WO2011114923A1 - Modified sulfur material and method for producing same - Google Patents

Modified sulfur material and method for producing same Download PDF

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Publication number
WO2011114923A1
WO2011114923A1 PCT/JP2011/055205 JP2011055205W WO2011114923A1 WO 2011114923 A1 WO2011114923 A1 WO 2011114923A1 JP 2011055205 W JP2011055205 W JP 2011055205W WO 2011114923 A1 WO2011114923 A1 WO 2011114923A1
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Prior art keywords
modified sulfur
sulfur
modified
sulfur material
surface area
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PCT/JP2011/055205
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French (fr)
Japanese (ja)
Inventor
勉 木原
敏夫 森弘
秀之 堀井
陽佳 井上
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Ｊｘ日鉱日石エネルギー株式会社
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Publication of WO2011114923A1 publication Critical patent/WO2011114923A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/36—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing sulfur, sulfides or selenium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention is useful for producing civil engineering and construction products from modified sulfur, and is a storable and easy-to-carry product that exhibits excellent flame retardancy as a non-hazardous material that is verified by a small gas flame ignition test.
  • the present invention relates to a quality sulfur material and a manufacturing method thereof.
  • Patent Document 1 discloses a modified sulfur using modified sulfur and fine aggregate that can be safely and easily used for manufacturing a sulfur product and can be handled as a non-hazardous material in a small gas flame ignition test. Materials and their manufacturing methods have been proposed.
  • Patent Documents 2 to 5 disclose that sulfur and a specific surface area of a brain are 2000 cm 2 / g or more as a method for producing a high-strength and high-density sulfur concrete by suppressing cracking due to shrinkage during solidification of the sulfur composition.
  • a technology for mixing mineral fine powder such as fly ash at a specific ratio has been proposed.
  • the blending of the fine mineral powder having a specific Blaine specific surface area described in these documents is for obtaining the strength and the like, and the sulfur concrete described in these documents is the sulfur modifier at the time of production. It is not intended for use, and no investigation has been made on the reaction control of melt-modified sulfur during production and the flame retardancy of the resulting sulfur concrete.
  • An object of the present invention is to provide a civil engineering / building product that can be handled as a non-hazardous material, exhibits excellent flame retardancy, can suppress an excessive increase in viscosity during melting, and uses modified sulfur safely and easily.
  • An object of the present invention is to provide a modified sulfur material that can be produced and a method for producing the same.
  • a modified sulfur binder containing polysulfide obtained by reacting sulfur with a sulfur modifier, and a fine aggregate having a particle size passing through a nominal opening of JIS standard sieve of 1.00 mm.
  • a modified sulfur material containing a JIS standard sieve with a maximum dimension of 101.6 mm or less A modified sulfur material characterized in that it contains coal ash having a Blaine specific surface area of 3000 to 5500 cm 2 / g as the fine aggregate.
  • a modification characterized by comprising a step (b) and a step (c) in which the mixture obtained in the step (b) is cooled and solidified to a maximum size of 101.6 mm or less using a JIS standard sieve.
  • a method for producing a sulfur material is provided.
  • the modified sulfur material of the present invention contains a modified sulfur binder containing polysulfide and coal ash having a specific brane specific surface area, so that it can be made non-hazardous and has excellent flame retardancy. It is excellent in mixing with coarse aggregate when producing civil engineering and building products, and excessive viscosity increase can be suppressed. Therefore, it is easy to manage, store and transport and is extremely useful for the production of sulfur products. Since the method for producing the modified sulfur material of the present invention includes the steps (a) to (c), the modified sulfur material of the present invention can be efficiently produced with easy control.
  • the modified sulfur material of the present invention comprises a modified sulfur binder containing polysulfide obtained by reacting sulfur and a sulfur modifier, and a specific brain having a particle diameter passing through a nominal opening of JIS standard sieve of 1.00 mm. And a fine aggregate having a specific surface area and having a maximum dimension of 101.6 mm or less with a JIS standard sieve.
  • the modified sulfur material of the present invention has a viscosity when heated and melted at 140 ° C., usually 0.05 to 3.0 Pa ⁇ s, preferably 0.2 to 2.0 Pa ⁇ s, particularly preferably 0.5 to 1.5 Pa ⁇ s.
  • the viscosity is a value measured with a B-type viscometer.
  • the modified sulfur binder that can be used in the modified sulfur material of the present invention includes a polysulfide obtained by polymerizing sulfur with a sulfur modifier, and is a reaction product of sulfur and the sulfur modifier.
  • the sulfur is ordinary sulfur alone.
  • the polysulfide contained in the modified sulfur binder is an insoluble component when extraction is performed at room temperature for 4 hours using a large excess of toluene in the modified sulfur binder.
  • the content ratio of the polysulfide contained in the modified sulfur binder is usually 5 to 30% by mass, preferably 8 to 25% by mass, and more preferably 12 to 25% by mass, based on the total amount of the modified sulfur binder. If the polysulfide content is less than 5% by mass, it may be difficult to ensure the desired flame retardancy. If it exceeds 30% by mass, the viscosity of the modified sulfur binder will increase and mix with fine aggregates. May be difficult.
  • Examples of the sulfur modifier used for the production of the modified sulfur binder include dicyclopentadiene (abbreviated as DCPD), tetrahydroindene (abbreviated as THI), ethylidene norbornene (abbreviated as ENB), or two or more kinds thereof. A mixture is mentioned.
  • Examples of DCPD include DCPD alone or a mixture mainly composed of DCPD and a cyclopentadiene di- to pentamer. The content of DCPD in the mixture is usually 70% by mass or more, preferably 85% by mass or more. Therefore, many commercially available products called so-called dicyclopentadiene can be used.
  • THI for example, one or two or more selected from the group consisting of THI alone or THI and a cyclopentadiene simple substance, a polymer of cyclopentadiene or butanediene, and a dimer to tetramer of cyclopentadiene are mainly used.
  • the mixture with what is comprised is mentioned.
  • the content of THI in the mixture is usually 50% by mass or more, preferably 65% by mass or more. Therefore, most of the by-product oil discharged from commercial products called tetrahydroindene and ENB production plants can be used as THI used in the present invention.
  • ENB examples include commercially available products called so-called ethylidene norbornene, and ENB purity of usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 98% by mass or more.
  • the crude ENB in the previous stage for purifying ENB in the production plant can contain a trace amount of vinyl norbornene, but can be used if the purity is satisfied.
  • the mixture containing 20 mass% or more of by-products, such as THI, as a by-product oil in an ENB manufacturing plant can also be used.
  • the fine aggregate contained in the modified sulfur material of the present invention contains coal ash having a specific surface area of 3000 to 5500 cm 2 / g, preferably 3500 to 4500 cm 2 / g, more preferably 3800 to 4500 cm 2 / g.
  • the brane specific surface area of the coal ash is low, the resulting modified sulfur material becomes flammable, whereas when the brane specific surface area is high, when the modified sulfur material of the present invention is produced, The viscosity rises in a short time, and the viscosity of the resulting modified sulfur material when heated to the above-mentioned 140 ° C. increases, which may hinder the production of civil engineering and building products.
  • the coal ash used in the present invention is discharged from various coal-fired furnaces for power generation and heating, and fly ash conventionally used as a concrete or civil engineering material mixture can be used. It can be obtained by blending standard products so as to be in the range.
  • fly ash that has been used as a modified sulfur material has a brane specific surface area of less than 3000 cm 2 / g, usually referred to as a specific surface area of 2500 cm 2 / g or more. Even when such coal ash is used, as described in Patent Document 1, a modified sulfur material that can be handled as a non-hazardous material in a small gas flame ignition test can be manufactured.
  • the flame retardancy is further improved, it has the above-mentioned viscosity range at 140 ° C., and it is easy to control the viscosity when producing civil engineering and building products.
