CN113426385B - Carbon aerogel pellet, preparation method thereof and application of carbon aerogel pellet as heavy metal adsorption material - Google Patents
Carbon aerogel pellet, preparation method thereof and application of carbon aerogel pellet as heavy metal adsorption material Download PDFInfo
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a carbon aerogel pellet, a preparation method thereof and application of the carbon aerogel pellet as a heavy metal adsorption material. Dissolving a phenolic compound, an aldehyde compound, chitosan and sodium alginate into water, and carrying out polymerization reaction to obtain a gel solution; dropwise adding the gel solution into a saturated boric acid solution containing calcium chloride to form gel beads; the carbon aerogel pellets are subjected to aging, drying and carbonization in sequence, so that the carbon aerogel pellets are obtained, have developed pore structures, large specific surface areas, are rich in heteroatoms, show excellent adsorption-passivation performance on heavy metals, can be widely used for treating heavy metal polluted water or heavy metal polluted soil, have the characteristics of high adsorption capacity and easiness in recovery, and have good industrial application prospects.
Description
Technical Field
The invention relates to a carbon aerogel pellet as well as a preparation method and application thereof, in particular to a carbon aerogel pellet doped with nano metal, a preparation method of the carbon aerogel pellet, and application of the carbon aerogel pellet as a heavy metal-containing wastewater adsorbent and a heavy metal contaminated soil passivator, and belongs to the technical field of environmental engineering.
Background
The carbon aerogel has the characteristics of large specific surface area, high conductivity, good chemical stability, good environmental compatibility, adjustable surface chemistry and the like due to the special three-dimensional space structure of the carbon aerogel. However, the carbon material has the characteristics of poor hydrophilicity, low surface activity and the like, and the development and application of the carbon material are restricted by the complicated preparation process. In the prior art, the preparation steps of the carbon aerogel are mainly divided into three steps: 1. and (3) a gelation stage: forming and strengthening a gel by a sol-gel and aging process; 2. and (3) drying: drying at normal temperature, freezing or supercritical conditions to obtain aerogel; 3. carbonizing: charring at high temperature under flowing nitrogen atmosphere to form Carbon aerogel ("Carbon Aerogels for Environmental Clean-Up", Gan G, et al.. European Journal of organic Chemistry,2019 (27): 3126-. The common preparation method is that resorcinol and formaldehyde are used as raw materials to form gel under the action of an alkaline catalyst, then carbon dioxide is used as a medium to carry out supercritical drying to prepare organic aerogel, and then the organic aerogel is pyrolyzed at high temperature under the protection of inert gas to obtain the carbon aerogel. The method has the defects that the gel is necessarily catalyzed by an alkaline catalyst when being prepared, the gel has great shrinkage in the supercritical drying and carbonization processes when the concentration of the catalyst is higher, and the low-density carbon aerogel is difficult to obtain, and the gel is not obtained when the concentration of the catalyst is lower (the preparation and application of the carbon aerogel and the composite material thereof, Yangzi 40503, Chinese university of science and technology, 2020. In recent years, the simplification of the preparation of carbon aerogel mainly focuses on the improvement and search of raw materials, and the characteristics of carbon materials are improved by adopting a doping modification method to obtain excellent performance.
Nitrogen is located adjacent to the right of carbon in the periodic table, and the nitrogen and the carbon are similar in chemical properties and are easier to combine. When nitrogen is doped into the carbon material, the nitrogen can replace carbon atoms in the carbon material, and the doping of the nitrogen atoms changes the surface electronic performance of the carbon material, increases defect sites (namely catalytic activity sites) of the carbon material, and further improves the catalytic activity; and secondly, the strong interaction between the basic groups on the surface of the nitrogen-containing carbon material and the active components is beneficial to the dispersion of the metal active components on the surface of the carbon material, can inhibit the formation of carbon deposition, and can enhance the hydrophilicity and the surface activity of the carbon material by improving the surface structure. In order to ensure the strength of a gel framework and the integrity of a pore channel, the framework strength is usually enhanced by adding some binding agents and crosslinking agents in the sol-gel process in the prior art.
