CN1849273A - Sulfur intermediate material, sulfur material and process for producing the same - Google Patents
Sulfur intermediate material, sulfur material and process for producing the same Download PDFInfo
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- CN1849273A CN1849273A CNA2004800261881A CN200480026188A CN1849273A CN 1849273 A CN1849273 A CN 1849273A CN A2004800261881 A CNA2004800261881 A CN A2004800261881A CN 200480026188 A CN200480026188 A CN 200480026188A CN 1849273 A CN1849273 A CN 1849273A
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- sulphur
- sulfur
- intermediate materials
- sulfur material
- aggregate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0243—Other after-treatment of sulfur
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
Abstract
A sulfur intermediate material that can be handled as a nondangerous material defined as one not igniting within 10 sec in the small-gas-flame ignition test and can be safely and easily used in the production of sulfur material; a sulfur material from the sulfur intermediate material; and a process for producing the same. There is provided a sulfur intermediate material comprising 100 parts by mass of fine aggregate of 5 mm or less grain diameter and 30 to 400 parts by mass of sulfur material of reformed sulfur, etc., characterized in that the maximum dimension thereof measured by JIS standard sifter is 101.6 mm or less. There is further provided a sulfur material obtained by mixing a melt of the sulfur intermediate material with a material containing coarse aggregate and solidifying the mixture.
Description
Technical field
The sulphur intermediate materials that the present invention relates to be applied to utilize the civil engineering work of sulphur preparation and build the non-hazardous material storage of can be used as of goods, be easy to transport uses the sulfur material of this intermediate materials preparation and makes the method for this sulfur material.
Technical background
Sulfur material is compared the material that has colour strength and well-known as a kind of with concrete.Yet sulphur is fire-hazardous hazardous material, therefore at the scene fusion to build be very difficult.Particularly, must neighbouringly at the construction field (site) make sulfur material,, therefore brought the problem of transportation aspect in the modifying process at sulphur because the sulphur and the additive that use belong to hazardous material in the occasion of the large ocean structure buildings that uses sulfur material.In addition, the preparation facilities of its sulfur material also must be explosion-proof, in the production scene, and must be in the fusion sulphur jar of special use with the sulphur keeping.Therefore, in the utilization of sulfur material, a transportation and the high problem of manufacturing cost are arranged also.
, fine aggregate is compared with coarse aggregate, and more difficult and sulphur mixes, and when utilizing fine aggregate to make sulfur material, in the occasion of using existing simple device, time-consuming and a take a lot of work problem is arranged also.
Consider above-mentioned all difficulties, proposed the various methods that prepare sulphur, such as following patent publications 1-31.But for the manufacturing that can be applied to sulfur material safely, expediently, and sulphur intermediate materials and the manufacture method thereof when carrying out little flare fire test, handled with interior non-ignitable non-hazardous material in 10 seconds, all not have to disclose.
Patent publications 1:JP-11-347514-A
Patent publications 2:JP-2002-60491-A
Patent publications 3:JP-2001-163649-A
Patent publications 4:JP-2002-69188-A
Patent publications 5:JP-2002-97060-A
Patent publications 6:JP-2002-97059-A
Patent publications 7:JP-2002-255625-A
Patent publications 8:JP-2001-170596-A
Patent publications 9:JP-2002-205032-A
Patent publications 10:JP-2002-241166-A
Patent publications 11:JP-11-349372-A
Patent publications 12:JP-2000-072523-A
Patent publications 13:JP-2000-264713-A
Patent publications 14:JP-2000-264714-A
Patent publications 15:JP-2000-281425-A
Patent publications 16:JP-2001-030213-A
Patent publications 17:JP-2001-048618-A
Patent publications 18:JP-2001-253759-A
Patent publications 19:JP-2001-261425-A
Patent publications 20:JP-2002-255623-A
Patent publications 21:JP-2002-255624-A
Patent publications 22:JP-2001-191322-A
Patent publications 23:JP-11-123376-A
Patent publications 24:JP-11-070375-A
Patent publications 25:JP-2001-121104-A
Patent publications 26:JP-2001-129509-A
Patent publications 27:JP-2002-126715-A
Patent publications 28:JP-10-072245-A
Patent publications 29:JP-10-114564-A
Patent publications 30:JP-10-114565-A
Patent publications 31:JP-9-124349-A
Summary of the invention
Purpose of the present invention, provide can be used as when carrying out little flare fire test carried out operatively with interior non-ignitable non-hazardous material in 10 seconds, can be safely and utilize sulphur intermediate materials in the manufacturing at sulfur material easily, use the sulfur material of this intermediate materials preparation and prepare the method for sulfur material.
