CN116535222A - Composite chrome corundum brick for chemical industry salt-containing wastewater incinerator and preparation method thereof - Google Patents
Composite chrome corundum brick for chemical industry salt-containing wastewater incinerator and preparation method thereof Download PDFInfo
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- CN116535222A CN116535222A CN202310367027.3A CN202310367027A CN116535222A CN 116535222 A CN116535222 A CN 116535222A CN 202310367027 A CN202310367027 A CN 202310367027A CN 116535222 A CN116535222 A CN 116535222A
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- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 58
- 239000010431 corundum Substances 0.000 title claims abstract description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011449 brick Substances 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 title claims abstract description 32
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000011651 chromium Substances 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 9
- 238000010304 firing Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 6
- 229910001691 hercynite Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 11
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 11
- 239000006104 solid solution Substances 0.000 abstract description 11
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052596 spinel Inorganic materials 0.000 abstract description 8
- 239000011029 spinel Substances 0.000 abstract description 8
- 239000010977 jade Substances 0.000 abstract description 7
- 229910000669 Chrome steel Inorganic materials 0.000 abstract description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 description 12
- 238000004321 preservation Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910015372 FeAl Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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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- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/105—Refractories from grain sized mixtures containing chromium oxide or chrome ore
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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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Abstract
The invention relates to a composite chrome corundum brick for a chemical saline wastewater incinerator and a preparation method thereof, belonging to the field of refractory materials. The composite chrome corundum brick is prepared by taking regenerated refractory raw materials with the grain diameter less than or equal to 3mm, fused white corundum with the grain diameter less than or equal to 3mm, chrome oxide micro powder with the grain diameter less than or equal to 8 mu m, iron aluminum spinel micro powder with the grain diameter less than or equal to 31 mu m and aluminum oxide micro powder with the grain diameter less than or equal to 4 mu m as raw materials, pressing the raw materials into a green body by adding a bonding agent, and firing the green body at the temperature of 1500-1600 ℃ for high Wen Luzhong and preserving heat for 3-5 hours. The invention adopts regenerated refractory raw material chrome corundum solid solution as raw material and uses corundum and chromium oxide to generate chrome corundum solid solution in situ in the sintering process, and introduces fine powder of iron-aluminum spinel into chrome steel jade to partially replace Cr 2 O 3 In situ generation of a multiple solid solution (Al 1‑x‑y Cr x Fe y ) 2 O 3 Cr is reduced 2 O 3 Content of Cr inhibition 6+ The production promotes the sintering, improves the high-temperature service performance of chrome steel jade bricks and the corrosion resistance of sodium sulfate slag, prolongs the service life of the chemical salt-containing wastewater incinerator, and realizes the recycling of resources.
Description
Technical Field
The invention belongs to the field of refractory materials, and particularly relates to a composite chrome corundum brick for a chemical saline wastewater incinerator and a preparation method thereof.
Background
With the rapid development of the chemical industry in China, the discharge amount of the chemical salt-containing wastewater is increased increasingly. The chemical salt-containing wastewater contains a large amount of inorganic salts and toxic organic matters with complex components, and if the chemical salt-containing wastewater is improperly treated, serious threat is caused to human health and ecological environment. The incineration treatment has the advantages of high treatment efficiency, safety, stability, energy recycling and the like, and the proportion of the incineration treatment in the treatment of the salt-containing wastewater in various national chemical engineering is larger and larger. The incinerator is used as key equipment for the incineration treatment of the chemical salt-containing wastewater, the service life of the refractory material is a key for determining whether the refractory material can safely and stably run for a long time, however, when the chemical salt-containing