Chinese patent (CN109647295B) discloses a preparation method and application of aerogel pellets. Respectively dissolving sodium alginate and N-succinyl chitosan in deionized water, uniformly mixing, fully mixing the two solutions, performing ultra-dispersion treatment, pouring into a film, freezing and molding, and freeze-drying to obtain the non-crosslinked sodium alginate/N-succinyl chitosan composite aerogel; and then immersing the composite aerogel into the calcium-aluminum ion mixed solution for crosslinking reaction, repeatedly washing the composite aerogel with deionized water after the reaction is finished, freezing the composite aerogel, and then freeze-drying the composite aerogel to obtain the crosslinked sodium alginate/N-succinyl chitosan composite aerogel. The sodium alginate/N-succinyl chitosan composite aerogel obtained by the patent technology has excellent surface affinity, high specific surface area and excellent mechanical properties. However, the pellet obtained by the patent technology has smaller specific surface area than that of the carbon aerogel pellet, needs to be freeze-dried for many times, needs more than 24 hours each time, needs more than four days in the whole preparation process, and takes longer time. At present, the application of the fresh aerogel pellets in heavy metal pollution treatment after carbonization treatment is carried out.
Disclosure of Invention
Aiming at the technical problems of complex synthesis process, low efficiency and the like in the prior art and the characteristics of low surface activity and the like of a conventionally prepared carbon aerogel material, the invention aims to provide a carbon aerogel pellet which has a developed pore structure, a large specific surface area, contains polar groups and is doped with nano metals, and the carbon aerogel pellet has high adsorption and passivation activity on water or heavy metals in soil.
The second purpose of the invention is to provide a preparation method of the carbon aerogel pellets, which has simple process operation and lower cost and is beneficial to large-scale production.
The third purpose of the invention is to provide an application of the carbon aerogel beads, the carbon aerogel beads are suitable for adsorbing and passivating heavy metals in water and soil, and the carbon aerogel beads can efficiently and quickly adsorb heavy metals in wastewater, passivate heavy metals in soil and achieve the purposes of purifying water quality polluted by heavy metals and repairing soil polluted by heavy metals.
In order to realize the technical purpose, the invention provides a method for preparing carbon aerogel beads based on a natural polymer template, which comprises the steps of dissolving a phenolic compound, an aldehyde compound, chitosan and sodium alginate into water, and carrying out polymerization reaction to obtain a gel solution; dropwise adding the gel solution into a saturated boric acid solution containing calcium chloride to form gel beads; and sequentially carrying out aging, drying and carbonization treatment on the gel pellets to obtain the gel pellets.
The key point of the technical scheme of the invention is that the carbon aerogel pellet is obtained by taking a phenolic compound, an aldehyde compound, chitosan and sodium alginate as raw materials. Firstly, uniformly dissolving a phenolic compound, an aldehyde compound, chitosan and sodium alginate in water, carrying out preliminary polymerization reaction on phenolic resin to form a uniform sol solution, then dropwise adding the sol solution into a saturated boric acid solution containing calcium chloride, and rapidly participating in calcium ion crosslinking by utilizing carboxyl in the sodium alginate to form an independent gel microsphere structure, and uniformly wrapping the phenolic compound, the aldehyde compound and a prepolymer in gel microspheres. The gel pellet uses a three-dimensional cross-linked network structure formed by sodium alginate and calcium chloride as a framework template of phenolic resin, and in the subsequent aging process, in-situ polymerization of phenolic compounds and aldehyde compounds and cross-linking reaction of phenolic prepolymer are carried out in the gel pellet to form a cross-linked phenolic resin structure, so that a cross-linked phenolic resin network and a natural polymer network penetrate through each other to form a double cross-linked network structure to obtain high-strength gel, and the cross-linked framework structure can be maintained after high-temperature carbonization, so that the three-dimensional carbon aerogel pellet with high specific surface area is obtained. As a preferred embodiment, the phenolic compound comprises phenol and/or resorcinol. These phenolic compounds are common phenolic resin raw materials.
