High-zirconium brick with high erosion resistance and preparation method thereof

Abstract

The invention provides a high-zirconium brick with high erosion resistance and a preparation method thereof, and belongs to the technical field of refractory materials, and the high-zirconium brick with high erosion resistance comprises the following components in parts by weight: 91-93 parts of zirconium oxide, 5-7 parts of silicon dioxide, 0.5-1 part of aluminum oxide, 2-3 parts of sodium oxide, 3-4 parts of praseodymium-doped calcium titanate and 3-3.5 parts of nickel chloride. After oxygen blowing by oxygen blowing equipment, the corrosion resistance of the prepared high-zirconium brick and the corrosion resistance maintaining capability under the high-humidity environment acceleration condition can be effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of refractories, and particularly relates to a high zirconia brick with high erosion resistance and a preparation method thereof. Background Art

[0002] Cast refractories have a series of advantages such as good chemical stability, high temperature thermal stability, high glass phase exudation temperature, and little pollution to the glass melt, and are widely used in glass furnaces. Different from sintered refractories, cast refractories are prepared by a melting-casting process to form a dense structure in which crystal grains are connected by an intergranular glass phase, so they have a higher density and better corrosion resistance to molten glass. Cast refractories containing more than 80 wt% zirconia (such as cast zirconia bricks) are usually called high zirconia refractories (high zirconia bricks), which are key materials for glass furnaces.

[0003] The high temperature (>1000 °C) environment inside the glass furnace causes water to evaporate rapidly, and free water hardly exists. High zirconia bricks are usually not exposed to a high humidity environment. However, during the furnace shutdown and maintenance period, after the furnace cools down, the outside humid air seeps into the furnace, which can form a hygroscopic / high humidity environment.

[0004] In the preparation of high zirconia bricks, sodium oxide is often added as a flux to lower the melting temperature of raw materials, promote the melting process, improve the fluidity of the high temperature melt, and facilitate casting and molding. However, sodium oxide usually forms a glass phase with silicon dioxide, etc., but there will also be residual free sodium oxide, and its alkalinity will increase the sensitivity to moisture, triggering a hydration reaction, and the hydration reaction will gradually increase the porosity inside the high zirconia brick, reduce the density of the high zirconia brick, and lead to the attenuation of the erosion resistance of the high zirconia brick. Summary of the Invention

[0005] To solve the problems in the background art, the present invention provides a high zirconia brick with high erosion resistance and a preparation method thereof, which can effectively improve the erosion resistance of the prepared high zirconia brick and the ability to maintain the erosion resistance under the accelerated conditions of a high humidity environment.

[0006] To achieve the above object, in the first aspect, the present invention provides a high zirconia brick with high erosion resistance, which comprises the following components in parts by weight: 91-93 parts of zirconia, 5-7 parts of silicon dioxide, 0.5-1 part of aluminum oxide, 2-3 parts of sodium oxide, 3-4 parts of praseodymium-doped calcium titanate, and 3-3.5 parts of nickel chloride.

[0007] Further, it comprises the following components in parts by weight: 92 parts of zirconia, 6 parts of silicon dioxide, 0.8 part of aluminum oxide, 2.5 parts of sodium oxide, 3.5 parts of praseodymium-doped calcium titanate, and 3.2 parts of nickel chloride

[0008] Further, the preparation method of the praseodymium-doped calcium titanate is as follows:

[0009] A1. At room temperature, 4.2 g of calcium acetate was weighed and dissolved in 15-20 mL of distilled water to obtain a calcium acetate solution; 0.053 g of praseodymium nitrate was dissolved in 8-12 mL of distilled water to obtain a praseodymium nitrate solution; 3.14 g of sodium dodecylbenzene sulfonate was dissolved in 30-40 mL of distilled water to obtain a sodium dodecylbenzene sulfonate solution; then the calcium acetate solution, the praseodymium nitrate solution and the sodium dodecylbenzene sulfonate solution were mixed to obtain a first mixed solution;

[0010] A2, add 5.4 mL of tetrabutyl titanate to the first mixed solution obtained in A1, stir, pour into a reactor, fill with distilled water to 70-80% of the volume of the reactor, and after hydrothermal reaction, obtain black powder;

[0011] A3. Wash the black powder obtained in A2 with distilled water and anhydrous ethanol for multiple times, dry it in a drying oven, and then calcine it in a muffle furnace to obtain the praseodymium-doped calcium titanate.

