CN107352554B - Preparation method and application of magnetic X-type molecular sieve - Google Patents
Preparation method and application of magnetic X-type molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a magnetic X-type molecular sieve, which comprises the steps of grinding coal gangue, and roasting and activating the coal gangue at high temperature by using sodium carbonate; oxidizing at low temperature, adding hydrochloric acid, soaking at 90 deg.C, filtering, and adding oxalic acid into the filtrate; washing the solid, drying, adding sodium hydroxide solid, grinding to be uniformly mixed, and carrying out alkali fusion at low temperature; adding deionized water and citric acid, aging at 60 deg.C, adding the above filtrate, and ultrasonic crystallizing to synthesize iron-doped molecular sieve; and (3) placing the iron-doped molecular sieve sample in a tubular furnace, and reducing at high temperature to obtain the magnetic X-type molecular sieve. The magnetic X-type molecular sieve prepared by the invention has the advantages of high specific surface area and strong adsorption performance, the solid-liquid separation of the product is easy through an external magnetic field, the problem of high cost synthesis of the molecular sieve is solved, a new way is provided for recycling, refining and efficient utilization of coal gangue, the effect of changing waste into valuable is achieved, and the requirements of environmental protection and low carbon are met.
Description
Technical Field
The invention belongs to the technical field of preparation of X-type molecular sieves, and particularly relates to a preparation method and application of a magnetic X-type molecular sieve.
Background
The coal gangue is solid waste discharged in the coal mining and coal dressing processes, is a black and gray rock with lower carbon content and harder than coal and is associated with a coal bed in the coal forming process, and the output is large. At present, the application of the coal gangue is mainly limited in the fields of building industry, energy industry, agriculture and the like, the utilization level and the proportion are low, and the accumulation of the coal gangue not only affects the environment, but also occupies a large amount of land. The molecular sieve prepared by the method can reduce pollution, expand the raw material sources of the molecular sieve, increase the added value of the molecular sieve and expand the utilization way of coal gangue. Molecular sieves are of two types, natural and synthetic: natural molecular sieves are mostly formed from the reaction of volcanic tuff and sedimentary rock in the sea or lake phase. At present, more than 1000 kinds of zeolite ores are found in the world, and more important are 35 kinds; the synthetic molecular sieve comes out from the 50 th of the 20 th century, greatly makes up for the deficiency of natural molecular sieve resources, and becomes the main force of the molecular sieve market.
The X-type molecular sieve has excellent performance and is widely applied to industry. However, the directly prepared X-type molecular sieve is generally nano or micron powder, which makes it difficult to separate from the liquid phase of the working fluid system. The patent utilizes the coal gangue in the clarified mining area to prepare the magnetic X-shaped molecular sieve, and Fe of the magnetic X-shaped molecular sieve is obtained after calcination2O3The content reaches 10.10%, and the iron in the prepared magnetic X-type molecular sieve is directly converted into magnetic iron without adding iron. The magnetic X-type molecular sieve prepared from coal gangue not only has the excellent performance of the molecular sieve, but also is endowed with magnetism, thereby being beneficial to separation from the working solution.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method and application of a magnetic X-type molecular sieve aiming at the defects of the prior art. The invention uses the coal gangue for preparing the magnetic molecular sieve and provides a new process for preparing the magnetic molecular sieve by using the coal gangue, which not only solves the problem of high cost of molecular sieve synthesis, but also provides a new way for recycling, refining and efficiently utilizing the coal gangue, achieves the effect of changing waste into valuable and meets the requirements of environmental protection and low carbon.
