CN108889278B - Preparation method of composite adsorption microspheres capable of removing mercury ions - Google Patents
Preparation method of composite adsorption microspheres capable of removing mercury ions Download PDFInfo
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Abstract
A preparation method of composite adsorption microspheres capable of removing mercury ions comprises the steps of pretreatment of illite; preparing cellulose ionic liquid; preparing an illite cellulose mixed solution: adding illite with different masses and pore-forming agents with corresponding proportions into the prepared cellulose ionic liquid, and uniformly stirring; preparing illite cellulose composite adsorption microspheres; and (3) preparing the modified illite cellulose composite adsorption microspheres. According to the invention, illite and cellulose are used as raw materials, the cellulose is dissolved through the ionic liquid, and the illite and the pore-forming agent are added to prepare the composite adsorption microspheres, so that the raw materials are cheap and easily available, nontoxic and harmless, and the ionic liquid is nontoxic, strong in solubility, recyclable and environment-friendly; by grafting the N-methyl-1-methylthio-2-nitrovinylamine modified illite cellulose composite adsorption microspheres, sulfydryl and amino are introduced into the composite adsorption microspheres, so that the adsorption efficiency of the composite adsorption microspheres on mercury ions is greatly improved.
Description
Technical Field
The invention relates to a preparation method of an adsorbent, in particular to a preparation method of composite adsorption microspheres used as a mercury removal adsorbent.
Background
In recent years, with the rapid development of society, environmental pollution caused by the discharge of industrial wastewater and domestic sewage is increasingly serious, wherein the problem of mercury ion pollution in water is the most serious and can cause serious harm to organisms. Therefore, the removal of mercury ions from water has become an environmental problem which needs to be solved urgently.
Illite is a potassium-rich silicate mica clay mineral, is gray in appearance, is crisp and fragile, has small particle size, large specific surface area, strong ion exchange capacity and the like. Cellulose is the most renewable resource in the world at present, and has no toxicity and many pore passages. Illite and cellulose are used as adsorbents themselves, and the adsorption efficiency of the illite and the cellulose to heavy metal ions is not high, so that the illite and the cellulose need to be modified to enhance the adsorption efficiency of the illite and the cellulose to heavy metal ions. The ionic liquid is a research hotspot in recent years, and the illite cellulose composite adsorption microspheres are prepared by utilizing the characteristics of no toxicity, easy recovery, strong dissolving capacity and the like of the ionic liquid, and can be modified to effectively improve the adsorption efficiency of the ionic liquid on heavy metal ions in water. The modified illite cellulose composite adsorption microspheres have good dispersibility in water, are easy to recover, and have good effect on solving the problem of heavy metal ions in water.
Disclosure of Invention
Aiming at the problems of the prior art, the invention provides a preparation method of composite adsorption microspheres capable of removing mercury ions, which comprises the steps of taking illite and cellulose as raw materials, dissolving the cellulose through ionic liquid, and adding the illite and a pore-forming agent to prepare the composite adsorption microspheres; sulfydryl and amino are introduced into the composite adsorption microspheres by grafting N-methyl-1-methylthio-2-nitrovinylamine, so that the adsorption efficiency of the composite adsorption microspheres on mercury ions is enhanced.
The technical problem of the invention is solved by the following technical scheme:
a preparation method of composite adsorption microspheres capable of removing mercury ions takes illite and cellulose as raw materials and comprises the following steps:
a. pretreatment of illite: weighing 10g of illite, cleaning, removing impurities, drying, and sieving with a 200-mesh sieve for later use;
b. preparation of cellulose ionic liquid: measuring 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, and stirring for 1h in a constant-temperature oil bath at 100 ℃ to completely dissolve the cellulose;
c. preparing an illite cellulose mixed solution: b, adding 0.5-2g of illite and 10-50% of pore-forming agent by mass into the cellulose ionic liquid prepared in the step b, and uniformly stirring;
d. preparing illite cellulose composite adsorption microspheres: preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; c, adding the illite cellulose mixed solution prepared in the step c into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain illite cellulose composite adsorption microspheres;
e. preparing modified illite cellulose composite adsorption microspheres: adding 1g of illite cellulose composite adsorption microspheres prepared in the step d into a 250ml three-neck flask, adding 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid, and adding the mixture into N2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; and (4) carrying out suction filtration, carrying out Soxhlet extraction on the obtained product for 12h, carrying out suction filtration again, and drying the product in a blast drying oven at 45 ℃ for 12h to obtain the modified illite cellulose composite adsorption microspheres.
