CN115007120A - Mesoporous composite material for selectively adsorbing manganese and preparation method and application thereof - Google Patents
Mesoporous composite material for selectively adsorbing manganese and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a mesoporous composite material for selectively adsorbing manganese and a preparation method and application thereof, wherein the preparation method comprises the following steps: carrying out first mixing on a rare earth metal salt, a mesoporous material and a solvent, carrying out first drying after solid-liquid separation to obtain a solid mixture; and carrying out second mixing on the sulfide solution and the solid mixture, carrying out second drying after solid-liquid separation, and obtaining the mesoporous composite material. The invention provides a mesoporous composite material with selective adsorption effect, which is prepared by reacting rare earth metal salt with sulfide solution in a mesoporous material to generate rare earth sulfide, and the prepared rare earth sulfide and the mesoporous material form the composite material.
Description
Technical Field
The invention belongs to the field of water treatment, relates to a mesoporous composite material, and particularly relates to a mesoporous composite material capable of selectively adsorbing manganese, and a preparation method and application thereof.
Background
In recent years, the use of unleaded gasoline, the exploitation of manganese ore and the development of the steel industry have led to an increase in the concentration of manganese in the environment, particularly in water. Manganese in water environment is mainly Mn 2+ And MnO 4 - The weak acids and weak acid salts exist in the form of, most of them are soluble compounds and are easy to migrate with water. Manganese in water can enter a human body through various ways and accumulate in the human body, and has great toxicity to the human body. Studies have shown that manganese can impair mitochondrial function leading to neurological damage and irreversible extrapyramidal motor dysfunction, resulting in clinical manifestations similar to parkinson's syndrome. Meanwhile, manganese can also damage the male reproductive system by influencing the oxidative stress state, destroy the spermatogenesis environment and reduce the activity of sperms, thereby reducing the fertility of the male. Excessive manganese can also have toxic effects on the heart, liver, etc.
At present, the methods for treating manganese-containing wastewater at home and abroad mainly comprise a precipitation method, an ion exchange method, a biological method, a membrane method, an electrocoagulation method, an adsorption method and the like. The precipitation method manganese removal technology is most commonly applied, but waste residues are generated, secondary pollution is caused, and the efficiency is not high; the ion exchange method and the membrane separation method have small treatment capacity, are more suitable for treating wastewater with single composition, have high cost and are commonly used for treating high added value; biological and coagulation methods are currently in the infancy. The adsorption method for removing manganese in water is concerned by people due to the advantages of simple operation, wide source of adsorption materials, good removal effect, no or little secondary pollution to the environment and the like. However, the adsorbing material in the prior art has poor selectivity, and can adsorb other metal ions coexisting in water while adsorbing manganese in the water; this will increase the subsequent treatment process and cost of manganese resource recycling.
CN113713774A discloses a high-efficiency reproducible nano demanganizer and a preparation method and application thereof, wherein the demanganizer comprises Fe 3 O 4 ，RGO、SiO 2 And EDTA, the preparation method comprises the first step of preparing Fe 3 O 4 The nano particles are loaded on the RGO surface to prepare Fe 3 O 4 RGO, followed by dropwise addition of TEOS ethanol solution to SiO 2 Coated with Fe 3 O 4 To obtain Fe 3 O 4 @SiO 2 the-RGO composite material is finally grafted on SiO by dripping EDTA 2 Thus obtaining the nano manganese remover. The nanometer manganese removing agent has poor selectivity although the adsorption capacity is large, can not remove manganese effectively in a targeted manner, and can preferentially remove other metal ions with high concentration.
CN112495339A discloses a method for adsorbing manganese ions by modified zeolite, which comprises the following steps: taking natural clinoptilolite, crushing and sieving, then putting zeolite into a sodium salt solution for reaction, cleaning and drying to obtain modified zeolite, finally taking industrial manganese-containing wastewater, adding the modified zeolite, reacting under the action of ultrasonic waves until the concentration of manganese ions in the wastewater is not changed, and filtering to realize solid-liquid separation. The method has the advantages of easily available raw materials, low price and excellent adsorption performance, but can not be used for large-scale treatment of general industrial wastewater, and the manganese can hardly be recycled.
