CN101755064B - Ore-powder caking material for enhancing hot strength, pellet made with the same, and process for producing the same - Google Patents
Ore-powder caking material for enhancing hot strength, pellet made with the same, and process for producing the same Download PDFInfo
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- CN101755064B CN101755064B CN2008800251233A CN200880025123A CN101755064B CN 101755064 B CN101755064 B CN 101755064B CN 2008800251233 A CN2008800251233 A CN 2008800251233A CN 200880025123 A CN200880025123 A CN 200880025123A CN 101755064 B CN101755064 B CN 101755064B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0046—Making spongy iron or liquid steel, by direct processes making metallised agglomerates or iron oxide
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
Abstract
An ore-powder caking material which is for use in enhancing hot strength in pelletizing an ore powder. It is equal or superior in cold strength to conventional caking materials and is excellent in the impartation of hot strength. Also provided are a pellet made with the caking material and a process for producing the pellet. The ore-powder caking material for enhancing hot strength comprises either or both of cement and lime, slag, and a siliceous substance and has a chemical composition comprising CaO, Al2O3, and SiO2, wherein the contents of CaO, Al2O3, and SiO2 are 3-56%, 3-40%, and 30-86%, respectively, based on the sum of these. The caking material may be one in which the proportion of the either or both of cement and lime is 1-76 parts, that of the slag is 2-95 parts, and that of the siliceous substance is 2-95 parts. The caking material may be one which further includes gypsum. The pellet comprises an ore powder, the caking material, and water. The pellet may be one in which the amount of the caking material is 3-20 parts per 100 parts of the ore powder, and the water/(ore powder + the caking material) ratio is 0.03-0.3.
Description
Technical field
The hot strength that the present invention relates to the ore powder that uses in a kind of granulation of the ore powder in generations such as iron work, steelworks and non-ferrous metal refineries strengthens solidify material, the pellet that uses this material and manufacture method thereof.
Background technology
In the past, under the background of the iron ore powder of the dust that in effectively utilizing factories such as iron work, steelworks and non-ferrous metal refinery, produces etc. and the exhaustion of high-quality mineral wealth, ore powder was implemented granulation.
As everyone knows, as the prilling process of ore powder, have use burn till after drum type (drum) and the granulation of pan type (pan) tablets press burn till comminution granulation, to save energy omits firing process as purpose cold comminution granulation.
As the solidify material of the ore powder that in the comminution granulation of these ore powders, uses, the known solidify material that the solidify material that formed by common portland cement is arranged, form by unslaked lime and blast-furnace slag, the solidify material that forms by calcium aluminate based compound and micro mist inorganic materials, the solidify material (with reference to non-patent literature 1, non-patent literature 2, patent documentation 1 and patent documentation 2) that forms by common portland cement and calcium aluminate.
But when using these solidify material, there are the following problems: hot strength is compared less with agglomerate, drops into behind the blast furnace that to produce air permeability bad owing to fine-powdered, so input amount limits to some extent.
The hot strength here is meant, for example will use the pellet of the hot strength enhancing solidify material of ore powder and this ore powder to put into after the blast furnace, 600～1000 ℃ of compressive strengths after burning till, use the hot strength of the solidify material of common portland cement to be about 3～5N/mm at present
2
On the other hand, cold strength is meant after field curing, be about to drop into the compressive strength before the blast furnace, is about 3～10N/mm usually
2Be necessary.
Non-patent literature 1: day wild numerous, Ah portion is fortunately great, one one-tenths at mountain pass, Song Gang are abundant directly, Tian HeZhi is grown directly from seeds, kept in Gao Yezheng city, phase field, the exploitation of the cold comminution granulation of cement, iron and steel, the 77th year (1991) No. 6,45～52 pages
Non-patent literature 2:Masanori Nakano, Masaaki Naito, Kenichi Higuchi and KojiMorimoto, non-spherical carbon composite cohesion piece: laboratory scale manufacturing and quality evalution, the ISIJ world, 44 volumes, 12 phases, 2079～2085 pages of (2004) (Non-spherical Carbon Composite Agglomerates:Lab-scale Manufacture and Quality Assessment, ISIJ International, Vol.44, No.12, pp.2079～2085 (2004))
Patent documentation 1: Japanese kokai publication hei 05-171303 communique.
Patent documentation 2: the special fair 05-073707 communique of Japan.
Summary of the invention
The hot strength that the purpose of this invention is to provide a kind of ore powder strengthens solidify material, and its cold strength is that the solidify material of ore powder in the past is above on an equal basis and hot strength is excellent more, and pellet and the manufacture method thereof of using this material.