According to the preparation method of the composite adsorption microsphere capable of removing mercury ions, the cellulose is one of microcrystalline cellulose, cotton fiber, straw cellulose or paper cellulose.
In the preparation method of the composite adsorption microsphere capable of removing mercury ions, the ionic liquid in the step b is 1-allyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium chloride.
In the preparation method of the composite adsorption microsphere capable of removing mercury ions, in the step c, the pore-forming agent is calcium carbonate.
According to the invention, illite and cellulose are used as raw materials, the cellulose is dissolved through ionic liquid, and the illite and pore-forming agent are added to prepare the composite adsorption microspheres, so that the raw materials are cheap and easily available, nontoxic and harmless, and the ionic liquid is nontoxic, strong in solubility, recyclable and environment-friendly; by grafting N-methyl-1-methylthio-2-nitrovinylamine modified illite cellulose composite adsorption microspheres and introducing sulfydryl and amino into the composite adsorption microspheres, the adsorption efficiency of the composite adsorption microspheres on mercury ions is greatly enhanced, and the maximum adsorption capacity of the composite adsorption microspheres on mercury ions reaches 350 mg/g; the composite adsorption microsphere prepared by the method is porous and large in specific surface area, and overcomes the defects of brittle illite, small specific surface area of cellulose and the like; in addition, the dispersion in water is good, the adsorption rate is high, the saturated adsorption capacity can be reached within about 10min, and the recovery can be realized. The invention fully utilizes the reproducibility of illite and cellulose, and has good application prospect for solving heavy metal pollution in water; the preparation method is simple, easy to operate, pollution-free and easy for industrial and large-scale production.
Drawings
FIG. 1 is a graph showing the influence of pH on the adsorption performance of composite adsorbent microspheres;
FIG. 2 is a graph showing the effect of adsorption time on the adsorption performance of composite adsorbent microspheres;
FIG. 3 is a graph showing the effect of initial concentration of mercury on the adsorption performance of composite adsorbent microspheres.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Building a test device table, cleaning and removing impurities from illite, drying, and sieving with a 200-mesh sieve for later use; taking 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, carrying out oil bath stirring at a constant temperature of 100 ℃ for 1h to completely dissolve the cellulose, then adding 0.5g of illite and 10% of pore-forming agent calcium carbonate by mass, and uniformly stirring to obtain an illite cellulose mixed solution; preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; adding the prepared illite cellulose mixed solution into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain the illite cellulose composite adsorption microspheres.
1g of prepared illite cellulose composite adsorption microspheres are placed into a 250ml three-neck flask, 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid are added into the flask, and the mixture is placed in a reactor2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; suction filtering, and Soxhlet extraction of the obtained product12 h; and performing suction filtration again, and drying for 12 hours in a blast drying oven at 45 ℃ to obtain the modified illite cellulose composite adsorption microspheres.
Preparing mercury-containing wastewater by using mercury acetate in a laboratory, adding 1g/L of adsorption microspheres for 100ppm of mercury-containing wastewater, oscillating for adsorption for 2h, filtering by using a needle tube with a filter head, diluting by multiple times step by step, and detecting by using an atomic fluorescence photometer to obtain adsorption equilibrium concentration, thereby calculating the adsorption capacity of the modified composite adsorption microspheres for the mercury-containing wastewater to be 83.4 mg/g.
