A low-viscosity binder for blast furnace anhydrous taphole mud based on titanate and preparation method thereof

Abstract

The present invention discloses a low-viscosity binder for anhydrous taphole mud for blast furnaces based on titanate and a preparation method thereof, and belongs to the technical field of refractory material preparation. The present invention uses environmentally friendly anthracene oil and environmentally friendly tar as main raw materials, adds liquid resin and hexamethylenetetramine cross-linking agent, and circulates and stirs at 100-120°C, dehydrates and removes part of the volatile matter to prepare a mixed binder; then, an organic viscosity reducer titanate is added to the mixed binder, and the circulation stirring is continued to prepare a low-viscosity binder for anhydrous taphole mud for blast furnaces based on titanate. The preparation method of the present invention is simple and has low production cost. The binder obtained is environmentally friendly and pollution-free, has high coking value and β-resin content, low impurity content, low viscosity, and stable performance. The anhydrous taphole mud prepared using the binder obtained by the present invention has good plasticity, stability, low-temperature strength and medium-temperature strength, which significantly improves the tapping time and iron mouth depth of the blast furnace.

Description

Technical Field

[0001] The invention belongs to the technical field of refractory material preparation, and particularly relates to a titanate-based low-viscosity binder for blast furnace anhydrous taphole mud and a preparation method thereof. Background Art

[0002] Taphole clay is a refractory material used in blast furnace ironmaking systems. After the blast furnace has finished tapping, it is used to seal the taphole, allowing smelting to continue. With the continuous intensification of blast furnace smelting and the increasing size of blast furnaces, the requirements for taphole clay are becoming increasingly stringent. Anhydrous taphole clay must not only possess good plasticity for ease of construction but also exhibit excellent resistance to erosion and scouring by slag and iron. Therefore, anhydrous taphole clay has gradually evolved from aqueous taphole clay to anhydrous taphole clay. Traditional anhydrous taphole clay is primarily based on tar as a binder, which contains a large amount of BAP, which poses a risk to environmental pollution. Furthermore, traditional tar has drawbacks such as poor stability, high viscosity, and low coking value, which severely limit its performance.

[0003] Anhydrous taphole mud using resin as an environmentally friendly binder has been developed. Invention Patent ZL201210445805.8 discloses a binder for large-scale blast furnace anhydrous taphole mud. The binder uses a combination of silicone resin, furan resin, and melamine formaldehyde resin as a curing component, and hydrogenated terphenyl as a synergist. The binder exhibits high plasticity and a low curing rate. The reduced curing rate of the binder improves the fluidity of the anhydrous taphole mud at high temperatures. As a result, the mud is less likely to clump within the mud cannon, exhibits excellent opening performance, resists erosion by high-temperature molten iron, and poses minimal environmental pollution. However, the addition of resin results in a high binder price and a low cost-performance ratio. Resin binders for anhydrous taphole mud also suffer from poor plasticity, a short storage life at room temperature, and the generation of pollutants such as aldehydes. Invention Patent Application CN103193406A discloses a binder for adjusting the plasticity of taphole mud. This binder, prepared by adding tar, ethylene glycol, and xylene, exhibits room-temperature stability and non-volatility, and improves the plasticity of the taphole mud. However, adding xylene and other binders is harmful to the human body and produces large amounts of BAP, which poses a significant environmental risk. While anhydrous taphole clay using resin as a binder can improve the working environment and address pollution issues, it significantly increases costs, cures quickly, and has a short shelf life, making it less practical. For example, Chinese patent application CN101580397A discloses a blast furnace taphole clay with a low benzopyrene content. This binder uses a carbon-containing resin and a carbon-containing resin solvent, and the benzopyrene content in the clay does not exceed 1000 ppm. Therefore, this binder is not ideal in practice.