The present invention is: a kind of hot strength of ore powder strengthens solidify material, and any one of mixed cement or lime or two kinds, slag and silicic acid metallic substance obtain, at CaO, Al
2O
3And SiO
2Total in, chemical constitution is: CaO is 3～56%, Al
2O
3Be 3～40%, SiO
2Be 31～86%.In this solidify material, the blending ratio of any one of cement or lime or two kinds, slag and silicic acid metallic substance is: any one of cement or lime or two kinds are 1～76 part, 2～76 parts in slag, 2～95 parts of silicic acid metallic substance.In this solidify material, the SiO of silicic acid metallic substance
2Composition is more than 45%.This solidify material also comprises gypsum.In this solidify material, in 100 parts solidify material, gypsum is less than 5 parts.This solidify material also contains water reducer.In this solidify material, with respect to this solidify material of 100 parts, water reducer is 0.5～8 part.In this solidify material, water reducer contains R
1O (A
10)
mR
2Represented alkene ether or Z[O (A
20)
nR
3]
aThe represented polyalkenylethers and the multipolymer of maleic anhydride; Wherein, A
10Be the mixture more than a kind or 2 kinds of 2～3 alkene oxygen base for carbonatoms, can add or add with block-wise in the time of more than 2 kinds with random shape; R
1It for carbonatoms 2～5 thiazolinyl; R
2It for carbonatoms 1～4 alkyl; M is the average interpolation mole number of alkene oxygen base, is 20～150; Z is the residue that contains the compound of 2～8 hydroxyls; A
20Be the mixture more than a kind or 2 kinds of 2～3 alkene oxygen base for carbonatoms, can add or add with block-wise in the time of more than 2 kinds with random shape; R
3It for carbonatoms 2～5 thiazolinyl; N is the average interpolation mole number of alkene oxygen base, is the number more than 0 or 1; A is 2～8.In addition, the present invention is a kind of pellet, contains ore powder, this solidify material and water.In this pellet, for 100 parts ore powder, this solidify material is 3～20 parts.In this pellet, water/(ore powder+this solidify material) is than being 0.03～0.3.In addition, the present invention is the manufacture method of this pellet.
According to the present invention, can provide a kind of hot strength of ore powder to strengthen solidify material, its cold strength is that the solidify material of ore powder in the past is above on an equal basis and hot strength is excellent more, and pellet and the manufacture method thereof of using this material is provided.
Description of drawings
Fig. 1 is that the expression water reducer is for the room temperature strength and the figure of the influence of cold strength (hot strength) gradually.
Fig. 2 is the figure (add the occasion of water reducer) of expression gypsum for room temperature strength and the gradually influence of cold strength (hot strength).
Embodiment
Below describe the present invention in detail.
In addition, in the present invention, if part or % do not have special stipulation then represent quality criteria.
The hot strength that the present invention relates to a kind of mixed cement, slag and silicic acid metallic substance ore powder that form, that have specific chemical constitution strengthens solidify material.
So-called ore powder is meant among the present invention, for example, with gold mine, silver ore, copper mine, lead ore, bismuth mineral, tin ore, zinc ore, iron ore, pyrites, chromite, manganese ore, tungsten ore, molybdenum ore, nickel minerals and cobalt ore etc. is the dust in generation source, can use a kind of or two or more in the middle of these.
There is no particular limitation for the cement that uses among the present invention, and common cement just can use.Particularly, common, various portland cements such as strong, super early strong, middle heat and low-heat etc. early be can enumerate, in these portland cements, the filler cement, waste utilization type cement, so-called eco-cement of limestone micropowder etc. etc. sneaked into; A kind of can the use separately or two or more and usefulness in these cement.
The lime that uses among the present invention is meant, unslaked lime that chemical formula CaO is represented or chemical formula Ca (OH)
2Represented slaked lime.
There is no particular limitation for unslaked lime, and usually, calcium oxide (CaO) is that the mechanicals more than 90% can use, and in addition, there is no particular limitation for slaked lime, and calcium oxide (CaO) is that the mechanicals more than 65% can use.They also can and be used.
The granularity of lime with Brian (Blaine) specific surface area value (following note is made the Brian value) expression, is preferably 2000cm
2More than/the g, 3000cm more preferably
2More than/the g.Beyond this scope, the cold strength of solidify material, hot strength have the danger of reduction.
As the slag that uses among the present invention, can enumerate: system steel slags such as converter slag that produces in blast furnace slag that produces as by product when utilizing blast furnace to make the pig iron or the gradually cold slag of blast furnace, the system steel operation or electric furnace slag, can use a kind of or two or more in them.From economy or must preferably use blast furnace slag easily to the aspect.
Scoriaceous granularity is represented with the Brian value, is preferably 2000cm
2More than/the g, 3000cm more preferably
2More than/the g.Beyond this scope, the cold strength of solidify material, hot strength have the danger of reduction.
Be meant as the silicic acid metallic substance of using among the present invention, as the SiO of chemical ingredients
2The content of composition is at the material more than 45%, for example, silicon ash, flying dust, cinder (coal ash), volcanic ash, diatomite, silicate carclazyte (Gui acid carclazyte), fused silica, white sand pearl (シ ラ ス パ Le one Application), quartz sand and rice hull ash (rice husk ash) etc. can be used a kind of or two or more in them.Wherein, also from the economy aspect, preferably use flying dust.
The particle shape of silicic acid metallic substance, the easy degree aspect that the neck during from the fillibility of particle and sintering reaction is grown up is preferably spherical.
In addition, the preferred silicic acid metallic substance that does not contain the sodium, potassium and the phosphorus composition that when blast furnace operation, become obstacle as far as possible of using.
