TW201245096A - Siliceous refractory brick - Google Patents

Abstract

The present invention provides a siliceous refractory brick which is made by mixing a matrix and a binder together, pressing for molding and carrying out firing. Based on the weight of the matrix, the matrix contains 80-90 wt% electrically molten silica sand and 10-20 wt% clay adjuvant. Based on 100 parts by weight of the matrix, the binder contains 3-5 parts by weight of phosphate salt. The siliceous refractory brick is featured by having zero expansion and is suitable for the heating wall of a coke oven.

Description

201245096 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a refractory material, and more particularly to a enamel fire resistance. [Prior Art] Tantalum refractory brick is a widely used refractory material with high load deformation temperature (1640~1680. 〇, close to phosphorus quartz, high melting point of cristobalite (1690~1730 °C), and can be used at high temperature Maintaining its mechanical strength; among them, the electric melting stone Xibei is the main monument used in the heating wall of the current coke oven. The coke oven is subjected to severe temperature changes for a long time, the friction force when the internal coal is pushed, and the net load of each equipment. The load, as well as the stress generated by the thermal expansion of the masonry, may cause damage to the bricks that make up the coke oven, such as intrusion, spalling, damage, etc., and even large areas that are difficult to repair and shorten the service life. The coke oven has been in operation for 26 years, and most of the furnace end wall refractory bricks have been destroyed. The first coke oven has been renovated since the end of 2001, and the Shiyue refractory monument has been introduced, in order to quickly heat up and work under severe temperature changes for a long time. It is necessary to shorten the construction period as much as possible so as not to affect the operation of the blast furnace. Most of the enamel refractory bricks used in the inner wall of the existing coke oven are made of electro-grinding eucalyptus as the substrate. In addition to the basic conditions of high load softening temperature, high refractoriness and high strength, refractory bricks have small thermal expansion coefficient, good thermal shock resistance, resistance to chemical intrusion (especially acid and chlorine), no cracks after rapid heating, etc. The advantage is therefore suitable for the heating wall of the coke oven. However, the main component of the monument is quartz, which is caused by the complicated volume change of quartz, which causes the thermal wall to have cracks and even peeling damage. It can be seen that the expansion problem of the enamel refractory brick and how to effectively improve the service life of the heating wall of the coke oven need to be achieved through research and development - an enamel refractory brick with zero expansion characteristics and various properties can meet the standard requirements. SUMMARY OF THE INVENTION In order to improve the problem of temperature rise and expansion of the existing enamel fire-resistant monument, it is necessary to take into account both thermal shock resistance and refractoriness. The inventors of the present invention developed a variety of tests with zero expansion characteristics, high heat resistance and good resistance. Thermal shock enamel refractory monument. It is therefore an object of the present invention to provide a enamel refractory brick by means of a matrix Mixture is mixed and compression-molded into a prepared baking; wherein the weight to the matrix, the matrix comprising electrically Rockstead f Xi sand 8〇~9〇