[0004] Therefore, researching a cannon mud binder that is environmentally friendly and pollution-free, has low production cost, good plasticity, stable performance and strong practicality has become an urgent problem that needs to be solved in the development of the current blast furnace anhydrous cannon mud industry. Summary of the Invention

[0005] To overcome the shortcomings of the above-mentioned prior art, the present invention provides a method for preparing a low-viscosity binder for anhydrous blast furnace taphole mud based on a titanate. The preparation method is simple, environmentally friendly, pollution-free, and low-cost. The present invention also provides a low-viscosity binder for anhydrous blast furnace taphole mud based on a titanate, which has low impurity content, low viscosity, good plasticity, and stable performance. This effectively solves the environmental pollution problems caused by using coal tar as a binder, and the short shelf life, high cost, and poor practicality caused by using resin as a binder.

[0006] In order to better solve the above problems, the technical solutions adopted by the present invention are as follows:

[0007] A method for preparing a low-viscosity binder for anhydrous blast furnace taphole mud based on titanate, comprising: in a circulation tank, using environmentally friendly anthracene oil and environmentally friendly tar as main raw materials, adding liquid resin, using triallyl isocyanurate as a cross-linking agent, and stirring through heating circulation under normal pressure, and adding a viscosity reducer to reduce the viscosity, to prepare the low-viscosity binder for anhydrous blast furnace taphole mud based on titanate.

[0008] Preferably, the benzopyrene content of the environmentally friendly anthracene oil and environmentally friendly tar is ≤50ppm.

[0009] Preferably, the coking value of the liquid resin is ≥40%.

[0010] Preferably, the cross-linking agent is one of hexamethylenetetramine, triallyl isocyanurate, and β-phenylacrylic acid.

[0011] Preferably, the heating temperature of the circulating stirring is 100-120° C., and the stirring rate is 150 r / min.

[0012] Preferably, the viscosity reducing agent is 1-3 wt% titanate.

[0013] Preferably, the method for preparing the low-viscosity binder for anhydrous taphole mud for blast furnaces based on titanate comprises the following specific steps: in a circulation tank, under normal pressure conditions, using 30-50wt% environmentally friendly anthracene oil and 30-50wt% environmentally friendly tar as main raw materials, adding 10-30wt% liquid resin and 1-3wt% cross-linking agent triallyl isocyanurate, and circulating and stirring for 30-60min at 100-120°C to dehydrate and remove some volatile components to obtain a mixed binder; then adding a viscosity reducer to the mixed binder, and continuing to circulate and stir for 10-30min to prepare a low-viscosity binder for anhydrous taphole mud for blast furnaces based on titanate.

[0014] Preferably, the titanate-based low-viscosity binder for anhydrous taphole mud for blast furnaces is prepared by the above-mentioned method for preparing the titanate-based low-viscosity binder for anhydrous taphole mud for blast furnaces.

[0015] Compared with the prior art, the present invention has the following advantages:

[0016] (1) The present invention adopts titanate as a viscosity reducer, which can not only significantly reduce the viscosity of the binder, but also the low viscosity binder is more conducive to reducing the friction between the particles and increasing the plasticity and stability of the taphole mud; and titanate provides titanium element to the taphole mud, and generates high melting point TiN, TiC and Ti (N, C) solid solution with carbon in a high temperature reducing atmosphere, which plays a role in protecting and repairing the furnace wall and furnace bottom around the inner side of the iron outlet.

[0017] (2) The present invention adopts one of hexamethylenetetramine, triallyl isocyanurate or β-phenyl acrylic acid as a cross-linking agent, which can effectively solve the problem of poor compatibility between resin and tar, which leads to the easy formation of crack defects inside the taphole mud. At the same time, the addition of the cross-linking agent promotes the cross-linking of tar pitch, thereby improving the coke rate of coal tar.

[0018] (3) The environmentally friendly anthracene oil and environmentally friendly tar used in the present invention have low benzopyrene content, which reduces the production of carcinogens or pollutants such as benzopyrene and aldehydes during the use of taphole mud, greatly reducing environmental pollution and harm to furnace workers.

[0019] (4) The present invention uses environmentally friendly anthracene oil and tar as the main raw materials and adopts liquid resin compounding, which can improve the residual carbon, coking value and β-resin content of the binder, thereby improving the performance of the cannon mud binder and improving the unstable conditions such as low residual carbon rate and poor coking value caused by the complex composition of ordinary tar. The liquid resin is easy to cross-link and usually forms glassy carbon with closed pores at high temperature, so that the anti-iron slag erosion performance and mechanical strength of the cannon mud are improved.

