CN105408275B - The manufacture method of hydraulic powder - Google Patents
The manufacture method of hydraulic powder Download PDFInfo
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- CN105408275B CN105408275B CN201480042498.6A CN201480042498A CN105408275B CN 105408275 B CN105408275 B CN 105408275B CN 201480042498 A CN201480042498 A CN 201480042498A CN 105408275 B CN105408275 B CN 105408275B
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- compound
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- salt
- triethanolamine
- sulfonic acid
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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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
-
- 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
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Disintegrating Or Milling (AREA)
Abstract
The present invention relates to a kind of manufacture method of hydraulic powder, it has the process that hydraulicity compound is crushed in the presence of triethanolamine and hydroxy methane sulfonic acid or its salt.
Description
Technical field
The present invention relates to the manufacture method of the hydraulic powder with the process for crushing hydraulicity compound.
Background technology
When the early strength of concrete is to the framed sliding speed in slip-form technique, freeze injury endurance, the dismounting of baffle plate
The judgement of the character at the initial stage of the concrete such as phase is important.Although for example, in JASS5 and building province's announcement during framed placement
Show in No. 110 and provided, but during the minimum placement of conduct, in temperature, more than 15 DEG C are 2~3 days (foundation, post, wall etc.).
It may be said that its embodiment for being primarily due to the long-term strength caused by the drying of the concrete after the demoulding is significantly deteriorated, especially
Be moisture within 3 days evaporation it is notable.In order to suppress such case, it is replaced with and promotes the hydration reaction and moisture of cement to be difficult to
The cement hydrates for drying (evaporation) are effective, from the long-term strength reduction suppressed caused by the drying of concrete hardening body
Viewpoint is set out, and it is important highly to embody 3 days intensity.
On the other hand, in cement industry, although by the discarded object produced in other industries etc. (common rubbish etc.), pair
Product as raw material, the energy, a part for product and be energetically used, but thus cement minerals composition change, have
When strength of cement significantly change.It is the sight from intensity as Europe, China for the specification of the quality of cement
Point out and send differentiation strength grade (3 grades of 28 days intensity and 2 grades of early strength), these combinations are come to the product of regulation cement
The 3 days intensity shown in matter, particularly early strength depend on the hydration reaction at initial stage of cement, easily occur by discarded object etc.
The variation of caused mineral composition.Therefore, highly embody early strength is from the viewpoint of the steady production of cement
Important.In addition, being used as the mixed of cement products as the blast-furnace slag of the accessory substance of other industries, the ash (fly ash) etc. that floats
Condensation material, can increase combined amount in the range of quality specification, cut down clinker quantity, to embody high strong of early strength
Degree.Moreover, it is important to cut down clinker quantity from the viewpoint of the discharge of the greenhouse gases produced when cutting down clinker manufacture.
In Japanese Unexamined Patent Application Publication 2008-542182 publications, on the manufacture of the powders such as cement, disclose including choosing will be contained
Helped from the crushing of at least one kind of polyalcohol from biomass (biomass) in glycol, triol or their mixture
Agent composition imported into the raising method of the crush efficiency of the particle constituted the step in particle.In Japanese Unexamined Patent Application Publication 2008-
Grinding aid composition has been recorded in No. 542182 publications can further contain triethanolamine, triisopropanolamine, diethanol amine
Obtained Deng grinding aid.
In addition, in Japanese Unexamined Patent Application 61-117142 publications, the cement composition promoted as hardening is public
The cement composition comprising hydroxy methane sodium sulfonate and thiocyanic acid sodium is opened.
In addition, in Japanese Unexamined Patent Publication 2013-79184 publications, Japanese Unexamined Patent Publication 2011-26197 publications, disclosing and using
Triethanolamine as cement grinding aid.
In US-A 2008/0308013, the hard adhesive composition of speed by base material of calcium salt is disclosed.
The content of the invention
The present invention relates to a kind of manufacture method of hydraulic powder, its have in triethanolamine and hydroxy methane sulfonic acid or
In the presence of its salt, the process for crushing hydraulicity compound.
Moreover, it relates to a kind of crushing compositions of additives of hydraulicity compound, its contain triethanolamine and
Hydroxy methane sulfonic acid or its salt, and triethanolamine and hydroxy methane sulfonic acid or the mass ratio (triethanolamine/hydroxy methane sulphur of its salt
Acid or its salt) it is more than 5/95 and less than 55/45.
Embodiment
In the past, improved and concrete for the raising of productivity ratio of hydraulic powder, the productivity ratio of concrete secondary product
The intensity of hardenite such as improves at the reason, in the manufacture method of hydraulic powder, in the comminuted of hydraulicity compound and uses
The compressive strength during hardening of the hydraulic-composition of the hydraulic powder of gained, especially the two aspects of early strength,
Expect further raising.
The present invention provide without prejudice to hydraulicity compound it is smashing in the case of to can be obtained by early strength high
The manufacture method of the hydraulic powder of hardenite.
The manufacture method of the hydraulic powder of the present invention be characterized by triethanolamine and hydroxy methane sulfonic acid or
In the presence of its salt crush hydraulicity compound process, and without prejudice to hydraulicity compound it is smashing in the case of, just
Compressive strength, particularly early strength when playing the hardening of the hydraulic-composition obtained by sening as an envoy to improve such effect.
The reasons why having given play to such effect does not know still, but can contemplate as follows.
In general, crush efficiency is performance obtained from being adsorbed in particle surface by making species monolayer, therefore, is being added
In the case that dosage is certain, the material of low molecule amount is effective in existing additive during crushing.Triethanolamine and hydroxyl
Loprazolam or its salt are low molecule amount (for example, the molecular weight 149.19 of triethanolamine, the molecular weight of hydroxy methane sodium sulfonate
134.09), thus speculate the two can monolayer adsorption in particle surface, and hydroxy methane sulfonic acid will not hinder the powder of triethanolamine
Broken efficiency.
Hydraulic powder after the crushing obtained by the manufacture method by the present invention prepares hydraulic-composition
In the case of, triethanolamine can be speculated by the chelation of appropriateness to promote the C of the mineralogical composition as hydraulic powder4AF
The Ion release of (calcium aluminoferrite).In the case where further containing mixing material (blast-furnace slag, the ash that floats etc.), hydroxyl can be speculated
Loprazolam promotes the Ion release of mixing material, and triethanolamine similarly promotes the Ion release of mixing material in addition.Its
As a result, contained in hydraulic powder come from C3S calcium ion and from mixing material and C4AF respective released ion is high
Effect ground Composite.In addition, can speculate as C3S calcium hydroxide of hydration product etc. turns into the hydration of porous crystal structure
Product, thus maintain water to enter to hydraulic powder surface, proceed in the case of without prejudice to hydration reaction, therefore carry
The high compressive strength since being contacted water after 3 days.
On the other hand, in the case of hydroxy methane sulfonic acid and triethanolamine not being added in mixing water when crushing,
These compounds need to be adsorbed in hydraulic powder to act on hydraulic powder.However, due to there is water-hydraulicity
The adsorption equilibrium of powder, thus make necessary addition quantitative change many to meet certain adsorbance to hydraulic powder.In this hair
In bright, it can speculate by making hydroxy methane sulfonic acid and triethanolamine exist when crushing hydraulicity compound, so that by above-mentioned
Such mechanism, is that considerably less amount also embodies hydration rate raising effect and hardening even if relative to hydraulicity compound
The early strength of body improves effect.Diethanol amine, the triisopropanolamine used in comparative example described later is crushing hydraulicity chemical combination
During thing to particle surface monolayer adsorption and the hydraulic powder when preparing hydraulic-composition Ion release in, with
Triethanolamine compared to be deteriorated, thus can speculate can not obtain the present invention effect.
Triethanolamine can use commercially available product.
