CN107663097A - A kind of high-performance densification composite titanium spinel brick and its manufacture method - Google Patents
A kind of high-performance densification composite titanium spinel brick and its manufacture method Download PDFInfo
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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Abstract
The invention belongs to fire resisting material field, and in particular to a kind of high-performance densification composite titanium spinel brick and its manufacture method.The high-performance densification composite titanium spinel brick is intended to substitute existing magnesian-chrome efractoy, the composite spinelle brick has compactness extent height, the porosity is low, the features such as compressive resistance is high, easy-sintering, low melting point mineral are few, possess high anti-scour property, good thermal shock, the final purpose for meeting to substitute traditional magnesian-chrome efractoy.
Description
Technical field
The invention belongs to fire resisting material field, and in particular to a kind of high-performance densification composite titanium spinel brick and its manufacturer
Method.
Background technology
Magnesian-chrome efractoy is widely used in cement, coloured and steel because of its good elevated temperature strength and erosion-resisting characteristics
The industries such as iron smelting, it is contemplated that magnesian-chrome efractoy is discarded after causes serious pollution and China's chrome ore to environment
The shortage of resource, progressively succeed in cement and steel industry Trend of Chrome-free with the development of resistance to ignition technique in recent years, only have
Color smelting industry is still widely used because of its special smelting and operating environment, magnesian-chrome efractoy.
With the further development of nonferrous smelting technology, scale, cause the use condition of existing magnesian-chrome efractoy more
Add harshness：Magnesian-chrome efractoy has to pass through mechanism, thermal stress and chemical action when in use.Mechanism is with blasting
Air capacity, air port parameter and air port operation in stove is closely related；Thermal stress and chemical stress effect then with refractory material
Property, operating procedure have very big contact.Failure mode is referred to as chemical erosion as caused by chemical action.Chemical erosion refers to resistance to
(physics, chemistry) reaction between the materials such as the same clinker of fiery material, melt, dust, flue gas is main to the destruction caused by brick body
The form of expression is the slagging of retractory, corrosion, containing the infiltration of the metal bath of active oxygen and sulphur and SO2The erosion of gas.
Analyzed for above-mentioned nonferrous smelting with refractory material use environment, develop a kind of pollution-free, high service life
The existing magnesian-chrome efractoy of products substitution, there is important practical significance and application prospect to nonferrous smelting sustainable development.
The content of the invention
In order to solve the above problems, object of the present invention is to provide a kind of high-performance densification composite titanium spinel brick and
Its manufacture method, it is intended to existing magnesian-chrome efractoy is substituted, the composite spinelle brick has compactness extent high, and the porosity is low,
The features such as compressive resistance is high, easy-sintering, low melting point mineral are few, possess high anti-scour property, and good thermal shock is final to meet
Substitute the purpose of traditional magnesian-chrome efractoy.
The object of the present invention is achieved like this：A kind of high-performance densification composite titanium spinel brick, the composite spinelle brick
It is to be formed by following raw materials by weight portion proportioning：
The fine and close compound ulvospinel 5-10 parts of 5-8mm,
The fine and close compound ulvospinel 10-15 parts of 3-5mm,
The fine and close compound ulvospinel 10-15 parts of 0.074-3mm,
The fine and close compound ulvospinel fine powder 5-10 parts of≤0.074mm,
5-8mm fused magnesite 5-10 parts,
3-5mm fused magnesite 20-25 parts,
0.074-3mm fused magnesite 20-25 parts,
≤ 0.074mm fused magnesite fine powder 5-10 parts,
≤ 0.074mm titanium dioxide 3-8 parts,
Nanoscale seawater magnesia fine powder 5-8 parts,
Uf-Al2O3 micro mist 5-10 parts,
Combined binder 3-5 parts；
The compound ulvospinel of the densification, nanoscale seawater magnesia fine powder, fused magnesite physical and chemical index are as follows：
| Project | Fine and close compound ulvospinel | Nanoscale seawater magnesia fine powder | Fused magnesite |
| MgO, % | ≥77.00 | ≥98.00 | ≥97.50 |
| Al2O3, % | ≥12.00 | ≤0.60 | ≤1.00 |
| Ti2O3, % | ≥6.00 | - | - |
| ∑SiO2+ Fe2O3, % | ≤1.00 | ≤0.80 | ≤1.50 |
| CaO/SiO2 | - | ≥2 | ≥2 |
| Bulk density, g/cm3 | ≥3.30 | ≥3.50 | ≥3.40 |
The uf-Al2O3Al in micro mist2O3 Content >=99%, TiO2 content >=99% in titanium dioxide.
