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CN-121609559-B - Titanium calcium aluminate refractory material with aluminum titanium slag as raw material and preparation method thereof

CN121609559BCN 121609559 BCN121609559 BCN 121609559BCN-121609559-B

Abstract

The invention relates to the technical field of materials, in particular to a titanium calcium aluminate refractory material taking aluminum titanium slag as a raw material and a preparation method thereof, and the material comprises the aluminum titanium slag, industrial alumina, modified zirconium magnesium powder, modified lanthanum yttrium powder, activated alumina and boric acid; according to the invention, the modified zirconium magnesium powder and the modified lanthanum yttrium powder are cooperated to resist fluoride ion erosion, and the activated alumina enhances the cooperated fluoride resistance function of the modified powder, so that the fluoride erosion resistance of the calcium titanate refractory material in a fluoride-enriched refining slag environment is improved, and the service life is prolonged compared with that of a conventional calcium titanate refractory material.

Inventors

  • FENG LI
  • QU ZHIYI
  • BAI LIN
  • WANG HUAXIN
  • WEI KANG
  • XU JIULIN
  • ZHAO ZHONGHUI

Assignees

  • 锦州国泰实业有限公司

Dates

Publication Date
20260508
Application Date
20260202

Claims (6)

  1. 1. The calcium titanate refractory material is characterized by comprising, by weight, 900-1100 parts of aluminum-titanium slag, 50-150 parts of industrial alumina, 35-50 parts of modified zirconium-magnesium powder, 25-40 parts of modified lanthanum-yttrium powder, 6-9 parts of activated alumina and 8-15 parts of boric acid; wherein the modified zirconium magnesium powder is composite powder prepared by ball milling and calcining zirconium oxide, calcium carbonate, magnesium oxide and aluminum oxide; the modified lanthanum yttrium powder is composite powder prepared by ball milling and calcining lanthanum oxide, yttrium oxide and aluminum oxide; the dosage of the activated alumina is 8% -12% of the total mass of the modified zirconium magnesium powder and the modified lanthanum yttrium powder; the preparation method of the modified zirconium magnesium powder comprises the following steps: S11, weighing zirconium oxide, calcium carbonate, magnesium oxide and aluminum oxide, placing the zirconium oxide, the calcium carbonate, the magnesium oxide and the aluminum oxide into a polytetrafluoroethylene ball milling tank, adding grinding balls and absolute ethyl alcohol, ball milling, and separating to obtain slurry A; S12, rotary evaporating the slurry A until ethanol is completely removed, transferring the slurry A into a high-purity alumina crucible, placing the high-purity alumina crucible into a high-temperature muffle furnace, heating to 500 ℃ and preserving heat, continuously heating to 1200 ℃ and preserving heat, naturally cooling to room temperature along with the furnace, taking out, grinding, sieving, and collecting undersize powder to obtain modified zirconium-magnesium powder; the preparation method of the modified lanthanum yttrium powder comprises the following steps: s21, immediately weighing and using lanthanum oxide after calcining, respectively weighing lanthanum oxide, yttrium oxide and aluminum oxide, placing the lanthanum oxide, yttrium oxide and aluminum oxide in a polytetrafluoroethylene ball milling tank, adding grinding balls and absolute ethyl alcohol, ball milling, and separating to obtain slurry B; S22, rotationally evaporating the slurry B to dryness, placing the slurry B into a high-purity alumina crucible, placing the high-purity alumina crucible into a muffle furnace, heating to 500 ℃ and preserving heat, continuously heating to 1150 ℃ and preserving heat, cooling to room temperature along with the furnace, taking out, grinding, sieving, immediately sealing and preserving in a dryer to obtain the modified lanthanum yttrium powder.
  2. 2. The calcium titanate refractory material with aluminum-titanium slag as a raw material according to claim 1, wherein the aluminum-titanium slag is metallurgical waste slag powder containing Al 2 O 3 、TiO 2 and CaO, and the content of Al 2 O 3 is more than or equal to 65%, the content of TiO 2 is more than or equal to 8% and the content of CaO is less than or equal to 15% by mass.
  3. 3. The calcium titanate refractory material with aluminum-titanium slag as a raw material according to claim 1, wherein the industrial alumina is alpha-Al 2 O 3 powder, and the grain size D50 is 1-10 μm.
  4. 4. The calcium titanate refractory material with aluminum-titanium slag as a raw material according to claim 1, wherein the activated alumina is gamma-Al 2 O 3 powder, the specific surface area is more than or equal to 200m 2 /g, the particle size D50 is 20-50nm, and the purity is more than or equal to 99.5%.
  5. 5. The calcium titanate refractory material with aluminum-titanium slag as raw material of claim 1, wherein the boric acid is of an analytical grade with a purity of 99.5% or more.
  6. 6. The method for preparing a calcium titanate refractory material from aluminum-titanium slag as claimed in any one of claims 1 to 5, comprising the steps of: s1, preparing a mixture, namely placing modified zirconium magnesium powder, modified lanthanum yttrium powder, activated alumina and boric acid into a high-speed mixer, and premixing for 10min to obtain a premix, adding the premix, aluminum titanium slag and industrial alumina into the mixer together, dry-mixing for 20min, adding calcium aluminate cement and water, and continuing wet mixing for 15min until the materials are uniform and plastic; S2, molding and drying, namely filling the mixture into a steel mold, pressing and molding on a hydraulic press, demolding the molded blank, transferring the molded blank into a blast drying oven, setting the temperature to be 60 ℃, drying for 12 hours, heating to be 110 ℃, and continuing to dry for 12 hours to obtain a dried blank; S3, sintering to prepare the refractory material, namely placing the dried blank body into a high-temperature kiln for sintering, wherein the sintering process comprises the steps of raising the temperature from room temperature to 300 ℃ at the rate of 2 ℃ per minute and preserving heat for 1h in the first stage, raising the temperature to 600 ℃ at the rate of 2 ℃ per minute and preserving heat for 1h in the second stage, raising the temperature to 1100 ℃ at the rate of 2 ℃ per minute and preserving heat for 1h in the third stage, raising the temperature to 1250 ℃ at the rate of 1.5 ℃ per minute and preserving heat for 2h in the fourth stage, raising the temperature to 1480 ℃ at the rate of 1 ℃ per minute and preserving heat for 4h in the fifth stage, lowering the temperature to 1000 ℃ at the rate of 2 ℃ per minute after the heat preservation is finished, and then naturally cooling the furnace to the room temperature by closing a heating power supply, thereby obtaining the calcium titanate refractory material taking aluminum titanium slag as a raw material.

