CN104909771B - Aluminous cement combined corundum matter castable and preparation method thereof - Google Patents
Aluminous cement combined corundum matter castable and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of aluminous cement combined corundum matter castable and preparation method thereof, using aluminous cement as bonding agent, plate diamond spar and activated alumina are key component, using titanium dioxide/calcium carbonate/fine magnesium oxide micro-powder as compound additive, the aluminous cement combined corundum matter castable of high intensity is prepared.The present invention combines titanium dioxide acceleration of sintering, and magnesia is reacted to form the characteristic that spinelle and calcium carbonate are converted into highly active calcium oxide at high temperature with corundum so that the intensity of corundum pouring material is increased substantially.High intensity aluminous cement combined corundum matter castable prepared by the present invention has excellent performance, can be applied to the industries such as building materials, metallurgical and petrochemical industry, effectively improves the equipment lives such as cement kilneye, coal injection pipe, sensing inner lining of furnace and high-temp wearproof lining.
Description
Technical field
The present invention relates to technical field of refractory materials, and in particular to a kind of aluminous cement combined corundum matter castable and its
Preparation method.
Background technology
Unshape refractory refers to the mixture being made up of aggregate, fine powder, bonding agent and additive, is delivery with bulk cargo
State is directly used.Unshape refractory with castable as representative has short technological process, energy consumption and low cost, fits
With the advantage such as in extensive range.Proportion of the Chinese unshape refractory in 2012 in refractory material total output is broken through first
40%, but compared with industrially developed country, the proportion of Chinese unshape refractory is relatively low, and its target is reached in the year two thousand twenty
60%.
In recent years, as national economy constantly increases to the demand of high-quality ferrous materials particularly clean steel, fire proofed wood
The condition of work of material is more and more severe, and non-ferrous metal metallurgy new technology and equipment development, the environmental protection of cement industry kiln
It is required that the fast development with incinerator, all to the performance requirement more and more higher of refractory material, its development to refractory material
Propose new challenge.Corundum has the characteristics of fusing point is high, density big, chemical resistance of concrete ability is strong, thus with corundum be main thing
The corundum pouring material of phase has the advantages that high temperature resistant, intensity high, resistance to slag and stability at elevated temperature are good, just because of corundum
Matter castable has excellent performance, and it has obtained good application on ladle is built by laying bricks or stones.The application site of corundum pouring material
Mainly include：The joint filling of ladle back stall, brick cup and electric furnace top；The burner block of heating furnace, edge brick and water cooling tube；The stove of refining furnace
The converter nose of lid, induction furnace and soaking pit；Big-and-middle-sized uhp electric arc furnace lid trigonum and LF refining steel ladle cover etc..In addition, urging
Change on cracking unit and CFBB, corundum pouring material also serves as wear resistance lining and uses.
At present, the coupling system commonly used in corundum pouring material is mainly made up of Hydraulic binding agent and micro mist, wherein, aluminic acid
Calcium cement is the most frequently used Hydraulic binding agent, but cement consumption is higher, conventional cement combine castable have the porosity it is high,
The shortcomings of short texture, low intensity.Due to adding micro mist (mainly silicon powder and α-Al2O3Micro mist) after, the application property of castable
Can be greatly improved with performance, the especially change of intensity, therefore, it is each to refractory material after the performance of micro mist and its addition
The influence of class performance, is one of emphasis of refractory material worker concern in recent years.On the other hand, regulate and control to pour using additive
Reaction in-situ in material feeding is widely used for the design and preparation of high-performance castable so as to optimize the performance of refractory material,
Important channel as exploitation novel high-performance refractory material.
In the prior art, the Chinese patent literature of Application No. 201310035589.4 reports a kind of calcium carbonate micro mist
Aluminous cement combined corundum matter castable and preparation method thereof, the castable includes the aggregate of plate diamond spar matter and thin
Powder, Reactive alumina, aluminous cement, calcium carbonate fine powder and water reducer.But, the calcium aluminate water of the calcium carbonate micro mist
The intensity of mud combined corundum matter castable is relatively low.
The content of the invention
It is an object of the invention to provide a kind of aluminous cement combined corundum matter castable and preparation method thereof, the castable
With intensity higher, cost is relatively low.
