by-product from the viewpoint of resource reuse as a filler material, and have previously made a filler and sulfur A molded product obtained by molding a mixture having a specific blending ratio under no or low pressure, or a filled product obtained by filling a mold with crushed powder obtained by crushing the molded product; By injecting the fluidized mixture, it was found that the voids in the molded product or the filling were sufficiently filled, and a strong and relatively large cured product was easily obtained, and the invention was completed.

That is, according to the present invention, a fluid obtained by heating and mixing sulfur 1 and fly ash 0.1 to 1.5 at a weight ratio of 120 to 160 ° C. is used. A method for producing a cured product of a sulfur composition, comprising: injecting a mixture obtained by molding the mixture at a temperature of 160 ° C. or less, injecting the mixture, integrating the mixture, and solidifying by cooling.

Further, the present invention is the above-mentioned method for producing a sulfur composition, wherein the density of the molded product is 1.3 or more.

The present invention also provides a method for crushing a molded product obtained by molding a mixture of fly ash 1 to 4 at a temperature of 160 ° C. or less with respect to a sulfur ratio of 1 and filling the crushed product in a mold. Next, fly ash 0.1-1.
5 is heated and mixed at 120 to 160 ° C. and poured into the mold, integrated with the filling in the mold, and cooled and solidified, thereby producing a cured sulfur composition. is there.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically.
The sulfur composition cured product of the present invention is composed of fly ash and sulfur as fillers, but may be one containing a known concrete aggregate. The sulfur used in the present invention may include elemental sulfur. Such sulfur may be obtained by any production method, and may be, for example, sulfur produced by-product in a petroleum refining step or commercially available as a reagent. The fly ash contained in the sulfur composition has an average particle diameter of 0.005 mm.
0.3 mm, preferably 0.005 to 0.1 mm, more preferably 0.007 mm to 0.030 mm.

The weight ratio of sulfur and fly ash to sulfur 1 is 1 to 4, preferably 2
-3 are blended and mixed. If the mixing ratio of fly ash exceeds 4 with respect to 1 of sulfur, the amount of sulfur having a function as a binder is relatively reduced, so that a hard cured product cannot be obtained. If the compounding ratio is less than 1 with respect to 1, the sulfur is undesirably solidified with considerable shrinkage and easily causing cracks and voids. The mixing can be carried out at room temperature, but desirably at 120-160 ° C., the mixture becomes more uniform. Any mixing method may be used as long as it is a known mixing or pulverization mixing operation. For example, the mixing can be performed using a pulverizer such as an iron ball mill. The mixing time may be appropriately selected depending on the processing amount, the mixing device, and the like, but is preferably approximately 5 minutes to 60 minutes. In addition, a known aggregate for concrete can be blended into the mixture, if necessary, in such a manner that a part of the fly ash blending amount is replaced.

The obtained mixture is heated at room temperature or at a temperature not exceeding 160 ° C., preferably at 120 to 160 ° C. to form a molded product (primary molded product). still,
If the heating temperature exceeds 160 ° C., the viscosity of the molten sulfur rapidly increases, which is not preferable. Molding method, preferably uniaxial press molding machine, extrusion molding machine, roll forming machine, using a briquetting machine, etc., 2000N / cm ² or less of the surface weight, more preferably in terms load of 300~1500N / cm ² Press molding. Even if a surface load exceeding 2,000 N / cm ² is applied, the improvement of the strength of the molded product can hardly be expected. If the surface load is less than 300 N / cm ² , the density of the molded product is undesirably low. In order to finally obtain a strong cured product, the density of the primary molded product needs to be 1.3 or more, and if the pressing force is increased, the density is also increased. Weight) is adjusted appropriately. If the primary molded article density is less than 1.3, it is difficult to form a strong cured product. Water, lower alcohol, etc. as a molding aid at the time of molding 1-5% by weight
It may be added to some extent.

Next, the same amount of sulfur and fly ash as described above is used in a weight ratio of 0.1 to 1.5, preferably 0.5 to 1.2, and most preferably about 1 with respect to 1 of sulfur. And kneading and mixing using a stirrer or kneader while heating to 120 to 160 ° C. Heating temperature is 120 ° C
If it is less than 10%, the sulfur does not melt, which is not preferable. The sulfur and fly ash used for this mixing are desirably those obtained by heating and melting sulfur at 120 to 160 ° C, and those obtained by heating fly ash to the same temperature as sulfur. If the amount of fly ash to be added to the sulfur is less than 0.1 in terms of the weight ratio to 1 of the sulfur, cracks due to solidification shrinkage of the sulfur during cooling are likely to occur.
An amount exceeding 5 is not preferred because the fluidity of the mixture is poor.