As a preferred embodiment, the aldehyde compound includes formaldehyde and/or furfural. These aldehyde compounds are common phenolic resin raw materials.
Preferably, the mass ratio of the phenolic compound to the aldehyde compound is 10: 1-1: 10; more preferably 3:1 to 1: 3.
In a preferred embodiment, the mass ratio of the chitosan to the phenolic compound is 10:1 to 1:10, and more preferably 5:1 to 3: 1.
According to a preferable scheme, the mass ratio of the sodium alginate to the chitosan is 2: 1-2.
As a preferable scheme, the total mass percentage content of the phenolic compound, the aldehyde compound, the chitosan and the sodium alginate in the mixed solution is 1-60%. More preferably 20 to 50%.
As a preferable scheme, the nano metal powder comprises at least one of nano iron powder, nano cobalt powder and nano nickel powder. The nano metal powder not only has the function of passivating heavy metals, but also endows the carbon aerogel material with magnetism, and is convenient to recover.
As a preferable scheme, the addition amount of the nano metal powder accounts for 0.5-10% of the mass of the gel solution; more preferably 0.6 to 3%.
As a preferable scheme, the mass percentage content of calcium chloride in the saturated boric acid solution containing calcium chloride is 1-10%; more preferably 2 to 5%.
As a preferred embodiment, the polymerization conditions are: the temperature is 20-60 ℃, the stirring speed is 600-2000 r/min, and the time is 60-250 min. Further preferably, the temperature is normal temperature; further preferably, the stirring speed is 800-1200 r/min; the preferable time is 150-250 min. The polymerization process mainly comprises phenolic aldehyde prepolymerization.
As a preferred embodiment, the aging reaction conditions are: the temperature is 25-90 ℃, and the time is 10-60 h. The aging reaction process mainly comprises the polycondensation reaction between the phenolic aldehyde and the crosslinking between the phenolic aldehyde prepolymers. The temperature is further preferably 40-70 ℃, and the reaction time is further preferably 24-48 h.
As a preferable scheme, the carbonization conditions are as follows: and preserving the heat for 1-24 hours at the temperature of 300-1200 ℃ in a protective atmosphere. The protective atmosphere is generally an inert atmosphere, and an inert atmosphere such as nitrogen or argon can be selected. The temperature is preferably 850 to 950 ℃, and the time is preferably 2 to 5 hours.
As a preferable scheme, the drying can be realized by common drying methods such as freeze drying, vacuum drying, supercritical drying, normal-temperature drying and the like, and since the three-dimensional structure of the gel beads prepared in the invention has a certain strength, the aerogel beads can be directly obtained by normal-temperature drying.
The invention also provides a carbon aerogel pellet, which is obtained by the preparation method.
Preferably, the size of the carbon aerogel spheres is 1-2 mm, and the specific surface area is 400-1200 m2Per g, pore volume of 0.24cm3/g～0.35cm3(ii) in terms of/g. Further preferably, the specific surface area is 600 to 800m2/g。
The invention also provides an application of the carbon aerogel beads, which are applied to adsorbing heavy metals in water or soil.
Sodium alginate and chitosan natural polymer materials adopted in the preparation process of the carbon aerogel pellet can obtain the gel pellet with a three-dimensional network structure as a skeleton template of the carbon aerogel through crosslinking, so that the strength of the hydrogel is greatly enhanced, and the gel pellet contains a large amount of-OH and-NH2And COOH (COO)-) The polar groups, residual polar groups and heteroatoms can improve the adsorption performance of the carbon aerogel spheres.