[0012] Furthermore, in A2, the stirring speed is 220-240 r / min, and the stirring time is 30 min.

[0013] Furthermore, in A3, the drying temperature is 50±5°C and the drying time is 50-70min.

[0014] Furthermore, in A3, the calcination temperature is 400±10°C, and the calcination time is 5.5-6h.

[0015] In a second aspect, the present invention provides a method for preparing the above-mentioned high-zirconium brick with high corrosion resistance, comprising the following steps:

[0016] S1, mixing zirconium oxide, silicon dioxide, aluminum oxide, sodium oxide, praseodymium-doped calcium titanate and nickel chloride to obtain a mixture;

[0017] S2, placing the mixed material obtained in S1 into an electric arc furnace, and blowing oxygen into the electric arc furnace to obtain a molten material;

[0018] S3, pouring the molten material obtained in S2 and annealing and cooling to obtain the high zirconium brick with high corrosion resistance.

[0019] Furthermore, in S2, the oxygen blowing time is 5 minutes and the melting time is 200 minutes.

[0020] Furthermore, in S2, the oxygen blowing treatment is performed at a temperature of 2800-3000°C.

[0021] Furthermore, in S2, the oxygen lance used for the oxygen blowing treatment is a metal ceramic oxygen lance or a high-density carbonaceous oxygen lance.

[0022] This application has the following beneficial effects:

[0023] The raw material components of the present invention include sodium oxide, nickel chloride and praseodymium-doped calcium titanate. The nickel chloride decomposes into nickel ions and chloride ions at high temperature. On the one hand, free chloride ions combine with calcium ions in praseodymium-doped calcium titanate to generate stable calcium chloride, which greatly reduces the possibility of chloride ions and sodium ions generating sodium chloride that is easily hygroscopic and soluble, and blocks the generation path of sodium chloride. On the other hand, although the partial replacement of zirconium ions in the high-zirconium brick lattice by nickel ions will cause charge imbalance, praseodymium ions (entering the calcium titanate lattice by praseodymium doping) can stabilize the lattice structure through charge compensation (such as forming oxygen vacancies), effectively avoiding the appearance of microcracks or pore channels.

[0024] Pr-doped calcium titanate TiO 6 The hydroxyl groups on the octahedral surface combine with free sodium ions to form a stable Na-O-Ti-Pr complex, which inhibits the direct contact between sodium ions and water; at the same time, nickel chloride and praseodymium-doped calcium titanate form a low-melting-point eutectic phase (such as NiO-CaO-TiO 2 -PrO x ), fill the grain boundary pores of high zirconium bricks, reduce the porosity of high zirconium bricks, significantly reduce the water penetration path, and improve the corrosion resistance retention rate of high zirconium bricks in high humidity environment.

[0025] Compared with the traditional high zirconium brick production, which does not have the oxygen blowing production link, the present invention adds oxygen blowing equipment (metal ceramic oxygen gun or high-density carbonaceous oxygen gun) during the production of high zirconium bricks, changes the production process, can improve the density of the bricks, and make the composition of the bricks more uniform. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 , a comparative trend chart of the test data of the initial erosion amount of the high zirconium brick samples obtained in Examples 1 to 3 of the present invention and Comparative Examples 1 to 3 and the erosion amount after high humidity environment treatment;

[0027] Figure 2 , a comparative trend chart of the erosion growth rate data of high zirconium brick samples (under accelerated conditions in a high humidity environment) obtained from Examples 1 to 3 of the present invention and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0028] The present application is further described in detail below with reference to the embodiments.