To achieve the above object, the present invention provides a kind of preparation method of aluminous cement combined corundum matter castable, bag
Include following steps：By the plate diamond spar particle of 70-88 weight portions, the plate diamond spar fine powder of 0.1-10 weight portions, 5-10 weight portions
Reactive alumina, the aluminous cement of 0.5-8 weight portions, the silicon powder of 1 weight portion, the titanium dioxide of 0.1-10 weight portions
Titanium/calcium carbonate/magnesia composite micro-powder additive, water reducer and water mixing, vibration moulding after stirring, temperature be 20-50 DEG C,
Relative humidity is warming up to 100-150 DEG C and is incubated 12-36 hours to be conserved 20-30 hours under conditions of 80-100%, obtains aluminic acid
Calcium cement combined corundum matter castable.
Preferably, the plate diamond spar particle, plate diamond spar fine powder, Reactive alumina, aluminous cement, silicon powder
It is 100 with the summation of titanium dioxide/calcium carbonate/magnesia composite micro-powder additive and the weight ratio of the water reducer：0.05-
0.25。
Preferably, the plate diamond spar particle, plate diamond spar fine powder, Reactive alumina, aluminous cement, silicon are micro-
The weight ratio of powder, the summation of titanium dioxide/calcium carbonate/magnesia composite micro-powder additive and water reducer and water is 100：4-6.
Preferably, the grain composition of the plate diamond spar particle is：
6-3mm plate diamond spars particle is 24-28 weight portions；
3-1mm plate diamond spars particle is 6-9 weight portions；
1-0.5mm plate diamond spars particle is 18-21 weight portions；
0.6-0.2mm plate diamond spars particle is 6-10 weight portions；
0.2-0mm plate diamond spars particle is 16-20 weight portions.
Preferably, the granularity of the plate diamond spar fine powder is 320-330 mesh.
Preferably, Chun Du≤99.5% of the Reactive alumina, granularity is 1-10 μm.
Preferably, the Al of the aluminous cement2O3Content is 69.5-70.5wt%.
Preferably, Chun Du≤94% of the silicon powder, Li Du≤2.5 μm.
Preferably, the titanium dioxide/calcium carbonate/magnesia composite micro-powder additive is prepared as follows：Will weight
Amount is than being 30-50：40-60：The mixing of the titanium dioxide of 5-10, calcium carbonate and magnesia, is ground to Li Du≤10 μm, and d50≦3μ
M, obtains titanium oxide/calcium carbonate/magnesia composite micro-powder additive.
Accordingly, the present invention also provides a kind of aluminous cement combined corundum matter castable, is prepared by following raw material：70-
The plate diamond spar particle of 88 weight portions, the plate diamond spar fine powder of 0.1-10 weight portions, the Reactive alumina of 5-10 weight portions,
The aluminous cement of 0.5-8 weight portions, the silicon powder of 1 weight portion, the titanium dioxide/calcium carbonate/magnesia of 0.1-10 weight portions
Composite micro-powder additive, water reducer and water.
Beneficial effects of the present invention：The invention provides a kind of aluminous cement combined corundum matter castable and its preparation side
Method.Compared with prior art, the present invention uses titanium dioxide/calcium carbonate/magnesia composite micro-powder additive.Wherein, titanium dioxide
Titanium forms solid solution with aluminum oxide, produces the lattice defects such as ionic vacancies, while as nucleating agent, accelerating the shape of calcium hexaluminate
Into；Adding a small amount of titanium dioxide can improve the consistency and intensity of aluminum oxide, and produce influence to the growth of alumina grain, from
And improve the intensity of castable.Second, in corundum pouring material system, calcium carbonate by decomposing generation activity at high temperature
CaO, with alumina powder reaction generation calcium hexaluminate, further improves the performance of castable.3rd, magnesia is anti-at high temperature
In-suit spinel should be generated, is conducive to improving the intensity and corrosion resistance of castable.Therefore, the calcium aluminate water that the present invention is provided
The preparation method raw material sources that mud combined corundum matter is poured are extensive, low cost, beneficial to industrialized production, the aluminous cement knot of preparation
Closing corundum pouring material has intensity higher.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
With reference to embodiment, the invention will be further described：
The invention provides a kind of preparation method of aluminous cement combined corundum matter castable, comprise the following steps：Will
The plate diamond spar particle of 70-88 weight portions, the plate diamond spar fine powder of 0.1-10 weight portions, 5-10 weight portions activated alumina it is micro-
Powder, the aluminous cement of 0.5-8 weight portions, the silicon powder of 1 weight portion, the titanium dioxide/calcium carbonate/oxidation of 0.1-10 weight portions
Magnesium composite micro-powder additive, water reducer and water mixing, vibration moulding after stirring, temperature be 20-50 DEG C, relative humidity be 80-
Conserved 20-30 hours under conditions of 100%, be warming up to 100-150 DEG C and be incubated 12-36 hours, obtained aluminous cement and combine just
Beautiful matter castable.
