A preparation method for producing 4A zeolite based on coal gangue

Abstract

The present invention relates to the technical field of 4A zeolite production, and discloses a preparation method for producing 4A zeolite based on coal gangue, comprising the following steps: using coal gangue, performing a roasting process, soda alkali melting, a refinement process, performing a three-stage extraction process, adjusting a mold, slurrying, crystallization, and drying to obtain 4A zeolite. With coal gangue as a raw material, the method of the present invention can fully extract alumina and silicon dioxide in the coal gangue, thereby increasing the yield of 4A zeolite, and the obtained 4A zeolite has the advantages of high crystallinity, high whiteness, low impurity content, and large cation exchange capacity.

Description

Technical Field

[0001] The invention relates to the technical field of 4A zeolite production, and in particular to a preparation method of 4A zeolite based on coal gangue. Background Art

[0002] Gangue is a solid waste discharged during the mining and washing process of coal. For every ton of coal mined, 150 kg to 250 kg of gangue will be produced. The accumulation of a large amount of gangue not only occupies land and causes surface water and groundwater pollution, but also because gangue contains some combustible carbon, sulfur and other components, the long-term accumulation of gangue mountains will naturally release a large amount of toxic and harmful gases and smoke such as sulfur dioxide, carbon monoxide, carbon dioxide, nitrogen oxides, etc., causing serious air pollution. In addition, due to the loose structure and poor stability of gangue mountains, geological disasters such as landslides, collapses, and mud-rock flows are very likely to occur.

[0003] The traditional synthesis methods of 4A zeolite include water glass method, activated clay method, bentonite method, kaolin method and coal gangue method. The water glass method is mature and easy to control, but the cost is high. The activated clay method and bentonite method require the addition of aluminum source, which is costly and the equipment needs to be corrosion-resistant. The gangue method utilizes the characteristic that its aluminum-silicon ratio is consistent with that of 4A zeolite, converts it into reactive metakaolin, and carries out hydrothermal crystallization conversion reaction in caustic soda aqueous solution to make zeolite. However, this process cannot fully extract alumina and silica during the preparation process, and alumina and silica generate sodium aluminosilicate solid during the extraction process, resulting in low utilization rate of gangue, and low yield and poor quality of the obtained 4A zeolite. In addition, since the aluminum-silicon ratio in gangue is not fixed, if the same extraction method is used, it cannot be achieved that the same method is applicable to gangue with any aluminum-silicon ratio, which will not only cause insufficient extraction of the aluminum-silicon ratio, but also cause waste of aluminum and silicon in the gangue. Therefore, different treatment methods are required for gangue with different aluminum-silicon ratios, so as to achieve full utilization of the gangue. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a preparation method for producing 4A zeolite based on coal gangue. With coal gangue as raw material, the method of the present invention can fully extract alumina and silica in the coal gangue, thereby increasing the yield of 4A zeolite, and the obtained 4A zeolite has the advantages of high crystallinity, high whiteness, low impurity content and large cation exchange capacity.

[0005] The present invention provides a preparation method for producing 4A zeolite based on coal gangue, comprising the following steps:

[0006] 4A zeolite is obtained by using coal gangue through roasting process, soda ash melting, refining process, three extraction processes, mold adjustment, slurrying, crystallization and drying; the coal gangue has an aluminum-silicon ratio of not less than 0.65 and less than 0.72.

[0007] Furthermore, the specific method of the roasting process includes: refining the particle size of coal gangue particles and then performing roasting treatment.

[0008] Furthermore, after the particle size of the coal gangue is refined, the particle size of the coal gangue is not less than 40 meshes.

[0009] Furthermore, the calcination temperature is 800°C-1200°C, and the calcination time is 10min-30min.

[0010] Furthermore, the specific steps of the soda ash melting include: uniformly mixing the coal gangue after the roasting process and sodium carbonate, and then heating.

[0011] Furthermore, based on mass, the ratio of coal gangue to sodium carbonate after the roasting process is (1:0.5-2.6).

[0012] Furthermore, the heating temperature is 1400° C.-1450° C., and the heating time is 50 min-60 min.

[0013] Furthermore, after the heating is completed, it is also necessary to ensure that the discharge temperature after heating is higher than 1050°C.

[0014] Furthermore, the specific process of the refinement process includes: quenching the product after the soda ash is melted, wet grinding the product after the water quenching with a dilute sodium hydroxide solution, diluting it to a liquid-solid ratio of (8:1-10:1), and finally performing solid-liquid separation.

[0015] Furthermore, the ratio of the product after alkali melting of the soda ash to the dilute sodium hydroxide solution during water quenching is (1:4-5) by mass.