[0020] (5) The binder prepared by the method provided by the present invention is environmentally friendly and pollution-free, has a low impurity content, a long storage period, and stable performance; moreover, the entire process is simple and the production cost is low, which effectively solves the pollution problem caused by the use of coal tar as a binder in traditional taphole mud or the short shelf life and high price caused by the use of resin as a binder.

[0021] (6) The anhydrous taphole mud further prepared by using the binder prepared by the present invention has good plasticity, stability, low temperature strength and medium temperature strength, and has excellent properties such as high bulk density, small sintering shrinkage, and resistance to slag and iron erosion, which significantly improves the iron-tapping time and iron mouth depth of the blast furnace. DETAILED DESCRIPTION

[0022] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with specific embodiments.

[0023] In the following examples, environmentally friendly anthracene oil and environmentally friendly tar were from (Hebei Yaotan Chemical Technology Co., Ltd.); liquid resin was from (Hebei Ruihan Anticorrosive Materials Co., Ltd.); cross-linking agents hexamethylenetetramine, triallyl isocyanurate or β-phenylacrylate were from (Shandong Polychemical Co., Ltd.); and viscosity reducer titanate was from (Guangdong Wengjiang Chemical Reagent Co., Ltd.).

[0024] The benzopyrene content of environmentally friendly anthracene oil and environmentally friendly tar is ≤50ppm; for liquid resin, the coking value is ≥40%.

[0025] Example 1:

[0026] In a circulation tank, under normal pressure conditions, 30wt% environmentally friendly anthracene oil and 50wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 1wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 50min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0027] Example 2:

[0028] In a circulation tank, under normal pressure conditions, 40wt% environmentally friendly anthracene oil and 40wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 1wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 50min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0029] Example 3:

[0030] In a circulation tank, under normal pressure conditions, 50wt% environmentally friendly anthracene oil and 30wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 1wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 50min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0031] Example 4:

[0032] In a circulation tank, under normal pressure conditions, 35wt% environmentally friendly anthracene oil and 35wt% environmentally friendly tar are used as the main binder raw materials, 30wt% liquid resin and 1wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 50min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0033] Example 5:

[0034] In a circulation tank, under normal pressure conditions, 45wt% environmentally friendly anthracene oil and 45wt% environmentally friendly tar are used as the main binder raw materials, 10wt% liquid resin and 1wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 50min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0035] Example 6:

[0036] In a circulation tank, under normal pressure conditions, 40wt% environmentally friendly anthracene oil and 40wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 1wt% triallyl isocyanurate are added, and the mixture is stirred at 100°C for 50min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0037] Example 7:

[0038] In a circulation tank, under normal pressure conditions, 40wt% of environmentally friendly anthracene oil and 40wt% of environmentally friendly tar are used as main binder raw materials, 20wt% of liquid resin and 1wt% of β-phenylacrylic acid are added, and the mixture is stirred at 100°C for 60min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% of organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for anhydrous taphole mud for blast furnaces.

[0039] Example 8:

[0040] In a circulation tank, under normal pressure conditions, 40wt% environmentally friendly anthracene oil and 40wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 2wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 60min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0041] Example 9:

[0042] In a circulation tank, under normal pressure conditions, 40wt% environmentally friendly anthracene oil and 40wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 3wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 60min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 2wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0043] Example 10:

[0044] In a circulation tank, under normal pressure conditions, 40wt% environmentally friendly anthracene oil and 40wt% environmentally friendly tar are used as the main binder raw materials, 20wt% liquid resin and 1wt% cross-linking agent hexamethylenetetramine are added, and the mixture is stirred at 100°C for 60min (150r / min) for dehydration and removal of some volatile components to prepare a mixed binder; then in the circulation tank, 3wt% organic viscosity reducer titanate is added to the mixed binder, and the stirring is continued for 30min (150r / min) to obtain a low-viscosity binder for blast furnace anhydrous taphole mud based on titanate.