The granularity of silicic acid metallic substance is represented with the Brian value, is preferably 2000cm
2More than/the g, 3000cm more preferably
2More than/the g.Beyond this scope, the cold strength of solidify material, hot strength have the danger of reduction.
Though the blending ratio of any one of cement or lime or two kinds, slag and silicic acid metallic substance has no particular limits, and is preferably: any one of cement or lime or two kinds 1～76 part, 2～95 parts in slag, 2～95 parts of silicic acid metallic substance.Under the situation of using cement, more preferably cement is 1～76 part, 2～76 parts in slag, 2～95 parts of silicic acid metallic substance; 3～75 parts of preferred especially cement, 4～74 parts in slag, 4～85 parts of silicic acid metallic substance.Under the situation of using lime, more preferably lime is 1～50 part, 2～95 parts in slag, 3～95 parts of silicic acid metallic substance; 2～48 parts in preferred especially lime, 2～93 parts in slag, 5～93 parts of silicic acid metallic substance.Beyond this scope, existence can not fully obtain the cold strength of solidify material, the danger of hot strength.
In the present invention, be purpose to improve cold strength, any one or two kinds, slag and the silicic acid metallic substance of cement or lime are mixed and the hot strength that obtains ore powder strengthens solidify material, at CaO, Al
2O
3And SiO
2Total in, chemical constitution is: CaO is 3～56%, Al
2O
3Be 3～40%, SiO
2Be 30～86%.In the hot strength enhancing solidify material (following note is made this solidify material) of ore powder, can contain gypsum.
Herein, as gypsum, can enumerate: dihydrate gypsum, semi-hydrated gypsum, II type dehydrated gyp-or III type dehydrated gyp-.Wherein, be preferably II type dehydrated gyp-, III type dehydrated gyp-.
The amount of gypsum is preferably less than 5 parts, is more preferably less than 3 parts.If the amount of gypsum surpasses this scope, just have the danger that hot strength descends.
The granularity of gypsum is represented with the Brian value, is preferably 2000cm
2More than/the g, 3000cm more preferably
2More than/the g.Beyond this scope, the cold strength of solidify material, hot strength have the danger of reduction.
In the present invention, in order further to improve hot strength, it is preferred further using water reducer.Kind for water reducer, can enumerate: the formalin condenses of alkylallyl sulfonate, naphthalenesulfonate, melamine sulfonate, polycarbonate-based macromolecular compound etc., one or more kinds of water reducers wherein be can use, liquid state or powder attitude also can be used.Especially preferred water reducer as described below wherein, this water reducer comprises R
1O (A
10)
mR
2Represented alkene ether or Z[O (A
20)
nR
3]
aThe represented polyalkenylethers and the multipolymer of maleic anhydride; Wherein, A
10Be the mixture more than a kind or 2 kinds of 2～3 alkene oxygen base for carbonatoms, can add or add with block-wise in the time of more than 2 kinds with random shape; R
1It for carbonatoms 2～5 thiazolinyl; R
2It for carbonatoms 1～4 alkyl; M is the average interpolation mole number of alkene oxygen base, is 20～150; Z is the residue that contains the compound of 2～8 hydroxyls; A
20Be the mixture more than a kind or 2 kinds of 2～3 alkene oxygen base for carbonatoms, can add or add with block-wise in the time of more than 2 kinds with random shape; R
3It for carbonatoms 2～5 thiazolinyl; N is the average interpolation mole number of alkene oxygen base, is the number more than 0 or 1; A is 2～8.
For 100 parts solidify material, the usage quantity of water reducer is preferably 0.5～8 part, more preferably 1～6 part.Because if less than 0.5 part, then there is not effect, if surpass 8 parts, then hot strength no longer rises, this is uneconomic, so be not preferred.
In the present invention, also can use cement with as the mixed cement of scoriaceous blast furnace cement, perhaps use cement with as the silica cement of silicic acid metallic substance, the mixed cement of fly ash cement.
Chemical constitution in this solidify material is at CaO, Al
2O
3And SiO
2Total in, CaO is 3～56%, Al
2O
3Be 3～40%, SiO
2 are30～86%; Preferably, CaO is 7～45%, Al
2O
3Be 5～35%, SiO
2Be 32～76%.Beyond this scope, existence can not fully obtain the danger of the hot strength of solidify material.
Do not limit for the method for mixing these materials useds is special, can before granulation, be pre-mixed, perhaps in granulation process, mix the material that each uses.
The granularity of this solidify material is represented with the Brian value, is preferably 2000cm
2More than/the g, 4000cm more preferably
2More than/the g.Beyond this scope, the danger that this solidify material exists cold strength to reduce.
For 100 parts ore powder, the usage quantity of this solidify material is preferably 3～20 parts, more preferably 5～15 parts.Less than this scope, then there is the bad danger of cold strength and hot strength, if more than this scope, since uneconomical, so be not preferred.
Water/(ore powder+this solidify material) is preferably 0.03～0.3 part, more preferably 0.05～0.2 part than there is no particular limitation.Less than this scope, then there is the bad danger of cold strength, the bad danger of reduction reaction behind the also existence input blast furnace.In addition, if surpass this scope, there is following danger: burn till the back owing to thermal contraction produces cracking and hot strength reduction.