In order to solve the problems, the invention adopts the technical scheme that:
a preparation method of a magnetic X-type molecular sieve comprises the following steps:
1) grinding the coal gangue into fine powder, adding sodium carbonate, roasting at 880-900 ℃, fully reacting and grinding to obtain a pretreated sample; wherein the mass ratio of the coal gangue powder to the sodium carbonate is (2-3) to 1;
2) oxidizing the pretreated coal gangue powder at 350-400 ℃, adding hydrochloric acid, soaking at 90-100 ℃, filtering to obtain filtered solid and filtrate, and adding oxalic acid into the filtrate for later use; wherein, oxalic acid and filterFe in liquid3+The molar ratio is 4-6;
3) washing and drying the solid obtained in the step 2), adding sodium hydroxide solid according to the mass ratio of 1:1, grinding until the sodium hydroxide solid is uniformly mixed, and carrying out alkali fusion at the temperature of 450-500 ℃; then adding deionized water and citric acid, carrying out aging reaction, and mixing the citric acid with Al in the solution2O3The molar ratio of (A) to (B) is 0.65-0.85; finally, adding the standby filtrate obtained in the step 2), and synthesizing the iron-doped molecular sieve by ultrasonic crystallization;
4) and (2) placing the synthesized iron-doped molecular sieve in a tubular furnace, introducing nitrogen to completely exhaust air, stopping introducing nitrogen, heating, introducing hydrogen, performing reduction reaction after the temperature is raised to 650-700 ℃, introducing nitrogen and then closing hydrogen after full reaction, cooling a sample to room temperature and then closing nitrogen to prepare the magnetic X-type molecular sieve.
In the step 1), the coal gangue is ground into 300-325 meshes and then added with sodium carbonate.
In the step 2), the mass concentration of the hydrochloric acid is 15%.
In the step 2), 0.450g to 0.675g of oxalic acid is correspondingly added into each gram of coal gangue.
In the step 3), the temperature of ultrasonic crystallization is 75-95 ℃, and the time is 6-10 h.
In the step 3), the aging reaction temperature is 60-70 ℃ and the time is 4-5 h.
In the step 4), the reduction reaction time is 2-3 h.
In the step 4), the introduction flow rate of the hydrogen is 50cm3/min。
The prepared magnetic X-type molecular sieve is applied to adsorbing heavy metal ions in wastewater. Especially for adsorbing lead ions in wastewater.
Compared with the prior art, the invention has the following advantages:
after grinding the coal gangue, roasting the coal gangue at high temperature by using sodium carbonate to activate the coal gangue; oxidizing at low temperature, adding hydrochloric acid, soaking at 90 deg.C, filtering, and adding oxalic acid into the filtrate; washing the solid, drying, adding sodium hydroxide solid, grinding to be uniformly mixed, and carrying out alkali fusion at low temperature; adding deionized water and citric acid, aging at 60 deg.C, adding the above filtrate, and ultrasonic crystallizing to synthesize iron-doped molecular sieve; and (3) placing the iron-doped molecular sieve sample in a tubular furnace, and reducing at high temperature to obtain the magnetic X-type molecular sieve. The magnetic X-type molecular sieve is prepared by adopting coal gangue as a raw material, dissolving iron in hydrochloric acid under ultrasonic waves, adding oxalic acid for complexing iron, and finally reducing at high temperature. Greatly reduces the preparation and application cost of the molecular sieve. In the preparation process, the coal gangue is used as a raw material, the citric acid and the oxalic acid which are added as auxiliary agents are added, and ultrasonic vibration heating is carried out, so that the reaction time is greatly shortened, the crystallization temperature is reduced, and the energy consumption is saved; meanwhile, the utilization rate of the molecular sieve is improved by utilizing magnetic separation, the method has strong commercial competitiveness and can greatly promote the rapid development of the molecular sieve in China.
The invention can effectively solve the problem that the reaction liquid is difficult to separate in the application of the molecular sieve. By the experiment of lead ion adsorption, the adsorption rate of the magnetic molecular sieve is more than 94%, and the magnetic molecular sieve is easily separated from reaction liquid by using an external magnetic field, so that the application of the magnetic molecular sieve in the adsorption industry is greatly improved. The magnetic X-type molecular sieve prepared by utilizing the coal gangue has the advantages of high crystallinity, uniform crystal distribution, uniform particle size, complete crystal form, regular crystal morphology, clear square edges and regular octahedron shape.
Drawings
FIG. 1 is an XRD pattern of a magnetic type X molecular sieve prepared in example 1 of the present invention;
FIG. 2 is an SEM picture of the magnetic X-type molecular sieve prepared in example 1 of the present invention.
