Environmentally friendly high-strength thermal insulation castable for coke oven bottom

Abstract

The present application relates to the technical field of refractory materials, and specifically discloses an environmentally friendly high-strength thermal insulation castable for coke oven bottoms, which is prepared by the following steps: Step S1, preparing the following raw materials in parts by weight: 50 parts of mullite porous clinker, 10 parts of ultrafine silicon powder, 16 parts of aluminate cement, 6 parts of deionized water, and 0.4 parts of an admixture; Step S2, pressurizing and molding; The present application adds an admixture, which consists of a functionalized binder and modified carbon fibers, wherein the functionalized binder contains a phosphate group, an ester group, a benzene ring, a nano-silica structure, and an epoxy group, and the modified carbon fibers are prepared by oxidizing carbon fibers with a nitric acid aqueous solution. Through the synergistic effect of the above structures, the mechanical strength and thermal insulation performance of the castable are improved.

Description

Technical Field

[0001] The present application relates to the technical field of refractory materials, and more specifically, to an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. Background Art

[0002] A coke oven is an industrial furnace used to produce metallurgical coke, widely used in the steel, chemical, and other fields. The coke oven floor is a crucial component of the structure, supporting the coke and charge, preventing collapse or leakage, and maintaining heat and chemical reactions within the oven. To prevent heat loss during operation, improve coke quality, and conserve energy, insulating castables are often added to enhance the thermal insulation of the coke oven floor.

[0003] Among them, lightweight thermal insulation castables have excellent thermal insulation performance and good chemical stability.

[0004] It is widely used as thermal insulation castable for coke oven bottom. However, lightweight thermal insulation castable has the problem of low mechanical strength. Summary of the Invention

[0005] In order to solve the problems mentioned in the above background technology, the present application provides an environmentally friendly high-strength thermal insulation castable for coke oven bottom.

[0006] Environmentally friendly high-strength thermal insulation castable for coke oven bottom is prepared by the following steps:

[0007] Step S1, prepare the following raw materials in parts by weight: 40-50 parts of mullite porous clinker, 8-10 parts of ultrafine silica powder, 12-16 parts of aluminate cement, 2-6 parts of deionized water, and 0.2-0.4 parts of admixture;

[0008] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and aluminate cement are mixed, deionized water is added, stirred evenly, admixtures are added, stirring is continued for 12-16 minutes, pressure molding is performed, curing is performed, and baking is performed to obtain an environmentally friendly high-strength thermal insulation castable for coke oven bottom.

[0009] Preferably, the particle size of the ultrafine silicon powder is ≤0.015 mm.

[0010] Preferably, the admixture consists of a functionalized binder and modified carbon fibers, wherein the functionalized binder accounts for 72-84% and the rest is modified carbon fibers.

[0011] Preferably, the pressure of the press molding is 150-180 kg / m 2 ; The time for pressurizing and molding is 10-20s.

[0012] Preferably, the functionalized binder is prepared by the following steps:

[0013] Step A1: uniformly mix carbon tetrachloride and anhydrous THF, add dibutyl phosphite, and then add triethylamine and diethanolamine under an ice-water bath. The temperature is raised to 45-55° C., stirred and reacted for 8-10 hours, filtered, and the filtrate is rotary evaporated to obtain a hydroxy phosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 60-70:30-40:5-7:1.8-2.2:3.8-5.4. In the above reaction process, a hydroxy phosphate compound containing a hydroxyl group is obtained by Michael addition reaction using dibutyl phosphite and diethanolamine as raw materials;

[0014] Step A2, adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, stirring evenly, heating to reflux, stirring and reacting for 4-6 hours to obtain a modified solution, ultrasonically dispersing nanosilica in anhydrous THF, adding the modified solution and deionized water, heating to 52-56 ° C, stirring for 4-5 hours, after the stirring is completed, filtering, washing the filter cake, and drying to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxy phosphate compound to anhydrous DMF, heating to 35-45 ° C, stirring evenly, then heating to 72-80 ° C, continuing to stir and react for 6-8 hours, rotary evaporation, washing, and drying to obtain esterified The monomer comprises a silane coupling agent KH-550, 4-hydroxyphthalic anhydride, and anhydrous DMF in a mass ratio of 2-4:1.5-2.9:30-40; a nano-silica, anhydrous THF, a modifying liquid, and deionized water in a mass ratio of 3-5:45-55:16-20:6-8; and a carboxylated silica, p-toluenesulfonic acid, a hydroxy phosphate compound, and anhydrous DMF in a mass ratio of 2-3:0.02-0.04:1.6-2.4:55-65. The amount of the hydroxy phosphate compound is controlled to be slightly higher than that of the carboxylated silica so that after the reaction is completed, there are still residual hydroxyl groups that can participate in the subsequent reaction process.