Use in the manufacturing of pellet of this solidify material,, can add coke powder in order to improve the reductibility that drops into the pellet behind the blast furnace.
In addition, in the scope of not damaging purpose of the present invention, can use in water reducer, high-performance water reducing agent, AE water reducer, liquid agent, tackifier, economization agent and the conditioning agent that condenses a kind of or two or more.
Use the manufacture method of the pellet of this solidify material to have no particular limits, except the tablets press granulation of using drum type (drum) and pan type (pan), for example can enumerate: extrusion forming method, wet type extrusion forming method and extrusion moulding etc.
In addition, there is no particular limitation in the maintenance process of the pellet of manufacturing, except the normal temperature and pressure maintenance, for example can enumerate: autoclave curing, vapor cure, wet air maintenance or heating curing etc.
Embodiment
Below, based on embodiment, further describe the present invention.The present invention is not subjected to the restriction of these embodiment.
Experimental example 1
Cement shown in the mixture table 1, slag and silicic acid metallic substance, preparation contains the CaO shown in the table 1, Al
2O
3And SiO
2The solidify material of chemical constitution.
For 100 parts ore powder, 13 parts of the solidify material that blended prepares.For adding up to 100 parts the ore powder and the solidify material of preparation, mix 15 parts water, prepare the thing that mixes.
The thing that mixes of 50g preparation is packed into
In the metal molding die of 40mm, utilize society of Shimadzu Seisakusho Ltd. system, SSP-10A type, FT-IR pressing machine, apply the forming pressure of 7.8MPa, kept 30 seconds, the demoulding obtains then
The pellet of 40 * 16mm.
Utilize the pellet of normal temperature and pressure method of curing maintenance preparation, measure the cold strength and the hot strength of pellet.The result is recorded in the table 1 together.
The material that uses
Cement a: electrochemical industry society system, trade(brand)name " normal portland cement ", Brian value 3150cm
2/ g, proportion 3.13, CaO 72%, Al
2O
36%, SiO
222%.
Slag: blast-furnace slag, blast furnace cement society of Nippon Steel system, trade(brand)name " Ai Simengtesipai (EsmentSuper)-60 ", Brian value 6000cm
2/ g, proportion 2.91, CaO 49%, Al
2O
316%, SiO
235%.
Silicic acid metallic substance A: flying dust, the coal heat power station produces, JIS II series products, Brian value 3700cm
2/ g, proportion 2.35, CaO 6%, Al
2O
327%, SiO
267%.
Silicic acid metallic substance B: flying dust, the coal heat power station produces, JIS II series products, Brian value 3700cm
2/ g, proportion 2.35, CaO 0%, Al
2O
332%, SiO
268%.
Silicic acid metallic substance C: flying dust, the coal heat power station produces, JIS II series products, Brian value 3700cm
2/ g, proportion 2.37, CaO 0%, Al
2O
346%, SiO
254%.
Silicic acid metallic substance D: fused silica, electrochemical industry society system, trade(brand)name " is worn card (DENKA) fused silica ", BET specific surface area value 11.3m
2/ g, proportion 2.26, CaO 0%, Al
2O
30%, SiO
2100%.
Silicic acid metallic substance E: sand powder (true sand powder), Izumi Industries Ltd.'s system, Brian value 10400cm
2/ g, proportion 3.63, CaO 3%, Al
2O
334%, SiO
263%.
Silicic acid metallic substance F: γ-2CaOSiO
2, the lime carbonate of reagent grade and the silicon-dioxide of reagent grade are with CaO/SiO
2Mol ratio is 2.0 to mix, and burns till synthetic obtaining in electric furnace under temperature is 1500 ℃ condition.After the burned material that obtains cooled off, making the Brian value was 6000cm
2/ g, proportion 3.01, CaO 63%, Al
2O
32%, SiO
235%.
Ore powder: iron ore powder, rhombohedral iron ore, proportion 4.95 sieves less than 3mm.
Water: tap water.
Maintenance process
The normal temperature and pressure maintenance: behind the preparation pellet, seal with string rubber then in the plastics bag of packing into, under 20 ℃ atmospheric pressure environment, maintenance 14 days.
Measuring method
Cold strength: with pellet normal temperature and pressure maintenance under 20 ℃ room temperature environment of preparation, the mensuration material age is 14 days a compressive strength.
Hot strength: with pellet normal temperature and pressure maintenance under 20 ℃ room temperature environment of preparation, material age is burnt till in the time of 14 days under the following conditions: under nitrogen atmosphere, be warming up to 860 ℃ of top temperatures with 10 ℃/minute heat-up rates.After reaching top temperature, take out outside the stove, measure compressive strength.
Table 1
Cement, slag and silicic acid metallic substance are in part
As can be seen from Table 1, the hot strength of ore powder of the present invention strengthens solidify material (this solidify material), and the raising of hot strength is remarkable.
That is, this solidify material by suitably mixed cement, slag and silicic acid metallic substance, demonstrates the cold strength identical or higher with embodiment, and has excellent hot strength.