From the viewpoint of the comminuted and early strength of hydraulicity compound, the amount of triethanolamine is relative to crushing
Used in the mass parts of hydraulicity compound 100 of raw material be preferably more than 0.0005 mass parts more preferably 0.001 mass
Part more than, it is more than more preferably 0.003 mass parts, still more preferably for 0.005 mass parts more than, still more preferably
More than 0.010 mass parts, still more preferably for 0.015 mass parts more than, still more preferably for 0.020 mass parts with
On, also, from the viewpoint of the comminuted and early strength of hydraulicity compound, below preferably 0.040 mass parts, from powder
From the viewpoint of additive cost when broken, below more preferably 0.035 mass parts.
Hydroxy methane sulfonic acid or its salt can use commercially available product.As salt, can enumerate alkali metal salt, alkali salt and
Ammonium salt, from the viewpoint of the time untill intensity needed for reaching hydraulic-composition from shortening, preferred as alkali salt.It is used as alkali
Metal salt, can enumerate sodium salt and sylvite, as alkali salt, can enumerate calcium salt, go out from the viewpoint of the easiness obtained
Hair, particular certain cancers.
Relative to the parts by weight of hydraulicity compound 100 of the raw material for crushing, from the comminuted of hydraulicity compound and
From the viewpoint of early strength, the amount of hydroxy methane sulfonic acid or its salt is preferably more than 0.0005 mass parts, more preferably
It is more than 0.001 mass parts, it is more than more preferably 0.005 mass parts, still more preferably for 0.010 mass parts more than, and
And, from the viewpoint of the comminuted and early strength of hydraulicity compound, below preferably 0.060 mass parts, more preferably
Below 0.050 mass parts, from the viewpoint of additive cost when crushing, below more preferably 0.030 mass parts, more
Below more preferably 0.024 mass parts.
Relative to the parts by weight of hydraulicity compound 100 of the raw material for crushing, triethanolamine and hydroxy methane sulfonic acid or
Total amount of its salt is preferably more than 0.001 mass parts and below 0.100 mass parts.From the comminuted of hydraulicity compound
From the viewpoint of early strength, the amount is preferably more than 0.001 mass parts, more than more preferably 0.004 mass parts, to enter
One step is preferably more than 0.010 mass parts, still more preferably for 0.020 mass parts more than, be still more preferably 0.025 matter
Measure more than part, still more preferably for 0.030 mass parts more than, also, from the comminuted and early strength of hydraulicity compound
From the viewpoint of, below preferably 0.100 mass parts, below more preferably 0.085 mass parts, more preferably 0.065 matter
Measure part below, still more preferably for 0.059 mass parts below.
The amount be based on crushing present in the process of hydraulicity compound, triethanolamine and hydroxy methane sulfonic acid or its
The amount of total total amount of salt, is based on untill the crushing of hydraulicity compound terminates, furthermore to arriving specifically
Up to the total of triethanolamine and hydroxy methane sulfonic acid or its salt existing untill the Blaine value as described later as target
Total amount amount.
In addition, triethanolamine and hydroxy methane sulfonic acid or its salt mass ratio (triethanolamine/hydroxy methane sulfonic acid or its
Salt) it is preferably more than 5/95 and less than 55/45.From the viewpoint of the comminuted and early strength of hydraulicity compound, the matter
Amount ratio more preferably more than 10/90, more preferably more than 15/85, it is still more preferably more than 25/75, further
Preferably more than 35/65, also, more preferably less than 50/50, from the viewpoint of early strength, more preferably 45/55
Below.
In the present invention, it can make selected from glycerine, monosaccharide or disaccharides, hydroxycarboxylic acid or its salt and condensed phosphoric acid
Or more than a kind of compound C in its salt exists with triethanolamine and hydroxy methane sulfonic acid or its salt simultaneously, and crush the hydraulicity
Compound.That is, the present invention provides a kind of manufacture method of hydraulic powder, its have triethanolamine, hydroxy methane sulfonic acid or
Its salt and more than a kind in glycerine, monosaccharide or disaccharides, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its salt
Compound C in the presence of, crush hydraulicity compound process.
Compound C is preferably glycerine.
Compound C can use two or more, it is, for example, possible to use 2 kinds or 3 kinds.Use two or more compound C situation
Under, glycerine is comprised at least preferably in compound C.In addition, in the case of using 2 kinds of compound C, comprising sweet in compound C
Oil, in compound C total amount, the ratio of glycerine is preferably more than 50 mass % more preferably more than 55 mass %, and
And, preferably below 95 mass %, more preferably below 80 mass %.In the case of using 3 kinds of compound C, in chemical combination
Glycerine is included in thing C, in compound C total amount, the ratio of glycerine is preferably more than 30 mass % more preferably 40 matter
Measure more than %, also, preferably below 95 mass %, more preferably below 80 mass %.Use more than 4 kinds compound C
In the case of, glycerine is included in compound C, in compound C total amount, the ratio of glycerine is preferably more than 20 mass %,
More preferably more than 30 mass %, also, preferably below 95 mass %, more preferably below 80 mass %.
As glycerine, the refined glycerine of commercially available product can be used, such as grease from coconut is obtained by ester exchange
Glycerine.From the viewpoint of the time untill intensity needed for hydraulic-composition of reaching is shortened, preferred refined glycerine.Glycerine can
To use commercially available product.
As monosaccharide, dihydroxyacetone (DHA), glyceraldehyde, erythrulose, erythrose, threose, ribulose, wooden ketone can be enumerated
Sugar, ribose, arabinose, xylose, lyxose, deoxyribose, psicose, fructose, sorbose, Tagatose, allose, A Zhuo
Sugar, glucose, mannose, gulose, idose, galactolipin, talose, fucose, fucose, rhamnose, red-spotted stonecrop heptanone
Sugar.As disaccharides, sucrose, lactose, maltose, trehalose, turanose, cellobiose can be enumerated.Wherein, in the present invention
In, from the viewpoint of the time untill reaching intensity needed for hydraulic-composition is shortened, preferably sucrose, fructose, maltose.It is single
Carbohydrate or disaccharides can use commercially available product.
As hydroxycarboxylic acid, gluconic acid, glycolic, lactic acid, hydroxymalonic acid, glyceric acid, malic acid, winestone can be enumerated
Acid, citric acid, salicylic acid, gallic acid.Wherein, in the present invention, from shortening reach hydraulic-composition needed for untill intensity
Time from the viewpoint of, preferably gluconic acid, citric acid.As the salt of hydroxycarboxylic acid, alkali metal salt, alkali earths can be enumerated
Metal salt and ammonium salt, from the viewpoint of the time untill reaching intensity needed for hydraulic-composition is shortened, preferred as alkali salt.
As alkali metal salt, sodium salt and sylvite can be enumerated, as alkali earth metal salt, calcium salt can be enumerated, from the easiness obtained
From the viewpoint of, particular certain cancers.Hydroxycarboxylic acid or its salt can use commercially available product.
As condensed phosphoric acid, pyrophosphoric acid, tripolyphosphate, four phosphoric acid, hexa metaphosphoric acid can be enumerated.Wherein, in the present invention,
From the viewpoint of the time untill intensity needed for hydraulic-composition of reaching is shortened, preferably hexa metaphosphoric acid, tripolyphosphate.As
The salt of condensed phosphoric acid, can enumerate alkali metal salt, alkali earth metal salt and ammonium salt, from shortening reach hydraulic-composition needed for it is strong
From the viewpoint of time untill degree, preferred as alkali salt.As alkali metal salt, sodium salt and sylvite can be enumerated, alkaline earth is used as
Metalloid salt, can enumerate calcium salt, from the viewpoint of the easiness obtained, particular certain cancers.Condensed phosphoric acid or its salt can make
Use commercially available product.
Triethanolamine, total mass ratio (triethanolamine/(hydroxyl first with hydroxy methane sulfonic acid or its salt and compound C
Alkyl sulfonic acid or its salt+compound C)) it is preferably more than 5/95, more preferably more than 30/70, more preferably more than 45/55,
Also, from the viewpoint of compressive strength raising, preferably less than 95/5, more preferably less than 85/15, more preferably
Less than 70/30, further from hydraulic powder it is comminuted from the viewpoint of, preferably less than 55/45.