The present invention can provide a kind of sulphur intermediate materials, includes
100 parts of (mass ratio) particle diameters below 5mm fine aggregate and
By original sulfur material 30-400 part mass unit that at least a kind is formed in sulphur or the modified sulfur, wherein
Described sulphur intermediate materials overall dimension under the JIS of Japanese Industrial Standards standard sieve is no more than 101.6mm.
In addition,, also obtain a mixture with the material mixing that comprises coarse aggregate, mixture solidified is prepared a kind of sulfur material by melts with above-mentioned sulphur intermediate materials according to the present invention.
And, according to the present invention, also provide a kind of method for preparing above-mentioned sulfur material, comprise
The material that contains the coarse aggregate when being preheating to 120-200 ℃ with after the melts of above-mentioned sulphur intermediate materials mixes, be cured again.
And, according to the present invention, also provide a kind of method for preparing above-mentioned sulfur material, comprise
The material that contains the coarse aggregate when being preheating to 120-200 ℃ with after the melts that remains on 120-160 ℃ above-mentioned sulphur intermediate materials mixes, be cured again.
The Combination of sulphur intermediate materials of the present invention and coarse aggregate is fine, can be used as non-hazardous material and uses, and has advantage in the manufacturing of management, storage, transportation, especially sulfur material.In addition, the manufacture method of sulfur material of the present invention, owing to used sulphur intermediate materials of the present invention, so can easy and easily obtain containing the sulfur material of the present invention of coarse aggregate.
Below, will illustrate in greater detail the present invention.
Sulphur intermediate materials of the present invention, comprise, the fine aggregate that the particle diameter 5mm of specified proportion is following and by original sulphur and at least a sulfur material of forming of modified sulfur, and sulphur intermediate materials overall dimension under the JIS standard sieve is no more than 101.6mm, preferably the non-hazardous material of examining and determine through too small combustion gas flare fire test.
The sulphur that uses in sulphur intermediate materials of the present invention is common sulphur monomer, for example, and the sulphur that desulfurization natural or by oil, natural gas generates.
Used modified sulfur in sulphur intermediate materials of the present invention is to utilize the sulphur denaturing agent and sulphur is carried out material after the polymerization,
The reactant of sulphur and sulphur denaturing agent preferably.
As the sulphur denaturing agent, for example: dicyclopentadiene (DCPD), tetrahydro-indenes (THI), or the mixture more than a kind or 2 kinds of the olefin(e) compound class of cyclopentadiene and its oligopolymer (2-5 amount body mixture), limonene, Vinyl toluene, dicyclo amylene etc. can use.
As above-mentioned DCPD, the monomer of general dicyclopentadiene, and be that the mixture that main body constituted can use by 2-5 amount body.As this mixture, the content of DCPD generally more than 70% (mass percent), is preferably in more than 85% (mass percent), in addition, is generally known as the commercially available product of so-called dicyclopentadiene, can use mostly.
As above-mentioned THI, generally can use the monomer of THI, or also can use by the polymkeric substance of monomer, cyclopentadiene and the divinyl of THI, cyclopentadiene, and from the 2-5 amount body of cyclopentadiene form select in the series be mixture that main body constituted more than a kind or 2 kinds.The content of THI in this mixture more than 50% (mass percent), is preferably in more than 65% (mass percent) usually.As this mixture, be generally known as the commercially available product of so-called tetrahydro-indenes and generate oil from the pair that the producing apparatus of ethyl norbornylene is discharged, can use mostly.
Above-mentioned modified sulfur can make by mixed melting sulphur and sulphur denaturing agent.
At this moment, as the usage ratio of sulphur denaturing agent with respect to the total amount of sulphur and sulphur denaturing agent, 0.01-30% (mass percent) normally, best ratio is 0.1-20% (mass percent).
Above-mentioned melting mixing, for example, generally can use internal mixer, pressure type masher, drum mixer, vertical mixing tank, mixing screw, high-speed mixing tank, static tube mixing tank etc. to carry out, preferably use such tube mixer of static tube mixing tank.
In the preparation process of above-mentioned modified sulfur, for example, when stating tube mixer in the use and carrying out, in tube mixer, can carry out melting mixing to sulphur and sulphur denaturing agent in 120-160 ℃ temperature range, up at 140 ℃ the time, viscosity degradation is to the 0.05-3.0Pas scope.In order to make sulphur sex change more efficiently, the melt mix temperature in the tube mixer at 130-155 ℃, is preferably in 130-150 usually.
