CN115475605A - Polyacid-loaded biochar composite material and preparation method and application thereof - Google Patents
Polyacid-loaded biochar composite material and preparation method and application thereof Download PDFInfo
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention belongs to the technical field of environmental remediation, and particularly relates to a polyacid-loaded biochar composite material, and a preparation method and application thereof. According to the invention, the kitchen waste aerobic fermentation product is used as the raw material, so that the acid and alkali resistance of the composite material can be improved, the mechanical strength and stability of the composite material can be improved, and the composite material can be recycled for multiple times; in addition, organic matters in the aerobic fermentation product of the kitchen waste contain a large number of functional groups such as-SH, -NH-, -CO-NH-and-COO-and the like, the adsorption sites are multiple, and the functional groups are rich in lone-pair electrons, so that the lone-pair electrons can be provided to promote the coordination of metals when heavy metals are adsorbed, and the adsorption capacity of the composite material on heavy metal ions is improved; and the polyacid ligand is loaded on the biochar, the composite material is electronegative due to the increase of the number of electrons and the existence of the carboxylic acid functional group, and the adsorption capacity of the composite material can be further improved through electrostatic adsorption.
Description
Technical Field
The invention belongs to the technical field of environmental remediation, and particularly relates to a polyacid-loaded biochar composite material, and a preparation method and application thereof.
Background
The rapid development of modern industry, while improving the quality of life of people, also brings about serious environmental problems, such as the generation of a large amount of wastewater containing heavy metals. Heavy metals in the wastewater are extremely easy to be enriched in organisms through a food chain because of being not metabolized and degraded, thereby bringing great threat to the ecological environment and the human life health. Therefore, the reasonable resource recycling of the heavy metals in the heavy metal wastewater is a major problem in environmental protection and treatment at present.
At present, precipitation, ion resin exchange, electrolysis, activated carbon adsorption, reverse osmosis and electrodialysis are commonly used for treating heavy metal wastewater. The methods achieve better results to a certain extent, but the problems of unsatisfactory treatment effect and the like generally exist. For example, the document "Europentening, carbon-based porous organic polymer composite material preparation and its adsorption performance research [ M ]. University of Chinese academy of sciences.2021" discloses a carbon-based porous organic polymer composite material, which improves the treatment effect on heavy metal wastewater to a certain extent, but still has the problem of insufficient adsorption capacity.
Disclosure of Invention
The invention aims to provide a polyacid-loaded biochar composite material, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a polyacid-loaded biochar composite material comprises the following steps:
(1) Sequentially grinding and drying the kitchen waste after the kitchen waste is subjected to aerobic anhydration fermentation to obtain kitchen waste aerobic fermentation product powder; the grain size of the kitchen waste aerobic fermentation powder is not more than 106 micrometers;
(2) Mixing the kitchen waste aerobic fermentation product powder, charcoal powder and an acid solution to obtain a modified solution;
(3) And mixing the modified solution and the polyacid solution, and then sequentially carrying out crosslinking reaction and solidification to obtain the polyacid-loaded biochar composite.
Preferably, the mass ratio of the charcoal powder to the aerobic fermentation powder of the kitchen waste is 1-3; the mass ratio of the charcoal powder to acid in the acid solution is 1;
the mass ratio of the charcoal powder to the polyacid in the polyacid solution is 2-6.
Preferably, the polyacid comprises one or more of 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid, (2-aminoethyl) tetraacetic acid, ethylenediaminetetraacetic acid, 3', 4' -p-triphenyldione tetracarboxylic acid and 1,2,4, 5-benzenetetracarboxylic acid.
Preferably, the temperature of the crosslinking reaction is 35-60 ℃, and the heat preservation time is 30-90 min.
Preferably, the preparation method of the charcoal powder comprises the following steps: grinding the biomass and then pyrolyzing to obtain charcoal powder.
Preferably, the pyrolysis temperature is 250-400 ℃, and the heat preservation time is 120-180 min.
Preferably, the aerobic drying fermentation comprises the following steps: mixing the kitchen waste, the wood blocks and the composite microbial inoculum at room temperature, and then carrying out aerobic drying fermentation; the mass ratio of the kitchen waste to the wood blocks is 3-5; the mass ratio of the wood block to the composite microbial inoculum is 2-3.
The invention also provides a polyacid-loaded biochar composite material prepared by the preparation method in the scheme, which comprises biochar, and a kitchen waste aerobic fermentation product and a polyacid ligand loaded on the biochar.
The invention also provides application of the polyacid-loaded biochar composite material in the scheme in removal of heavy metals and basic dye pollutants in wastewater.