In addition, hydroxy methane sulfonic acid or its salt, the mass ratio (hydroxy methane sulfonic acid or its salt/compound C) with compound C
Preferably more than 5/95, more preferably more than 20/80, more preferably more than 30/70, also, preferably less than 95/5, more
Preferably less than 80/20, more preferably less than 70/30.
Relative to the mass parts of hydraulicity compound 100, compound C amount is preferably more than 0.0005 mass parts, more
More than preferably 0.0015 mass parts, more than more preferably 0.0030 mass parts, it is still more preferably 0.0035 mass
More than part, also, below preferably 0.04 mass parts, below more preferably 0.01 mass parts, more preferably 0.007 mass
Below part.
In order that triethanolamine and hydroxy methane sulfonic acid or its salt exist and crushed, preferably hydraulicity compound,
For example in the raw material comprising clinker, add triethanolamine and hydroxy methane sulfonic acid or its salt to carry out., can as the method for addition
With enumerate by the liquid object containing triethanolamine and hydroxy methane sulfonic acid or its salt, preferred aqueous solutions by be added dropwise, spraying etc. come
The method of supply.Triethanolamine and hydroxy methane sulfonic acid or its salt can be distinguished in the form of liquid object, preferred aqueous solutions respectively
It is added in hydraulicity compound, can also be in hydraulicity compound be added to after the two is mixed.In addition, as it is other into
Point, in addition to above-claimed cpd C, defoamer, water etc. can be used.In the case of using compound C, preferably with triethanolamine and
Hydroxy methane sulfonic acid or its salt are added in hydraulicity compound together.Three ethanol into the raw material comprising hydraulicity compound
The addition of amine and hydroxy methane sulfonic acid or its salt or triethanolamine and hydroxy methane sulfonic acid or its salt and other compositions, example
Addition such as compound C can add together it is final used in total amount, can also be added batch-wise.Furthermore it is possible to continuously or
Intermittently add.
In the manufacture method of the hydraulic powder of the present invention, hydraulicity compound is crushed and hydraulic powder is obtained.Water
Rigid compound refers to there is the material that the property hardened is reacted with water by representative of clinker；And with the ash that floats, height
Stove clinker etc. for representative it is independent for do not have hardening, if but with water, alkali substance reaction and harden
Both the combinations of substances of property, the then material for hydrate being formed by interaction by water and being hardened.The hydraulicity
Compound is hydraulicity material.As the material with the property reacted and hardened with water, alkaline-earth metal can be enumerated
Oxide, SiO2、Al2O3、Fe2O3、TiO2、P2O5, the oxide such as ZnO.They typically form water under normal temperature or hydrothermal condition
Compound.For example, in clinker, including 3CaOSiO2(C3S：Tricalcium silicate), 2CaOSiO2(C2S：Dicalcium silicate), 3CaO
Al2O3(C3A：Calcium aluminate), 4CaOAl2O3·Fe2O3(C4AF：Calcium aluminoferrite) it is used as composition.In addition, for being used as individually not
With hardening, if but with water, alkali substance reaction and the combinations of substances of property hardened, pass through by water
The material for interacting and forming hydrate and hardening, for example, can enumerate the material with solidifying hard (pozzolan) effect
(float ash, silica flour, volcanic ash, silicate clay), material (blast-furnace slag) and C with latent hydraulicity3A or C4AF reactions
Material (limestone (limestone)) etc..In the present invention, will individually for do not have hardening, if but with water, alkalescence
Substance reaction and the combinations of substances of property hardened, then form hydrate by interaction by water and harden
Material Definitions be " mixing material ".In addition, when mentioning hydraulicity compound, refer to single hydraulicity compound and comprising
Both a variety of different mixtures of hydraulicity compound.
Hydraulicity compound be preferably containing with water, alkali substance reaction and the change of the material of property hardened
Compound, the more preferably compound containing the material with the property reacted and hardened with water, especially containing ripe
The chemical combination of material and more than a kind of the mixing material (hereinafter referred to as mixing material (a)) in blast-furnace slag, float ash and silica flour
Thing.From the viewpoint of the intensity improving rate from no added of 3 days intensity, in hydraulicity compound, mixing material (a)
Content be preferably more than 8 mass % more preferably more than 25 mass %, more preferably more than 40 mass %, also, excellent
Elect as below 80 mass %, more preferably below 70 mass %, more preferably below 60 mass %.The content it is remaining excellent
Elect the material with the property reacted and hardened with water as.Therefore, for the above-mentioned hydraulicity containing mixing material (a)
For compound, the content of the material with the property reacted and hardened with water such as clinker is preferably in hydraulicity compound
More than 20 mass %, more preferably more than 30 mass %, more preferably more than 40 mass %, also, preferably 92 matter
Measure below %, more preferably more preferably below 75 mass %, below 60 mass %.In addition, clinker etc. has and water, alkali
Total content of property substance reaction and the material of property that hardens and above-mentioned mixing material (a) is excellent in hydraulicity compound
Elect as more than 70 mass %, more preferably more than 90 mass %, also, preferably below 100 mass %, can be 100 matter
Measure %.The manufacture method of the present invention is suitable as blended cement (such as JIS R 5211~5213) manufacture method.
In the case where obtaining Portland cement as hydraulic powder, for example Portland cement will be to lime stone, viscous
The raw materials such as soil, scum (iron さ い) burnt till obtained by hydraulicity compound i.e. clinker (also referred to as clinker, be also mixed into sometimes
There is gypsum.) crushing is prepared, appropriate gypsum is added, finishing crushing is carried out, compares surface with defined so as to produce
Product, such as Blaine value 2500cm2/ more than g or BET specific surface area 0.8m2The powder of/more than g specific surface area.Can be simultaneously
The hydraulic powder containing mixing material is similarly manufactured using clinker and above-mentioned mixing material.
In the manufacture method of the hydraulic powder of the present invention, powder is adjusted according to raw material, purposes (strength grade of cement) etc.
Broken condition is to obtain the powder of appropriate particle diameter.In general, it is such to be individually for clinker in hydraulicity compound
There is the material of property for reacting and hardening with water in the case of, preferably carry out the crushing of hydraulicity compound until cloth
Lai En values reach preferred 2500cm2/ more than g, more preferably 3000cm2/ more than g, also, preferably 5000cm2/ below g, more preferably
4000cm2/ below g powder.React and occur hard with water in addition, having as hydraulicity compound contains clinker
In the case of the material and mixing material of the property of change, the density (proportion) of hydraulicity compound is failed to understand and is difficult to determine sometimes
Blaine value.In this case, it can be replaced with BET specific surface area.BET specific surface area is to make nitrogen (N2) etc. gas particle inhale
Solids are invested, the gas adsorption method of surface area is determined by the amount adsorbed.Specifically, utilize pressure P's and adsorbance V
Relation and by BET formulas (Brunauer, Emmet and Teller ' s equation), determines unimolecule adsorbance VM, thus
Specific surface area can be obtained.Crush containing have as clinker with water react and the material of the property that hardens,
In the case of the hydraulicity compound of mixing material, the crushing of hydraulicity compound is preferably carried out until BET specific surface area reaches
To preferred 0.8m2/ more than g, more preferably 1.2m2/ more than g, also, preferably 3.0m2/ below g, more preferably 2.5m2/ below g powder
Body.Target specific surface area can be crushed under the either case in for Blaine value, BET specific surface area for example, by adjustment
Time and obtain.If in the presence of increase grinding time, specific surface area becomes big, if shortening grinding time, what specific surface area diminished
Tendency.On specific surface area, if for example, increasing grinding time using the manufacture method of the present invention and increasing hydraulic powder
BET specific surface area, then can further shorten the time untill intensity needed for reaching hydraulic-composition.