wastewater is incinerated, a large amount of alkali metal salt in the wastewater can cause serious corrosion to the refractory material of a furnace lining, and the refractory material is easy to damage under the comprehensive actions of mechanical abrasion, thermal stress and chemical corrosion. This requires that the refractory for the chemical salt-containing wastewater incinerator have high mechanical strength to resist flushing of wastewater, good thermal shock stability to withstand severe temperature changes, and excellent erosion resistance to resist chemical attack of alkali metal salts at high temperatures. Cr (Cr) 2 O 3 The extremely low solubility in various aggressive media imparts excellent erosion resistance to chrome corundum bricksThe chrome steel jade brick has high refractoriness, high mechanical strength and good wear resistance, and is expected to be one of suitable working liners of the chemical salt-containing wastewater incinerator. However, under the severe high-temperature environment of the chemical salt-containing wastewater incinerator and the corrosion condition of alkali metal salt, the performance of the chrome steel jade brick still needs to be further improved. The iron-aluminum spinel has excellent structural flexibility, high fracture energy, good alkaline slag corrosion resistance and excellent kiln coating performance, and is widely applied to the field of refractory materials for cement kilns. The invention adopts regenerated refractory raw material chrome corundum solid solution as raw material and uses corundum and chromium oxide to generate chrome corundum solid solution in situ in the sintering process, and introduces iron aluminum spinel into chrome corundum brick to partially replace Cr 2 O 3 The micropowder is used for generating a multi-element solid solution (Al 1-x-y Cr x Fe y ) 2 O 3 Cr is reduced 2 O 3 The content of the slag is superior to that of common chrome corundum bricks in terms of inhibiting hexavalent chromium generation, promoting sintering, high-temperature service performance and corrosion resistance to sodium sulfate-containing slag. The service life of the lining refractory material of the chemical salt-containing wastewater incinerator is prolonged, and the recycling of resources is realized.
Disclosure of Invention
The invention aims to provide a composite chrome corundum brick for a chemical salt-containing wastewater incinerator and a preparation method thereof, which solve the problems of corrosion resistance, permeation resistance and low high-temperature strength of common refractory bricks and prepare the composite chrome corundum brick with excellent comprehensive properties such as corrosion resistance, permeation resistance, high-temperature strength and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the composite chrome corundum brick for the chemical salt-containing wastewater incinerator is prepared from the following raw materials in percentage by mass and aluminum dihydrogen phosphate which is an external binding agent and accounts for 2-5% of the raw materials; wherein the raw materials comprise:
the mass percentage of the regenerated refractory raw material electro-fused chrome corundum with the grain diameter less than or equal to 3mm is 35-50%;
electrofused white corundum with particle size less than or equal to 3mm, wherein w (Al 2 O 3 ) 99% or more, and 20-45% by mass;
chromium oxide micropowder with particle size less than or equal to 8 μm, wherein w (Cr 2 O 3 ) More than or equal to 99 percent, and the mass percentage is 4-12 percent;
fine powder of hercynite with particle size less than or equal to 31 mu m: 3-12% by mass;
alumina micropowder with particle size less than or equal to 4 μm, wherein w (Al 2 O 3 ) More than or equal to 99 percent and the mass percentage is 1 to 6 percent.
Further, the regenerated refractory raw material electro-fused chrome corundum in the composite chrome corundum brick is obtained by treating aluminum-chrome slag generated by smelting metallic chrome, wherein w (Al 2 O 3 )+w(Cr 2 O 3 )≥93％，w(Cr 2 O 3 )≥12％。
Further, w (Al 2 O 3 )≥55％，w(Fe 2 O 3 ) Not less than 43% to raise the density of the corundum brick, normal temperature and high temperature strength and corrosion resistance of sodium sulfate slag;
the preparation method of the composite chrome corundum brick for the chemical salt-containing wastewater incinerator comprises the following steps:
1) Mixing: weighing raw materials according to the proportion, and uniformly mixing in a mixer;
2) Trapping: placing the uniformly stirred raw materials into a sealing bag, and trapping for 12-24 hours, wherein the distribution of the binding agent and the water is more uniform, which is more beneficial to molding;
3) And (3) forming: weighing the trapped materials, filling the weighed materials into a die, and forming under 120-180MPa by using a hydraulic press;
4) And (3) drying: drying the formed green body for 24 hours at the drying temperature of 110-150 ℃;
5) Firing: and (5) sintering the dried sample at 1500-1600 ℃ for 3-5 hours under the heat preservation of Wen Luzhong.