CN111266081A discloses a preparation method and application of a hydroxyl ferric oxide modified vermiculite composite adsorption material for removing Mn from underground water, wherein the preparation method comprises the following steps: placing the treated vermiculite in a water-soluble ferric salt solution, performing ultrasonic oscillation to obtain a mixed solution, adjusting the pH value to be alkaline, then continuing stirring, performing constant-temperature aging, cooling, performing solid-liquid separation to obtain an initial product of the composite adsorption material, and finally washing, drying and cooling the initial product of the composite adsorption material to obtain the composite adsorption material. The prepared composite adsorbing material has good stability and is easy to recover, but the preparation period is longer, the adsorption capacity is only 2.94mg/g, and the composite adsorbing material is only suitable for adsorbing and treating low-concentration manganese-containing wastewater.
The mesoporous composite materials prepared at present have certain defects, have the problems of complex preparation method, low adsorption capacity and poor selective adsorption capacity, and are difficult to meet the actual requirement of efficient removal of manganese in production and life. Therefore, it is very important to develop a novel mesoporous composite material and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a mesoporous composite material for selectively adsorbing manganese and a preparation method and application thereof.
In order to achieve the technical effect, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a mesoporous composite material for selectively adsorbing manganese, the preparation method comprising the following steps:
(1) carrying out first mixing on a rare earth metal salt, a mesoporous material and a solvent, carrying out first drying after solid-liquid separation to obtain a solid mixture;
(2) and (2) carrying out second mixing on the sulfide solution and the solid mixture obtained in the step (1), carrying out second drying after solid-liquid separation, and obtaining the mesoporous composite material.
According to the preparation method, the rare earth sulfide is generated by reacting the rare earth metal salt with the sulfide solution in the mesoporous material, the rare earth sulfide and the mesoporous material form the composite material, and the rare earth sulfide is filled in the pore passage of the mesoporous material instead of being adsorbed on the surface of the mesoporous material, so that the mesoporous composite material with the selective adsorption effect is obtained. The mesoporous composite material has the advantages of high adsorption efficiency, strong selectivity and environment-friendly preparation method, can be widely used for treating manganese-containing wastewater, and has a good application prospect.
As a preferred embodiment of the present invention, the rare earth metal in the rare earth metal salt of step (1) includes any one or a combination of at least two of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium, and the combination is typically, but not limited to, exemplified by: a combination of scandium and yttrium, a combination of yttrium and lanthanum, a combination of cerium and praseodymium, a combination of neodymium and promethium, a combination of samarium and europium, a combination of gadolinium and terbium, a combination of holmium and erbium, a combination of ytterbium and lutetium, a combination of scandium, yttrium and lanthanum, or a combination of lanthanum, cerium, praseodymium and neodymium, and the like.
Preferably, the rare earth metal salt in step (1) includes any one of sulfate, chloride, acetate or nitrate or a combination of at least two thereof, as typical but non-limiting examples: combinations of sulfate and chloride, chloride and acetate, acetate and nitrate, or sulfate, chloride and acetate, and the like.
As a preferred technical solution of the present invention, the mesoporous material in step (1) includes any one or a combination of at least two of mesoporous molecular sieve, mesoporous resin, mesoporous carbon, or carbon nanotube, and the combination is exemplified by, typically but not limited to: a combination of mesoporous molecular sieve and mesoporous resin, a combination of mesoporous resin and mesoporous carbon, a combination of mesoporous carbon and carbon nanotube, or a combination of mesoporous molecular sieve, mesoporous resin and mesoporous carbon.