  • the brain specific surface area is a value measured by a method defined in JIS A6201 (fly ash for concrete).
  • the fine aggregate used in the present invention includes, for example, natural stone, sand, rubble, dredged sand, steel slag, ferronickel slag, copper slag, by-products generated during metal production, fuel incineration ash, electric current collection
  • Other fine aggregates such as inorganic and organic materials that do not contain powder or harmful substances equivalent to these may be included.
  • the content of these other fine aggregates is usually about 0 to 10% by mass, preferably about 0 to 5% by mass, based on the total amount of fine aggregates.
  • the blending ratio of the modified sulfur binder and the fine aggregate is 25 to 300 parts by mass of the fine aggregate, preferably 100 parts by mass of the modified sulfur binder. 30 to 250 parts by mass. If the proportion of fine aggregate is small, it may be difficult to satisfy the requirements of being certified as non-dangerous goods by the small gas flame ignition test. On the other hand, when the blending ratio of the fine aggregate is large, the modified sulfur binder and the fine aggregate may be separated and it may be difficult to obtain a uniform material.
  • the modified sulfur material of the present invention can be obtained, for example, by the production method of the present invention described below.
  • the production method of the present invention includes a step (a) in which sulfur and a sulfur modifier are mixed and reacted at 120 to 150 ° C. in order to obtain a modified sulfur binder containing polysulfide.
  • the ratio of the sulfur modifier used when mixing and reacting sulfur and the sulfur modifier is usually 0.1 to 25% by mass with respect to the total amount of sulfur and sulfur modifier. Preferably, it is 1.0 to 5.0% by mass.
  • the use ratio of the sulfur modifier is small, the reaction time becomes long, and the desired excellent physical properties and performance may not be obtained.
  • reaction control becomes difficult and there is a possibility that it becomes economically disadvantageous.
  • the reaction conditions in the step (a) are 120 to 150 ° C., preferably 130 to 150 ° C., more preferably 135 to 140 ° C., preferably depending on the type and use ratio of the sulfur modifier. Can be carried out in a reaction time in which the amount of polysulfide produced is in the above range. Such a reaction time is usually about 1 to 10 hours, preferably about 2 to 6 hours.
  • the mixing reaction can be performed, for example, by a method in which sulfur is first heated and melted, and then a predetermined amount of the sulfur modifier is added little by little.
  • a predetermined amount of the sulfur modifier is added little by little.
  • the phase change from solid to liquid begins at 119 ° C.
  • the whole is stirred and the viscosity is measured with an appropriate viscometer, for example, a B-type viscometer.
  • an appropriate viscometer for example, a B-type viscometer.
  • the speed of the viscosity increase of the melt during the mixing reaction is related to the reaction temperature, and the higher the temperature, the faster. If the melt mixing temperature is less than 120 ° C., sulfur is not easily modified. On the other hand, when the melt mixing temperature exceeds 150 ° C., the viscosity rises rapidly and tends to be difficult to control. When the melt mixing temperature is about 130 ° C., the polymerization reaction between sulfur and the sulfur modifier is slow, no sudden heat generation and no viscosity increase occur, and only a slight temperature increase and viscosity increase are observed. maintain. Therefore, after confirming that no exotherm occurs, the mixing reaction of step (a) can be performed by gradually raising the temperature to the temperature range.
  • a mixer for liquid stirring is mainly used. Is preferred. Examples thereof include an internal mixer, a roll mill, a drum mixer, a pony mixer, a ribbon mixer, a homomixer, and a static mixer.
  • the production method of the present invention comprises a nominal opening of a JIS standard sieve comprising a melt of the modified sulfur binder obtained in step (a) and coal ash having a specific surface area of 3000 to 5500 cm 2 / g.
  • the mixing ratio of the modified sulfur binder obtained in the step (a) and the fine aggregate is usually 10 to 50:90 to 50, preferably 15 to 30:85 in mass ratio. ⁇ 70.
  • the most desirable is the case where the modified sulfur binder is blended in such an amount that fills the voids when the fine aggregate has a close-packed structure, in which case the strength is highest.
  • the mixing ratio of the modified sulfur binder is less than the above range, the surface of the fine aggregate cannot be sufficiently wetted, the strength is not sufficiently developed, and the water shielding property may not be maintained. On the other hand, when the mixing ratio exceeds the above range, the strength tends to decrease.
  • the heat mixing is usually performed at 0.05 to 3.0 Pa ⁇ s, preferably 0.2 to 2.0 Pa ⁇ s, when the obtained melt of the modified sulfur material is converted to 140 ° C., for example. s, particularly preferably in a range of 0.5 to 1.5 Pa ⁇ s.
  • Such heating and mixing is preferably performed in a mixer in which the modified sulfur binder and fine aggregate heated and melted to 120 to 150 ° C., particularly preferably 130 to 140 ° C., are preheated to 120 to 155 ° C. in advance. It can be carried out at the same time and can be carried out at a temperature of usually 120 to 150 ° C., preferably 130 to 140 ° C.
  • the mixing time is usually about 1 minute to 1 hour, preferably about 5 to 30 minutes.
  • the mixing time is less than 1 minute, uniform mixing tends to be difficult.
  • the mixing time exceeds 1 hour, the viscosity of the modified sulfur binder may increase. .
  • the mixing in the step (b) may be performed using any mixer as long as the mixing can be sufficiently performed, and preferably for solid-liquid stirring.
  • any mixer for example, an internal mixer, a roll mill, a ball mill, a drum mixer, a screw extruder, a pug mill, a pony mixer, a ribbon mixer, and a kneader can be used.
  • the production method of the present invention includes a step (c) of cooling and solidifying the mixture obtained in the step (b) so that the maximum dimension is 101.6 mm or less using a JIS standard sieve.
  • cooling and solidification can be performed by cooling the mixture obtained in step (b) to below 120 ° C.
  • the mixture can be made into a desired form such as a molded product, a pellet, a crushed product or a granular product.
  • the mixture obtained in the step (b) can be cooled to an irregular shape to obtain a lump solidified product, and the solidified product can be crushed to the above size to obtain a modified sulfur material.
  • the modified sulfur material obtained by the production method of the present invention can be made into an arbitrary structure by reheating, and exhibits excellent flame retardancy.
  • panel materials, floor materials, wall materials, etc. can be used as a roof tile, an underwater structure, and as a granular material, it can also be used as a landfill material, a roadbed material, a banking material, and an aggregate for concrete.
  • this excellent flame retardancy makes the transportation safer and easier, and enables mass production at a place other than the site.
  • Ignition resistance Evaluated according to the ignitability test for the evaluation of flammable solids (dangerous goods type 2) in the Japanese Fire Service Act. A type 1 combustible solid that ignites within 3 seconds and continues to burn for 10 seconds or more and a type 2 combustible solid that ignites within 10 seconds over 3 seconds and continues to burn “Ignition”, those that ignite for more than 10 seconds, and those that do not continue combustion were designated as “no danger”.
  • Viscosity A value measured with a B-type viscometer. The fine aggregate used was adjusted in advance to a particle size that passed through a nominal opening of 1.00 mm of a JIS standard sieve using a JIS sieve.
  • Example 1 After putting 970 g of solid sulfur in the stirring and mixing tank and melting at 140 ° C., 30 g of ENB was slowly added. The reaction started and a temperature increase of about 5 ° C. was observed, after which the temperature decreased and the reaction was continued at 140 ° C. The viscosity gradually increased, and after 4 hours, when the viscosity reached 0.06 Pa ⁇ s, the heating was immediately stopped, poured into an appropriate mold or container, and cooled at room temperature to obtain a modified sulfur binder. The modified sulfur binder was powdered, extracted with a large excess of toluene at room temperature for 4 hours, and the insoluble content was measured to be 15.2% by mass (polysulfide content).
