CN114195168B - Method for preparing NaA molecular sieve from silicomanganese slag - Google Patents

Method for preparing NaA molecular sieve from silicomanganese slag Download PDF

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CN114195168B
CN114195168B CN202111464157.6A CN202111464157A CN114195168B CN 114195168 B CN114195168 B CN 114195168B CN 202111464157 A CN202111464157 A CN 202111464157A CN 114195168 B CN114195168 B CN 114195168B
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molecular sieve
naa molecular
silicomanganese slag
slag
clinker
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CN114195168A (en
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刘泽
朱思雨
苏壮飞
韩凤兰
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China University of Mining and Technology Beijing CUMTB
North Minzu University
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North Minzu University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/14—Type A
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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    • C01—INORGANIC CHEMISTRY
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Abstract

The invention provides a method for preparing a NaA molecular sieve from silicomanganese slag, and belongs to the technical field of solid waste resource utilization. According to the invention, the silicomanganese slag and the fly ash are used as raw materials, so that the silicomanganese slag can be consumed in a large amount, and meanwhile, the doping of the fly ash can reduce the proportion of elements which are not beneficial to NaA molecular sieve synthesis in the silicomanganese slag, so that the NaA molecular sieve synthesis efficiency is improved; the mass ratio of silicon oxide to aluminum oxide in the mixture can be adjusted by the fly ash and the aluminum source, and the high-performance NaA molecular sieve prepared by using silicomanganese slag of different batches is ensured by controlling the mass ratio of the silicon oxide to the aluminum oxide; the prepared NaA molecular sieve has high purity and small particle size, and can be widely applied to the wastewater treatment process. The results of the examples show that the NaA molecular sieve provided by the invention has the highest crystallinity of more than 80 percent and the particle size of 2-3 μm.

Description

Method for preparing NaA molecular sieve from silicomanganese slag
Technical Field
The invention relates to the technical field of solid waste resource utilization, in particular to a method for preparing a NaA molecular sieve from silicomanganese slag.
Background
The silicomanganese slag is industrial waste slag formed by water quenching of high-temperature slag discharged when raw materials such as manganese ore, manganese-rich slag, lime, coke, silica and the like are used for smelting silicomanganese alloy in a submerged arc furnace in iron alloy enterprises. According to statistics, 1.2-1.3 t of silicon-manganese slag is generated when 1t of silicon-manganese alloy is produced. The silicon-manganese slag discharged in large quantity is piled up in the open air, which not only occupies land and pollutes environment, but also causes resource waste. Although the silicomanganese slag is combined with the building material industry to be used for manufacturing cement, microcrystalline glass, water permeable bricks, concrete additives and the like to obtain certain economic benefits, the silicomanganese slag is not enough to completely digest waste slag with increasing discharge amount, and the additional value of the silicomanganese slag is still very low. Therefore, a new way for recycling the silicomanganese slag is needed to be explored.
Although the manganese content in the silicomanganese slag varies greatly according to the difference of manganese ore resources and smelting technology in various regions, the silicomanganese slag contains a large amount of SiO 2 、CaO、Al 2 O 3 And MnO. Wherein, siO 2 、Al 2 O 3 As an active component, the silicomanganese slag has the potential of synthesizing NaA molecular sieve. The NaA molecular sieve is an alkali metal aluminum silicate with microporous cubic lattice, and has good application prospect in petroleum, chemical industry, metallurgy and other industries.
At present, fly ash is mostly applied in the synthesis of NaA molecular sieves by industrial solid wastes, and because silicomanganese slag contains more impurities and the contents of components in different batches of silicomanganese slag are different, the problems of low crystallinity, poor purity and yield, large particle size and poor adsorption performance of the NaA molecular sieves exist in the process of preparing the NaA molecular sieves by using the silicomanganese slag, and the method is not suitable for industrial production. Therefore, a method for preparing the NaA molecular sieve with good crystallinity and small particle size by using the silicomanganese slag is needed.