The carbon aerogel pellet has the characteristics of large specific surface area and developed pore structure, and endows the carbon aerogel with higher physical adsorption performance, and the cross-linked hydrogel generated by chitosan and natural macromolecules of sodium alginate is used as a framework template to introduce a large amount of heteroatoms and polar groups into the carbon aerogel, so that the coordination adsorption performance of the carbon aerogel on heavy metals is greatly improved, and in addition, the nano metal is introduced, so that the carbon aerogel pellet has higher heavy metal adsorption and passivation capabilities.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the preparation method of the nano-metal doped carbon aerogel spheres provided by the invention is simple in process, green and environment-friendly, mild in reaction conditions, good in performance of the produced carbon aerogel spheres and suitable for large-scale production.
2. The carbon aerogel pellet provided by the invention has a larger specific surface area and a large adsorption capacity for heavy metal ions, and can be used for efficiently adsorbing heavy metal pollution in wastewater and soil so as to achieve an optimal treatment effect.
3. The carbon aerogel beads provided by the invention are convenient to use, can achieve a good removal effect by adding a small amount of the carbon aerogel beads in heavy metal pollution treatment, and have the potential of magnetic recovery-desorption recycling.
Drawings
FIG. 1 is an SEM photograph of the CTS-900 material of example 1 after adsorbing Cr; the existence of a large amount of Cr in the material can be seen from the figure, which shows that the CTS-900 has good adsorption performance on Cr.
FIG. 2 is the EDS chart of the CTS-900 material in example 1 after adsorbing Cr.
FIG. 3 is a scanning electron microscopy micrograph of CTS-900-Fe in example 2; the figure shows that the material is rough, has rich pore structure, has rough oval sphere filling in a plurality of micropores and is probably a nano iron particle successfully loaded.
FIG. 4 is a Scanning Electron Microscope (SEM) atlas of the CTS-900-Fe adsorbed heavy metal Cr in example 2.
FIG. 5 is an EDS diagram of the CTS-900-Fe material containing a small amount of Fe and N elements after adsorbing the heavy metal Cr in example 2, wherein the heavy metal Cr is uniformly adsorbed on the material.
FIG. 6 is N for CTS-900-Fe in example 2 and CTS-700-Fe in example 42Adsorption and desorption curves; the adsorption isotherm of the carbon aerogel pellet can be seen to be a typical class II adsorption isotherm from a nitrogen adsorption and desorption curve, a is CTS-700-Fe, b is CTS-900-Fe, and the comparison of a and b shows that the specific surface area of the carbon aerogel pellet is obviously increased along with the increase of the carbonization temperature.
FIG. 7 is a drawing showing N for CTS-700 in example 3 and CTS-900 in example 12Adsorption and desorption curves; the adsorption isotherm type of the carbon aerogel pellet can be seen from the nitrogen adsorption and desorption curve to be changed from microporous type to non-porous type along with the temperature rise, wherein a is CTS-700-Fe, and b is CTS-900-Fe.
Detailed Description
The invention will be further described with reference to specific embodiments, but the scope of the invention is not limited thereto.
Example 1
Adding 7.33g of resorcinol, 1.5g of chitosan and 2g of sodium alginate into a 200ml plastic beaker, adding 90ml of deionized water, stirring at the stirring speed of 800-1000 r/min for 1h at 25 ℃ to form a uniform mixed solution, adding 10ml of formaldehyde into the uniform solution, and stirring uniformly to finish the preparation of the solution A. Preparation of solution B: adding 2g of CaCl into deionized water2As a stabilizing agent, the three-dimensional structure of the formed hydrogel globule is stabilized. Then, the solution A is sucked up by a needle tube, and the liquid is dripped into the solution B in a liquid drop state to form yellow phenolic hydrogel pellets. The solution B containing the hydrogel beads was placed in an oven at 60 ℃ for reaction for 48 h. And after the reaction is finished, drying the filtered yellow hydrogel pellets at normal pressure, heating the yellow hydrogel pellets for 2 hours at 900 ℃ in a tubular furnace in the nitrogen atmosphere, cooling, and taking out black solids to obtain the carbon aerogel pellets CTS-900 based on the polymer as the template. The average particle diameter of the nitrogen-doped carbon aerogel pellet is 1.2mm, and the specific surface area is 277.167m2G, average pore diameter of 3.142nm and pore volume of 0.202cm3/g。