Preferably, the application comprises the steps of:
mixing the wastewater to be treated and the biological carbon composite material loaded with the polyacid, and stirring and adsorbing.
The invention provides a preparation method of a polyacid-loaded biochar composite material. According to the invention, biochar is taken as a main body material, and modification of biochar is realized by loading a kitchen waste aerobic fermentation product and a polyacid ligand, so that the polyacid-loaded biochar composite material is obtained. Organic matters in the aerobic fermentation product of the kitchen waste contain a large number of functional groups such as-SH, -NH-, -CO-NH-, and-COO-, and the like, the adsorption sites are multiple, and the functional groups are rich in lone-pair electrons, so that the lone-pair electrons can be provided to promote the coordination of metals when heavy metals are adsorbed, and the adsorption capacity of the composite material on heavy metal ions is improved; in addition, the polyacid ligand is loaded on the biochar, so that the number of carboxylic acid groups contained in the biochar is greatly increased, the composite material has higher adsorption capacity, the polyacid ligand has a large number of N atoms, the N atoms are rich in lone-pair electrons, and the coordination to heavy metal ions can be realized by providing electrons, and the synergistic effect is favorable for further improving the adsorption capacity of the composite material to the heavy metal ions; in addition, the number of electrons is increased, so that the composite material is electronegative due to the existence of the carboxylic acid functional group, and the adsorption capacity of the composite material can be further improved through electrostatic adsorption; in addition, the aerobic fermentation product of the kitchen waste is rich in inorganic salt components, so that the acid and alkali resistance of the composite material can be improved, the mechanical strength and stability of the composite material can be improved, and the repeated recycling of the composite material is facilitated.
The invention takes the aerobic fermentation product of the kitchen waste as the raw material, has rich raw materials and low cost, and realizes the resource utilization of the waste. The preparation method provided by the invention has the advantages of simple steps, convenience in operation, low raw material cost and environmental friendliness.
The invention also provides the polyacid-loaded biochar composite material prepared by the preparation method in the scheme. The polyacid-loaded biochar composite material provided by the invention has the advantages of rough surface, different pore canal sizes and higher specific surface area, the contact area of the composite material with water is large due to the structure, the composite material has better adsorption capacity for heavy metal and basic dye pollutants, particularly lead ions, under low concentration and high concentration, the adsorption capacity for heavy metal ions and basic dye pollutants is strong, and the removal efficiency is high.
The polyacid-loaded biochar composite material provided by the invention has a wide application range, can adsorb heavy metal ions and basic dye pollutants in a wide pH value range, has strong adaptability, has good tolerance to organic matters, and has little influence of organic pollutants on the effect of the composite material on adsorbing heavy metals.
The polyacid-loaded biochar composite material provided by the invention can be recycled for multiple times, the regeneration capacity is strong, and the recovery steps are simple; the biodegradable plastic is biodegradable and environment-friendly; the composite material has good stability for adsorbing heavy metal and basic dye pollutants, inhibits the leakage or desorption of the heavy metal and basic dye pollutants adsorbed by the composite material, avoids the secondary pollution of the heavy metal and basic dye pollutants to water, and is safe to use.
The invention also provides application of the polyacid-loaded biochar composite material in the scheme in removing heavy metal and basic dye pollutants. The polyacid-loaded biochar composite material provided by the invention can be used in a wastewater environment containing various heavy metal ions and basic dye pollutants, and particularly has an excellent effect of removing lead ions in ionic rare earth ore in-situ leaching wastewater, lead storage battery industrial wastewater, electroplating industrial wastewater and the like.
Furthermore, the use method of the biological carbon composite material loaded with the polyacid is simple, the operation is convenient, and the biological carbon composite material can be applied to large-scale industrialization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a scanning electron microscope image of a polyacid-loaded biochar composite prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a polyacid-loaded biochar composite material, which comprises the following steps:
(1) Carrying out aerobic drying fermentation on the kitchen waste, and then sequentially grinding and drying to obtain kitchen waste aerobic fermentation product powder; the grain size of the kitchen waste aerobic fermentation powder is not more than 106 microns;
(2) Mixing the kitchen waste aerobic fermentation product powder, the charcoal powder and an acid solution to obtain a modified solution;
(3) And mixing the modified solution and the polyacid solution, and then sequentially carrying out crosslinking reaction and solidification to obtain the polyacid-loaded biochar composite.
