CN110756165B - Preparation method of carboxyl carbon spheres for adsorbing heavy metal ions and products thereof - Google Patents
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Abstract
The invention discloses a preparation method of carboxyl carbon spheres for adsorbing heavy metal ions and a product thereof, belonging to the technical field of adsorbent preparation and wastewater treatment. The method comprises the steps of taking glucose and olefine acid monomers as precursors, carrying out hydrothermal one-step hydrothermal reaction, then calcining in a muffle furnace, activating with alkali liquor, washing with water, and drying to obtain carboxyl carbon spheres; the carboxyl carbon spheres are used for adsorbing heavy metal ions, the removal rate is up to 95 percent, and the adsorption quantity of the adsorbents prepared by the method without calcination and alkali activation is improved by 1.5-4.5 times compared with that of the adsorbents prepared by the method without calcination and alkali activation; and the carboxyl carbon spheres still have good heavy metal ion adsorption effect after being regenerated for 5 times. The carboxyl carbon sphere adsorbent obtained by the invention is spherical particle powder with the diameter of 2 mu m, and contains about 5mmol/g carboxyl.
Description
Technical Field
The invention belongs to the technical field of preparation of water treatment materials, and particularly relates to a preparation method of carboxyl carbon spheres for adsorbing heavy metal ions and a product thereof.
Background
The efficient removal and recovery of heavy metal ions in water is one of the hot problems in water pollution control. Because the concentration of heavy metal ions is generally low (0.1-200 mg/L), the traditional method is adoptedThe precipitation method of (A) consumes a large amount of alkali or sulfide and produces heavy metal precipitates, H2S gas, etc., which cause serious secondary pollution problems and generally are difficult to meet increasingly stringent emission concentration standards. It is proposed that the removal capacity is improved to some extent by the macromolecule trapping agent coupled flocculation precipitation technology, but the application bottleneck still exists. The physical and chemical technologies such as electrolysis, ultrafiltration membrane, reverse osmosis and the like also have the defects of high energy consumption, frequent replacement of components and the like, and are only suitable for pretreatment of high-concentration single heavy metal wastewater. In contrast, the adsorption method is a technology for selectively grabbing heavy metal ions by using an adsorbent and separating the heavy metal ions from a water phase, and has the great advantages of simplicity, low consumption, low secondary pollution and renewable recycling. The design and preparation of the adsorbent are key problems. As is well known, common heavy metal ions have high affinity to solid-phase carboxyl, and mainly have electrostatic attraction and ion exchange effects. Therefore, the adsorbent rich in carboxyl can effectively remove heavy metal ions. However, most of the currently reported carboxyl adsorbents are prepared by high molecular polymerization reaction (CN201310330339.3), high-temperature calcination and concentrated acid oxidation (CN201710163288.8), and have high preparation cost, complex production process and high environmental protection pressure. Chinese patent ZL201510278212.0 discloses a preparation method of a heavy metal adsorbent which is rich in carboxyl and can be magnetically recycled, the method is prepared by calcining sodium gluconate and an iron source at 200-500 ℃, the process is simple, and the effect of removing heavy metal ions is excellent. However, the sheet-shaped adsorbent has poor abrasion resistance in the practical application process, so that nano-scale fragments are easily generated to enter a water body, and the regeneration stability of the adsorbent is difficult to ensure. The southern Kao university academic paper 'one-step hydrothermal synthesis glucose-based carbon spheres and adsorption research thereof on heavy metal lead ions' adopts carboxyl carbon spheres obtained by one-step hydrothermal method from glucose and acrylic acid, and the maximum adsorption capacity of the carboxyl carbon spheres on the lead ions under ideal conditions is only 65.6mg/g (namely 0.32 mmol/g). Similarly, the academic paper of northeast agriculture and forestry university "hydrothermal preparation, characterization and activation of carbon microspheres" reports that the adsorption capacity of the carbon spheres obtained by the glucose secondary hydrothermal method on lead ions with the initial concentration of 60mmol/L (namely 12g/L) reaches 2.4mmol/g, and the adsorption capacity on lead ions with the initial concentration of lower (about 2mmol/L) is up to 2.4mmol/gOnly about 0.3 mmol/g. And the size of the prepared carbon spheres is 300-1200 nm, and the adsorbent is not easy to recover. In addition, the paper also suggests that the specific surface area of the carbon spheres can be increased by high-temperature alkali activation (700 ℃) in an inert gas protective atmosphere, and the paper does not study the adsorption performance of the carbon spheres on heavy metal ions under the process condition. However, it is presumed that the oxygen content of the carbon spheres decreases with the increase in pore volume due to the mechanism of carbonization, and is not favorable for adsorption of heavy metals.