FIG. 3 is an X photoelectron spectrum of the magnetic X-type molecular sieve prepared in example 1 of the present invention;
FIG. 4 is an IR spectrum of the magnetic X-type molecular sieve prepared in example 2 of the present invention.
Detailed Description
The invention relates to a preparation method of a magnetic X-type molecular sieve, which comprises the following steps:
step one, grinding the coal gangue to 300-325 meshes, placing the coal gangue in an ash pan, then adding sodium carbonate into the ash pan, roasting for 2-3 h at the temperature of 880-900 ℃, and grinding to obtain a pretreated sample; the mass ratio of the coal gangue to the sodium carbonate is (2-3) to 1;
secondly, oxidizing the pretreated coal gangue powder at 350-400 ℃ for 1.5-2H, adding hydrochloric acid with the mass concentration of 15%, soaking at 90-100 ℃ for 2-3H, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 4-6 for later use; wherein, 0.450 g-0.675 gH is correspondingly added into each gram of coal gangue2C2O4；
Step three, after the solid in the step two is washed, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding the mixture until the mixture is uniformly mixed, carrying out alkali fusion at the temperature of 450-500 ℃ for 1.5-2 h, and adding deionized water and C6H8O7/Al2O3Aging citric acid with the molar ratio of 0.65-0.85 for 4-5 h at the temperature of 60-70 ℃; then adding the standby filtrate, and carrying out ultrasonic crystallization at the temperature of 75-95 ℃ for 6-10 h to synthesize the iron-doped molecular sieve;
step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, discharging air in the tube furnace after 1-1.5 hours, switching on a power supply to set the temperature at 650-700 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow at 50cm3And/min, reacting for 2-3 h when the temperature rises to the set temperature, introducing nitrogen, then closing hydrogen, cooling the sample to room temperature, and then closing nitrogen to prepare the magnetic X-type molecular sieve.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
The coal gangue used in the embodiments 1 to 6 is coal gangue produced in a Chengji mining area in Shaanxi. The chemical composition (wt%) of the coal gangue is detected to be shown in table 1:
TABLE 1
| Components | SiO2 | Al2O3 | Fe2O3 | CaO | MgO |
| Weight content (%) | 58.80 | 25.61 | 10.10 | 2.09 | 0.21 |
Example 1
The preparation of the magnetic X-type molecular sieve by using the coal gangue comprises the following steps:
step one, grinding coal gangue to 325 meshes, placing the powder into an ash pan, adding 1: 3 of coal gangue and sodium carbonate into the ash pan, roasting for 2 hours at the temperature of 900 ℃, and grinding to obtain a pretreated sample;
step two, oxidizing the pretreated coal gangue powder at 350 ℃ for 2H, adding hydrochloric acid with the mass concentration of 15%, soaking at 90 ℃ for 2H, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 4 for standby;
step threeWashing the solid obtained in the step two, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding until the sodium hydroxide solid is uniformly mixed, carrying out alkali fusion for 2h at 450 ℃, and adding deionized water and C6H8O7/Al2O3Aging citric acid with a molar ratio of 0.65 at 70 deg.C for 4 hr; and adding the filtrate for later use, and performing ultrasonic crystallization at the temperature of 75 ℃ for 10 hours to synthesize the iron-doped molecular sieve.
Step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, after 1 hour, after the air in the tube furnace is completely discharged, switching on a power supply, setting the temperature to be 650 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow to be 50cm3And/min, reacting for 2h when the temperature rises to the set temperature, introducing nitrogen, closing hydrogen, cooling the sample to room temperature, and closing nitrogen to prepare the magnetic X-type molecular sieve.
The magnetic X-type molecular sieve prepared in this example was characterized by XRD, SEM and XPS, and the results are shown in fig. 1 to 3. Fig. 1 is an XRD pattern of the magnetic X-type molecular sieve prepared in example 1, and it can be seen from the XRD pattern of the magnetic X-type molecular sieve prepared in this example is consistent with the XRD pattern (JCPDS card No.38.0237) of the standard NaX-type molecular sieve, that is, strong diffraction peaks appear around 15.70, 23.66, 27.04, and 31.36, respectively, in 2 θ. From the whole XRD pattern, the diffraction peak is sharp and has large intensity, which indicates that the product has high crystallization degree.
