Iron-containing corundum-high iron mullite solid solution raw material and preparation method thereof

Abstract

The application discloses a kind of iron-containing corundum-high iron mullite solid solution raw materials and preparation method thereof, it is related to refractory material field, low-grade bauxite is selected, and it is obtained by crushing-flotation-sintering process;Including the following components: alumina, silicon dioxide, iron oxide, titanium dioxide, calcium oxide and other impurities;The application precisely controls Al / Si / Fe ratio by sulfonic acid-phosphoric acid double-modified cellulose as depressor in flotation process, realizes raw material homogenization and composition optimization, the micro-distribution of Fe2O3 and Al2O3 in flotation concentrate is more uniform, homogeneous solid solution is formed when sintering, avoid generating low melting point phase, improve material fire resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of refractory materials, in particular to a kind of iron-containing corundum-high iron mullite solid solution raw material and preparation method thereof. BACKGROUND

[0002] Bauxite is a very important strategic resource. In recent years, with the rapid development of high alumina bauxite clinker, the problems are increasingly exposed: (1) excessive exploitation and consumption lead to the depletion of high-quality bauxite resources in China, and a large amount of medium and low-grade ore and ore are abandoned due to high processing cost and difficulty in development and utilization, causing great waste of resources and environmental pollution; (2) the quality stability of calcined high alumina bauxite clinker is poor, and cannot win the market in quality, and looking at the development trend of refractory raw materials, high-quality synthetic raw materials are more used in high-efficiency products for many important uses.

[0003] Low-grade bauxite has lower Al2O3 content and higher SiO2 content. In order to economically and reasonably utilize the medium and low alumina-silicon ratio bauxite resources in China, since the 1970s of last century, many small-scale flotation desilication tests have been carried out on diaspore, and finally various beneficiation process flows such as stage grinding-flotation desilication process, stage grinding-stage beneficiation, selective agglomeration flotation and selective grinding-selective agglomeration flotation are determined. The SiO2 content of the raw material after beneficiation can be effectively reduced, but the Fe2O3 in the raw ore cannot be effectively removed.

[0004] Therefore, the present application introduces the flotation process into the production of raw materials for refractory materials, and adjusts the alumina-silicon ratio in the material through flotation, and plays a homogenizing role on the composition of the material. In view of the problem of high Fe content in the raw material, based on the design of Fe2O3-Al2O3-SiO2 ternary system, a low-temperature liquid phase sintering method for preparing iron-rich mullite is invented, which solves the problem of low mullite conversion rate in traditional solid phase sintering process. SUMMARY

[0005] In order to solve the above technical problems, the present application provides an iron-containing corundum-high iron mullite solid solution raw material and a preparation method thereof.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material, comprising the following steps:

[0008] S1, selecting low-grade bauxite as raw material, crushing the raw material to obtain pretreated particles;

[0009] S2, the pretreated particles are mixed and stacked, and the homogenization is carried out for 2-3 days by using the method of flat laying, to obtain homogenized ore particles;

[0010] S3, performing a flotation process on the homogenized ore particles, and performing pressure filtration and drying on the concentrate obtained by the flotation to obtain concentrate particles;

[0011] S4, adding lignin sulfonate with a mass fraction of 3-5% to the concentrate particles, pressing into a cylindrical blank by a hydraulic press, and performing gradient sintering on the cylindrical blank, and after holding for 4-6 h, cooling in the furnace to 200-400 ℃ and then discharging from the furnace to obtain an iron-containing corundum-high iron mullite solid solution raw material.

[0012] Further, the aluminum-silicon ratio of the low-grade bauxite in the step S1 is 1.5-2.6:1, the alumina content is 40-60%, and the main mineral phase is diaspore.

[0013] Further, the flotation process in the step S3 includes 1-2 times of roughing, 1-2 times of cleaning, and 1-2 times of scavenging.

[0014] Further, the flotation process in the step S3 is:

[0015] (1) performing grinding treatment on the homogenized ore particles to obtain ore powder material with a particle size of ≤0.075 mm, performing concentration treatment on the ore powder material to obtain concentrated ore slurry with a mass concentration of 30-50%, and sequentially adding 2-3 kg / t of an adjusting agent, 0.5-1.2 kg / t of an inhibitor, and 0.8-1.5 kg / t of a collector to perform roughing once to obtain roughing concentrate and roughing tailings;

[0016] (2) supplementing 0.1-0.3 kg / t of the inhibitor and 0.05-0.1 kg / t of the collector in the roughing concentrate, maintaining the pH at 9.0-9.5, and performing cleaning once to obtain cleaning concentrate and cleaning tailings;

[0017] (3) mixing the roughing tailings and the cleaning tailings, supplementing 0.2-0.4 kg / t of the collector, and performing scavenging once to obtain scavenging concentrate and scavenging tailings, discarding the scavenging tailings, returning the scavenging concentrate to the roughing operation, and performing closed-circuit flotation to finally obtain the concentrate.

[0018] Further, the adjusting agent is sodium carbonate, the inhibitor is sulfonic acid-phosphoric acid double-modified cellulose, and the collector is a mixture of dodecylamine and sodium oleate, wherein the weight ratio of dodecylamine to sodium oleate is 3:1.

[0019] Further, the preparation method of the sulfonic acid-phosphoric acid double-modified cellulose is:

[0020] Sulfonated carboxymethyl cellulose is obtained by dispersing carboxymethyl cellulose in deionized water, stirring for 20-40 min, adding sulfamic acid, adjusting pH to 5-6 with 5% sodium hydroxide solution, water bath reaction at 60-100 ℃ for 2-5 h, cooling to room temperature, precipitating and washing with ethanol, and vacuum drying at 50-70 ℃.

[0021] Further, the use amount ratio of the carboxymethyl cellulose, deionized water and sulfamic acid is 8-15 g: 120-180 mL: 2-5 g; the use amount ratio of the sulfonated carboxymethyl cellulose, deionized water, sodium tripolyphosphate and urea is 8-15 g: 80-150 mL: 1-5 g: 0.5-1.0 g.

[0022] Further, the plate and frame filter press is used for pressure filtration in the step S3, the pressure is set to 0.8-1.2 MPa, and the obtained filter cake has a water content of ≤18%; the drying is performed in a rotary drying kiln, the temperature is controlled to be 200-250 ℃, the time is 1-2 h, and the outlet moisture is ≤1%.