In above-mentioned preparation process, the present invention is as bonding agent, plate diamond spar and activated alumina using aluminous cement
Key component, using titanium dioxide/calcium carbonate/fine magnesium oxide micro-powder as compound additive, prepares the calcium aluminate water of high intensity
Mud combined corundum matter castable.The present invention combines titanium dioxide acceleration of sintering, and magnesia reacts to form spinelle and carbon with corundum
Sour calcium is converted into the characteristic of highly active calcium oxide at high temperature so that the intensity of corundum pouring material is increased substantially.The present invention
Prepared high intensity aluminous cement combined corundum matter castable has excellent performance, it is adaptable to building materials, metallurgy and petrochemical industry
Etc. industry, the equipment lives such as cement kilneye, coal injection pipe, sensing inner lining of furnace and high-temp wearproof lining are effectively improved.
For aluminous cement combined corundum matter castable, its main reaction in-situ is generation calcium hexaluminate, therefore, this
The formation of invention regulation and control calcium hexaluminate and pattern optimize aluminous cement combined corundum matter castable.TiO2Formed with aluminum oxide
Solid solution, will produce the lattice defects such as ionic vacancies, and it as nucleating agent, can also further speed up the shape of calcium hexaluminate
Into.Add a small amount of TiO2The consistency and intensity of aluminium oxide ceramics can be improved, and influence is produced on the growth of alumina grain.
In corundum pouring material system, using nanometer or micro mist calcium carbonate, by the active CaO and aluminum oxide that decompose generation at high temperature
Micro mist reaction generation calcium hexaluminate, improves the performance of castable.It is also favourable that magnesia reacts generation In-suit spinel at high temperature
In the intensity and corrosion resistance that improve castable.
Preferably, the plate diamond spar particle is preferably 76-79 weight portions, more preferably 78-79 weight portions；Plate
Shape corundum fine powder is preferably 6-8 weight portions；Reactive alumina is preferably 7-9 weight portions；Aluminous cement is preferably 1-4 weights
Amount part；Titanium dioxide/calcium carbonate/magnesia composite micro-powder additive is preferably 2-6 weight portions.In preparation process, maintenance
Temperature is preferably 20-40 DEG C, more preferably 25 DEG C；The humidity of maintenance is preferably 90-100%, more preferably 100%；During maintenance
Between be preferably 22~28 hours, more preferably 24 hours；The temperature heated up after maintenance is preferably 110-140 DEG C, more preferably
110-130℃；Soaking time is preferably 15-30 hours, more preferably 18-25 hours.
Preferably, the plate diamond spar particle, plate diamond spar fine powder, Reactive alumina, aluminous cement,
The summation of silicon powder and titanium dioxide/calcium carbonate/magnesia composite micro-powder additive is preferably with the weight ratio of the water reducer
100：0.05-0.25, more preferably 100：0.1-0.2.That is, water reducer is preferably plate diamond spar particle, plate diamond spar fine powder, work
Property alumina powder, aluminous cement, silicon powder and titanium dioxide/calcium carbonate/magnesia composite micro-powder additive quality summation
0.05-0.25wt%, more preferably 0.1-0.2wt%.
The plate diamond spar particle, plate diamond spar fine powder, Reactive alumina, aluminous cement, silicon powder, titanium dioxide
The summation of titanium/calcium carbonate/magnesia composite micro-powder additive and water reducer and the weight ratio preferably 100 of water：4-6, more preferably
It is 100：4.3-6.
The grain composition of the plate diamond spar particle is preferably：
6-3mm plate diamond spars particle is 24-28 weight portions；
3-1mm plate diamond spars particle is 6-9 weight portions；
1-0.5mm plate diamond spars particle is 18-21 weight portions；
0.6-0.2mm plate diamond spars particle is 6-10 weight portions；
0.2-0mm plate diamond spars particle is 16-20 weight portions.
It is furthermore preferred that the grain composition of the plate diamond spar particle is：
6-3mm plate diamond spars particle is 25-28 weight portions；
3-1mm plate diamond spars particle is 6-8 weight portions；
1-0.5mm plate diamond spars particle is 19-21 weight portions；
0.6-0.2mm plate diamond spars particle is 6-8 weight portions；
0.2-0mm plate diamond spars particle is 18 weight portions.
The granularity of the plate diamond spar fine powder is preferably 320-330 mesh, more preferably 325 mesh.The activated alumina is micro-
Chun Du≤99.5% of powder, granularity is preferably 1-10 μm, more preferably 3-8 μm.The aluminous cement is pure calcium aluminate cement,
Al2O3Content is preferably 69.5-70.5wt%.Chun Du≤94% of the silicon powder, Li Du≤2.5 μm.