Disclosure of Invention
The invention aims to provide a method for preparing a NaA molecular sieve from silicomanganese slag.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a NaA molecular sieve from silicomanganese slag, which comprises the following steps:
(1) Mixing and melting silicomanganese slag and an alkali fusing agent to obtain aluminosilicate clinker;
(2) Mixing the aluminosilicate clinker obtained in the step (1) with fly ash and an aluminum source to obtain a mixture;
(3) Mixing the mixture obtained in the step (2) with alkali liquor and water, and then aging to obtain aged clinker;
(4) Carrying out hydrothermal crystallization on the aged clinker obtained in the step (3) to obtain a NaA molecular sieve;
the mass ratio of the silicomanganese slag in the step (1) to the fly ash in the step (2) is 1: (0.5-1);
the mass ratio of the silicon oxide to the aluminum oxide in the mixture in the step (2) is 1.0-2.0.
Preferably, the granularity of the silicon-manganese slag in the step (1) is more than or equal to 100 meshes.
Preferably, the alkali flux in the step (1) is sodium hydroxide, and the mass ratio of the silicomanganese slag to the alkali flux is 1: (1-2).
Preferably, the melting temperature in the step (1) is 600-800 ℃, and the melting time is 2-4 h.
Preferably, the aluminum source in the step (2) is NaAlO 2 。
Preferably, the alkali liquor in the step (3) is a sodium hydroxide solution, and the concentration of the alkali liquor is 1.5-3 mol/L.
Preferably, the aging time in the step (3) is 3 to 6 hours.
Preferably, the alkalinity of the aged clinker in the step (3) is 1.2-2.4 mol/L.
Preferably, the temperature of hydrothermal crystallization in the step (4) is 60-100 ℃, and the time of hydrothermal crystallization is 4-12 h.
The invention provides the NaA molecular sieve prepared by the method in the technical scheme.
The invention provides a method for preparing a NaA molecular sieve from silicomanganese slag, which comprises the following steps: (1) Mixing and melting silicomanganese slag and an alkali fusing agent to obtain aluminosilicate clinker; (2) Mixing the aluminosilicate clinker obtained in the step (1) with fly ash and an aluminum source to obtain a mixture; (3) Mixing the mixture obtained in the step (2) with alkali liquor and water, and then aging to obtain aged clinker; (4) Carrying out hydrothermal crystallization on the aged clinker obtained in the step (3) to obtain a NaA molecular sieve; the mass ratio of the silicomanganese slag in the step (1) to the fly ash in the step (2) is 1: (0.5 to 1); the mass ratio of the silicon oxide to the aluminum oxide in the mixture in the step (2) is 1.0-2.0. According to the invention, the silicomanganese slag and the fly ash are used as raw materials, and the dosage ratio of the silicomanganese slag to the fly ash is limited, so that the silicomanganese slag can be consumed in a large amount, and simultaneously, the doping of the fly ash can reduce the proportion of elements (such as Ca elements) which are not beneficial to NaA molecular sieve synthesis in the silicomanganese slag, and the synthesis efficiency of the NaA molecular sieve is improved; the mass ratio of silicon oxide to aluminum oxide in the mixture can be adjusted by the fly ash and the aluminum source, and the high-performance NaA molecular sieve prepared by using silicomanganese slag of different batches is ensured by controlling the mass ratio of the silicon oxide to the aluminum oxide; the preparation process is simple, a green new way is provided for resource utilization of the silicomanganese slag, and the problems of resource waste, environmental pollution and the like caused by solid wastes are solved; the prepared NaA molecular sieve has high purity and small particle size, can be widely applied to the wastewater treatment process, and has important application potential in the aspect of being used as a cheap adsorbent. The results of the examples show that the NaA molecular sieve provided by the invention has the highest crystallinity of more than 80%, the particle size of 2-3 mu m, and good adsorption performance, and can be widely applied to the wastewater treatment process.
Drawings
FIG. 1 is an XRD pattern of a NaA molecular sieve prepared in example 5 of the present invention;
FIG. 2 is an SEM image of a NaA molecular sieve prepared in example 5 of the invention.