[0023] Further, the gradient sintering method in the step S4 is as follows:

[0024] Stage 1: room temperature-600 ℃, the temperature rising speed is 2 ℃ / min;

[0025] Stage 2: 600 ℃-1450 ℃, the temperature rising speed is 5 ℃ / min;

[0026] Stage 3: 1450 ℃-1600 ℃, the temperature rising speed is 2 ℃ / min.

[0027] An iron-containing corundum-high-iron mullite solid solution raw material includes the following components in percentage by weight: 5-30 wt% of silicon dioxide, 5-12 wt% of iron oxide, 1-3 wt% of titanium dioxide, 1-3 wt% of calcium oxide, 0.1-1 wt% of other impurities, and the balance of aluminum oxide.

[0028] The present application has the following beneficial effects:

[0029] (1) The sulfonic acid-phosphoric acid double-modified cellulose has a phosphoric acid ester group (-PO4 2‐) and Al-OH in bauxite specifically, forming stable Al-O-P bonds, effectively inhibiting the excessive floating of aluminum minerals, while Fe2O3 minerals are not affected due to the difference in surface properties, the recovery rate of Al2O3 is improved, and the retention rate of Fe2O3 is increased, ensuring the stability of the iron-aluminum ratio in subsequent sintering, in addition, the sulfonic acid-phosphoric acid double-modified cellulose has weak inhibition on silicate minerals, and can efficiently remove silicon in combination with the collector to avoid the generation of too much glass phase during sintering, which affects the high-temperature performance, and the sulfonic acid-phosphoric acid double-modified cellulose inhibitor precisely regulates the Al / Si / Fe ratio, realizes raw material homogenization and composition optimization;

[0030] (2) The sulfonic acid group (-SO3H) has a synergistic effect, which enhances the water solubility and dispersibility of the sulfonic acid-phosphoric acid double-modified cellulose, avoids the agglomeration of the reagent, and makes the inhibitor uniformly cover the surface of the aluminum mineral, reducing the reagent dosage;

[0031] (3) The micro-distribution of Fe2O3 and Al2O3 in the flotation concentrate is more uniform, and Fe 3+ is more easily diffused into the corundum lattice to form a homogeneous solid solution, inhibiting the aggregation of free Fe2O3, and the uniformly distributed Fe2O3 reduces the Fe2O3→Fe3O4 reduction reaction caused by local enrichment, avoiding the generation of low-melting-point phases, improving the refractoriness of the material, and realizing efficient conversion of low-grade bauxite to high-performance refractory materials, with the improvement of resource utilization rate and product added value. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0033] The gradient sintering method in each of the following examples is as follows:

[0034] Stage 1: room temperature-600℃, heating rate 2℃ / min;

[0035] Stage 2: 600℃-1450℃, heating rate 5℃ / min;

[0036] Stage 3: 1450℃-1600℃, heating rate 2℃ / min.

[0037] Example 1

[0038] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material, comprising the following steps:

[0039] S1, a low-grade bauxite (aluminum-silicon ratio of 1.5:1; alumina content of 40%, main mineral phase is diaspore) is selected as raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then sieved through a 100-mesh sieve to obtain pretreated particles;

[0040] S2, the pretreated particles are mixed and stacked, and a flat stacking method is used to homogenize for 2 days to obtain homogenized ore particles;

[0041] S3, the homogenized ore particles are subjected to a flotation process, the concentrate obtained by flotation is pressure filtered (a plate and frame filter press is used, the pressure is set to 0.8 MPa, and the moisture content of the obtained filter cake is ≤18%), and dried (in a rotary drying kiln, the temperature is controlled at 200°C, the time is 1h, and the outlet moisture content is ≤1%), to obtain concentrate particles;

[0042] S4, 3% by mass of sodium lignosulfonate is added to the concentrate particles, and a hydraulic press is used to press into a cylindrical blank, and the cylindrical blank is subjected to gradient sintering, and after holding for 4h, the furnace is cooled to 200°C and then discharged, to obtain an iron-containing corundum-high iron mullite solid solution raw material with a bulk density of 2.4g / cm 3 The iron-containing corundum-high iron mullite solid solution raw material has a bulk density of 2.4g / cm

[0043] The flotation process in step S3 is as follows:

[0044] (1) The homogenized ore particles are subjected to grinding treatment to obtain a mineral powder material with a particle size of ≤0.075 mm, the mineral powder material is subjected to concentration treatment to obtain a concentrated slurry with a mass concentration of 30%, 2kg / t of sodium carbonate, 0.5kg / t of sulfonic acid-phosphoric acid double-modified cellulose, 0.8kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are sequentially added, and once roughing is performed to obtain roughing concentrate and roughing tailings;

[0045] (2) 0.1kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 0.05kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added to the roughing concentrate, the pH is maintained at 9.0, and once cleaning is performed to obtain cleaning concentrate and cleaning tailings;

[0046] (3) The roughing tailings and the cleaning tailings are mixed, 0.2kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added, and once scavenging is performed to obtain scavenging concentrate and scavenging tailings, the scavenging tailings are discarded, and the scavenging concentrate is returned to the roughing operation for closed-circuit flotation (once roughing, once cleaning, and once scavenging), and finally the concentrate is obtained.

[0047] The preparation method of the sulfonic acid-phosphoric acid double modified cellulose is as follows:

[0048] 8.0 g of carboxymethyl cellulose was dispersed in 120 mL of deionized water, stirred for 20 min, 2.0 g of sulfamic acid was added, the pH was adjusted to 5.0 with 5% sodium hydroxide solution, and the reaction was carried out in a water bath at 60℃ for 2 h, then cooled to room temperature, precipitated with ethanol and washed, and dried in a vacuum at 50℃ to obtain sulfonated carboxymethyl cellulose; 8.0 g of sulfonated carboxymethyl cellulose was mixed with 80 mL of deionized water, 1.0 g of sodium tripolyphosphate and 0.5 g of urea were added, the pH was adjusted to 9.0 with 5% sodium hydroxide solution, and the reaction was carried out at 70℃ for 3 h, then the reaction solution was adjusted to pH 7.0 with hydrochloric acid, precipitated with ethanol and washed, and dried to obtain sulfonic acid-phosphoric acid double modified cellulose.