In the present invention, the reducing mechanism for the crushing of hydraulicity compound is not particularly limited, for example,
The general ball mill in the crushing of cement etc..The material of the crushing medium (crushing ball) of the device preferably has and pulverized thing
(such as being calcium aluminate in the case of clinker) equal or the hardness more than it, in general in obtainable commercially available product,
For example, steel, stainless steel, aluminum oxide, zirconium oxide, titanium dioxide, tungsten carbide etc..
, can also be simultaneously from the viewpoint of intensity decreases caused by the increase of air capacity from hydraulic-composition is suppressed
Use defoamer.In addition, by making defoamer exist in the crushing of hydraulicity compound, so that defoamer can also be made equably
The surface of obtained hydraulic powder is distributed in, above-mentioned inhibition is more effectively embodied.That is, by with three ethanol
The manufacture of the hydraulic powder of the process of hydraulicity compound is crushed in the presence of amine, hydroxy methane sulfonic acid or its salt and defoamer
Method, so as to shorten to the time untill reaching desired particle diameter.In addition, by with triethanolamine, hydroxy methane
The manufacturer of the hydraulic powder of the process of hydraulicity compound is crushed in the presence of sulfonic acid or its salt, compound C and defoamer
Method, so as to shorten to the time untill reaching desired particle diameter.That is, crush efficiency is good, further, it is possible to suppress air capacity
The compressive strength reduction of hydraulic-composition caused by increase.
It is used as defoamer, preferably silicone-based defoamer, fatty acid ester system defoamer and ether system defoamer, silicone-based defoamer
In, more preferably dimethyl polysiloxane, in fatty acid ester system defoamer, more preferably polyalkylene glycol fatty acid esters, ether system disappears
In infusion, more preferably polyalkylene glycol ethers.
When having used by the hydraulic-composition of hydraulic powder obtained from the manufacture method of the present invention as hardening
Compressive strength, the hydraulic-composition that especially early strength is improved.As hydraulic powder, Portland can be enumerated
Cement (JIS R 5210), blast-furance cement (JIS R 5211), silicon-dioxide cement (JIS R 5212), the ash concrete that floats (JIS R
5213), alundum cement etc., the blended cement that preferable blendstocks are obtained by mixing by a certain percentage.
Concrete structure, concrete product may be used as by the obtained hydraulic powder of manufacture method of the present invention
Material.The concrete of the hydraulic powder obtained by manufacture method of the invention has been used to have the following advantages that：Due to from connecing
Tactile water starts such compressive strength at initial stage after 3 days and improved, thus, for example obtained even in the manufacture method by the present invention
In hydraulic powder coordinate, replace contact water after initial material age low intensity hydraulic powder (blast-furnace slag, the ash that floats, silica flour,
Lime stone etc.), compared with having used the situation of unenforced hydraulic powder of the invention, can also obtain more than equal from connecing
Tactile water starts compressive strength after 3 days etc..
In addition, from the viewpoint of the operability during crushing for improving hydraulicity compound, in the hydraulicity powder of the present invention
In the manufacture method of body, it can use containing triethanolamine and hydroxy methane sulfonic acid or its salt, and triethanolamine and hydroxy methane
The mass ratio (triethanolamine/hydroxy methane sulfonic acid or its salt) of sulfonic acid or its salt is more than 5/95 and less than 55/45 present invention
Hydraulicity compound crushing compositions of additives.In the crushing compositions of additives of the hydraulic powder of the present invention,
The mass ratio (triethanolamine/hydroxy methane sulfonic acid or its salt) of triethanolamine and hydroxy methane sulfonic acid or its salt is preferably above-mentioned ratio
Rate scope.
From the viewpoint of the operability such as addition operation are improved, the crushing of hydraulic powder of the invention is combined with additive
The form of thing is preferably fluid composition.In order that form is fluid composition, the crushing of hydraulic powder is combined with additive
Thing can contain solvent.It is used as solvent, preferably water.The content of solvent is preferably more than 20 mass % more preferably 30 mass %
More than, more preferably more than 40 mass %, also, preferably below 95 mass %, more preferably below 90 mass %, enter
It is still more preferably below 70 mass % below 80 mass % that one step, which is preferably, is still more preferably below 60 mass %.
In addition, the crushing compositions of additives of the hydraulic powder of the present invention can contain other additives such as defoamer.
From the viewpoint of 3 days intensity for improving hydraulic-composition, the crushing of hydraulic powder of the invention is added
The total amount of triethanolamine and hydroxy methane sulfonic acid or its salt in agent composition is preferably more than 5 mass % more preferably 10
More than quality %, more preferably more than 20 mass %, are still more preferably more than 30 mass %, still more preferably for
More than 40 mass %, also, from the viewpoint of the operability of addition operation etc., preferably below 80 mass %, more preferably
Below 70 mass %, more preferably below 60 mass %.
The crushing compositions of additives of the hydraulic powder of the present invention, which can contain, is selected from glycerine, monosaccharide or disaccharides
More than a kind of compound C in class, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its salt.Compound C concrete example and excellent
Select scheme same as described above.
The present invention hydraulic powder crushing compositions of additives in, triethanolamine, with hydroxy methane sulfonic acid or its
Salt and compound C total mass ratio (triethanolamine/(hydroxy methane sulfonic acid or its salt+compound C)) be preferably 5/95 with
On, more preferably more than 30/70, more preferably more than 45/55, also, from the viewpoint of compressive strength raising, preferably
For less than 95/5, more preferably less than 85/15, more preferably less than 70/30, further from the comminuted of hydraulic powder
From the viewpoint of, preferably less than 55/45.
In addition, in the crushing compositions of additives of the hydraulic powder of the present invention, hydroxy methane sulfonic acid or its salt and change
Compound C mass ratio (hydroxy methane sulfonic acid or its salt/compound C) is preferably more than 95/5, and more preferably more than 80/20, enter
One step is preferably more than 70/30, also, preferably less than 5/95, more preferably less than 20/80, more preferably 30/70 with
Under.
For the crushing compositions of additives of the hydraulic powder of the present invention, in the crushing of hydraulicity compound
When, triethanolamine and hydroxy methane sulfonic acid or the respective amount of its salt and their total amount are preferably according to reaching above-mentioned presence
The mode of amount is added in hydraulic-composition.Using during compound C similarly.
The crushing of the hydraulic powder of the present invention may be used as hydraulic powder intensity enhancer with compositions of additives
Composition.Hydraulic powder is with intensity enhancer composition, being applicable the above-mentioned hydraulic powder on the present invention
The item of crushing compositions of additives.
The solution of the present invention illustrates as follows.
<1>A kind of manufacture method of hydraulic powder, it has depositing in triethanolamine and hydroxy methane sulfonic acid or its salt
In the process of lower crushing hydraulicity compound.
<2>As described above<1>The manufacture method of described hydraulic powder, wherein, the amount of the triethanolamine is relative
It is preferably more than 0.0005 mass parts, more than more preferably 0.001 mass parts, to enter in the above-mentioned mass parts of hydraulicity compound 100
One step is preferably more than 0.003 mass parts, still more preferably for 0.005 mass parts more than, be still more preferably 0.010 matter
Measure more than part, still more preferably for 0.015 mass parts more than, still more preferably for 0.020 mass parts more than, it is also, excellent
Elect as below 0.040 mass parts, below more preferably 0.035 mass parts.
<3>As described above<1>Or<2>The manufacture method of described hydraulic powder, wherein, the hydroxy methane sulfonic acid or its
The amount of salt is preferably more than 0.0005 mass parts more preferably 0.001 relative to the mass parts of hydraulicity compound 100
It is more than mass parts, it is more than more preferably 0.005 mass parts, still more preferably for 0.010 mass parts more than, further
More than preferably 0.020 mass parts, also, below preferably 0.060 mass parts, below more preferably 0.050 mass parts, enter one
Step be preferably 0.030 mass parts below, still more preferably for 0.024 mass parts below.