[0015] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, raise the temperature to 64-68°C while stirring, then add triethylamine and toluene, add epichlorohydrin dropwise, complete the dropwise addition, stir and react for 3-4 hours, filter after the reaction, rotary evaporate, dissolve the rotary evaporated product in acetone, filter, and rotary evaporate the filtrate to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin and acetone is 42-64:520-640:2.8-4.6:6-12:22-26:320-360. In the above reaction process, with anhydrous DMF as solvent, triethylamine as catalyst, and toluene as dehydrating agent, the hydroxyl group on the esterification monomer and the chlorine atom on the epichlorohydrin undergo nucleophilic substitution reaction to obtain a functionalized binder.

[0016] Preferably, the modified carbon fiber is prepared by the following steps:

[0017] The carbon fiber is placed in acetone, stirred at 45-55°C for 8-12 hours, then taken out and washed to obtain pretreated carbon fiber. The pretreated carbon fiber is placed in a nitric acid aqueous solution, stirred at 80-90°C for 2-3 hours, filtered, and the filter cake is washed until the washing liquid is neutral to obtain modified carbon fiber, wherein the mass ratio of carbon fiber to acetone is 3-5:40, and the mass ratio of pretreated carbon fiber to nitric acid aqueous solution is 5:50-60. Acetone is used to remove impurities on the surface of the carbon fiber, and then it is oxidized with concentrated nitric acid to increase the oxygen-containing groups on the surface of the carbon fiber.

[0018] Preferably, the mass fraction of the nitric acid aqueous solution is 66-68%.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] In order to improve the thermal insulation performance and mechanical strength of the thermal insulation castable, the present application adds an admixture, which is composed of a functionalized binder and modified carbon fiber. The functionalized binder contains phosphate groups, ester groups, benzene rings, nano-silica structures and epoxy groups. The presence of phosphate groups and ester groups can produce multiple hydrogen bonds with the surface of cement hydration products and the active hydroxyl groups of modified carbon fibers, and the large steric hindrance of the rigid benzene ring improves the mechanical strength of the castable. The existence of the nano-silica structure, on the one hand, exerts the excellent mechanical properties and thermal stability of the inorganic particles themselves, and on the other hand, On the one hand, the silanol groups on nano-silica can also produce multiple hydrogen bonds with the surface of cement hydration products and the active hydroxyl groups of modified carbon fibers, thereby improving their compatibility while further improving the thermal insulation properties and mechanical strength of the castable. The presence of epoxy groups can chemically cross-link with the surface of cement hydration products and the active hydroxyl groups of modified carbon fibers, further improving the thermal insulation properties and mechanical strength of the castable. The presence of carbon fibers exerts its own reinforcing and toughening effects, and through the synergistic effect of functionalized binders and modified carbon fibers, the thermal insulation properties and mechanical strength of the castable are improved. DETAILED DESCRIPTION

[0021] In order to make the implementation methods of the present application easier to understand, the present application will be described in detail below with reference to specific examples. These examples are only for illustration and are not intended to limit the scope of application of the present application.

[0022] The contents of the main raw materials and their components used in the examples and comparative examples are as follows:

[0023] The porous mullite clinker is produced by Zibo Baoxing Industry and Trade Co., Ltd., with a compressive strength of 55MPa and a refractory temperature of 1700℃. The ultrafine silica powder is 325-mesh quartz powder, an industrial-grade high-purity ultrafine white ceramic silica powder produced by Lingshou Yongshun Mineral Products Processing Plant, with a melting point of 1750℃. The aluminate cement is Kerui Refractory Material Brand CA-60 refractory cement produced by Zhengzhou Kerui Refractory Material Co., Ltd., with a thermal conductivity of 0.030-0.035W / (m·K) and a flexural strength of 2.5-10.0MPa. The carbon fiber is chopped carbon fiber produced by Carboene Technology (Shenzhen) Co., Ltd., with a diameter of 7µm.

[0024] The present application is further described in detail below with reference to the following examples and comparative examples.

[0025] Preparation Examples 1-3 and Comparative Preparation Example 1 provide methods for preparing modified carbon fibers.

[0026] Preparation Example 1

[0027] This preparation example provides a method for preparing modified carbon fiber, which is prepared by the following steps:

[0028] The carbon fiber was placed in acetone, stirred at 45°C and a rotation speed of 500 rpm for 8 hours, then taken out and washed to obtain pretreated carbon fiber. The pretreated carbon fiber was placed in an aqueous nitric acid solution, stirred at 80°C and a rotation speed of 600 rpm for 2 hours, filtered, and the filter cake was washed with deionized water until the washing liquid was neutral to obtain modified carbon fiber, wherein the mass ratio of carbon fiber to acetone was 3:40, the mass ratio of pretreated carbon fiber to nitric acid aqueous solution was 5:50, and the mass fraction of nitric acid aqueous solution was 66%.

[0029] Preparation Example 2

[0030] This preparation example provides a method for preparing modified carbon fiber, which is prepared by the following steps:

[0031] The carbon fiber was placed in acetone, stirred at 50°C and a rotation speed of 550 rpm for 10 hours, then taken out and washed to obtain pretreated carbon fiber. The pretreated carbon fiber was placed in a nitric acid aqueous solution, stirred at 85°C and a rotation speed of 650 rpm for 2.5 hours, filtered, and the filter cake was washed with deionized water until the washing liquid was neutral to obtain modified carbon fiber, wherein the mass ratio of carbon fiber to acetone was 4:40, the mass ratio of pretreated carbon fiber to nitric acid aqueous solution was 5:55, and the mass fraction of nitric acid aqueous solution was 67%.