[0016] The water quenching in the present invention refers to rapidly immersing the molten clinker obtained after melting soda ash into a dilute sodium hydroxide solution at high temperature for water quenching treatment to obtain solid fine particles.

[0017] Furthermore, the specific step of wet grinding with dilute sodium hydroxide solution includes: using dilute sodium hydroxide solution as a wet grinding agent, wet grinding the product after water quenching to a particle size between 200 meshes and 400 meshes.

[0018] In the present invention, those skilled in the art may use ball milling or other grinding methods to refine the particle size of the product after water quenching.

[0019] Furthermore, during wet grinding, the mass ratio of the dilute sodium hydroxide solution to the product after water quenching is (3:1-5:1).

[0020] Furthermore, the mass percentage concentration of the dilute sodium hydroxide solution is 3%-5%.

[0021] Furthermore, the preparation method of the dilute sodium hydroxide solution comprises dissolving sodium hydroxide in water.

[0022] Furthermore, the caustic Na2O in the diluted solution K The concentration is not less than 200g / L.

[0023] Furthermore, the diluted solution includes a water-quenched solution and a dilute sodium hydroxide solution.

[0024] In the present invention, it should be understood by those skilled in the art that, although the solution used for dilution is the water-quenched solution and the dilute sodium hydroxide solution, the dilute solution is mainly the dilute sodium hydroxide solution. Generally speaking, there is no strict dosage ratio between the water-quenched solution and the dilute sodium hydroxide solution. As long as the caustic Na2O in the diluted solution can be controlled, K The concentration should be no less than 200g / L.

[0025] Furthermore, during the dilution process, by controlling the caustic Na2O K The concentration of sodium aluminate and sodium silicate can be completely separated, which is beneficial to the mold adjustment and slurry process. During the dilution process, stirring can be used to promote sufficient dilution and separation of sodium aluminate and sodium silicate. As an example, the stirring speed can be 20 rpm-30 rpm.

[0026] Furthermore, the specific process of the three-extraction process includes: in the first extraction, the filter residue after the refinement process is added to the caustic soda solution to remove the water in the solution to obtain an intermediate product; the intermediate product is dissolved in a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, and the caustic Na2O in the dissolved solution K The concentration is not less than 250g / L, filter once, and the filtrate is set aside; for the second extraction, the filter residue after the first filtration is added to the caustic soda solution again to obtain a mixed slurry, grind, heat to react, and dilute with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, filter twice, and the second filtrate is set aside; for the third extraction, the filter residue after the second filtration is added to the caustic soda solution again to obtain a mixed slurry, grind, heat to react, and dilute with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, filter three times, and the three filtrates are set aside.

[0027] Furthermore, the mass percentage concentration of the caustic soda solution is 45%-50%.

[0028] Furthermore, the caustic soda solution is a sodium hydroxide solution.

[0029] Furthermore, the method for removing water from the solution is specifically: using a heating method, and the heating temperature is 320°C-550°C.

[0030] Furthermore, in the first extraction, the molar ratio of the filter residue to the caustic soda solution is (1:2-2.4) based on silicon dioxide and the molar ratio of the caustic soda solution to sodium hydroxide.

[0031] Furthermore, the preparation method of the caustic soda solution includes: dissolving sodium hydroxide in water.

[0032] Furthermore, in the second extraction, the mass percentage concentration of sodium hydroxide in the mixed slurry is 26%-34%.

[0033] Furthermore, the second extraction is performed by grinding the solid particles in the mixed slurry to a particle size of 200-400 mesh.

[0034] Furthermore, in the second extraction, the heating reaction temperature is 100°C-105°C, and the heating reaction time is 3min-5min.

[0035] Those skilled in the art should understand that during dilution, the substance can be made uniform, which is beneficial for the second extraction. Therefore, stirring can be performed during dilution, and the stirring speed can be 60 rpm-90 rpm.

[0036] Furthermore, after the second extraction is diluted, the mass percentage concentration of sodium hydroxide in the solution is 14%-18%.

[0037] Furthermore, in the third extraction, the mass percentage concentration of sodium hydroxide in the mixed slurry is 28%-34%.

[0038] Furthermore, the third extraction is performed by grinding the solid particles in the mixed slurry to a particle size of 200-400 mesh.

[0039] Furthermore, in the third extraction, the heating reaction temperature is 105°C-110°C, and the heating reaction time is 3min-5min.

[0040] Furthermore, after the third extraction and dilution, the mass percentage concentration of sodium hydroxide in the solution is 18%-20%.

[0041] Furthermore, the specific method for adjusting the mold includes: combining the filtrate after the refinement process and the filtrate of the three extraction processes, adding aluminum hydroxide to adjust the mold, and after adding aluminum hydroxide, the molar ratio of aluminum oxide to silicon dioxide in the filtrate is (1:1.57-1.62).