Fig. 2 is an SEM photograph of the magnetic X-type molecular sieve prepared in this example, and the product has high crystallinity, uniform crystal distribution, uniform particle size, clear crystal grains, complete crystal form, regular crystal morphology, and clear square edges, and the crystal grains are octahedral. FIG. 3 is an X photoelectron spectrum of a magnetic X-type molecular sieve, in which the spectral lines clearly show Si2p、A12p、OlsAnd NalsThe equipeaks show that elements such as Si, Al, O, Na and the like exist on the surface of the magnetic molecular sieve, and weak Fe appears in a spectral line2pThe peak shows that Fe exists on the surface, and the calculation shows that Fe on the surface of the magnetic molecular sieve3O4The content is 2.60% by mass in combination with the above chemical analysisIt shows that the iron entering the molecular sieve by isomorphous replacement is unstable, and basically generates Fe under the condition of high-temperature reduction3O4In addition, the magnetic molecular sieve prepared by the method is also shown, and the generated Fe3O4In admixture with the molecular sieve formed.
The adsorption performance of the magnetic X-type molecular sieve prepared by the implementation on lead ions in wastewater is measured by a spectrophotometry, and the measured adsorption rate reaches 94.2%.
Example 2
The preparation of the magnetic X-type molecular sieve by using the coal gangue comprises the following steps:
step one, grinding coal gangue to 325 meshes, placing the powder into an ash pan, adding 1: 3 of coal gangue and sodium carbonate into the ash pan, roasting for 2 hours at the temperature of 900 ℃, and grinding to obtain a pretreated sample;
step two, oxidizing the pretreated coal gangue powder at 350 ℃ for 2H, adding hydrochloric acid with the mass concentration of 15%, soaking at 90 ℃ for 2H, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 6 for standby;
step three, after the solid in the step two is washed, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding the mixture until the mixture is uniformly mixed, carrying out alkali fusion for 2 hours at the temperature of 450 ℃, and adding deionized water and C6H8O7/Al2O3Aging citric acid with a molar ratio of 0.75 at 60 deg.C for 5 hr; and adding the standby filtrate, and performing ultrasonic crystallization at the temperature of 75 ℃ for 6 hours to synthesize the iron-doped molecular sieve.
Step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, after 1 hour, after the air in the tube furnace is completely discharged, switching on a power supply, setting the temperature to be 650 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow to be 50cm3And/min, reacting for 2h when the temperature rises to the set temperature, introducing nitrogen, closing hydrogen, cooling the sample to room temperature, and closing nitrogen to prepare the magnetic X-type molecular sieve.
The adsorption performance of the magnetic X-type molecular sieve prepared by the implementation on lead ions in wastewater is measured by a spectrophotometry, and the measured adsorption rate reaches 94.6%.
Example 3
The preparation of the magnetic X-type molecular sieve by using the coal gangue comprises the following steps:
step one, grinding coal gangue to 325 meshes, placing the powder into an ash pan, adding 1: 3 of coal gangue and sodium carbonate into the ash pan, roasting for 2 hours at the temperature of 900 ℃, and grinding to obtain a pretreated sample;
step two, oxidizing the pretreated coal gangue powder at 350 ℃ for 2H, adding hydrochloric acid with the mass concentration of 15%, soaking at 90 ℃ for 2H, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 5 for standby;
step three, after the solid in the step two is washed, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding the mixture until the mixture is uniformly mixed, carrying out alkali fusion for 2 hours at the temperature of 450 ℃, and adding deionized water and C6H8O7/Al2O3Aging citric acid with a molar ratio of 0.85 at 70 deg.C for 4 hr; and adding the standby filtrate, and carrying out ultrasonic crystallization at the temperature of 85 ℃ for 8 hours to synthesize the iron-doped molecular sieve.
Step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, after 1 hour, after the air in the tube furnace is completely discharged, switching on a power supply, setting the temperature to be 650 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow to be 50cm3And/min, reacting for 2h when the temperature rises to the set temperature, introducing nitrogen, closing hydrogen, cooling the sample to room temperature, and closing nitrogen to prepare the magnetic X-type molecular sieve.