The initial reaction of sulphur that is taken place in tube mixer and sulphur denaturing agent owing to be that sulphur and sulphur denaturing agent react, is the exothermic reaction that generates the initial resultant of modified sulfur.Therefore, in tube mixer, confirm take place sharply heating phenomenon on one side, stir the companion continuously on one side, make in the tube mixer temperature rise to 120-160 ℃ gradually for well.
When in tube mixer, making the reaction of sulphur and sulphur denaturing agent, can generate the molecular weight of measuring with gel permeation chromatography (GPC) is the initial resultant of modified sulfur of 150-500, in reaction system, the growing amount of the initial resultant of above-mentioned modified sulfur remains on 0.01-45% (mass percent) and is advisable, and preferably remains on 1-40% (mass percent).
The mensuration of above-mentioned molecular weight can be that sulphur is joined the insides such as sulphur denaturing agent that are dissolved in dithiocarbonic anhydride or toluene, utilizes GPC to measure.For example, this molecular weight determination can use chloroform solvent at room temperature to carry out, under the flow velocity that 1ml/ divides, use the UV254Nm detector, according to measure dithiocarbonic anhydride 1 mass/volume % concentration with polystyrene, i.e. mass volume ratio, the typical curve of sample solution made is measured.
The flow velocity of above-mentioned tube mixer and pressure can suitably be set according to the diameter of pipe, the preparation amount difference of product, and flow velocity is preferably in 0.1-100cm/ second, for the assurance time between 1 second-30 minutes.
In addition, in sulphur and sulphur denaturing agent reaction beginning, generate after the initial resultant of modified sulfur, owing to there is not the problem of sulphur denaturing agent evaporation, after this reaction beginning, do not use tube mixer passable yet, can import drum mixer or holding tube to material by tube mixer, make it inside to stop, make initial resultant of modified sulfur and fusion sulphur polymerization reaction take place, carry out polymer and quantize.
The residence time in above-mentioned drum mixer or holding tube, can suitably set according to diameter, the manufacture difference of pipe, be preferably in 1 minute-24 hours degree.
The residence time in holding tube, can be according to the usage quantity of sulphur denaturing agent and to some extent difference different with melt temperature.
Make the reaction finish-time of sulphur modification, can be according to the viscosity decision of melts.For example, viscosity degradation is relatively good to the scope of 0.05-3.0Pas in the time of 140 ℃, but from the viewpoint of the operation of the sulphur intermediate materials intensity that obtains and manufacturing engineering, and to be in the scope of 0.05-2.0Pas the most suitable on the whole for viscosity in the time of 140 ℃.
In addition, modified sulfur also can pass through batch preparations.
Original sulfur material in the sulphur intermediate materials of the present invention, what preferably have higher proportion is very high modified sulfur, perhaps in fact only comprises modified sulfur, can improve the intensity of final resulting sulfur material and weather resistance etc. so better.
Sulphur intermediate materials of the present invention, can prepare becomes when little combustion gas flare fire test 10 seconds with interior non-ignitable non-hazardous material.For example, for modified sulfur used when the sulphur intermediate materials is made, when adjusting this modified sulfur, generally reach this effect by the usage ratio that strengthens employed sulphur denaturing agent.Sulphur denaturing agent by about 30% (mass percent) of the total amount of using relative sulphur and sulphur denaturing agent just can reach best effect, further increases content and changes seldom.On the other hand, if contain quantity not sufficient 0.01% (mass percent), do not reach the ideal effect by using modified sulfur to improve intensity so.
Sulphur intermediate materials of the present invention, the relative 100 parts of mass units of fine aggregate that will discuss of back, above-mentioned sulfur material contain the proportional 30-400 of being generally part mass unit, preferably 50-300 part mass unit.If 30 parts of mass units of less than, the homogeneity of resulting sulphur intermediate materials will be undesirable, if surpassed 400 parts of mass units, sulfur material will separate with fine aggregate, can not obtain uniform material.
Sulphur intermediate materials of the present invention, can prepare becomes when little combustion gas flare fire test 10 seconds with interior non-ignitable non-hazardous material, such as, by improving the content of fine aggregate.With respect to 100 parts of mass units of sulfur material, the ratio of this fine aggregate is generally 25-300 part mass unit, preferably 30-250 part mass unit.