[0049] Example 2

[0050] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material comprises the following steps:

[0051] S1, low-grade bauxite (aluminum-silicon ratio of 2.6:1; aluminum oxide content of 60%, main mineral phase of diaspore) is selected as raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then sieved through a 100-mesh sieve to obtain pretreated particles;

[0052] S2, the pretreated particles are mixed and stacked, and are homogenized by the flat stacking method for 3 days to obtain homogenized ore particles;

[0053] S3, the homogenized ore particles are subjected to a flotation process, the concentrate obtained by flotation is pressure filtered (a plate and frame filter press is used, the pressure is set to 1.2 MPa, and the moisture content of the obtained filter cake is ≤18%), and is dried (in a rotary drying kiln, the temperature is controlled at 250℃, the time is 1 h, and the moisture content at the outlet is ≤1%) to obtain concentrate particles;

[0054] S4, 5% sodium lignosulfonate is added to the concentrate particles, and the mixture is pressed into a cylindrical green body by a hydraulic press, and the cylindrical green body is subjected to gradient sintering, and after holding for 6 h, the furnace is cooled to 400℃ and then discharged, to obtain an iron-containing corundum-high iron mullite solid solution raw material with a bulk density of 3.2 g / cm 3 The iron-containing corundum-high iron mullite solid solution raw material has the following components by weight percentage: 15 wt% of silicon dioxide, 12 wt% of iron oxide, 3 wt% of titanium dioxide, 3 wt% of calcium oxide, 1 wt% of other impurities, and the balance being aluminum oxide.

[0055] The flotation process in step S3 is as follows:

[0056] (1) The homogenized ore particles are subjected to grinding treatment to obtain ore powder materials with a particle size of ≤0.075 mm, the ore powder materials are subjected to concentration treatment to obtain concentrated ore slurry with a mass concentration of 50%, 3 kg / t of sodium carbonate, 1.2 kg / t of sulfonic acid-phosphoric acid double-modified cellulose, 1.5 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are sequentially added, and one roughing is performed to obtain roughing concentrate and roughing tailings;

[0057] (2) 0.3 kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 0.1 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added to the roughing concentrate, the pH is maintained at 9.5, one cleaning is performed, and cleaning concentrate and cleaning tailings are obtained;

[0058] (3) The roughing tailings and the cleaning tailings are mixed, 0.4 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added, one scavenging is performed, and scavenging concentrate and scavenging tailings are obtained, the scavenging tailings are discarded, and the scavenging concentrate is returned to the roughing operation for closed-circuit flotation (one roughing, one cleaning, and two scavengings), and finally the concentrate is obtained.

[0059] The preparation method of the sulfonic acid-phosphoric acid double-modified cellulose is as follows:

[0060] 15.0 g of carboxymethyl cellulose is dispersed in 180 mL of deionized water, stirred for 40 min, 5.0 g of sulfamic acid is added, the pH is adjusted to 6.0 with a 5% sodium hydroxide solution, and the reaction is carried out in a water bath at 100℃ for 5 h, then cooled to room temperature, precipitated with ethanol and washed, and dried at 70℃ under vacuum to obtain sulfonated carboxymethyl cellulose; 15.0 g of sulfonated carboxymethyl cellulose is mixed with 150 mL of deionized water, 5.0 g of sodium tripolyphosphate and 1.0 g of urea are added, the pH is adjusted to 10.0 with a 5% sodium hydroxide solution, and the reaction is carried out at 90℃ for 5 h, then the reaction solution is adjusted to pH 7.5 with hydrochloric acid, precipitated with ethanol and washed, and dried to obtain sulfonic acid-phosphoric acid double-modified cellulose.

[0061] Example 3

[0062] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material includes the following steps:

[0063] S1, low-grade bauxite (aluminum-silicon ratio of 2.1:1; aluminum oxide content of 50%, main mineral phase of diaspore) is selected as a raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh screen to obtain pretreated particles;

[0064] S2, the pretreated particles are mixed and stacked, and are homogenized by the flat stacking method for 2.5 days to obtain homogenized ore particles;

[0065] S3, performing a flotation process on the homogenized ore particles, performing pressure filtration (using a plate-and-frame filter press, with a pressure setting of 1.0 MPa, to obtain filter cake with a water content of ≤18%) on the flotation concentrate, and performing drying (in a rotary drying kiln, with a temperature control of 225℃ and a time of 1.5h, to obtain an outlet moisture content of ≤1%) to obtain concentrate particles;

[0066] S4, adding sodium lignosulfonate with a mass fraction of 4% to the concentrate particles, pressing the concentrate particles into a cylindrical green body using a hydraulic press, and performing gradient sintering on the cylindrical green body, and after holding for 5h, cooling the cylindrical green body in the furnace to 300℃ and then discharging the cylindrical green body from the furnace to obtain an iron-containing corundum-high-iron mullite solid solution raw material with a bulk density of 2.8g / cm 3 , by weight percentage, including the following components: silicon dioxide 16.4wt%, iron oxide 8.5wt%, titanium dioxide 2wt%, calcium oxide 2wt%, other impurities 0.55wt%, and the balance being aluminum oxide.

[0067] The flotation process in step S3 is as follows:

[0068] (1) performing grinding treatment on the homogenized ore particles to obtain a mineral powder material with a particle size of ≤0.075mm, performing concentration treatment on the mineral powder material to obtain a concentrated ore slurry with a mass concentration of 40%, and sequentially adding 2.5kg / t of sodium carbonate, 0.85kg / t of sulfonic acid-phosphoric acid double-modified cellulose, 1.15kg / t of dodecylamine, and sodium oleate (with a weight ratio of dodecylamine to sodium oleate of 3:1) to perform one roughing to obtain a roughing concentrate and a roughing tailing;

[0069] (2) supplementing 0.2kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 0.07kg / t of dodecylamine and sodium oleate (with a weight ratio of dodecylamine to sodium oleate of 3:1) in the roughing concentrate, maintaining the pH at 9.2, and performing one cleaning to obtain a cleaning concentrate and a cleaning tailing;

[0070] (3) mixing the roughing tailing and the cleaning tailing, supplementing 0.3kg / t of dodecylamine and sodium oleate (with a weight ratio of dodecylamine to sodium oleate of 3:1), and performing one scavenging to obtain a scavenging concentrate and a scavenging tailing, discarding the scavenging tailing, and returning the scavenging concentrate to the roughing operation to perform closed-circuit flotation (one roughing, one cleaning, and one scavenging) to finally obtain the concentrate.