[0045] Example 11

[0046] The titanate-based anhydrous blast furnace taphole mud prepared in Examples 1-10 was tested with a low-viscosity binder for the following tests: moisture content, ash content, volatile matter, coke, residual carbon, β-resin content, benzopyrene content and 60°C viscosity.

[0047] 1) Moisture test

[0048] Weigh 100 grams of the mixed sample (accurate to 0.2 grams) and 50 milliliters of toluene at room temperature, place them in a clean, dry distillation flask, and shake carefully. According to the expected moisture content in the substance to be tested, select an appropriate receiving tube, connect the distillation flask, receiving tube and cooling tube. Plug the upper end of the cooling tube with a little absorbent cotton to prevent moisture in the air from condensing inside the cooling tube. Heat and boil until the condensate drips from the end of the cooling tube at a rate of 2 to 5 drops per second. When the moisture in the receiving tube no longer increases, increase the flame or voltage, and stop distilling after heating for at least 5 minutes. When the temperature of the liquid in the receiving tube reaches room temperature, read the volume of the water layer. If the liquid in the receiving tube is turbid, place the receiving tube in warm water to clarify it, then cool it to room temperature and read the reading.

[0049] The moisture content of the sample (X1)% is calculated as follows:

[0050] X1(%)=V / M×100%

[0051] Where: V is the volume of water in the receiving tube, in milliliters (ml);

[0052] m—sample mass, in grams (g).

[0053] Note: Assume that the density of water in the receiving tube is 1.00 g / mL at room temperature.

[0054] 2) Ash content test

[0055] Weigh 2g of sample (accurate to 0.0002g) and place it in a porcelain evaporating dish that has been pre-heated to 900±10°C and weighed constantly. Slowly heat the dish over a gas burner over low heat (just enough to stop smoking) until most of the volatiles have evaporated. Then, place it in the open door of a muffle furnace heated to 900±10°C. Once the volatiles have completely evaporated, slowly push the dish into the furnace. Incubate for 1 hour, remove it, and inspect for the presence of black particles. Cool in air for 5 minutes, then place it in a desiccator, cool to room temperature, and weigh it. Continue to check for constant weight every 15 minutes until the difference between two consecutive weights is within 0.0006g. Use the last weight for calculations.

[0056] The calculation of ash content is shown in the formula.

[0057] A(%)=(m1-m2) / (m-m1)×100%

[0058] Where:

[0059] A—ash content of air-dried sample, mass fraction (%);

[0060] m1—weight of evaporating dish, in grams (g);

[0061] m2—the mass of the evaporating dish and residue after burning, in grams (g);

[0062] m—The mass of the evaporating dish and sample, in grams (g).

[0063] The arithmetic mean of the two measurement results is taken as the measurement result of the sample.

[0064] 3) Coking value test

[0065] Weigh 1g of the sample (accurate to 0.0002g) and spread it flat in a clean 20ml porcelain crucible that has been constant-weighted at 550±10℃, then cover it with a lid. Place the crucible containing the sample into a 100ml crucible that has been pre-paved with 10±1mm thick coke particles. Then fill the space between the two crucibles with coke particles until the 20ml crucible is completely buried. Cover the outer crucible with a lid. Place the loaded crucible on a nickel-chromium wire stand and then place the entire crucible in a box-type high-temperature furnace at 550±10℃. Return to a constant temperature within 10 minutes. After two hours, remove the crucible from the furnace and cool in air for 5-10 minutes. Remove the inner crucible and remove any attached coke powder. Place the inner crucible in a desiccator, cool to room temperature, and weigh it (accurate to 0.0002g). Clean a 20ml porcelain crucible and its lid, discard the residue, place it in a high-temperature furnace at 700-1000℃ and burn it to remove the residue for later use.

[0066] The coking value of coal tar is calculated as follows:

[0067] K(%)=(m2-m1) / m×100%

[0068] Where: K is the value of the coking value of coal tar pitch, the unit is mass fraction (%);

[0069] m2—the mass of the 20ml porcelain crucible and the residue, in grams (g);

[0070] m1—the mass of a 20ml porcelain crucible, in grams (g);

[0071] m—the numerical value of the sample mass, in grams (g).