Description

Titanium calcium aluminate refractory material with aluminum titanium slag as raw material and preparation method thereof Technical Field The invention relates to the technical field of materials, in particular to a titanium calcium aluminate refractory material taking aluminum titanium slag as a raw material and a preparation method thereof. Background The method is characterized in that aluminum titanium slag is used as a main raw material, a solid phase reaction sintering method is adopted to prepare a titanium calcium aluminate refractory material, and the titanium calcium aluminate refractory material is an important way for recycling industrial solid waste and producing high-performance refractory products, in the process, a sodium-containing compound (such as borax) with low cost is often added to be used as a fluxing agent to promote sintering, however, when the sodium-containing refractory material is applied to a furnace lining, an air brick and other parts of ladle refining (in particular an LF furnace), fluorite (CaF 2) added for optimizing a desulfurization effect in the refining process reacts with sodium ions (Na +) in the material at a high temperature to generate low-melting-point sodium fluoride (NaF), and a grain boundary phase of the refractory material is washed and dissolved, so that the structure is rapidly loosened, the high-temperature strength is suddenly reduced, and the service life is shortened. To solve the above problems caused by the reaction of sodium and fluorine, those skilled in the art use a sodium-free or low-sodium composite flux in the preparation stage to avoid rapid attack by sodium ions introduced by the material itself. However, the inventor finds that even if the calcium titanate refractory material prepared by adopting the non-sodium fluxing agent is used in the environment of fluorite-rich CaO-SiO 2-Al2O3 -based refined slag in the LF furnace for a long time, the damage speed is relieved, but the damage speed is still faster. Intensive studies have found that fluoride ions (F -) in the refining slag have extremely strong permeability and reactivity, can directly attack and destroy silicate and other binding phases at the grain boundaries of the refractory material, gradually depolymerize grain boundary networks by forming volatile SiF 4 or low-melting fluorosilicate intermediate products, and finally also lead to structural weakening and exfoliation of the material. Disclosure of Invention (1) Technical problem to be solved The invention aims to provide a calcium titanate refractory material with aluminum titanium slag as a raw material and a preparation method thereof, so as to solve the problem that fluoride ions in refining slag damage the refractory material when an LF furnace is in service. (2) Technical proposal In order to achieve the aim, on the one hand, the invention provides a titanium calcium aluminate refractory material taking aluminum titanium slag as a raw material, which comprises, by weight, 900-1100 parts of aluminum titanium slag, 50-150 parts of industrial alumina, 35-50 parts of modified zirconium magnesium powder, 25-40 parts of modified lanthanum yttrium powder, 6-9 parts of activated alumina and 8-15 parts of boric acid; wherein the modified zirconium magnesium powder is composite powder prepared by ball milling and calcining zirconium oxide, calcium carbonate, magnesium oxide and aluminum oxide; the modified lanthanum yttrium powder is composite powder prepared by ball milling and calcining lanthanum oxide, yttrium oxide and aluminum oxide; the dosage of the activated alumina is 8% -12% of the total mass of the modified zirconium magnesium powder and the modified lanthanum yttrium powder. Further, the aluminum-titanium slag is metallurgical waste slag powder containing Al 2O3、TiO2 and CaO, and the content of Al 2O3 is more than or equal to 65%, the content of TiO 2 is more than or equal to 8% and the content of CaO is less than or equal to 15% by mass. Further, the industrial alumina is alpha-Al 2O3 powder, and the particle size D50 is 1-10 mu m. Further, the active alumina is gamma-Al 2O3 powder, the specific surface area is more than or equal to 200m 2/g, the particle size D50 is 20-50nm, and the purity is more than or equal to 99.5%. Further, the boric acid is of an analytical grade, and the purity is more than or equal to 99.5%. Further, the preparation method of the modified zirconium magnesium powder comprises the following steps: S11, weighing zirconium oxide, calcium carbonate, magnesium oxide and aluminum oxide, placing the zirconium oxide, the calcium carbonate, the magnesium oxide and the aluminum oxide into a polytetrafluoroethylene ball milling tank, adding grinding balls and absolute ethyl alcohol, ball milling, and separating to obtain slurry A; S12, rotary evaporating the slurry A until ethanol is completely removed, transferring the slurry A into a high-purity alumina crucible, placing the high-purity alumina crucible