CN111484343A - Hydration-resistant magnesium-calcium tundish coating and preparation method thereof - Google Patents
Hydration-resistant magnesium-calcium tundish coating and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of refractory materials. The invention provides a hydration-resistant magnesium-calcium tundish coating which comprises the following components in parts by weight: 5-73 parts of dead burned magnesia particles; 20-88 parts of a calcium raw material; 1.1-1.3 parts of fiber; 3-5 parts of a nano binder; 0.05-1 part of organic plasticizer; 0.1-0.3 part of an explosion-proof agent; 1-2 parts of a water reducing agent. The invention also provides a preparation method of the hydration-resistant magnesium-calcium tundish coating. The organic plasticizer is beneficial to improving the plasticity and viscosity of the material, ensures the construction performance of the coating, and does not fall off in the construction process; the fiber and the explosion-proof agent are compounded for use, so that capillary vent holes can be formed in the coating, the magnesium-calcium coating is prevented from bulging when water vapor and gas released by decomposition of calcium raw materials are exhausted in the maintenance process, and the magnesium-calcium coating is prevented from collapsing and falling off when being rapidly baked.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to a hydration-resistant magnesium-calcium tundish coating and a preparation method thereof.
Background
In the steel smelting process, the continuous casting tundish is the last container in contact with molten steel, and is very important for improving the quality of the molten steel and preparing clean molten steel. Therefore, the tundish working lining is required to have less pollution to molten steel and absorb non-metallic inclusions in the molten steel.
CaO can adsorb impurities, S, P and other harmful elements in the steel, and has good molten steel purifying capacity. At the same time, CaO has the best high-temperature stability, and oxygen is rarely added into steel. However, the CaO waterproofing technology is not complete, and the CaO is very easy to hydrate and expand, so that the material is pulverized, cracked or cracked. About 20 percent of water is required to be added in the coating material construction process, and higher requirements are provided for the waterproof performance of the magnesium-calcium coating.
Disclosure of Invention
The invention aims to provide a hydration-resistant magnesium-calcium tundish coating and a preparation method thereof. Aiming at the problem of poor waterproof performance of the magnesium-calcium paint, one or more of limestone, dolomite, slaked lime and light calcium carbonate are selected and used as a calcium source, so that the problem of CaO hydration is thoroughly solved, and the generated free CaO can purify molten steel.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a hydration-resistant magnesium-calcium tundish coating which comprises the following components in parts by weight:
preferably, the grain size of the dead burned magnesia grains is less than or equal to 1 mm.
Preferably, the calcium raw material is one or more of limestone particles, dolomite particles, slaked lime powder, light calcium carbonate powder and calcined high-iron dolomite particles; the particle size of the limestone particles is less than or equal to 1 mm; the particle size of the dolomite particles and the calcined high-iron dolomite particles is 1-3 mm; the particle size of the slaked lime powder and the light calcium carbonate powder is less than or equal to 0.075 mm.
Preferably, the fibers are a mixture of hemp fibers and organic fibers in a weight ratio of 10:1, or a mixture of paper fibers and organic fibers in a weight ratio of 10: 1.
Preferably, the nano-binder is silicon powder or clay, and the particle size of the nano-binder is less than or equal to 50 nm.
Preferably, the organic plasticizer is dextrin and/or sodium carboxymethyl cellulose.
Preferably, the explosion-proof agent is metal aluminum powder, and the particle size of the explosion-proof agent is less than or equal to 80 meshes.
Preferably, the water reducing agent is sodium tripolyphosphate and sodium hexametaphosphate in a mass ratio of 1-3: 1-3.
The invention also provides a preparation method of the hydration-resistant magnesium-calcium tundish coating, which comprises the following steps:
1) mixing a calcium raw material and dead burned magnesia particles to obtain a first mixture;
2) mixing the first mixture and fibers to obtain a second mixture;
3) mixing the second mixture with a nano-binder and a water reducing agent to obtain a third mixture;
4) and mixing the third mixture with an organic plasticizer and an explosion-proof agent to obtain the hydration-resistant magnesium-calcium tundish coating.
Preferably, the mixing time in the step 1) is 1-3 min, the mixing time in the step 2) is 0.5-1.5 min, the mixing time in the step 3) is 0.5-1.5 min, and the mixing time in the step 4) is 7-9 min.
The beneficial effects of the invention include the following:
1) the addition of the nano-binder can generate strength at various temperature points, and the performance of the coating can reach that of the coating combined by the traditional silicon dioxide powder.
2) The addition of the organic plasticizer is beneficial to improving the plasticity and viscosity of the material, ensures the construction performance of the coating and prevents the coating from falling off in the construction process.