[0072] The average of two repeated measurements was taken as the measurement result.

[0073] 4) Volatile matter test

[0074] Use a porcelain crucible with a lid that has been pre-calcined at 900±10℃ to a constant mass, weigh 1±0.01g (accurate to 0.0001g) of a sample with a particle size of less than 0.2mm and stirred evenly, spread the sample flat, cover it with a lid, and place it on the crucible rack (Note: If there are less than six samples to be measured, place an empty crucible in the vacant space on the crucible rack to fill the gap).

[0075] Open the door of a box-shaped high-temperature furnace, preheated to 900±10°C, and quickly place the rack containing the crucible into the constant temperature zone of the furnace. Immediately start the stopwatch, close and close the furnace door, and heat the crucible continuously for 7 minutes. After the crucible and rack are placed, the furnace temperature will drop slightly, but it must be restored to 900±10°C within 3 minutes and maintained at this temperature until the end of the test; otherwise, the test will be invalid. After 7 minutes, immediately remove the crucible from the furnace and cool it in air for about 5 minutes. Then transfer it to a desiccator to cool to room temperature (about 20 minutes) and weigh it.

[0076] The test results are calculated according to the following formula

[0077] V ad (%) = (m-m1) / m×100-M ad

[0078] Where: Vad—volatile matter content of the analyzed sample, %;

[0079] m—mass of the sample, g;

[0080] m1—mass of coke residue after heating, g;

[0081] Mad—Moisture content of the analyzed sample, %.

[0082] 5) Toluene insoluble matter test

[0083] (1) Preliminary preparation

[0084] Treatment of absorbent cotton: Soak the absorbent cotton in toluene for more than 24 hours, take it out and dry it, then dry it in a drying oven at 115℃~120℃ and set aside.

[0085] To make a filter paper tube: Concentrically overlap medium-speed quantitative filter paper with an outer layer of 150mm diameter and an inner layer of 125mm diameter. Place a test tube at the center of the filter paper circle. Fold the double-layer filter paper toward the test tube wall to form a double-layer filter paper tube with a diameter of approximately 25mm. Soak the filter paper tube in toluene for 24 hours, remove it, cool it, place it in a weighing bottle, and dry it in a drying oven at 115°C to 120°C before use.

[0086] (2) Operation steps

[0087] First, place a small piece of treated absorbent cotton in a filter paper tube. Place this in a weighing bottle and dry in a drying oven at 115°C to 120°C until constant weight is reached (the difference in mass between two weighings should not exceed 0.001g). Remove the absorbent cotton and set aside. Then, weigh approximately 3±0.2g (accurate to 0.0001g) of the coal tar analysis sample into the filter paper tube. Remove the filter paper tube from the weighing bottle and immediately place it in a 100ml beaker containing 60ml of toluene. Once the toluene has penetrated the filter paper tube, gently stir the sample in the filter paper tube with a glass rod for 2 minutes to evenly disperse the sample in the toluene. Remove the filter paper tube and wipe the glass rod with the absorbent cotton. Place this absorbent cotton in the filter paper tube. Place the flat-bottom flask containing 120ml of toluene in an electric heating mantle. Place the filter paper tube in the extraction tube, ensuring that the upper edge of the filter paper tube is 20mm above the reflux tube. Connect the extraction cylinder to a flat-bottom flask and add approximately 30 ml of toluene along the inner wall of the filter paper cylinder. Connect the condenser to the extraction cylinder and connect the cooling water supply. Connect the electric heating mantle to heat the flat-bottom flask, maintaining a toluene extraction rate of 1 to 1.5 minutes per extraction. One extraction is considered complete when the toluene extract fully flows back into the flat-bottom flask through the reflux tube. Repeat at least 50 extractions. The extraction is complete when the toluene extract washes the filter paper cylinder, leaving it white or light yellow and the extract in the extraction cylinder clear. Stop heating and disconnect the heating mantle. Allow to cool slightly after heating. Remove the filter paper cylinder and place it in the original weighing bottle, uncovered, in a fume hood. After the toluene evaporates, place the weighing bottle and cap in a drying oven at 115°C to 120°C for 2 hours. After capping the weighing bottle, remove it from a desiccator, cool it to room temperature, and weigh it. Dry for another 0.5 hours and check for constant weight until the mass difference is within 0.001 g or increases for two consecutive times. The last mass is used for calculation. If there is any weight increase, the mass before the weight increase is used as the basis for calculation.