  • Example 2 A modified sulfur material (B) was prepared in the same manner as in Example 1 except that the reaction time between sulfur and ENB was 2.5 hours, and coal ash having a specific surface area of 3720 cm 2 / g was used. did.
  • the viscosity at 140 ° C. of the modified sulfur material (B) was 0.53 Pa ⁇ s.
  • the polysulfide content of the modified sulfur binder obtained in the middle was 11.5% by mass.
  • Example 1 A modified sulfur material (C) was prepared in the same manner as in Example 1 except that coal ash having a specific surface area of 1880 cm 2 / g was used.
  • the viscosity at 140 ° C. of the modified sulfur material (C) was 0.47 Pa ⁇ s.
  • the polysulfide content of the modified sulfur binder obtained in the middle was 15.2% by mass as in Example 1.
  • Example 2 A sulfur material (D) was prepared in the same manner as in Example 2 except that ENB was not used and the binder was pure sulfur.
  • the viscosity at 140 ° C. of the sulfur material (D) was 0.08 Pa ⁇ s.
  • Example 3 A modified sulfur material (E) was prepared in the same manner as in Example 1, except that coal ash having a specific surface area of 5990 cm 2 / g was used.
  • the viscosity at 140 ° C. of the modified sulfur material (E) was as extremely high as about 48 Pa ⁇ s, and it was difficult to uniformly distribute the coal ash, and the handleability was poor.
  • the polysulfide content of the modified sulfur binder obtained in the middle was 15.2% by mass as in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Structural Engineering (AREA)
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Abstract

Disclosed is a modified sulfur material, which exhibits superior flame resistance, in which excessive viscosity increases can be controlled during melting and which can safely and easily produce civil engineering and construction products that use modified sulfur. Also disclosed is a method of producing the same. The modified sulfur material contains a modified sulfur bonding material that includes a polysulfide and is obtained by reacting sulfur and a sulfur modifier, and a fine aggregate with a particle diameter that passes through a JIS standard sieve with nominal diameter openings of 1.00 mm. The maximum dimension of the modified sulfur material is 101.6 mm or less using a JIS standard sieve and coal ash for which the Blaine specific surface area is 3000 - 5500 cm2/g is included for the fine aggregate.

Description

改質硫黄資材およびその製造方法Modified sulfur material and method for producing the same
　本発明は、改質硫黄から土木・建設製品を製造するのに有用であり、小ガス炎着火試験によって検定される非危険物として優れた難燃性を示す、貯蔵可能で運搬が容易な改質硫黄資材及びその製造方法に関する。 The present invention is useful for producing civil engineering and construction products from modified sulfur, and is a storable and easy-to-carry product that exhibits excellent flame retardancy as a non-hazardous material that is verified by a small gas flame ignition test. The present invention relates to a quality sulfur material and a manufacturing method thereof.
　硫黄資材は、コンクリートに比べて優れた強度を有する材料として知られている。しかし、硫黄は危険物扱いであり、現場で溶融し打設することが困難であった。
　そこで、硫黄資材を非危険物とし、更に強度等の改善を目的に、硫黄を硫黄改質剤により重合反応させた改質硫黄を用いる技術が多数提案されている。例えば、特許文献１には、安全に且つ容易に硫黄製品の製造に利用でき、小ガス炎着火試験において非危険物としての取り扱いが可能な改質硫黄と細骨材とを用いた改質硫黄資材及びその製造方法が提案されている。
　しかし、このような改質硫黄を用いて、骨材と溶融混合する場合、溶融改質硫黄の反応による粘度変化が生じ易く、その製造時における制御が困難である。そこで、このような粘度変化を制御するために、硫黄改質剤の種類等を検討した技術も提案されている。また、特許文献１に提案される、小ガス炎着火試験において非危険物と判定された改質硫黄資材の更なる難燃性の向上が望まれている。 Sulfur materials are known as materials having superior strength compared to concrete. However, sulfur is handled as a hazardous material, and it has been difficult to melt and place it on site.
Therefore, many techniques using modified sulfur obtained by making sulfur materials non-dangerous and further subjecting sulfur to a polymerization reaction with a sulfur modifier have been proposed for the purpose of improving strength and the like. For example, Patent Document 1 discloses a modified sulfur using modified sulfur and fine aggregate that can be safely and easily used for manufacturing a sulfur product and can be handled as a non-hazardous material in a small gas flame ignition test. Materials and their manufacturing methods have been proposed.
However, when such modified sulfur is used and melt-mixed with the aggregate, a viscosity change due to the reaction of the melt-modified sulfur is likely to occur, and control during production is difficult. Therefore, in order to control such a change in viscosity, a technique has been proposed in which the type of sulfur modifier is examined. Moreover, the further improvement of the flame retardance of the modified sulfur material determined as a non-dangerous substance in the small gas flame ignition test proposed by patent document 1 is desired.
　ところで、特許文献２～５には、硫黄組成物の固化時の収縮による亀裂発生を抑制し、高強度で高緻密な硫黄コンクリートを製造する方法として、硫黄と、ブレーン比表面積２０００ｃｍ2／ｇ以上のフライアッシュ等の鉱物質微粉末とを特定割合で混合する技術が提案されている。
　しかし、これらの文献に記載された特定のブレーン比表面積を有する鉱物質微粉末の配合は、強度等を得るためであって、これらに記載された硫黄コンクリートは、製造時における硫黄改質剤の使用については意図しておらず、製造時における溶融改質硫黄の反応制御や、得られる硫黄コンクリートの難燃性の点については何等検討されていない。 By the way, Patent Documents 2 to 5 disclose that sulfur and a specific surface area of a brain are 2000 cm 2 / g or more as a method for producing a high-strength and high-density sulfur concrete by suppressing cracking due to shrinkage during solidification of the sulfur composition. A technology for mixing mineral fine powder such as fly ash at a specific ratio has been proposed.
However, the blending of the fine mineral powder having a specific Blaine specific surface area described in these documents is for obtaining the strength and the like, and the sulfur concrete described in these documents is the sulfur modifier at the time of production. It is not intended for use, and no investigation has been made on the reaction control of melt-modified sulfur during production and the flame retardancy of the resulting sulfur concrete.
特開２００５－８２４７５号公報JP 2005-82475 A 特開平１１－３４９３７２号公報JP 11-349372 A 特開２０００－７２５２３号公報JP 2000-72523 A 特開２０００－２８１４２５号公報JP 2000-281425 A 特開２００２－２５５６２３号公報JP 2002-255623 A
　本発明の課題は、非危険物としての取り扱いが可能で、優れた難燃性を示し、溶融時に過度な粘度上昇を抑制でき、安全に且つ容易に改質硫黄を用いた土木・建築製品を製造することができる改質硫黄資材及びその製造方法を提供することにある。 An object of the present invention is to provide a civil engineering / building product that can be handled as a non-hazardous material, exhibits excellent flame retardancy, can suppress an excessive increase in viscosity during melting, and uses modified sulfur safely and easily. An object of the present invention is to provide a modified sulfur material that can be produced and a method for producing the same.
　本発明によれば、硫黄と硫黄改質剤とを反応させて得たポリスルフィドを含む改質硫黄結合材と、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径の細骨材とを含む、JIS標準ふるいで最大寸法が１０１．６ｍｍ以下である改質硫黄資材であって、
　前記細骨材として、ブレーン比表面積が３０００～５５００ｃｍ2／ｇの石炭灰を含有することを特徴とする改質硫黄資材が提供される。
　また本発明によれば、ポリスルフィドを含む改質硫黄結合材を得るために、硫黄と硫黄改質剤とを１２０～１５０℃で混合反応させる工程(a)と、工程(a)で得られた改質硫黄結合材の溶融物と、ブレーン比表面積が３０００～５５００ｃｍ2／ｇの石炭灰を含む、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径の細骨材とを加熱混合する工程(b)と、工程(b)で得られた混合物を、JIS標準ふるいで最大寸法が１０１．６ｍｍ以下となるように冷却・固化する工程(c)とを含むことを特徴とする改質硫黄資材の製造方法が提供される。 According to the present invention, a modified sulfur binder containing polysulfide obtained by reacting sulfur with a sulfur modifier, and a fine aggregate having a particle size passing through a nominal opening of JIS standard sieve of 1.00 mm. A modified sulfur material containing a JIS standard sieve with a maximum dimension of 101.6 mm or less,
A modified sulfur material characterized in that it contains coal ash having a Blaine specific surface area of 3000 to 5500 cm 2 / g as the fine aggregate.
