CN108516845A - A kind of oxidation chromium composite spinelle brick and preparation method thereof - Google Patents
A kind of oxidation chromium composite spinelle brick and preparation method thereof Download PDFInfo
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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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
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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
- C04B2235/3241—Chromium oxides, chromates, 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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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Abstract
The present invention discloses a kind of oxidation chromium composite spinelle brick and preparation method thereof, and original material includes matrix and aggregate, and aggregate is electric smelting chrome oxide particle；Matrix is chromium oxide fine powder, aluminum oxide fine powder, composite spinelle micro mist；Parts by weight are added in matrix：20 parts 45 parts；Aggregate is electric smelting chrome oxide particle.By on the basis of existing oxidation chrome brick technology of preparing, in the case where not adding zirconium oxide, by introducing the composite spinelle of synthesis, oxidation chromium composite spinelle brick being made, compared with existing oxidation chrome brick：In the case where thermal shock resistance does not reduce, there is excellent anti-cinder erosion performance, anti-cinder permeance property.
Description
Technical field
The invention belongs to fire resisting material field more particularly to a kind of oxidation chromium composite spinelle brick and preparation method thereof, it
It is coal water slurry gasification inner lining of furnace critical material.
Background technology
Gasification furnace is the key equipment of water coal slurry pressurized gasification technology, the usual working condition of coal water slurry pressurized gasifier
For：1250-1550 DEG C of operating temperature, pressure 2.0-8.5MPa, strongly reducing atmosphere, acid slag erosion, slag tap, driving and parking
When larger temperature fluctuation and pressure oscillation impact；And coal slurry gasifier side towards the fire with brick be related to gasification furnace can be normal
The critical material of operating.Currently, oxidation chrome brick is the work lining material for being used successfully to water-coal-slurry pressurization steam stove, the oxidation chrome brick
It is Cr2O3Oxygen usually is added in oxidation chrome brick in order to improve the thermal shock resistance of product in firing chrome oxide product containing amount≤80%
Change zirconium, content 2-7%.
However, China is the more rare country of zirconium oxide resource, zirconium oxide is mainly by import, and zirconium oxide is also accompanied by
A small amount of radioactive hafnium oxide, however coal slurry gasifier is in China's fast development, has been more than every with high-chrome brick demand
Years ten thousand tons, and also growth trend, this demand necessarily to aoxidizing chrome brick is put forward higher requirements.The present invention is a kind of by synthesizing
Composite spinelle is introduced into oxidation chrome brick, in the case where not adding zirconium oxide, has reached the property of original oxidation chrome brick
Can, and improve the erosion-resisting characteristics of brick.
Invention content
The present invention is directed to China's zirconium oxide resource scarcity, and industrial zirconium oxide largely leans on import, and coal slurry gasifier is in China
Fast development has been more than annual ten thousand tons with high-chrome brick demand, and also growth trend, this necessarily to aoxidize chrome brick demand
It puts forward higher requirements.The present invention is by proposing a kind of oxidation chromium composite spinelle brick, using composite spinelle as the second coupling
Enter into oxidation chrome brick, in the case where it does not add zirconium oxide, has reached and performance similar in former chromium oxide, such as low stomata
Rate, high compressive resistance and anti-cinder erosion performance, thermal shock resistance etc..Chromium composite spinelle brick is aoxidized as water-coal-slurry
The working lining of gasification furnace can meet current coal slurry gasifier enlargement, high pressure, high production capacity, the harsh conditions of high request, carry
The service life of high entire gasification inner lining of furnace.
A kind of oxidation chromium composite spinelle brick, original material include matrix and aggregate, and aggregate is added parts by weight and is：55 parts-
80 parts, matrix is added parts by weight and is：20 parts -45 parts；Aggregate is electric smelting chrome oxide particle；Matrix is chromium oxide fine powder, oxidation
Aluminium fine powder, composite spinelle micro mist；Parts by weight are added in chromium oxide fine powder：25-65 parts, parts by weight are added in aluminum oxide fine powder
Number is：10-25 parts, composite spinelle micro mist is added parts by weight and is：25-50 parts, additional bonding agent, bonding agent addition
For the 1-10 % of original material total weight.
The bonding agent is phosphoric acid or aluminum phosphate solution.
Wherein aggregate size is 10 mm-0.088mm.
Wherein the powder particle size of chromium oxide fine powder, aluminum oxide fine powder is less than 0.088mm.