Preferably, the mesoporous material of step (1) has a particle size of 2-12nm, such as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm or 12nm, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass ratio of the rare earth metal salt to the mesoporous material in the step (1) is 1 (4-16), and may be, for example, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14 or 1:16, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
According to the invention, the mass ratio of the rare earth metal salt to the mesoporous material is limited to be 1 (4-16), when the mass ratio of the rare earth metal salt to the mesoporous material is lower, the content of rare earth sulfide in the mesoporous composite material is lower, which is not beneficial to the adsorption of manganese ions in manganese-containing wastewater, so that the removal efficiency of manganese is low; when the mass ratio of the rare earth metal salt to the mesoporous material is higher, excessive rare earth sulfide is generated to block the pore channel of the mesoporous material, the effect of the nano confinement effect cannot be shown, and the performance of the mesoporous composite material for selectively adsorbing manganese is reduced.
As a preferred technical scheme of the invention, the solvent in the step (1) comprises deionized water.
Preferably, the ratio of the solvent to the total mass of the rare earth metal salt and the mesoporous material in step (1) is (20-80):1, and may be, for example, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1 or 80:1, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, when the mass of the deionized water is less than 20 times of the sum of the mass of the rare earth metal salt and the mesoporous material, the rare earth ions cannot be completely ionized to form corresponding ions to enter the pore channels of the mesoporous material, so that the generation of rare earth sulfides is influenced, and when the mass of the deionized water is more than 80 times of the sum of the mass of the rare earth metal salt and the mesoporous material, the usage amount of water and the volume of the whole system are too large, so that the rare earth ions entering the pore channels of the mesoporous material are diluted, and the generation of the rare earth sulfides is influenced.
As a preferred technical solution of the present invention, the first mixing in step (1) includes sequentially performing the ultrasonic and the first stirring.
Preferably, the sonication time is between 0.1 and 1 hour, for example 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 hour, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the rotation speed of the first stirring is 100-500rpm, such as 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the first stirring time is 3-5h, for example, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the first drying in step (1) is 60 to 100 ℃, for example 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the first drying time in step (1) is 6-12h, such as 6h, 7h, 8h, 9h, 10h, 11h or 12h, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the solid-liquid separation in step (1) comprises filtration and washing sequentially.
According to the invention, the washing is carried out for at least 3 times by using deionized water, and the rare earth metal salt adsorbed on the surface of the mesoporous material can be washed away by the washing, so that the reaction between sulfide and the rare earth metal salt on the surface of the mesoporous material is avoided.
As a preferred technical solution of the present invention, the sulfide in the sulfide solution in step (2) includes any one or a combination of at least two of sodium sulfide, potassium sulfide or iron sulfide, and the combination is typically but not limited to: combinations of sodium sulfide and potassium sulfide, potassium sulfide and iron sulfide, iron sulfide and sodium sulfide, or sodium sulfide, potassium sulfide and iron sulfide, and the like.
Preferably, the mass fraction of sulfide in the sulfide solution in step (2) is 10 to 30 wt%, and may be, for example, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, or 30 wt%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass ratio of the sulfide solution in step (2) to the rare earth metal salt in step (1) is (4-14):1, and may be, for example, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1 or 14:1, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred embodiment of the present invention, the second mixing in step (2) includes second stirring.
Preferably, the second stirring temperature is 70-80 ℃, for example 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, but not limited to the enumerated values, and other unrecited values in this range of values are also applicable.
Preferably, the rotation speed of the second stirring is 100-500rpm, such as 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the second stirring time is 3-5h, for example 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
In the invention, the second stirring temperature can affect the performance of the mesoporous composite material, and when the stirring temperature is lower, the reaction between the sulfide solution and the rare earth metal salt is too slow, so that the rare earth sulfide cannot be effectively generated; when the stirring temperature is too high, the reaction is too violent and the rare earth sulfide having a good phase cannot be formed.
Preferably, the temperature of the second drying in step (2) is 60-100 ℃, for example 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the second drying time in step (2) is 6-12h, such as 6h, 7h, 8h, 9h, 10h, 11h or 12h, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the solid-liquid separation in step (2) comprises filtration and washing sequentially.