The method comprises the steps of sequentially grinding (marked as first grinding) and drying (marked as first drying) the kitchen waste after carrying out aerobic drying fermentation on the kitchen waste to obtain the mealPowder of aerobic fermentation product of kitchen garbage. In the invention, the grain size of the kitchen waste aerobic fermentation powder is not more than 106 microns, preferably 38-106 microns, and more preferably 38-74 microns; the kitchen waste preferably comprises one or more of fruits and vegetables, bones, meat and nut shells, and does not comprise plastics, ceramics and glass; the aerobic drying fermentation preferably comprises the following steps: mixing the kitchen waste, the wood blocks and the composite microbial inoculum at room temperature, and then carrying out aerobic dry fermentation; the size of the wood block is preferably 1-10 cm 3 More preferably 1 to 7cm 3 More preferably 1 to 3cm 3 The wood block has certain rigidity, the mixed wood block can improve the porosity of the mixture, oxygen in the air can enter the mixture, and in addition, the wood block can provide a certain carbon source for the fermentation of the composite microbial inoculum.
In the invention, the compound microbial inoculum preferably comprises lactobacillus plantarum, lactobacillus buchneri, lactobacillus acidophilus, bacillus subtilis, aspergillus niger and actinobacillus alalundii polyspora; the viable count of the lactobacillus plantarum is preferably 10 6 ～10 7 CFU/mL, more preferably 0.5X 10 7 CFU/mL; the viable count of the lactobacillus buchneri is preferably 10 7 ～10 8 CFU/mL, more preferably 0.5X 10 8 CFU/mL; the number of viable bacteria of the Lactobacillus acidophilus is preferably 10 8 ～10 9 CFU/mL, more preferably 0.5X 10 9 CFU/mL; the number of viable bacteria of the bacillus subtilis is preferably 10 6 ～10 7 CFU/mL, more preferably 0.5X 10 7 CFU/mL; the number of the viable bacteria of the Aspergillus niger is preferably 10 7 ～10 8 CFU/mL, more preferably 0.5X 10 8 CFU/mL; the viable count of the Actinomyces alata is preferably 10 6 ～10 7 CFU/mL, more preferably 0.5X 10 7 CFU/mL。
In the invention, the mass ratio of the kitchen waste to the wood blocks is preferably 3-5; the mass ratio of the wood block to the composite microbial inoculum is preferably 2-3, more preferably 2.5-3; the mixing mode is preferably stirring, and the rotating speed of the stirring is preferably 50-100 rpm, more preferably 80rpm; said aerobic anhydration is fermentedThe time is preferably 48 to 72 hours, and more preferably 60 to 70 hours; preferably screening the obtained kitchen waste aerobic fermentation product after the aerobic drying fermentation is finished, and screening out large building blocks and kitchen waste; the volume of the building blocks and kitchen garbage is preferably more than 1cm 3 The building blocks and kitchen garbage may have the phenomenon of incomplete aerobic drying fermentation and are not used as the raw material for the first grinding; preferably, the large building blocks and the kitchen garbage are subjected to aerobic drying fermentation repeatedly until the aerobic drying fermentation is complete; the method has no requirement on the rotating speed and time of the first grinding, and the kitchen waste aerobic fermentation product is ground to a target particle size; preferably, after the first grinding is completed, the ground product is sieved to reach the target particle size range; the temperature of the first drying is preferably 45 to 52 ℃, more preferably 50 ℃, and the drying is carried out to constant weight.
After the kitchen waste aerobic fermentation powder is obtained, mixing the kitchen waste aerobic fermentation powder, charcoal powder and an acid solution (marked as first mixing) to obtain a modified solution. In the present invention, the preparation method of the charcoal powder preferably comprises the steps of: grinding the biomass (marked as second grinding) and then pyrolyzing to obtain charcoal powder; the particle size of the biomass obtained by the second grinding is preferably not more than 106 microns, more preferably 38-106 microns, and further preferably 38-74 microns; the biomass preferably comprises one or more of chitosan, glucose, fructose, chitin, starch and cyclodextrin; the invention has no requirement on the rotating speed and time of the second grinding, and the biomass is ground to the target particle size; preferably, after the second grinding is finished, screening the ground product to reach the target particle size range; the pyrolysis temperature is preferably 200-400 ℃, more preferably 300-350 ℃, and the heat preservation time is preferably 120-180 min, more preferably 140-160 min; the acid solution preferably comprises one or more of 1v/v% -2 v/v% acetic acid solution, 10v/v% diluted hydrochloric acid, 10v/v% -15 v/v% diluted sulfuric acid, trifluoroacetic acid and formic acid.
In the invention, the mass ratio of the charcoal powder to the aerobic fermentation product powder of the kitchen waste is preferably 1-3, more preferably 2; the mass ratio of the charcoal powder to the acid in the acid solution is preferably 1; the first mixing preferably comprises the steps of: mixing and grinding the kitchen waste aerobic fermentation product powder and charcoal powder, and dissolving the obtained mixed powder into an acid solution to obtain a modified solution; the mixing and grinding time is preferably 5-10 min, and more preferably 7-9 min; the dissolving mode is preferably stirring; the stirring speed is preferably 300-500 rpm, more preferably 350-450 rpm, the stirring time is preferably 20-30 min, more preferably 25min, and the obtained modified solution is a gray yellow semitransparent viscous solution.