Example 2
Building a test device table, cleaning and removing impurities from illite, drying, and sieving with a 200-mesh sieve for later use; taking 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, carrying out oil bath stirring at a constant temperature of 100 ℃ for 1h to completely dissolve the cellulose, then adding 1g of illite and 10% of pore-forming agent calcium carbonate by mass, and uniformly stirring to obtain an illite cellulose mixed solution; preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; adding the prepared illite cellulose mixed solution into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain the illite cellulose composite adsorption microspheres.
1g of prepared illite cellulose composite adsorption microspheres are placed into a 250ml three-neck flask, 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid are added into the flask, and the mixture is placed in a reactor2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; carrying out suction filtration, and Soxhlet extracting the obtained product for 12 h; and performing suction filtration again, and drying for 12 hours in a blast drying oven at 45 ℃ to obtain the modified illite cellulose composite adsorption microspheres.
Preparing mercury-containing wastewater by using mercury acetate in a laboratory, adding 1g/L of adsorption microspheres for 100ppm of mercury-containing wastewater, oscillating for adsorption for 2h, filtering by using a needle tube with a filter head, diluting by multiple times step by step, and detecting by using an atomic fluorescence photometer to obtain adsorption equilibrium concentration, thereby calculating the adsorption capacity of the modified composite adsorption microspheres for the mercury-containing wastewater to be 85.2 mg/g.
Example 3
Building a test device table, cleaning and removing impurities from illite, drying, and sieving with a 200-mesh sieve for later use; taking 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, carrying out oil bath stirring at a constant temperature of 100 ℃ for 1h to completely dissolve the cellulose, then adding 1.5g of illite and 10% of pore-forming agent calcium carbonate by mass, and uniformly stirring to obtain an illite cellulose mixed solution; preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; adding the prepared illite cellulose mixed solution into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain the illite cellulose composite adsorption microspheres.
1g of prepared illite cellulose composite adsorption microspheres are placed into a 250ml three-neck flask, 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid are added into the flask, and the mixture is placed in a reactor2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; carrying out suction filtration, and Soxhlet extracting the obtained product for 12 h; and performing suction filtration again, and drying for 12 hours in a blast drying oven at 45 ℃ to obtain the modified illite cellulose composite adsorption microspheres.
Preparing mercury-containing wastewater by using mercury acetate in a laboratory, adding 1g/L of adsorption microspheres for 100ppm of mercury-containing wastewater, oscillating for adsorption for 2h, filtering by using a needle tube with a filter head, diluting by multiple times step by step, and detecting by using an atomic fluorescence photometer to obtain adsorption equilibrium concentration, thereby calculating the adsorption capacity of the modified composite adsorption microspheres for mercury-containing wastewater to be 81.4 mg/g.
Example 4
Building a test device table, cleaning and removing impurities from illite, drying, and sieving with a 200-mesh sieve for later use; taking 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, carrying out oil bath stirring at a constant temperature of 100 ℃ for 1h to completely dissolve the cellulose, then adding 1.5g of illite and 30% by mass of pore-forming agent calcium carbonate, and uniformly stirring to obtain an illite cellulose mixed solution; preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; adding the prepared illite cellulose mixed solution into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain the illite cellulose composite adsorption microspheres.
1g of prepared illite cellulose composite adsorption microspheres are placed into a 250ml three-neck flask, 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid are added into the flask, and the mixture is placed in a reactor2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; carrying out suction filtration, and Soxhlet extracting the obtained product for 12 h; and performing suction filtration again, and drying for 12 hours in a blast drying oven at 45 ℃ to obtain the modified illite cellulose composite adsorption microspheres.
Preparing mercury-containing wastewater by using mercury acetate in a laboratory, adding 1g/L of adsorption microspheres for 100ppm of mercury-containing wastewater, oscillating for adsorption for 2h, filtering by using a needle tube with a filter head, diluting by multiple times step by step, and detecting by using an atomic fluorescence photometer to obtain adsorption equilibrium concentration, thereby calculating the adsorption capacity of the modified composite adsorption microspheres for the mercury-containing wastewater to be 83.8 mg/g.