Contained fine aggregate in the sulphur intermediate materials of the present invention, general aggregate can use, have no particular limits, general aggregate used in concrete, the pair that generates when for example, natural stone, sand, gravel, silica sand, iron steel slag, ferronickel dross, copper slag, metal are made produces that thing, stone carbon ash, fuel ablate that ash, electric precipitation are grey, the mixture of molten slag class, shell and these materials etc.In addition, humite, alumina, silica powder, capel, clay mineral, activated carbon, glass powder or can use with aggregates such as the equal inorganic system that does not contain hazardous substance of these materials, organic systems.Wherein, in these fine aggregates, if it is easy, even from the adjustment of size distribution, can obtain in a large number easily on this point again, can select stone carbon ash, silica sand, humite, silica powder, sand, glass powder and form the material of selecting in the series more than a kind or 2 kinds proper from the electric precipitation ash.
In the sulphur intermediate materials of the present invention, can utilize industry byproduct, because sulfur material carries out harmless treatment to these byproducts as fine aggregate.
Fine aggregate is generally by below the particle diameter 5mm, preferably be made up of the aggregate below the 1mm.If the particle diameter of above-mentioned fine aggregate has surpassed 5mm, just make the sulphur intermediate materials be difficult to fusion once again rapidly.The particle diameter of fine aggregate can adopt the conventional art adjustment.For example, can adjust by sieve.Particle diameter can use the JIS standard sieve to adjust.
Sulphur intermediate materials of the present invention is except the sulfur material and fine aggregate be made up of above-mentioned sulphur and/or modified sulfur, so long as in the scope that does not influence effect that the present invention expects, can contain the cellulosic filling material that will discuss the back etc. in right amount.
Sulphur intermediate materials of the present invention is no more than 101.6mm according to its overall dimension of JIS standard sieve.If surpass 101.6mm, difficulty will take place in transportation.In order to reach such size, it is pulverized, and the method for screening can use traditional method to get final product.
Sulphur intermediate materials of the present invention is generally 5MNmm
2Above intensity preferably can reach 10-60MNmm
2Intensity.In addition, in the fusion and when combining with concrete again of sulphur intermediate materials, itself and concrete adhesion strength (JIS A 6910) are at 1.5N/mm
2More than, be preferably in 2-5N/mm
2Between.
Sulphur intermediate materials of the present invention mixes the melts of above-mentioned original sulfur material and fine aggregate etc., solidify and make.This product material can be directly or after the processing of overmolding, pulverizing, processing, fusion etc. again, comes into operation as sulfur material.
Sulfur material of the present invention is to make after the melts of aforesaid sulphur intermediate materials of the present invention and the material that contains coarse aggregate are mixed, solidify.When solidifying, can carry out moulding according to the shape of being expected.The cured article conducting powder is broken, processing, after fusion etc. is handled again, come into operation as sulfur material.
Sulfur material of the present invention, the particle diameter of its coarse aggregate should preferably surpass 5mm and be advisable, but maximum can not surpass 50mm more than 5mm according to the AS standard sieve.If the particle diameter of coarse aggregate surpasses 50mm, when in preparation process, mixing, need long time.The size adjusting of coarse aggregate can utilize conventional art to realize, for example, can adjust with sieve.The kind of coarse aggregate is not particularly limited, and for example, can use the material with the above-mentioned same kind of fine aggregate.
Sulfur material of the present invention, with respect to 100 parts of mass units of melts of sulphur intermediate materials, its coarse aggregate contain the proportional 10-700 of being generally part mass unit, be preferably between 50-500 part mass unit.If 10 parts of mass unit of less than, would be difficult to obtain enough intensity, if but surpass 700 parts of mass units, because its original sulfur material is very few, will produces and solidify difficulty.
Sulfur material of the present invention is a benchmark with sulfur material integral body, and the ratio of the aggregate that its fine aggregate and coarse aggregate are formed is preferably in 50-90% (mass percent).If the cooperation ratio of aggregate surpasses 90% (mass percent), can not fully be soaked by original sulfur material on inorganic based material surface as aggregate, aggregate presents and exposes state, and its intensity can not show fully, can not keep its water-repellancy simultaneously.On the other hand, the proportioning of aggregate is fruit less than 50% (mass percent) for example, can not reach sufficient intensity.
The present invention contains the sulfur material of coarse aggregate, except coarse aggregate, can also contain, for example, fine aggregate, cellulosic filling material, fibrous particle, lamelliform particle etc., with the flexural strength of further raising sulfur material, make material accomplish slimming, lightweight, thereby can be made as panel, slabstone etc. from body.These materials can be included in aforesaid sulphur intermediate materials of the present invention the inside.
The cellulosic filling material can comprise, carbon fiber, glass fibre, steel fiber, amorphous fiber, nylon fiber, polypropylene fibre, polyethylene fibre, Kevlar, and the mixture of these materials etc.