[0042] Furthermore, stirring is required during the mold adjustment process, and the stirring rate is 20 rpm to 30 rpm.

[0043] Furthermore, the specific process of the slurrying includes: adding a directing agent to the adjusted solution for mixing; during mixing, controlling the stirring speed to 60 rpm-120 rpm and the temperature to 60°C-80°C; after the mixing is completed, controlling the stirring speed to 60 rpm-120 rpm and the stirring time to 20min-30min.

[0044] Furthermore, the guiding agent is prepared with four substances: aluminum hydroxide, sodium hydroxide, sodium hydroxide and water. When preparing the guiding agent, the aluminum hydroxide is calculated as alumina, the sodium hydroxide is calculated as silicon dioxide, and the ratio of aluminum hydroxide, sodium hydroxide, sodium hydroxide and water is (1:15:19-20:300-350) by mass.

[0045] In the present invention, the guiding agent is prepared from four substances, aluminum hydroxide, sodium hydroxide, and water, to form a 4A zeolite seed solution. The amount of seeds in the 4A zeolite seed solution is calculated and determined based on 1%-3% of the designed 4A zeolite output. After determining the amount of seeds in the 4A zeolite seed solution, the ratio of aluminum hydroxide, sodium hydroxide, sodium hydroxide, and water is (1:15:19-20:300-350) according to the weight of aluminum hydroxide, sodium hydroxide, sodium hydroxide, and water, and the specific amount of raw materials aluminum hydroxide, sodium hydroxide, sodium hydroxide, and water when preparing the guiding agent can be determined.

[0046] Furthermore, the preparation process of the directing agent includes: controlling the temperature of the solution after mixing aluminum hydroxide, sodium hydroxide, sodium hydroxide and water to 45°C-65°C, continuously stirring for 20min-30min at a stirring speed of 60 rpm-90 rpm, and then letting the solution stand for 24h-48h. The directing agent after standing is used for slurrying within 30min-60min.

[0047] Furthermore, the specific process of the crystallization includes: heating the slurried solution.

[0048] Furthermore, the heating temperature is 90° C.-98° C., the heating time is 1 h-3 h, stirring is performed during the heating process, and the stirring speed is 20 rpm-30 rpm.

[0049] Furthermore, the specific process of the drying includes: washing and drying the crystallized solid to obtain 4A zeolite.

[0050] Furthermore, the drying temperature is 95°C-105°C.

[0051] It should be understood by those skilled in the art that the washing process is to remove the impurity ions adsorbed on the surface and in the crystal lattice of 4A zeolite, and to improve the ion adsorption and exchange capacity of the 4A zeolite product. Therefore, it is necessary to use deionized water for washing, and then dry to remove the adsorbed water. The selection of the drying temperature in the present invention is based on the stability of the product structure to achieve the effect of removing the adsorbed water.

[0052] The embodiments of the present invention have the following technical effects:

[0053] 1. In the method of the present invention, the coal gangue is first activated by a roasting process, which can not only decompose the alumina and silica present in the coal gangue in the form of coal-based kaolin into free alumina and silica, but also facilitate the full conversion of alumina and silica in the coal gangue during the soda alkali melting; the roasting process can also remove organic matter such as combustible carbon and humic acid in the coal gangue, which helps to improve the whiteness and quality of the 4A zeolite obtained after crystallization;

[0054] The product after the soda ash is melted is subjected to a refinement process. In the refinement process, the product after the soda ash is melted is water quenched, which is conducive to the product being broken into fine particles under the action of surface tension, which can not only increase the specific surface area of ​​the product, thereby facilitating the full extraction of alumina and silica in the first extraction process, but also lays a foundation for full wet grinding, thereby facilitating the decomposition of sodium aluminosilicate during the wet grinding process;

[0055] Adding dilute sodium hydroxide solution during wet grinding can, on the one hand, assist wet grinding and promote the decomposition of water-insoluble sodium aluminosilicate generated by alumina and silica in the soda ash alkali melt, thereby facilitating the full separation of silica and alumina in the gangue. On the other hand, it can reduce the amount of sodium aluminosilicate residue in the filter residue after solid-liquid separation, thereby reducing the processing cost of the subsequent three extraction processes.