[0071] The preparation method of the sulfonic acid-phosphoric acid double-modified cellulose is as follows:

[0072] Sulfonated carboxymethyl cellulose was prepared by dispersing 11.0 g of carboxymethyl cellulose in 150 mL of deionized water, stirring for 30 min, adding 3.5 g of sulfamic acid, adjusting the pH to 5.5 with a 5% sodium hydroxide solution, and reacting in a water bath at 80°C for 3.5 h. The reaction mixture was cooled to room temperature, precipitated with ethanol, washed, and dried in a vacuum oven at 60°C. Sulfonated carboxymethyl cellulose was prepared by mixing 11.0 g of sulfonated carboxymethyl cellulose with 115 mL of deionized water, adding 3.0 g of sodium tripolyphosphate and 0.75 g of urea, adjusting the pH to 9.5 with a 5% sodium hydroxide solution, and reacting at 80°C for 4 h. The reaction mixture was adjusted to pH 7.2 with hydrochloric acid, precipitated with ethanol, washed, and dried to obtain sulfonate-phosphate double-modified cellulose.

[0073] Example 4

[0074] A preparation method of an iron-containing corundum-high-iron mullite solid solution raw material includes the following steps:

[0075] S1, a low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%; main mineral phase of diaspore) is selected as a raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh sieve to obtain pretreated particles;

[0076] S2, the pretreated particles are mixed and stacked, and are homogenized by the flat stacking method for 3 days to obtain homogenized ore particles;

[0077] S3, the homogenized ore particles are subjected to a flotation process, the concentrate obtained by flotation is pressure-filtered (a plate-and-frame filter press is used, the pressure is set to 1.0 MPa, and the moisture content of the obtained filter cake is ≤18%), and is dried (in a rotary drying kiln, the temperature is controlled at 200°C, the time is 1 h, and the moisture content at the outlet is ≤1%) to obtain concentrate particles;

[0078] S4, 5% sodium lignosulfonate is added to the concentrate particles, and the mixture is pressed into a cylindrical green body by a hydraulic press. The cylindrical green body is subjected to gradient sintering, and after holding for 5 h, the furnace is cooled to 300°C and then discharged, to obtain an iron-containing corundum-high-iron mullite solid solution raw material with a bulk density of 2.9 g / cm 3 , which includes the following components in terms of weight percentage: 14.8 wt% of silicon dioxide, 11.21 wt% of iron oxide, 2.06 wt% of titanium dioxide, 2.52 wt% of calcium oxide, 0.1 wt% of other impurities, and the balance being aluminum oxide.

[0079] The flotation process in step S3 is as follows:

[0080] (1) The homogenized ore particles are subjected to grinding treatment to obtain ore powder materials with a particle size of ≤0.075 mm, the ore powder materials are subjected to concentration treatment to obtain concentrated ore slurry with a mass concentration of 30%, 2.5 kg / t of sodium carbonate, 0.80 kg / t of sulfonic acid-phosphoric acid double-modified cellulose, 1.10 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are sequentially added, and one roughing is performed to obtain roughing concentrate and roughing tailings;

[0081] (2) 0.2 kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 0.05 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added to the roughing concentrate, the pH is maintained at 9.0, one cleaning is performed, and cleaning concentrate and cleaning tailings are obtained;

[0082] (3) The roughing tailings and the cleaning tailings are mixed, 0.3 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added, one scavenging is performed, and scavenging concentrate and scavenging tailings are obtained, the scavenging tailings are discarded, and the scavenging concentrate is returned to the roughing operation for closed-circuit flotation (one roughing, one cleaning, and one scavenging), and finally the concentrate is obtained.

[0083] The preparation method of the sulfonic acid-phosphoric acid double-modified cellulose is as follows:

[0084] 10.0 g of carboxymethyl cellulose is dispersed in 150 mL of deionized water, stirred for 30 min, 3.2 g of sulfamic acid is added, a 5% sodium hydroxide solution is used to adjust the pH to 5.5, and the water bath is reacted at 80°C for 3 h, cooled to room temperature, precipitated and washed with ethanol, and dried at 60°C under vacuum to obtain sulfonated carboxymethyl cellulose; 10.0 g of sulfonated carboxymethyl cellulose is mixed with 100 mL of deionized water, 2.1 g of sodium tripolyphosphate and 0.5 g of urea are added, a 5% sodium hydroxide solution is used to adjust the pH to 9.5, and the reaction is carried out at 85°C for 4 h, the reaction solution is adjusted to pH 7.0 with hydrochloric acid, precipitated and washed with ethanol, and dried to obtain sulfonic acid-phosphoric acid double-modified cellulose.

[0085] Example 5

[0086] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material includes the following steps:

[0087] S1, low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%, main mineral phase of diaspore) is selected as a raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh screen to obtain pretreated particles;

[0088] S2, the pretreated particles are mixed and stacked, and are homogenized by the flat stacking method for 3 days to obtain homogenized ore particles;

[0089] S3, performing a flotation process on the homogenized ore particles, performing pressure filtration (using a plate-and-frame filter press, with a pressure setting of 1.0 MPa, to obtain filter cake with a water content of ≤18%) on the flotation concentrate, and performing drying (in a rotary drying kiln, with a temperature control of 200℃ and a time of 1h, to obtain an outlet moisture content of ≤1%) to obtain concentrate particles;

[0090] S4, adding 5% by mass of sodium lignosulfonate to the concentrate particles, pressing into a cylindrical green body using a hydraulic press, and performing gradient sintering on the cylindrical green body, with a holding time of 5h, and then furnace cooling to 300℃ before discharging, to obtain an iron-containing corundum-high-iron mullite solid solution raw material with a bulk density of 3.0g / cm 3 , by weight percentage, including the following components: 15.8wt% of silicon dioxide, 9.24wt% of iron oxide, 2.18wt% of titanium dioxide, 1.73wt% of calcium oxide, 0.1wt% of other impurities, and the balance being aluminum oxide.