While the kneaded mixture has fluidity, it is poured into the molded product (primary molded product) obtained by the above-mentioned molding as an injectable material. The injection method is, for example, when the cured molded product (secondary molded product) to be finally obtained and the primary molded product have substantially the same shape and dimensions, if the primary molded product is obtained by molding, the molded product is placed in a mold. It is only necessary to pour the injection directly into the mold while holding it. Also, in the case of a molded product obtained by another molding method or when the secondary molded product is larger than the primary molded product, the primary molded product is generally placed in a form having an inner shape corresponding to the secondary molded product. It is sufficient to fill only the amount that can be filled and pour the infusate into this.
Desirably, it is necessary to consider the shape of the primary molded product in advance so that a gap is not generated as much as possible when the primary molded product is filled in the mold. In any case, it is recommended that the mold be heated to 50 to 160 ° C. at the time of pouring, since the cooling and solidification of sulfur immediately after pouring can be prevented, and more uniform filling is recommended to every corner. You. Further, when the injection is performed while the mold is vibrated, the injection time can be reduced and the injection can be performed without unevenness. After the injection, the solidified product is cooled and solidified by natural cooling, water cooling, or the like, whereby a cured product (a secondary molded product) in which the molded product and the injected product are integrated can be obtained. In the case where a molded article having a complicated shape or the like is to be used, it is more preferable to perform the following method.

According to another embodiment of the present invention, the same raw material as above is mixed with sulfur 1 and fly ash 1-4 at a weight ratio of 160 ° C. or less, and the mixture is heated to 160 ° C. by any known molding technique. A primary molded product having an arbitrary bulk density molded below is crushed, and the crushed powder is filled in a mold having a desired shape. Next, the same sulfur and fly ash as described above, with respect to sulfur 1 by weight ratio, fly ash 0.1 to 1.5,
It is preferably blended to be 0.5 to 1.2,
The mixture is kneaded and mixed using a stirrer or a kneader while heating to ~ 160 ° C. The obtained fluid mixture is used as an injection, and injected into a mold filled with crushed powder. Desirably, at the time of the injection, heating the mold to 50 to 160 ° C. can prevent the solidification of the sulfur immediately after the injection, so that the sulfur is uniformly filled to every corner. After the casting, the mold contents are cooled and solidified by natural cooling, water cooling, or the like, whereby a cured product (secondary molded product) in which the crushed powder filling and the casting are integrated can be obtained.

[0015]

[Example 1-4] 74μ classified and adjusted with a sieve
m and a fly ash powder having an average particle diameter of 20 μm were blended in a weight ratio shown in Table 1, and pulverized and mixed at room temperature for 30 minutes using an iron ball in an iron ball mill. After mixing, the mixture was discharged from the ball mill into a stainless steel vat, which was heated in a high-temperature bath at about 150 ° C. for 180 minutes, and the heated mixture was uniaxially pressed into a 50 × 50 × 50 mm cubic shape at a surface pressure of 1000 N / cm ^2. It was pressed. Table 1 shows the bulk density (calculated from the volume and weight calculated from the shape and dimensions) of the obtained molded product. 500 moldings of 500 × 500 × 500
mm. Next, after mixing and pulverizing a mixture of sulfur and fly ash composed of the same raw materials and the same as described above at room temperature for 10 minutes using an iron ball in an iron ball mill, the mixed and pulverized product was discharged into a stainless steel vat, and this was subjected to about 150 mm in a high-temperature bath. The mixture was heated at 180 ° C. for 180 minutes, and the mixture was kneaded with a stirrer. While this kneaded material has fluidity, it is used as an infusate,
1000 cubic moldings were filled and poured into a mold heated to about 130 ° C. At the time of pouring the injection, only the mold of Example 5 was placed on a vibration table and injection was performed while vibrating. In each case, after heating was performed until the pouring was completed, the mixture was allowed to cool naturally to be solidified, then removed from the mold, and the cured product was taken out. The obtained cured product was measured for bulk density (calculated from the volume and weight calculated from the shape and dimensions) and measured for compressive strength (by a method based on JIS R1108). The results are shown in Table 1. No cracks were observed in any of the cured products.