Disclosure of Invention
The invention aims to solve the technical problems of providing a preparation method of carboxyl carbon spheres for adsorbing heavy metal ions, and solving the problems of high preparation cost, complex production process, high environmental protection pressure and the like in the existing preparation method. The invention aims to solve another technical problem of providing a carboxyl carbon sphere for adsorbing and removing heavy metal ions, and solving the problems that the existing adsorbent has poor anti-abrasion capability in the practical application process, adsorbent fragments are easy to enter a water body, the adsorbent is difficult to separate solid from liquid, and the like. The invention also aims to solve the technical problems of application of the carboxyl carbon spheres in adsorption of heavy metal ions, and solves the problems of small capacity, poor regeneration stability and the like of the adsorbent.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of carboxyl carbon spheres for adsorbing heavy metal ions comprises the steps of taking glucose and olefine acid monomers as precursors, carrying out one-step hydrothermal reaction, then calcining in a muffle furnace, and then carrying out alkali liquor activation, water washing and drying to obtain the carboxyl carbon spheres. The method specifically comprises the following steps:
(1) preparing a mixed aqueous solution of glucose and olefine acid monomers, performing hydrothermal reaction in a high-pressure reaction kettle, and performing centrifugal filtration to obtain first-stage carboxyl carbon spheres; the mass fraction of the glucose is 5-20%, the mass fraction of the olefine acid monomer is 5-20%, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 10-24 hours;
(2) calcining the first-stage carboxyl carbon spheres in a muffle furnace to obtain second-stage carboxyl carbon spheres; calcining in a muffle furnace at the temperature of 300-350 ℃ for 3-6 h;
(2) activating the second-stage carboxyl carbon spheres in alkali liquor, filtering, washing with water to be stable and neutral, drying, and grinding to obtain target carboxyl carbon spheres; the concentration of the alkali liquor is 1-4 mol/L, and the activation time is 0.5-5 h.
According to the preparation method of the carboxyl carbon sphere for adsorbing heavy metal ions, the olefine acid monomer is acrylic acid or maleic acid, and the alkali liquor is potassium hydroxide solution.
According to the preparation method of the carboxyl carbon spheres for adsorbing heavy metal ions, the mass fraction of glucose is 10%, and the mass fraction of the olefine acid monomer is 10%.
According to the preparation method of the carboxyl carbon spheres for adsorbing heavy metal ions, the temperature of the hydrothermal reaction is 180 ℃, the time of the hydrothermal reaction is 15 hours, the temperature of the muffle furnace for calcination is 300 ℃, the calcination time is 6 hours, the concentration of alkali liquor is 2mol/L, and the activation time is 2 hours.