In the invention, a dry product is obtained after the second drying in the step (2), and the dry product is washed by deionized water to obtain the mesoporous composite material.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing the rare earth metal salt and the mesoporous material with the solvent according to the mass ratio of 1 (4-16), carrying out ultrasonic stirring for 0.1-1h at the rotating speed of 100-500rpm for 3-5h, carrying out solid-liquid separation, and drying at the temperature of 60-100 ℃ for 6-12h to obtain a solid mixture;
the ratio of the solvent to the total mass of the rare earth metal salt and the mesoporous material in the step (1) is (20-80): 1;
(2) mixing 10-30 wt% of sulfide solution with the solid mixture in the step (1), stirring at the rotating speed of 100-500rpm at 70-80 ℃ for 3-5h, and drying at 60-100 ℃ for 6-12h after solid-liquid separation to obtain the mesoporous composite material;
the mass ratio of the sulfide solution in the step (2) to the rare earth metal salt in the step (1) is (4-14): 1.
In a second aspect, the invention provides a mesoporous composite material capable of selectively adsorbing manganese, and the mesoporous composite material is prepared by the preparation method of the first aspect.
The mesoporous composite material has a particle size of 2 to 15nm, and may be, for example, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm or 15nm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The specific surface area of the mesoporous composite material is 245.2-266.2m 2 Per g, for example, 245.2m 2 /g、247.2m 2 /g、249.2m 2 /g、250.2m 2 /g、252.2m 2 /g、255.2m 2 /g、257.2m 2 /g、260.2m 2 /g、263.2m 2 G or 266.2m 2 In the following description,/g is not limited to the values listed, but other values not listed in the numerical range are equally applicable.
In a third aspect, the present invention provides a use of the mesoporous composite material according to the second aspect for selectively adsorbing manganese.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, rare earth sulfide is generated by reacting rare earth metal salt with sulfide solution in a mesoporous material, and the rare earth sulfide and the mesoporous material form a composite material to obtain the mesoporous composite material with selective adsorption; the preparation method does not need an organic solvent, is subjected to high-temperature calcination treatment, meets the requirement of environmental protection, and has large-scale industrial production and application potential; compared with the rare earth sulfide produced in a commercial way, the mesoporous composite material has the advantages that the removal rate of manganese reaches 99.4%, and the mesoporous composite material has excellent selective adsorption capacity on manganese; can be widely used for treating manganese-containing wastewater.
Drawings
FIG. 1 is a transmission electron microscope image of a mesoporous composite material prepared in embodiment 1 of the present invention;
FIG. 2 shows N of the mesoporous composite material prepared in embodiment 1 of the present invention 2 Adsorption and desorption curve graphs;
FIG. 3 is a graph showing the pore size distribution of the mesoporous composite material prepared in example 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a mesoporous composite material for selectively adsorbing manganese, which comprises the following steps:
(1) mixing cerium chloride with a mass ratio of 1:15:500, a mesoporous molecular sieve SAB-15 with a pore size of 5-6nm and deionized water, performing ultrasonic treatment for 0.5h, stirring at a rotating speed of 200rpm for 4h, filtering, washing with deionized water for 3 times, and drying at 90 ℃ for 12h to obtain a solid mixture;
(2) mixing a 15 wt% sodium sulfide aqueous solution with the solid mixture in the step (1), stirring at the temperature of 80 ℃ for 4 hours at the rotating speed of 200rpm, filtering, washing with deionized water for 3 times, and drying at the temperature of 90 ℃ for 12 hours to obtain the mesoporous composite material; the mass ratio of the sodium sulfide aqueous solution to the cerium chloride in the step (1) is 5: 1.
Example 2
This example differs from example 1 only in that it is the same as example 1 except that it is stirred in step (2) at 70 ℃ for 3 hours at 100 rpm.
Example 3
This example is different from example 1 only in that it is the same as example 1 except that "sodium sulfide" in step (2) is replaced with "iron sulfide".
Example 4
This example differs from example 1 only in that it is the same as example 1 except that "cerium chloride" in step (1) is replaced with "cerium sulfate".
Example 5
The difference between the embodiment and the embodiment 1 is only that the embodiment is the same as the embodiment 1 except that the mass ratio of the cerium chloride, the 5-6nm mesoporous molecular sieve SAB-15 and the deionized water in the step (1) is 1:2: 95.