<4>As described above<1>~<3>Any one of hydraulic powder manufacture method, wherein, the triethanolamine
It is preferably relative to the mass parts of hydraulicity compound 100 with total amount of the hydroxy methane sulfonic acid or its salt
More than 0.001 mass parts, more than more preferably 0.004 mass parts, more than more preferably 0.010 mass parts, further
It is more than preferably 0.020 mass parts, still more preferably for 0.025 mass parts more than, be still more preferably 0.030 mass parts
More than, also, below preferably 0.100 mass parts, below more preferably 0.085 mass parts, more preferably 0.065 mass
It is part following, still more preferably for 0.059 mass parts below.
<5>As described above<1>~<4>Any one of hydraulic powder manufacture method, wherein, the triethanolamine
Mass ratio (triethanolamine/hydroxy methane sulfonic acid or its salt) with the hydroxy methane sulfonic acid or its salt is preferably more than 5/95,
More preferably more than 10/90, more preferably more than 15/85, it is still more preferably more than 25/75, still more preferably
Below more than 35/65, also, 55/45, preferably less than 50/50, more preferably less than 45/55.
<6>As described above<1>~<5>Any one of hydraulic powder manufacture method, wherein, the hydraulicity
Compound contains：1 kind with the material of property for reacting and hardening with water and in blast-furnace slag, float ash and silica flour
Mixing material above,
The content of the material with the property reacted and hardened with water is preferred in the hydraulicity compound
For more than 20 mass %, more preferably more preferably more than 30 mass %, more than 40 mass %, also, preferably 92 matter
Below %, more preferably more preferably below 75 mass %, 60 mass % are measured,
The content of the mixing material is preferably more than 8 mass %, more preferably 25 matter in the hydraulicity compound
Measure more than %, more preferably more than 40 mass %, also, preferably below 80 mass %, more preferably 70 mass % with
Under, more preferably below 60 mass %.
<7>As described above<6>The manufacture method of described hydraulic powder, wherein, it is described to occur hard with being reacted with water
Total content of the material of the property of change and the mixing material is preferably more than 70 mass % in hydraulicity compound, more excellent
Elect as more than 90 mass %, also, preferably below 100 mass %, more preferably 100 mass %.
<8>As described above<6>Or<7>The manufacture method of described hydraulic powder, wherein, the hydraulicity compound contains
With the material of property and mixing material for reacting and hardening with water, and carry out the crushing of hydraulicity compound until into
It is preferably 0.8m for BET specific surface area2/ more than g, more preferably 1.2m2/ more than g and preferably 3.0m2It is/below g, more excellent
Elect 2.5m as2Untill/below g powder.
<9>As described above<1>~<8>Any one of hydraulic powder manufacture method, wherein, the powder for crushing
Crushing device is ball mill, and the material of crushing ball is 1 in steel, stainless steel, aluminum oxide, zirconium oxide, titanium dioxide, tungsten carbide
More than kind.
<10>As described above<1>~<9>Any one of hydraulic powder manufacture method, wherein, make selected from glycerine,
More than a kind of compound C and described three in monosaccharide or disaccharides, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its salt
Monoethanolamine and the hydroxy methane sulfonic acid or its salt exist simultaneously, and crush hydraulicity compound.
<11>As described above<10>The manufacture method of described hydraulic powder, wherein, the triethanolamine and the hydroxyl
Total mass ratio (triethanolamine/(hydroxy methane sulfonic acid or its salt+compound of Loprazolam or its salt and the compound C
C)) be more than 5/95, preferably more than 30/70, more preferably more than 45/55, also, for less than 95/5, preferably 85/15 with
Under, more preferably less than 70/30, it is still more preferably less than 55/45.
<12>As described above<10>Or<11>The manufacture method of described hydraulic powder, wherein, the hydroxy methane sulfonic acid
Or its salt and the compound C mass ratio (hydroxy methane sulfonic acid or its salt/compound C) are more than 5/95, more preferably
More than 20/80, more preferably more than 30/70, also, preferably less than 95/5, more preferably less than 80/20, further
Preferably less than 70/30.
<13>As described above<10>~<12>Any one of hydraulic powder manufacture method, wherein, the chemical combination
Thing C amount is more than 0.0005 mass parts preferably 0.0015 mass relative to the mass parts of hydraulicity compound 100
More than part, it is more than more preferably 0.0030 mass parts, still more preferably for 0.0035 mass parts more than, also, for 0.04 matter
Measure below part, below more preferably 0.01 mass parts, below more preferably 0.007 mass parts.
<14>A kind of crushing compositions of additives of hydraulicity compound, it contains triethanolamine and hydroxy methane sulphur
Acid or its salt, and triethanolamine and hydroxy methane sulfonic acid or the mass ratio (triethanolamine/hydroxy methane sulfonic acid or its salt) of its salt
For more than 5/95 and less than 55/45.
<15>As described above<14>The crushing compositions of additives of described hydraulicity compound, its form is liquid combination
Thing.
<16>As described above<15>The crushing compositions of additives of described hydraulicity compound, it contains solvent, preferably
Water, the content of solvent is preferably more than 20 mass %, more preferably more than 30 mass %, more preferably 40 mass % with
On, also, preferably below 95 mass %, more preferably below 90 mass %, more preferably below 80 mass %, more enter
It is still more preferably below 60 mass % below 70 mass % that one step, which is preferably,.
<17>As described above<14>~<16>Any one of hydraulicity compound crushing compositions of additives, its
In, the conjunction of the triethanolamine and the hydroxy methane sulfonic acid or its salt in the crushing compositions of additives of hydraulic powder
Metering preferably more than 5 mass %, more preferably more preferably more than 10 mass %, more than 20 mass %, further
Preferably more than 30 mass %, are still more preferably more than 40 mass %, also, preferably below 80 mass %, more preferably
For below 70 mass %, more preferably below 60 mass %.
<18>As described above<14>~<17>Any one of hydraulicity compound crushing compositions of additives, its
Contain more than a kind of the change in glycerine, monosaccharide or disaccharides, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its salt
Compound C.
<19>As described above<18>The crushing compositions of additives of described hydraulicity compound, wherein, three ethanol
Amine, total mass ratio (triethanolamine/(hydroxy methane sulfonic acid with the hydroxy methane sulfonic acid or its salt and the compound C
Or its salt+compound C)) it is preferably more than 5/95, more preferably more than 30/70, more preferably more than 45/55, also,
Preferably less than 95/5, more preferably less than 85/15, more preferably less than 70/30, still more preferably for 55/45 with
Under.
<20>As described above<18>Or<19>The crushing compositions of additives of described hydraulicity compound, wherein, it is described
Hydroxy methane sulfonic acid or its salt, with the mass ratio (hydroxy methane sulfonic acid or its salt/compound C) of the compound C for 5/95 with
On, more preferably more than 20/80, more preferably more than 30/70, also, preferably less than 95/5, more preferably 80/20
Hereinafter, more preferably less than 70/30.
<21>It is above-mentioned<14>~<20>Any one of hydraulicity compound crushing compositions of additives in water
Application in the crushing of rigid compound.
<22>As described above<21>The described application in the crushing of hydraulicity compound, wherein, the hydraulicity chemical combination
Thing contains：1 kind with the material of property for reacting and hardening with water and in blast-furnace slag, float ash and silica flour with
On mixing material,
The content of the material with the property reacted and hardened with water is preferred in the hydraulicity compound
For more than 20 mass %, more preferably more preferably more than 30 mass %, more than 40 mass %, also, preferably 92 matter
Below %, more preferably more preferably below 75 mass %, 60 mass % are measured,
The content of the mixing material is preferably more than 8 mass %, more preferably 25 matter in the hydraulicity compound
Measure more than %, more preferably more than 40 mass %, also, preferably below 80 mass %, more preferably 70 mass % with
Under, more preferably below 60 mass %.
<23>As described above<22>The described application in the crushing of hydraulicity compound, wherein, it is described with anti-with water
The material of property and total content of mixing material answered and hardened are preferably 70 matter in the hydraulicity compound
More than %, more preferably more than 90 mass % are measured, and are below 100 mass %, more preferably 100 mass %.