The preparation method of the carboxyl carbon spheres for adsorbing heavy metal ions comprises the following steps:
(1) preparing a mixed aqueous solution of 10% by mass of glucose and 10% by mass of acrylic acid monomer, transferring the mixed aqueous solution to polytetrafluoroethylene endostatin, carrying out hydrothermal reaction in a high-pressure reaction kettle at the reaction temperature of 180 ℃ for 15h, and carrying out centrifugal filtration after the reaction is finished to obtain first-stage carboxyl carbon spheres;
(2) calcining the first-stage carboxyl carbon spheres in a muffle furnace to obtain second-stage carboxyl carbon spheres; the calcining temperature in the muffle furnace is 300 ℃, and the calcining time is 6 h;
(3) and (3) activating the second-stage carboxyl carbon spheres in 2mol/L KOH solution for 2h, filtering, washing with water until the second-stage carboxyl carbon spheres are stable and neutral, drying, and grinding to obtain the target carboxyl carbon spheres.
The carboxyl carbon spheres prepared by the preparation method for adsorbing heavy metal ions are provided.
The application of the carboxyl carbon spheres in adsorbing heavy metal ions.
The application of the carboxyl carbon spheres in the adsorption of heavy metal ions comprises the following steps:
(1) placing the carboxyl carbon spheres in a solution containing heavy metal ions, and adsorbing for 1-3 h; the content of the heavy metal ions is 1-300 mg/L, and the adding amount of the carboxyl carbon spheres is 0.2-2 g/L;
(2) filtering the carboxyl carbon balls in the step (1), sequentially regenerating the carboxyl carbon balls by using sulfuric acid, NaOH and water, and filtering the carboxyl carbon balls to enter a second round of adsorption;
(3) adding the adsorbent carboxyl carbon spheres obtained in the step (2) into the solution containing heavy metal ions again according to the method in the step (1), and adsorbing for 1-3 h;
(4) the regeneration and adsorption are repeated as in steps (2) and (3).
The carboxyl carbon spheres are applied to adsorbing heavy metal ions, wherein the heavy metal ions are copper ions, lead ions, cadmium ions or nickel ions.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the preparation method only needs glucose and olefine acid monomers, and can be prepared by one-step hydrothermal reaction, low-temperature calcination in a muffle furnace and activation by alkali liquor. The whole reaction is carried out at a lower temperature (lower than 350 ℃) without inert gas protection. Therefore, the process is simple, the cost is low, and the method is suitable for mass production.
(2) The carboxyl carbon spheres prepared by the method are micron-sized spherical particles, have excellent wear-resistant performance, have micron-sized particle size and good sedimentation performance, and provide powerful guarantee for practical application.
(3) Under the same conditions, compared with a control group (which is not calcined and is not subjected to alkali activation), the adsorbent prepared by the method disclosed by the invention has the adsorption capacity respectively increased by 4.5 and 1.5 times.
(4) The adsorbent is regenerated by acid and alkali after adsorbing heavy metals, can be stably recycled for multiple times, and has stable adsorption effect.
Drawings
FIG. 1 is an SEM photograph of a carboxyl carbon sphere prepared in example 1;
FIG. 2 is a graph of carbon sphere settlement according to the present invention;
FIG. 3 is an infrared spectrum of the adsorbent prepared in different ways.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
A preparation method of carboxyl carbon spheres for adsorbing heavy metal ions comprises the following steps:
(1) preparing 60mL of mixed aqueous solution of 10% by mass of glucose and 10% by mass of acrylic monomer, uniformly mixing by ultrasonic, transferring the mixed solution to polytetrafluoroethylene inner liner, heating to 180 ℃ in a high-pressure reaction kettle, reacting for 15h, and performing centrifugal filtration to obtain a first-stage carboxyl carbon sphere;
(2) calcining the first-stage carboxyl carbon spheres in a muffle furnace at a low temperature of 300 ℃ for 5 hours to obtain second-stage carboxyl carbon spheres;
(3) and stirring the second-stage carboxyl carbon spheres in 2mol/L KOH solution for 2h, filtering, washing with water, adding hydrochloric acid in the washing process to adjust the pH until the supernatant is stable to be neutral, filtering, drying and grinding to obtain the target carboxyl carbon spheres M1.