Further, according to the present invention, in order to obtain a modified sulfur binding material containing polysulfide, the step (a) in which sulfur and the sulfur modifier are mixed and reacted at 120 to 150 ° C. and the step (a) are obtained. Heat-mix the melt of the modified sulfur binder and fine aggregate with a particle size passing through a nominal opening of JIS standard sieve containing coal ash having a specific surface area of 3000 to 5500 cm 2 / g. A modification characterized by comprising a step (b) and a step (c) in which the mixture obtained in the step (b) is cooled and solidified to a maximum size of 101.6 mm or less using a JIS standard sieve. A method for producing a sulfur material is provided.
　本発明の改質硫黄資材は、ポリスルフィドを含む改質硫黄結合材と、特定のブレーン比表面積を有する石炭灰とを含有するので、非危険物とすることが可能で、優れた難燃性を示し、且つ土木・建築製品を製造する際の粗骨材との混合性に優れ、その際の過度な粘度上昇を抑制することができる。従って、管理、保管、運搬が容易で、硫黄製品の製造に極めて有用である。
　本発明の改質硫黄資材の製造方法は、上記工程(a)～(c)を含むので、本発明の改質硫黄資材を、容易な制御で、効率良く製造することができる。 The modified sulfur material of the present invention contains a modified sulfur binder containing polysulfide and coal ash having a specific brane specific surface area, so that it can be made non-hazardous and has excellent flame retardancy. It is excellent in mixing with coarse aggregate when producing civil engineering and building products, and excessive viscosity increase can be suppressed. Therefore, it is easy to manage, store and transport and is extremely useful for the production of sulfur products.
Since the method for producing the modified sulfur material of the present invention includes the steps (a) to (c), the modified sulfur material of the present invention can be efficiently produced with easy control.
　以下、本発明を更に詳細に説明する。
　本発明の改質硫黄資材は、硫黄及び硫黄改質剤を反応させて得たポリスルフィドを含む改質硫黄結合材と、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径の特定のブレーン比表面積を有する細骨材とを含み、JIS標準ふるいで最大寸法が１０１．６ｍｍ以下の大きさを有する。
　本発明の改質硫黄資材は、１４０℃で加熱溶融した際の粘度が、通常０．０５～３．０Ｐａ・ｓ、好ましくは０．２～２．０Ｐａ・ｓ、特に好ましくは０．５～１．５Ｐａ・ｓである。該粘度が低い場合には、土木・建築製品を製造する際の粘度制御が困難になる恐れがあり、一方、該粘度が高い場合には、土木・建築製品を製造する際の粗骨材との混合性が低下し、均一製品の製造が困難になる恐れがある。
　ここで、該粘度は、Ｂ型粘度計により測定した値である。 Hereinafter, the present invention will be described in more detail.
The modified sulfur material of the present invention comprises a modified sulfur binder containing polysulfide obtained by reacting sulfur and a sulfur modifier, and a specific brain having a particle diameter passing through a nominal opening of JIS standard sieve of 1.00 mm. And a fine aggregate having a specific surface area and having a maximum dimension of 101.6 mm or less with a JIS standard sieve.
The modified sulfur material of the present invention has a viscosity when heated and melted at 140 ° C., usually 0.05 to 3.0 Pa · s, preferably 0.2 to 2.0 Pa · s, particularly preferably 0.5 to 1.5 Pa · s. If the viscosity is low, it may be difficult to control the viscosity when producing civil engineering / building products. On the other hand, if the viscosity is high, the coarse aggregate used for producing civil engineering / building products Therefore, it is difficult to produce a uniform product.
Here, the viscosity is a value measured with a B-type viscometer.
　本発明の改質硫黄資材に用いることができる改質硫黄結合材は、硫黄改質剤により硫黄を重合したポリスルフィドを含むものであって、硫黄と硫黄改質剤との反応物である。該硫黄は、通常の硫黄単体であり、例えば、天然産又は、石油や天然ガスの脱硫によって生成した硫黄を用いることができる。
　改質硫黄結合材に含まれるポリスルフィドとは、改質硫黄結合材に大過剰のトルエンを用いて室温で４時間抽出を行った際の不溶分である。
　改質硫黄結合材に含まれるポリスルフィドの含有割合は、改質硫黄結合材全量基準で、通常５～３０質量％、好ましくは８～２５質量％、更に好ましくは１２～２５質量％である。ポリスルフィドの含有割合が、５質量％未満では、所望の難燃性確保が困難になる恐れがあり、３０質量％を超えると、改質硫黄結合材の粘度が上昇し、細骨材との混合が困難になる恐れがある。 The modified sulfur binder that can be used in the modified sulfur material of the present invention includes a polysulfide obtained by polymerizing sulfur with a sulfur modifier, and is a reaction product of sulfur and the sulfur modifier. The sulfur is ordinary sulfur alone. For example, sulfur produced naturally or by desulfurization of oil or natural gas can be used.
The polysulfide contained in the modified sulfur binder is an insoluble component when extraction is performed at room temperature for 4 hours using a large excess of toluene in the modified sulfur binder.
The content ratio of the polysulfide contained in the modified sulfur binder is usually 5 to 30% by mass, preferably 8 to 25% by mass, and more preferably 12 to 25% by mass, based on the total amount of the modified sulfur binder. If the polysulfide content is less than 5% by mass, it may be difficult to ensure the desired flame retardancy. If it exceeds 30% by mass, the viscosity of the modified sulfur binder will increase and mix with fine aggregates. May be difficult.
　改質硫黄結合材の製造に用いる硫黄改質剤としては、例えば、ジシクロペンタジエン（ＤＣＰＤと略す）、テトラハイドロインデン（ＴＨＩと略す）、エチリデンノルボルネン（ＥＮＢと略す）又はこれらの２種以上の混合物が挙げられる。
　ＤＣＰＤとしては、ＤＣＰＤ単体、若しくはＤＣＰＤと、シクロペンタジエンの２～５量体を主体に構成される混合物が挙げられる。混合物中のＤＣＰＤの含有量は、通常７０質量％以上、好ましくは８５質量％以上である。従って、いわゆるジシクロペンタジエンと称する市販品の多くは使用可能である。 Examples of the sulfur modifier used for the production of the modified sulfur binder include dicyclopentadiene (abbreviated as DCPD), tetrahydroindene (abbreviated as THI), ethylidene norbornene (abbreviated as ENB), or two or more kinds thereof. A mixture is mentioned.
Examples of DCPD include DCPD alone or a mixture mainly composed of DCPD and a cyclopentadiene di- to pentamer. The content of DCPD in the mixture is usually 70% by mass or more, preferably 85% by mass or more. Therefore, many commercially available products called so-called dicyclopentadiene can be used.