Wt% and clay adjuvant 〇 2 2 () wt%; the binder comprises 3 to 5 parts by weight of the phosphate based on the basis weight of the substrate. In 疋, the enamel refractory brick of the present invention comprises a specific proportion of smelting sand and clay auxiliaries to form a matrix and a specific component containing a salt-filling binder. The physical properties are in line with the requirements of the specification, and can maintain zero expansion characteristics in a rapid temperature rise and fall environment. [Embodiment] The stone refractory brick of the present invention is prepared by mixing a matrix with a binder and pressing the money; wherein, according to the weight of the matrix, the matrix comprises an electric lava stone 8G to 9〇wt% and clay adjuvant ig~2() plus %: The binder comprises 3 to 5 parts by weight of 201245096 parts by weight of the base of 1 GG by weight. Preferably, the total amount of the matrix is 100 wt%, and the electro-rultic sand comprises a first electro-rultic sand having a particle diameter of 1 to 3 mm, 3 to 4 wt%, and a particle diameter of 0.075. 1 mm of the first electric lava stone 25 to 37 wt%, and a particle size between 〇, 001~0.075 111111 electro-melting enamel micro-powder 2 〇 ~ 25 wish 1%. The particle size range of the fused silica is preferably 0.001 to 3 mm. When the particle size of the fused silica is more than 3 mm, the mechanical properties of the enamel refractory brick produced are not good. The phosphate may be, for example but not limited to, phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate, aluminum dihydrogen phosphate (ί^4), and the like. Preferably, the phosphate is monoaluminum phosphate. More preferably, the phosphate is an aqueous solution of aluminum dihydrogen phosphate having a concentration of 8 Torr to 9 (%). Preferably, the clay adjuvant comprises tantalum powder and clay, and the clay contains 20 to 30 wt% of Al2〇3' and 〇8~2 of 2%. If the content of Al2〇3 is too high, the sintering temperature will also increase, and the physical properties of the monument will be caused by the shirting. If the content of the barley 2〇3 is too low, the strength at high temperature will be insufficient. Fe2〇3 is a low melting material of refractory material. When the content of FhO3 is too high, there will be a low melting material on the surface after sintering, which will cause damage to the monument; 0.8~2 wt% of Fe2〇3 is contained. Although a small amount of low-melting material is produced after sintering, it helps to improve the physical properties of the monument. The clay may be, for example, woody soil, white clay, kaolin, or the like. Preferably, the clay is a golden soil. Preferably, the weight ratio of the tantalum powder to the clay ranges from 1:1 to 1:2. When the proportion of the clay is too low, the plasticity is poor, which has a negative impact on the forming yield of the subsequent stone brick; when the proportion of the clay is too high, since the clay is a mixture of 3 low melting materials, the low melting material Will affect the physical properties of the bricks 5 201245096 ring. When the phosphate is aluminum dihydrogen phosphate, the aluminum dihydrogen phosphate can be combined with Ah 〇 3 contained in the clay; when the enamel refractory brick is heated to 13 Torr. 〇, “ο” will be converted into a phosphorus-quartz type Α1Ρ〇4. When the temperature reaches 135〇〇c, the chemical bond between the two increases, and the low-temperature strength is significantly improved. The aluminum dihydrogen phosphate is used as a binder, except for the retention. The high refractoriness and service temperature of the slabs can significantly improve the mechanical strength of the slabs in low and medium temperature environments. In addition to low melting at high temperatures, it can also enhance thermal shock resistance and wear resistance. High temperature toughness and other properties necessary in a warm working environment. In addition, aluminum dihydrogen phosphate has water solubility at room temperature 'very easy to use. The preparation method of the enamel refractory brick of the present invention can be applied by a press forming process or a boring forming process. The machine forming process first needs to prepare the substrate, and then the substrate and the bonding agent are put into a machine (such as a friction machine forming machine) for kneading, molding, and sintering temperature of 800 to 1 〇〇〇t. Sintering is carried out in a range. The infusion molding process is to mix the substrate with the binder, and then into the mold, and finally to sinter at a sintering temperature range of 8 Torr to 1 Torr. The following examples are further illustrated, but it should be understood that the examples are for illustrative purposes only and are not to be construed as limiting the invention. <Examples> [Chemicals] 99% Electrolytic cerium sand, particle size 3~5 mm: purity 99%. 99/〇 electric melt sand 1~3 mm: purity 99%.

S 6 201245096 99% electro-grown sand, the particle size is 〇力 is ~丨min: purity 99%. 99/ό电融石夕砂' particle size is 0.Q01~〇.ου mm: purity 99%. Golden Gate soil: Contains Al2〇3 20 52 wt% ' and 125. Shi Xifen: The origin is Norway, model SF-971U. Dihydrogen phosphate: The origin is Taiwan, with a concentration of 5〇%.

[Example 1J] The electro-rultic sand was dry-blended with a clay excipient for 2 minutes to obtain a substrate comprising, by weight of the substrate, 90 wt% of yttrium sand and 10 wt% of clay adjuvant. α The total weight of the electric melting stone is 4 100 wt%, and the electric melting stone contains 37.5 wt% of the first electric melting stone with a particle size of 3 mm, and the particle diameter is 0.075~1. The second electrofusion of mm 27 27 27 5 〇 〇 / 0, and a particle size of 0.001 ~ 0.075 fused stone fine powder 25 correction%. The clay adjuvant t 3 Μ 5 wt% and the Golden Gate soil 5 wt%. The amounts of the components of the electrofusion sand and the clay excipient of Example t are described in detail in Table i. Further, the above-mentioned substrate and the binder were kneaded at room temperature for 6 minutes, and the matrix was (10) parts by weight, and the binder contained 5 parts by weight of dihydrogen. After the completion of the kneading, the product was pressed and formed by a friction molding machine, and fired at 9 ,, to obtain the sand refractory brick of Example 1. Example! The amounts of each component are described in detail in Table i. [Comparative Example 1] The fused silica was mixed with the clay Hf1 auxiliaries for 1 to 2 minutes to obtain a substrate. Based on the weight of the substrate, the substrate comprises 90% by weight of the fused silica and 1% by weight of the clay adjuvant.兮 乱 1 , ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 2Swt% of the second electro-rultic sand at 0.〇75~1 mm, 1〇wt% of a third electro-rultic sand with a particle size of 3~5 mm, and a particle size of 0.001~0.075 mm Melting fine powder 25 wt%. The clay excipients include Shi Xi ♦ knife 5 wt% and Jinmen soil 5 wt%. The amounts of the components of the electrofused sand and clay excipients of Comparative Example i are detailed in Table 1. Further, the above-mentioned substrate and the binder are kneaded at normal temperature for 4 to 6 minutes. The binder contains a resetter of aluminum dihydrogen phosphate 5 in terms of the weight of the substrate. After the mixing is completed, it is produced by a friction molding machine and is fired at 900 C to obtain a stone refractory monument of Comparative Example i. The amounts of the components of Comparative Example 1 are described in detail in Table 1.