Example 6
The difference between the embodiment and the embodiment 1 is only that the embodiment is the same as the embodiment 1 except that the mass ratio of the cerium chloride, the 5-6nm mesoporous molecular sieve SAB-15 and the deionized water in the step (1) is 1:18: 600.
Example 7
The difference between the embodiment and the embodiment 1 is only that the embodiment is the same as the embodiment 1 except that the mass ratio of the cerium chloride, the 5-6nm mesoporous molecular sieve SAB-15 and the deionized water in the step (1) is 1:15: 280.
Example 8
The difference between the embodiment and the embodiment 1 is only that the embodiment is the same as the embodiment 1 except that the mass ratio of the cerium chloride, the 5-6nm mesoporous molecular sieve SAB-15 and the deionized water in the step (1) is 1:15: 1360.
Example 9
This example differs from example 1 only in that it is the same as example 1 except that in step (2) it is stirred at 90 ℃ for 4 hours at 200 rpm.
Example 10
This example differs from example 1 only in that it is the same as example 1 except that in step (2) it is stirred at 60 ℃ for 4 hours at 200 rpm.
Comparative example 1
This comparative example differs from example 1 only in that it is the same as example 1 except that the step (1) "mesoporous molecular sieve SAB-15 having a pore diameter of 5 to 6 nm" is replaced with "beta type molecular sieve having a pore diameter of 0.5 to 0.7 nm".
Comparative example 2
This comparative example differs from example 1 only in that it is the same as example 1 except that the step (1) "mesoporous molecular sieve SAB-15 having a pore diameter of 5 to 6 nm" is replaced with "a macroporous carbon material having a pore diameter of 100 and 200 nm".
Comparative example 3
This comparative example differs from example 1 only in that it is the same as example 1 except that step (1) of deionized water washing was not performed 3 times.
Comparative example 4
The comparative example provides a preparation method of a mesoporous composite material selectively adsorbing manganese, and the preparation method comprises the following steps: cerium chloride with the mass ratio of 1:15:75:500, mesoporous molecular sieve SAB-15 with the pore diameter of 5-6nm, and sodium sulfide aqueous solution with the mass fraction of 15 wt% are mixed with deionized water and subjected to ultrasonic treatment for 0.5h, the mixture is stirred for 4h at the temperature of 80 ℃ and at the rotating speed of 200rpm, the mixture is washed for 3 times by the deionized water after filtration, and the mixture is dried for 12h at the temperature of 90 ℃ to obtain the mesoporous composite material.
Comparative example 5
The comparative example differs from comparative example 4 only in that cerium chloride was not added and the rest was the same as comparative example 4.
Comparative example 6
The comparative example differs from comparative example 4 only in that the aqueous sodium sulfide solution was not added, and the rest was the same as comparative example 4.
Comparative example 7
This comparative example differs from example 1 only in that it is the same as example 1 except that "cerium chloride" in step (1) is replaced with "copper chloride".
As can be seen from fig. 1, the rare earth sulfide in the mesoporous composite material prepared in example 1 is filled in the pores of the mesoporous material.
As can be seen from FIGS. 2 to 3, the mesoporous composite material prepared in example 1 had a specific surface area of 266.2m 2 /g。
The mesoporous composite materials obtained by the preparation methods of examples 1 to 10 and comparative examples 1 to 7 were tested, and the test methods were as follows:
500mg of the mesoporous composite materials prepared in examples 1 to 10 and comparative examples 1 to 7 were weighed and placed in an erlenmeyer flask, 150mL of a solution containing Mn, Pd, As, V, Co and Ba in an ion concentration of 10mg/L was added to the erlenmeyer flask, the solution was ultrasonically treated in an ultrasonic cleaning machine for 30min, the solution was then shaken and shaken on a constant temperature shaker at an oscillation rate of 150rpm for 2h, the solution in the erlenmeyer flask was sampled and filtered, and then an ICP instrument was used to measure the ion solubility of the solution, and the removal rates of Mn, Pd, As, V, Co and Ba were shown in Table 1.