Compared with the prior art, the invention has the beneficial effects that:
the iron-aluminum spinel is widely applied to the field of refractory materials for cement kilns due to the excellent structural flexibility, higher fracture energy, better alkaline slag erosion resistance and excellent kiln coating hanging performance. The invention adopts the regenerated refractory raw material chrome corundum solid solution as the raw material and uses corundum and chrome oxide raw material in the sintering processThe site generates chrome corundum solid solution, and the fine powder of the iron-aluminum spinel is introduced into chrome steel jade to partially replace Cr 2 O 3 In situ generation of a multiple solid solution (Al 1-x-y Cr x Fe y ) 2 O 3 Cr is reduced 2 O 3 The content of hexavalent chromium is inhibited, sintering is promoted, the high-temperature service performance of the chrome steel jade brick and the corrosion resistance of sodium sulfate slag are improved, the service life of the chemical salt-containing wastewater incinerator is prolonged, and the recycling of resources is realized.
Drawings
FIG. 1 is a photograph showing a cross-sectional view of a crucible of a composite chrome corundum brick prepared in example 1 after a sample of the brick has been eroded with sodium sulfate-containing slag;
FIG. 2 is a photograph showing a cross-sectional view of a crucible of a composite chrome corundum brick prepared in example 2 after a sample of the brick has been eroded with sodium sulfate-containing slag;
FIG. 3 is a photograph showing a cross-sectional view of a crucible of a composite chrome corundum brick prepared in example 3 after a sample of the brick has been eroded with sodium sulfate-containing slag;
FIG. 4 is an SEM image of a sample of the composite chrome corundum brick prepared in the comparative example after erosion;
FIG. 5 is an SEM image of a sample of the composite chrome corundum brick prepared in example 2 after erosion;
FIG. 6 is the relative content (wt%) of Na element at various depths in the etched samples of comparative example and example 2.
Detailed Description
The technical scheme and effect of the present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
Comparative example
The composite chrome corundum brick for the chemical salt-containing wastewater incinerator is prepared from the following raw materials in percentage by mass and aluminum dihydrogen phosphate serving as an external binding agent accounting for 3% of the raw materials; wherein the raw materials comprise:
electro-fused chromia corundum as a regenerated refractory material with the grain diameter less than or equal to 3mm, wherein w (Al 2 O 3 )+w(Cr 2 O 3 )≥93％，w(Cr 2 O 3 ) More than or equal to 12 percent, and the mass percentage is 48 percent;
electrofused white corundum with particle size less than or equal to 3mm, wherein w (Al 2 O 3 ) 99% or more, and 39% by mass;
chromium oxide micropowder with particle size less than or equal to 8 μm, wherein w (Cr 2 O 3 ) 99% or more, 9% by mass;
alumina micropowder with particle size less than or equal to 4 μm, wherein w (Al 2 O 3 ) 99% or more and 4% by mass.
Mixing the raw materials according to the required proportion, uniformly mixing the raw materials in a mixer, pressing and forming the mixture by using a hydraulic press, wherein the forming pressure is 150MPa, and sintering the formed and dried green body at 1550 ℃ under the high Wen Luzhong heat preservation for 4 hours.
Example 1
The composite chrome corundum brick for the chemical salt-containing wastewater incinerator is prepared from the following raw materials in percentage by mass and aluminum dihydrogen phosphate serving as an external binding agent accounting for 3% of the raw materials; wherein the raw materials comprise:
electro-fused chromia corundum as a regenerated refractory material with the grain diameter less than or equal to 3mm, wherein w (Al 2 O 3 )+w(Cr 2 O 3 )≥93％，w(Cr 2 O 3 ) More than or equal to 12 percent, and the mass percentage is 44 percent;
electrofused white corundum with particle size less than or equal to 3mm, wherein w (Al 2 O 3 ) 99% or more, 40% by mass;
chromium oxide micropowder with particle size less than or equal to 8 μm, wherein w (Cr 2 O 3 ) 99% or more, 11% by mass;
fine powder of hercynite with particle size less than or equal to 31 mu m: 3% by mass;
alumina micropowder with particle size less than or equal to 4 μm, wherein w (Al 2 O 3 ) 99% or more and 2% by mass.