　ＴＨＩとしては、例えば、ＴＨＩ単体、若しくはＴＨＩと、シクロペンタジエンの単体、シクロペンタジエン又はブタンジエンの重合物、シクロペンタジエンの２～４量体からなる群より選択される１種又は２種以上を主体に構成されるものとの混合物が挙げられる。該混合物中のＴＨＩの含有量は、通常５０質量％以上、好ましくは６５質量％以上である。従って、いわゆるテトラハイドロインデンと称する市販品やＥＮＢの製造プラントから排出される副生成油の多くは本発明に用いるＴＨＩとして使用可能である。 As THI, for example, one or two or more selected from the group consisting of THI alone or THI and a cyclopentadiene simple substance, a polymer of cyclopentadiene or butanediene, and a dimer to tetramer of cyclopentadiene are mainly used. The mixture with what is comprised is mentioned. The content of THI in the mixture is usually 50% by mass or more, preferably 65% by mass or more. Therefore, most of the by-product oil discharged from commercial products called tetrahydroindene and ENB production plants can be used as THI used in the present invention.
　ＥＮＢとしては、いわゆるエチリデンノルボルネンと称する市販品や、ＥＮＢの純度が通常８０質量％以上、好ましくは９０質量％以上、更に好ましくは９５質量％以上、最も好ましくは９８質量％以上のものが挙げられる。従って、製造プラントにおいてＥＮＢを精製する前段の粗ＥＮＢは、微量のビニルノルボルネンを含み得るが、前記純度を満足すれば使用可能である。また、ＥＮＢ製造プラントにおける副生油としての、ＴＨＩ等の副生物を２０質量％以上含む混合物も使用可能である。 Examples of ENB include commercially available products called so-called ethylidene norbornene, and ENB purity of usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 98% by mass or more. . Accordingly, the crude ENB in the previous stage for purifying ENB in the production plant can contain a trace amount of vinyl norbornene, but can be used if the purity is satisfied. Moreover, the mixture containing 20 mass% or more of by-products, such as THI, as a by-product oil in an ENB manufacturing plant can also be used.
　本発明の改質硫黄資材に含まれる細骨材は、ブレーン比表面積３０００～５５００ｃｍ2／ｇ、好ましくは３５００～４５００ｃｍ2／ｇ、更に好ましくは３８００～４５００ｃｍ2／ｇの石炭灰を含む。該石炭灰のブレーン比表面積が低い場合には、得られる改質硫黄資材が、易燃性になり、一方、ブレーン比表面積が高い場合には、本発明の改質硫黄資材の製造時において、短時間で粘度上昇が生じ、得られる改質硫黄資材の上述の１４０℃に加熱した際の粘度が上昇し、土木・建築製品の製造に支障をきたすおそれがある。 The fine aggregate contained in the modified sulfur material of the present invention contains coal ash having a specific surface area of 3000 to 5500 cm 2 / g, preferably 3500 to 4500 cm 2 / g, more preferably 3800 to 4500 cm 2 / g. When the brane specific surface area of the coal ash is low, the resulting modified sulfur material becomes flammable, whereas when the brane specific surface area is high, when the modified sulfur material of the present invention is produced, The viscosity rises in a short time, and the viscosity of the resulting modified sulfur material when heated to the above-mentioned 140 ° C. increases, which may hinder the production of civil engineering and building products.
　本発明に用いる前記石炭灰は、発電用、加熱用の各種石炭焚燃焼炉から排出され、コンクリートや土木資材混合材として従来から利用されているフライアッシュを用いることができ、ブレーン比表面積を上記範囲となるように、規格品をブレンド等することにより得ることができる。尚、従来、改質硫黄資材に用いられることがあったフライアッシュは、通常、ブレーン比表面積が２５００ｃｍ2／ｇ以上と称される、ブレーン比表面積が３０００ｃｍ2／ｇ未満のものであった。このような石炭灰を用いた場合にも、特許文献１に記載されるとおり、小ガス炎着火試験において非危険物としての取り扱いが可能な改質硫黄資材を製造することができるが、本発明の改質硫黄資材の場合は、その難燃性を更に改善し、上述の１４０℃における粘度範囲を有し、しかも、土木・建築製品を製造する際の粘度制御が容易である。
　ここで、ブレーン比表面積は、JIS A6201(コンクリート用フライアッシュ)に規定される方法により測定した値である。 The coal ash used in the present invention is discharged from various coal-fired furnaces for power generation and heating, and fly ash conventionally used as a concrete or civil engineering material mixture can be used. It can be obtained by blending standard products so as to be in the range. Conventionally, fly ash that has been used as a modified sulfur material has a brane specific surface area of less than 3000 cm 2 / g, usually referred to as a specific surface area of 2500 cm 2 / g or more. Even when such coal ash is used, as described in Patent Document 1, a modified sulfur material that can be handled as a non-hazardous material in a small gas flame ignition test can be manufactured. In the case of the modified sulfur material, the flame retardancy is further improved, it has the above-mentioned viscosity range at 140 ° C., and it is easy to control the viscosity when producing civil engineering and building products.
Here, the brain specific surface area is a value measured by a method defined in JIS A6201 (fly ash for concrete).
　本発明に用いる細骨材は、上記石炭灰の他に、例えば、天然石、砂、れき、硅砂、鉄鋼スラグ、フェロニッケルスラグ、銅スラグ、金属製造時に生成する副生物、燃料焼却灰、電気集塵灰、溶融スラグ類、貝殻及びこれらの混合物等からなる群より選択される１種又は２種以上の細骨材や、シリカヒューム、アルミナ、石英粉、石英質岩石、粘土鉱物、活性炭、ガラス粉末やこれらと同等の有害物質を含有しない無機系、有機系等の他の細骨材を含んでいても良い。
　これら他の細骨材の含有割合は、細骨材全量基準で、通常、０～１０質量％、好ましくは０～５質量％程度である。 In addition to the coal ash, the fine aggregate used in the present invention includes, for example, natural stone, sand, rubble, dredged sand, steel slag, ferronickel slag, copper slag, by-products generated during metal production, fuel incineration ash, electric current collection One or more fine aggregates selected from the group consisting of dust ash, molten slag, shells and mixtures thereof, silica fume, alumina, quartz powder, quartz rock, clay mineral, activated carbon, glass Other fine aggregates such as inorganic and organic materials that do not contain powder or harmful substances equivalent to these may be included.
The content of these other fine aggregates is usually about 0 to 10% by mass, preferably about 0 to 5% by mass, based on the total amount of fine aggregates.
　本発明の改質硫黄資材において、前記改質硫黄結合材と前記細骨材との配合割合は、改質硫黄結合材１００質量部に対して、前記細骨材２５～３００質量部、好ましくは３０～２５０質量部である。細骨材の配合割合が少ない場合には、小ガス炎着火試験によって非危険物と検定される要件を充足させることが困難になる恐れがある。一方、細骨材の配合割合が多い場合には、改質硫黄結合材と細骨材とが分離して均一な材料が得られ難いおそれがある。 In the modified sulfur material of the present invention, the blending ratio of the modified sulfur binder and the fine aggregate is 25 to 300 parts by mass of the fine aggregate, preferably 100 parts by mass of the modified sulfur binder. 30 to 250 parts by mass. If the proportion of fine aggregate is small, it may be difficult to satisfy the requirements of being certified as non-dangerous goods by the small gas flame ignition test. On the other hand, when the blending ratio of the fine aggregate is large, the modified sulfur binder and the fine aggregate may be separated and it may be difficult to obtain a uniform material.
　本発明の改質硫黄資材は、例えば、以下に説明する本発明の製造方法により得ることができる。
　本発明の製造方法は、ポリスルフィドを含む改質硫黄結合材を得るために、硫黄と硫黄改質剤とを１２０～１５０℃で混合反応させる工程(a)を含む。
　工程(a)において、硫黄と硫黄改質剤とを混合反応させる際の硫黄改質剤の使用割合は、硫黄と硫黄改質剤との合計量に対して、通常０．１～２５質量％、好ましくは１．０～５．０質量％である。硫黄改質剤の使用割合が少ない場合は、反応時間が長くなり、また、所望の優れた物性及び性能が得られないおそれがある。一方、硫黄改質剤の使用割合が多い場合は、反応制御が困難になり、更に経済的に不利になるおそれがある。 The modified sulfur material of the present invention can be obtained, for example, by the production method of the present invention described below.