TABLE 1
As can be seen from Table 1:
(1) the mesoporous composite material prepared by the invention has the advantages of high adsorption efficiency, strong selectivity and environment-friendly preparation method, can be widely used for treating manganese-containing wastewater, and has better application prospect;
(2) as can be seen from the comparison between example 1 and examples 5-6, the mass ratio of the rare earth metal salt to the mesoporous material in the present invention affects the performance of the mesoporous composite material, and when the mass ratio of the rare earth metal salt to the mesoporous material is lower than 1:4, the content of the rare earth sulfide in the mesoporous composite material is relatively low, which is not favorable for the adsorption of manganese ions in the manganese-containing wastewater, thereby reducing the removal efficiency of manganese; when the mass ratio of the rare earth metal salt to the mesoporous material is higher than 1:16, excessive rare earth sulfide is generated to block the pore channel of the mesoporous material, the nanometer confinement effect cannot be shown, and the performance of the mesoporous composite material for selectively adsorbing manganese is reduced;
(3) comparing the embodiment 1 with the embodiments 7 to 8, it can be seen that when the mass of the deionized water is less than 20 times of the sum of the masses of the rare earth metal salt and the mesoporous material, the rare earth ions cannot be completely ionized to form corresponding ions, which enter into the pores of the mesoporous material, and the generation of the rare earth sulfide is affected, and when the mass of the deionized water is more than 80 times of the sum of the masses of the rare earth metal salt and the mesoporous material, the usage amount of water and the volume of the whole system are too large, and the rare earth ions entering into the pores of the mesoporous material are diluted, and the generation of the rare earth sulfide is affected;
(4) as can be seen from the comparison between example 1 and examples 9 to 10, when the second stirring temperature is relatively low, the reaction between the sulfide solution and the rare earth metal salt is too slow to effectively produce rare earth sulfide; when the temperature of the second stirring is higher, the reaction is too violent, rare earth sulfide with a better phase cannot be formed, and the acid-base substance introduced at high temperature can influence the framework structure of the mesoporous material, so that the nano confinement effect is influenced;
(5) as can be seen from the comparison between example 1 and comparative examples 1-2, the mesoporous composite material with higher selectivity can be obtained by using the mesoporous material, when the mesoporous material is replaced by the microporous material, the composite material is very easy to block, and when manganese is adsorbed to a certain degree, the manganese cannot be continuously adsorbed, so that the adsorption efficiency of the composite material is low; when the mesoporous material is replaced by the macroporous material, the specific surface area of the composite material is reduced, the contact area of the composite material and the waste liquid of the manganese-containing solution is reduced, and the adsorbed manganese is easy to separate from the adsorption material, so that the adsorption efficiency is reduced; to some extent, the combination of mesoporous materials with rare earth sulfides may lead to differences in the selective adsorption of heavy metals;
(6) compared with the comparative example 3, it can be seen that the performance of the mesoporous composite material for selectively adsorbing manganese is reduced because the pores of the mesoporous material are covered and blocked by the generated rare earth sulfide due to the reaction of the rare earth salt attached to the surface of the mesoporous material and the sulfide without being washed by deionized water;
(7) as can be seen from the comparison between example 1 and comparative examples 4 to 6, when the mesoporous composite material is prepared by one-step mixing, cerium chloride and an aqueous solution of sodium sulfide react quickly to directly generate a cerium sulfide precipitate, cerium sulfide cannot be generated in the pore channel of the mesoporous material, and the mesoporous composite material cannot be prepared, so that the performance of selectively adsorbing manganese is reduced; when only the sodium sulfide aqueous solution is contained, the performance of selectively adsorbing manganese of the material is reduced because rare earth sulfide cannot be generated; when only cerium chloride is contained, the performance of the material for selectively adsorbing manganese is reduced because rare earth sulfide cannot be generated;
(8) comparing example 1 with comparative example 7, it is known that when copper chloride is used to react with sodium sulfide in the mesoporous material, the performance of the mesoporous composite material for selectively adsorbing manganese is reduced because the generated copper sulfide has no selective adsorption to manganese.