The adsorption performance of the magnetic X-type molecular sieve prepared by the implementation on lead ions in wastewater is measured by a spectrophotometry, and the measured adsorption rate reaches 94.5%.
Example 4
The preparation of the magnetic X-type molecular sieve by using the coal gangue comprises the following steps:
step one, grinding coal gangue to 325 meshes, placing the powder into an ash pan, adding 1: 3 of coal gangue and sodium carbonate into the ash pan, roasting for 2 hours at the temperature of 900 ℃, and grinding to obtain a pretreated sample;
step two, oxidizing the pretreated coal gangue powder at 350 ℃ for 2H, adding hydrochloric acid with the mass concentration of 15%, soaking at 90 ℃ for 2H, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 5 for standby;
step three, after the solid in the step two is washed, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding the mixture until the mixture is uniformly mixed, carrying out alkali fusion for 2 hours at the temperature of 450 ℃, and adding deionized water and C6H8O7/Al2O3Aging citric acid with a molar ratio of 0.65 at 70 deg.C for 4 hr; and adding the filtrate for later use, and performing ultrasonic crystallization at the temperature of 95 ℃ for 8 hours to synthesize the iron-doped molecular sieve.
Step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, after 1 hour, after the air in the tube furnace is completely discharged, switching on a power supply, setting the temperature to 700 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow to be 50cm3And/min, reacting for 2h when the temperature rises to the set temperature, introducing nitrogen, closing hydrogen, cooling the sample to room temperature, and closing nitrogen to prepare the magnetic X-type molecular sieve.
The adsorption performance of the magnetic X-type molecular sieve prepared by the implementation on lead ions in wastewater is measured by a spectrophotometry, and the measured adsorption rate reaches 95.1%.
Example 5
The preparation of the magnetic X-type molecular sieve by using the coal gangue comprises the following steps:
step one, grinding coal gangue to 325 meshes, placing the powder into an ash pan, adding 1: 3 of coal gangue and sodium carbonate into the ash pan, roasting for 2 hours at the temperature of 900 ℃, and grinding to obtain a pretreated sample;
step two, oxidizing the pretreated coal gangue powder at 350 ℃ for 2h, adding hydrochloric acid with the mass concentration of 15 percent into the oxidized coal gangue powderSoaking at 90 deg.C for 2 hr, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 5 for standby;
step three, after the solid in the step two is washed, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding the mixture until the mixture is uniformly mixed, carrying out alkali fusion for 2 hours at the temperature of 450 ℃, and adding deionized water and C6H8O7/Al2O3Aging citric acid with a molar ratio of 0.75 at 60 deg.C for 3 h; and adding the standby filtrate, and carrying out ultrasonic crystallization at the temperature of 85 ℃ for 8 hours to synthesize the iron-doped molecular sieve.
Step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, after 1 hour, after the air in the tube furnace is completely discharged, switching on a power supply, setting the temperature to be 650 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow to be 50cm3And/min, reacting for 2h when the temperature rises to the set temperature, introducing nitrogen, closing hydrogen, cooling the sample to room temperature, and closing nitrogen to prepare the magnetic X-type molecular sieve.
The adsorption performance of the magnetic X-type molecular sieve prepared by the implementation on lead ions in wastewater is measured by a spectrophotometry, and the measured adsorption rate reaches 94.9%.
Example 6
The preparation of the magnetic X-type molecular sieve by using the coal gangue comprises the following steps:
step one, grinding coal gangue to 325 meshes, placing the powder into an ash pan, adding 1: 3 of coal gangue and sodium carbonate into the ash pan, roasting for 2 hours at the temperature of 900 ℃, and grinding to obtain a pretreated sample;
step two, oxidizing the pretreated coal gangue powder at 350 ℃ for 2H, adding hydrochloric acid with the mass concentration of 15%, soaking at 90 ℃ for 2H, filtering, and adding H into the filtrate2C2O4/Fe3+Oxalic acid with the molar ratio of 5 for standby;
step three, after the solid in the step two is washed, adding sodium hydroxide solid according to the mass ratio of 1:1, grinding the mixture until the mixture is uniformly mixed, carrying out alkali fusion for 2 hours at the temperature of 450 ℃, and adding deionized waterAnd C6H8O7/Al2O3Aging citric acid with a molar ratio of 0.85 at 70 deg.C for 3 hr; and adding the standby filtrate, and performing ultrasonic crystallization at the temperature of 95 ℃ for 6 hours to synthesize the iron-doped molecular sieve.