Use chemical constitution within the scope of the present invention (at CaO, Al
2O
3And SiO
2Total in, CaO is 3～56%, Al
2O
3Be 3～40%, SiO
2Be 30～86%) pellet of solidify material, cold strength and hot strength all very excellent (experiment 1-2～1-6,1-9～1-13,1-15～1-20,1-22,1-23).If CaO is less than 3%, hot strength height and cold strength extremely low (experiment 1-1), if CaO surpasses 56%, cold strength height and hot strength deficiency (experiment 1-7) are if Al
2O
3Less than 3%, hot strength height and cold strength low (experiment 1-8) are if Al
2O
3Surpass 40%, cold strength and hot strength all low (experiment 1-14) are if SiO
2Less than 30%, if cold strength height and hot strength deficiency are SiO
2Surpass 86%, cold strength and hot strength all low (experiment 1-21), therefore, the chemical constitution of solidify material is preferably above-mentioned scope.
Experimental example 2
Except the cement shown in the mixture table 2, slag and silicic acid metallic substance, other identical with experimental example 1.The result is recorded in the table 2 together.
Table 2
Cement, slag and silicic acid metallic substance are in part
From the result of table 2 as can be seen, this solidify material, excellence aspect the raising of hot strength.
That is, this solidify material by suitably mixed cement, slag and silicic acid metallic substance, demonstrates the cold strength identical or higher with comparative example, and has excellent hot strength.
Experimental example 3
Except the cement shown in the mixture table 3, slag and silicic acid metallic substance, other identical with experimental example 1.The result is recorded in the table 3 together.
The material that uses
Cement b: in hot portland cement, electrochemical industry society system, trade(brand)name " is worn hot portland cement in the card (DENKA) ", Brian value 3050cm
2/ g, proportion 3.20, CaO 70%, Al
2O
34%, SiO
226%.
Cement c: low-heat portland cement, Pacific Ocean cement society system, trade(brand)name " low-heat portland cement ", Brian value 3470cm
2/ g, proportion 3.21, CaO 69%, Al
2O
33%, SiO
228%.
Blast furnace cement: electrochemical industry society system, trade(brand)name " is worn card (DENKA) blast furnace cement ", Brian value 3970cm
2/ g, proportion 3.05, CaO 63%, Al
2O
39%, SiO
228%.
Fly ash cement: electrochemical industry society system, trade(brand)name " is worn card (DENKA) fly ash cement (category-B) ", Brian value 3500cm
2/ g, proportion 2.96, CaO 71%, Al
2O
35%, SiO
224%.
Table 3
Cement, slag and silicic acid metallic substance are in part, and * 1 is the mixture of 75 parts of blast furnace cements and 25 parts of silicic acid metallic substance, and * 2 is 10 parts of fly ash cements and 90 parts of scoriaceous mixtures
From the result of table 3 as can be seen, hot strength of the present invention strengthens solidify material, and is irrelevant with the kind of cement, excellence aspect the raising of hot strength.In addition, by suitably mixing blast furnace cement and silicic acid metallic substance, fly ash cement and slag, can realize effect of the present invention.
Experimental example 4
Except the cement shown in the mixture table 4, slag, silicic acid metallic substance and gypsum, other identical with experimental example 1.The result is recorded in the table 4 together.
The material that uses
Dehydrated gyp-: Thailand produces, the natural dehydrated gyp-of II type, Brian value 8100cm
2/ g, proportion 2.94, CaO 95%, Al
2O
32%, SiO
23%.
Table 4
Cement, slag, silicic acid metallic substance and gypsum are in part
From the result of table 4 as can be seen, this solidify material owing to contain the gypsum of appropriate amount, can make cold strength improve.
That is, hot strength of the present invention strengthens solidify material, and by suitably mixed cement, slag, silicic acid metallic substance and gypsum, compare with comparative example and can make cold strength improve, and the expression power excellence of hot strength.
Experimental example 5
Use 32 parts of cement a, 44 parts in slag and silicic acid metallic substance A24 part to prepare solidify material.With respect to 100 parts iron ore powder, mix according to the amount shown in the table 1.In addition, other is identical with experimental example 1.The result is recorded in the table 5 together.
Table 5
| The experiment sequence number | Solidify material | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 5-1 5-2 5-3 5-4 5-5 5-6 | 0 3 5 10 15 20 | 4 13 14 17 26 31 | 3 10 11 13 19 23 | Comparative example EXAMPLE Example EXAMPLE Example embodiment |
Solidify material is the umber of the amount of the ore powder with respect to 100 parts
From the result of table 5 as can be seen, this solidify material, owing in ore powder, mixed suitable amount, thus demonstrated the cold strength identical or higher with comparative example, and, the expression power excellence of hot strength.
Experimental example 6
Use 32 parts of cement a, 44 parts in slag and silicic acid metallic substance A24 part to prepare solidify material.For 100 parts iron ore powder, 13 parts of the solidify material that is mixed with.For adding up to 100 parts the ore powder and the solidify material of preparation, the water shown in the mixture table 6.In addition, other is identical with experimental example 1.The result is recorded in the table 6 together.