The combined binder by zirconium oxychloride, calcium lignosulfonate and water in sealed pressure vessel by dissolving-
After crystallization reaction, it is formulated.
A kind of manufacture method of high-performance densification composite titanium spinel brick, comprises the following steps：
（1）Raw material crushes：Broken described successively by jaw crusher, pair roller type respectively containing ulvospinel and fused magnesite raw material
Broken machine and thunder cover flour mill and are crushed, sieved, be milled, and the particle that granularity is respectively 5-8mm, 3-5mm, 0.074-3mm is made
Material is≤0.074mm fine powder materials with granularity.
（2）Fine powder premixes：By nanoscale seawater magnesia fine powder and uf-Al2O3 micro mists, required parts by weight are matched somebody with somebody on request
Than well mixed.
（3）Batch mixing：All raw materials are kneaded in the parts by weight feeding high speed mixing smelting machine on request, its charging sequence
It is followed successively by：First granularity is mixed 5 minutes for 5-8mm, 3-5mm, 0.074-3mm containing ulvospinel and fused magnesite, Ran Houjia
Enter bonding agent to mix 5 minutes, add step（2）Pre- mixed fine powder mixes 8 minutes, is discharged after well mixed.
（4）Shaping：Predetermined weight pug is weighed, is uniformly inserted in brick machine die cavity, high-pressure molding.
（5）Dry：Adobe is molded in drying kiln for drying 12-15 hours, drying temperature 70-100 degree.
（6）Burn till：Above-mentioned shaping adobe is piled up on kiln car, directly carrying out high temperature through tunnel cave burns till, and burns
Into 1600-1650 DEG C of temperature.
（7）Selection, processing and packaging：Enter warehouse for finished product after choosing, packing after kiln discharge cooling.
Preferably, step（4）Pressurization schedule is carried out using the principle of first light rear weight during shaping.
Compared with prior art, the beneficial effects of the present invention are.
1st, by introducing the fine and close compound ulvospinel of high fine and close and low impurity, CaO/SiO2>=2 high-purity sea water magnesia
Sand and fused magnesite, using the characteristic of fine and close compound ulvospinel high-compactness and low impurity, improve finished bricks bulk density, drop
Low-porosity, low melting point mineral facies are reduced, product is possessed good anti-slag penetration and resistance to flaking.
2nd, composite spinelle brick introduces fine and close compound ulvospinel and burnt till by high temperature, and magnesia spinel is dissolved a certain amount of magnesium
After ulvospinel so that the increased activity of magnesia spinel, acceleration of sintering, improve bulk density, reduce the porosity.
3rd, the Mg in the fine and close compound ulvospinel being introduced into2TiO4Can be with CaO reactions generation high-melting-point CaTiO in slag3
（1915 DEG C of fusing point）, this material be blocked in greatly enhanced in stomata composite spinelle brick resistance slag corrosion ability.
4th, the nanoscale seawater magnesia and fineness ＜ 1um uf-Al with particle diameter between 10-50nm2O3 Micro mist strengthens base
Matter, increase its specific surface area, reduce sintering temperature, easy-sintering, the article substrate part combination after high temperature is burnt till is finer and close, carries
High volume density and compressive resistance, increase between particle directly in conjunction with intensity, improve elevated temperature strength and thermal shock resistance.
5th, combined binder passes through dissolving-analysis by zirconium oxychloride, calcium lignosulfonate and water in sealed pressure vessel
After crystalline substance reaction, it is formulated, combined binder can make to tend to a large amount of secondary spinelles occur in brick between magnesia particle, improve fine and close
Spend and then improve brick anti-scour property.