The Fibre diameter of cellulosic filling material, the difference to some extent because material is different is generally 5um-1mm.Though staple fibre, or continuous fibre can, in the occasion of staple fibre, its fiber length can the homodisperse effect of easier realization between 2-30mm.If continuous fibre, promptly passable as long as its reticulation can be vacated between the crack that aggregate passes through, no matter be that weave cotton cloth structure or non woven fabric structure can be selected for use.
When cooperating the cellulosic filling material, its cooperation ratio is generally mass percent 0.1-10% in resulting sulfur material, preferably between 0.5-3%.
Sulfur material of the present invention or sulphur intermediate materials in order to improve its toughness etc., can mix and add fibrous particle, lamelliform particle etc.
Fibrous particle has the wollastonite of mean length below 1mm, alumina, mullite etc.
Lamelliform particle has the Muscovitum of mean particle size below 1mm, talcum sheet, vermiculite in flake, alumina sheet etc.
When mixing adding fibrous particle and/or person were lamelliform particle, its cooperation ratio generally accounted for mass percent below 35% in sulfur material, be preferably between the 10-25%.
Sulfur material of the present invention or sulphur intermediate materials so long as do not influence desired effect of the present invention, except above-mentioned, can add other composition as required.
Sulfur material of the present invention generally will be brought into play 10N/mm
2Above intensity, its intensity is preferably in 10-80N/mm
2Between.
In order to make sulfur material required for the present invention, can use following method to carry out.For example, can contain in the material of the coarse aggregate of 120-200 ℃ of preheating, be dropped in the melts of the above-mentioned sulphur intermediate materials of 120-160 ℃ of maintenance, be cured again after the mixing; Also can in the melts of the above-mentioned sulphur intermediate materials of 120-160 ℃ of maintenance, drop into the material that contains coarse aggregate, be cured again after the mixing through 120-160 ℃ of preheating; In addition, can also on above-mentioned sulphur intermediate materials fused temperature, work hard, for example, can be in the mixing machine of 120-160 ℃ of maintenance, input is through the material that contains coarse aggregate of 120-200 ℃ of preheating, and the state that preferably remains on 120-160 ℃ mixes down, is cured etc. again.
In the manufacture method of the present invention, because used sulphur intermediate materials of the present invention, it can be used as solid and low price and keeping easily, can be used as non-hazardous material again operates, so do not need to use fusion sulphur jar.
In the manufacture method of the present invention, contain the preheating of the material of coarse aggregate, can use primary heater unit to carry out.
In the manufacture method of the present invention,, preferably use the heating units such as mold that can heat, again be mixed into suitable through 120-200 ℃ of preheating its inside at the melts that mixes the sulphur intermediate materials with when containing the material of coarse aggregate.Mixing machine preferably also is preheating to 120-155 ℃ in advance.
Above-mentioned primary heater unit and heating unit because do not need explosion-proof equipment, so can use naked light, on these devices, also can use the cellar for storing things stove.Because the melts of sulphur intermediate materials and the mixing that contains the material of coarse aggregate are very easy to carry out, so can use easy device such as mold.In addition, short advantage of melting mixing time is also arranged.In the traditional method that does not prepare the sulphur intermediate materials, because the mixing of aggregate and sulphur is not easy evenly, the intensity of the inhomogeneous resulting sulfur material of sulfur material is lower.
At the melts that mixes above-mentioned sulphur intermediate materials with when containing the material of coarse aggregate, should be with the sulfur material of contained molten state, when particularly containing 140 ℃ of sulfur material of modified sulfur viscosity maintain be mixed in the scope of 0.05-3.0Pas suitable.Because the polymerization of sulphur, the viscosity that contains the sulfur material of above-mentioned modified sulfur increases along with time lengthening, preferably viscosity controller is advisable in the suitableeest maneuverable range of viscosities.During this viscosity deficiency 0.05Pas, can reduce the intensity of resulting sulfur material, the effect of utilizing modified sulfur to improve is undesirable.On the other hand, along with the rising of viscosity, the effect of improving intensity also can strengthen, if but surpass 3.0Pas, will cause when melting mixing, stirring difficulty, operational difficulty should be avoided.
The mixing machine that uses when above-mentioned mixing as long as can realize mixing fully, has no particular limits mixing machine, preferably uses solid-liquid to stir the mixing machine of usefulness.For example, paddle board mixing tank, internal mixer, pressure type masher, ball mill, drum mixer, spiral rolling press, pug mill, pony mixer, mixing screw, kneader can use.
In curing schedule of the present invention, can be by the mixture of above-mentioned molten state importing mold, utilize method such as cooling curing to finish again.