[0056] In order to fully extract the alumina and silica in the gangue, the filter residue after the refinement process needs to be processed by three extraction processes. In the first extraction process, the caustic Na2O K The concentration of 4A zeolite is increased, so that the residual sodium aluminosilicate is completely decomposed; and the cooperation of the first extraction, the second extraction and the third extraction is conducive to fully extracting alumina and silica, improving the extraction rate of alumina and silica in the raw material gangue, increasing the output of 4A zeolite, and improving the economic efficiency of the utilization of gangue raw materials;

[0057] In the three extraction processes, the filter residue from the first extraction process is dissolved to control the caustic Na2O in the dissolution process. K The concentration can improve the reaction kinetics of sodium hydroxide, prevent the regeneration of sodium aluminosilicate, and is conducive to the maximum extraction of alumina and silicon dioxide, thereby increasing the yield of 4A zeolite;

[0058] During the mold adjustment process, aluminum hydroxide is added as a mold adjustment agent. On the one hand, it is to adjust the concentration of aluminum oxide so that the chemical composition ratio of aluminum oxide and silicon dioxide meets the composition of 4A zeolite, thereby laying the foundation for the formation of 4A zeolite; on the other hand, aluminum hydroxide, a mold adjustment agent, will also consume part of the sodium hydroxide, reducing the concentration of sodium hydroxide, which is conducive to the atomic arrangement of the formed crystals in the direction of the 4A zeolite crystal structure, thereby ensuring the quality of 4A zeolite;

[0059] During the slurrying process, the directing agent of the present invention is prepared and used immediately, which is beneficial to further promote the atomic arrangement of the generated crystals to grow towards the 4A zeolite crystal structure;

[0060] Finally, through crystallization, the 4A zeolite crystals are grown, and finally the 4A zeolite is obtained.

[0061] 2. Through the method of the present invention, for coal gangue with an Al2O3 mass percentage of 34.70%, an SiO2 mass percentage of 51.11%, and an aluminum-silicon ratio of 0.65<0.68<0.72, the extraction and utilization rate of Al2O3 in the coal gangue raw material of the present invention reaches 97.26%, and the extraction and utilization rate of SiO2 reaches 95.81%; the extracted aluminum oxide and silicon dioxide account for a total of 96.40% of the total amount of aluminum oxide and silicon dioxide in the coal gangue raw material, and account for more than 82% of the total amount of the coal gangue raw material.

[0062] 3. The calcium exchange capacity, whiteness, crystallinity, particle size and pH value of the 4A zeolite produced from coal gangue by the method of the present invention all meet the product quality standards of 4A zeolite for detergent additives. DETAILED DESCRIPTION

[0063] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0064] In a first aspect, some embodiments of the present invention provide a method for producing 4A zeolite based on coal gangue, comprising the following steps:

[0065] 4A zeolite is obtained by using coal gangue through roasting process, soda ash melting, refining process, three extraction processes, mold adjustment, slurrying, crystallization and drying; the coal gangue has an aluminum-silicon ratio of not less than 0.65 and less than 0.72.

[0066] In some embodiments, the specific method of the roasting process includes: refining the particle size of coal gangue particles and then performing roasting treatment.

[0067] In some embodiments, after the particle size of the coal gangue is refined, the particle size of the coal gangue is not less than 40 mesh.

[0068] In some embodiments, the calcination temperature is 800° C.-1200° C., and the calcination time is 10 min-30 min.

[0069] In some embodiments, the specific steps of melting the soda ash include: uniformly mixing the coal gangue after the roasting process and sodium carbonate, and then heating.

[0070] In some embodiments, the ratio of coal gangue to sodium carbonate after the roasting process is (1:0.5-2.6) by mass.

[0071] In some embodiments, the heating temperature is 1400° C.-1450° C., and the heating time is 50 min-60 min.

[0072] In some embodiments, after heating, it is also necessary to ensure that the discharge temperature after heating is higher than 1050°C.

[0073] In the present invention, by controlling the temperature of the soda ash fusion, it is ensured that the aluminum oxide and silicon dioxide in the coal gangue are fully converted into sodium aluminate and sodium silicate, and the sodium aluminosilicate solid formed between the aluminum oxide and silicon dioxide is reduced, which is conducive to extracting aluminum oxide and silicon dioxide from the coal gangue to the maximum extent.

[0074] In some embodiments, the specific process of the refinement process includes: quenching the product after soda ash melting with a dilute sodium hydroxide solution, wet grinding the product after water quenching with a dilute sodium hydroxide solution, diluting it to a liquid-solid ratio of (8:1-10:1), and finally performing solid-liquid separation.

[0075] In some embodiments, the ratio of the product after alkali melting of soda ash to the dilute sodium hydroxide solution during water quenching is (1:4-5) by mass.

[0076] In some embodiments, the specific step of wet grinding with dilute sodium hydroxide solution includes: using dilute sodium hydroxide solution as a wet grinding agent, wet grinding the product after water quenching to a particle size between 200 mesh and 400 mesh.

[0077] In some embodiments, during wet grinding, the mass ratio of the dilute sodium hydroxide solution to the product after water quenching is (3:1-5:1).