Example 5
Building a test device table, cleaning and removing impurities from illite, drying, and sieving with a 200-mesh sieve for later use; taking 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, carrying out oil bath stirring at a constant temperature of 100 ℃ for 1h to completely dissolve the cellulose, then adding 1.5g of illite and pore-forming agent calcium carbonate with the mass fraction of 50%, and uniformly stirring to obtain an illite cellulose mixed solution; preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; adding the prepared illite cellulose mixed solution into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain the illite cellulose composite adsorption microspheres.
1g of prepared illite cellulose composite adsorption microspheres are placed into a 250ml three-neck flask, 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid are added into the flask, and the mixture is placed in a reactor2Under the protection of the protective sleeve, the protective sleeve is arranged,stirring and reacting for 15min at 35 ℃, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; carrying out suction filtration, and Soxhlet extracting the obtained product for 12 h; and performing suction filtration again, and drying for 12 hours in a blast drying oven at 45 ℃ to obtain the modified illite cellulose composite adsorption microspheres.
Preparing mercury-containing wastewater by using mercury acetate in a laboratory, adding 1g/L of adsorption microspheres for 100ppm of mercury-containing wastewater, oscillating for adsorption for 2h, filtering by using a needle tube with a filter head, diluting by multiple times step by step, and detecting by using an atomic fluorescence photometer to obtain adsorption equilibrium concentration, thereby calculating the adsorption capacity of the modified composite adsorption microspheres for mercury-containing wastewater to be 87.5 mg/g.
Example 6
Building a test device table, cleaning and removing impurities from illite, drying, and sieving with a 200-mesh sieve for later use; taking 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, carrying out oil bath stirring at a constant temperature of 100 ℃ for 1h to completely dissolve the cellulose, then adding 1g of illite and 30% of pore-forming agent calcium carbonate by mass fraction, and uniformly stirring to obtain an illite cellulose mixed solution; preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; adding the prepared illite cellulose mixed solution into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain the illite cellulose composite adsorption microspheres.
1g of prepared illite cellulose composite adsorption microspheres are placed into a 250ml three-neck flask, 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid are added into the flask, and the mixture is placed in a reactor2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; carrying out suction filtration, and Soxhlet extracting the obtained product for 12 h; and performing suction filtration again, and drying for 12 hours in a blast drying oven at 45 ℃ to obtain the modified illite cellulose composite adsorption microspheres.
Preparing mercury-containing wastewater by using mercury acetate in a laboratory, adding 1g/L of adsorption microspheres for 100ppm of mercury-containing wastewater, oscillating for adsorption for 2h, filtering by using a needle tube with a filter head, diluting by multiple times step by step, and detecting by using an atomic fluorescence photometer to obtain adsorption equilibrium concentration, thereby calculating the adsorption capacity of the modified composite adsorption microspheres for mercury-containing wastewater to be 86.1 mg/g.
Referring to table 1, the modified composite adsorption microspheres prepared by the method disclosed by the invention are porous and have large specific surface area, and the defects of brittle illite and small specific surface area of cellulose are overcome.
TABLE 1 comparison of specific surface area and pore size of adsorbents
| Illite stone | Microcrystalline cellulose | Illite cellulose composite microsphere | |
| Specific surface area (m)2/g） | 23.11 | 1.167 | 4.299 |
| Pore size (nm) | 26.19 | 17.51 | 19.07 |
Referring to FIG. 1, under the conditions that the initial concentration of mercury is 100mg/L, the dosage of the composite adsorption microspheres is 1g/L, and the oscillation adsorption is carried out for 2 hours, the adsorption capacity of the composite adsorption microspheres on mercury ions is increased along with the increase of the pH value of the solution. Meanwhile, when the pH value is 1, the adsorption capacity can also reach 65mg/g, which shows that the composite adsorption microsphere has good adsorption performance under strong acid and wide application range.