[0032] Preparation Example 3

[0033] This preparation example provides a method for preparing modified carbon fiber, which is prepared by the following steps:

[0034] The carbon fiber was placed in acetone, stirred at 55°C and a rotation speed of 550 rpm for 12 hours, then taken out and washed to obtain pretreated carbon fiber. The pretreated carbon fiber was placed in a nitric acid aqueous solution, stirred at 90°C and a rotation speed of 700 rpm for 3 hours, filtered, and the filter cake was washed with deionized water until the washing liquid was neutral to obtain modified carbon fiber, wherein the mass ratio of carbon fiber to acetone was 5:40, the mass ratio of pretreated carbon fiber to nitric acid aqueous solution was 5:60, and the mass fraction of nitric acid aqueous solution was 68%.

[0035] Comparative Preparation Example 1

[0036] This comparative preparation example provides a method for preparing modified carbon fiber, which is prepared by the following steps:

[0037] The carbon fiber was placed in acetone, stirred at 45°C and a rotation speed of 500 rpm for 8 hours, then taken out and washed to obtain pretreated carbon fiber. The pretreated carbon fiber was placed in anhydrous ethanol, stirred at 80°C and a rotation speed of 600 rpm for 2 hours, filtered, and the filter cake was washed with deionized water until the washing liquid was neutral to obtain modified carbon fiber, wherein the mass ratio of carbon fiber to acetone was 3:40, and the mass ratio of pretreated carbon fiber to anhydrous ethanol was 5:50.

[0038] Preparation Examples 4-6 and Comparative Preparation Examples 2-4 provide methods for preparing modified carbon fibers.

[0039] Preparation Example 4

[0040] This preparation example provides a method for preparing a functionalized binder, which is prepared by the following steps:

[0041] Step A1, stirring carbon tetrachloride and anhydrous THF at a speed of 550 rpm for 25 minutes until uniform, adding dibutyl phosphite, and then adding triethylamine and diethanolamine in an ice-water bath, raising the temperature to 45°C, maintaining the speed unchanged, stirring and reacting for 8 hours, filtering, and rotary evaporating the filtrate to remove anhydrous THF. The rotary evaporation temperature is controlled at 65°C to obtain a hydroxy phosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 60:30:5:1.8:3.8;

[0042] Step A2, adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, controlling the speed to 600 rpm, stirring for 20 minutes until uniform, heating to reflux, maintaining the speed unchanged, stirring and reacting for 4 hours to obtain a modified liquid, ultrasonically dispersing nanosilica in anhydrous THF, controlling the ultrasonic frequency to 35 kHz, the ultrasonic power to 550 w, ultrasonicating for 35 minutes, adding the modified liquid and deionized water, heating to 52 ° C, stirring at a speed of 650 rpm for 4 hours, after the stirring is completed, filtering, washing the filter cake with anhydrous ethanol and deionized water 3 times, and drying at 50 ° C to constant weight to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxy phosphate compound In anhydrous DMF, the temperature was raised to 35°C, the rotation speed was controlled at 650rpm, and the mixture was stirred for 25 minutes until uniform. The temperature was then raised to 72°C, and the stirring reaction was continued for 6 hours. The rotary evaporation temperature was controlled at 84°C, and the filtrate was rotary evaporated to remove anhydrous DMF. The mixture was then washed three times with anhydrous ethanol and deionized water, and dried at 55°C to constant weight to obtain an esterified monomer, wherein the mass ratio of silane coupling agent KH-550, 4-hydroxyphthalic anhydride and anhydrous DMF was 2:1.5:30, the mass ratio of nanosilica, anhydrous THF, modifying liquid and deionized water was 3:45:16:6, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF was 2:0.02:1.6:55;

[0043] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, control the ultrasonic frequency to 30kHz, the ultrasonic power to 500w, ultrasonicate for 30min, stir at a speed of 500rpm and raise the temperature to 64°C, then add triethylamine and toluene, add epichlorohydrin dropwise, control the dripping to be completed within 10min, maintain the speed unchanged, stir and react for 3h, after the reaction is completed, filter, control the rotary evaporation temperature to 82°C, rotary evaporate the filtrate to remove anhydrous DMF, place the rotary evaporation product in acetone and dissolve it, filter to remove triethylamine hydrochloride, control the rotary evaporation temperature to 40°C, and rotary evaporate the filtrate to remove acetone to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin and acetone is 42:520:2.8:6:22:320.