Above-mentioned curing can utilize the general method of forming to carry out, and for example, pours into mold, carries out cooling curing, can be made into shape arbitrarily.As the shape of mold, lattice template, slabstone type, brick type etc. are arranged, other shape also has.
When above-mentioned curing molding, the vibration that can be suited also can be shone ultrasound.
Sulfur material of the present invention as the formed body of desirable shape, can be directly utilizes as the various structures of fragment of brick etc.For example, can be used as slabstone, fragment of brick, lattice sheet material, flooring board, fish shelter, embankment material, manufacturing algae field uses with material.In addition, the road that also can be used as boundary line, walkway fragment of brick, flat board, chain fragment of brick etc. uses with goods, can also use as the goods for building of fish shelter, wave absorption fragment of brick, anti-ripple fragment of brick, vegetation fragment of brick etc., and use with material with civil constructions such as wall, board-like stakes as imperial cob wall, retaining wall, L type.
In these purposes, also needn't use sulfur material in whole forming composition, also can realize this purpose even use at surface portion.For example, can be configured in this sulfur material on the concrete system shore protection wall.The purposes that also has other, for example, for slabstone, fragment of brick, lattice sheet material, flooring board, wall material, can make up with concrete equally, be made as two layers structure, and, can be clipped in concrete the centre of sulphur intermediate materials, be made as three-layer structure and multi-ply construction.
Embodiment
Below, utilize embodiment and comparative example, the present invention will be described in more detail, just is not limited to these examples of the present invention certainly.In addition, for each sulphur intermediate materials and sulfur material of making in the example, can measure and estimate according to method shown below.
Little combustion gas flare fire test calibrating:
According to the judgement of Japan's fire service law hazardous material the 2nd class Flammable Solid Class 4.1 class test, in little combustion gas flare fire test, 10 seconds with interior when missing of ignition decidable be non-hazardous material.
Compressive strength:
Determine according to JIS A 1108 methods.
The granularity adjustment of aggregate: in advance utilize the JIS standard sieve to adjust.
The manufacturing of modified sulfur
Mix in the groove in closed, add solid sulfur 95kg, 120 ℃ heat fusing after, remain on 130 ℃.Then, slowly be added on the dicyclopentadiene 5kg of about 50 ℃ of heat fused, stir about is 10 minutes gently, after the temperature rising of confirming to cause owing to initial reaction is controlled, is warmed up to 140 ℃.Along with the reaction beginning, viscosity rises, and after about 1 hour, stops heating immediately when viscosity reaches 0.1Pas, pours in the suitable model or container, and at room temperature cooling obtains modified sulfur (C-1).
The adjustment of fine aggregate and coarse aggregate
Directly use the following stone carbon ash of particle diameter 1mm, as fine aggregate ((A-1).
Utilize sieve, select the coarse aggregate blast furnace slag that particle diameter surpasses 5mm, produce the coarse aggregate of forming above the blast furnace slag of 5mm by particle diameter (A-2).
Embodiment 1
To almost put into simultaneously in the mixing machine (special-purpose mixing tank) that remains on 140 ℃ at fine aggregate (A-1) 20kg of 140 ℃ of preheatings and modified sulfur (C-1) 20kg at 130 ℃ of solutes after carrying out the reheat fusing.Then, mixed 10 minutes.This mix products is circulated into tabular molding (in 46cm * 55cm * 6cm).Cooling is crushed to 100mm or littler.With this as sulphur intermediate materials (B-1).
The little combustion gas flare fire test calibrating of sulphur intermediate materials (B-1).Further fragmentation of sulphur intermediate materials (B-1), make the fritter of 10 3g, implement little combustion gas flare fire test.As a result, all fritters 10 seconds with interior all missing of ignition, decidable is non-hazardous material.
Next, put into sulphur intermediate materials (B-1) 20kg with in coarse aggregate (A-2) 30kg of 180 ℃ of preheatings two paddle board mixing tanks of 140 ℃, mixed 5 minutes.With the cylindrical mold of the high 20cm of this mixture injection diameter 10cm, cool to room temperature.The compressive strength of the test body (sulfur material) behind the disengaging model is up to 82N/mm
2
Comparative example 1
With sulphur intermediate materials (B-1) 20kg with at fine aggregate (A-1) 10kg of 140 ℃ of preheatings, or with coarse aggregate (A-2) 30kg with at 130 ℃ of modified sulfur (C-1) 10kg that carry out reheat, put in two paddle board mixing tanks of 140 ℃ of preheatings, mixed 5 minutes.With the cylindrical mold of the high 20Cm of this mixture injection diameter 10cm, cool to room temperature, the demoulding.In resulting test body, modified sulfur be not distributed to equably fine aggregate ((A-1) or coarse aggregate (and (A-2) lining, outward appearance class is refuted, its compressive strength does not show ideal numerical value yet.