FIG. 1 is an SEM image of the above-mentioned carboxyl carbon sphere M1, and it can be seen from FIG. 1 that the carboxyl carbon sphere M1 is spherical particles having a diameter of about 2 μ M. Fig. 2 is a prepared carbon sphere sedimentation diagram, and it can be known that a product, namely carboxyl carbon spheres M1 with the size of 2 μ M can be naturally sedimented, which is beneficial to M1 separation and recovery, and effectively solves the problem that the existing nanoparticles are suspended in an adsorption solution and are difficult to separate.
Comparative product 1: preparing 60mL of mixed aqueous solution of 10% by mass of glucose and 10% by mass of acrylic acid monomer, uniformly mixing by ultrasonic, transferring the mixed solution to polytetrafluoroethylene inner liner, heating to 180 ℃ in a high-pressure reaction kettle, reacting for 20h, and performing centrifugal filtration to obtain the adsorbent C1.
Comparative product 2: (1) preparing 60mL of mixed aqueous solution of 10% by mass of glucose and 10% by mass of acrylic monomer, uniformly mixing by ultrasonic, transferring the mixed solution to polytetrafluoroethylene inner liner, heating to 180 ℃ in a high-pressure reaction kettle, reacting for 15h, and performing centrifugal filtration to obtain a first-stage carboxyl carbon sphere; (2) and (3) calcining the first-stage carboxyl carbon spheres in a muffle furnace at the low temperature of 300 ℃ for 5h, and grinding to obtain the adsorbent C2.
The infrared spectrograms of C1, C2 and M1 are shown in figure 3 and are 1600-1715 cm-1All the compounds have obvious absorption peaks of O ═ C-O, and the content of O ═ C-O in M1 is increased due to muffle furnace calcination, and the O ═ C-O bond can be further hydrolyzed into active carboxyl by alkali activation, which is favorable for heavy metal adsorption.
The elemental contents of C1, C2 and M1 are shown in Table 1, and it can be seen from Table 1 that the oxygen content is C1 < C2 < M1.
TABLE 1 content of different adsorbent elements
| Adsorbent and process for producing the same | C1 | C2 | M1 |
| C | 71.4 | 65.1 | 63.1 |
| O | 25.7 | 30.5 | 31.2 |
| Others (K, Na, H, etc.) | 2.9 | 4.4 | 5.7 |
Example 2
The procedure and conditions were the same as in example 1 except that acrylic acid was replaced with maleic acid to obtain a carboxyl carbon sphere M2.
Example 3
The implementation process and conditions are the same as example 1, except that the hydrothermal temperature in step 1 is 200 ℃ and the hydrothermal time is 15h, and the carboxyl carbon spheres M3 are obtained.
Example 4
The implementation process and conditions are the same as example 1, except that the hydrothermal temperature in step 1 is 160 ℃, and the hydrothermal time is 24h, so as to obtain the carboxyl carbon spheres M4.
Example 5
The procedure and conditions were the same as in example 1 except that the calcination temperature in step 2 was 350 ℃ and the calcination time was 3 hours, to obtain carboxycarbon spheres M5.
Example 6
The procedure and conditions were the same as in example 1 except that the calcination time in step 2 was 6 hours, to obtain carboxymethylcapsules M6.
Example 7
The procedure and conditions were the same as in example 1, except that the KOH concentration in step 3 was 4mol/L and the activation time was 0.5h, to obtain carboxyl carbon spheres M7.
Example 8
The procedure and conditions were the same as in example 1, except that the KOH concentration in step 3 was 1mol/L and the activation time was 3 hours, to obtain carboxyl carbon spheres M8.
Example 9
A lead nitrate solution with a concentration of 1mmol/L was prepared using pure water. Respectively weighing 25mg of adsorbents C1, C2, M1, M2, M3, M4, M5, M6, M7 and M8, respectively placing the adsorbents in 50mL of the lead nitrate solution, covering the adsorbent, placing the adsorbent in a shaking table for shaking adsorption for 3 hours, measuring the concentration of lead ions in each group before and after adsorption, and calculating the lead adsorption capacity, wherein the results are shown in Table 2. As can be seen from Table 2, the adsorbents prepared by the method of the present invention all adsorbed lead ions in an amount of 1.97mmol/g at the maximum, higher than that of the adsorbents prepared in the comparative examples.