[0078] In some embodiments, the mass percentage concentration of the dilute sodium hydroxide solution is 3%-5%.

[0079] In some embodiments, the method for preparing the dilute sodium hydroxide solution comprises dissolving sodium hydroxide in water.

[0080] In some embodiments, the caustic Na2O in the diluted solution K The concentration is not less than 200g / L.

[0081] In some embodiments, the diluted solution includes a water-quenched solution and a dilute sodium hydroxide solution.

[0082] In some embodiments, the specific process of performing the three extraction processes includes: in the first extraction, the filter residue after the refinement process is added to the caustic soda solution to remove the water in the solution to obtain an intermediate product; the intermediate product is dissolved in a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, and the caustic Na2O in the dissolved solution is K The concentration is not less than 250g / L, filter once, and the filtrate is set aside; for the second extraction, the filter residue after the first filtration is added again to the caustic soda solution to obtain a mixed slurry, grind, heat to react, and dilute with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, filter twice, and the second filtrate is set aside; for the third extraction, the filter residue after the second filtration is added again to the caustic soda solution to obtain a mixed slurry, grind, heat to react, and dilute with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, filter three times, and the three filtrates are set aside.

[0083] In some embodiments, the mass percent concentration of the caustic soda solution is 45%-50%.

[0084] In some embodiments, the caustic soda solution is a sodium hydroxide solution.

[0085] In some embodiments, the method for removing water from the solution is specifically: using a heating method, and the heating temperature is 320°C-550°C.

[0086] In some embodiments, during the first extraction, the molar ratio of the filter residue to the caustic soda solution is (1:2-2.4) based on silicon dioxide and the molar ratio of the caustic soda solution to sodium hydroxide.

[0087] In some embodiments, the method for preparing the caustic soda solution includes: dissolving sodium hydroxide in water.

[0088] In some embodiments, during the second extraction, the mass percentage concentration of sodium hydroxide in the mixed slurry is 26%-34%.

[0089] In some embodiments, during the second extraction, the solid particles in the mixed slurry are ground to a particle size of 200-400 mesh.

[0090] In some embodiments, during the second extraction, the heating reaction temperature is 100° C.-105° C., and the heating reaction time is 3 min-5 min.

[0091] In some embodiments, during the second extraction, after dilution, the mass percentage concentration of sodium hydroxide in the diluted solution is 14%-18%.

[0092] In some embodiments, during the third extraction, the mass percentage concentration of sodium hydroxide in the mixed slurry is 28%-34%.

[0093] In some embodiments, during the third extraction, the solid particles in the mixed slurry are ground to a particle size of 200-400 mesh.

[0094] In some embodiments, during the third extraction, the heating reaction temperature is 105° C.-110° C., and the heating reaction time is 3 min-5 min.

[0095] In some embodiments, during the third extraction, after dilution, the mass percentage concentration of sodium hydroxide in the diluted solution is 18%-20%.

[0096] In some embodiments, the specific method of adjusting the mold includes: combining the filtrate after the refinement process and the filtrate of the three extraction processes, adding aluminum hydroxide to adjust the mold, and after adding aluminum hydroxide, the molar ratio of aluminum oxide to silicon dioxide in the filtrate is (1:1.57-1.62).

[0097] In some embodiments, stirring is required during the mold adjustment process, and the stirring rate is 20 rpm to 30 rpm.

[0098] In some embodiments, the specific process of the slurrying includes: adding a directing agent to the solution after mold adjustment for mixing; during mixing, controlling the stirring speed to 60 rpm-120 rpm and the temperature to 60°C-80°C; after mixing, controlling the stirring speed to 60 rpm-120 rpm and the stirring time to 20min-30min.

[0099] In some embodiments, further, the guiding agent is prepared with four substances: aluminum hydroxide, sodium hydroxide, sodium hydroxide and water; when preparing the guiding agent, the aluminum hydroxide is calculated as alumina, the sodium hydroxide is calculated as silicon dioxide, and the ratio of aluminum hydroxide, sodium hydroxide, sodium hydroxide and water is (1:15:19-20:300-350) by mass.

[0100] In some embodiments, the preparation process of the directing agent includes: controlling the temperature of the solution after mixing aluminum hydroxide, sodium hydroxide, sodium hydroxide and water to 45°C-65°C, continuously stirring for 20min-30min at a stirring speed of 60 rpm-90 rpm, and then letting the solution stand for 24h-48h. The directing agent after standing is used for slurrying within 30min-60min.

[0101] In some embodiments, the specific process of the crystallization includes: heating the slurried solution.

[0102] In some embodiments, the heating temperature is 90° C.-98° C., the heating time is 1 h-3 h, stirring is performed during the heating process, and the stirring speed is 20 rpm-30 rpm.