3) The fiber and the explosion-proof agent are compounded for use, so that capillary vent holes can be formed in the coating, the magnesium-calcium coating is prevented from bulging when water vapor and gas released by decomposition of calcium raw materials are exhausted in the maintenance process, and the magnesium-calcium coating is prevented from collapsing and falling off when being rapidly baked. The principle of the method is that the added fibers are mutually connected in a bridging way, and are shrunk and burnt off during baking to form a reticular capillary exhaust hole, so that the overlarge internal vapor pressure generated during liner baking can be reduced, and burst is prevented.
4) The addition of the water reducing agent is beneficial to reducing the water consumption of the coating material and improving the operation performance.
Detailed Description
The invention provides a hydration-resistant magnesium-calcium tundish coating which comprises the following components in parts by weight:
the hydration-resistant magnesia-calcia tundish coating comprises 5-73 parts of dead burned magnesia particles, preferably 8-70 parts, and more preferably 15-60 parts.
The granularity of the dead burnt magnesia particles is preferably less than or equal to 1mm, and more preferably less than or equal to 0.9 mm.
In the dead burnt magnesia particles, 5 to 73 parts by weight of the component with the particle size of less than or equal to 1mm contains the component with the particle size of less than or equal to 0.075mm, preferably 5 to 30, and more preferably 10 to 25.
The content of MgO in the dead-burned magnesite grains is preferably equal to or more than 91 percent, and more preferably equal to or more than 93 percent.
The hydration-resistant magnesium-calcium tundish coating comprises 20-88 parts of calcium raw materials, preferably 25-80 parts, and further preferably 30-75 parts.
The calcium raw material is preferably one or more of limestone particles, dolomite particles, slaked lime powder, light calcium carbonate powder and calcined high-iron dolomite particles; the granularity of the limestone particles is preferably less than or equal to 1mm, and is further preferably less than or equal to 0.9 mm; the granularity of the dolomite particles and the calcined high-iron dolomite particles is preferably 1-3 mm, and further preferably 2 mm; the particle size of the slaked lime powder and the light calcium carbonate powder is preferably less than or equal to 0.075mm, and further preferably less than or equal to 0.07 mm.
The calcined high-iron dolomite is preferably prepared by calcining high-quality dolomite serving as a raw material in a rotary kiln at a temperature of more than or equal to 1850 ℃.
One or more of limestone particles, dolomite particles, slaked lime powder, light calcium carbonate powder and calcined dolomite particles with reasonable granularity and dosage are selected as calcium raw materials to be matched with the dead-burned magnesia particles for use, so that the coating material has good hydration resistance. CaO generated by in-situ decomposition of the calcium raw material at high temperature exists in the form of f-CaO, and is beneficial to cleaning molten steel and adsorbing Al in the molten steel2O3、SiO2And the content of harmful element S, P in the steel is reduced, which is very important for clean steel smelting.
The content of CaO in the magnesium-calcium coating prepared by the method is 8-46%, and the requirements of different smelting steel types on different calcium contents can be met. MgCO in dolomite3Decomposition temperature is 790 ℃ CaCO3The decomposition temperature is 940 ℃, the decomposition temperature of limestone is about 1000 ℃, the invention utilizes the decomposition temperature difference between the two to lead the limestone to be alternately decomposed at high temperature, and the generated gas is discharged in sequence, thus avoiding bulging and collapsing caused by concentrated decomposition. The calcined high-iron dolomite has the characteristics of high chemical purity, good sintering degree and strong slag resistance. The invention adopts the calcined high-iron dolomite with a certain proportion to avoid overlarge high-temperature shrinkage and Fe-coated CaO in the calcined high-iron dolomite2O3Stable and not easy to hydrate. Because the dead burnt magnesia can expand at high temperature, the calcium raw material of the invention decomposes to produce shrinkage, and the combination of the two does not influence the use of the dead burnt magnesia at high temperature.
The hydration-resistant magnesium-calcium tundish coating comprises 1.1-1.3 parts of fibers, and preferably 1.2 parts.
The fibers of the present invention are preferably a mixture of hemp fibers and organic fibers in a weight ratio of 10:1, or a mixture of paper fibers and organic fibers in a weight ratio of 10: 1.
The melting point of the organic fiber is preferably 60-80 ℃, and further preferably 70 ℃.
The hydration-resistant magnesium-calcium tundish coating comprises 3-5 parts of a nano binding agent, and preferably 4 parts.
The nano-binder is preferably silicon powder or clay, and the particle size of the nano-binder is preferably less than or equal to 50nm, and more preferably less than or equal to 48 nm.