Example 2
In a 200ml plastic beaker, 7.33g resorcinol and 1.5g chitosan and 2g seaweed were addedAnd adding 90ml of deionized water into the sodium, stirring for 0.5h at the stirring speed of 800-1000 r/min at 25 ℃, then adding 0.8g of nano zero-valent iron, continuously stirring for 1h at the stirring speed of 800-1000 r/min to form a uniform mixed solution, adding 10ml of formaldehyde into the uniform solution, and stirring uniformly to complete the preparation of the solution A. Solution B was prepared as above. And (3) placing the ground flask containing the solution B on a magnetic stirring device, stirring at a stirring speed of 800-1000 r/min to enable the liquid in the ground flask to be in a flowing state, sucking the solution A by using a needle tube, and dripping the solution A into the solution B in a liquid drop state to form black iron-containing phenolic hydrogel pellets. The solution B containing the hydrogel beads was placed in an oven at 60 ℃ for reaction for 48 h. And after the reaction is finished, drying the filtered black hydrogel pellets at normal pressure, heating the black hydrogel pellets in a tube furnace at 900 ℃ for 2h in the nitrogen atmosphere, cooling and taking out black solids to obtain the iron-doped carbon aerogel pellets CTS-900-Fe based on the polymer as the template. The nitrogen-doped carbon aerogel has an average particle size of 1.5mm and a specific surface area of 300.268m2G, average pore diameter of 2.284nm and pore volume of 0.213cm3/g。
Example 3
Adding 7.33g of resorcinol, 1.5g of chitosan and 2g of sodium alginate into a 200ml plastic beaker, adding 90ml of deionized water, stirring at the stirring speed of 800-1000 r/min for 1h at 25 ℃ to form a uniform mixed solution, adding 10ml of formaldehyde into the uniform solution, and stirring uniformly to finish the preparation of the solution A. Solution B was prepared as above. Then, the solution A is sucked up by a needle tube, and the liquid is dripped into the solution B in a liquid drop state to form yellow phenolic hydrogel pellets. The solution B containing the hydrogel beads was placed in an oven at 60 ℃ for reaction for 48 h. And after the reaction is finished, drying the filtered yellow hydrogel pellets at normal pressure, heating the yellow hydrogel pellets for 2 hours in a tubular furnace at 700 ℃ in the nitrogen atmosphere, cooling, and taking out black solids to obtain the carbon aerogel pellets CTS-700 based on the polymer as the template. The nitrogen-doped carbon aerogel has an average particle size of 1.2mm and a specific surface area of 255.238m2G, average pore diameter of 2.207nm and pore volume of 0.141cm3/g。
Example 4
In a 200ml plastic beaker, 7.33g resorcinol and 1.5g chitosan and 2g seaweed were addedAnd adding 90ml of deionized water into the sodium, stirring for 0.5h at the stirring speed of 800-1000 r/min at 25 ℃, then adding 0.8g of nano zero-valent iron, continuously stirring for 1h at the stirring speed of 800-1000 r/min to form a uniform mixed solution, adding 10ml of formaldehyde into the uniform solution, and stirring uniformly to complete the preparation of the solution A. Solution B was prepared as above. And (3) placing the ground flask containing the solution B on a magnetic stirring device, stirring at a stirring speed of 800-1000 r/min to enable the liquid in the ground flask to be in a flowing state, sucking the solution A by using a needle tube, and dripping the solution A into the solution B in a liquid drop state to form black iron-containing phenolic hydrogel pellets. The solution B containing the hydrogel beads was placed in an oven at 60 ℃ for reaction for 48 h. And after the reaction is finished, drying the filtered black hydrogel pellets at normal pressure, heating the black hydrogel pellets in a tube furnace at 700 ℃ for 2h in the nitrogen atmosphere, cooling and taking out black solids to obtain the iron-doped carbon aerogel pellets CTS-700-Fe based on the polymer as the template. The nitrogen-doped carbon aerogel has an average particle size of 1.4mm and a specific surface area of 252.434m2G, average pore diameter of 2.400nm and pore volume of 0.151cm3/g。
Example 5 (Condition comparative example)
Under the same experimental conditions as in example 1, chitosan was not added to the raw materials, and the hydrogel microspheres obtained under the same aging conditions were fused, and the three-dimensional hydrogel structure was easily collapsed.