[0029] Unless otherwise specified, the raw materials used in the examples and comparative examples of the present application are all commercially available.

[0030] Example 1: (1) Preparation of praseodymium-doped calcium titanate, the preparation method is as follows:

[0031] A1. At room temperature, 4.2 g of calcium acetate was weighed and dissolved in 18 mL of distilled water to obtain a calcium acetate solution; 0.053 g of praseodymium nitrate was dissolved in 10 mL of distilled water to obtain a praseodymium nitrate solution; 3.14 g of sodium dodecylbenzene sulfonate was dissolved in 38 mL of distilled water to obtain a sodium dodecylbenzene sulfonate solution; and the calcium acetate solution, the praseodymium nitrate solution and the sodium dodecylbenzene sulfonate solution were mixed to obtain a first mixed solution.

[0032] A2. Add 5.4 mL of tetrabutyl titanate to the first mixed solution obtained in A1, stir at a speed of 230 r / min for 30 min, then pour into a reactor, fill with distilled water to 75% of the volume of the reactor, heat to about 180°C at a rate of 5°C / min, high temperature promotes lattice doping and crystallinity, maintain for 18 hours to ensure that praseodymium ions are fully incorporated into the calcium titanate lattice and that the crystal growth is complete. After the hydrothermal reaction, cool naturally to room temperature to avoid structural defects caused by sudden cooling to obtain a black powder.

[0033] A3. Wash the black powder obtained in A2 three times with distilled water and anhydrous ethanol respectively, then dry it in a drying oven at a temperature of about 50°C for about 60 minutes, and then calcine it in a muffle furnace at a temperature of about 400°C for about 5.8 hours. After calcination, praseodymium-doped calcium titanate is obtained.

[0034] (2) Preparation of high zirconium bricks with high corrosion resistance, the preparation method is as follows:

[0035] S1. By weight, 92 parts of zirconium oxide (purity ≥ 95% and particle size 1-5 μm), 6 parts of silicon dioxide (≤ 10 μm), 0.8 parts of aluminum oxide (≤ 10 μm), 2.5 parts of sodium oxide, 3.5 parts of praseodymium-doped calcium titanate and 3.2 parts of nickel chloride were mixed. Nickel chloride (analytical grade) was purchased from Shenyang Ketuo Chemical Co., Ltd. A planetary ball mill was used with alcohol as the medium, a ball-to-material ratio of 3:1, a rotation speed of 300 rpm, and a time of 4-6 hours to ensure that the raw materials were mixed evenly. Spray drying was performed to prepare a mixture with good fluidity for subsequent melting.

[0036] S2, putting the mixed material obtained in S1 into an electric arc furnace, and blowing oxygen into the electric arc furnace. The oxygen lance used for the oxygen blowing treatment is a metal ceramic oxygen lance, and the oxygen blowing treatment is carried out at a temperature of 2900° C. (under 5 atmospheres) and the oxygen blowing time is maintained for 5 minutes, and the melting time is 200 minutes to obtain a molten material.

[0037] S3. Pour the molten material obtained in S2 (after the temperature is reduced to about 2000 °C), and conduct annealing and cooling in an incubator. The temperature control of the annealing and cooling adopts gradient cooling, 100 °C / h (10 h) → 50 °C / h (16 h) → 20 °C / h, to balance stress release and production cycle, reduce segregation and reduce cracks to improve the yield. Until the temperature drops to about 25 °C, avoid residual thermal stress, then the annealing can be ended, taken out, and after passing the inspection, it is then subjected to cutting and grinding processing to obtain a high-zirconia brick with high erosion resistance.

[0038] Example 2: The difference between this example and Example 1 lies in that in the preparation of the high-zirconia brick with high erosion resistance, the dosage ratios of the raw material components are different.