In summary, in the invention, rare earth metal salt reacts with sulfide solution in the mesoporous material to generate rare earth sulfide, and the rare earth sulfide and the mesoporous material form a composite material to obtain the mesoporous composite material with selective adsorption; the mesoporous composite material has the advantages of high adsorption efficiency and environment-friendly preparation method, can be widely used for treating manganese-containing wastewater, and has large-scale industrial production and application potential; compared with the rare earth sulfide produced in a commercial way, the mesoporous composite material has stronger selective adsorption effect and stronger removal effect on manganese in the wastewater.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the mesoporous composite material for selectively adsorbing manganese is characterized by comprising the following steps of:
(1) carrying out first mixing on a rare earth metal salt, a mesoporous material and a solvent, carrying out first drying after solid-liquid separation to obtain a solid mixture;
(2) and (2) carrying out second mixing on the sulfide solution and the solid mixture obtained in the step (1), carrying out second drying after solid-liquid separation, and obtaining the mesoporous composite material.
2. The production method according to claim 1, wherein the rare earth metal in the rare earth metal salt of step (1) includes any one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium, or a combination of at least two thereof;
preferably, the rare earth metal salt in step (1) includes any one of sulfate, chloride, acetate or nitrate or a combination of at least two thereof.
3. The method according to claim 1 or 2, wherein the mesoporous material of step (1) comprises any one or a combination of at least two of mesoporous molecular sieve, mesoporous resin, mesoporous carbon, or carbon nanotube;
preferably, the particle size of the mesoporous material in the step (1) is 2-12 nm;
preferably, the mass ratio of the rare earth metal salt to the mesoporous material in the step (1) is 1 (4-16).
4. The method according to any one of claims 1 to 3, wherein the solvent of step (1) comprises deionized water;
preferably, the ratio of the solvent to the total mass of the rare earth metal salt and the mesoporous material in the step (1) is (20-80): 1.
5. The production method according to any one of claims 1 to 4, wherein the first mixing of step (1) comprises sequentially performing the ultrasonic treatment and the first stirring;
preferably, the time of the ultrasonic treatment is 0.1-1 h;
preferably, the rotation speed of the first stirring is 100-500 rpm;
preferably, the first stirring time is 3-5 h;
preferably, the temperature of the first drying in the step (1) is 60-100 ℃;
preferably, the first drying time in the step (1) is 6-12 h;
preferably, the solid-liquid separation in step (1) comprises filtration and washing sequentially.
6. The production method according to any one of claims 1 to 5, wherein the sulfide in the sulfide solution of step (2) comprises any one of sodium sulfide, potassium sulfide, or iron sulfide or a combination of at least two thereof;
preferably, the mass fraction of sulfide in the sulfide solution in the step (2) is 10-30 wt%;
preferably, the mass ratio of the sulfide solution in the step (2) to the rare earth metal salt in the step (1) is (4-14): 1.
7. The method according to any one of claims 1 to 6, wherein the second mixing of step (2) comprises second stirring;
preferably, the temperature of the second stirring is 70-80 ℃;
preferably, the rotation speed of the second stirring is 100-500 rpm;
preferably, the second stirring time is 3-5 h;
preferably, the temperature of the second drying in the step (2) is 60-100 ℃;
preferably, the second drying time in the step (2) is 6-12 h;
preferably, the solid-liquid separation in step (2) comprises filtration and washing sequentially.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) mixing the rare earth metal salt and the mesoporous material with the solvent according to the mass ratio of 1 (4-16), ultrasonically stirring for 0.1-1h at the rotating speed of 100-500rpm for 3-5h, and drying for 6-12h at the temperature of 60-100 ℃ after solid-liquid separation to obtain a solid mixture;
the ratio of the solvent to the total mass of the rare earth metal salt and the mesoporous material in the step (1) is (20-80): 1;
(2) mixing 10-30 wt% of sulfide solution with the solid mixture in the step (1), stirring at the rotating speed of 100-500rpm at 70-80 ℃ for 3-5h, and drying at 60-100 ℃ for 6-12h after solid-liquid separation to obtain the mesoporous composite material;
the mass ratio of the sulfide solution in the step (2) to the rare earth metal salt in the step (1) is (4-14): 1.