Example 6
The carbon aerogel pellets in the embodiments 1, 2, 3 and 4 are respectively used as adsorbents to prepare Cr with different concentration gradients6+Adding a heavy metal solution (with the concentration of 20-500 ppm, specifically 20ppm, 40ppm, 80ppm, 100ppm, 150ppm, 200ppm, 300ppm, 400ppm and 500ppm) into a carbon aerogel pellet and an iron-doped carbon aerogel pellet at the addition of 1g/L, adsorbing for 200min at the temperature of 25 ℃ and at the speed of 200r/min, and analyzing a water sample after adsorption, wherein the saturated adsorption amounts of the carbon aerogel nano-microspheres and the iron-doped carbon aerogel nano-microspheres synthesized in the examples 1-4 are respectively as follows: 265.31mg/g, 355.67mg/g, 155.39mg/g, 225.42 mg/g.
Claims (10)
1. A method for preparing carbon aerogel beads based on a natural polymer template is characterized by comprising the following steps: dissolving a phenolic compound, an aldehyde compound, chitosan and sodium alginate into water, and carrying out polymerization reaction to obtain a gel solution; dropwise adding the gel solution into a saturated boric acid solution containing calcium chloride to form gel beads; sequentially carrying out aging, drying and carbonization treatment on the gel pellets to obtain the gel pellets;
the mass ratio of the chitosan to the phenolic compound is 10: 1-1: 10;
the mass ratio of the sodium alginate to the chitosan is 2: 1-2;
adding nano metal powder into the gel solution;
the nano metal powder comprises at least one of nano iron powder, nano cobalt powder and nano nickel powder.
2. The method for preparing carbon aerogel beads based on the natural polymer template as claimed in claim 1, wherein:
the phenolic compound comprises phenol and/or resorcinol;
the aldehyde compound comprises formaldehyde and/or furfural;
the mass ratio of the phenolic compound to the aldehyde compound is 10: 1-1: 10;
the total mass percentage content of the phenolic compound, the aldehyde compound, the chitosan and the sodium alginate in the water is 1-60%.
3. The method for preparing carbon aerogel beads based on the natural polymer template as claimed in claim 1, wherein:
the addition amount of the nano metal powder accounts for 0.5-10% of the mass of the gel solution.
4. The method for preparing carbon aerogel beads based on the natural polymer template as claimed in claim 1, wherein: the mass percentage content of calcium chloride in the saturated boric acid solution containing calcium chloride is 1-10%.
5. The method for preparing carbon aerogel beads based on the natural polymer template as claimed in claim 1, wherein: the conditions of the polymerization reaction are as follows: the temperature is 20-60 ℃, the stirring speed is 600-2000 r/min, and the time is 60-250 min.
6. The method for preparing carbon aerogel beads based on the natural polymer template as claimed in claim 1, wherein: the aging conditions are as follows: the temperature is 25-90 ℃, and the time is 10-60 h.
7. The method for preparing carbon aerogel beads based on the natural polymer template as claimed in claim 1, wherein: the carbonization conditions are as follows: and preserving the heat for 1-24 hours at the temperature of 300-1200 ℃ in a protective atmosphere.
8. A carbon aerogel pellet characterized by: the preparation method of any one of claims 1 to 7.
9. A carbon aerogel pellet as claimed in claim 8, wherein: the size of the carbon aerogel small ball is 1-2 mm, and the specific surface area is 400-1200 m2Per g, pore volume of 0.24cm3/g~0.35cm3/g。
10. Use of a carbon aerogel pellet as claimed in claim 8 or 9, wherein: the method is applied to adsorbing heavy metals in water or soil.
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