In summary, the high-performance densification composite titanium spinel brick that the present invention produces has easy-sintering, low melting point mineral
Seldom, possesses the features such as high anti-scour property, good thermal shock, compactness extent is high, and the porosity is low, and compressive resistance is high, finally
Meet the purpose for substituting traditional magnesian-chrome efractoy.The series of products can be used in converter, anode furnace of nonferrous smelting etc. and set
On standby stove, particularly in converter and anode furnace, magnesian-chrome efractoy use can be substituted completely.
Embodiment 1
A kind of high-performance densification composite titanium spinel brick, be by following raw material by weight ratio made of：
Fine and close compound 5 parts of the ulvospinels of 5-8mm,
Fine and close compound 10 parts of the ulvospinels of 3-5mm,
Fine and close compound 10 parts of the ulvospinels of 0.074-3mm,
Fine and close compound 5 parts of the ulvospinel fine powders of≤0.074mm,
5 parts of 5-8mm fused magnesites,
20 parts of 3-5mm fused magnesites,
20 parts of 0.074-3mm fused magnesites,
5 parts of≤0.074mm fused magnesites fine powder,
3 parts of≤0.074mm titanium dioxides,
5 parts of nanoscale seawater magnesia fine powder,
9 parts of uf-Al2O3 micro mists,
3 parts of combined binder.
The nanoscale seawater magnesia fine powder, fine and close compound ulvospinel, fused magnesite physical and chemical index are as follows：
| Project | Fine and close compound ulvospinel | Nanoscale seawater magnesia fine powder | Fused magnesite |
| MgO, % | ≥77.00 | ≥98.00 | ≥97.50 |
| Al2O3, % | ≥12.00 | ≤0.60 | ≤1.00 |
| Ti2O3, % | ≥6.00 | - | - |
| ∑SiO2+ Fe2O3, % | ≤1.00 | ≤0.80 | ≤1.50 |
| CaO/SiO2 | - | ≥2 | ≥2 |
| Bulk density, g/cm3 | ≥3.30 | ≥3.50 | ≥3.40 |
A kind of manufacture method of above-mentioned high-performance densification composite titanium spinel brick, is comprised the technical steps that：
1）Raw material crushes：By the compound ulvospinel of the densification and fused magnesite raw material respectively successively by jaw crusher, right
Kibbler roll and thunder cover flour mill and are crushed, sieved, be milled, and it is respectively 5-8mm, 3-5mm, 0.074-3mm that granularity, which is made,
Particulate material and granularity be≤0.074mm fine powder materials.
2）Fine powder premixes：By nanoscale seawater magnesia fine powder and uf-Al2O3 micro mists required weight on request
It is well mixed；
3）Batch mixing：All raw materials are kneaded in the parts by weight feeding high speed mixing smelting machine on request, its charging sequence is successively
For：First by granularity be 5-8mm, 3-5mm, 0.074-3mm fine and close compound ulvospinel and fused magnesite mixing 5 minutes, then
Add bonding agent to mix 5 minutes, add step（2）Pre- mixed fine powder mixes 8 minutes, is discharged after well mixed；
4）Shaping：Predetermined weight pug is weighed, is uniformly inserted in brick machine die cavity, kiloton forcing press high-pressure molding, is added during shaping
Compacting degree is carried out using the principle of first light rear weight；
5）Dry：Adobe is molded in drying kiln for drying 12 hours, 70 degree of drying temperature.
6）Burn till：Above-mentioned shaping adobe is piled up on kiln car, directly carrying out high temperature through tunnel cave burns till, and burns till
1650 DEG C of temperature；
The embodiment finished product test the results are shown in Table 1.
Embodiment 2
A kind of high-performance densification composite titanium spinel brick, be by following raw material by weight ratio made of：
Fine and close compound 8 parts of the ulvospinels of 5-8mm,
Fine and close compound 10 parts of the ulvospinels of 3-5mm,
Fine and close compound 10 parts of the ulvospinels of 0.074-3mm,
Fine and close compound 7 parts of the ulvospinel fine powders of≤0.074mm,
8 parts of 5-8mm fused magnesites,
17 parts of 3-5mm fused magnesites,
15 parts of 0.074-3mm fused magnesites,
5 parts of≤0.074mm fused magnesites fine powder,
5 parts of≤0.074mm titanium dioxides,
5 parts of nanoscale seawater magnesia fine powder,
6 parts of uf-Al2O3 micro mists,
4 parts of combined binder.