After obtaining the modified solution, mixing the modified solution and the polyacid solution (marked as second mixing), and then sequentially carrying out crosslinking reaction and curing to obtain the polyacid-loaded biochar composite; the mass ratio of the polyacid in the polyacid solution in the charcoal powder and the polyacid solution is preferably 2-6, more preferably 3-5; the polyacid preferably comprises one or more of 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid, (2-aminoethyl) tetraacetic acid, ethylene diamine tetraacetic acid, 3', 4' -p-triphenyl diketone tetracarboxylic acid, 1,2,4, 5-benzene tetracarboxylic acid and pyromellitic anhydride; the solvent of the polyacid solution preferably comprises one or more of ethanol, acetonitrile, acetone and water; the water is preferably deionized water; the concentration of the polyacid solution is preferably 0.15-0.70 g/mL, and more preferably 0.35-0.60 g/mL; the reaction is preferably carried out under stirring conditions, the stirring speed is preferably 400-800 rpm, more preferably 500-700 rpm, the temperature of the crosslinking reaction is preferably 35-60 ℃, more preferably 40-55 ℃, more preferably 45 ℃, the holding time is preferably 60-90 min, more preferably 70-80 min, and the load is fully reacted; in the invention, the polyacid solution is preferably added dropwise (recorded as the first addition) into the modification solution; the rate of the first dropping is preferably 0.4 to 2.5mL/min, more preferably 0.8 to 2.0mL/min.
In the present invention, the curing preferably comprises the steps of: mixing a product system obtained by the crosslinking reaction with an alkali solution (marked as third mixing), and then stirring and curing; the alkali solution preferably comprises sodium hydroxide solution and sodium hydroxide solution; the concentration of the alkali solution is preferably 1 to 1.5mol/L, and more preferably 1.2 to 1.5mol/L; the mass ratio of the alkali solution to the product obtained by the crosslinking reaction is 5-15, more preferably 8-11; preferably, a product system obtained by crosslinking reaction is dripped (marked as second dripping) into an alkali solution; the second dripping speed is preferably 5-10 mL/min, and more preferably 7-8 mL/min; the rotation speed of the stirring solidification is preferably 200-400 rpm, more preferably 250-350 rpm, and the stirring solidification time is preferably 20-30 h, more preferably 24-27 h, so that the material is fully solidified. The product obtained by the crosslinking reaction has high solubility in an acid solution and is insoluble in an alkali solution, the product is dripped into the alkali solution, the alkali solution can neutralize the unreacted acid, the shell of the biological carbon composite material loaded with polyacid is quickly solidified to form a spherical shell, then the alkali solution permeates into the composite material through a pore channel on the surface of the composite material, the acid in the composite material is completely neutralized, and the interior of the composite material is gradually solidified to form the stable spherical composite material.
In the invention, after the curing is finished, the product obtained by curing is preferably subjected to filtration (marked as first filtration), water washing and drying (marked as second drying) in sequence, and secondary curing is performed during drying; the temperature of the first filtration is preferably room temperature, and the pressure is preferably 0.05 to 0.10MPa, and more preferably 0.07 to 0.08MPa; the water for washing is preferably deionized water; the number of washing with water is preferably 2 or more, more preferably 3 to 5; in the invention, preferably, the product obtained by the first filtration is soaked in water and then washed and filtered in sequence (marked as the second filtration); the water immersion is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 100-200 rpm, more preferably 120-180 rpm; the water immersion time is preferably 3-5 min, and more preferably 4min; the mass ratio of the water for water immersion to the product obtained by solidification is preferably 5 to 10; the mass ratio of the washing water to the product obtained by solidification is preferably 2-10; the temperature of the second filtration is preferably normal temperature, and the pressure is preferably 0.05 to 0.10MPa, and more preferably 0.06 to 0.08MPa; the temperature of the second drying is preferably 40-60 ℃, more preferably 45-55 ℃, and the holding time is preferably 24-30 h, more preferably 26-28 h.
The invention also provides a polyacid-loaded biochar composite material prepared by the preparation method in the scheme, which comprises biochar, and a kitchen waste aerobic fermentation product and a polyacid ligand loaded on the biochar.
In the invention, the mass ratio of the charcoal powder to the aerobic fermentation product of the kitchen waste is preferably 2-3, more preferably 2.5-3; the mass ratio of the charcoal powder to the polyacid is preferably 2 to 3, more preferably 2.5 to 3.