[0103] In some embodiments, the method further includes drying, and the specific process of drying includes: washing and drying the crystallized solid to obtain 4A zeolite.

[0104] In some embodiments, the drying temperature is 95°C-105°C.

[0105] The following is described in conjunction with some specific embodiments:

[0106] Embodiment 1:

[0107] A coal gangue with an Al2O3 mass percentage of 34.70%, a SiO2 mass percentage of 51.11%, and an aluminum-silicon ratio of 0.68 is ground to a particle size of 50 meshes. The coal gangue is calcined at 1000°C for 20 minutes to complete the calcination process.

[0108] Soda ash alkali melting: Mix the coal gangue after the roasting process and sodium carbonate, heat and perform alkali melting treatment to obtain molten clinker. The coal gangue after the roasting process and sodium carbonate are mixed according to the mass ratio of coal gangue: sodium carbonate = 1:2, react at a heating temperature of 1450℃ for 55 minutes, maintain the discharge temperature above 1050℃, and obtain molten clinker.

[0109] Refining process: The molten clinker obtained by the soda ash alkali melting treatment is quickly quenched with a dilute sodium hydroxide solution with a mass percentage concentration of 4% while at high temperature. During the water quenching, the ratio of the product after the soda ash alkali melting to the dilute sodium hydroxide solution is 1:5 by mass to obtain solid fine particles; the solid fine particles are input into the wet grinding process; the dilute sodium hydroxide solution with a mass percentage concentration of 4% is used for wet grinding, and the wet grinding is completed when the fineness is 300 mesh. The mass ratio of the dilute sodium hydroxide solution and the product after water quenching is 4:1. The slurry obtained by wet grinding is diluted with the water quenched solution and the dilute sodium hydroxide solution with a mass percentage concentration of 4%, and diluted to a liquid-solid ratio of 8:1-10:1. In this range, the caustic Na2O in the solution is controlled. K ≥200g / L, stir continuously at 25 rpm during dilution; filter immediately after dilution and keep the filtrate for later use;

[0110] Three extraction processes are performed:

[0111] First extraction: add caustic soda solution with a mass percentage concentration of 47% to the filter cake after the refinement process, the filter residue is calculated as silicon dioxide, and the caustic soda solution is calculated as sodium hydroxide, the molar ratio of the filter residue to the caustic soda solution is 1:2.2, and heat the reaction at 350°C until the material becomes a dry powder to obtain an intermediate product; dissolve the intermediate product with a dilute sodium hydroxide solution with a mass percentage concentration of 4%, and control the caustic Na2O in the solution after dissolution. K ≥250g / L; After dissolving, filter once immediately, and the filtrate is set aside; the filter cake obtained by the first filtration is used for the second extraction;

[0112] Second extraction: add the filter cake to a caustic soda solution with a mass percentage concentration of 47%, and the mass percentage concentration of sodium hydroxide in the mixed slurry after adding the caustic soda solution is 30%; grind the mixed slurry to 300 mesh solid particles in the slurry, and heat at 100°C for 3 minutes; dilute the slurry after the reaction with a dilute sodium hydroxide solution with a mass percentage concentration of 4%, and stir evenly at 80 rpm, and the amount of the dilute sodium hydroxide solution added is based on the mass percentage concentration of sodium hydroxide in the dilute slurry after adding the dilute sodium hydroxide solution. 16%; after dilution, immediately filter twice; the secondary filtrate is set aside, and the filter cake obtained by the secondary filtration is extracted for the third time;

[0113] The third extraction: add the filter cake to a caustic soda solution with a mass percentage concentration of 47%, and the mass percentage concentration of sodium hydroxide in the mixed slurry after adding the caustic soda solution is 32%; grind the mixed slurry to a solid particle size of 200-400 mesh in the slurry, and heat at 105°C for reaction for 3 minutes; dilute the slurry after the reaction with a dilute sodium hydroxide solution with a mass percentage concentration of 4%, and stir evenly at 80 rpm, and the amount of the dilute sodium hydroxide solution added is 18% of the mass percentage concentration of sodium hydroxide in the dilute slurry after adding the dilute sodium hydroxide solution; after dilution, filter three times immediately; the three filtrates are set aside, and the filter cake obtained by three filtrations is washed with 95°C hot water until the pH is ≤11;

[0114] Mold adjustment: The filtrates after the refinement process and the three extraction processes are combined, and aluminum hydroxide is added for mold adjustment. The molar ratio of Al2O3 and SiO2 in the solution is adjusted, and solid aluminum hydroxide is added under continuous stirring at a stirring speed of 25 rpm to dissolve all the added aluminum hydroxide. After adding aluminum hydroxide, the molar ratio of alumina to silicon dioxide in the filtrate is 1:1.6.