Detailed Description
The invention provides a method for preparing a NaA molecular sieve from silicomanganese slag, which comprises the following steps:
(1) Mixing and melting silicomanganese slag and an alkali fusing agent to obtain aluminosilicate clinker;
(2) Mixing the aluminosilicate clinker obtained in the step (1) with fly ash and an aluminum source to obtain a mixture;
(3) Mixing the mixture obtained in the step (2) with alkali liquor and water, and then aging to obtain aged clinker;
(4) Carrying out hydrothermal crystallization on the aged clinker obtained in the step (3) to obtain a NaA molecular sieve;
the mass ratio of the silicomanganese slag in the step (1) to the fly ash in the step (2) is 1: (0.5 to 1);
the mass ratio of the silicon oxide to the aluminum oxide in the mixture in the step (2) is 1.0-2.0.
The silicomanganese slag and the alkali fusing agent are mixed and fused to obtain the aluminosilicate clinker. The concrete operation of the mixing is not specially limited, and the silicomanganese slag and the alkali fusing agent can be uniformly mixed. The silicomanganese slag and the alkali fusing agent are mixed and fused, so that the fused alkali fusing agent can carry out alkali excitation on the silicomanganese slag to generate aluminosilicate.
In the invention, the granularity of the silicomanganese slag is preferably larger than or equal to 100 meshes, and more preferably larger than or equal to 150 meshes. In the invention, when the granularity of the silicomanganese slag does not meet the requirement, the silicomanganese slag is preferably ground. In the present invention, the silicomanganese slag is preferably dried before use. The invention limits the granularity of the silicomanganese slag within the range, and can further improve the alkali excitation effect of the alkali fusing agent on the silicomanganese slag.
In the present invention, the alkali fusing agent is preferably sodium hydroxide; the mass ratio of the silicomanganese slag to the alkali flux is preferably 1: (1-2), more preferably 1:1.5. the invention adopts sodium hydroxide as an alkali flux, can avoid introducing impurity elements and improve the synthesis efficiency of the NaA molecular sieve.
In the present invention, the temperature of the melting is preferably 600 to 800 ℃, more preferably 650 to 750 ℃, and most preferably 700 ℃; the time for the melting is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, most preferably 3 hours. The invention limits the melting temperature and time within the range, can ensure the complete melting of the alkali fusing agent, has good alkali excitation effect, can convert crystalline substances in the silicomanganese slag into amorphous substances, and ensures that the finally obtained aluminosilicate clinker is in an amorphous state basically.
After the melting is completed, the invention preferably sequentially cools and grinds the molten product to obtain the aluminosilicate clinker. In the present invention, the cooling is preferably natural cooling; the final temperature of the cooling is preferably room temperature. The specific operation of the grinding and the final grain size of the ground aluminosilicate clinker are not particularly limited, and the method can be judged according to the technical common knowledge of the technicians in the field.
After the aluminosilicate clinker is obtained, the aluminosilicate clinker is mixed with the fly ash and the aluminum source to obtain a mixture.
In the invention, the mass ratio of the silicomanganese slag to the fly ash is 1: (0.5 to 1), preferably 1: (0.6 to 0.9), more preferably 1: (0.7-0.8). The specific source of the fly ash is not particularly limited in the present invention, and commercially available products well known to those skilled in the art can be used. According to the invention, by adding the fly ash, the proportion of elements (such as Ca elements) which are not beneficial to NaA molecular sieve synthesis in the silicon-manganese slag can be reduced, the NaA molecular sieve synthesis efficiency is improved, and meanwhile, the fly ash can adjust the mass ratio of silicon oxide to aluminum oxide in the mixture, so that the high-performance NaA molecular sieve can be prepared by using silicon-manganese slag of different batches.
In the present invention, the aluminum source is preferably a meta-aluminate, more preferably NaAlO 2 . The invention has no special requirements on the specific dosage of the aluminum source, and the ratio of the amounts of the silicon oxide and the aluminum oxide in the mixture can meet the requirements. The invention can adjust the mass ratio of silicon oxide to aluminum oxide in the mixture by adding aluminum source, improves the crystallization rate and the adsorption performance of the NaA molecular sieve, and uses NaAlO 2 As an aluminum source, impurity elements can be avoided from being introduced.