The invention also provides application of the polyacid-loaded biochar composite material in the scheme in removing heavy metals and basic dye pollutants in wastewater.
In the invention, the heavy metal is preferably one or more of lead, chromium, mercury and copper; the basic dye contaminants preferably include one or more of rhodamine, nile red, basic orange, and crystal violet.
In the present invention, the application preferably comprises the steps of: mixing the wastewater to be treated and the biological carbon composite material loaded with the polyacid, and stirring and adsorbing. In the invention, the mass concentration of heavy metal ions in the wastewater to be treated is preferably 10-1000 mg/L, more preferably 30-200 mg/L, the mass concentration of basic dye pollutants is preferably 5-400 mg/L, more preferably 5-100 mg/L, and the heavy metal ions and the basic dye pollutants can exist at the same time; the mass-volume ratio of the polyacid-loaded biochar composite material to the wastewater to be treated is preferably 1g; before the wastewater to be treated and the biological carbon composite material loaded with the polyacid are mixed, the wastewater to be treated and the pH buffer solution are preferably mixed, and then the obtained mixed solution is mixed with the biological carbon composite material loaded with the polyacid; the dosage relation of the wastewater to be treated and the pH buffer solution is preferably determined according to the optimal pH range of pollutant adsorption in the wastewater to be treated; the concentration of the pH buffer solution is preferably 0.5-3 mol/L, more preferably 1mol/L, and the pH of the pH buffer solution is preferably 4.4-5.2, more preferably 5.0; the rotation speed of the stirring adsorption is preferably 1500-2000 rpm, more preferably 1600-1800 rpm, the time of the stirring adsorption is preferably 1-1.5 h, more preferably 1.2-1.5 h, so that the composite material is contacted with the wastewater to be treated and adsorbed as fully as possible; after the stirring adsorption is finished, preferably filtering the obtained product system (marked as third filtration) and separating the composite material from the product system; the invention has no special requirement on the third filtration, and the composite material is separated from the product system.
After the third filtration is finished, the polyacid-loaded biochar composite is preferably regenerated; the regeneration preferably comprises the steps of: sequentially carrying out acid washing, water washing and drying on the polyacid-loaded biochar composite material obtained by the third filtration; the acid for pickling preferably comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and formic acid; the concentration of the acid for pickling is preferably 0.05 to 0.15mol/L, and more preferably 0.08 to 0.12mol/L; the number of the acid washing is preferably 3 or more, more preferably 3 to 5; the dosage of acid for each acid washing is preferably 2-6 mL/g (1 g of polyacid-loaded biochar composite), more preferably 3-5 mL/g, and heavy metal and alkaline dye pollutants adsorbed by the composite are eluted by the acid washing; the water for washing is preferably deionized water, and the deionized water is used for cleaning acid liquor remained on the composite material; the drying temperature is preferably 40 to 60 ℃, more preferably 45 to 55 ℃, and the time is preferably 10 to 24 hours, more preferably 15 to 20 hours. The polyacid-loaded biochar composite material provided by the invention has good regeneration performance, and the adsorption capacity of the material can still reach more than 85% of the adsorption capacity in the first use under the condition of recycling for 5 times.
In order to further illustrate the invention, the following detailed description of the embodiments of the invention is given with reference to the accompanying drawings and examples, which are not to be construed as limiting the scope of the invention.