[0115] Preparation of guiding agent: The dosage of guiding agent is determined by calculation based on 2% of the designed 4A zeolite output; the guiding agent is prepared with aluminum hydroxide, sodium hydroxide, sodium hydroxide and water, with aluminum hydroxide being calculated as alumina and sodium hydroxide being calculated as silicon dioxide; the ratio of aluminum hydroxide, sodium hydroxide, sodium hydroxide and water is 1:15:19:300 by mass, and the temperature of the mixed solution is controlled to be 55°C. After continuous stirring at a stirring speed of 75 rpm for 25 minutes, the solution is allowed to stand for 40 hours. The guiding agent after standing is used in the slurrying stage within 30 minutes.

[0116] Slurrying: The prepared 4A zeolite directing agent is slowly added to the solution adjusted with aluminum hydroxide under continuous stirring to obtain a dilute gel solution; during slurrying, the stirring speed of the two solutions is controlled at 100 rpm and the temperature after mixing is 70°C; after the two solutions are mixed, the stirring speed is maintained at 100 rpm for continuous stirring for 25 minutes.

[0117] Crystallization: After slurrying, the temperature of the solution was rapidly raised to 95°C, the stirring speed was reduced to 25 rpm, and stirring was continued for 2 hours to complete crystallization.

[0118] Drying: The 4A zeolite filter cake obtained by filtering and washing after crystallization is dried at a temperature of 100° C. to obtain a 4A zeolite product.

[0119] In this embodiment, the mass percentage concentration of the caustic soda solution is 47%, and the mass percentage concentration of the dilute sodium hydroxide solution is 4%.

[0120] Comparative Example 1:

[0121] The preparation method of Comparative Example 1 is the same as that of Example 1, but Comparative Example 1 does not have a calcination process step.

[0122] Comparative Example 2:

[0123] The preparation method of Comparative Example 2 is the same as that of Example 1, but the heating temperature of Comparative Example 2 is 1200° C. and the heating time is 30 minutes in a soda ash melt.

[0124] Comparative Example 3:

[0125] The preparation method of Comparative Example 3 is the same as that of Example 1, but in Comparative Example 3, no dilute sodium hydroxide solution is added during wet grinding.

[0126] Comparative Example 4:

[0127] The preparation method of Comparative Example 4 is the same as that of Example 1, but Comparative Example 4 does not have a roasting process, and the heating temperature is 1200° C. and the heating time is 30 minutes in the soda ash melt.

[0128] Comparative Example 5: The preparation method of Comparative Example 5 is the same as that of Example 1, but the aluminum-silicon ratio of the coal gangue in Comparative Example 5 is 0.75.

[0129] The products obtained from the embodiments and comparative examples of the present invention were tested.

[0130] Calcium exchange capacity detection method: loss on ignition method.

[0131] Whiteness detection method: color difference method.

[0132] Method for detecting crystallinity: X-ray diffraction method.

[0133] Particle size detection method: sedimentation method.

[0134] pH value detection method: potentiometric method.

[0135] Results and Analysis:

[0136] Table 1 Test results of products obtained from the examples and comparative examples

[0137]

[0138] It can be found in Table 1 that the 4A zeolite product obtained by the present invention meets the quality standards of 4A zeolite products for detergent builders in terms of calcium exchange capacity, whiteness, particle size, and pH value, and the product of the present invention is significantly better than Comparative Examples 1 to 5 in terms of calcium exchange capacity, whiteness, and crystallinity. It can be seen that through the interaction between the steps of the method of the present invention, not only the extraction rate of alumina and silica is improved, but also a 4A zeolite with better quality is obtained.

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention.