Table 6
| The experiment sequence number | Water | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 6-1 6-2 6-3 6-4 6-5 | 0.03 0.05 0.1 0.2 0.3 | 29 25 21 18 14 | 24 21 18 13 11 | EXAMPLE Example EXAMPLE Example embodiment |
The amount of water is the quality % with respect to the total of ore powder and this solidify material
From the result of table 6 as can be seen, this solidify material is because water/(ore powder+this solidify material) is than in suitable scope, so can make hot strength improve.
That is, by mixed cement, slag, silicic acid metallic substance, and have suitable water/(ore powder+this solidify material) ratio, hot strength of the present invention strengthens solidify material, demonstrates the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Experimental example 7
Use 32 parts of cement a, 44 parts in slag and silicic acid metallic substance A24 part to prepare solidify material.For 100 parts iron ore powder, mix the solidify material of 13 parts preparation.For adding up to 100 parts the iron ore powder and the solidify material of preparation, mix 15 parts of water, the preparation pellet.
According to the maintenance process after the granulation of the preparation pellet shown in the table 7, carry out maintenance.In addition, other is identical with experimental example 1.The result is recorded in the table 7 together.
Maintenance process
Vapor cure: behind the preparation pellet, at first placed 2 hours, afterwards, carry out vapor cure: heat up with 15 ℃/minute speed, kept 3 hours down for 70 ℃ in top temperature with following condition.The 2nd day, from the maintenance groove, take out, maintenance is 13 days under 20 ℃ environment.
Autoclave curing: behind the preparation pellet, putting into gas pressure vessel, is that 10 normal atmosphere, temperature are maintenance 6 hours under 170 ℃ the condition in vapour pressure.After the maintenance, maintenance to 14 day under 20 ℃ room temperature environment.
Wet air maintenance: behind the preparation pellet, be maintenance 14 days under 100%, 20 ℃ the room temperature environment in humidity.
Heating curing: behind the preparation pellet, maintenance 1 day under 20 ℃ room temperature environment under sealed state.After the maintenance 1 day, maintenance is 13 days in 40 ℃ drying machine under 20 ℃ the room temperature environment.
Table 7
| The experiment sequence number | Maintenance process | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 1-5 7-1 7-2 7-3 7-4 | Normal temperature and pressure maintenance vapor cure autoclave curing wet air maintenance heating curing | 20 23 26 21 22 | 16 19 17 15 17 | EXAMPLE Example EXAMPLE Example embodiment |
From the result of table 7 as can be seen, this solidify material, irrelevant with maintenance process, have excellent hot strength.
Experimental example 8
1 part of mixed cement a50 part, 40 parts in slag, 10 parts of silicic acid metallic substance A and dehydrated gyp-, change ground in solid substance and add water reducer: 0,0.6,1.2,3.0 mass parts (respectively do for oneself: 0,1.0,2.0,5.0 mass parts) by the adding rate with aqueous solution.In addition, other is identical with experimental example 4.The strength detection result is as shown in table 8.In addition, water reducer for the influence of cold strength and hot strength as shown in Figure 1.
The material that uses
Water reducer: commercially available product, the multipolymer of polyalkenyl ether and maleic anhydride, 60% the aqueous solution.
Table 8
| The experiment sequence number | Water reducer | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 8-1 8-2 8-3 8-4 | 0 1.0 2.0 5.0 | 14 18 16 25 | 5 7 8 11 | The EXAMPLE Example EXAMPLE Example |
The amount of water reducer is with respect to the umber with 100 parts of formed materials
From table 8 and Fig. 1 as can be seen, this solidify material, under the situation of adding water reducer, along with the increase of adding rate, cold strength and hot strength increase simultaneously.That is, hot strength of the present invention strengthens solidify material, and by suitable mixed cement, slag, silicic acid metallic substance, gypsum and water reducer, comparing cold strength can be improved with comparative example, and, the expression power excellence of hot strength.
Experimental example 9
50 parts of mixed cement a, 40 parts in slag, 10 parts of silicic acid metallic substance A and 1 part of water reducer (solid substance), the combined amount of dehydrated gyp-is respectively 0,1,2,3 part.In addition, other is identical with experimental example 8.The strength detection result is as shown in table 9.In addition, gypsum for the influence of cold strength and hot strength (adding the occasion of water reducer) as shown in Figure 2.
Table 9
| The experiment sequence number | Gypsum | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 9-1 9-2 9-3 9-4 | 0 1 2 3 | 17 18 16 17 | 6 7 8 7 | The EXAMPLE Example EXAMPLE Example |
The amount of gypsum is the umber with respect to 100 parts of solidify material
From table 9 and Fig. 2 as can be seen, in the occasion of adding water reducer, before 2 parts, hot strength increases in the combined amount of dehydrated gyp-, more than 3 parts after, then no longer include effect.
Experimental example 10
According to combined lime shown in the table 10, slag and silicic acid metallic substance, preparation contains the CaO shown in the table 10, Al
2O
3, SiO
2The solidify material of chemical constitution.In addition, other is identical with experimental example 1.The result is recorded in the table 10 together.