Water reducer includes two major classes：One class is the electrolytes water reducer that Quadrafos is representative, and another kind of is various have
Machine salt is the surfactant of representative, belongs to high efficiency water reducing agent.It is more excellent present invention preferably employs polycarboxylic type high performance water reducer
It is the high efficiency water reducing agent of FS60 to elect the trade mark that BASF Aktiengesellschaft produced as.
Titanium dioxide/the calcium carbonate/magnesia composite micro-powder additive is preferably prepared as follows：By weight ratio
It is 30-50：40-60：The mixing of the titanium dioxide of 5-10, calcium carbonate and magnesia, is ground to Li Du≤10 μm, and d50≤ 3 μm, obtain
To titanium oxide/calcium carbonate/magnesia composite micro-powder additive, the weight of the titanium dioxide, calcium carbonate and magnesia is than preferred
It is 35-45：45-55：7-10.
Wherein, titanium dioxide forms solid solution with aluminum oxide, the lattice defects such as ionic vacancies is produced, while as forming core
Agent, accelerates the formation of calcium hexaluminate；Adding a small amount of titanium dioxide can improve the consistency and intensity of aluminum oxide, and brilliant to aluminum oxide
The growth of grain produces influence, so as to improve the intensity of castable.Second, in corundum pouring material system, calcium carbonate by
Generation activity CaO is decomposed under high temperature, with alumina powder reaction generation calcium hexaluminate, further improves the performance of castable.The
Three, magnesia reacts generation In-suit spinel at high temperature, is conducive to improving the intensity and corrosion resistance of castable.
After high-temperature heat treatment being carried out to aluminous cement combined corundum matter castable prepared by the present invention, strength at normal temperature
More than 50MPa.
Accordingly, the present invention also provides a kind of aluminous cement combined corundum matter castable, is prepared by following raw material：70-
The plate diamond spar particle of 88 weight portions, the plate diamond spar fine powder of 0.1-10 weight portions, the Reactive alumina of 5-10 weight portions,
The aluminous cement of 0.5-8 weight portions, the silicon powder of 1 weight portion, the titanium dioxide/calcium carbonate/magnesia of 0.1-10 weight portions
Composite micro-powder additive, water reducer and water.
From above scheme as can be seen that the invention provides a kind of aluminous cement combined corundum matter castable and its preparation
Method, using titanium dioxide/calcium carbonate/fine magnesium oxide micro-powder as compound additive, the mobility influence on castable is little.This
Invention raw material sources extensively, low cost, beneficial to industrialized production, the aluminous cement combined corundum matter castable of preparation have compared with
Intensity high.
For a further understanding of the present invention, the technical scheme that the present invention is provided is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
The raw material that the embodiment of the present invention is used for：
Plate diamond spar particle, 6-3mm particles are 25.7 weight portions, and 3-1mm particles are 7.8 weight portions, and 1-0.5mm particles are
19.5 weight portions, 0.6-0.2mm particles are 8 weight portions, and 0.2-0mm particles are 18 weight portions.
Plate diamond spar particle and plate diamond spar fine powder are from the product T60 of An Mai Aluminums Co., Ltd production；
Products C L370 of the activated alumina from the production of An Mai Aluminums Co., Ltd；
Product Secar71 of the aluminous cement from the production of Kai Nuosi companies；
Product 951U of the silicon powder from the production of Ai Ken companies；
The high efficiency water reducing agent FS60 that water reducer is produced from BASF Aktiengesellschaft.
Embodiment 1
Prepare titanium dioxide/calcium carbonate/magnesia composite micro-powder additive
It is 40 by weight ratio：50：The mixing of 10 titanium dioxide, calcium carbonate stone and magnesia, is ground to Li Du≤10 μm, and
Average grain d50=2.4 μm, obtain titanium oxide/calcium carbonate/magnesia composite micro-powder additive.
Embodiment 2
By above-mentioned plate diamond spar particle, the plate diamond spar fine powder of 6.8 weight portions, the Reactive alumina of 7 weight portions,
Titanium dioxide/carbonic acid prepared by the aluminous cement of 3.7 weight portions, the silicon powder of 1 weight portion, the embodiment 1 of 2.5 weight portions
The water mixing of calcium/magnesia composite micro-powder additive, 0.2 weight portion water reducer and additional 4.3 weight portion, stirs, and vibrates
Shaping, temperature be 25 DEG C, relative humidity be 100% under conditions of conserve 24 hours, be warming up to 110 DEG C be incubated 24 hours, obtain
To aluminous cement combined corundum matter castable.