[0088] (3) Result calculation

[0089] The toluene insoluble matter content (TI) in coal tar is calculated according to the following formula:

[0090] TI(%)=(m2-m1) / m×100 / (100-M)×100

[0091] Where: TI—toluene insoluble matter content in the sample, %;

[0092] m—sample mass, g;

[0093] m1—mass of weighing bottle and filter paper tube (or including sand and absorbent cotton), g;

[0094] m2—Total mass of toluene-insoluble matter in the weighing bottle and filter paper tube (or including sand and absorbent cotton), g.

[0095] M—moisture content of coal tar, %.

[0096] 6) Quinoline insoluble matter test

[0097] Weigh 1g of the prepared sample (accurate to 0.0002g), place the coal tar sample in a clean 100ml beaker, and the modified asphalt sample in a centrifuge tube. Add 25ml of quinoline and stir evenly with a glass rod. Immerse the beaker or centrifuge tube containing the sample together with the washing bottle containing quinoline in a constant temperature water bath at 75±5℃, stir occasionally, take out after 30 minutes, and prepare for filtration. The centrifuge tube containing the modified asphalt sample should be placed in a centrifuge, centrifuged at 4000r / min for 20 minutes, then taken out and filtered. Install the filter funnel, put in a double layer of filter paper, and let the filter paper fit tightly on the funnel without any gaps. Soak it with quinoline, and slowly pour the dissolved sample into the filter paper. Pour the sample as much as possible in the middle of the funnel while filtering. Wash the beaker or centrifuge tube with approximately 20 ml of quinoline several times (5 ml to 7 ml each time) to transfer all the residue to the filter paper. Then wash the residue on the filter paper with approximately 30 ml of hot quinoline several times (5 ml to 7 ml each time) while filtering. After draining, repeat the filtration and washing with about 10 ml of hot toluene each time until there is no obvious yellow color. After filtration, remove the filter paper and place it in the original weighing bottle. Dry it in a drying oven at 115°C to 120°C for 90 minutes, then remove it, cool it slightly, place it in a desiccator to cool to room temperature, and weigh it to a constant weight.

[0098] Test result calculation

[0099] W(%)=(G2-G1) / G×100

[0100] In the formula: W (%)—percentage of quinoline insoluble matter;

[0101] G2—total mass of weighing bottle, filter paper and quinoline insoluble matter in g;

[0102] G1—mass of filter paper and weighing bottle, g;

[0103] G—sample mass, g.

[0104] 7) β resin content (%) = toluene insoluble matter (TI (%)) - quinoline insoluble matter (W (%)). The toluene insoluble matter and quinoline insoluble matter contents are tested through the above steps and the β resin content is calculated.

[0105] 8) The viscosity test was performed using a Shanghai Fangrui viscosity tester at a speed of 6 rpm and a temperature of 60°C.

[0106] 9) Benzo(a)pyrene content (ppm). Benzo(a)pyrene was tested in accordance with the national standard, "Determination of Benzo(a)pyrene" (GB / T 17651-1998). Specifically, infrared spectroscopy was used: the infrared absorption spectrum of benzo(a)pyrene was measured using an infrared spectrometer to determine the position of its infrared absorption peak, thereby determining the benzo(a)pyrene content.

[0107] Table 1: Comparative table of performance indicators of binders in Examples 1-10

[0108]

[0109]

[0110] From Table 1, we can conclude that:

[0111] (1) The invention of an environmentally friendly binder significantly reduced the benzopyrene content in taphole mud;

[0112] (2) Increasing the content of environmentally friendly resin can improve the coking value, residual carbon and β-resin content of the binder;

[0113] (3) Titanate as a viscosity reducer can significantly reduce the viscosity of the binder;

[0114] (4) The addition of cross-linking agent and the increase of circulation stirring time are conducive to more uniform mixing of tar and resin.