Embodiment
Implementation of the following examples to the present invention is described.Embodiment is described to the illustration of the present invention, but simultaneously
It is not used in the restriction present invention.
(1) hydraulicity compound
Use the different following hydraulicitys of the mixing material content for being obtained by mixing clinker, dihydrate gypsum, mixing material
Compound.
The mass % of mixing material content 0 hydraulicity compound：It is mixed with the mass % of clinker 95, the matter of dihydrate gypsum 5
Measure %.
The mass % of mixing material content 5 hydraulicity compound：It is mixed with the mass % of clinker 90, the matter of dihydrate gypsum 5
Measure %, the mass % of blast furnace granulated slag 5.
The mass % of mixing material content 10 hydraulicity compound：It is mixed with the mass % of clinker 86, the matter of dihydrate gypsum 4
Measure %, the mass % of blast furnace granulated slag 5, float grey 5 mass %.
The mass % of mixing material content 30 hydraulicity compound：It is mixed with the mass % of clinker 67, the matter of dihydrate gypsum 3
Measure %, the mass % of blast furnace granulated slag 15, float grey 15 mass %.
The mass % of mixing material content 47 hydraulicity compound：It is mixed with the mass % of clinker 50, the matter of dihydrate gypsum 3
Measure %, the mass % of blast furnace granulated slag 25, float grey 22 mass %.
The mass % of mixing material content 70 hydraulicity compound：It is mixed with the mass % of clinker 28, the matter of dihydrate gypsum 2
Measure %, the mass % of blast furnace granulated slag 35, float grey 35 mass %.
Clinker, dihydrate gypsum, blast furnace granulated slag, the ash that floats are following substances.
Clinker：Turn into CaO according to composition：About 65%, SiO2：About 22%, Al2O3：About 5%, Fe2O3：About 3%, MgO
Deng：The mode of about 3% (quality criteria), lime stone, clay, silica, raw iron oxide material etc. are combined and burnt till, will thus
Obtained by burned material carry out normal portland cement clinker (3.5mm obtained from once crushing using disintegrating machine and grinder
Sieve passes through thing)
Dihydrate gypsum：Reagent is superfine, Wako Pure Chemical Industries, Ltd.'s system
Blast furnace granulated slag：Thing obtained from once crushing is carried out to blast furnace granulated slag using disintegrating machine and grinder
It is designated as " Slag " in matter (3.5mm sieves pass through thing), table.
Float ash：It is designated as " FA " in commercially available product, Chubu Electric Power Co.'s system, table.
(2) preparation of the crushing compositions of additives of hydraulicity compound
Triethanolamine and hydroxy methane sodium sulfonate are mixed with blending ratio shown in table 1~5, according to being formed, solid constituent is dense
Degree (active ingredient concentration) adds water for the mode of the 50 mass % aqueous solution and adjusts concentration.Any crushing compositions of additives
Without muddiness etc., the uniform aqueous solution has been obtained.It should be noted that triethanolamine, hydroxy methane sodium sulfonate are following material.
Triethanolamine：Wako Pure Chemical Industries, Ltd.'s system
Hydroxy methane sodium sulfonate：Tokyo HuaCheng Industry Co., Ltd's system
(3) measure of the BET specific surface area of hydraulic powder
The measure of BET specific surface area uses Macsorb HM-model 1201 (Mountech company systems), in following bar
Carried out under part.
Degassing：100 DEG C × 30 minutes, cooling × 4 minutes
Determine gas：Using helium as carrier gas, cooling agent and adsorbate are used as using nitrogen.In addition, mixed gas
Concentration is set to 30.4%, flow and is set to 25ml/min..
(4) preparation of hydraulic-composition and compressive strength experiment
According to physical test method (JIS R 5201) annex 2 (measure of the test method intensity of cement) of cement, system
It is standby go out hydraulic-composition.According to physical test method (JIS R 5201) (test method-intensity of cement of annex 2 of cement
Measure) have rated the compressive strength of resulting hydraulic-composition.
<Embodiment 1 and comparative example 1>
In the mass % of mixing material content 47 hydraulicity compound 600g, the additive shown in table 1 is used into addition to crush
Amount addition of the form of agent composition as shown in table 1, in the presence of additive, hydraulic powder is manufactured with ball mill crushing.
Ball mill develops AXB-15 using Co., Ltd.'s Seiwa skills, and stainless steel kettle capacity is set to 18 liters (external diameter 300mm),
Stainless steel ball uses 70 30mm φ (nominal value 13/16), 70 20mm φ (nominal value 3/4), 35 30mm φ aluminum oxide
Ball adds up to 175 balls, and the rotating speed of ball mill is set to 45rpm.In addition, determining the BET specific surface area after crushing 38 minutes.
Using the hydraulic powder obtained after crushing 38 minutes, after hydraulic-composition is prepared, with 28 days after determining 3 days
Compressive strength afterwards.As a result it is shown in table 1.
In comparative example 1-1, in the manufacture of hydraulic powder (during crushing), triethanolamine and hydroxy methane sodium sulfonate are not
Addition, in comparative example 1-2, after being pulverized by the additive of the ormal weight shown in table to crush the form with compositions of additives
It is added in mixing water when preparing mortar.In addition, in comparative example 1-3, in the manufacture of hydraulic powder (during crushing), only will
Triethanolamine is added with the form of the aqueous solution, in comparative example 1-4, in the manufacture of hydraulic powder (during crushing), only by hydroxyl
Loprazolam sodium is added with the form of the 50 mass % aqueous solution.In addition, in comparative example 1-5 and comparative example 1-6, when crushing, generation
For hydroxy methane sodium sulfonate, and promoted with crushing with the hardening described in the form of compositions of additives has used patent document 2
Agent composition, i.e. sodium hydrogensulfite or calcium nitrate.In addition, in comparative example 1-7 and comparative example 1-8, when crushing, instead of three ethanol
Amine, and alkanolamine, i.e. diethanol amine (in table, being designated as " DEA ") has been used with the form of compositions of additives or three different with crushing
Propanolamine (in table, is designated as " TiPA ").
[table 1]
*, comparative example 1-1 result is set to 100 relative value
In table 1, as described in comparative example 1-2, even if regarding triethanolamine and hydroxy methane sodium sulfonate as addition after being pulverized
Agent and be added in hydraulic powder, intensity is not also greatly improved within 3 days.On the other hand understand：In embodiment 1-1, pass through
Triethanolamine is set to exist with both hydroxy methane sodium sulfonates when crushing hydraulicity compound, so that with a small amount of addition with regard to energy
Enough produce the hydraulic powder of the comminuted hardenite for becoming well and 3 days excellent strengths can be obtained.Thus, by three ethanol
The difference for the effect that the addition period of amine and hydroxy methane sodium sulfonate is brought is obvious.As described in comparative example 1-7,1-8, i.e.,
Triethanolamine is replaced using the similar diethanol amine of structure or triisopropanolamine, intensity will not also be greatly improved within 3 days.Thus,
Difference by the effect brought as alkanolamine using triethanolamine is obvious.
<Embodiment 2 and comparative example 2>
In embodiment 1-1, according to the total amount of triethanolamine and hydroxy methane sodium sulfonate relative to hydraulicity compound 100
Mass parts are added for the mode of 0.080 mass parts, in addition, are tested in the same manner as embodiment 1-1.In addition, with being compared
Example 1-2 is same, and the additive of the ormal weight shown in table is also used addition by comparative example 2-1, comparative example 2-2 to crush after being pulverized
The form of agent composition is added in mixing water when preparing mortar.As a result it is shown in table 2.
[table 2]
*, comparative example 1-1 result is set to 100 relative value
Will also realize that by the result of table 2, as described in embodiment 2-1, by make triethanolamine and hydroxy methane sodium sulfonate this two
Person exists when crushing hydraulicity compound, so that can just be produced with a small amount of addition comminuted become good and can obtained
Obtain the hydraulic powder of the hardenite of 3 days excellent strengths.