The production method of the present invention includes a step (a) in which sulfur and a sulfur modifier are mixed and reacted at 120 to 150 ° C. in order to obtain a modified sulfur binder containing polysulfide.
In the step (a), the ratio of the sulfur modifier used when mixing and reacting sulfur and the sulfur modifier is usually 0.1 to 25% by mass with respect to the total amount of sulfur and sulfur modifier. Preferably, it is 1.0 to 5.0% by mass. When the use ratio of the sulfur modifier is small, the reaction time becomes long, and the desired excellent physical properties and performance may not be obtained. On the other hand, when the use ratio of the sulfur modifier is large, reaction control becomes difficult and there is a possibility that it becomes economically disadvantageous.
　工程(a)における反応条件は、１２０～１５０℃、好ましくは１３０～１５０℃、より好ましくは１３５～１４０℃の温度条件で、硫黄改質剤の種類や使用割合に応じて、好ましくは、反応により生成するポリスルフィド量が上述の範囲となる反応時間で行うことができる。このような反応時間は、通常、１～１０時間、好ましくは２～６時間程度である。 The reaction conditions in the step (a) are 120 to 150 ° C., preferably 130 to 150 ° C., more preferably 135 to 140 ° C., preferably depending on the type and use ratio of the sulfur modifier. Can be carried out in a reaction time in which the amount of polysulfide produced is in the above range. Such a reaction time is usually about 1 to 10 hours, preferably about 2 to 6 hours.
　上記混合反応は、例えば、先ず硫黄を加熱溶融した後、所定量の上記硫黄改質材を少しずつ添加する方法により行うことができる。
　通常、固体硫黄を加熱していくと１１９℃で固体から液体への相変化が始まるので、硫黄を液化させてから全体を撹拌し、適当な粘度計、例えばＢ型粘度計で粘度を測定しながら、１３０℃程度まで温度を上昇させた後に、上記硫黄改質材を添加することが、反応制御が容易な点で好ましい。 The mixing reaction can be performed, for example, by a method in which sulfur is first heated and melted, and then a predetermined amount of the sulfur modifier is added little by little.
Usually, when solid sulfur is heated, the phase change from solid to liquid begins at 119 ° C. After liquefying the sulfur, the whole is stirred and the viscosity is measured with an appropriate viscometer, for example, a B-type viscometer. However, it is preferable in terms of easy reaction control that the sulfur modifier is added after the temperature is raised to about 130 ° C.
　前記混合反応時の溶融物の粘度上昇速度は、反応温度に関係し、温度が高いほど速い。溶融混合温度が１２０℃未満では硫黄は容易に変性しない。一方、溶融混合温度が１５０℃を超えると、粘度上昇が急激で制御が困難になる傾向が高い。溶融混合温度が１３０℃程度では、硫黄と硫黄改質材との重合反応は遅く、急な発熱及び粘度上昇は起こらず、僅かな温度上昇と粘度上昇がみられるだけで、ほぼ一定の粘度を維持する。従って、発熱の起こらないことを確認後、前記温度範囲まで次第に温度上昇させることにより工程(a)の混合反応を行うことができる。 The speed of the viscosity increase of the melt during the mixing reaction is related to the reaction temperature, and the higher the temperature, the faster. If the melt mixing temperature is less than 120 ° C., sulfur is not easily modified. On the other hand, when the melt mixing temperature exceeds 150 ° C., the viscosity rises rapidly and tends to be difficult to control. When the melt mixing temperature is about 130 ° C., the polymerization reaction between sulfur and the sulfur modifier is slow, no sudden heat generation and no viscosity increase occur, and only a slight temperature increase and viscosity increase are observed. maintain. Therefore, after confirming that no exotherm occurs, the mixing reaction of step (a) can be performed by gradually raising the temperature to the temperature range.
　工程(a)の混合反応に使用する混合機は、混合が十分に行えるものであれば公知のものが使用でき、改質硫黄結合材の製造には、主に液体撹拌用の混合機の使用が好ましい。例えば、インターナルミキサー、ロールミル、ドラムミキサー、ポニーミキサー、リボンミキサー、ホモミキサー、スタティックミキサーが挙げられる。 As the mixer used for the mixing reaction in the step (a), a known one can be used as long as the mixing can be sufficiently performed. For the production of the modified sulfur binder, a mixer for liquid stirring is mainly used. Is preferred. Examples thereof include an internal mixer, a roll mill, a drum mixer, a pony mixer, a ribbon mixer, a homomixer, and a static mixer.
　本発明の製造方法は、工程(a)で得られた改質硫黄結合材の溶融物と、ブレーン比表面積が３０００～５５００ｃｍ2／ｇの石炭灰を含む、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径の細骨材とを加熱混合する工程(b)を含む。
　工程(b)において、工程(a)で得られた改質硫黄結合材と、上記細骨材との混合割合は、質量比で通常１０～５０：９０～５０、好ましくは１５～３０：８５～７０である。最も望ましいのは、細骨材が最密充填構造をとった場合のその空隙を埋める量の改質硫黄結合材が配合された場合であり、この際に強度は最も高くなる。改質硫黄結合材の混合割合が前記範囲に満たない場合は、細骨材の表面を十分に濡らすことができず、強度が十分発現しないと共に遮水性が維持できないおそれがある。一方、混合割合が前記範囲を超える場合は、強度が低下する傾向にある。 The production method of the present invention comprises a nominal opening of a JIS standard sieve comprising a melt of the modified sulfur binder obtained in step (a) and coal ash having a specific surface area of 3000 to 5500 cm 2 / g. A step (b) of heating and mixing fine aggregate having a particle diameter passing through 00 mm;
In the step (b), the mixing ratio of the modified sulfur binder obtained in the step (a) and the fine aggregate is usually 10 to 50:90 to 50, preferably 15 to 30:85 in mass ratio. ~ 70. The most desirable is the case where the modified sulfur binder is blended in such an amount that fills the voids when the fine aggregate has a close-packed structure, in which case the strength is highest. When the mixing ratio of the modified sulfur binder is less than the above range, the surface of the fine aggregate cannot be sufficiently wetted, the strength is not sufficiently developed, and the water shielding property may not be maintained. On the other hand, when the mixing ratio exceeds the above range, the strength tends to decrease.
　工程(b)において加熱混合は、得られる改質硫黄資材の溶融物が、例えば、１４０℃に換算した際に通常０．０５～３．０Pa・s、好ましくは０．２～２．０Pa・s、特に好ましくは０．５～１．５Pa・sの範囲内の粘度となるように行うことができる。
　このような加熱混合は、好ましくは１２０～１５０℃、特に好ましくは１３０～１４０℃に加熱溶融した改質硫黄結合材と細骨材とを、予め、１２０～１５５℃に予熱した混合機にほぼ同時に投入し、通常１２０～１５０℃、好ましくは１３０～１４０℃の温度条件で行うことができる。
　混合の時間は、通常１分～１時間、好ましくは５～３０分間程度である。改質硫黄結合材の重合反応による高粘度化、更には硬化を避けるため、混合は極力短時間による混合が望ましい。しかし、混合時間が１分間未満の場合は、均一な混合が困難である傾向にあり、一方、混合時間が１時間を超える場合は、改質硫黄結合材の高粘度化が進行する恐れがある。 In the step (b), the heat mixing is usually performed at 0.05 to 3.0 Pa · s, preferably 0.2 to 2.0 Pa · s, when the obtained melt of the modified sulfur material is converted to 140 ° C., for example. s, particularly preferably in a range of 0.5 to 1.5 Pa · s.