Referring to fig. 2, under the conditions that the initial concentration of mercury is 100mg/L, the dosage of the composite adsorption microspheres is 1g/L, and the pH value of the solution is 3, the adsorption capacity of the composite adsorption microspheres on mercury ions increases along with the increase of the adsorption time. As can be seen from the figure, the composite adsorption microspheres basically reach equilibrium when adsorbing for 10min, which shows that the adsorption rate of the composite adsorption microspheres is high.
Referring to fig. 3, the adsorption capacity of the composite adsorption microspheres for different initial concentrations of mercury is determined under the conditions that the addition amount of the composite adsorption microspheres is 1g/L, the oscillation adsorption is carried out for 2 hours, and the pH value of the solution is 3. As can be seen from the figure, the maximum adsorption capacity of the composite adsorption microspheres for mercury ions is 350mg/g, which shows that the composite adsorption microspheres have great adsorption capacity and good application prospects.
Claims (4)
1. A preparation method of composite adsorption microspheres capable of removing mercury ions takes illite and cellulose as raw materials, and is characterized by comprising the following steps:
a. pretreatment of illite: weighing 10g of illite, cleaning, removing impurities, drying, and sieving with a 200-mesh sieve for later use;
b. preparation of cellulose ionic liquid: measuring 40ml of ionic liquid, adding 1g of cellulose into the ionic liquid, and stirring for 1h in a constant-temperature oil bath at 100 ℃ to completely dissolve the cellulose;
c. preparing an illite cellulose mixed solution: b, adding 0.5-2g of illite and 10-50% of pore-forming agent by mass into the cellulose ionic liquid prepared in the step b, and uniformly stirring;
d. preparing illite cellulose composite adsorption microspheres: preparing 150ml of 1mol/L hydrochloric acid solution in a 250ml beaker, and placing the beaker on a magnetic stirrer for stirring; c, adding the illite cellulose mixed solution prepared in the step c into a constant-pressure funnel, slowly dropwise adding the illite cellulose mixed solution into a hydrochloric acid solution, stirring for 1h, filtering to obtain adsorption microspheres, washing the adsorption microspheres to be neutral, and freeze-drying to obtain illite cellulose composite adsorption microspheres;
e. preparing modified illite cellulose composite adsorption microspheres: adding 1g of illite cellulose composite adsorption microspheres prepared in the step d into a 250ml three-neck flask, adding 200ml of ceric ammonium nitrate solution and 0.4ml of pure nitric acid, and adding the mixture into N2Stirring and reacting for 15min at 35 ℃ under protection, then slowly adding 1g N-methyl-1-methylthio-2-nitrovinylamine into a three-neck flask, and stirring and reacting for 3h at 35 ℃; and (4) carrying out suction filtration, carrying out Soxhlet extraction on the obtained product for 12h, carrying out suction filtration again, and drying the product in a blast drying oven at 45 ℃ for 12h to obtain the modified illite cellulose composite adsorption microspheres.
2. The method for preparing the composite adsorption microspheres capable of removing mercury ions according to claim 1, wherein the method comprises the following steps: the cellulose is one of microcrystalline cellulose, cotton fiber, straw cellulose or paper cellulose.
3. The method for preparing the composite adsorption microspheres capable of removing mercury ions according to claim 2, wherein the method comprises the following steps: and the ionic liquid in the step b is 1-allyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole chloride salt.
4. The method for preparing the composite adsorption microspheres capable of removing mercury ions according to claim 3, wherein the method comprises the following steps: in the step c, the pore-forming agent is calcium carbonate.
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| CN103566846B (en) * | 2013-11-07 | 2015-12-30 | 华北电力大学（保定） | A kind of porous functionalization microcapsules, Preparation method and use |
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| US20170210641A1 (en) * | 2015-12-14 | 2017-07-27 | The Governors Of The University Of Alberta | Biosorbents for removal of contaminants from waste/oil sand process-affected water (ospw) and consolidation of oil sands tailings |
| CN106693916A (en) * | 2016-12-07 | 2017-05-24 | 郑州源冉生物技术有限公司 | Heavy metal adsorbent prepared from illite, as well as method and application |
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