Example 1
The method for preparing the polyacid-loaded biochar composite material comprises the following specific steps:
(1) Preparing a composite microbial inoculum for aerobic dry fermentation, wherein the composite microbial inoculum is lactobacillus plantarum, lactobacillus buchneri and acidophilic lactobacillusLactobacillus, bacillus subtilis, aspergillus niger and actinobacillus alatus polyspora, wherein the viable count of the lactobacillus plantarum is 0.5 multiplied by 10 7 CFU/mL, the viable count of the lactobacillus buchneri is 0.5 multiplied by 10 8 CFU/mL, the viable count of the Lactobacillus acidophilus is 0.5 × 10 9 CFU/mL, the viable count of the bacillus subtilis is 0.5 multiplied by 10 7 CFU/mL, the viable count of the Aspergillus niger is 0.5 multiplied by 10 8 CFU/mL, the viable count of the Actinomyces alata is 0.5 multiplied by 10 7 CFU/mL；
(2) At room temperature, 5g of kitchen waste (fruits, vegetables, bones, meat and nutshells) and 2.5g of kitchen waste with volume of 5cm are mixed 3 The wood block and 1g of the composite microbial inoculum are stirred at 80rpm and then are subjected to aerobic drying fermentation for 72 hours to obtain an aerobic fermentation product of the kitchen waste, and the volume of the aerobic fermentation product is larger than 1cm 3 Grinding the kitchen waste aerobic fermentation product, sieving with a 200-mesh sieve, and taking undersize products to obtain kitchen waste aerobic fermentation product powder; grinding chitosan, sieving with 200 mesh sieve, taking undersize, and pyrolyzing at 350 deg.C for 150min to obtain chitosan charcoal powder;
(3) Weighing 1.7g of the obtained chitosan charcoal powder and 1.2g of the obtained kitchen waste aerobic fermentation powder, mixing, placing in a mortar, repeatedly grinding and uniformly mixing to obtain mixed powder;
(4) Dissolving the obtained mixed powder in 58mL of 1.6% (volume fraction) glacial acetic acid solution, stirring at 370rpm for 28 min at room temperature, and dissolving completely to obtain modified solution (which is gray yellow and semitransparent viscous solution);
(5) Weighing 0.6g of 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid, and dissolving the weighed solution in 1.4mL of deionized water to obtain a 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid solution;
(6) Slowly dripping the obtained 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid solution into the obtained modified solution at the dripping speed of 1min/mL, and stirring for 76 minutes at the rotating speed of 600rpm after finishing dripping to fully react and finish loading;
(7) Dropwise adding the obtained reaction liquid into 450mL of NaOH solution with the concentration of 1.2mol/L by using a dropper, and stirring at 340rpm for 24 hours to fully solidify the material;
(8) Filtering the product obtained by solidification, washing with 3L of deionized water for 3 times, soaking with 1L of water each time, stirring at 160rpm for 5 minutes, and then filtering;
(9) And (3) drying the obtained polyacid-loaded biochar composite material in a 45 ℃ oven for 26 hours, drying and curing for the second time, and using the polyacid-loaded biochar composite material after drying.
The method for using the biological carbon composite material loaded with the polyacid comprises the following specific steps:
preparing 100mg/L, 300mg/L, 500mg/L, 800mg/L and 1000mg/L lead ion solutions, taking 10mL of each lead ion solution with each concentration, adding 0.1g of composite material into the lead ion solutions for adsorption, filtering after adsorption balance, measuring the concentration of the residual lead ion solution in the solution, and finally calculating to obtain the maximum theoretical adsorption amount of the composite material to lead ions, wherein the maximum theoretical adsorption amount is 112mg/g.
Example 2
The method for preparing the biological carbon composite material loaded with the polyacid comprises the following specific steps:
(1) Preparing a composite microbial inoculum in aerobic dry fermentation, wherein the composite microbial inoculum is lactobacillus plantarum, lactobacillus buchneri, lactobacillus acidophilus, bacillus subtilis, aspergillus niger and actinomyces alalundii polyspora, and the viable count of the lactobacillus plantarum is 10 7 CFU/mL, the viable count of the lactobacillus buchneri is 10 8 CFU/mL, the viable count of the acidophilic lactobacillus is 10 9 CFU/mL, the viable count of the bacillus subtilis is 10 7 CFU/mL, the viable count of the Aspergillus niger is 10 8 CFU/mL, the viable count of the actinobacillus alalundii polyspora is 10 7 CFU/mL；
(2) At room temperature, 4.4g of kitchen waste (fruits, vegetables, bones, meat and nutshells) and 2.3g of kitchen waste with volume of 5cm are mixed 3 Stirring the wood blocks with 0.9g of the composite microbial inoculum at 80rpm, then carrying out aerobic drying fermentation for 72 hours to obtain an aerobic fermentation product of the kitchen waste, and screening out the kitchen waste with the volume of more than 1cm 3 Grinding the aerobic fermentation product of the kitchen waste, sieving the ground aerobic fermentation product with a 200-mesh sieve, and taking the undersize productObtaining the aerobic fermentation product powder of the kitchen waste; grinding chitosan, sieving with 200 mesh sieve, taking undersize, and pyrolyzing at 344 deg.C for 145min to obtain chitosan charcoal powder;
(3) Weighing 1.5g of the chitosan charcoal powder and 1.1g of the kitchen waste aerobic fermentation powder, mixing, placing in a mortar, repeatedly grinding and uniformly mixing to obtain mixed powder;
(4) Dissolving the obtained mixed powder in 58mL of 1.6% (volume fraction) glacial acetic acid solution, stirring at 370rpm for 28 min at room temperature, and dissolving completely to obtain modified solution (the solution is gray yellow and is semitransparent viscous solution);
(5) Weighing 0.7g of 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid, and dissolving the weighed solution in 1.5mL of deionized water to obtain a 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid solution;
(6) Slowly dripping the obtained 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid solution into the obtained modified solution at the dripping speed of 1min/mL, and stirring at the rotating speed of 600rpm for 80 minutes after finishing dripping to fully react and finish loading;
(7) Dropwise adding the obtained reaction liquid into 400mL of NaOH solution with the concentration of 1.1mol/L by using a dropper, and stirring at 300rpm for 24 hours to fully solidify the material;
(8) Filtering the product obtained by solidification, washing with 3L of deionized water for 3 times, soaking with 1L of water each time, stirring at 120rpm for 5 minutes, and filtering;
(9) And (3) drying the obtained polyacid-loaded biochar composite material in a drying oven at 40 ℃ for 28 hours, drying and carrying out secondary curing, and using the polyacid-loaded biochar composite material after drying.