Such heating and mixing is preferably performed in a mixer in which the modified sulfur binder and fine aggregate heated and melted to 120 to 150 ° C., particularly preferably 130 to 140 ° C., are preheated to 120 to 155 ° C. in advance. It can be carried out at the same time and can be carried out at a temperature of usually 120 to 150 ° C., preferably 130 to 140 ° C.
The mixing time is usually about 1 minute to 1 hour, preferably about 5 to 30 minutes. In order to prevent the modified sulfur binder from increasing in viscosity due to the polymerization reaction and further to cure, it is desirable that the mixing be performed in a short time as much as possible. However, when the mixing time is less than 1 minute, uniform mixing tends to be difficult. On the other hand, when the mixing time exceeds 1 hour, the viscosity of the modified sulfur binder may increase. .
　工程(b)における混合は、混合が十分に行えるものであればどんなミキサーを使用して行っても良く、好ましくは固液撹拌用が使用できる。例えば、インターナルミキサー、ロールミル、ボールミル、ドラムミキサー、スクリュー押出し機、パグミル、ポニーミキサー、リボンミキサー、ニーダーが使用できる。 The mixing in the step (b) may be performed using any mixer as long as the mixing can be sufficiently performed, and preferably for solid-liquid stirring. For example, an internal mixer, a roll mill, a ball mill, a drum mixer, a screw extruder, a pug mill, a pony mixer, a ribbon mixer, and a kneader can be used.
　本発明の製造方法は、工程(b)で得られた混合物を、JIS標準ふるいで最大寸法が１０１．６ｍｍ以下となるように冷却・固化する工程(c)を含む。
　工程(c)において、冷却・固化は、工程(b)で得られた混合物を、１２０℃未満に冷却することにより行うことができる。該冷却時に、混合物を、成型物、ペレット、破砕物若しくは粒状物等の所望の形態とすることができる。また、工程(b)で得られた混合物を不定形に冷却し、塊状固化物を得、該固化物を上記大きさとなるように破砕して改質硫黄資材を得ることもできる。 The production method of the present invention includes a step (c) of cooling and solidifying the mixture obtained in the step (b) so that the maximum dimension is 101.6 mm or less using a JIS standard sieve.
In step (c), cooling and solidification can be performed by cooling the mixture obtained in step (b) to below 120 ° C. During the cooling, the mixture can be made into a desired form such as a molded product, a pellet, a crushed product or a granular product. Alternatively, the mixture obtained in the step (b) can be cooled to an irregular shape to obtain a lump solidified product, and the solidified product can be crushed to the above size to obtain a modified sulfur material.
　本発明の製造方法により得られる改質硫黄資材は、再加熱することにより、任意の構造に作製可能であり、また、優れた難燃性を示すので、例えば、パネル材、床材、壁材、瓦、水中構造物とすることができる他、粒状物として、埋立材、路盤材、盛土材、コンクリート用骨材として利用することもできる。更に、この優れた難燃性の点から、運搬がより安全で容易となり、現場以外の場所での大量生産が可能である。 The modified sulfur material obtained by the production method of the present invention can be made into an arbitrary structure by reheating, and exhibits excellent flame retardancy. For example, panel materials, floor materials, wall materials, etc. Besides, it can be used as a roof tile, an underwater structure, and as a granular material, it can also be used as a landfill material, a roadbed material, a banking material, and an aggregate for concrete. Furthermore, this excellent flame retardancy makes the transportation safer and easier, and enables mass production at a place other than the site.
　以下、実施例及び比較例により更に詳細に説明するが、本発明はこれらの例に限定されない。例中の評価は、以下に示す方法に従い行なった。
　耐着火性：日本国消防法における可燃性固体（危険物第２類）評価のための着火性試験に準拠して評価した。３秒以内に着火し、かつ１０秒以上燃焼を継続する第１種可燃性固体並びに３秒を超えて１０秒以内に着火し、かつ燃焼を継続する第２種可燃性固体に相当するものを「着火性あり」、１０秒を超えて着火するもの及び燃焼を継続しないものを「危険性なし」とした。結果を表１に示す。
　粘度：Ｂ型粘度計により測定した値である。
　尚、用いた細骨材は、事前にJISふるいを用いて、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径に調整した。 Hereinafter, although an example and a comparative example explain in detail, the present invention is not limited to these examples. The evaluation in the examples was performed according to the following method.
Ignition resistance: Evaluated according to the ignitability test for the evaluation of flammable solids (dangerous goods type 2) in the Japanese Fire Service Act. A type 1 combustible solid that ignites within 3 seconds and continues to burn for 10 seconds or more and a type 2 combustible solid that ignites within 10 seconds over 3 seconds and continues to burn “Ignition”, those that ignite for more than 10 seconds, and those that do not continue combustion were designated as “no danger”. The results are shown in Table 1.
Viscosity: A value measured with a B-type viscometer.
The fine aggregate used was adjusted in advance to a particle size that passed through a nominal opening of 1.00 mm of a JIS standard sieve using a JIS sieve.
　実施例１
　攪拌混合槽の中に固体硫黄９７０ｇを入れ、１４０℃で溶融した後、ＥＮＢ ３０ｇをゆっくりと添加した。反応が開始され、約５℃の温度上昇が見られたが、その後温度は下降し、１４０℃で反応を続行した。次第に粘度が上昇し、４時間後、粘度が０．０６Ｐａ・ｓに達したところで直ちに加熱を停止し、適当な型又は容器に流し込んで室温で冷却し、改質硫黄結合材を得た。
　なお、改質硫黄結合材を粉末状とし、大過剰のトルエンを用いて室温で４時間抽出を行い、不溶分を測定したところ、１５．２質量％であった（ポリスルフィド量）。
　次いで、１４０℃で予熱したブレーン比表面積４０４０ｃｍ2／ｇの石炭灰４１３ｇと、改質硫黄結合材Ａ８４０ｇを１４０℃に再加熱した溶融物とを、１４０℃に保った混錬機内にほぼ同時に投入した。続いて、５分間混連し、これを適当な型又は容器に流し込んで室温で冷却し、改質硫黄資材（Ａ）を調製した。得られた改質硫黄資材（Ａ）の１４０℃における粘度は、０．７３Ｐａ・ｓであった。 Example 1
After putting 970 g of solid sulfur in the stirring and mixing tank and melting at 140 ° C., 30 g of ENB was slowly added. The reaction started and a temperature increase of about 5 ° C. was observed, after which the temperature decreased and the reaction was continued at 140 ° C. The viscosity gradually increased, and after 4 hours, when the viscosity reached 0.06 Pa · s, the heating was immediately stopped, poured into an appropriate mold or container, and cooled at room temperature to obtain a modified sulfur binder.
The modified sulfur binder was powdered, extracted with a large excess of toluene at room temperature for 4 hours, and the insoluble content was measured to be 15.2% by mass (polysulfide content).
Next, 413 g of coal ash having a Blaine specific surface area of 4040 cm 2 / g preheated at 140 ° C. and a melt obtained by reheating the modified sulfur binder A840 g to 140 ° C. are charged almost simultaneously into a kneader maintained at 140 ° C. did. Subsequently, the mixture was mixed for 5 minutes, poured into an appropriate mold or container, and cooled at room temperature to prepare a modified sulfur material (A). The viscosity of the obtained modified sulfur material (A) at 140 ° C. was 0.73 Pa · s.
　実施例２
　硫黄とＥＮＢとの反応時間を２．５時間とし、ブレーン比表面積が３７２０ｃｍ2／ｇの石炭灰を使用した以外は、全て実施例１と同様に操作して改質硫黄資材（Ｂ）を調製した。改質硫黄資材（Ｂ）の１４０℃における粘度は、０．５３Ｐａ・ｓであった。
　また、途中で得られた改質硫黄結合材のポリスルフィド量は、１１．５質量％であった。 Example 2
A modified sulfur material (B) was prepared in the same manner as in Example 1 except that the reaction time between sulfur and ENB was 2.5 hours, and coal ash having a specific surface area of 3720 cm 2 / g was used. did. The viscosity at 140 ° C. of the modified sulfur material (B) was 0.53 Pa · s.