[0091] The flotation process in step S3 is as follows:

[0092] (1) performing grinding treatment on the homogenized ore particles to obtain a mineral powder material with a particle size of ≤0.075mm, performing concentration treatment on the mineral powder material to obtain a concentrated slurry with a mass concentration of 30%, and sequentially adding 2.5kg / t of sodium carbonate, 0.80kg / t of sulfonic acid-phosphoric acid double-modified cellulose, 1.10kg / t of dodecylamine, and sodium oleate (with a weight ratio of dodecylamine to sodium oleate of 3:1) to perform one roughing, to obtain a roughing concentrate and a roughing tailing;

[0093] (2) supplementing 0.2kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 0.05kg / t of dodecylamine and sodium oleate (with a weight ratio of dodecylamine to sodium oleate of 3:1) in the roughing concentrate, maintaining the pH at 9.0, and performing one cleaning to obtain a cleaning concentrate and a cleaning tailing;

[0094] (3) mixing the roughing tailing and the cleaning tailing, supplementing 0.3kg / t of dodecylamine and sodium oleate (with a weight ratio of dodecylamine to sodium oleate of 3:1), and performing one scavenging to obtain a scavenging concentrate and a scavenging tailing, discarding the scavenging tailing, and returning the scavenging concentrate to the roughing operation to perform closed-circuit flotation (one roughing, one cleaning, and two scavengings), to finally obtain a concentrate.

[0095] The preparation method of the sulfonic acid-phosphoric acid double-modified cellulose is as follows:

[0096] Sulfonated carboxymethyl cellulose was prepared by dispersing 10.0 g of carboxymethyl cellulose in 150 mL of deionized water, stirring for 30 min, adding 3.2 g of sulfamic acid, adjusting the pH to 5.5 with a 5% sodium hydroxide solution, and reacting in a water bath at 80°C for 3 h. The solution was cooled to room temperature, precipitated with ethanol, washed, and dried at 60°C under vacuum. Sulfonated carboxymethyl cellulose was obtained. Sulfonic-phosphoric double-modified cellulose was prepared by mixing 10.0 g of sulfonated carboxymethyl cellulose with 100 mL of deionized water, adding 2.1 g of sodium tripolyphosphate and 0.5 g of urea, adjusting the pH to 9.5 with a 5% sodium hydroxide solution, and reacting at 85°C for 4 h. The reaction solution was adjusted to pH 7.0 with hydrochloric acid, precipitated with ethanol, washed, and dried to obtain sulfonic-phosphoric double-modified cellulose.

[0097] Comparative Example 1

[0098] A preparation method of an iron-containing corundum-high-iron mullite solid solution raw material includes the following steps:

[0099] S1, a low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%; main mineral phase of diaspore) is selected as a raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh sieve to obtain pretreated particles;

[0100] S2, the pretreated particles are mixed and stacked, and are homogenized by the flat stacking method for 3 days to obtain homogenized ore particles;

[0101] S3, the homogenized ore particles are subjected to a flotation process, the concentrate obtained by flotation is pressure filtered (a plate and frame filter press is used, the pressure is set to 1.0 MPa, and the moisture content of the obtained filter cake is ≤18%), and is dried (in a rotary drying kiln, the temperature is controlled at 200°C, the time is 1 h, and the moisture content at the outlet is ≤1%) to obtain concentrate particles;

[0102] S4, 5% by mass of sodium lignosulfonate is added to the concentrate particles, and the mixture is pressed into a cylindrical green body by a hydraulic press. The cylindrical green body is subjected to gradient sintering, and after holding for 5 h, the furnace is cooled to 300°C and then discharged, to obtain an iron-containing corundum-high-iron mullite solid solution raw material with a bulk density of 2.43 g / cm 3 The iron-containing corundum-high-iron mullite solid solution raw material includes the following components by weight percentage: 29.7 wt% of silicon dioxide, 6.5 wt% of iron oxide, 2.11 wt% of titanium dioxide, 2.03 wt% of calcium oxide, 0.15 wt% of other impurities, and the balance being aluminum oxide.

[0103] The flotation process in step S3 is as follows:

[0104] (1) The homogenized ore particles are subjected to grinding treatment to obtain a mineral powder material with a particle size of ≤0.075 mm, the mineral powder material is subjected to concentration treatment to obtain a concentrated ore slurry with a mass concentration of 30%, 2.5 kg / t of sodium carbonate, 0.80 kg / t of carboxymethyl cellulose, 1.10 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are sequentially added, and one roughing is performed to obtain a roughing concentrate and a roughing tailing;

[0105] (2) 0.2 kg / t of carboxymethyl cellulose and 0.05 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added to the roughing concentrate, the pH is maintained at 9.0, one cleaning is performed to obtain a cleaning concentrate and a cleaning tailing;

[0106] (3) The roughing tailing and the cleaning tailing are mixed, 0.3 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added, one scavenging is performed to obtain a scavenging concentrate and a scavenging tailing, the scavenging tailing is discarded, and the scavenging concentrate is returned to the roughing operation to perform closed-circuit flotation (one roughing, one cleaning and one scavenging), and finally the concentrate is obtained.

[0107] Comparative Example 2

[0108] A preparation method of an iron-containing corundum-high-iron mullite solid solution raw material, comprising the following steps:

[0109] S1, a low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%, main mineral phase is diaspore) is selected as a raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh sieve to obtain pretreated particles;

[0110] S2, the pretreated particles are mixed and stacked, and are homogenized by the flat stacking method for 3 days to obtain homogenized ore particles;

[0111] S3, the homogenized ore particles are subjected to a flotation process, the concentrate obtained by flotation is pressure filtered (a plate and frame filter press is used, the pressure is set to 1.0 MPa, and the moisture content of the obtained filter cake is ≤18%), and is dried (in a rotary drying kiln, the temperature is controlled at 200℃, the time is 1h, and the outlet moisture content is ≤1%), to obtain concentrate particles;

[0112] S4, 5% of sodium lignosulfonate by mass fraction is added to the concentrate particles, and a hydraulic press is used to press into a cylindrical blank, the cylindrical blank is subjected to gradient sintering, after holding for 5h, the furnace is cooled to 300℃, and then discharged, to obtain a corundum-high-iron mullite solid solution raw material with a bulk density of 2.52 g / cm 3An iron-containing corundum-high iron mullite solid solution raw material, by weight percentage, includes the following components: 27.6wt% of silicon dioxide, 7.0wt% of iron oxide, 2.08wt% of titanium dioxide, 2.31wt% of calcium oxide, 0.14wt% of other impurities, and the balance of aluminum oxide.