[0044] Preparation Example 5

[0045] This preparation example provides a method for preparing a functionalized binder, which is prepared by the following steps:

[0046] Step A1, stirring carbon tetrachloride and anhydrous THF at a speed of 600 rpm for 30 minutes until uniform, adding dibutyl phosphite, and then adding triethylamine and diethanolamine in an ice-water bath, heating to 50°C, maintaining the speed unchanged, stirring and reacting for 9 hours, filtering, and rotary evaporating the filtrate until the anhydrous THF is removed. The rotary evaporation temperature is controlled at 66°C to obtain a hydroxy phosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 65:35:6:2.0:4.6;

[0047] Step A2, adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, controlling the speed to 550 rpm, stirring for 25 minutes until uniform, heating to reflux, maintaining the speed unchanged, stirring and reacting for 5 hours to obtain a modified solution, ultrasonically dispersing nanosilica in anhydrous THF, controlling the ultrasonic frequency to 40 kHz, the ultrasonic power to 600 w, and ultrasonicating for 30 minutes, adding the modified solution and deionized water, heating to 54°C, stirring at a speed of 630 rpm for 4.5 hours, after the stirring is completed, filtering, washing the filter cake with anhydrous ethanol and deionized water 4 times, and drying at 55°C to constant weight to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxyphosphate compound to anhydrous D The mixture was heated to 40°C in MF, the rotation speed was controlled at 700 rpm, and the mixture was stirred for 30 min until uniform. The rotation speed was maintained constant, and the mixture was heated to 76°C and the stirring reaction was continued for 7 h. The rotary evaporation temperature was controlled at 82°C, and the anhydrous DMF was removed by rotary evaporation. The mixture was then washed with anhydrous ethanol and deionized water for 4 times, and dried at 60°C to constant weight to obtain an esterified monomer, wherein the mass ratio of silane coupling agent KH-550, 4-hydroxyphthalic anhydride and anhydrous DMF was 3:2.2:35, the mass ratio of nano-silica, anhydrous THF, modification liquid and deionized water was 4:50:18:7, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF was 2.5:0.03:2.0:60.

[0048] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, control the ultrasonic frequency to 35kHz, the ultrasonic power to 550w, ultrasonic for 35min, and the speed to 600rpm while stirring and heating to 66°C, then add triethylamine and toluene, add epichlorohydrin dropwise, control the dripping to be completed within 10min, and stir the reaction for 3.5h. After the reaction is completed, filter, control the rotary evaporation temperature to 84°C, and rotary evaporate the filtrate to remove anhydrous DMF. The rotary evaporation product is placed in acetone and dissolved, and triethylamine hydrochloride is filtered to remove the triethylamine hydrochloride. The rotary evaporation temperature is controlled to 42°C, and the filtrate is rotary evaporated until the acetone is removed to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin and acetone is 53:580:3.7:9:24:340.

[0049] Preparation Example 6

[0050] This preparation example provides a method for preparing a functionalized binder, which is prepared by the following steps:

[0051] Step A1, stirring carbon tetrachloride and anhydrous THF at 650 rpm for 35 minutes until uniform, adding dibutyl phosphite, and then adding triethylamine and diethanolamine in an ice-water bath, heating to 55°C, stirring and reacting for 10 hours, filtering, and rotary evaporating the filtrate to remove anhydrous THF. The rotary evaporation temperature is controlled at 67°C to obtain a hydroxy phosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 70:40:7:2.2:5.4;

[0052] Step A2, adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, controlling the speed to 600 rpm, stirring for 30 minutes until uniform, heating to reflux, maintaining the speed unchanged, stirring and reacting for 6 hours to obtain a modified solution, ultrasonically dispersing nanosilica in anhydrous THF, controlling the ultrasonic frequency to 30 kHz, the ultrasonic power to 500 w, and ultrasonicating for 40 minutes, adding the modified solution and deionized water, heating to 56 ° C, stirring at a speed of 610 rpm for 5 hours, after the stirring is completed, filtering, washing the filter cake with anhydrous ethanol and deionized water 5 times, and drying at 60 ° C to constant weight to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxyphosphate compound to anhydrous D In MF, the temperature was raised to 45°C, the rotation speed was controlled to 750 rpm, and the mixture was stirred for 35 min until uniform. The rotation speed was maintained unchanged, and the temperature was raised to 80°C, and the stirring reaction was continued for 8 h. The rotary evaporation temperature was controlled to 82°C, and the anhydrous DMF was removed by rotary evaporation. The mixture was then washed with anhydrous ethanol and deionized water for 5 times, and dried at 65°C to constant weight to obtain an esterified monomer, wherein the mass ratio of silane coupling agent KH-550, 4-hydroxyphthalic anhydride and anhydrous DMF was 4:2.9:40, the mass ratio of nano-silica, anhydrous THF, modifying liquid and deionized water was 5:55:20:8, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF was 3:0.04:2.4:65.

[0053] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, control the ultrasonic frequency to 40kHz, the ultrasonic power to 600w, ultrasonic for 40min, and the speed to 700rpm while stirring and heating to 68°C, then add triethylamine and toluene, add epichlorohydrin dropwise, control the dripping to be completed within 10min, and stir the reaction for 4h. After the reaction is completed, filter, control the rotary evaporation temperature to 86°C, and rotary evaporate the filtrate to remove anhydrous DMF. The rotary evaporation product is placed in acetone and dissolved, and triethylamine hydrochloride is filtered to remove. The rotary evaporation temperature is controlled to 44°C, and the filtrate is rotary evaporated to remove acetone to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin and acetone is 64:640:4.6:12:26:360.