TABLE 2 lead loading results for different adsorbents
Example 10
Preparing copper nitrate, lead nitrate, cadmium nitrate and nickel nitrate solutions with the pH values of 3 and 5 and the heavy metal ion concentration of 0.5mmol/L respectively. 25mg of carboxyl carbon spheres M1 obtained in example 1 were weighed, placed in 50mL of each of the above solutions, capped, placed in a shaking table, shaken and adsorbed for 3 hours, and the concentrations of each heavy metal ion before and after adsorption were measured to calculate the adsorption amount.
Table 3 shows the adsorption capacity of the carboxyl carbon spheres M1 to different heavy metal ions under different pH conditions, and proves that M1 has better adsorption to four heavy metal ions when the pH value is 3-5. When the pH value is 5, the removal rate of four heavy metal ions is higher than 90 percent.
TABLE 3 results of adsorption amounts of adsorbent M1 for different heavy metal ions under different pH conditions
Example 11
The adsorption performance of the carboxyl carbon spheres M1 on copper ions in example 1 was evaluated by using simulated electroplating cleaning wastewater. The preparation method of the simulated electroplating wastewater comprises the following steps: using tap water as background water to prepare a mixed solution of copper sulfate, pyrophosphoric acid and ammonia water, wherein the concentrations are 2mmol/L, 2mmol/L and 8mmol/L in sequence, and the pH value is 9. 100mg of M1 was added to 100mL of the above simulated plating cleaning aqueous solution, and the solution was adsorbed at room temperature for 3 hours, and the copper ion concentration before and after adsorption was measured to calculate the adsorption amount and removal rate. The removal rate of copper ions was 84%, and the amount of adsorption was 1.65 mmol/g.
Example 12 (Recycling)
(1) 50mg of the carboxyl carbon sphere M1 in example 1 was weighed into a 100mL, 1mmol/L lead nitrate solution. Covering, placing in a shaking table, shaking for 2h, sampling, measuring the lead ion concentration before and after adsorption, and calculating the first round of adsorption amount;
(2) the adsorbent M1 in (1) was filtered, regenerated with 5mL, 1mol/L sulfuric acid, 5mL, 1mol/L NaOH, and 10mL of water in this order, and the filtrate was passed to the second round of adsorption.
(3) Adding the adsorbent M1 obtained in the step (2) into the lead nitrate solution obtained in the step (1), covering, placing in a shaking table, shaking for adsorption for 2 hours, sampling, measuring the concentration of lead ions before and after adsorption, and calculating the second round of adsorption capacity;
(4) and (3) repeating the regeneration and the adsorption to obtain the lead adsorption quantity of the third round, the fourth round and the fifth round. After the fifth round of regeneration the adsorbent was dried and its mass was weighed.
Table 4 is a five-time adsorption stability chart, it can be seen that the adsorption amount is basically maintained, the adsorption amount in the fifth round is reduced by 5.4% compared with that in the first round, and the mass change is less than 3%, which indicates that the carboxyl carbon spheres as the adsorbent prepared by the present invention have stable effect in the process of adsorbent regeneration and adsorption.