Mixing the above raw materials according to the required proportion, uniformly mixing with a mixer, pressing and forming by a hydraulic press, wherein the forming pressure is 160MPa, and sintering the green body after forming and drying at 1600 ℃ under Wen Luzhong heat preservation for 3 hours.
Example 2
The composite chrome corundum brick for the chemical salt-containing wastewater incinerator is prepared from the following raw materials in percentage by mass and aluminum dihydrogen phosphate serving as an external binding agent accounting for 3% of the raw materials; wherein the raw materials comprise:
electro-fused chromia corundum as a regenerated refractory material with the grain diameter less than or equal to 3mm, wherein w (Al 2 O 3 )+w(Cr 2 O 3 )≥93％，w(Cr 2 O 3 ) Not less than 12% and 42% by mass;
electrofused white corundum with particle size less than or equal to 3mm, wherein w (Al 2 O 3 ) 99% or more, and 39% by mass;
chromium oxide micropowder with particle size less than or equal to 8 μm, wherein w (Cr 2 O 3 ) 99% or more, 9% by mass;
fine powder of hercynite with particle size less than or equal to 31 mu m: the mass percentage is 6%;
alumina micropowder with particle size less than or equal to 4 μm, wherein w (Al 2 O 3 ) 99% or more and 4% by mass.
Mixing the raw materials according to the required proportion, uniformly mixing the raw materials in a mixer, pressing and forming the mixture by using a hydraulic press, wherein the forming pressure is 150MPa, and sintering the formed and dried green body at 1550 ℃ under the high Wen Luzhong heat preservation for 4 hours.
Example 3
The composite chrome corundum brick for the chemical salt-containing wastewater incinerator is prepared from the following raw materials in percentage by mass and aluminum dihydrogen phosphate serving as an external binding agent accounting for 3% of the raw materials; wherein the raw materials comprise:
electro-fused chromia corundum as a regenerated refractory material with the grain diameter less than or equal to 3mm, wherein w (Al 2 O 3 )+w(Cr 2 O 3 )≥93％，w(Cr 2 O 3 ) More than or equal to 12 percent, and the mass percentage is 40 percent;
electrofused white corundum with particle size less than or equal to 3mm, wherein w (Al 2 O 3 ) 99% or more, and 42% by mass;
chromium oxide micropowder with particle size less than or equal to 8 μm, wherein w (Cr 2 O 3 ) 99% or more, and 5% by mass;
fine powder of hercynite with particle size less than or equal to 31 mu m: the mass percentage is 10%;
alumina micropowder with particle size less than or equal to 4 μm, wherein w (Al 2 O 3 ) 99% or more and 3% by mass.
Mixing the raw materials according to the required proportion, uniformly mixing the raw materials in a mixer, pressing and forming the mixture by using a hydraulic press, wherein the forming pressure is 150MPa, and sintering the formed and dried green body at 1550 ℃ under the high Wen Luzhong heat preservation for 4 hours.
Physical and chemical indexes of the composite chrome corundum bricks prepared in examples 1-3 are shown in table 1.
Table 1 physicochemical indexes of the composite chrome corundum bricks prepared in examples 1 to 3
| Physical and chemical properties | Example 1 | Example 2 | Example 3 |
| Apparent porosity/% | 12.4 | 11.9 | 12.8 |
| Bulk Density/g/cm 3 | 3.41 | 3.42 | 3.40 |
| Normal temperature fracture resistance/Mpa | 40.6 | 42.3 | 40.2 |
| Pressure-resistant at normal temperature/Mpa | 197.0 | 216.1 | 201.3 |
| High temperature fracture resistance (1300 ℃ C.)/Mpa | 22.5 | 24.1 | 22.6 |
As is clear from Table 1, the composite chrome corundum bricks of examples 1, 2 and 3 have low porosity, large bulk density, high normal temperature flexural strength and compressive strength, and excellent 1300 ℃ high temperature flexural strength.
As can be seen from FIGS. 1-3, the materials of examples 1, 2 and 3 were subjected to an erosion experiment at 1200 ℃ for 12 hours with sodium sulfate-containing slag by a static crucible method, and after crucible erosion, the crucible profile was clear and complete without obvious erosion phenomenon.