The material that uses
Lime a: the pure pharmaceutical worker's industry of unslaked lime and light society system, reagent grade, pulverizing product, Brian value 6000cm
2/ g, proportion 3.31, CaO 100%, Al
2O
30%, SiO
20%.
Table 10
Lime, slag and silicic acid metallic substance are in part
From the result of table 10 as can be seen, the hot strength raising aspect excellence of this solidify material.
That is, this solidify material by suitable combined lime, slag and silicic acid metallic substance, demonstrates the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Use chemical constitution within the scope of the present invention (at CaO, Al
2O
3And SiO
2Total in, CaO is 3～56%, Al
2O
3Be 3～40%, SiO
2Be 30～86%.) pellet of solidify material, cold strength and hot strength all very excellent (experiment 10-2～10-6,10-9～10-13,10-16～10-20,10-22,10-23).Relative therewith, if CaO less than 3%, hot strength height and cold strength extremely low (experiment 10-1), if CaO surpasses 56%, cold strength height and hot strength deficiency (experiment 10-7) are if Al
2O
3Less than 3% or surpass 40%, hot strength height and cold strength low (experiment 10-8, experiment 10-14) are if SiO
2Less than 30%, cold strength height and hot strength deficiency (experiment 10-15) are if SiO
2Surpass 86%, hot strength height and cold strength extremely low (experiment 10-21), therefore, the chemical constitution of solidify material is preferably above-mentioned scope.
Experimental example 11
Except according to combined lime shown in the table 11, slag and the silicic acid metallic substance, other identical with experimental example 10.The result is recorded in the table 11 together.
Materials used
Lime b: the pure pharmaceutical worker's industry of slaked lime and light society system, reagent grade, pulverizing product, Brian value 6000cm
2/ g, proportion 2.08, CaO 100%, Al
2O
30%, SiO
20%.
Table 11
Lime, slag and silicic acid metallic substance are in part
From the result of table 11 as can be seen, the hot strength raising aspect excellence of this solidify material.
That is, this solidify material by suitable combined lime, slag and silicic acid metallic substance, demonstrates the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Experimental example 12
Except according to combined lime shown in the table 12, slag and the silicic acid metallic substance, other identical with experimental example 10.The result is recorded in the table 12 together.
Materials used
Table 12
Lime, slag and silicic acid metallic substance are in part
From the result of table 12 as can be seen, the hot strength raising aspect excellence of this solidify material.
That is, this solidify material by suitable combined lime, slag and silicic acid metallic substance, demonstrates the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Experimental example 13
Except according to combined lime shown in the table 13, slag and the silicic acid metallic substance, other identical with experimental example 10.The result is recorded in the table 13 together.
Table 13
Lime, slag and silicic acid metallic substance are in part
From the result of table 13 as can be seen, the hot strength raising aspect excellence of this solidify material.
That is, this solidify material by suitable combined lime, slag and silicic acid metallic substance, demonstrates the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Experimental example 14
Except according to combined lime shown in the table 14, slag, silicic acid metallic substance and the gypsum, other identical with experimental example 10.The result is recorded in the table 14 together.
Materials used
Dehydrated gyp-: Thailand produces, the natural dehydrated gyp-of II type, Brian value 8100cm
2/ g, proportion 2.94, CaO 95%, Al
2O
32%, SiO
23%.
Table 14
Lime, slag, silicic acid metallic substance and gypsum are in part
From the result of table 14 as can be seen, this solidify material owing to contain the gypsum of appropriate amount, can make cold strength improve.
That is, hot strength of the present invention strengthens solidify material, and by suitably combined lime, slag, silicic acid metallic substance and gypsum, compare with comparative example and can make cold strength improve, and the expression power excellence of hot strength.
Experimental example 15
Use 3 parts of lime a, 27 parts in slag and 70 parts of preparations of silicic acid metallic substance A solidify material.For 100 parts ore powder, mix according to the amount shown in the table 15.In addition, other is identical with experimental example 10.The result is recorded in the table 15 together.
Table 15
| The experiment sequence number | Solidify material | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 15-1 15-2 15-3 15-4 15-5 15-6 | 0 3 5 10 15 20 | 4 14 13 15 24 32 | 3 9 10 13 18 21 | Comparative example EXAMPLE Example EXAMPLE Example embodiment |
The amount of solidify material is the umber with respect to 100 parts of ore powders
From the result of table 15 as can be seen, this solidify material, owing in ore powder, mixed suitable amount, thus demonstrated the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Experimental example 16
Use 3 parts of lime a, 27 parts in slag and silicic acid metallic substance A70 part to prepare solidify material.For 100 parts ore powder, mix the solidify material of 13 parts preparation.For adding up to 100 parts the ore powder and the solidify material of preparation, the water shown in the mixture table 16.In addition, other is identical with experimental example 10.The result is recorded in the table 16 together.
Table 16
| The experiment sequence number | Water | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 16-1 16-2 16-3 16-4 16-5 | 0.03 0.05 0.1 0.2 0.3 | 25 21 17 14 13 | 21 18 15 13 9 | EXAMPLE Example EXAMPLE Example embodiment |
The amount of water is the per-cent with respect to the total of ore powder and this solidify material.