The method for using the biological carbon composite material loaded with the polyacid comprises the following specific steps:
taking river water, using the river water as a simulated actual sample, preparing 100mg/L, 300mg/L, 500mg/L, 800mg/L and 1000mg/L lead ion solutions which are sequentially marked as No. 1, no. 2, no. 3, no. 4 and No. 5, and performing adsorption treatment as a simulated water sample of lead ions in the environment; 10mL of each lead ion solution was taken, 0.1g of the composite material was added thereto for adsorption, filtration was performed after adsorption equilibrium was reached, and the concentration of the remaining lead ion solution in the solution was measured, and the results are shown in Table 1:
table 1 lead ion concentrations before and after adsorption of polyacid-loaded biochar composites prepared in example 2
| Sample number | Concentration of lead ion before adsorption | Lead ion concentration after adsorption | Removal rate |
| 1 | 100mg/L | 13mg/L | 87.00％ |
| 2 | 300mg/L | 45mg/L | 85.00％ |
| 3 | 500mg/L | 63mg/L | 87.40％ |
| 4 | 800mg/L | 98mg/L | 87.75％ |
| 5 | 1000mg/L | 134mg/L | 86.60％ |
According to table 1, the polyacid-loaded biochar composite material provided by the invention has excellent lead ion adsorption capacity for both low-concentration wastewater and high-concentration wastewater, and in practical use, the polyacid-loaded biochar composite material provided by the invention can be added into high-concentration wastewater to adsorb most of lead ions to obtain low-concentration wastewater, then the polyacid-loaded biochar composite material is added to further adsorb the low-concentration wastewater, and the adsorption is repeated until most of lead ions are removed.
Taking river water, using the river water as a simulated actual sample, preparing alkaline orange solutions of 100mg/L, 300mg/L, 500mg/L, 800mg/L and 1000mg/L, sequentially marking as No. 1, no. 2, no. 3, no. 4 and No. 5, and performing adsorption treatment as a simulated water sample of the alkaline orange in the environment; 10mL of each basic orange solution was taken, 0.1g of the composite material was added thereto for adsorption, filtration was performed after adsorption equilibrium was reached, and the concentration of the remaining basic orange solution in the solution was measured, and the results are shown in Table 2:
table 2 basic orange concentrations before and after adsorption of the polyacid-loaded biochar composite prepared in example 2
According to table 2, the polyacid-loaded biochar composite material provided by the invention has excellent basic dye pollutant adsorption capacity for both low-concentration wastewater and high-concentration wastewater, and in practical use, the polyacid-loaded biochar composite material provided by the invention can be added into high-concentration wastewater to adsorb most of basic dye pollutants to obtain low-concentration wastewater, then the polyacid-loaded biochar composite material is added to further adsorb the low-concentration wastewater, and the adsorption is repeated until most of the basic dye pollutants are removed.
The regeneration performance test of the polyacid-loaded biochar composite material prepared in the embodiment 1 of the invention is carried out, and the test method comprises the following steps: according to the use method in the example 1, the heavy metal in the test solution is adsorbed by the composite material for the first time, the composite material is filtered after the adsorption balance, the residual concentration of the heavy metal in the test solution is calculated, and the adsorption amount of the composite material to the heavy metal is calculated as Q 0 (ii) a According to the regeneration step, carrying out acid washing, water washing and drying on the heavy metal on the composite material to realize material regeneration; repeating the steps on the regenerated composite material, namely an adsorption-desorption regeneration cycle; the adsorption capacity of the regenerated composite material in each time is recorded as Q 1 、Q 2 、Q 3 、Q 4 、Q 5 、Q 6 8230the results show that when the composite material is used for 5 times in a circulating way, Q is obtained 5 /Q 0 Greater than 85%, i.e., the composite still has more than 85% of its initial capacity to be adsorbed during initial use. Therefore, the biological carbon composite material loaded with polyacid provided by the invention has good regeneration performance.