<Embodiment 3~7 and comparative example 3~7>
In embodiment 1-1, the hydraulicity compound that the content of mixing material is different is used, in addition, with embodiment
1-1 is similarly tested.In addition, comparative example is similarly, it is added to after being pulverized with crushing with the form of compositions of additives
In mixing water when preparing mortar.As a result it is shown in table 3.In table 3, embodiment 1-1, comparative example 1-1,1-2 result are also recorded in the lump.
[table 3]
*, the result of each comparative example of sub- sequence number with " -1 " is set to 100 relative value
As shown in Table 3, with the ratio increase of the mixing material in hydraulicity compound, intensity has the tendency of reduction within 3 days,
But in the embodiment using the method for the present invention, for including the hydraulicity compound of mixing material in any proportion,
The comminuted hydraulic powder for becoming well and can obtain the excellent hardenite of early strength can be produced.
<Embodiment 8>
In embodiment 1-1, in addition to changing the mass ratio of triethanolamine and hydroxy methane sodium sulfonate, with embodiment 1-1
Similarly tested.As a result it is shown in table 4.In table 4, embodiment 1-1, comparative example 1-1 result are also recorded in the lump.
[table 4]
*, comparative example 1-1 result is set to 100 relative value
As shown in Table 4, triethanolamine and hydroxy methane sulfonic acid or the mass ratio (triethanolamine/hydroxy methane sulfonic acid of its salt
Or its salt) there is scope preferably.
<Embodiment 9>
In embodiment 1-1, in addition to changing total addition of triethanolamine and hydroxy methane sodium sulfonate, with embodiment
1-1 is similarly tested.As a result it is shown in table 5.In table 5, embodiment 1-1, comparative example 1-1 result are also recorded in the lump.
[table 5]
*, comparative example 1-1 result is set to 100 relative value
As shown in Table 5, there is scope preferably in total amount of triethanolamine and hydroxy methane sulfonic acid or its salt.Especially
It understands, if total amount of triethanolamine and hydroxy methane sulfonic acid or its salt is relative to the hydraulicity compound 100 of raw material
Parts by weight are that more than 0.02 mass parts, then comminuted and early strength is further improved.
<Embodiment 10~13 and comparative example 10~13>
(1) hydraulicity compound
By clinker, dihydrate gypsum, mixing material (float ash and limestone) mixing, it is the mass % of clinker 65, two to obtain composition
The mass % of water gypsum 6, the grey 17 mass % that floats, the mass % of limestone 12 hydraulicity compound.
Clinker, dihydrate gypsum, float ash, limestone are following substances.
Clinker：Turn into CaO according to composition：About 65%, SiO2：About 22%, Al2O3：About 5%, Fe2O3：About 3%, MgO
Deng：The mode of about 3% (quality criteria), lime stone, clay, silica, raw iron oxide material etc. are combined and burnt till, will thus
Obtained by burned material carry out normal portland cement clinker (3.5mm obtained from once crushing using disintegrating machine and grinder
Sieve passes through thing)
Dihydrate gypsum：By normal portland cement with dihydrate gypsum using disintegrating machine and grinder carry out once crush and
Obtained dihydrate gypsum (3.5mm sieves pass through thing)
Float ash：Commercially available product, Chubu Electric Power Co.'s system
Limestone：Lime stone as clinker raw material is carried out obtained from once crushing using disintegrating machine and grinder
Limestone (3.5mm sieves pass through thing)
(2) preparation of the crushing compositions of additives of hydraulicity compound
Triethanolamine, hydroxy methane sodium sulfonate and compound C are mixed with blending ratio shown in table 6~9, according to shape
Water is added for the mode of the 50 mass % aqueous solution adjust concentration into solids content concn (active ingredient concentration).Any crush is used
Compositions of additives without muddiness etc., has obtained the uniform aqueous solution.It should be noted that triethanolamine, hydroxy methane sulphur
Sour sodium, glycerine, sucrose, fructose, maltose, sodium gluconate, sodium citrate, calgon, sodium tripolyphosphate are following thing
Matter.
Triethanolamine：Wako Pure Chemical Industries, Ltd.'s system
Hydroxy methane sodium sulfonate：Tokyo HuaCheng Industry Co., Ltd's system
Glycerine：Kao Corp's system " refined glycerine "
Sucrose：Wako Pure Chemical Industries, Ltd.'s system
Fructose：Wako Pure Chemical Industries, Ltd.'s system
Maltose：Wako Pure Chemical Industries, Ltd.'s system
Sodium gluconate：Wako Pure Chemical Industries, Ltd.'s system
Trisodium citrate (crystal)：Wako Pure Chemical Industries, Ltd.'s system
Calgon：Wako Pure Chemical Industries, Ltd.'s system
Sodium tripolyphosphate：Wako Pure Chemical Industries, Ltd.'s system
(3) manufacture and evaluation of hydraulic powder
In above-mentioned hydraulicity compound 600g, by additive shown in table 6~9 to crush the shape with compositions of additives
Amount addition of the state as shown in table 1, in the presence of additive, hydraulic powder is manufactured with ball mill crushing.Ball mill is used
Ball mill same as Example 1, its use condition is also same as Example 1.But, BET specific surface area is being crushed 100 minutes
After determine.Using the hydraulic powder obtained after crushing 100 minutes, after hydraulic-composition is prepared, with 28 days after determining 3 days
Compressive strength afterwards.Show the result in table 6~9.
[table 6]
As shown in Table 6, if make selected from glycerine, monosaccharide or disaccharides, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its
More than a kind of compound C in salt exists simultaneously with triethanolamine and hydroxy methane sulfonic acid or its salt, and crushes hydraulicity chemical combination
Thing, then comminuted and early strength is further improved.
[table 7]
[table 8]
[table 9]
*, comparative example 10-1 result is set to 100 relative value
From table 7~9, triethanolamine, total mass ratio (three with hydroxy methane sulfonic acid or its salt and compound C
Monoethanolamine/(hydroxy methane sulfonic acid or its salt+compound C) has scope preferably.
Claims (23)
1. a kind of manufacture method of hydraulic powder, it has in the presence of triethanolamine and hydroxy methane sulfonic acid or its salt
The process for crushing hydraulicity compound,
The hydraulicity compound is clinker or is clinker and mixing material, also, the mixing material is defined as individually
For do not have hardening, if but with water, alkali substance reaction and the combinations of substances of property hardened, rely on
Water forms hydrate and the material hardened by interaction,
Total amount of the triethanolamine and the hydroxy methane sulfonic acid or its salt is relative to the hydraulicity compound 100
Mass parts be 0.001 mass parts more than and 0.100 mass parts below,
The mass ratio of the triethanolamine and the hydroxy methane sulfonic acid or its salt, with triethanolamine/hydroxy methane sulfonic acid or its
Salt is represented, is more than 5/95 and less than 55/45.
2. the manufacture method of hydraulic powder as claimed in claim 1, wherein, the triethanolamine and the hydroxy methane sulphur
The mass ratio of acid or its salt, is represented with triethanolamine/hydroxy methane sulfonic acid or its salt, is more than 15/85 and less than 55/45.
3. the manufacture method of hydraulic powder as claimed in claim 1 or 2, wherein, the amount of the triethanolamine is relative
In the mass parts of hydraulicity compound 100 for more than 0.0005 mass parts and below 0.040 mass parts.
4. the manufacture method of hydraulic powder as claimed in claim 1 or 2, wherein, the hydroxy methane sulfonic acid or its salt
Amount is more than 0.0005 mass parts and below 0.060 mass parts relative to the mass parts of hydraulicity compound 100.
5. the manufacture method of hydraulic powder as claimed in claim 1 or 2, wherein, the hydraulicity compound contains：It is ripe
Material and more than a kind of the mixing material in blast-furnace slag, float ash and silica flour,
The content of the clinker is more than 20 mass % and below 92 mass %, the mixing material in the hydraulicity compound
The content of material is more than 8 mass % and below 80 mass % in the hydraulicity compound.