As can be seen from fig. 4 and 5, the non-iron-aluminum spinel and the sample of example 2 are both composed of the erosion-penetrated layer CPL and the raw brick layer UL, and the erosion-penetrated layer is formed by the raw slag (Na 2 SO 4 ) The erosion penetration of the raw brick layer becomes denser, and the porosity of the raw brick layer is relatively higher; along with FeAl 2 O 4 The depth of the erosion-penetration layer of the test specimen was reduced from 5.4mm to 2.4mm. The corrosion resistance of the slag containing sodium sulfate is excellent.
FIG. 6 shows the relative content (wt%) of Na element at various depths in the etched samples. The penetration depth of the slag into the refractory material was expressed by analyzing the Na element distribution at various locations in the erosion samples of the comparative example (not doped with hercynite) and example 2 using an energy spectrometer (EDS) dotting analysis. As can be seen from FIG. 6, the erosion-permeated layer in example 2 has a smaller content of sodium element, a smaller erosion depth and a better erosion resistance to sodium sulfate slag.
The invention uses the regenerated refractory raw material electro-fused chrome corundum obtained by treating the aluminum-chrome slag for producing metal chrome as raw material, and adds a certain quantity of steel into the ingredientsThe fine jade powder or the fine powder and the chromium oxide fine powder generate chromium corundum solid solution in situ in the sintering process, and meanwhile, the fine iron-aluminum spinel powder is introduced to generate a multi-element solid solution (Al in the sintering process 1-x-y Cr x Fe y ) 2 O 3 The prepared composite chrome corundum brick reduces Cr in the firing and using processes 6+ The production of the alloy promotes sintering, has good density, high strength at normal temperature and high temperature and better corrosion resistance of sodium sulfate-containing slag. The service life of the chemical salt-containing wastewater incinerator is prolonged, the recycling of resources is realized, the cost is saved, and the incinerator has better economic and social benefits.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The composite chrome corundum brick for the chemical salt-containing wastewater incinerator is characterized by being prepared from the following raw materials in percentage by mass and 2-5% of externally added binding agent aluminium dihydrogen phosphate; wherein the raw materials comprise:
the mass percentage of the regenerated refractory raw material electro-fused chrome corundum with the grain diameter less than or equal to 3mm is 35-50%;
electrofused white corundum with particle size less than or equal to 3mm, wherein w (Al 2 O 3 ) 99% or more, and 20-45% by mass;
chromium oxide micropowder with particle size less than or equal to 8 μm, wherein w (Cr 2 O 3 ) More than or equal to 99 percent, and the mass percentage is 4-12 percent;
fine powder of hercynite with particle size less than or equal to 31 mu m: 3-12% by mass;
alumina micropowder with particle size less than or equal to 4 μm, wherein w (Al 2 O 3 ) More than or equal to 99 percent and the mass percentage is 1 to 6 percent.
2. The composite chrome corundum brick for chemical salt-containing wastewater incinerator according to claim 1, characterized in that the following is adoptedThe electro-fused chrome corundum in the composite chrome corundum brick is obtained by treating aluminum-chrome slag generated by smelting metallic chrome, wherein w (Al 2 O 3 ) + w(Cr 2 O 3 )≥93%，w(Cr 2 O 3 )≥12%。
3. The composite chrome corundum brick for chemical industry salt-containing wastewater incinerator according to claim 1 characterized in that w (Al 2 O 3 )≥55%，w(Fe 2 O 3 )≥43%。
4. The preparation method of the composite chrome corundum brick for the chemical salt-containing wastewater incinerator is characterized by comprising the following steps of:
1) Mixing: weighing raw materials according to the proportion, and uniformly mixing in a mixer;
2) Trapping: filling the uniformly stirred raw materials into a sealing bag, and standing for 12-24h;
3) And (3) forming: weighing the trapped materials, filling the weighed materials into a die, and forming under 120-180MPa by using a hydraulic press;
4) And (3) drying: drying the formed green body for 24 hours at the drying temperature of 110-150 ℃;
5) Firing: and (5) sintering the dried sample at 1500-1600 ℃ and Wen Luzhong for 3-5 hours.
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