The nanoscale seawater magnesia fine powder, fine and close compound ulvospinel, fused magnesite physical and chemical index are as follows：
| Project | Fine and close compound ulvospinel | Nanoscale seawater magnesia fine powder | Fused magnesite |
| MgO, % | ≥77.00 | ≥98.00 | ≥97.50 |
| Al2O3, % | ≥12.00 | ≤0.60 | ≤1.00 |
| Ti2O3, % | ≥6.00 | - | - |
| ∑SiO2+ Fe2O3, % | ≤1.00 | ≤0.80 | ≤1.50 |
| CaO/SiO2 | - | ≥2 | ≥2 |
| Bulk density, g/cm3 | ≥3.30 | ≥3.50 | ≥3.40 |
A kind of manufacture method of above-mentioned high-performance densification composite titanium spinel brick, its processing step walk with technique described in embodiment 1
It is rapid identical.The embodiment finished product test the results are shown in Table 1.
Embodiment 3
A kind of high-performance densification composite titanium spinel brick, be by following raw material by weight ratio made of：
Fine and close compound 10 parts of the ulvospinels of 5-8mm,
Fine and close compound 10 parts of the ulvospinels of 3-5mm,
Fine and close compound 10 parts of the ulvospinels of 0.074-3mm,
Fine and close compound 5 parts of the ulvospinel fine powders of≤0.074mm,
10 parts of 5-8mm fused magnesites,
20 parts of 3-5mm fused magnesites,
15 parts of 0.074-3mm fused magnesites,
5 parts of≤0.074mm fused magnesites fine powder,
4 parts of≤0.074mm titanium dioxides,
6 parts of nanoscale seawater magnesia fine powder,
5 parts of uf-Al2O3 micro mists,
5 parts of combined binder；
The nanoscale seawater magnesia fine powder, fine and close compound ulvospinel, fused magnesite physical and chemical index are as follows：
| Project | Fine and close compound ulvospinel | Nanoscale seawater magnesia fine powder | Fused magnesite |
| MgO, % | ≥77.00 | ≥98.00 | ≥97.50 |
| Al2O3, % | ≥12.00 | ≤0.60 | ≤1.00 |
| Ti2O3, % | ≥6.00 | - | - |
| ∑SiO2+ Fe2O3, % | ≤1.00 | ≤0.80 | ≤1.50 |
| CaO/SiO2 | - | ≥2 | ≥2 |
| Bulk density, g/cm3 | ≥3.30 | ≥3.50 | ≥3.40 |
A kind of manufacture method of above-mentioned high-performance densification composite titanium spinel brick, its processing step walk with technique described in embodiment 1
It is rapid identical.The embodiment finished product test the results are shown in Table 1.
Traditional magnesite-chrome brick uses magnesia, and synthetic magnesia chromite clinker and chrome ore production, detailed index are seen the above table.
Visible by result, compared with traditional magnesite-chrome brick, composite titanium spinel brick performance of the invention is more excellent,
Characteristic with high-compactness and low impurity, finished bricks bulk density is improved, reduce the porosity, significantly improve elevated temperature strength
And thermal shock resistance.
The refractory material slag resistance test methods of national standard GB/T 8931-1988 are used by copper ashes erosion test（Experiment temperature
1600 DEG C of degree, 3 rpms of rotational speed changes slag frequency 2 hour 10 times, adds up to test period 20 hours）, contrast 4 groups of samples
Erosion results are as follows.
| Traditional magnesite-chrome brick | Example 1 | Example 2 | Example 3 |
| Melting loss depth：13.7mm | Melting loss depth：7.6 | Melting loss depth：11.5 | Melting loss depth：9.2 |
| Penetration depth：17.1mm | Penetration depth：10.7 | Penetration depth：14.8 | Penetration depth：12.9 |
Visible by result, compared with traditional magnesite-chrome brick, composite titanium spinel brick of the invention possesses good anti-stove
Slag permeability and resistance to flaking, greatly enhance the ability of composite titanium spinel brick resistance slag corrosion.