Embodiment 2 (directly using intermediate materials)
Sulphur intermediate materials (B-1) put in two paddle board mixing tanks of 140 ℃ fusion 10 minutes.Draw this melts 10cc, tile concrete slab (on 300 * 300 * 60mm).After the melts of sulphur intermediate materials (B-1) solidifies 1 hour, build the abrading type adhesion test according to the regulation of JIS A 6910 the insides, the result, clinging power is up to 3.5N/mm
2
Claims (9)
1, a kind of sulphur intermediate materials, comprise, the fine aggregate of the particle diameter of 100 parts of mass units below 5mm, the original sulfur material that comprises at least a sulphur and sex change sulphur with 30-400 part mass unit, sulfur material is under the JIS standard sieve in the middle of described, and the maximum particle diameter size is no more than 101.6mm.
2, sulphur intermediate materials according to claim 1 is characterized in that: described sulphur intermediate materials has in little combustion gas flare fire test, and 10 seconds with interior non-ignitable characteristic.
3, sulphur intermediate materials according to claim 1, described sulphur intermediate materials again the fusing and attached to the adhesion strength on the concrete (JIS A 6910) at 1.5N/mm
2More than.
4, sulphur intermediate materials according to claim 1 is characterized in that: described fine aggregate is selected from stone carbon ash, silicon sand, humite, silica powder, sand, glass powder, electric precipitation ash and composition thereof.
5, a kind of sulfur material, by the sulphur intermediate materials as claimed in claim 1 that will melt with comprise the coarse aggregate material mixing and prepare to obtain mixture and to solidify.
6, sulfur material according to claim 5 is characterized in that, the particle diameter of its coarse aggregate under the JIS standard sieve more than 5mm.
7, sulfur material according to claim 5 is characterized in that, the aggregate that fine aggregate and coarse aggregate are formed accounts for the 50-90% of described sulfur material quality.
8, a kind of manufacture method of sulfur material may further comprise the steps,
The material that contains coarse aggregate that is preheating to 120-200 ℃ mixed obtaining mixture with the sulphur intermediate materials as claimed in claim 1 of fusing, then, solidify this mixture.
9, the manufacture method of sulfur material according to claim 8 is characterized in that: the temperature of fusion of described sulphur intermediate materials is 120-160 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP320308/2003 | 2003-09-11 | ||
| JP2003320308A JP4040000B2 (en) | 2003-09-11 | 2003-09-11 | Sulfur intermediate material, sulfur material and manufacturing method thereof |
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| Publication Number | Publication Date |
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| CN1849273A true CN1849273A (en) | 2006-10-18 |
| CN100436358C CN100436358C (en) | 2008-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800261881A Expired - Fee Related CN100436358C (en) | 2003-09-11 | 2004-08-27 | Sulfur intermediate material, sulfur material and process for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4040000B2 (en) |
| CN (1) | CN100436358C (en) |
| EA (1) | EA009098B1 (en) |
| WO (1) | WO2005026071A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105492381A (en) * | 2012-06-22 | 2016-04-13 | 韩国科学技术研究院 | Modified sulfur, method for preparing same, apparatus for preparing same, and use thereof |
| CN105540552A (en) * | 2016-01-22 | 2016-05-04 | 上海京海（安徽）化工有限公司 | Preparation method of pressure-resisting sulphur with high bonding strength |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006306634A (en) * | 2005-04-26 | 2006-11-09 | Nippon Oil Corp | Porous modified sulfur solidified body composed mainly of shell pulverized product and civil engineering/building structure |
| JP4531626B2 (en) * | 2005-05-13 | 2010-08-25 | 新日本石油株式会社 | Modified sulfur intermediate material flake manufacturing method and manufacturing system thereof |
| JP4007997B2 (en) * | 2005-05-13 | 2007-11-14 | 新日本石油株式会社 | Modified sulfur solidified body production system |