The hydration-resistant magnesium-calcium tundish coating comprises 0.05-1 part of organic plasticizer, preferably 0.1-0.8 part, and more preferably 0.2-0.7 part.
The organic plasticizer is preferably dextrin and/or sodium carboxymethyl cellulose.
The hydration-resistant magnesium-calcium tundish coating comprises 0.1-0.3 part of an explosion-proof agent, preferably 0.1-0.2 part, and further preferably 0.2 part.
The explosion-proof agent is preferably metal aluminum powder, and the granularity of the explosion-proof agent is preferably less than or equal to 80 meshes, and is further preferably less than or equal to 70 meshes.
The metal aluminum powder reacts with water to generate Al (OH)3And release H2Before the paint sets H2Escape to form capillary exhaust holes, thereby improving air permeability.
The hydration-resistant magnesium-calcium tundish coating comprises 1-2 parts of a water reducing agent, preferably 1.5-2 parts, and more preferably 1.5 parts.
The water reducing agent is preferably a mixture of sodium tripolyphosphate and sodium hexametaphosphate, and the mass ratio of the sodium tripolyphosphate to the sodium hexametaphosphate is preferably 1-3: 1-3, and more preferably 1: 1.
The invention also provides a preparation method of the hydration-resistant magnesium-calcium tundish coating, which comprises the following steps:
1) mixing a calcium raw material and dead burned magnesia particles to obtain a first mixture;
2) mixing the first mixture and fibers to obtain a second mixture;
3) mixing the second mixture with a nano-binder and a water reducing agent to obtain a third mixture;
4) and mixing the third mixture with an organic plasticizer and an explosion-proof agent to obtain the hydration-resistant magnesium-calcium tundish coating.
The mixing time in the step 1) is preferably 1-3 min, and more preferably 2 min; the mixing time in the step 2) is preferably 0.5-1.5 min, and further preferably 1 min; the mixing time in the step 3) is preferably 0.5-1.5 min, and further preferably 1 min; the mixing time in the step 4) is preferably 7-9 min, and further preferably 8 min.
The mixing according to the invention is preferably carried out in a 750 planetary forced mixer.
The water-resistant magnesium calcium tundish coating and the preparation method thereof according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
In examples 1 to 4, all the raw materials were processed according to the following requirements for chemical composition and particle grade:
and (3) re-burning magnesia particles: MgO (magnesium oxide)>91％，SiO2<4% burn and abate<0.3％。
Limestone particles: CaO 55.07%, and ignition loss 42.3%.
Dolomite particles: 21.28 percent of MgO, 30.62 percent of CaO and 44.4 percent of causticity.
Slaked lime powder: 64.69% of CaO and 25.54% of causticity.
Light calcium carbonate powder: 54.56 percent of CaO and 43.17 percent of causticity.
Calcining the high-iron dolomite particles: 38.01 percent of MgO, 54.57 percent of CaO, and Fe2O35.48 percent, and the bulk density is more than or equal to 3.25g/cm3。
The particle size of limestone particles is less than or equal to 1 mm; the particle size of the dolomite particles and the calcined high-iron dolomite particles is 1-3 mm; the particle size of the slaked lime powder and the light calcium carbonate powder is less than or equal to 0.075 mm; the granularity of the dead burnt magnesia particles is less than or equal to 1 mm.
Example 1
Mixing 20kg of dolomite particles and 73kg of dead burnt magnesia particles (30 kg of dead burnt magnesia particles with the particle size less than or equal to 0.075 mm) in a 750 planetary type forced sand mixer for 2min, then adding 1.2kg of paper fibers and organic fibers for mixing for 1min, then adding 3kg of nano-binder, 0.5kg of sodium tripolyphosphate and 0.5kg of sodium hexametaphosphate for mixing for 1min, finally adding 0.5kg of sodium carboxymethylcellulose and 0.2kg of metal aluminum powder for mixing for 8min, stirring uniformly and bagging.
Example 2
20kg of calcined high-iron dolomite particles, 20kg of limestone particles and 53kg of dead burnt magnesia particles (30 kg of dead burnt magnesia particles with the particle size of less than or equal to 0.075 mm) are mixed in a 750 planetary type forced sand mixer for 2min, then 1.2kg of fibrilia and organic fiber are added and mixed for 1min, 5kg of nano-binder, 0.75kg of sodium tripolyphosphate and 0.75kg of sodium hexametaphosphate are added and mixed for 1min, finally 0.05kg of sodium carboxymethylcellulose and 0.2kg of metal aluminum powder are added and mixed for 8min, and the mixture is stirred uniformly and bagged.