Moreover, the polysulfide content of the modified sulfur binder obtained in the middle was 11.5% by mass.
　比較例１
　ブレーン比表面積が１８８０ｃｍ2／ｇの石炭灰を使用した以外は、全て実施例１と同様に操作して改質硫黄資材（Ｃ）を調製した。改質硫黄資材（Ｃ）の１４０℃における粘度は、０．４７Ｐａ・ｓであった。尚、途中で得られた改質硫黄結合材のポリスルフィド量は、実施例１と同様に１５．２質量％であった。 Comparative Example 1
A modified sulfur material (C) was prepared in the same manner as in Example 1 except that coal ash having a specific surface area of 1880 cm 2 / g was used. The viscosity at 140 ° C. of the modified sulfur material (C) was 0.47 Pa · s. In addition, the polysulfide content of the modified sulfur binder obtained in the middle was 15.2% by mass as in Example 1.
　比較例２
　ＥＮＢを用いず、結合材を純硫黄としたこと以外は、全て実施例２と同様に操作して硫黄資材（Ｄ）を調製した。硫黄資材（Ｄ）の１４０℃における粘度は、０．０８Ｐａ・ｓであった。 Comparative Example 2
A sulfur material (D) was prepared in the same manner as in Example 2 except that ENB was not used and the binder was pure sulfur. The viscosity at 140 ° C. of the sulfur material (D) was 0.08 Pa · s.
　比較例３
　ブレーン比表面積が５９９０ｃｍ2／ｇの石炭灰を使用した以外は、全て実施例１と同様に操作して改質硫黄資材（Ｅ）を調製した。改質硫黄資材（Ｅ）の１４０℃における粘性は、４８Ｐａ・ｓ程度と極めて高く、石炭灰を均一に分布させることは困難であり、取り扱い性は劣悪であった。尚、途中で得られた改質硫黄結合材のポリスルフィド量は、実施例１と同様に１５．２質量％であった。 Comparative Example 3
A modified sulfur material (E) was prepared in the same manner as in Example 1, except that coal ash having a specific surface area of 5990 cm 2 / g was used. The viscosity at 140 ° C. of the modified sulfur material (E) was as extremely high as about 48 Pa · s, and it was difficult to uniformly distribute the coal ash, and the handleability was poor. In addition, the polysulfide content of the modified sulfur binder obtained in the middle was 15.2% by mass as in Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (8)

  1. 　硫黄と硫黄改質剤とを反応させて得たポリスルフィドを含む改質硫黄結合材と、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径の細骨材とを含む、JIS標準ふるいで最大寸法が１０１．６ｍｍ以下である改質硫黄資材であって、
    　前記細骨材として、ブレーン比表面積が３０００～５５００ｃｍ2／ｇの石炭灰を含有することを特徴とする改質硫黄資材。     A JIS standard sieve containing a modified sulfur binder containing polysulfide obtained by reacting sulfur with a sulfur modifier and a fine aggregate having a particle size passing through a nominal opening of JIS standard sieve of 1.00 mm. A modified sulfur material having a maximum dimension of 101.6 mm or less,
    A modified sulfur material comprising coal ash having a Blaine specific surface area of 3000 to 5500 cm 2 / g as the fine aggregate.
  2. 　前記石炭灰のブレーン比表面積が３５００～４５００ｃｍ2／ｇである請求項１記載の改質硫黄資材。 The modified sulfur material according to claim 1, wherein the bran specific surface area of the coal ash is 3500 to 4500 cm 2 / g.
  3. 　前記改質硫黄結合材中のポリスルフィド量が、５～３０質量％である請求項１又は２記載の改質硫黄資材。 The modified sulfur material according to claim 1 or 2, wherein the amount of polysulfide in the modified sulfur binder is 5 to 30% by mass.
  4. 　１４０℃で加熱溶融した際の粘度が、０．０５～３．０Ｐａ・ｓの範囲内となる物性を示すことを特徴とする請求項１～３のいずれかに記載の改質硫黄資材。 The modified sulfur material according to any one of claims 1 to 3, wherein the modified sulfur material exhibits physical properties such that a viscosity when heated and melted at 140 ° C is in a range of 0.05 to 3.0 Pa · s.
  5. 　ポリスルフィドを含む改質硫黄結合材を得るために、硫黄と硫黄改質剤とを１２０～１５０℃で混合反応させる工程(a)と、
    　工程(a)で得られた改質硫黄結合材の溶融物と、ブレーン比表面積が３０００～５５００ｃｍ2／ｇの石炭灰を含む、JIS標準ふるいの公称目開き１．００ｍｍを通過する粒径の細骨材とを加熱混合する工程(b)と、
    　工程(b)で得られた混合物を、JIS標準ふるいで最大寸法が１０１．６ｍｍ以下となるように冷却・固化する工程(c)とを含むことを特徴とする改質硫黄資材の製造方法。     A step of mixing and reacting sulfur and a sulfur modifier at 120 to 150 ° C. in order to obtain a modified sulfur binder containing polysulfide;
    A particle diameter of a JIS standard sieve having a nominal aperture of 1.00 mm, containing a melt of the modified sulfur binder obtained in step (a) and coal ash having a Blaine specific surface area of 3000 to 5500 cm 2 / g. A step (b) of heating and mixing the fine aggregate;
    A method for producing a modified sulfur material, comprising: a step (c) of cooling and solidifying the mixture obtained in step (b) so that the maximum dimension is 101.6 mm or less using a JIS standard sieve.
  6. 　工程(a)の反応を、得られる改質硫黄結合材に含まれるポリスルフィド量が、５～３０質量％となるように制御することを特徴とする請求項５記載の改質硫黄資材の製造方法。 6. The process for producing a modified sulfur material according to claim 5, wherein the reaction in step (a) is controlled so that the amount of polysulfide contained in the resulting modified sulfur binder is 5 to 30% by mass. .
  7. 　前記石炭灰のブレーン比表面積が３５００～４５００ｃｍ2／ｇである請求項５又は６記載の改質硫黄資材の製造方法。 The method for producing a modified sulfur material according to claim 5 or 6, wherein the coal ash has a Blaine specific surface area of 3500 to 4500 cm 2 / g.
  8. 　工程(b)の加熱混合条件を、得られる改質硫黄資材を１４０℃で加熱溶融した際に、０．０５～３．０Ｐａ・ｓの粘度を示すように制御することを特徴とする請求項５～７のいずれかに記載の改質硫黄資材の製造方法。 The heating and mixing conditions in the step (b) are controlled so as to exhibit a viscosity of 0.05 to 3.0 Pa · s when the obtained modified sulfur material is heated and melted at 140 ° C. The method for producing a modified sulfur material according to any one of 5 to 7.
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JPH11349372A (en) * 1998-06-05 1999-12-21 Taiheiyo Cement Corp Sulfur composition
JP2002255623A (en) * 2001-02-28 2002-09-11 Taiheiyo Cement Corp Sulfur composition and its manufacturing method
JP2005082475A (en) * 2003-09-11 2005-03-31 Nippon Oil Corp Intermediate sulfur material, sulfur material and its producing method

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JPH11349372A (en) * 1998-06-05 1999-12-21 Taiheiyo Cement Corp Sulfur composition
JP2002255623A (en) * 2001-02-28 2002-09-11 Taiheiyo Cement Corp Sulfur composition and its manufacturing method
JP2005082475A (en) * 2003-09-11 2005-03-31 Nippon Oil Corp Intermediate sulfur material, sulfur material and its producing method

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