[Comparative Example 2J The electric lava stone was dry mixed with a clay excipient for 2 minutes to obtain - base X. The heavy leaf of the substrate. The substrate contained 90 wt% of the electric fused silica and 10 wt / of the adhesive. . The content of each component of the matrix and the clay adjuvant was the same as in Comparative Example 1. The amounts of the components of the electric (iv) sand and clay excipients of Comparative Example 2 are detailed in Table 1. Then, the above substrate is kneaded at room temperature for 4 to 6 minutes to be kneaded to complete y, discharged and formed by a friction molding machine, and fired at 9 Torr, that is, the refractory brick of Comparative Example 2 . The amounts of the components of Comparative Example 2 are described in detail in Table 1. 201245096 Table 1 Formula Red Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Matrix (calculated as 100 parts by weight) Electrofusion &gt; 6 Xisha (90 wt%) Electric Melting _ 3-5 mm 0 10 10 11 Electric crushed sand 1 ~ 3 mm 37.5 30 30 32 Electric stone shisha _ 0.075~1 mm 27.5 25 25 22 Electric lava stone 0.001 ~ 〇. 〇 75mm 25 25 25 20 Clay accessories (10 wt%) _ Golden Gate Soil 5 5 5 5 . 矽 powder 5 5 5 5 binder (parts by weight) aluminum dihydrogen phosphate 5 5 0 5

[Comparative Examples 3 to 7J Comparative Examples 3 to 7 are commercially available Shiyue refractory bricks. Comparative Example 3 was purchased from Yuyou and the company's appearance was reddish brown; Comparative Example 4 was from the light and company, the outer enamel was white, and it was pressed by a brick press; Comparative Example 5 was purchased from LIGHT and the company, and the appearance was white. , was made by hand; Comparative Example 6 was purchased from Dajingong. Comparative Example 7 was purchased from Danieli c〇r〇us Eur〇pe c〇, and the actual product was made by Velbates & Division, Comparative Example 7 was only partial. Test&gt;, nature measurement and comparison of the stone eve f-resistance of the examples 1 to 7 respectively, physical illusion, chemical composition analysis and special property requirements can be seen by the actual test of each coke oven to achieve the highest operation benefit. Brother's tone...the coking 1 ·Physical properties: (1) Forming specific gravity. (2) The specific gravity of the burn. 201245096 (3) Burning line change; follow JIS R2654 test standard. (4) Financial strength; in accordance with JIS R2553 test standard. (5) Apparent Porosity: According to JIS R2205 test standard. (6) Absorption rate; in accordance with JIS R2205 test standard. (7) Depending on the specific gravity; follow the JIS R2505 test standard. (8) Bulk Density: According to JIS R2505 test standard. (9) Permanent Linear Change: According to the JIS R2654 test standard, the test was carried out for 3 hours at 1300 ° C and 1400 ° C respectively. (10) Cold Crushing temperature: According to JIS R2553 test standard. The physical property test results of Example 1 and Comparative Examples 1 to 7 are summarized in Table 2. 2. Chemical composition analysis: Si〇2, AI2O3, Fe2〇3, Ti〇2, CaO, MgO contained in Example 1 and Comparative Examples 3 to 7 after firing were analyzed in accordance with JIS R2212-1 to 5. The chemical composition and crystal phase composition of Na20, K20, P205, C, S, etc., analysis results and demand criteria are detailed in Table 3. Comparative Examples 1 and 2 did not perform chemical composition analysis because their physical properties did not meet the requirements of the enamel fire resistance monument. 3. Evaluation of special properties: (1) Thermal Shock Resistance: Take 40x40x40mm samples of each example and comparative example, place the sample in the environment of 1100 °C for 30 minutes, and then water quench for 30 minutes. , counted as once, then