6. the manufacture method of hydraulic powder as claimed in claim 5, wherein, total content of the clinker and mixing material
It is more than 70 mass % and below 100 mass % in the hydraulicity compound.
7. the manufacture method of hydraulic powder as claimed in claim 5, wherein, the hydraulicity compound contains clinker and institute
Mixing material is stated, and hydraulicity compound crush until being 0.8m as BET specific surface area2/ more than g and 3.0m2/ g with
Under powder.
8. the manufacture method of hydraulic powder as claimed in claim 1 or 2, wherein, it is ball to crush used reducing mechanism
Grinding machine, and the material of crushing ball is more than a kind in stainless steel, aluminum oxide, zirconium oxide, titanium dioxide, tungsten carbide.
9. the manufacture method of hydraulic powder as claimed in claim 1 or 2, wherein, make to be selected from glycerine, monosaccharide or disaccharides
More than a kind of compound C in class, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its salt, with the triethanolamine and described
Hydroxy methane sulfonic acid or its salt exist simultaneously, so as to crush hydraulicity compound.
10. the manufacture method of hydraulic powder as claimed in claim 9, wherein, the triethanolamine and the hydroxy methane
Total mass ratio of sulfonic acid or its salt and the compound C, with triethanolamine/(hydroxy methane sulfonic acid or its salt+compound C)
Represent, be more than 5/95 and less than 55/45.
11. the manufacture method of hydraulic powder as claimed in claim 9, wherein, the hydroxy methane sulfonic acid or its salt and institute
Compound C mass ratio is stated, is represented with hydroxy methane sulfonic acid or its salt/compound C, is more than 5/95 and less than 95/5.
12. the manufacture method of hydraulic powder as claimed in claim 9, wherein, the amount of the compound C is relative to institute
The mass parts of hydraulicity compound 100 are stated for more than 0.0005 mass parts and below 0.040 mass parts.
13. a kind of crushing compositions of additives of hydraulicity compound, its contain triethanolamine and hydroxy methane sulfonic acid or its
Salt, also, the mass ratio of triethanolamine and hydroxy methane sulfonic acid or its salt represents with triethanolamine/hydroxy methane sulfonic acid or its salt
For more than 5/95 and less than 55/45, total amount of the triethanolamine and the hydroxy methane sulfonic acid or its salt relative to
The mass parts of hydraulicity compound 100 be 0.001 mass parts more than and 0.100 mass parts below,
The hydraulicity compound is clinker or is clinker and mixing material, also, the mixing material is defined as individually
For do not have hardening, if but with water, alkali substance reaction and the combinations of substances of property hardened, rely on
Water forms hydrate and the material hardened by interaction.
14. the crushing compositions of additives of hydraulicity compound according to claim 13, wherein, the triethanolamine
With the hydroxy methane sulfonic acid or the mass ratio of its salt, represented with triethanolamine/hydroxy methane sulfonic acid or its salt, be 15/85 with
It is upper and less than 55/45.
15. the crushing compositions of additives of hydraulicity compound as claimed in claim 13, it contains selected from glycerine, monose
More than a kind of compound C in class or disaccharides, hydroxycarboxylic acid or its salt and condensed phosphoric acid or its salt.
16. the crushing compositions of additives of hydraulicity compound as claimed in claim 15, wherein, the triethanolamine,
With the hydroxy methane sulfonic acid or its salt and total mass ratio of the compound C, with triethanolamine/(hydroxy methane sulfonic acid
Or its salt+compound C) represent, it is more than 5/95 and less than 55/45.
17. the crushing compositions of additives of the hydraulicity compound as described in claim 15 or 16, wherein, the hydroxyl first
The mass ratio of alkyl sulfonic acid or its salt and the compound C, is represented with hydroxy methane sulfonic acid or its salt/compound C, is more than 5/95
And less than 95/5.
18. the crushing compositions of additives of the hydraulicity compound as any one of claim 13~16, its form
For fluid composition.
19. the crushing compositions of additives of the hydraulicity compound as any one of claim 13~16, it contains
Solvent, and the content of solvent is more than 20 mass % and below 95 mass %.
20. the crushing compositions of additives of the hydraulicity compound as any one of claim 13~16, wherein, water
The triethanolamine and the hydroxy methane sulfonic acid or its salt in the crushing compositions of additives of rigid compound it is total
Measure as more than 5 mass % and below 80 mass %.
21. the crushing compositions of additives of the hydraulicity compound any one of claim 14~20 is in the hydraulicity
Application in the crushing of compound, wherein, the hydraulicity compound is clinker or is clinker and mixing material, also, described
Mixing material be defined as individually for do not have hardening, if but with water, alkali substance reaction and harden
The combinations of substances of property, the then material for hydrate being formed by interaction by water and being hardened.
22. the application in the crushing of hydraulicity compound as claimed in claim 21, wherein, the hydraulicity compound contains
Have：Clinker and more than a kind of the mixing material in blast-furnace slag, float ash and silica flour, the content of the clinker is in the water
It is more than 20 mass % and below 92 mass % in rigid compound, the content of the mixing material is in the hydraulicity compound
In be more than 8 mass % and below 80 mass %.
23. the application in the crushing of hydraulicity compound as claimed in claim 22, wherein, the clinker and mixing material
Total content in the hydraulicity compound be more than 70 mass % and below 100 mass %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-201200 | 2013-09-27 | ||
| JP2013201200 | 2013-09-27 | ||
| PCT/JP2014/074627 WO2015045995A1 (en) | 2013-09-27 | 2014-09-18 | Method for manufacturing hydraulic powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105408275A CN105408275A (en) | 2016-03-16 |
| CN105408275B true CN105408275B (en) | 2017-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201480042498.6A Active CN105408275B (en) | 2013-09-27 | 2014-09-18 | The manufacture method of hydraulic powder |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5802815B2 (en) |
| CN (1) | CN105408275B (en) |
| BR (1) | BR112016004217A2 (en) |
| MX (1) | MX2016002965A (en) |
| WO (1) | WO2015045995A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018101140A1 (en) * | 2016-11-29 | 2018-06-07 | 花王株式会社 | Additive for hydraulic-setting composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346812A (en) * | 2001-08-14 | 2002-05-01 | 刘长林 | Grinding aid for cement |
| CN101184702A (en) * | 2005-06-02 | 2008-05-21 | 格雷斯公司 | Biomass-derived grinding aids |
| CN102099311A (en) * | 2008-07-18 | 2011-06-15 | 花王株式会社 | Method for producing hydraulic powder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61117142A (en) * | 1984-11-08 | 1986-06-04 | 藤沢薬品工業株式会社 | Cement composition |
| JP5798395B2 (en) * | 2010-07-16 | 2015-10-21 | 花王株式会社 | Method for producing hydraulic powder |
-
2014
- 2014-09-18 BR BR112016004217-4A patent/BR112016004217A2/en not_active IP Right Cessation
- 2014-09-18 WO PCT/JP2014/074627 patent/WO2015045995A1/en active Application Filing
- 2014-09-18 MX MX2016002965A patent/MX2016002965A/en unknown
- 2014-09-18 CN CN201480042498.6A patent/CN105408275B/en active Active
- 2014-09-18 JP JP2014189534A patent/JP5802815B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346812A (en) * | 2001-08-14 | 2002-05-01 | 刘长林 | Grinding aid for cement |
| CN101184702A (en) * | 2005-06-02 | 2008-05-21 | 格雷斯公司 | Biomass-derived grinding aids |
| CN102099311A (en) * | 2008-07-18 | 2011-06-15 | 花王株式会社 | Method for producing hydraulic powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015086130A (en) | 2015-05-07 |
| MX2016002965A (en) | 2016-11-07 |
| WO2015045995A1 (en) | 2015-04-02 |
| BR112016004217A2 (en) | 2020-10-27 |
| CN105408275A (en) | 2016-03-16 |
| JP5802815B2 (en) | 2015-11-04 |
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