According to the embodiments, the polyacid-loaded biochar composite material provided by the invention has good heavy metal adsorption capacity under low concentration and high concentration, and is strong in heavy metal ion adsorption capacity, especially lead ion adsorption capacity, high in adsorption capacity and high in removal efficiency.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyacid-loaded biochar composite material comprises the following steps:
(1) Sequentially grinding and drying the kitchen waste after the kitchen waste is subjected to aerobic anhydration fermentation to obtain kitchen waste aerobic fermentation product powder; the grain size of the kitchen waste aerobic fermentation powder is not more than 106 microns;
(2) Mixing the kitchen waste aerobic fermentation product powder, charcoal powder and an acid solution to obtain a modified solution;
(3) And mixing the modified solution and the polyacid solution, and then sequentially carrying out crosslinking reaction and solidification to obtain the polyacid-loaded biochar composite.
2. The preparation method of claim 1, wherein the mass ratio of the charcoal powder to the aerobic fermentation product powder of the kitchen waste is 1-3; the mass ratio of the charcoal powder to acid in the acid solution is 1;
the mass ratio of the charcoal powder to the polyacid in the polyacid solution is 2-6.
3. The method according to claim 1 or 2, wherein the polyacid comprises one or more of 1,4,7, 10-tetraazacyclododecane-N, N, N, N-tetraacetic acid, (2-aminoethyl) tetraacetic acid, ethylenediaminetetraacetic acid, 3', 4' -p-triphenyldione tetracarboxylic acid, and 1,2,4, 5-benzenetetracarboxylic acid.
4. The method according to claim 1, wherein the temperature of the crosslinking reaction is 35 to 60 ℃ and the holding time is 30 to 90min.
5. The preparation method of claim 1, wherein the preparation method of the charcoal powder comprises the following steps: grinding the biomass and then pyrolyzing to obtain charcoal powder.
6. The preparation method according to claim 5, wherein the pyrolysis temperature is 250-400 ℃ and the holding time is 120-180 min.
7. The preparation method of claim 1, wherein the aerobic dry fermentation comprises the following steps: mixing the kitchen waste, the wood blocks and the composite microbial inoculum at room temperature, and then carrying out aerobic drying fermentation; the mass ratio of the kitchen waste to the wood blocks is 3-5; the mass ratio of the wood block to the composite microbial inoculum is 2-3.
8. The polyacid-loaded biochar composite material obtained by the preparation method of any one of claims 1 to 7 comprises biochar and kitchen waste aerobic fermentation products and polyacid ligands loaded on the biochar.
9. Use of the polyacid-loaded biochar composite of claim 8 in the removal of heavy metals and basic dye contaminants from wastewater.
10. The application according to claim 9, characterized in that it comprises the following steps:
mixing the wastewater to be treated and the biological carbon composite material loaded with the polyacid, and stirring and adsorbing the mixture.
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| JP2002177770A (en) * | 2000-12-08 | 2002-06-25 | Yoshikazu Kumihigashi | Heavy metal adsorbent and method of preparing the same |
| CN106890624A (en) * | 2017-03-20 | 2017-06-27 | 湖南大学 | A kind of shitosan/anhydride modified biological carbon composite and preparation method thereof and purposes |
| CN111408376A (en) * | 2019-01-08 | 2020-07-14 | 湖南农业大学 | Preparation method and application of multifunctional biochar with heavy metal adsorption and organic matter degradation functions |
| JP2021074708A (en) * | 2019-11-07 | 2021-05-20 | 浙江研基科技有限公司 | Modified nanomaterial and application thereof in antimony-containing wastewater treatment |
| CN114259985A (en) * | 2021-12-21 | 2022-04-01 | 中州水务控股有限公司 | Method for preparing biochar by using kitchen waste as biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002177770A (en) * | 2000-12-08 | 2002-06-25 | Yoshikazu Kumihigashi | Heavy metal adsorbent and method of preparing the same |
| CN106890624A (en) * | 2017-03-20 | 2017-06-27 | 湖南大学 | A kind of shitosan/anhydride modified biological carbon composite and preparation method thereof and purposes |
| CN111408376A (en) * | 2019-01-08 | 2020-07-14 | 湖南农业大学 | Preparation method and application of multifunctional biochar with heavy metal adsorption and organic matter degradation functions |
| JP2021074708A (en) * | 2019-11-07 | 2021-05-20 | 浙江研基科技有限公司 | Modified nanomaterial and application thereof in antimony-containing wastewater treatment |
| CN114259985A (en) * | 2021-12-21 | 2022-04-01 | 中州水务控股有限公司 | Method for preparing biochar by using kitchen waste as biomass |
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