[0039] Specifically, (1) Prepare praseodymium-doped calcium titanate, and its preparation method is as follows:

[0040] A1. At room temperature, weigh 4.2 g of calcium acetate and dissolve it in 18 mL of distilled water to obtain a calcium acetate solution; dissolve 0.053 g of praseodymium nitrate in 10 mL of distilled water to obtain a praseodymium nitrate solution; dissolve 3.14 g of sodium dodecylbenzenesulfonate in 38 mL of distilled water to obtain a sodium dodecylbenzenesulfonate solution; then mix the calcium acetate solution, praseodymium nitrate solution and sodium dodecylbenzenesulfonate solution to obtain a first mixed solution.

[0041] A2. Add 5.4 mL of tetrabutyl titanate to the first mixed solution obtained in A1, the stirring speed is 230 r / min, the stirring time is 30 min, then pour it into a reaction kettle, fill it with distilled water to 75% of the volume of the reaction kettle, and heat it to about 180 °C at a rate of 5 °C / min. High temperature promotes lattice doping and crystallinity, keep it for 18 h to ensure that praseodymium ions are fully incorporated into the calcium titanate lattice, and at the same time ensure the complete growth of crystals. After the hydrothermal reaction, cool it naturally to room temperature to avoid structural defects caused by rapid cooling, and obtain a black powder.

[0042] A3. Wash the black powder obtained in A2 three times with distilled water and anhydrous ethanol respectively, then put it into a drying oven for drying, the drying temperature is about 50 °C, the drying time is about 60 min, and then put it into a muffle furnace for calcination, the calcination temperature is about 400 °C, the calcination time is about 5.8 h. After the calcination is completed, praseodymium-doped calcium titanate is obtained.

[0043] (2) Prepare a high-zirconia brick with high erosion resistance, and its preparation method is as follows:

[0044] S1. By weight, mix 91 parts of zirconia, 5 parts of silicon dioxide, 0.5 part of aluminum oxide, 2 parts of sodium oxide, 3 parts of praseodymium-doped calcium titanate and 3 parts of nickel chloride to obtain a mixed material.

[0045] S2. Put the mixed material obtained in S1 into an electric arc furnace and perform oxygen blowing treatment in the electric arc furnace. The oxygen gun used for the oxygen blowing treatment is a metal ceramic oxygen gun. The oxygen blowing treatment is performed at a temperature of 2800° C., the oxygen blowing time is 5 minutes, and the melting time is 200 minutes to obtain a molten material.

[0046] S3, pouring the molten material obtained in S2 and annealing and cooling to obtain high zirconium bricks with high corrosion resistance.

[0047] Example 3: The difference between this example and Example 1 is that in the preparation of high-zirconium bricks with high corrosion resistance, the dosage ratio of each raw material component is different.

[0048] Specifically, (1) preparing praseodymium-doped calcium titanate, the preparation method thereof is as follows:

[0049] A1. At room temperature, 4.2 g of calcium acetate was weighed and dissolved in 18 mL of distilled water to obtain a calcium acetate solution; 0.053 g of praseodymium nitrate was dissolved in 10 mL of distilled water to obtain a praseodymium nitrate solution; 3.14 g of sodium dodecylbenzene sulfonate was dissolved in 38 mL of distilled water to obtain a sodium dodecylbenzene sulfonate solution; and the calcium acetate solution, the praseodymium nitrate solution and the sodium dodecylbenzene sulfonate solution were mixed to obtain a first mixed solution.

[0050] A2. Add 5.4 mL of tetrabutyl titanate to the first mixed solution obtained in A1, stir at a speed of 230 r / min for 30 min, then pour into a reactor, fill with distilled water to 75% of the volume of the reactor, heat to about 180°C at a rate of 5°C / min, high temperature promotes lattice doping and crystallinity, maintain for 18 hours to ensure that praseodymium ions are fully incorporated into the calcium titanate lattice and that the crystal growth is complete. After the hydrothermal reaction, cool naturally to room temperature to avoid structural defects caused by sudden cooling to obtain a black powder.