Wherein the granularity of composite spinelle micro mist is less than 44 μm.
Composite spinelle group of the present invention is divided into chromium oxide, aluminium oxide, iron oxide, magnesia.
The parts by weight of the composite spinelle component are respectively that chromic oxide content is 10-55 parts, and alumina content is
15-50 parts, iron oxide content is 10-20 parts, and content of magnesia is 10-25 parts.
The crystalline phase of composite spinelle is：Chromohercynite 70-75%, chromium-aluminium spinel 12-15%, spinelle 8-12%.
It is a kind of oxidation chromium composite spinelle brick preparation method be：
Step 1: by aggregate in sand mixer after mixing, 2/3 part of mixing of bonding agent total amount is added, fine powder mixing is then added,
Mixing is eventually adding remaining bonding agent, then about 5 minutes mixed；
Step 2: ageing mixture 1-2 hours, is pressed into green compact, dry, 1600-1800 DEG C of firing, obtains this oxygen in shuttle kiln
Change chromium composite spinelle brick.
To be burnt under neutral atmosphere or weak reducing atmosphere in shuttle kiln, because the composite spinelle is must be
It is prepared under this atmosphere, otherwise can influence the final performance of final products.
The principle of the present invention is：The present invention is not by the basis of existing oxidation chrome brick technology of preparing, adding oxygen
In the case of changing zirconium, with chromium oxide, aluminium oxide as primary raw material, and the composite spinelle micro mist of synthesis is introduced, due to compound
The crystalline phase of spinelle is：Chromohercynite 70-75%, chromium-aluminium spinel 12-15%, spinelle 8-12%.In addition chromium oxide, oxygen
Change the rational proportion of aluminium and composite spinelle micro mist, aluminium oxide can generate unlimited solid solution at high temperature with chromium oxide, compound
Spinelle is introduced into micronized form in oxidation chrome brick, just because of the crystalline phase of composite spinelle is：Chromohercynite 70-75%,
Chromium-aluminium spinel 12-15%, spinelle 8-12%；Especially chromohercynite and chromium-aluminium spinel crystalline phase, after sintering with this
Chrome oxide particle matrix weave in invention forms fine and close network structure, and the porosity for showing as product is smaller, separately
Outside since Spinel micropowder is different from the coefficient of expansion of chrome oxide particle, the thermal shock resistance of product is also improved.Make
With in the process, since composite spinelle structure is dense, for the matrix of the present invention, the permeance property of slag is hindered more
By force, so reduce slag infiltration and erosion, to extend the service life of product.
Since composite spinelle micro mist part has reached Ultramicro-powder grade, in subsequent preparation process, compound point is brilliant
The small powder of stone crystalline phase ultra micro penetrates into chromium oxide, chromium oxide crystal phase structure gap, forms firm skeleton function, significantly improves
The compressive resistance and thermal shock resistance of working lining, composite spinelle crystalline phase plays the role of that slag is hindered further to permeate, to significantly
Improve anti-cinder erosion performance.
By the Analysis of residual bricks to current coal water slurry pressurized gasifier chromium oxide, damage of the cinder to oxidation chrome brick is found
It mainly corrodes and peels off.Erosion is mainly shown as that silica in slag, iron oxide, the impurity such as calcium oxide rush oxidation chrome brick
It hits, it is continuous, slowly.Spinel layer in the present invention plays the role of that slag is hindered further to permeate；Calcium oxide is shown as
Eutectic is generated in the inside of brick, and is permeated deeper.Peeling is mainly shown as brick after a period of use, the block on the hot face of brick
Shape, sheet are fallen, it is instantaneous, block-like, intermittent.Since aluminium oxide and chromium oxide can generate infinitely admittedly at high temperature
Solution, the present invention are introduced by synthesizing a kind of compound chromium ferro-aluminum magnesia spinel in oxidation chrome brick, so reached with
Performance, such as low porosity similar in original oxidation chrome brick, high compressive resistance, erosion-resisting characteristics, and due to composite spinelle
Coefficient of thermal expansion is different from chromium oxide, and the thermal shock resistance of product can also be improved by introducing composite spinelle.
The beneficial effects of the invention are as follows：
The present invention is by the basis of existing oxidation chrome brick technology of preparing, in the case where not adding zirconium oxide, passing through introducing
Oxidation chromium composite spinelle brick is made, compared with existing oxidation chrome brick in the composite spinelle of synthesis：It is not reduced in thermal shock resistance
In the case of, there is excellent anti-cinder erosion performance, anti-cinder permeance property.