S 10 201245096 Repeat the above steps until the sample is cracked. Table 2 shows the number of trials for the first occurrence of cracks in each sample. (2) Refractoriness: According to JIS R8101 test standard, the fire resistance of enamel refractory bricks must be greater than SK26 (SK26 = PCE23, which is 1580 °C). (3) Refractoriness under load (Ding 2): According to JIS R2209 test standard, the load softening temperature needs 21450 °C. (4) Crystal phase analysis: The sample was ground to &lt;150 mesh (about 50 g), and subjected to crystal phase analysis using an X-ray Diffraction (available from Rigaku Co., Ltd.). The ideal enamel refractory brick has a crystalline phase which is amorphous, and the content of the crystalline phase composition contained in the cumber must be less than 0.5 wt% in order to have zero expansion characteristics. (5) Thermal Expansion: According to the JIS R2207 test standard, observe the thermal expansion of the enamel refractory brick and calculate the thermal expansion rate. The specific properties (1) to (4) of the examples and Comparative Examples 1 to 7 are shown in Table 2, and the results of the thermal expansion test of (5) of Example 1 are shown in Table 4. 11 201245096 Specification Requirements &quot; ^250 I VII 21.76" $0.2 All &gt;26 Handmade 215 Mechanism 225 寸 Inch Amorphous Comparative Example 7 Qualified Qualified | 19.93 1 1 1 1 -0.08 cn » Ή o 1 1 &lt; 26 22.8 Untested sapphire quartz comparison example 6 Qualified 1 1 Qualified 1 Qualified I 21.93 1 1 1 1 (N r-* T—^ 0.15 1 0.19 1 KO (N CN 22.9 1615 Amorphous Comparative Example 5 1 Qualified U qualified | 1 qualified 1 qualified | 15.94 1 1 1 1 oo 00 -0.12 -0.14 1 1 &lt;26 24.3 1575 Squamous quartz comparative example 4 Qualified pass qualified 14.77 1 1 1 1 CN O) 0.02 0.02 i &lt;n &lt;26 38.2 1600 Quartz Comparative Example 3 Qualified | Qualified | 1 Qualified I 1 Qualified I 14.77 1 1 1 1 Γ 0.02 0.02 F—&lt; oom V£&gt; (N as 00 1650 Squamous Quartz Comparative Example 2 Η 00 〇 \ VO 〇m inch 24.47 14.56 2.23 00 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Comparative example 1 〇00 v〇ο 00 inch 25.77 15.72 (N CN s »-H (N 〇-0.19 ! ^45 &gt;26 1 1 1 1 1 1 Example 1 2.04 Os -0.37 〇VO CN 13.10 1 1 1 1 CN O) -0.35 cn o &lt;N m &gt;26 35.9 1630 Amorphous Formulation Specific Gravity Specific Gravity g/cm3) Sintering line change (%) Compressive strength (kg/cm2) Porosity (%) Water absorption (%) /&gt;-V m ε &quot;3b ψπ jl3 5 /—\ m ε Amount 1300° C 1400°C Thermal Shock Test Refractoriness Test (SK) Normal Temperature Crushing Temperature (°C) Load Softening Temperature (°C) Crystal Phase 婼t.绂茛&lt;屯^“:”. Find 2 11 s 201245096 Specifications 〇〇〇\ All ^ 3.0 Ο in ο VII ^ 0.2 d VII o VII ^ 0.2 (N d VII VII ^ 0.4 ^ 0.1 ^ 0.5 Comparative Example 7 95.60 0.926 0.219 0.019 0.035 0.069 0.033 0.017 1.45 1 1 1 1 &lt; 0.5 Comparison Example 6 97.15 0.620 0.065 II 0.026 0.010 0.008 0.005 1.360 0.028 0.010 &lt;0.5 Comparative Example 5 94.10 1.980 0.087 1 1 0.048 0.088 0.008 0.010 1.800 0.394 0.013 &lt; 0.5 Comparative Example 4 94.25 1.930 0.106 1 1 0.0048 0.088 0.008 0.010 1.700 0.204 od &lt 0.5 Comparative Example 3 96.94 0.51.0 0.055 1 1 0.270 0.030 0.086 0.011 0.900 0.254 0.049 &lt; 0.5 Example 1 96.84 0.690 0.078 1 1 0.047 0.021 0.012 0.006 1.090 0.040 0.011 &lt; 0.5 Formulation Group SiO 2 ai2o3 Fe2〇3 Ti02 CaO MgO Na2〇〇(N 〇(S Oh UC/) crystal phase composition the amount .绂茛-&lt;长^":".捃13 201245096 Table 4 —^A(°C) 18 _ Thermal expansion rate f〇/n, ί Temperature (°c) A thermal expansion y〇l ^ 450 50 0.01 500 oTol~~~' 100 0.01 550 0.02~~ ^ 150 0.01 600 0 02 200 Γ 0.01 650 oo? ~ 250 0.0048 700 _0.02^ 〇T〇2^^ 0.002 750 350 0.0027 800 0 L____400 - v · \/ j _ See Table 1 and Table 2 for examples! In comparison with Comparative Example, the binder of Example i was a divalent amount of bismuth phosphate, and it was able to be smoothly molded, based on 100 parts by weight of the substrate. The matrix of Comparative Example 2 was poorly punctured during kneading and was not easily formed later, and the easy-to-cut angle was not uniform, so it did not meet the molding requirements and was not suitable for mass production. Li Ba compares Example 1 with the comparison. In the part of the electric melting stone, the comparative example i contains a large amount of electro-rultic sand (3~5 mm), and the prepared stone refractory brick has a specific gravity; ^, compressive strength and porosity The bulk density is not in the normative demand, and the rate of change of the reheat line is small, which is not suitable. See Table 2 and Table 3. In Comparative Example 4 and Comparative Example 5, the content of Si〇2 was insufficient, and the content of P2〇5 was higher than the standard value. The excessive content of 1&gt;2〇5 reacted with water to form a low-melt, resulting in zero-expansion bricks after sintering. The surface has a low melting point; and the fire resistance of the fire resistant monument is not good (&lt;SK26), and the comparative example 5 has the problem that the crushing temperature at normal temperature is too low. The contents of the components of Comparative Example 6 and Comparative Example 7 were all in accordance with the specifications of the refractory bricks, but subsequent tests showed that the porosity was too high and the temperature was crushed at room temperature.