Step four, placing the synthesized iron-doped molecular sieve sample in a small porcelain boat, placing the porcelain boat in a tube furnace, connecting two ends of a furnace core with rubber plugs with rubber tubes, opening a nitrogen valve to introduce nitrogen, after 1 hour, after the air in the tube furnace is completely discharged, switching on a power supply, setting the temperature to be 650 ℃, simultaneously opening a hydrogen valve, closing the nitrogen valve, and controlling the flow to be 50cm3And/min, reacting for 2h when the temperature rises to the set temperature, introducing nitrogen, closing hydrogen, cooling the sample to room temperature, and closing nitrogen to prepare the magnetic X-type molecular sieve.
The adsorption performance of the magnetic X-type molecular sieve prepared by the implementation on lead ions in wastewater is measured by a spectrophotometry, and the measured adsorption rate reaches 95.5%.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. The preparation method of the magnetic X-type molecular sieve is characterized by comprising the following steps of:
1) grinding the coal gangue into fine powder, adding sodium carbonate, roasting at 880-900 ℃, fully reacting and grinding to obtain a pretreated sample; wherein the mass ratio of the coal gangue powder to the sodium carbonate is (2-3) to 1;
2) oxidizing the pretreated coal gangue powder at 350-400 ℃, adding hydrochloric acid, soaking at 90-100 ℃ under ultrasonic wave, filtering to obtain filtered solid and filtrate, and adding oxalic acid into the filtrate for later use; wherein, the oxalic acid and the Fe in the filtrate3+The molar ratio is 4-6; adding 0.450 g-0.675 g oxalic acid into each gram of coal gangue;
3) washing and drying the solid obtained in the step 2), adding sodium hydroxide solid according to the mass ratio of 1:1, grinding until the mixture is uniformly mixed,alkali fusion at 450-500 deg.c; then adding deionized water and citric acid, carrying out aging reaction, and mixing the citric acid with Al in the solution2O3The molar ratio of (A) to (B) is 0.65-0.85; finally, adding the standby filtrate obtained in the step 2), and synthesizing the iron-doped molecular sieve by ultrasonic crystallization;
4) and (2) placing the synthesized iron-doped molecular sieve in a tubular furnace, introducing nitrogen to completely exhaust air, stopping introducing nitrogen, heating, introducing hydrogen, performing reduction reaction after the temperature is raised to 650-700 ℃, introducing nitrogen and then closing hydrogen after full reaction, cooling a sample to room temperature and then closing nitrogen to prepare the magnetic X-type molecular sieve.
2. The method for preparing a magnetic X-type molecular sieve according to claim 1, wherein in the step 1), sodium carbonate is added after the coal gangue is ground into 300-325 meshes.
3. The method for preparing a magnetic X-type molecular sieve according to claim 1, wherein the hydrochloric acid concentration in step 2) is 15% by mass.
4. The method for preparing the magnetic X-type molecular sieve according to claim 1, wherein in the step 3), the temperature of ultrasonic crystallization is 75-95 ℃ and the time is 6-10 h.
5. The method for preparing the magnetic X-type molecular sieve according to claim 1, wherein in the step 3), the aging reaction temperature is 60-70 ℃ and the time is 4-5 h.
6. The method for preparing the magnetic X-type molecular sieve according to claim 1, wherein in the step 4), the reduction reaction time is 2-3 h.
7. The method for preparing a magnetic X-type molecular sieve according to claim 1, wherein in the step 4), the flow rate of hydrogen is 50cm3/min。
8. Use of the magnetic X-type molecular sieve prepared by the preparation method of any one of claims 1 to 7 in adsorption of heavy metal ions in wastewater.
9. The use according to claim 8 for adsorbing lead ions in wastewater.
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