[0051] A3. Wash the black powder obtained in A2 three times with distilled water and anhydrous ethanol respectively, then dry it in a drying oven at a temperature of about 50°C for about 60 minutes, and then calcine it in a muffle furnace at a temperature of about 400°C for about 5.8 hours. After calcination, praseodymium-doped calcium titanate is obtained.

[0052] (2) Preparation of high zirconium bricks with high corrosion resistance, the preparation method is as follows:

[0053] S1. Mix 93 parts of zirconium oxide, 7 parts of silicon dioxide, 1 part of aluminum oxide, 3 parts of sodium oxide, 4 parts of praseodymium-doped calcium titanate and 3.5 parts of nickel chloride by weight to obtain a mixture.

[0054] S2. Put the mixed material obtained in S1 into an electric arc furnace and perform oxygen blowing treatment in the electric arc furnace. The oxygen gun used for the oxygen blowing treatment is a metal ceramic oxygen gun. The oxygen blowing treatment is performed at a temperature of 3000° C., the oxygen blowing time is 5 minutes, and the melting time is 200 minutes to obtain a molten material.

[0055] S3, pouring the molten material obtained in S2 and annealing and cooling to obtain high zirconium bricks with high corrosion resistance.

[0056] Comparative Example 1: The difference between this comparative example and Example 1 is that praseodymium-doped calcium titanate and nickel chloride are deleted from the raw materials for preparing high-zirconium bricks.

[0057] Specifically, a high-zirconium brick with high corrosion resistance is prepared, and the preparation method is as follows:

[0058] S1. Mix 92 parts of zirconium oxide, 6 parts of silicon dioxide, 0.8 parts of aluminum oxide and 2.5 parts of sodium oxide by weight to obtain a mixture.

[0059] S2. Put the mixed material obtained in S1 into an electric arc furnace and perform oxygen blowing treatment in the electric arc furnace. The oxygen gun used for the oxygen blowing treatment is a metal ceramic oxygen gun. The oxygen blowing treatment is performed at a temperature of 2900° C., the oxygen blowing time is 5 minutes, and the melting time is 200 minutes to obtain a molten material.

[0060] S3, pouring the molten material obtained in S2 and annealing and cooling to obtain high zirconium bricks with high corrosion resistance.

[0061] Comparative Example 2: The difference between this comparative example and Example 1 is that praseodymium-doped calcium titanate is deleted from the raw materials for preparing high-zirconium bricks.

[0062] Specifically, a high-zirconium brick with high corrosion resistance is prepared, and the preparation method is as follows:

[0063] S1. Mix 92 parts of zirconium oxide, 6 parts of silicon dioxide, 0.8 parts of aluminum oxide, 2.5 parts of sodium oxide and 3.2 parts of nickel chloride by weight to obtain a mixture.

[0064] S2. Put the mixed material obtained in S1 into an electric arc furnace and perform oxygen blowing treatment in the electric arc furnace. The oxygen gun used for the oxygen blowing treatment is a metal ceramic oxygen gun. The oxygen blowing treatment is performed at a temperature of 2900° C., the oxygen blowing time is 5 minutes, and the melting time is 200 minutes to obtain a molten material.

[0065] S3, pouring the molten material obtained in S2 and annealing and cooling to obtain high zirconium bricks with high corrosion resistance.

[0066] Comparative Example 3: The difference between this comparative example and Example 1 is that nickel chloride is deleted from the raw materials for preparing high zirconium bricks.

[0067] Specifically, a high-zirconium brick with high corrosion resistance is prepared, and the preparation method is as follows:

[0068] S1. Mix 92 parts of zirconium oxide, 6 parts of silicon dioxide, 0.8 parts of aluminum oxide, 2.5 parts of sodium oxide and 3.5 parts of praseodymium-doped calcium titanate by weight to obtain a mixture.

[0069] S2. Put the mixed material obtained in S1 into an electric arc furnace and perform oxygen blowing treatment in the electric arc furnace. The oxygen gun used for the oxygen blowing treatment is a metal ceramic oxygen gun. The oxygen blowing treatment is performed at a temperature of 2900° C., the oxygen blowing time is 5 minutes, and the melting time is 200 minutes to obtain a molten material.