[0113] The flotation process in the step S3 is:

[0114] (1) The homogenized ore particles are subjected to grinding treatment to obtain ore powder materials with a particle size of ≤0.075 mm, the ore powder materials are subjected to concentration treatment to obtain concentrated ore slurry with a mass concentration of 30%, 2.5 kg / t of sodium carbonate, 0.80 kg / t of sulfonated carboxymethyl cellulose, 1.10 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are sequentially added, and one roughing is performed to obtain roughing concentrate and roughing tailings;

[0115] (2) 0.2 kg / t of sulfonated carboxymethyl cellulose and 0.05 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added to the roughing concentrate, the pH is maintained at 9.0, one cleaning is performed to obtain cleaning concentrate and cleaning tailings;

[0116] (3) The roughing tailings and the cleaning tailings are mixed, 0.3 kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added, one scavenging is performed to obtain scavenging concentrate and scavenging tailings, the scavenging tailings are discarded, and the scavenging concentrate is returned to the roughing operation to perform closed-circuit flotation (one roughing, one cleaning, and one scavenging), and finally the concentrate is obtained.

[0117] The preparation method of the sulfonated carboxymethyl cellulose is:

[0118] 10.0 g of carboxymethyl cellulose is dispersed in 150 mL of deionized water, stirred for 30 min, 3.2 g of sulfamic acid is added, a 5% mass fraction sodium hydroxide solution is used to adjust the pH to 5.5, water bath reaction is performed at 80℃ for 3 h, cooling to room temperature, precipitated and washed with ethanol, and vacuum dried at 60℃ to obtain sulfonated carboxymethyl cellulose.

[0119] Comparative Example 3

[0120] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material includes the following steps:

[0121] S1, a low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%, main mineral phase of diaspore) is selected as a raw material, the raw material is coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh sieve to obtain pretreated particles;

[0122] S2, the pretreated particles are mixed and stacked, and are leveled for 3 days to obtain leveled ore particles;

[0123] S3, the leveled ore particles are subjected to a flotation process, the concentrate obtained by flotation is pressure filtered (using a plate and frame filter press, the pressure is set to 1.0 MPa, and the moisture content of the obtained filter cake is ≤18%), and is dried (in a rotary drying kiln, the temperature is controlled at 200℃, the time is 1h, and the moisture content at the outlet is ≤1%), to obtain concentrate particles;

[0124] S4, 5% by mass of sodium lignosulfonate is added to the concentrate particles, and is pressed into a cylindrical blank by a hydraulic press, and the cylindrical blank is subjected to gradient sintering, and is cooled to 300℃ in the furnace after holding for 5h, and is discharged from the furnace, to obtain an iron-containing corundum-high iron mullite solid solution raw material with a bulk density of 2.63g / cm 3 , which comprises the following components in percentage by weight: 25.9wt% of silicon dioxide, 7.3wt% of iron oxide, 2.54wt% of titanium dioxide, 2.07wt% of calcium oxide, 0.18wt% of other impurities, and the balance being aluminum oxide.

[0125] The flotation process in step S3 is as follows:

[0126] (1) The leveled ore particles are subjected to grinding treatment to obtain a mineral powder material with a particle size of ≤0.075mm, the mineral powder material is subjected to concentration treatment to obtain a concentrated ore slurry with a mass concentration of 30%, 2.5kg / t of sodium carbonate, 0.80kg / t of phosphonated carboxymethyl cellulose, 1.10kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are sequentially added, and a roughing is performed to obtain a roughing concentrate and a roughing tailing;

[0127] (2) 0.2kg / t of phosphonated carboxymethyl cellulose and 0.05kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added to the roughing concentrate, the pH is maintained at 9.0, a cleaning is performed, and a cleaning concentrate and a cleaning tailing are obtained;

[0128] (3) The cleaning tailing and the roughing tailing are mixed, 0.3kg / t of dodecylamine and sodium oleate (the weight ratio of dodecylamine to sodium oleate is 3:1) are added, a scavenging is performed, a scavenging concentrate and a scavenging tailing are obtained, the scavenging tailing is discarded, and the scavenging concentrate is returned to the roughing operation for closed-circuit flotation (one roughing, one cleaning, and one scavenging), and finally a concentrate is obtained.

[0129] The preparation method of the phosphonated carboxymethyl cellulose is as follows:

[0130] 10.0 g of carboxymethyl cellulose was mixed with 100 mL of deionized water, 2.1 g of sodium tripolyphosphate and 0.5 g of urea were added, the pH was adjusted to 9.5 with 5% sodium hydroxide solution, and the reaction was carried out at 85°C for 4 h. The reaction solution was adjusted to pH 7.0 with hydrochloric acid, precipitated with ethanol and washed, and dried to obtain phosphonated carboxymethyl cellulose.

[0131] Comparative Example 4

[0132] A preparation method of an iron-containing corundum-high-iron mullite solid solution raw material, comprising the following steps:

[0133] S1, a low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%, main mineral phase of diaspore) was selected as a raw material, the raw material was coarsely crushed to a particle size of ≤50 mm by a jaw crusher, and then finely crushed to a particle size of ≤2 mm by a hammer crusher, and then passed through a 100-mesh screen to obtain pretreated particles;

[0134] S2, the pretreated particles were mixed and stacked, and were homogenized by the flat stacking method for 3 days to obtain homogenized ore particles;

[0135] S3, the homogenized ore particles were subjected to a flotation process, the concentrate obtained by flotation was pressure filtered (a plate and frame filter press was used, the pressure was set to 1.0 MPa, and the moisture content of the obtained filter cake was ≤18%), and was dried (in a rotary drying kiln, the temperature was controlled at 200°C, the time was 1 h, and the moisture content at the outlet was ≤1%) to obtain concentrate particles;

[0136] S4, 5% sodium lignosulfonate was added to the concentrate particles, and a hydraulic press was used to press the concentrate particles into a cylindrical green body. The cylindrical green body was subjected to gradient sintering, and after holding for 5 h, the furnace was cooled to 300°C and then discharged, to obtain an iron-containing corundum-high-iron mullite solid solution raw material with a bulk density of 2.9 g / cm 3 , which comprises the following components in terms of weight percentage: 22.8 wt% of silicon dioxide, 7.5 wt% of iron oxide, 1.86 wt% of titanium dioxide, 1.52 wt% of calcium oxide, 0.13 wt% of other impurities, and the balance being aluminum oxide.