Claims (7)
- A kind of 1. high-performance densification composite titanium spinel brick, it is characterised in that：The fine and close composite titanium spinel brick is by following original Material proportioning in parts by weight forms：The fine and close compound ulvospinel 5-10 parts of 5-8mm,The fine and close compound ulvospinel 10-15 parts of 3-5mm,The fine and close compound ulvospinel 10-15 parts of 0.074-3mm,The fine and close compound ulvospinel fine powder 5-10 parts of≤0.074mm,5-8mm fused magnesite 5-10 parts,3-5mm fused magnesite 20-25 parts,0.074-3mm fused magnesite 20-25 parts,≤ 0.074mm fused magnesite fine powder 5-10 parts,≤ 0.074mm titanium dioxide 3-8 parts,Nanoscale seawater magnesia fine powder 5-8 parts,Uf-Al2O3 micro mist 5-10 parts,Combined binder 3-5 parts.
- 2. a kind of high-performance densification composite titanium spinel brick according to claim 1, it is characterised in that the densification is compound Ulvospinel, nanoscale seawater magnesia fine powder, fused magnesite physical and chemical index are as follows：
Project Fine and close compound ulvospinel Nanoscale seawater magnesia fine powder Fused magnesite MgO , % ≥77.00 ≥98.00 ≥97.50 Al2O3, % ≥12.00 ≤0.60 ≤1.00 Ti2O3, % ≥6.00 - - ∑SiO2+Fe2O3, % ≤1.00 ≤0.80 ≤1.50 CaO/SiO2 - ≥2 ≥2 Bulk density, g/cm3 ≥3.30 ≥3.50 ≥3.40 。 - A kind of 3. high-performance densification composite titanium spinel brick according to claim 1, it is characterised in that：The uf-Al2O3 Al in micro mist2O3 Content >=99%, TiO2 content >=99% in the titanium dioxide.
- A kind of 4. high-performance densification composite titanium spinel brick according to claim 1, it is characterised in that：The nanoscale sea The granularity of water magnesia is 10-50nm, the uf-Al2O3Fineness ＜ 1um.
- A kind of 5. high-performance densification composite titanium spinel brick according to claim 1, it is characterised in that：The mixed binding Agent by zirconium oxychloride, calcium lignosulfonate and water in sealed pressure vessel after dissolving-crystallization reaction, be formulated.
- A kind of a kind of 6. manufacture method of high-performance densification composite titanium spinel brick as claimed in claim 1, it is characterised in that Comprise the following steps：（1）Raw material crushes：Broken described successively by jaw crusher, pair roller type respectively containing ulvospinel and fused magnesite raw material Broken machine and thunder cover flour mill and are crushed, sieved, be milled, and the particle that granularity is respectively 5-8mm, 3-5mm, 0.074-3mm is made Material is≤0.074mm fine powder materials with granularity；（2）Fine powder premixes：By nanoscale seawater magnesia fine powder and uf-Al2O3 micro mists, required parts by weight proportioning is mixed on request Close uniform；（3）Batch mixing：All raw materials are kneaded in the parts by weight feeding high speed mixing smelting machine on request, its charging sequence is successively For：It is first being mixed 5 minutes containing ulvospinel and fused magnesite for 5-8mm, 3-5mm, 0.074-3mm by granularity, then adds knot Mixture mixes 5 minutes, adds step（2）Pre- mixed fine powder mixes 8 minutes, is discharged after well mixed；（4）Shaping：Predetermined weight pug is weighed, is uniformly inserted in brick machine die cavity, high-pressure molding；（5）Dry：Adobe is molded in drying kiln for drying 12-15 hours, drying temperature 70-100 degree；（6）Burn till：Above-mentioned shaping adobe is piled up on kiln car, directly carrying out high temperature through tunnel cave burns till, and burns till temperature 1600-1650 DEG C of degree；（7）Selection, processing and packaging：Enter warehouse for finished product after choosing, packing after kiln discharge cooling.
- A kind of 7. manufacture method of high-performance densification composite titanium spinel brick according to claim 4, it is characterised in that step Suddenly（4）Pressurization schedule is carried out using the principle of first light rear weight during shaping.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115417658A (en) * | 2022-08-17 | 2022-12-02 | 辽宁中镁新材料有限公司 | Novel magnesium aluminate spinel brick for cement kiln burning zone and production method thereof |
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| CN107663097B (en) | 2020-10-16 |
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