1, oxidation chromium composite spinelle brick is made in the present invention, in the case where being not added with zirconium oxide, compared with original aoxidizes chrome brick
Its thermal shock resistance can be quite.
2, oxidation chromium composite spinelle brick produced by the present invention disclosure satisfy that coal slurry gasifier enlargement, high pressure, height
The harsh conditions of production capacity provide a new selection for coal water slurry pressurized gasifier inner lining fireproof material.
Specific implementation mode：
Can be with invention is further described in detail with reference to following embodiment, but the invention is not limited in these embodiments.
Embodiment 1：
A kind of oxidation chromium composite spinelle brick, original material include matrix and aggregate, and aggregate is added parts by weight and is：55 parts, matrix
Parts by weight, which are added, is：45 parts；Aggregate is electric smelting chrome oxide particle；Matrix is chromium oxide fine powder, aluminum oxide fine powder, compound point
Spar micro mist；Parts by weight are added in chromium oxide fine powder：25 parts, aluminum oxide fine powder is added parts by weight and is：It is 25 parts, compound
Parts by weight are added in Spinel micropowder：50 parts, the parts by weight of wherein composite spinelle component are respectively that chromic oxide content is
10 parts, alumina content is 50 parts, and iron oxide content is 20 parts, and content of magnesia is 20 parts；Additional phosphoric acid, phosphoric acid addition are
1 % of original material total weight.
Embodiment 2：
A kind of oxidation chromium composite spinelle brick, original material include matrix and aggregate, and aggregate is added parts by weight and is：80 parts, matrix
Parts by weight, which are added, is：20 parts；Aggregate is electric smelting chrome oxide particle；Matrix is chromium oxide fine powder, aluminum oxide fine powder, compound point crystalline substance
Stone micro mist；Parts by weight are added in chromium oxide fine powder：65 parts, aluminum oxide fine powder is added parts by weight and is：10 parts, compound point
Parts by weight are added in spar micro mist：25 parts, it is 55 that the parts by weight of wherein composite spinelle component, which are respectively chromic oxide content,
Part, alumina content is 15 parts, and iron oxide content is 10 parts, and content of magnesia is 20 parts；Additional phosphoric acid, phosphoric acid addition are original
10 % of total weight of expecting.
Embodiment 3：
A kind of oxidation chromium composite spinelle brick, original material include matrix and aggregate, and aggregate is added parts by weight and is：75 parts, matrix
Parts by weight, which are added, is：25 parts；Aggregate is electric smelting chrome oxide particle；Matrix is chromium oxide fine powder, aluminum oxide fine powder, compound point crystalline substance
Stone micro mist；Parts by weight are added in chromium oxide fine powder：45 parts, aluminum oxide fine powder is added parts by weight and is：25 parts, compound point
Parts by weight are added in spar micro mist：30 parts, it is 40 that the parts by weight of wherein composite spinelle component, which are respectively chromic oxide content,
Part, alumina content is 20 parts, and iron oxide content is 20 parts, and content of magnesia is 20 parts；Additional aluminum phosphate, aluminum phosphate addition
For 8 % of original material total weight.
The preparation method of the embodiment of the present invention 1,2,3 is：
Step 1: by aggregate in sand mixer after mixing, 2/3 part of mixing of bonding agent total amount is added, fine powder mixing is then added,
Mixing is eventually adding remaining bonding agent, then about 5 minutes mixed；
Step 2: ageing mixture 1-2 hours, is pressed into green compact, dry, 1600-1800 DEG C of firing, obtains this oxygen in shuttle kiln
Change chromium composite spinelle brick.
The performance of embodiment 1-3 and comparative example resulting product is as shown in the table.Apparent porosity, bulk density, room temperature pressure resistance
Intensity and heat-resistant knocking stability energy press relative national standards and carry out performance detection.
Claims (8)
1. a kind of oxidation chromium composite spinelle brick, it is characterised in that：Original material includes matrix and aggregate, and parts by weight are added in aggregate
For：55 parts -80 parts, matrix is added parts by weight and is：20 parts -45 parts；Aggregate is electric smelting chrome oxide particle；Matrix is that chromium oxide is thin
Powder, aluminum oxide fine powder, composite spinelle micro mist；Parts by weight are added in chromium oxide fine powder：25-65 parts, aluminum oxide fine powder adds
Entering parts by weight is：10-25 parts, composite spinelle micro mist is added parts by weight and is：25-50 parts, additional bonding agent, in conjunction with
Agent addition is the 1-10 % of original material total weight.