In the present invention, the ratio of the amount of the substances of silica and alumina in the mixture is 1.0 to 2.0, preferably 1.2 to 1.8, more preferably 1.3 to 1.6. According to the method, the ratio of the amounts of the silicon oxide and the aluminum oxide is controlled, so that the high-performance NaA molecular sieve can be prepared even if different batches of silicomanganese slag are used, and the crystallization rate of the NaA molecular sieve is improved.
After the mixture is obtained, the mixture is mixed with alkali liquor and water and then is aged to obtain aged clinker.
In the present invention, the alkali solution is preferably a sodium hydroxide solution; the concentration of the alkali liquor is preferably 1.5-3 mol/L, and more preferably 2-2.5 mol/L. The alkali concentration of the system can be adjusted by adding alkali liquor, so that the crystal form of the NaA molecular sieve is adjusted, and the crystallinity is improved.
In the present invention, the water is preferably deionized water. The specific amount of the deionized water is not particularly limited, and the deionized water can be added according to the required alkalinity. The present invention can adjust the system to the required alkalinity by adding water.
In the present invention, the aging time is preferably 3 to 6 hours, more preferably 3.5 to 5 hours, and most preferably 4 to 4.5 hours; the temperature of the aging is preferably room temperature. In the present invention, the aging is preferably carried out under stirring conditions, and the stirring rate is not particularly limited in the present invention, and may be determined according to the common technical knowledge of those skilled in the art. The invention can form a stable system in the aging clinker through the aging process, thereby improving the crystallization rate of the NaA molecular sieve.
In the present invention, the basicity of the aged clinker is preferably 1.2 to 2.4mol/L, more preferably 1.5 to 2.0mol/L. The invention can further improve the synthesis efficiency of the NaA molecular sieve and improve the crystallization rate by controlling the alkalinity of the aged clinker.
After the aging clinker is obtained, the aging clinker is subjected to hydrothermal crystallization in sequence to obtain the NaA molecular sieve.
In the invention, the temperature of the hydrothermal crystallization is preferably 60-100 ℃, and more preferably 80-90 ℃; the time for the hydrothermal crystallization is preferably 4 to 12 hours, more preferably 6 to 10 hours, and most preferably 7 to 8 hours. The invention limits the parameters of hydrothermal crystallization in the above range, and can further improve the crystallization rate of the NaA molecular sieve.
After the hydrothermal crystallization is finished, the product of the hydrothermal crystallization is preferably sequentially filtered, washed and dried to obtain the NaA molecular sieve. The specific operation of the filtration is not particularly limited, and the solid-liquid separation can be carried out. In the present invention, the specific operation of the washing is not particularly limited, and the pH of the washed product may be set to be 7 to 8. In the present invention, the temperature of the drying is preferably 50 to 70 ℃, more preferably 60 ℃; the drying time is preferably 10 to 15 hours, more preferably 13 to 14 hours. The invention can remove the water in the NaA molecular sieve through drying treatment.
The preparation method provided by the invention has a simple process, provides a green new way for resource utilization of the silicomanganese slag, and solves the problems of resource waste, environmental pollution and the like caused by solid wastes.
The invention provides the NaA molecular sieve prepared by the method in the technical scheme. The NaA molecular sieve provided by the invention has the crystallinity of 40-80% and the particle size of 2-3 mu m, can be widely applied to the wastewater treatment process, and has important application potential in the aspect of being used as a cheap adsorbent.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing a NaA molecular sieve from silicomanganese slag comprises the following steps:
(1) Grinding the silicomanganese slag to ensure that the granularity of the silicomanganese slag is more than or equal to 100 meshes, then drying the silicomanganese slag, mixing 2.5g of the silicomanganese slag with 3.75g of sodium hydroxide, melting for 4 hours at 750 ℃, naturally cooling to room temperature, and grinding to obtain aluminosilicate clinker;
(2) Mixing the aluminosilicate clinker obtained in the step (1) with 1.875g of fly ash and 0.762g of NaAlO 2 Mixing to obtain a mixture; the mass ratio of the silicon oxide to the aluminum oxide in the mixture is 1.6;
(3) Uniformly mixing the mixture obtained in the step (2) with 11.94g of sodium hydroxide solution and 39.06g of deionized water, and stirring and aging at room temperature for 4 hours to obtain an aged clinker; the concentration of the sodium hydroxide solution is 2.4mol/L; the alkalinity of the aged clinker is 2.4mol/L;
(4) Transferring the aged clinker obtained in the step (3) into a reaction kettle, performing hydrothermal crystallization at 90 ℃ for 12 hours, filtering, washing the solid until the pH value is 8, and finally drying at 60 ℃ for 8 hours to obtain a NaA molecular sieve;
the silicomanganese slag comprises the following components: siO 2 2 ：43.30wt.％，Al 2 O 3 :18.48wt.%, mnO:6.71wt.%, caO:19.69wt.%, and the balance impurities; the main crystalline phases of the silicomanganese slag are silicon carbide, quartz and manganite, and the silicomanganese slag is sieved by a 100-mesh sieve.