[0054] Comparative Preparation Example 2

[0055] This comparative preparation example provides a method for preparing a functionalized binder, which is prepared by the following steps:

[0056] Step A1, stirring carbon tetrachloride and anhydrous THF at a speed of 550 rpm for 25 minutes until uniform, adding dibutyl maleate, and then adding triethylamine and diethanolamine in an ice-water bath, heating to 45°C, maintaining the speed unchanged, stirring and reacting for 8 hours, filtering, and rotary evaporating the filtrate to remove anhydrous THF. The rotary evaporation temperature is controlled at 65°C to obtain a hydroxyphosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl maleate, triethylamine and diethanolamine is 60:30:5:1.8:3.8;

[0057] Step A2, adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, controlling the speed to 600 rpm, stirring for 20 minutes until uniform, heating to reflux, maintaining the speed unchanged, stirring and reacting for 4 hours to obtain a modified liquid, ultrasonically dispersing nanosilica in anhydrous THF, controlling the ultrasonic frequency to 35 kHz, the ultrasonic power to 550 w, ultrasonicating for 35 minutes, adding the modified liquid and deionized water, heating to 52 ° C, stirring at a speed of 650 rpm for 4 hours, after the stirring is completed, filtering, washing the filter cake with anhydrous ethanol and deionized water 3 times, and drying at 50 ° C to constant weight to obtain carboxylated silica; carboxylated silica, p-toluenesulfonic acid and hydroxy phosphate are mixed. The product was added to anhydrous DMF, heated to 35°C, controlled at a speed of 650rpm, stirred for 25min until uniform, then heated to 72°C, continued to stir and react for 6h, controlled at a rotary evaporation temperature of 84°C, and the filtrate was rotary evaporated to remove anhydrous DMF, and then washed with anhydrous ethanol and deionized water three times in sequence, and dried at 55°C to constant weight, wherein the mass ratio of silane coupling agent KH-550, 4-hydroxyphthalic anhydride and anhydrous DMF was 2:1.5:30, the mass ratio of nano-silica, anhydrous THF, modification liquid and deionized water was 3:45:16:6, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF was 2:0.02:1.6:55;

[0058] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, control the ultrasonic frequency to 30kHz, the ultrasonic power to 500w, ultrasonicate for 30min, stir at a speed of 500rpm and raise the temperature to 64°C, then add triethylamine and toluene, add epichlorohydrin dropwise, control the dripping to be completed within 10min, maintain the speed unchanged, stir and react for 3h, after the reaction is completed, filter, control the rotary evaporation temperature to 82°C, rotary evaporate the filtrate to remove anhydrous DMF, place the rotary evaporation product in acetone and dissolve it, filter to remove triethylamine hydrochloride, control the rotary evaporation temperature to 40°C, and rotary evaporate the filtrate to remove acetone to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin and acetone is 42:520:2.8:6:22:320.

[0059] Comparative Preparation Example 3

[0060] This comparative preparation example provides a method for preparing a functionalized binder, which is prepared by the following steps:

[0061] Step A1, stirring carbon tetrachloride and anhydrous THF at a speed of 550 rpm for 25 minutes until uniform, adding dibutyl phosphite, and then adding triethylamine and diethanolamine in an ice-water bath, raising the temperature to 45°C, maintaining the speed unchanged, stirring and reacting for 8 hours, filtering, and rotary evaporating the filtrate to remove anhydrous THF. The rotary evaporation temperature is controlled at 65°C to obtain a hydroxy phosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 60:30:5:1.8:3.8;

[0062] Step A2, adding silane coupling agent KH-550 and 2-methylsuccinic anhydride to anhydrous THF, controlling the speed to 600 rpm, stirring for 20 minutes until uniform, heating to reflux, maintaining the speed unchanged, stirring and reacting for 4 hours to obtain a modified solution, ultrasonically dispersing nanosilica in anhydrous THF, controlling the ultrasonic frequency to 35 kHz, the ultrasonic power to 550 w, ultrasonicating for 35 minutes, adding the modified solution and deionized water, heating to 52 ° C, stirring at a speed of 650 rpm for 4 hours, after the stirring is completed, filtering, washing the filter cake with anhydrous ethanol and deionized water 3 times, and drying at 50 ° C to constant weight to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxyphosphate compound In anhydrous DMF, the temperature was raised to 35°C, the rotation speed was controlled at 650rpm, and the mixture was stirred for 25 minutes until uniform. The temperature was then raised to 72°C, and the stirring reaction was continued for 6 hours. The rotary evaporation temperature was controlled at 84°C, and the filtrate was rotary evaporated to remove anhydrous DMF. The mixture was then washed three times with anhydrous ethanol and deionized water, and dried at 55°C to constant weight to obtain an esterified monomer, wherein the mass ratio of silane coupling agent KH-550, 2-methylsuccinic anhydride and anhydrous DMF was 2:1.5:30, the mass ratio of nanosilica, anhydrous THF, modification liquid and deionized water was 3:45:16:6, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF was 2:0.02:1.6:55;

[0063] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, control the ultrasonic frequency to 30kHz, the ultrasonic power to 500w, ultrasonicate for 30min, stir at a speed of 500rpm and raise the temperature to 64°C, then add triethylamine and toluene, add epichlorohydrin dropwise, control the dripping to be completed within 10min, maintain the speed unchanged, stir and react for 3h, after the reaction is completed, filter, control the rotary evaporation temperature to 82°C, rotary evaporate the filtrate to remove anhydrous DMF, place the rotary evaporation product in acetone and dissolve it, filter to remove triethylamine hydrochloride, control the rotary evaporation temperature to 40°C, and rotary evaporate the filtrate to remove acetone to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin and acetone is 42:520:2.8:6:22:320.