Example 3
Mixing 30kg of calcined high-iron dolomite particles, 20kg of limestone particles, 10kg of light calcium carbonate powder and 33kg of dead burnt magnesia particles (20 kg of dead burnt magnesia particles with the particle size of less than or equal to 0.075 mm) in a 750 planetary type forced sand mixer for 2min, then adding 1.2kg of fibrilia and organic fibers for mixing for 1min, then adding 4kg of nano-binder, 1kg of sodium tripolyphosphate and 1kg of sodium hexametaphosphate for mixing for 1min, finally adding 0.5kg of dextrin and 0.2kg of metal aluminum powder for mixing for 8min, stirring uniformly and bagging.
Example 4
Mixing 38kg of calcined high-iron dolomite particles, 20kg of limestone particles, 10kg of slaked lime powder and 25kg of dead burnt magnesia particles (5 kg of dead burnt magnesia particles with the particle size of less than or equal to 0.075 mm) in a 750 planetary type forced sand mixer for 2min, then adding 1.2kg of paper fibers and organic fibers for mixing for 1min, then adding 3.5kg of nano-binder, 1kg of sodium tripolyphosphate and 1kg of sodium hexametaphosphate for mixing for 1min, finally adding 0.8kg of dextrin and 0.2kg of metal aluminum powder for mixing for 8min, stirring uniformly and bagging.
Performing performance detection on sample block
The products prepared in the embodiments 1-4 are mixed with a proper amount of water, the mixture is uniformly mixed and then is subjected to vibration forming, a sample with the thickness of 160mm × 40mm and × 40mm is obtained, the sample is maintained for 24 hours and then is demoulded, 3 sample blocks are respectively prepared, 12 sample blocks are dried at 110 ℃ for 24 hours, one dried sample block is directly detected, the volume density, the normal-temperature flexural strength and the normal-temperature compressive strength are tested, the other two dried sample blocks are respectively treated at 1100 ℃ and 1500 ℃ for 3 hours, the normal-temperature flexural strength, the normal-temperature compressive strength and the linear change are detected after the sample blocks are returned to the room temperature, and the performance detection results are shown in table 1.
TABLE 1 Performance test results of Mg-Ca tundish coating compositions of examples 1-4
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The anti-hydration magnesium-calcium tundish coating is characterized by comprising the following components in parts by weight:
2. the water-hydration-resistant magnesia-calcium tundish coating according to claim 1, wherein the grain size of the dead burned magnesia particles is less than or equal to 1 mm.
3. The water-resistant magnesium calcium tundish coating according to claim 1 or 2, wherein the calcium raw material is one or more of limestone particles, dolomite particles, slaked lime powder, light calcium carbonate powder and calcined high-iron dolomite particles; the particle size of the limestone particles is less than or equal to 1 mm; the particle size of the dolomite particles and the calcined high-iron dolomite particles is 1-3 mm; the particle size of the slaked lime powder and the light calcium carbonate powder is less than or equal to 0.075 mm.
4. The water hydration resistant magnesium-calcium tundish coating according to claim 3, wherein the fiber is a mixture of hemp fiber and organic fiber in a weight ratio of 10:1, or a mixture of paper fiber and organic fiber in a weight ratio of 10: 1.
5. The water hydration resistant magnesium-calcium tundish coating according to claim 4, wherein the nano-binder is silicon powder or clay, and the particle size of the nano-binder is less than or equal to 50 nm.
6. The water-hydration-resistant magnesium-calcium tundish paint according to claim 5, wherein the organic plasticizer is dextrin and/or sodium carboxymethyl cellulose.
7. The anti-hydration magnesium-calcium tundish paint according to claim 6, wherein the anti-explosion agent is metal aluminum powder, and the particle size of the anti-explosion agent is less than or equal to 80 meshes.
8. The hydration-resistant magnesium-calcium tundish coating according to claim 7, wherein the water reducing agent is sodium tripolyphosphate and sodium hexametaphosphate in a mass ratio of 1-3: 1-3.
9. The preparation method of the anti-hydration magnesium-calcium tundish coating according to any one of claims 1 to 8, characterized by comprising the following steps:
1) mixing a calcium raw material and dead burned magnesia particles to obtain a first mixture;
2) mixing the first mixture and fibers to obtain a second mixture;
3) mixing the second mixture with a nano-binder and a water reducing agent to obtain a third mixture;
4) and mixing the third mixture with an organic plasticizer and an explosion-proof agent to obtain the hydration-resistant magnesium-calcium tundish coating.
10. The preparation method according to claim 9, wherein the mixing time in step 1) is 1-3 min, the mixing time in step 2) is 0.5-1.5 min, the mixing time in step 3) is 0.5-1.5 min, and the mixing time in step 4) is 7-9 min.
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