[0016]

[Table 1]

[Example 6-8] Table 1 shows flake-like sulfur in a heat-resistant glass container heated to 150 ° C in a high-temperature bath and fly ash powder separately heated to 150 ° C and having an average particle diameter of 20 µm. They were blended in a weight ratio, placed in a stainless steel container heated and maintained at 150 ° C., and mixed with a stirrer for 30 minutes. While the mixture was warm, it was filled into a mold and a 10 mm cubic molded product was molded with a briquette machine. After molding, the bulk density of the molded product was calculated in the same manner as in Example 1. On the other hand, the same flaky sulfur and fly ash powder were each heated at 150 ° C., and these heated materials were mixed and kneaded for 30 minutes using a hand mixer in a container heated to 150 ° C. so as to have the composition shown in Table 1. A flowable injection was made. Then, the inner diameter 500 × 5
A mold having a size of 00 × 500 mm was filled with 7,000 cubic products of 10 mm 3 previously prepared, and the injection material was poured into the mold. After the filling and pouring were completed, the heating was stopped, the mixture was allowed to cool naturally to be solidified, and then released from the mold to obtain a cured product. The bulk density and compressive strength of the obtained cured product were calculated in the same manner as in Example 1. The results are shown in Table 1. No cracks were observed in any of the cured products.

[Example 9-12] Classified and adjusted 74 μm
m and fly ash powder having an average particle diameter of 20 μm were blended at the weight ratio shown in Table 1, and pulverized and mixed at room temperature for 30 minutes using an iron ball in an iron ball mill. After mixing, the mixture was discharged from the ball mill into a stainless steel vat, which was heated in a high-temperature bath at about 150 ° C. for 180 minutes. The heated mixture is subjected to a surface pressure of 500 N / cm ² at 1000 × 1000 × 10
It was uniaxially pressed into a 00 mm cube. This molded product is disintegrated with a jaw crusher and 300 μm
The following ground powder was obtained. On the other hand, the same sulfur powder and fly ash powder as described above were pulverized at room temperature using an iron ball in an iron ball mill with the composition shown in Table 1, and then the pulverized material was discharged into a stainless steel vat. While heating
The mixture was mixed and kneaded with a stirrer for 60 minutes. The obtained kneaded material having fluidity was used as an injectable material, and was simultaneously mixed with the crushed powder at room temperature.
It was filled in a wood pattern of 00 × 1600 × 1600 mm. This was allowed to cool naturally to be solidified and then demolded to obtain a cured product.
The cured product was measured for bulk density and compressive strength in the same manner as in Example 1. The results are shown in Table 1. No cracks were observed in any of the cured products.

Comparative Example 1-3 A cured product was prepared in the same manner as in Example 1 except that the same sulfur powder and fly ash powder as in Example 1 were used, and only the compounding ratio was set to the value shown in Table 1. Produced. Cracks were observed in all of the obtained cured products.
The bulk density and compressive strength were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 Sulfur powder having a particle size of less than 74 μm and fly ash powder having an average particle diameter of 20 μm were subjected to classification adjustment.
They were blended in the weight ratio shown in Table 1 and mixed with a hand mixer in an oil bath heated to 150 ° C. While the mixture was warm, it was poured into a mold at room temperature as an injection, allowed to cool naturally, and removed from the mold to obtain a cured product. In the obtained cured product, cracking was considerably observed. The bulk density and compressive strength were measured in the same manner as in Example 1. The results are shown in Table 1.

[0021]

According to the method for producing a cured product of a sulfur composition of the present invention, a sulfur concrete product or the like which conventionally required a large-scale pressurizing device can be made strong and strong even with a simple and low-pressure device. A dense and large cured product can be easily obtained.

Claims (3)

[Claims] 1. Sulfur 1 and fly ash 0.1 by weight ratio
To 1.5 are heated and mixed at 120 to 160 ° C., and sulfur 1 and fly ash 1 to 4 are mixed in a weight ratio of 160 to 160.
Injected into a molded product obtained by molding a mixture mixed at a temperature of
A method for producing a cured sulfur composition, which is integrated and cooled and solidified. 2. The method for producing a cured sulfur composition according to claim 1, wherein the density of the molded product is 1.3 or more. 3. The method of claim 1 wherein the weight ratio of sulfur to 1 and fly ash is 1.
-4 are mixed at a temperature of 160 ° C. or less, the molded product is crushed, and the crushed material is filled in a mold. Then, 0.1 to 1.5 fly ash is added to sulfur at a weight ratio of 1 to 1. 120-
A fluid obtained by heating and mixing at 160 ° C. is poured into the mold,
A method for producing a cured sulfur composition, which is integrated with a filling in a mold and solidified by cooling.