By aluminous cement combined corundum matter castable manufactured in the present embodiment in 1450 DEG C of Temperature Treatments 5 hours, test
Its strength at normal temperature, as shown in table 1.
Embodiment 2：
By above-mentioned plate diamond spar particle, the plate diamond spar fine powder of 6.6 weight portions, the Reactive alumina of 7 weight portions,
Titanium dioxide/calcium carbonate prepared by the aluminous cement of 1.4 weight portions, the silicon powder of 1 weight portion, the embodiment 1 of 5 weight portions/
The water mixing of magnesia composite micro-powder additive, 0.2 weight portion water reducer and additional 4.3 weight portion, stirs, and vibrates into
Type, temperature be 25 DEG C, relative humidity be 100% under conditions of conserve 24 hours, be warming up to 110 DEG C be incubated 24 hours, obtain
Aluminous cement combined corundum matter castable.
By aluminous cement combined corundum matter castable manufactured in the present embodiment in 1450 DEG C of Temperature Treatments 5 hours, test
Its strength at normal temperature, as shown in table 1.
Comparative example
By plate diamond spar particle, the plate diamond spar fine powder of 7 weight portions, the Reactive alumina of 7 weight portions, 6 weight portions
Aluminous cement, the silicon powder of 1 weight portion, the water mixing of 0.2 weight portion water reducer and additional former 4.3 weight portion, stirring is equal
It is even, vibration moulding, temperature be 25 DEG C, relative humidity be 100% under conditions of conserve 24 hours, be warming up to 110 DEG C insulation 24
Hour, obtain aluminous cement combined corundum matter castable.
Aluminous cement combined corundum matter castable prepared by this comparative example is in 1450 DEG C of Temperature Treatments 5 hours, test
Its strength at normal temperature, as shown in table 1.
The room temperature rupture strength of castable sample prepared by the embodiment of table 1 and comparative example
Claims (2)
1. a kind of preparation method of aluminous cement combined corundum matter castable, it is characterised in that comprise the following steps：
By the plate diamond spar particle of 70-88 weight portions, the plate diamond spar fine powder of 0.1-10 weight portions, 5-10 weight portions active oxygen
Change aluminium micro mist, the aluminous cement of 0.5-8 weight portions, the silicon powder of 1 weight portion, the titanium dioxide/carbonic acid of 0.1-10 weight portions
Calcium/magnesia composite micro-powder additive, water reducer and water mixing, vibration moulding after stirring, temperature be 20-50 DEG C, it is relatively wet
Spend to be conserved 20-30 hours under conditions of 80-100%, be warming up to 100-150 DEG C and be incubated 12-36 hours, obtain aluminous cement
Combined corundum matter castable,
The plate diamond spar particle, plate diamond spar fine powder, Reactive alumina, aluminous cement, silicon powder and titanium dioxide/
The summation of calcium carbonate/magnesia composite micro-powder additive is 100 with the weight ratio of the water reducer：0.05-0.25,
The grain composition of the plate diamond spar particle is：
6-3mm plate diamond spars particle is 24-28 weight portions；
3-1mm plate diamond spars particle is 6-9 weight portions；
1-0.5mm plate diamond spars particle is 18-21 weight portions；
0.6-0.2mm plate diamond spars particle is 6-10 weight portions；
0.2-0mm plate diamond spars particle is 16-20 weight portions,
The granularity of the plate diamond spar fine powder is 320-330 mesh,
Chun Du≤99.5% of the Reactive alumina, granularity is 1-10 μm,
The Al of the aluminous cement2O3Content is 69.5-70.5wt%,
Chun Du≤94% of the silicon powder, Li Du≤2.5 μm,
Titanium dioxide/the calcium carbonate/magnesia composite micro-powder additive is prepared as follows：It is 30-50 by weight ratio：
40-60：The mixing of the titanium dioxide of 5-10, calcium carbonate and magnesia, is ground to Li Du≤10 μm, and d50≤ 3 μm, aoxidized
Titanium/calcium carbonate/magnesia composite micro-powder additive.
2. preparation method according to claim 1, it is characterised in that the plate diamond spar particle, plate diamond spar fine powder, work
Property alumina powder, aluminous cement, silicon powder, titanium dioxide/calcium carbonate/magnesia composite micro-powder additive and water reducer
Summation is 100 with the weight ratio of water：4-6.
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| TiO2在低水泥Al2O3-MgO尖晶石浇注料致密化中的作用;尹洪基;《耐火与石灰》;20080630;第33卷(第3期);第27-30页第1、2、4节 * |
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