[0115] The environmentally friendly tar and anthracene oil used in the present invention have low benzopyrene content, which reduces the generation of carcinogens or pollutants such as benzopyrene and aldehydes during use of the taphole mud, greatly reducing environmental pollution and harm to furnace workers. The high-performance environmentally friendly binder for anhydrous taphole mud prepared by the present invention significantly improves the binder's carbon residue, coking value, and beta resin content, thereby improving the binder's performance and alleviating the instability caused by the complex composition of ordinary tar. Furthermore, the liquid resin is easily cross-linked and typically forms closed-pore glassy carbon at high temperatures, thereby improving the taphole mud's resistance to iron slag corrosion and mechanical strength. The addition of the liquid resin to the binder significantly improves the taphole mud's plasticity, allowing the mud gun to smoothly press the taphole mud into the iron mouth passage without looseness or holes. The taphole mud can fill the iron mouth passage, ensuring sufficient iron filling. During plugging, no molten iron can be mixed in or form iron mouth mud bags, ensuring sufficient iron mouth depth. Using one of hexamethylenetetramine, triallyl isocyanurate, or β-phenylacrylate as a crosslinking agent solves the problem of cracks and defects easily forming within the taphole clay due to poor compatibility between the resin and tar. The addition of the crosslinking agent also promotes crosslinking of the tar pitch, thereby increasing the coke yield of the coal tar. The reduced viscosity increases the wettability and fluidity of the binder, significantly improving the plasticity of the taphole clay. The present invention uses titanate as a viscosity reducer, significantly reducing the viscosity of the binder. Low-viscosity binders are more conducive to reducing friction between particles, increasing the plasticity and stability of the taphole clay. Furthermore, the titanate provides titanium to the taphole clay, which reacts with carbon and other substances in a high-temperature reducing atmosphere to form high-melting-point TiN, TiC, and Ti(N, C) solid solutions, which protect and repair the furnace walls and furnace bottom surrounding the inside of the taphole.

[0116] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a low-viscosity binder for anhydrous blast furnace taphole mud based on titanate. During the preparation process, 1-3wt% titanate is used to reduce the viscosity of the binder; in a circulation tank, 30-50wt% environmentally friendly anthracene oil and 30-50wt% environmentally friendly tar are used as main raw materials, 10-30wt% liquid resin and 1-3wt% cross-linking agent are added, and the mixture is stirred by heating circulation under normal pressure, and 1-3wt% titanate is added to reduce the viscosity to prepare a high-performance environmentally friendly binder for anhydrous blast furnace taphole mud; the environmentally friendly anthracene oil and environmentally friendly tar have benzopyrene ≤50ppm; the coking value of the liquid resin is ≥40%; and the cross-linking agent is one of hexamethylenetetramine, triallyl isocyanurate, or β-phenylacrylate.

2. The method for preparing a low-viscosity binder for anhydrous taphole mud based on titanate according to claim 1, characterized in that: The heating temperature of the circulating stirring is 100-120°C; the stirring rate is 150r / min.

3. The method for preparing a low-viscosity binder for anhydrous taphole mud based on titanate according to claim 1, characterized in that: The specific steps are: in a circulation tank, under normal pressure conditions, using 30-50wt% environmentally friendly anthracene oil and 30-50wt% environmentally friendly tar as main raw materials, adding 10-30wt% liquid resin and 1-3wt% cross-linking agent triallyl isocyanurate, and circulating and stirring at 100-120°C for 30-60min to dehydrate and remove some volatile components to obtain a mixed binder; then adding 1-3wt% titanate to the mixed binder, and continuing to circulate and stir for 10-30min to obtain a high-performance environmentally friendly binder for blast furnace anhydrous taphole mud based on titanate.

4. The method for preparing a low-viscosity binder for anhydrous taphole mud based on titanate according to any one of claims 1 to 3, wherein the high-performance environmentally friendly binder for anhydrous taphole mud based on titanate is prepared.

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