Example 2
The adding amount of the fly ash is changed to 2.5g 2 The amount of sodium hydroxide solution added was changed to 0.783g and 18.77g, and the other conditions were the same as in example 1.
Example 3
NaAlO is added 2 The amount of the mixture was changed to 1.962g, the amount of the sodium hydroxide solution was changed to 30.55g, the ratio of the amounts of the silica and alumina in the mixture was 1.0, and the other conditions were the same as in example 2.
Example 4
The addition of deionized water was changed to 46.88g, the addition of sodium hydroxide solution was changed to 4.13g, the concentration of sodium hydroxide solution was changed to 2.0mol/L, the alkalinity of the aged clinker was changed to 2.0mol/L, and the other conditions were the same as in example 1.
Example 5
The addition of deionized water was changed to 46.88g, the addition of sodium hydroxide solution was changed to 10.96g, the concentration of sodium hydroxide solution was changed to 2.0mol/L, the alkalinity of the aged clinker was changed to 2.0mol/L, and the other conditions were the same as in example 2.
Example 6
The temperature for hydrothermal crystallization was changed to 60 ℃ and the other conditions were the same as in example 5.
Example 7
The hydrothermal crystallization time was changed to 8 hours, and the other conditions were the same as in example 5.
Example 8
The hydrothermal crystallization time was changed to 4 hours, and the other conditions were the same as in example 5.
Example 9
NaAlO is added 2 The adding amount of the sodium hydroxide solution is changed to 0.783g, and the adding amount of the sodium hydroxide solution is changed to 7.08g; the silicon-manganese slag comprises the following components: siO 2 2 ：32.00wt.％，Al 2 O 3 :25.87wt.%, mnO:10.95wt.%, caO:18.17wt.%, and the balanceThe impurities of (a); the main crystalline phases of the silicomanganese slag are quartz and manganite, and other conditions are the same as those in the example 7.
Example 10
The adding amount of the fly ash is changed to 1.875g 2 The amount of (3) was changed to 0.726g, and the amount of sodium hydroxide solution added was changed to 4.13g, under the same conditions as in example 9.
Example 11
The addition amount of the fly ash is changed to 1.25g 2 The amount of (2) was changed to 0.668g, and the other conditions were the same as in example 9.
Example 12
NaAlO is added 2 The amount of (2) was changed to 1.005g, the ratio of the amounts of silica and alumina in the mixture was 1.3, and the other conditions were the same as in example 11.
Example 13
NaAlO is added 2 The amount of the silica-alumina mixture added was changed to 1.535g, the ratio of the amounts of the silica and the alumina in the mixture was 1.0, and the other conditions were the same as in example 11.
Example 14
The temperature for hydrothermal crystallization was changed to 60 ℃ and the other conditions were the same as in example 12.
Example 15
The hydrothermal crystallization time was changed to 4 hours, and the other conditions were the same as in example 12.
Comparative example 1
The addition amount of the fly ash is changed to 1.25g 2 Was changed to 0.726g, and the amount of sodium hydroxide solution was changed to 50.92g, and the other conditions were the same as in example 1, to obtain a product.