2. a kind of oxidation chromium composite spinelle brick according to claim 1, it is characterised in that：Aggregate size is 10 mm-
0.088mm。
3. a kind of oxidation chromium composite spinelle brick according to claim 1, it is characterised in that：Chromium oxide fine powder, aluminium oxide
The powder particle size of fine powder is less than 0.088mm.
4. a kind of oxidation chromium composite spinelle brick according to claim 1, it is characterised in that：The grain of composite spinelle micro mist
Degree is less than 44 μm.
5. a kind of oxidation chromium composite spinelle brick according to claim 1, it is characterised in that：Composite spinelle group is divided into oxygen
Change chromium, aluminium oxide, iron oxide, magnesia, it is 10-55 parts that the parts by weight of composite spinelle component, which are respectively chromic oxide content,
Alumina content is 15-50 parts, and iron oxide content is 10-20 parts, and content of magnesia is 10-25 parts.
6. a kind of oxidation chromium composite spinelle brick according to claim 5, it is characterised in that：The crystalline phase of composite spinelle
For：Chromohercynite 70-75%, chromium-aluminium spinel 12-15%, spinelle 8-12%.
7. a kind of preparation method of oxidation chromium composite spinelle brick according to claim 1, it is characterised in that：Step 1:
By aggregate in sand mixer after mixing, 2/3 part of mixing of bonding agent total amount is added, fine powder mixing is then added, mixing finally adds
Enter remaining bonding agent, then about 5 minutes mixed；Step 2: ageing mixture 1-2 hours, is pressed into green compact, dry, the 1600- in shuttle kiln
1800 DEG C of firings, obtain this oxidation chromium composite spinelle brick.
8. a kind of preparation method of oxidation chromium composite spinelle brick according to claim 7, it is characterised in that：In shuttle kiln
To be burnt under neutral atmosphere or weak reducing atmosphere.
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| CN109608175A (en) * | 2019-02-20 | 2019-04-12 | 中钢集团耐火材料有限公司 | A kind of nonferrous smelting fusing furnace walls mouth refractory material and preparation method thereof |
| CN109608215A (en) * | 2019-02-20 | 2019-04-12 | 中钢集团耐火材料有限公司 | A kind of nonferrous smelting fusing furnace hearth refractory material and preparation method thereof |
| CN109626972A (en) * | 2019-02-20 | 2019-04-16 | 中钢集团耐火材料有限公司 | A kind of nonferrous smelting fusing smelting furnace top furnace wall refractory material and preparation method thereof |
| CN109626971A (en) * | 2019-02-20 | 2019-04-16 | 中钢集团耐火材料有限公司 | A kind of nonferrous smelting fusing smelting furnace liquidus top furnace wall refractory material and preparation method thereof |
| CN109627027A (en) * | 2019-02-20 | 2019-04-16 | 中钢集团耐火材料有限公司 | A kind of magnalium ferropicotite composite material and preparation method |
| CN109626970A (en) * | 2019-02-20 | 2019-04-16 | 中钢集团耐火材料有限公司 | A kind of nonferrous smelting fusing smelting furnace liquidus lower section furnace wall refractory material and preparation method thereof |
| CN109650856A (en) * | 2019-02-20 | 2019-04-19 | 中钢集团耐火材料有限公司 | A kind of high-strength fusing smelting furnace of coloured strengthening smelting |
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| CN116332631A (en) * | 2023-04-04 | 2023-06-27 | 中钢洛耐科技股份有限公司 | Chromium-aluminum-magnesium-zirconium refractory brick and preparation method thereof |
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| KR20210038974A (en) * | 2019-02-20 | 2021-04-08 | 시노스틸 루오나이 머티리얼즈 테크놀로지 코퍼레이션 | High-strength melting furnace for color reinforcement smelting |
| CN109627027B (en) * | 2019-02-20 | 2022-02-01 | 中钢洛耐科技股份有限公司 | Aluminum-magnesium-iron-chromium spinel composite material and preparation method thereof |
| CN109608175A (en) * | 2019-02-20 | 2019-04-12 | 中钢集团耐火材料有限公司 | A kind of nonferrous smelting fusing furnace walls mouth refractory material and preparation method thereof |
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