TABLE 4 results of lead adsorption during adsorbent reuse
| Number of cycles | 1 | 2 | 3 | 4 | 5 |
| Adsorption capacity of lead | 1.91 | 1.90 | 1.86 | 1.83 | 1.81 |
Claims (8)
1. A preparation method of carboxyl carbon spheres for adsorbing heavy metal ions is characterized in that glucose and olefine acid monomers are used as precursors, and the carboxyl carbon spheres are prepared through one-step hydrothermal reaction, then calcination in a muffle furnace, alkali liquor activation, water washing and drying; the olefine acid monomer is acrylic acid or maleic acid, and the alkali liquor is potassium hydroxide solution; the method specifically comprises the following steps:
(1) preparing a mixed aqueous solution of glucose and olefine acid monomers, carrying out hydrothermal reaction in a high-pressure reaction kettle, and carrying out centrifugal filtration to obtain first-stage carboxyl carbon spheres; the mass fraction of the glucose is 5-20%, the mass fraction of the olefine acid monomer is 5-20%, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 10-24 hours;
(2) calcining the first-stage carboxyl carbon spheres in a muffle furnace to obtain second-stage carboxyl carbon spheres; calcining in a muffle furnace at the temperature of 300-350 ℃ for 3-6 h;
(3) activating the second-stage carboxyl carbon spheres in alkali liquor, filtering, washing with water to be stable and neutral, drying, and grinding to obtain target carboxyl carbon spheres; the concentration of the alkali liquor is 1-4 mol/L, and the activation time is 0.5-5 h.
2. The method for preparing carboxyl carbon beads for adsorbing heavy metal ions according to claim 1, wherein the mass fraction of the glucose is 10%, and the mass fraction of the alkene monomer is 10%.
3. The preparation method of carboxyl carbon spheres for adsorbing heavy metal ions as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 180 ℃, the time of the hydrothermal reaction is 15h, the temperature of the muffle furnace calcination is 300 ℃, the calcination time is 6h, the concentration of the alkali liquor is 2mol/L, and the activation time is 2 h.
4. The preparation method of carboxyl carbon spheres for adsorbing heavy metal ions according to claim 1, which comprises the following steps:
(1) preparing a mixed aqueous solution of 10% by mass of glucose and 10% by mass of acrylic acid monomer, transferring the mixed aqueous solution to polytetrafluoroethylene endostatin, carrying out hydrothermal reaction in a high-pressure reaction kettle at the reaction temperature of 180 ℃ for 15h, and carrying out centrifugal filtration after the reaction is finished to obtain first-stage carboxyl carbon spheres;
(2) calcining the first-stage carboxyl carbon spheres in a muffle furnace to obtain second-stage carboxyl carbon spheres; the calcining temperature in the muffle furnace is 300 ℃, and the calcining time is 6 h;
(3) and (3) activating the second-stage carboxyl carbon spheres in 2mol/L KOH solution for 2h, filtering, washing with water until the second-stage carboxyl carbon spheres are stable and neutral, drying, and grinding to obtain the target carboxyl carbon spheres.
5. The carboxyl carbon spheres prepared by the preparation method of the carboxyl carbon spheres for adsorbing heavy metal ions as claimed in any one of claims 1 to 4.
6. Use of the carboxyl carbon spheres of claim 5 for adsorbing heavy metal ions.
7. The application of the carboxyl carbon spheres in adsorbing heavy metal ions according to claim 6, which is characterized by comprising the following steps:
(1) placing the carboxyl carbon spheres in a solution containing heavy metal ions, and adsorbing for 1-3 h; the content of the heavy metal ions is 1-300 mg/L, and the adding amount of the carboxyl carbon spheres is 0.2-2 g/L;
(2) filtering the carboxyl carbon balls in the step (1), sequentially regenerating the carboxyl carbon balls by using sulfuric acid, NaOH and water, and filtering the carboxyl carbon balls to enter a second round of adsorption;
(3) adding the adsorbent carboxyl carbon spheres obtained in the step (2) into the solution containing heavy metal ions again according to the method in the step (1), and adsorbing for 1-3 h;
(4) the regeneration and adsorption are repeated as in steps (2) and (3).
8. The use of carboxyl carbon spheres as claimed in claim 6 or 7 for adsorbing heavy metal ions, wherein the heavy metal ions are copper ions, lead ions, cadmium ions or nickel ions.
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