9. A mesoporous composite material for selectively adsorbing manganese, which is characterized in that the mesoporous composite material is prepared by the preparation method of any one of claims 1 to 8;
the particle size of the mesoporous composite material is 2-15 nm;
the specific surface area of the mesoporous composite material is 245.2-266.2m 2 /g。
10. Use of the mesoporous composite material according to claim 9 for the selective adsorption of manganese.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959152A (en) * | 2015-06-01 | 2015-10-07 | 常州大学 | Preparation method of porous carbon-loaded nanometer metal sulfide |
| US20160151768A1 (en) * | 2013-05-13 | 2016-06-02 | University Of Connecticut | Mesoporous materials and processes for preparation thereof |
| WO2017219793A1 (en) * | 2016-06-20 | 2017-12-28 | 广东工业大学 | Short-pore ordered mesoporous carbon-loaded sulfur-indium-cobalt and sulfur-indium-nickel ternary composite photocatalyst, preparation method therefor, and application thereof |
| CN109786117A (en) * | 2017-11-14 | 2019-05-21 | 天津大学 | Carbon nano tube-cobaltosic sulfide composite material and preparation method and application thereof |
| CN109802135A (en) * | 2019-02-15 | 2019-05-24 | 中科廊坊过程工程研究院 | A kind of lithium sulfur battery anode material, and its preparation method and application |
| FR3092104A1 (en) * | 2019-01-29 | 2020-07-31 | Panjin Institute Of Industrial Technology, Dalian University Of Technology | Process for the preparation of a binder-free composite molecular sieve and its use in desulfurization by adsorption of petroleum |
| CN112973618A (en) * | 2021-03-05 | 2021-06-18 | 江西理工大学 | Layered metal sulfide adsorbent, preparation method thereof and method for selectively enriching lead ions from heavy metal wastewater |
| CN114105226A (en) * | 2020-08-28 | 2022-03-01 | 南京理工大学 | Nickel-cobalt-manganese sulfide @ hollow mesoporous carbon sphere nano composite material and preparation method thereof |
-
2022
- 2022-05-24 CN CN202210572088.9A patent/CN115007120B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160151768A1 (en) * | 2013-05-13 | 2016-06-02 | University Of Connecticut | Mesoporous materials and processes for preparation thereof |
| CN104959152A (en) * | 2015-06-01 | 2015-10-07 | 常州大学 | Preparation method of porous carbon-loaded nanometer metal sulfide |
| WO2017219793A1 (en) * | 2016-06-20 | 2017-12-28 | 广东工业大学 | Short-pore ordered mesoporous carbon-loaded sulfur-indium-cobalt and sulfur-indium-nickel ternary composite photocatalyst, preparation method therefor, and application thereof |
| CN109786117A (en) * | 2017-11-14 | 2019-05-21 | 天津大学 | Carbon nano tube-cobaltosic sulfide composite material and preparation method and application thereof |
| FR3092104A1 (en) * | 2019-01-29 | 2020-07-31 | Panjin Institute Of Industrial Technology, Dalian University Of Technology | Process for the preparation of a binder-free composite molecular sieve and its use in desulfurization by adsorption of petroleum |
| CN109802135A (en) * | 2019-02-15 | 2019-05-24 | 中科廊坊过程工程研究院 | A kind of lithium sulfur battery anode material, and its preparation method and application |
| CN114105226A (en) * | 2020-08-28 | 2022-03-01 | 南京理工大学 | Nickel-cobalt-manganese sulfide @ hollow mesoporous carbon sphere nano composite material and preparation method thereof |
| CN112973618A (en) * | 2021-03-05 | 2021-06-18 | 江西理工大学 | Layered metal sulfide adsorbent, preparation method thereof and method for selectively enriching lead ions from heavy metal wastewater |
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