Claims

1. A method for producing 4A zeolite based on coal gangue, characterized in that: The steps include: Using coal gangue, 4A zeolite is obtained through roasting process, soda ash melting, refining process, three extraction processes, mold adjustment, slurrying, crystallization and drying; the coal gangue is coal gangue with an aluminum-silicon ratio of not less than 0.65 and less than 0.72; The refinement process specifically includes: quenching the product after the soda ash is melted with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, wet grinding the product after the water quenching with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, diluting, and finally performing solid-liquid separation; The product after the soda ash is melted and the dilute sodium hydroxide solution during water quenching, the ratio of the product after the soda ash is melted to the dilute sodium hydroxide solution is (1:4-5) by mass; During wet grinding, the mass ratio of dilute sodium hydroxide solution to the product after water quenching is (3:1-5:1); The specific process of the three-extraction process includes: in the first extraction, the filter residue after the refinement process is added into the caustic soda solution to remove the water in the solution to obtain the intermediate product; the intermediate product is dissolved in a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, and the caustic Na2O in the dissolved solution is K The concentration is not less than 250g / L, filter once, and the filtrate is set aside; extract for the second time, add the filter residue after the first filtration to the caustic soda solution again to obtain a mixed slurry, grind, heat to react, dilute with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, filter for the second time, and the filtrate is set aside; extract for the third time, add the filter residue after the second filtration to the caustic soda solution again to obtain a mixed slurry, grind, heat to react, dilute with a dilute sodium hydroxide solution with a mass percentage concentration of 3%-5%, filter for the third time, and the filtrate is set aside; The mass percentage concentration of the caustic soda solution is 45%-50%; The method for removing water from the solution is specifically: using a heating method, the heating temperature is 350° C.; During the first extraction, the molar ratio of the filter residue to the caustic soda solution is (1:2-2.4) based on silicon dioxide and the molar ratio of the caustic soda solution to sodium hydroxide. During the second extraction, the mass percentage concentration of sodium hydroxide in the mixed slurry is 26%-34%; During the second extraction, the heating reaction temperature is 100°C-105°C, and the heating reaction time is 3min-5min; During the second extraction, after dilution, the mass percentage concentration of sodium hydroxide in the diluted solution is 14%-18%; During the third extraction, the mass percentage concentration of sodium hydroxide in the mixed slurry is 28%-34%; During the third extraction, the heating reaction temperature is 105°C-110°C, and the heating reaction time is 3min-5min; During the third extraction, after dilution, the mass percentage concentration of sodium hydroxide in the diluted solution is 18%-20%; The specific method for adjusting the mold includes: combining the filtrate after the refinement process and the filtrate after the three extraction processes, and adding aluminum hydroxide to adjust the mold.

2. The preparation method according to claim 1, characterized in that: The specific method of the roasting process includes: refining the particle size of coal gangue and then roasting it; After the coal gangue particles are refined, the particle size of the coal gangue shall not be less than 40 meshes; The temperature of the calcination treatment is 800° C.-1200° C., and the time of the calcination treatment is 10 min-30 min.

3. The preparation method according to claim 1, characterized in that: The specific steps of the soda ash melting include: uniformly mixing the coal gangue after the roasting process and sodium carbonate, and then heating; The ratio of coal gangue to sodium carbonate after the roasting process is (1:0.5-2.6) by mass; The heating temperature is 1400°C-1450°C, and the heating time is 50min-60min; After heating, it is also necessary to ensure that the discharge temperature after heating is higher than 1050°C.

4. The preparation method according to claim 3, characterized in that: The refinement process specifically includes: quenching the product after the soda ash is melted with a dilute sodium hydroxide solution, wet grinding the product after the water quenching with a dilute sodium hydroxide solution, diluting it to a liquid-solid ratio of (8:1-10:1), and finally performing solid-liquid separation; The specific steps of wet grinding with dilute sodium hydroxide solution include: using dilute sodium hydroxide solution as a wet grinding agent to wet grind the product after water quenching to a particle size of 200-400 mesh; The caustic Na2O in the diluted solution K The concentration is not less than 200g / L.

5. The preparation method according to claim 1, characterized in that: During the second extraction, the solid particles in the mixed slurry are ground to a particle size of 200-400 mesh; During the third extraction, the solid particles in the mixed slurry are ground to a particle size of 200-400 meshes.

6. The preparation method according to claim 1, characterized in that: During the mold adjustment process, after adding aluminum hydroxide, the molar ratio of aluminum oxide to silicon dioxide in the filtrate is (1:1.57-1.62); Stirring is also required during the mold adjustment process, and the stirring rate is 20 rpm-30 rpm.

7. The preparation method according to claim 1, characterized in that: The specific process of the slurrying includes: adding a directing agent to the solution after mold adjustment for mixing; during mixing, controlling the stirring speed to 60 rpm-120 rpm and the temperature to 60° C.-80° C.; after the mixing is completed, controlling the stirring speed to 60 rpm-120 rpm and the stirring time to 20 min-30 min; The guiding agent is prepared with four substances: aluminum hydroxide, sodium hydroxide, sodium hydroxide and water. When preparing the guiding agent, the aluminum hydroxide is calculated as alumina, the sodium hydroxide is calculated as silicon dioxide, and the ratio of aluminum hydroxide, sodium hydroxide, sodium hydroxide and water is (1:15:19-20:300-350) by mass.

8. The preparation method according to claim 1, characterized in that: The specific process of the crystallization includes: heating the slurried solution; The heating temperature is 90° C.-98° C., the heating time is 1 h-3 h, stirring is performed during the heating process, and the stirring speed is 20 rpm-30 rpm.

9. The preparation method according to claim 1, characterized in that: The drying temperature is 95°C-105°C.

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