S 14 201245096 is too low, and Comparative Example 7 also has a problem of poor fiscal performance, which is not in line with regulatory requirements. The content of each component of Comparative Example 3 was the same as the specification standard of the cut refractory brick, but in the thermal shock test, the crack occurred in the breakage, so it was not broken, but the thermal shock resistance of the formulation of Comparative Example 3 was not shown to be good. The content of each component of the compliant embodiment 1 and the subsequent tests are in accordance with the demand standard of the stone refractory monument, and the crystalline phase is amorphous, and the thermal expansion coefficient thereof is as shown by 纟4, and is 0.03% between 18 and 800 tons. Below, it has the characteristics of zero expansion. In summary, the present invention is prepared by mixing a mixture of different sizes of the fused silica, which is composed of a certain proportion, of a sulphate-containing sulphate-containing binder in a specific ratio. The physical properties of the refractory monument are in line with the normative requirements' and can be used to quickly lift the temperature of the environmental towel, keeping the volume zero. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made in accordance with the scope of the invention and the description of the invention. All remain within the scope of the invention patent. [Simple description of the schema] Benefit 15 201245096 [Explanation of main component symbols]

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Claims (1)

201245096 VII. Patent application scope: 1 · An enamel refractory brick is made by mixing, pressing and firing a matrix with a binder; wherein 'the weight of the matrix*10' It comprises 8 〇 9 〇 wt% of the fused silica and 1 〇 2 黏土 of the clay auxiliaries; the binder comprises 3 to 5 parts by weight of the phosphate based on 1 part by weight of the substrate. 2. The enamel refractory brick according to the invention of claim 2, wherein the fused silica comprises a first fused concrete having a particle size of 1 to 3 mm, based on 100% by weight of the total weight of the substrate. Sand 35~4〇wt%, a second electro-melting 矽 sand 25~3〇% with a particle size of 0.075~1 mm, and a micro-powder 20~ with a particle size between 0-001~0.075 mm 25 wt%. 3. The enamel refractory brick according to claim 1, wherein the phosphate is aluminum dihydrogen phosphate. ^ According to the scope of application of the patent, the seven-quality fire-resistant monument, wherein the clay auxiliary material is cut into powder and clay, and the clay contains 胄2. ~ Μ 2 AI2O3 ’ and 0·8~2 wt% Fe2〇3. According to the enamel refractory monument described in item 4 of the patent application, the weight ratio of 矽 powder to clay is i: i~i : 2. , side 17