[0070] S3, pouring the molten material obtained in S2 and annealing and cooling to obtain high zirconium bricks with high corrosion resistance.

[0071] Test example: Test object: High zirconium brick samples were prepared according to Example 1-Example 3 and Comparative Example 1-Comparative Example 3; the sample specifications were (10±0.05) mm×(10±0.05) mm×(70±0.5) mm.

[0072] Test items and methods: ① Under the condition of ordinary soda-lime glass melt at 1500℃, measure the glass liquid erosion amount of each test object sample under static state for 24 hours (the erosion amount at half of the liquid surface line) according to the standard JC / T806-2013, and record it as the initial erosion amount A 0 (mm), the smaller the value, the stronger the initial corrosion resistance of the sample;

[0073] ② Take new test samples of each object, soak them in 80℃ water for 3 days (accelerated condition of high humidity environment), dry them naturally, and then measure the erosion amount of glass liquid under static state for 24 hours (erosion amount at half of the liquid level line) under the condition of ordinary soda-lime glass melt at 1500℃ according to standard JC / T806-2013, and record it as the erosion amount after high humidity environment treatment A 1 (mm); Then, calculate the erosion growth rate X (%), X = (A 1 -A 0 ) / A 0 ×100%, the smaller the value, the stronger the ability of the corresponding sample to maintain anti-corrosion performance (under accelerated conditions of high humidity environment).

[0074] Test results: See Table 1.

[0075] Table 1. Test data of the experimental example

[0076]

[0077] Result analysis: Analyze Example 1-Example 3 and combine the data in Table 1 and Figure 1-Figure 2It can be seen that the 24h initial erosion amount of the high zirconium brick samples prepared by the present invention (Example 1-Example 3) is as low as below 0.74mm; after being treated under the accelerated conditions of the high humidity environment in the test example, the erosion growth rate is as low as below 4.11%, indicating that the high zirconium bricks prepared by the present invention have excellent corrosion resistance and have excellent corrosion resistance retention ability under the accelerated conditions of the high humidity environment.

[0078] Analyze Example 1 and Comparative Examples 1-3 and combine the data in Table 1 and Figure 1-Figure 2 By comparing Comparative Example 1 and Comparative Example 2, it can be seen that compared with Comparative Example 1 (sodium oxide is included in the raw material components), nickel chloride is added to the raw material components of Comparative Example 2 alone. As a result, the initial erosion amount of the high-zirconium brick sample obtained is increased (i.e., the corrosion resistance is reduced), and the corrosion growth rate after being treated under high-humidity environment accelerated conditions is also increased (i.e., the ability to maintain corrosion resistance under high-humidity environment accelerated conditions is reduced). This is because after adding nickel chloride alone, it decomposes into nickel ions and chloride ions at high temperatures; on the one hand, free chloride ions combine with sodium ions in sodium oxide to form sodium chloride, which remains in the material after sintering. When the material is exposed to a humid environment, sodium chloride absorbs moisture and dissolves and releases sodium ions, increasing the probability of sodium ions contacting water and aggravating the hydration reaction of sodium oxide; on the other hand, nickel ions partially replace zirconium ions in the zirconium brick lattice, resulting in charge imbalance and lattice distortion, reducing the density of high-zirconium bricks, forming microcracks or pore channels, providing a path for water penetration, and accelerating the hydration reaction of sodium oxide.

[0079] By comparing Comparative Example 1 and Comparative Example 3, it can be seen that compared with Comparative Example 1 (sodium oxide is included in the raw material components), the raw material components of Comparative Example 3 alone add the praseodymium-doped calcium titanate of the present invention, resulting in a decrease in the initial erosion amount of the high-zirconium brick sample (i.e., the corrosion resistance is improved), and the corrosion growth rate after treatment under high-humidity environment accelerated conditions is also reduced (i.e., the ability to maintain corrosion resistance under high-humidity environment accelerated conditions is improved). Combined with Example 1 for comparison, it can be seen that when sodium oxide is included in the raw material components for preparing high-zirconium bricks, adding nickel chloride and the praseodymium-doped calcium titanate of the present invention at the same time can produce a synergistic effect, synergistically improving the corrosion resistance of the high-zirconium bricks and the ability to maintain corrosion resistance under high-humidity environment accelerated conditions.