[0137] The flotation process in step S3 is as follows:

[0138] (1) The homogenized ore particles were subjected to grinding treatment to obtain a mineral powder material with a particle size of ≤0.075 mm, the mineral powder material was subjected to concentration treatment to obtain a concentrated slurry with a mass concentration of 30%, 2.5 kg / t of sodium carbonate, 0.80 kg / t of sulfonic acid-phosphoric acid double-modified cellulose, and 1.10 kg / t of dodecylamine were sequentially added, and a roughing process was carried out to obtain a roughing concentrate and a roughing tailing;

[0139] (2) In the rough concentrate, supplement 0.2 kg / t of sulfonic acid-phosphoric acid double modified cellulose and 0.05 kg / t of dodecylamine, maintain pH at 9.0, conduct once concentration, obtain concentration concentrate and concentration tailings;

[0140] (3) Mix the rough tailings and the concentration tailings, supplement 0.3 kg / t of dodecylamine, conduct once scavenging, obtain scavenging concentrate and scavenging tailings, discard the scavenging tailings, return the scavenging concentrate to the rough operation, conduct closed circuit flotation (one rough, one concentration, one scavenging), finally obtain the concentrate.

[0141] The preparation method of the sulfonic acid-phosphoric acid double modified cellulose is:

[0142] Disperse 10.0 g of carboxymethyl cellulose in 150 mL of deionized water, stir for 30 min, add 3.2 g of sulfamic acid, adjust pH to 5.5 with 5% sodium hydroxide solution, and react in a water bath at 80°C for 3 h, cool to room temperature, precipitate with ethanol and wash, dry at 60°C under vacuum to obtain sulfonated carboxymethyl cellulose; mix 10.0 g of sulfonated carboxymethyl cellulose with 100 mL of deionized water, add 2.1 g of sodium tripolyphosphate and 0.5 g of urea, adjust pH to 9.5 with 5% sodium hydroxide solution, react at 85°C for 4 h, adjust the reaction solution to pH 7.0 with hydrochloric acid, precipitate with ethanol and wash, and dry to obtain sulfonic acid-phosphoric acid double modified cellulose.

[0143] Comparative Example 5

[0144] A preparation method of an iron-containing corundum-high iron mullite solid solution raw material, comprising the following steps:

[0145] S1, select low-grade bauxite (aluminum-silicon ratio of 1.9:1; aluminum oxide content of 56%, main mineral phase is diaspore) as raw material, coarsely crush the raw material to a particle size of ≤50 mm with a jaw crusher, then finely crush to a particle size of ≤2 mm with a hammer crusher, pass through a 100 mesh sieve, and obtain pretreated particles;

[0146] S2, mix and stack the pretreated particles, homogenize for 3 days by the flat laying method, and obtain homogenized ore particles;

[0147] S3, conduct flotation process on the homogenized ore particles, filter (use plate and frame filter press, pressure is set to 1.0 MPa, the obtained filter cake has a water content of ≤18%) and dry (in a rotary drying kiln, temperature is controlled at 200°C, time is 1 h, outlet moisture is ≤1%) the concentrate obtained by flotation, and obtain concentrate particles;

[0148] S4, 5% sodium lignosulfonate is added in the concentrate particles, and the cylinder blank is pressed by a hydraulic press, gradient sintering is performed on the cylinder blank, after holding for 5h, the cylinder blank is cooled to 300℃ in the furnace and then discharged, to obtain an iron-containing corundum-high iron mullite solid solution raw material with a bulk density of 2.9g / cm 3 21.4wt% of silicon dioxide, 7.7wt% of iron oxide, 2.36wt% of titanium dioxide, 2.12wt% of calcium oxide, 0.17wt% of other impurities, and the balance being aluminum oxide.

[0149] The flotation process in the step S3 is as follows:

[0150] (1) The homogenized ore particles are subjected to grinding treatment to obtain ore powder materials with a particle size of ≤0.075mm, the ore powder materials are subjected to concentration treatment to obtain concentrated ore slurry with a mass concentration of 30%, 2.5kg / t of sodium carbonate, 0.80kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 1.10kg / t of sodium oleate are sequentially added, and once rough selection is performed to obtain rough selection concentrate and rough selection tailings;

[0151] (2) 0.2kg / t of sulfonic acid-phosphoric acid double-modified cellulose and 0.05kg / t of sodium oleate are added to the rough selection concentrate, the pH is maintained at 9.0, once selection is performed to obtain selection concentrate and selection tailings;

[0152] (3) The rough selection tailings and the selection tailings are mixed, 0.3kg / t of sodium oleate is added, and once scavenging is performed to obtain scavenging concentrate and scavenging tailings, the scavenging tailings are discarded, and the scavenging concentrate is returned to the rough selection operation to perform closed-circuit flotation (once rough selection, once selection, and once scavenging), and finally the concentrate is obtained.

[0153] The preparation method of the sulfonic acid-phosphoric acid double-modified cellulose is as follows:

[0154] 10.0g of carboxymethyl cellulose is dispersed in 150mL of deionized water, stirred for 30min, 3.2g of sulfamic acid is added, a 5% sodium hydroxide solution is used to adjust the pH to 5.5, and water bath reaction is performed at 80℃ for 3h, the reaction solution is cooled to room temperature, precipitated with ethanol and washed, and dried at 60℃ under vacuum to obtain sulfonated carboxymethyl cellulose; 10.0g of sulfonated carboxymethyl cellulose is mixed with 100mL of deionized water, 2.1g of sodium tripolyphosphate and 0.5g of urea are added, a 5% sodium hydroxide solution is used to adjust the pH to 9.5, and reaction is performed at 85℃ for 4h, the reaction solution is adjusted to pH 7.0 with hydrochloric acid, precipitated with ethanol and washed, and dried to obtain sulfonic acid-phosphoric acid double-modified cellulose.