| JP4725956B2 (en) * | 2005-07-01 | 2011-07-13 | Ｊｘ日鉱日石エネルギー株式会社 | Modified sulfur solidified body casting device |
| KR100632574B1 (en) | 2005-07-08 | 2006-10-09 | 에스케이 주식회사 | Liquid/solid dual mode process for preparing modified sulfur binder |
| AT502255A1 (en) | 2005-08-11 | 2007-02-15 | Holcim Ltd | METHOD AND DEVICE FOR REMOVING VOLATILE ORGANIC COMPONENTS FROM EXHAUST GASES FROM A CEMENT LINK SYSTEM |
| JP2007054783A (en) * | 2005-08-26 | 2007-03-08 | Nippon Oil Corp | Apparatus for spraying sulfur material |
| JP4815200B2 (en) * | 2005-11-30 | 2011-11-16 | Ｊｘ日鉱日石エネルギー株式会社 | Modified sulfur material manufacturing equipment |
| JP4648172B2 (en) * | 2005-11-30 | 2011-03-09 | Ｊｘ日鉱日石エネルギー株式会社 | Surface solidification prevention device for sulfur solidified body |
| JP4820970B2 (en) * | 2006-03-28 | 2011-11-24 | Ｊｘ日鉱日石エネルギー株式会社 | Form for sulfur molded body and method for producing sulfur molded body |
| JP5213492B2 (en) | 2008-03-25 | 2013-06-19 | Ｊｘ日鉱日石エネルギー株式会社 | Method and apparatus for producing sulfur solidified body |
| JP5132494B2 (en) | 2008-09-12 | 2013-01-30 | Ｊｘ日鉱日石エネルギー株式会社 | Forming equipment for sulfur solidified products |
| JP5258508B2 (en) * | 2008-10-28 | 2013-08-07 | Ｊｘ日鉱日石エネルギー株式会社 | How to repair sulfur solidified products |
| KR101289314B1 (en) * | 2009-12-01 | 2013-07-24 | 한국과학기술연구원 | Modified Sulfur Binder which is possible mixing workability because of maintained a liquid form from normal temperature and the fabrication method thereof, Hydraulic Modified Sulfur Materials Composition and the fabrication method thereof containing the Modified Sulfur Binder |
| JP2011190142A (en) * | 2010-03-15 | 2011-09-29 | Jx Nippon Oil & Energy Corp | Modified sulfur material and method for producing the same |
| JP6195048B2 (en) * | 2013-02-05 | 2017-09-13 | 鳥海 伸行 | Box-type structure for storing radioactive waste |
| RU2607845C1 (en) * | 2015-10-19 | 2017-01-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кузбасский государственный технический университет имени Т.Ф. Горбачева" (КузГТУ) | Method of recycling cake from sulphuric acid production to produce sulphur concrete |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103638B (en) * | 1985-05-28 | 1986-10-22 | 铁道部第三工程公司 | Material for binding concrete structure |
| PL187670B1 (en) * | 1998-05-27 | 2004-08-31 | Myslowski Wlodzimierz | Method of obtaining sulphuric binders and sulphuric binders obtained thereby |
| JP3436736B2 (en) * | 1999-08-20 | 2003-08-18 | 新日本石油株式会社 | Civil and architectural materials, their production and their use |
| JP2001261425A (en) * | 2000-03-14 | 2001-09-26 | Taiheiyo Cement Corp | Sulfur composition molding raw material and its manufacturing method |
-
2003
- 2003-09-11 JP JP2003320308A patent/JP4040000B2/en not_active Expired - Lifetime
-
2004
- 2004-08-27 CN CNB2004800261881A patent/CN100436358C/en not_active Expired - Fee Related
- 2004-08-27 EA EA200600562A patent/EA009098B1/en not_active IP Right Cessation
- 2004-08-27 WO PCT/JP2004/012359 patent/WO2005026071A1/en active Application Filing
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105492381A (en) * | 2012-06-22 | 2016-04-13 | 韩国科学技术研究院 | Modified sulfur, method for preparing same, apparatus for preparing same, and use thereof |
| US10179736B2 (en) | 2012-06-22 | 2019-01-15 | Korea Institute Of Science And Technology | Modified sulfur, method for preparing same, apparatus for preparing same, and use thereof |
| US10994995B2 (en) | 2012-06-22 | 2021-05-04 | Korea Institute Of Science And Technology | Modified sulfur, method for preparing same, apparatus for preparing same, and use thereof |
| US11434134B2 (en) | 2012-06-22 | 2022-09-06 | Korea Institute Of Science And Technology | Modified sulfur, method for preparing same, apparatus for preparing same, and use thereof |
| CN105540552A (en) * | 2016-01-22 | 2016-05-04 | 上海京海（安徽）化工有限公司 | Preparation method of pressure-resisting sulphur with high bonding strength |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100436358C (en) | 2008-11-26 |
| WO2005026071A1 (en) | 2005-03-24 |
| JP4040000B2 (en) | 2008-01-30 |
| EA200600562A1 (en) | 2006-08-25 |
| JP2005082475A (en) | 2005-03-31 |
| EA009098B1 (en) | 2007-10-26 |
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