[0064] Comparative Preparation Example 4

[0065] This comparative preparation example provides a method for preparing a functionalized binder, which is prepared by the following steps:

[0066] Step A1, stirring carbon tetrachloride and anhydrous THF at a speed of 550 rpm for 25 minutes until uniform, adding dibutyl phosphite, and then adding triethylamine and diethanolamine in an ice-water bath, raising the temperature to 45°C, maintaining the speed unchanged, stirring and reacting for 8 hours, filtering, and rotary evaporating the filtrate to remove anhydrous THF. The rotary evaporation temperature is controlled at 65°C to obtain a hydroxy phosphate compound, wherein the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 60:30:5:1.8:3.8;

[0067] Step A2, adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, controlling the speed to 600 rpm, stirring for 20 minutes until uniform, heating to reflux, maintaining the speed unchanged, stirring and reacting for 4 hours to obtain a modified liquid, ultrasonically dispersing nanosilica in anhydrous THF, controlling the ultrasonic frequency to 35 kHz, the ultrasonic power to 550 w, ultrasonicating for 35 minutes, adding the modified liquid and deionized water, heating to 52 ° C, stirring at a speed of 650 rpm for 4 hours, after the stirring is completed, filtering, washing the filter cake with anhydrous ethanol and deionized water 3 times, and drying at 50 ° C to constant weight to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxy phosphate compound In anhydrous DMF, the temperature was raised to 35°C, the rotation speed was controlled at 650rpm, and the mixture was stirred for 25 minutes until uniform. The temperature was then raised to 72°C, and the stirring reaction was continued for 6 hours. The rotary evaporation temperature was controlled at 84°C, and the filtrate was rotary evaporated to remove anhydrous DMF. The mixture was then washed three times with anhydrous ethanol and deionized water, and dried at 55°C to constant weight to obtain an esterified monomer, wherein the mass ratio of silane coupling agent KH-550, 4-hydroxyphthalic anhydride and anhydrous DMF was 2:1.5:30, the mass ratio of nanosilica, anhydrous THF, modifying liquid and deionized water was 3:45:16:6, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF was 2:0.02:1.6:55;

[0068] Step A3, ultrasonically disperse the esterification monomer in anhydrous DMF, control the ultrasonic frequency to 30kHz, the ultrasonic power to 500w, ultrasonicate for 30min, stir at a speed of 500rpm and raise the temperature to 64°C, then add triethylamine and toluene, add 2-chloropropane dropwise, control the dripping to be completed within 10min, maintain the speed unchanged, stir and react for 3h, after the reaction is completed, filter, control the rotary evaporation temperature to 82°C, rotary evaporate the filtrate to remove anhydrous DMF, dissolve the rotary evaporation product in acetone, filter to remove triethylamine hydrochloride, control the rotary evaporation temperature to 40°C, and rotary evaporate the filtrate to remove acetone to obtain a functionalized binder, wherein the mass ratio of the esterification monomer, anhydrous DMF, triethylamine, toluene, 2-chloropropane and acetone is 42:520:2.8:6:22:320.

[0069] Examples 1-3 and comparative examples 1-4 provide environmentally friendly high-strength thermal insulation castables for coke oven bottoms.

[0070] Example 1

[0071] This embodiment provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0072] Step S1, preparing the following raw materials in parts by weight: 40 parts of mullite porous clinker, 8 parts of ultrafine silica powder, 12 parts of CA-60 aluminate cement, 2 parts of deionized water, and 0.2 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Preparation Example 4 and the modified carbon fiber prepared in Preparation Example 1, with the functionalized binder accounting for 72% and the remainder being the modified carbon fiber;

[0073] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1100 rpm for 3 minutes until mixed, deionized water is added, the speed is adjusted to 600 rpm and stirred for 20 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 12 minutes, pressure molding is performed, and then placed at a temperature of 25 ° C and a relative humidity of 95% RH for 2 days, and then baked at 110 ° C for 36 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 150 kg / m 2 , the press molding time is 10s.