[0155] The following further effect detection is made on the iron-containing corundum-high iron mullite solid solution raw material prepared by the present application: flotation efficiency: Al2O3 recovery rate (%) and concentrate aluminum-silicon ratio (A / S); sintered body performance: after the flotation concentrate is pressed and sintered, the performance of the obtained sintered body: high-temperature bending strength (MPa) and Fe2O3 solid solution amount (%); the detection results are as follows.

[0156] The results are recorded in Table 1;

[0157] Table 1: test results

[0158]

[0159] According to the data in Table 1, it can be known from the comparison of the examples and the comparative examples of the present application that the sulfonic acid-phosphoric acid double-modified cellulose prepared by the present application can be used as an inhibitor in the flotation process to achieve high concentrate grade, high recovery rate, improve the aluminum-silicon ratio of bauxite concentrate, reduce the generation of low-melting-point silicate impurities in the subsequent sintering process, realize efficient conversion of low-grade bauxite to high-performance refractory materials, and improve resource utilization rate and product added value.

[0160] The above content is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the concept of the present application or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. A method for preparing an iron-containing corundum-high-ferrous mullite solid solution raw material, characterized in that, Includes the following steps: S1. Low-grade bauxite is selected as raw material, and the raw material is crushed to obtain pre-treated particles. S2. Mix and stack the pretreated particles, and homogenize them for 2-3 days using the flat-laying and direct-take method to obtain homogenized ore particles. S3. The homogenized ore particles are subjected to flotation process, and the concentrate obtained by flotation is filtered and dried to obtain concentrate particles. S4. Add 3-5% lignin sulfonate by mass to the concentrate particles, press it into a cylindrical blank using a hydraulic press, perform gradient sintering on the cylindrical blank, hold it at the temperature for 4-6 hours, and then cool it in the furnace to 200-400℃ before taking it out of the furnace to obtain iron-containing corundum-high-iron mullite solid solution raw material. The flotation process in step S3 is as follows: (1) The homogenized ore particles are ground to obtain ore powder with a particle size ≤0.075mm. The ore powder is concentrated to obtain a concentrated slurry with a mass concentration of 30-50%. 2-3kg / t of modifier, 0.5-1.2kg / t of inhibitor, and 0.8-1.5kg / t of collector are added in sequence for roughing to obtain roughing concentrate and roughing tailings. (2) Add 0.1-0.3 kg / t of inhibitor and 0.05-0.1 kg / t of collector to the rough concentrate, maintain the pH at 9.0-9.5, and carry out a first cleaning to obtain clean concentrate and clean tailings; (3) Mix the roughing tailings and the cleaning tailings, add 0.2-0.4 kg / t of collector, and perform one scavenging to obtain scavenging concentrate and scavenging tailings. Discard the scavenging tailings and return the scavenging concentrate to the roughing operation for closed-circuit flotation to finally obtain the concentrate. The modifier is sodium carbonate, the inhibitor is sulfonic acid-phosphate dual-modified cellulose, and the collector is a mixture of dodecylamine and sodium oleate, wherein the weight ratio of dodecylamine to sodium oleate is 3:

1. The preparation method of the sulfonic acid-phosphate dual-modified cellulose is as follows: Carboxymethyl cellulose was dispersed in deionized water and stirred for 20-40 min. Aminosulfonic acid was added, and the pH was adjusted to 5-6 with a 5% sodium hydroxide solution. The mixture was reacted in a water bath at 60-100℃ for 2-5 h. After cooling to room temperature, the mixture was precipitated with ethanol and washed. The precipitate was then dried under vacuum at 50-70℃ to obtain sulfonated carboxymethyl cellulose. Sulfonated carboxymethyl cellulose was mixed with deionized water, and sodium tripolyphosphate and urea were added. The pH was adjusted to 9-10 with a 5% sodium hydroxide solution. The mixture was reacted at 70-90℃ for 3-5 h. The pH of the reaction solution was adjusted to 7-7.5 with hydrochloric acid, and the solution was precipitated with ethanol and washed. After drying, sulfonic acid-phosphate dual-modified cellulose was obtained.

2. The method for preparing an iron-containing corundum-high-ferrous mullite solid solution raw material according to claim 1, characterized in that, In step S1, the low-grade bauxite has an aluminum-silicon ratio of 1.5-2.6:1, an alumina content of 40-60%, and its main mineral phase is gibbsite monohydrate.

3. The method for preparing an iron-containing corundum-high-ferrous mullite solid solution raw material according to claim 1, characterized in that, The ratio of carboxymethyl cellulose, deionized water and aminosulfonic acid is 8-15g: 120-180mL: 2-5g; the ratio of sulfonated carboxymethyl cellulose, deionized water, sodium tripolyphosphate and urea is 8-15g: 80-150mL: 1-5g: 0.5-1.0g.

4. The method for preparing an iron-containing corundum-high-ferrous mullite solid solution raw material according to claim 1, characterized in that, In step S3, a plate and frame filter press is used for filtration, with the pressure set at 0.8-1.2 MPa, and the resulting filter cake has a moisture content of ≤18%. Drying is carried out in a rotary kiln, with the temperature controlled at 200-250℃ and the time at 1-2 hours, resulting in an outlet moisture content of ≤1%.

5. The method for preparing an iron-containing corundum-high-ferrous mullite solid solution raw material according to claim 1, characterized in that, The gradient sintering method in step S4 is as follows: Stage 1: Room temperature - 600℃, heating rate is 2℃ / min; Phase 2: 600℃-1450℃, heating rate is 5℃ / min; Phase 3: 1450℃-1600℃, heating rate is 2℃ / min.

6. The raw material prepared by the method for preparing an iron-containing corundum-high-ferrous mullite solid solution raw material according to any one of claims 1-5, characterized in that, By weight percentage, it includes the following components: 5-30 wt% silicon dioxide, 5-12 wt% iron oxide, 1-3 wt% titanium dioxide, 1-3 wt% calcium oxide, 0.1-1 wt% other impurities, and the balance being aluminum oxide.

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