From the result of table 16 as can be seen, this solidify material is because water/(ore powder+this solidify material) is than in suitable scope, so can make hot strength improve.
Promptly, by combined lime, slag and silicic acid metallic substance, feasible ratio with suitable water/(ore powder+this solidify material), hot strength of the present invention strengthens solidify material, demonstrate the cold strength identical or higher with comparative example, and the expression power excellence of hot strength.
Experimental example 17
Use 3 parts of lime a, 27 parts in slag and 70 parts of preparations of silicic acid metallic substance A solidify material.For 100 parts ore powder, mix the solidify material of 13 parts preparation.For adding up to 100 parts the ore powder and the solidify material of preparation, mix 15 parts of water, the preparation pellet.
According to the maintenance process after the granulation of the preparation pellet shown in the table 17, carry out maintenance (vapor cure, autoclave curing, wet air maintenance, heat-cured various conditions are identical with embodiment 7).In addition, other is identical with experimental example 10.The result is recorded in the table 17 together.
Table 17
| The experiment sequence number | Maintenance process | Cold strength (N/mm 2) | Hot strength (N/mm 2) | Remarks |
| 10-4 17-1 17-2 17-3 17-4 | Normal temperature and pressure maintenance vapor cure autoclave curing wet air maintenance heating curing | 16 18 21 16 18 | 14 17 15 14 15 | EXAMPLE Example EXAMPLE Example embodiment |
From the result of table 17 as can be seen, this solidify material, irrelevant with maintenance process, have excellent hot strength.
Utilizability on the industry
The hot strength of ore powder of the present invention strengthens solidify material, not only have and the equal above cold strength of former solidify material, and can have good hot strength, can be applicable to the granulation of the dust that produces or collect in iron work, steelworks and non-ferrous metal refinery etc.
Claims (11)
1. the hot strength of an ore powder strengthens solidify material, it is characterized in that, any one of mixed cement or lime or two kinds, slag and silicic acid metallic substance obtain, at CaO, A1
2O
3And SiO
2Total in, chemical constitution is: CaO is 3～56%, A1
2O
3Be 3～40%, SiO
2Be 30～86%, and also contain water reducer in the described solidify material,
The blending ratio of any one of described cement or lime or two kinds, slag and silicic acid metallic substance is: when all being 100 parts, any one of cement or lime or two kinds are 1～76 part, and slag is 2～95 parts, and the silicic acid metallic substance is 2～95 parts,
And with respect to 100 parts aforementioned solidify material, aforementioned water reducer is 0.5～8 part.
2. the hot strength of ore powder according to claim 1 strengthens solidify material, it is characterized in that the SiO of aforementioned silicic acid metallic substance
2Composition is more than 45%.
3. the hot strength of ore powder according to claim 1 strengthens solidify material, it is characterized in that, also contains gypsum.
4. the hot strength of ore powder according to claim 3 strengthens solidify material, it is characterized in that in 100 parts aforementioned solidify material, aforementioned gypsum is less than 5 parts.
5. the hot strength of ore powder according to claim 1 strengthens solidify material, it is characterized in that described water reducer comprises R
1O (A
10)
mR
2Represented alkene ether or Z[O (A
20)
nR
3]
aRepresented polyalkenylethers, and the multipolymer of maleic anhydride;
Wherein, A
10Be the mixture more than a kind or 2 kinds of 2～3 alkene oxygen base for carbonatoms, add with block-wise in the time of more than 2 kinds or add with random shape; R
1It for carbonatoms 2～5 thiazolinyl; R
2It for carbonatoms 1～4 alkyl; M is the average interpolation mole number of alkene oxygen base, is 20～150;
Z is the residue that contains the compound of 2～8 hydroxyls; A
20Be the mixture more than a kind or 2 kinds of 2～3 alkene oxygen base for carbonatoms, add with block-wise in the time of more than 2 kinds or add with disorganized form; R
3It for carbonatoms 2～5 thiazolinyl; N is the average interpolation mole number of alkene oxygen base, is the number more than 0 or 1; A is 2～8.
6. a pellet is characterized in that, contains: the hot strength of any described ore powder strengthens solidify material and water in ore powder, the claim 1～claim 5.
7. pellet according to claim 6 is characterized in that, with respect to 100 parts ore powder, aforementioned solidify material is 3～20 parts.
8. pellet according to claim 6 is characterized in that, water/(ore powder+aforementioned solidify material) is than being 0.03～0.3.
9. the manufacture method of a pellet is characterized in that, the hot strength of any described ore powder in ore powder, the claim 1～claim 5 is strengthened solidify material and water mix the material that obtains and be shaped to pellet, carries out maintenance.
10. the manufacture method of pellet according to claim 9 is characterized in that, with respect to 100 parts ore powder, mixes 3～20 parts aforementioned solidify material.
11. the manufacture method of pellet according to claim 9 is characterized in that, water/(ore powder+aforementioned solidify material) is than being 0.03～0.3.
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| PCT/JP2008/063709 WO2009014255A1 (en) | 2007-07-25 | 2008-07-24 | Ore-powder caking material for enhancing hot strength, pellet made with the same, and process for producing the same |
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