[0074] Example 2

[0075] This embodiment provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0076] Step S1, preparing the following raw materials in parts by weight: 45 parts of mullite porous clinker, 9 parts of ultrafine silica powder, 14 parts of CA-60 aluminate cement, 4 parts of deionized water, and 0.3 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Preparation Example 5 and the modified carbon fiber prepared in Preparation Example 2, with the functionalized binder accounting for 78% and the remainder being the modified carbon fiber;

[0077] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1200 rpm for 4 minutes until mixed, deionized water is added, the speed is adjusted to 700 rpm and stirred for 22 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 14 minutes, pressure molding is performed, and then placed at a temperature of 25°C and a relative humidity of 95% RH for 2.5 days, and then baked at 115°C for 42 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 165 kg / m 2 , the press molding time is 15s.

[0078] Example 3

[0079] This embodiment provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0080] Step S1, preparing the following raw materials in parts by weight: 50 parts of mullite porous clinker, 10 parts of ultrafine silica powder, 16 parts of CA-60 aluminate cement, 6 parts of deionized water, and 0.4 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Preparation Example 6 and the modified carbon fiber prepared in Preparation Example 3, with the functionalized binder accounting for 84% and the remainder being the modified carbon fiber;

[0081] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1300 rpm for 5 minutes until mixed, deionized water is added, the speed is adjusted to 800 rpm and stirred for 24 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 16 minutes, pressure molding is performed, and then placed at a temperature of 25°C and a relative humidity of 95% RH for 3 days, and then baked at 120°C for 48 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 180 kg / m 2 , the press molding time is 20s.

[0082] Comparative Example 1

[0083] This comparative example provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0084] Step S1, preparing the following raw materials in parts by weight: 40 parts of mullite porous clinker, 8 parts of ultrafine silica powder, 12 parts of CA-60 aluminate cement, 2 parts of deionized water, and 0.2 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Preparation Example 4 and the modified carbon fiber prepared in Comparative Preparation Example 1, with the functionalized binder accounting for 72% and the remainder being the modified carbon fiber;

[0085] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1100 rpm for 3 minutes until mixed, deionized water is added, the speed is adjusted to 600 rpm and stirred for 20 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 12 minutes, pressure molding is performed, and then placed at a temperature of 25 ° C and a relative humidity of 95% RH for 2 days, and then baked at 110 ° C for 36 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 150 kg / m 2 , the press molding time is 10s.

[0086] Comparative Example 2

[0087] This comparative example provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0088] Step S1, preparing the following raw materials in parts by weight: 40 parts of mullite porous clinker, 8 parts of ultrafine silica powder, 12 parts of CA-60 aluminate cement, 2 parts of deionized water, and 0.2 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Comparative Preparation Example 2 and the modified carbon fiber prepared in Preparation Example 1, with the functionalized binder accounting for 72% and the remainder being the modified carbon fiber;

[0089] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1100 rpm for 3 minutes until mixed, deionized water is added, the speed is adjusted to 600 rpm and stirred for 20 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 12 minutes, pressure molding is performed, and then placed at a temperature of 25 ° C and a relative humidity of 95% RH for 2 days, and then baked at 110 ° C for 36 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 150 kg / m 2 , the press molding time is 10s.

[0090] Comparative Example 3

[0091] This comparative example provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0092] Step S1, preparing the following raw materials in parts by weight: 40 parts of mullite porous clinker, 8 parts of ultrafine silica powder, 12 parts of CA-60 aluminate cement, 2 parts of deionized water, and 0.2 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Comparative Preparation Example 3 and the modified carbon fiber prepared in Preparation Example 1, with the functionalized binder accounting for 72% and the remainder being the modified carbon fiber;

[0093] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1100 rpm for 3 minutes until mixed, deionized water is added, the speed is adjusted to 600 rpm and stirred for 20 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 12 minutes, pressure molding is performed, and then placed at a temperature of 25 ° C and a relative humidity of 95% RH for 2 days, and then baked at 110 ° C for 36 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 150 kg / m 2 , the press molding time is 10s.

[0094] Comparative Example 4

[0095] This comparative example provides an environmentally friendly high-strength thermal insulation castable for a coke oven bottom. The environmentally friendly high-strength thermal insulation castable for a coke oven bottom is prepared by the following steps:

[0096] Step S1, preparing the following raw materials in parts by weight: 40 parts of mullite porous clinker, 8 parts of ultrafine silica powder, 12 parts of CA-60 aluminate cement, 2 parts of deionized water, and 0.2 parts of an admixture, wherein the admixture is composed of the functionalized binder prepared in Comparative Preparation Example 4 and the modified carbon fiber prepared in Preparation Example 1, with the functionalized binder accounting for 72% and the remainder being the modified carbon fiber;

[0097] Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and CA-60 aluminate cement are stirred at 1100 rpm for 3 minutes until mixed, deionized water is added, the speed is adjusted to 600 rpm and stirred for 20 minutes until mixed, admixtures are added, the speed is maintained unchanged, stirring is continued for 12 minutes, pressure molding is performed, and then placed at a temperature of 25 ° C and a relative humidity of 95% RH for 2 days, and then baked at 110 ° C for 36 hours to obtain an environmentally friendly high-strength coke oven bottom insulation castable, wherein the pressure of the pressure molding is 150 kg / m 2 , the press molding time is 10s.

[0098] Performance testing

[0099] The flexural strength is tested in accordance with GB / T3001-2007; the compressive strength is tested in accordance with GB / T5072-2008; the thermal conductivity is tested in accordance with GB / T 10294-2008, as shown in Table 1.