Comparative example 2
NaAlO is added 2 The amount of the sodium hydroxide solution added was changed to 0.248g, the amount of the sodium hydroxide solution added was changed to 13.41g, the ratio of the amounts of the silica and alumina in the mixture was 2.2, and the other conditions were the same as in example 2, to obtain a product.
Comparative example 3
The amount of deionized water added was changed to 93.75g, the alkalinity of the aged clinker was 1.0mol/L, and the other conditions were the same as in example 2, to obtain a product.
Comparative example 4
The temperature of hydrothermal crystallization was changed to 120 ℃, and the other conditions were the same as in example 5, to obtain a product.
Comparative example 5
The hydrothermal crystallization time was changed to 2 hours, and the other conditions were the same as in example 5 to obtain a product.
Comparative example 6
The hydrothermal crystallization time was changed to 4 hours, and the other conditions were the same as in example 2, to obtain a product.
Comparative example 7
The amount of deionized water added was changed to 93.75g, the basicity of the aged clinker was 1.0mol/L, and the other conditions were the same as in example 12, to obtain a product.
Comparative example 8
A method for preparing NaA molecular sieve, comprising the steps of:
(1) 2.0g of fly ash and 0.138g of NaAlO 2 Mixing to obtain a mixture; the mass ratio of the silicon oxide to the aluminum oxide in the mixture is 1.6;
(2) Uniformly mixing the mixture obtained in the step (1) with 16.38g of sodium hydroxide solution, and stirring and aging at room temperature for 4 hours to obtain an aged clinker; the concentration of the sodium hydroxide solution is 2.0mol/L; the alkalinity of the aged clinker is 2.0mol/L;
(4) And (4) transferring the aged clinker obtained in the step (3) into a reaction kettle, performing hydrothermal crystallization at 90 ℃ for 4 hours, filtering, washing the solid until the pH value is 8, and finally drying at 60 ℃ for 8 hours to obtain the NaA molecular sieve.
The products obtained in examples 1 to 15 and comparative examples 1 to 8 are shown in Table 1;
TABLE 1 products obtained in examples 1 to 15 and comparative examples 1 to 8
Figure BDA0003390600860000091
Figure BDA0003390600860000101
By comparing the final products prepared in examples 1-2 and comparative example 1 and comparing the final products prepared in examples 9-11, it can be seen that, when other conditions are the same, the higher the crystallinity of the NaA molecular sieve is with the increase of the amount of the fly ash, and when the amount of the fly ash is too small, only calcium aluminosilicate can be prepared, but the NaA molecular sieve cannot be obtained, which indicates that the amount of the fly ash affects the crystallization rate of the NaA molecular sieve.
By comparing the final products prepared in examples 2 to 3 and comparative example 2 and comparing the final products prepared in examples 11 to 13, it can be seen that when the other conditions are the same, the crystallinity of the NaA molecular sieve tends to increase and then decrease as the ratio of the amounts of the substances of silicon oxide and aluminum oxide increases, and when the ratio of the amounts of the substances of silicon oxide and aluminum oxide is too high, the NaA molecular sieve cannot be obtained, only cancrinite can be obtained, indicating that the ratio of the amounts of the substances of silicon oxide and aluminum oxide affects the crystallization rate of the NaA molecular sieve.
By comparing the final products prepared in examples 3 and 5 with the final product prepared in comparative example 3 and comparing the final products prepared in example 15 with the final product prepared in comparative example 7, it can be seen that, when other conditions are the same, too low alkalinity of the raw material in the hydrothermal crystallization reaction process may cause crystallization failure, and thus NaA molecular sieve may not be obtained, while too high alkalinity may also cause reduction of the crystallinity of NaA molecular sieve, which indicates that alkalinity may affect the crystallization rate of NaA molecular sieve.
By comparing the final products obtained in examples 5 to 6 with the final product obtained in comparative example 4, and comparing the final products obtained in examples 14 and 15, it can be seen that, when the other conditions are the same, the crystallinity of the NaA molecular sieve gradually increases with the increase of the reaction temperature of the hydrothermal crystallization, but when the reaction temperature of the hydrothermal crystallization reaches 120 ℃, the NaA molecular sieve cannot be obtained, which indicates that the synthesis of the NaA molecular sieve is not facilitated due to the excessively high reaction temperature of the hydrothermal crystallization, and also indicates that the synthesis of the NaA molecular sieve and the crystallization rate are affected by the reaction temperature of the hydrothermal crystallization.