[0080] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0081] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A high zirconium brick with high corrosion resistance, characterized in that: The invention comprises the following components by weight: 91-93 parts of zirconium oxide, 5-7 parts of silicon dioxide, 0.5-1 parts of aluminum oxide, 2-3 parts of sodium oxide, 3-4 parts of praseodymium-doped calcium titanate and 3-3.5 parts of nickel chloride.

2. The high-zirconium brick with high corrosion resistance according to claim 1 is characterized in that: The composition includes the following components by weight: 92 parts of zirconium oxide, 6 parts of silicon dioxide, 0.8 parts of aluminum oxide, 2.5 parts of sodium oxide, 3.5 parts of praseodymium-doped calcium titanate and 3.2 parts of nickel chloride.

3. The high-zirconium brick with high corrosion resistance according to claim 1 or 2, characterized in that: The preparation method of the praseodymium-doped calcium titanate is as follows: A1. At room temperature, 4.2 g of calcium acetate was weighed and dissolved in 15-20 mL of distilled water to obtain a calcium acetate solution; 0.053 g of praseodymium nitrate was dissolved in 8-12 mL of distilled water to obtain a praseodymium nitrate solution; 3.14 g of sodium dodecylbenzene sulfonate was dissolved in 30-40 mL of distilled water to obtain a sodium dodecylbenzene sulfonate solution; then the calcium acetate solution, the praseodymium nitrate solution and the sodium dodecylbenzene sulfonate solution were mixed to obtain a first mixed solution; A2, add 5.4 mL of tetrabutyl titanate to the first mixed solution obtained in A1, stir, pour into a reactor, fill with distilled water to 70-80% of the volume of the reactor, and after hydrothermal reaction, obtain black powder; A3. Wash the black powder obtained in A2 with distilled water and anhydrous ethanol for multiple times, dry it in a drying oven, and then calcine it in a muffle furnace to obtain the praseodymium-doped calcium titanate.

4. The high-zirconium brick with high corrosion resistance according to claim 2 is characterized in that: In A2, the stirring speed is 220-240 r / min and the stirring time is 30 min.

5. The high-zirconium brick with high corrosion resistance according to claim 1 is characterized in that: In A3, the drying temperature is 50±5°C and the drying time is 50-70min.

6. The high-zirconium brick with high corrosion resistance according to claim 1 is characterized in that: In A3, the calcination temperature is 400±10°C and the calcination time is 5.5-6h.

7. A method for preparing a high-zirconium brick with high corrosion resistance as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: S1, mixing zirconium oxide, silicon dioxide, aluminum oxide, sodium oxide, praseodymium-doped calcium titanate and nickel chloride to obtain a mixture; S2, placing the mixed material obtained in S1 into an electric arc furnace, and blowing oxygen into the electric arc furnace to obtain a molten material; S3, pouring the molten material obtained in S2 and annealing and cooling to obtain the high zirconium brick with high corrosion resistance.

8. The method for preparing high-zirconium bricks with high corrosion resistance according to claim 7, characterized in that: In S2, the oxygen blowing time is 5 minutes and the melting time is 200 minutes.

9. The method for preparing high-zirconium bricks with high corrosion resistance according to claim 7, characterized in that: In S2, oxygen blowing treatment is performed at a temperature of 2800-3000°C.

10. The method for preparing high-zirconium bricks with high corrosion resistance according to claim 7, characterized in that: In S2, the oxygen lance used for the oxygen blowing treatment is a metal ceramic oxygen lance or a high-density carbonaceous oxygen lance.

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