[0100] Table 1 Mechanical strength and thermal conductivity test of thermal insulation castables obtained in Examples 1-3 and Comparative Examples 1-4

[0101]

[0102] It can be seen from Table 1 that compared with Comparative Examples 1-4, the environmentally friendly high-strength coke oven bottom insulation castables used in Examples 1-3 have better flexural strength and higher flexural strength, and lower thermal conductivity, which shows that the insulation castables prepared in this application have better mechanical strength and thermal insulation performance.

[0103] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. Environmentally friendly high-strength thermal insulation castable for coke oven bottom, characterized by: Prepared by the following steps: Step S1, prepare the following raw materials in parts by weight: 40-50 parts of mullite porous clinker, 8-10 parts of ultrafine silica powder, 12-16 parts of aluminate cement, 2-6 parts of deionized water, and 0.2-0.4 parts of admixture; Step S2, pressure molding: Mullite porous clinker, ultrafine silica powder and aluminate cement are mixed, deionized water is added, stirred evenly, admixtures are added, stirring is continued for 12-16 minutes, pressure molding is performed, curing is performed, and baking is performed to obtain an environmentally friendly high-strength thermal insulation castable for coke oven bottom; The admixture is composed of a functionalized binder and modified carbon fibers, wherein the functionalized binder accounts for 72-84% and the rest is modified carbon fibers; The functionalized binder is prepared by the following steps: Step A1: Mix carbon tetrachloride and anhydrous THF, add dibutyl phosphite, add triethylamine and diethanolamine under ice-water bath, raise the temperature to 45-55°C, stir and react for 8-10 hours, filter with suction, and rotary evaporate the filtrate to obtain a hydroxy phosphate compound; Step A2: adding silane coupling agent KH-550 and 4-hydroxyphthalic anhydride to anhydrous THF, stirring evenly, heating to reflux, stirring and reacting for 4-6 hours to obtain a modified solution, ultrasonically dispersing nanosilica in anhydrous THF, adding the modified solution and deionized water, heating to 52-56° C., stirring for 4-5 hours, and filtering after the stirring is completed. The filter cake is washed and dried to obtain carboxylated silica; adding carboxylated silica, p-toluenesulfonic acid and hydroxyphosphate compound to anhydrous DMF, heating to 35-45° C., stirring evenly, then heating to 72-80° C., continuing to stir and react for 6-8 hours, rotary evaporation, washing, and drying to obtain an esterified monomer; Step A3, ultrasonically dispersing the esterified monomer in anhydrous DMF, raising the temperature to 64-68° C. while stirring, then adding triethylamine and toluene, and dropwise adding epichlorohydrin. After the addition is complete, stirring and reacting for 3-4 hours. After the reaction is completed, filtering, rotary evaporation, dissolving the rotary evaporation product in acetone, filtering, and rotary evaporation of the filtrate to obtain a functionalized binder; The modified carbon fiber is firstly prepared by treating carbon fiber with acetone to obtain pretreated carbon fiber, and then undergoing oxidation reaction with concentrated nitric acid.

2. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: In the step A1, the mass ratio of carbon tetrachloride, anhydrous THF, dibutyl phosphite, triethylamine and diethanolamine is 60-70:30-40:5-7:1.8-2.2:3.8-5.

4.

3. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: In step A2, the mass ratio of silane coupling agent KH-550, 4-hydroxyphthalic anhydride and anhydrous DMF is 2-4:1.5-2.9:30-40, the mass ratio of nano-silica, anhydrous THF, modifying liquid and deionized water is 3-5:45-55:16-20:6-8, and the mass ratio of carboxylated silica, p-toluenesulfonic acid, hydroxyphosphate compound and anhydrous DMF is 2-3:0.02-0.04:1.6-2.4:55-65.

4. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: In the step A3, the mass ratios of the esterification monomer, anhydrous DMF, triethylamine, toluene, epichlorohydrin, and acetone are 42-64: 520-640: 2.8-4.6: 6-12: 22-26: 320-360.

5. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: The modified carbon fiber is prepared by the following steps: The carbon fiber is placed in acetone, stirred at 45-55°C for 8-12 hours, taken out, and washed to obtain pretreated carbon fiber. The pretreated carbon fiber is placed in 66-68% concentrated nitric acid by mass, stirred at 80-90°C for 2-3 hours, filtered, and the filter cake is washed until the washing liquid is neutral to obtain modified carbon fiber.

6. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 5, characterized in that: The mass ratio of the carbon fiber to acetone is 3-5:40, and the mass ratio of the pretreated carbon fiber to concentrated nitric acid is 5:50-60.

7. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: In step S1, the particle size of the ultrafine silicon powder is ≤0.015 mm.

8. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: In step S1, the aluminate cement is CA-60 aluminate cement.

9. The environmentally friendly high-strength thermal insulation castable for coke oven bottom according to claim 1, characterized in that: The pressure of the press molding is 150-180 kg / m 2 ; The time for pressurizing and molding is 10-20s.

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