By comparing the final products prepared in examples 6 to 8 and comparative example 5, and comparing the final products prepared in examples 12 and 15, it can be seen that, when the other conditions are the same, when the reaction time of hydrothermal crystallization is too short, naA molecular sieve cannot be generated, and as the reaction time of hydrothermal crystallization is prolonged, naA molecular sieve is generated, and the crystallinity of NaA molecular sieve shows a tendency of increasing and then decreasing, which indicates that the time of hydrothermal crystallization affects the synthesis and crystallization rate of NaA molecular sieve.
It can be seen from the comparison between example 7 and example 9 that, by controlling the addition amount of fly ash, the ratio of the amounts of substances of silicon oxide and aluminum oxide, the alkalinity and the reaction parameters of hydrothermal crystallization during the preparation process, even if different batches of silicomanganese slag are used as raw materials, the NaA molecular sieve with high crystallization rate can be prepared, which indicates that the source and the components of the silicomanganese slag do not influence the crystallization rate of the NaA molecular sieve.
As can be seen from the comparison between example 8 and comparative example 8, the crystallization rate of the NaA molecular sieve prepared by using the silicomanganese slag and the fly ash as raw materials is very close to that of the existing NaA molecular sieve prepared by using the fly ash as raw materials, which indicates that the invention provides a green new way for resource utilization of the silicomanganese slag and solves the problems of resource waste, environmental pollution and the like caused by solid wastes; the prepared NaA molecular sieve can be applied to the wastewater treatment process and has important application potential in the application aspect of cheap adsorbents.
The observation of the NaA molecular sieve prepared in example 5 was carried out using Smartlab and JSM-7001F manufactured by Japan K.K., and the XRD pattern and SEM pattern of the obtained NaA molecular sieve are shown in FIGS. 1 and 2, respectively. As can be seen from FIG. 1, the NaA molecular sieve prepared in the invention in the example 5 has strong and sharp characteristic peaks, indicating high crystallinity. As can be seen from FIG. 2, the NaA molecular sieve prepared in example 5 of the present invention has a typical cubic structure, is completely crystallized, and has a particle size of about 2 to 3 μm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A method for preparing a NaA molecular sieve from silicomanganese slag comprises the following steps:
(1) Mixing and melting silicomanganese slag and an alkali fusing agent to obtain aluminosilicate clinker;
(2) Mixing the aluminosilicate clinker obtained in the step (1) with fly ash and an aluminum source to obtain a mixture;
(3) Mixing the mixture obtained in the step (2) with alkali liquor and water, and then aging to obtain aged clinker;
(4) Carrying out hydrothermal crystallization on the aged clinker obtained in the step (3) to obtain a NaA molecular sieve;
the alkali flux in the step (1) is sodium hydroxide, and the mass ratio of the silicomanganese slag to the alkali flux is 1: (1~2);
the melting temperature in the step (1) is 600 to 800 ℃, and the melting time is 2 to 4 hours;
the mass ratio of the silicomanganese slag in the step (1) to the fly ash in the step (2) is 1: (0.5 to 1);
the mass ratio of the silicon oxide to the aluminum oxide in the mixture in the step (2) is 1.3 to 1.6;
the alkalinity of the aged clinker in the step (3) is 1.2 to 2.4mol/L.
2. The method according to claim 1, wherein the granularity of the silicomanganese slag in the step (1) is more than or equal to 100 meshes.
3. The method as claimed in claim 1, wherein the aluminum source in step (2) is NaAlO 2 。
4. The method as claimed in claim 1, wherein the alkali liquor in the step (3) is sodium hydroxide solution, and the concentration of the alkali liquor is 1.5 to 3mol/L.
5. The method as claimed in claim 1, wherein the aging time in the step (3) is 3 to 6 hours.
6. The method as claimed in claim 1, wherein the temperature of hydrothermal crystallization in the step (4) is 60 to 100 ℃, and the time of hydrothermal crystallization is 4 to 12h.
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