Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the problem that the ammonia nitrogen removal efficiency of the traditional charcoal adsorbent in acidic wastewater is not good, the preparation method of the corn straw charcoal-based composite adsorbent is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
(1) drying and crushing the corn straws, and sieving the corn straws with a 20-mesh sieve to obtain corn straw powder;
(2) mixing 20-30 parts of corn straw powder, 5-8 parts of vinasse, 5-8 parts of fungus residues, 5-8 parts of cow dung and 20-30 parts of deionized water, fermenting, filtering, drying, ball-milling, sieving with a 40-mesh sieve, and gradually heating and carbonizing to obtain a carbonized material;
(3) according to the weight parts, sequentially taking 30-40 parts of modified polyvinyl alcohol liquid, 50-60 parts of carbonized material, 20-30 parts of peach gum liquid, 5-8 parts of glutaraldehyde solution and 5-8 parts of hydrochloric acid, stirring and mixing the modified polyvinyl alcohol liquid and the peach gum liquid, sequentially adding the hydrochloric acid, the glutaraldehyde solution and the carbonized material, stirring and mixing, filtering, washing and vacuum drying to obtain pretreated biochar;
(4) according to the weight parts, 10-20 parts of modified montmorillonite, 60-80 parts of organic solvent, 20-30 parts of deionized water, 10-20 parts of pretreated biochar, 8-10 parts of ethyl orthosilicate and 5-8 parts of phospholipid are sequentially taken, the modified montmorillonite and the organic solvent are mixed and subjected to ultrasonic treatment, then the deionized water, the pretreated biochar and the phospholipid are added, stirring and mixing are carried out, then the ethyl orthosilicate is dropwise added, and stirring is continued, so that the corn straw biochar-based composite adsorbent is obtained.
The step-by-step temperature rise carbonization condition in the step (2) is as follows; the nitrogen filling rate is 60-90 mL/min, the temperature rising rate is 8-10 ℃/min, the carbonization temperature is 450-650 ℃, and the carbonization time is 2-3 h.
The preparation process of the modified polyvinyl alcohol solution in the step (3) comprises the following steps: mixing polyvinyl alcohol and water according to a mass ratio of 1: 30-1: 50, standing and swelling, heating, stirring and dissolving, then dropwise adding hydrochloric acid with the mass of 0.3-0.5 time of that of polyvinyl alcohol, heating, stirring and mixing, then adding crotonaldehyde with the mass of 0.3-0.5 time of that of polyvinyl alcohol and acetaldehyde with the mass of 0.3-0.5 time of that of polyvinyl alcohol, heating, stirring and reacting, then dropwise adding sodium hydroxide solution to adjust the pH, then adding urea with the mass of 0.1-0.2 time of that of polyvinyl alcohol, stirring and mixing to obtain the modified polyvinyl alcohol solution.
The preparation process of the peach gum solution in the step (3) comprises the following steps: peach gum and water are mixed according to the mass ratio of 1: 30-1: 50, standing for swelling, heating, stirring and dissolving to obtain peach gum solution.
The preparation process of the modified montmorillonite in the step (4) comprises the following steps: mixing calcium-based montmorillonite and water according to a mass ratio of 1: 10-1: 20, stirring and mixing, adding sodium carbonate which is 0.2-0.3 time of the mass of the calcium-based montmorillonite, stirring and reacting at a constant temperature, adding octadecyl trimethyl ammonium chloride which is 0.4-0.5 time of the mass of the calcium-based montmorillonite, treating in a constant-temperature water bath, and drying to obtain the modified montmorillonite.
The organic solvent in the step (4) is any one of xylene, pentane, hexane, dichlorobenzene or dichloromethane.
And (4) the phospholipid is any one of soybean phospholipid, yolk phospholipid or milk phospholipid.
The invention has the beneficial effects that:
the invention adds the pretreated biochar and the modified montmorillonite, during the use process, firstly, the pretreated biochar contains a gel structure sensitive to pH, when the product is added, the gel system is in a shrinkage state near the isoelectric point of gelatin, and can expand or shrink along with the change of the pH of the environment when deviating from the isoelectric point, when the water body is in a meta-acid state, the pH around the gel is reduced, amino groups are protonated and carry out mutual repulsion of like positive charges, the gel system expands, the gel expands, the expansion stress enables pores of a silicon oxide layer on the surface of the system to be enlarged, the adsorption efficiency of the system to ammonium ions is improved, the ammonia nitrogen removal efficiency of the product is improved, secondly, hydrogen ions and ammonium ions compete to the adsorption sites, and under the meta-acid condition, the biochar reduces the adsorption quantity of the ammonium ions due to the increase of the competition of the hydrogen ions and the ammonium ions to the adsorption sites, but the inside positive charge that has of biological charcoal has played the effect of attracting hydrogen ion while keeping off hydrogen ion at this moment, has reduced hydrogen ion and has adsorbed the interference to modified montmorillonite, and the sodium ion exchange speed between ammonium ion and the modified montmorillonite lamella is accelerated, and a large amount of ammonium ions get into and are adsorbed by modified montmorillonite in the system to reduce the competitive absorption of hydrogen ion and ammonium ion, thereby further promoted the efficiency that the product got rid of the ammonia nitrogen.
Detailed Description
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 30-1: 50, placing the mixture into a No. 1 beaker, stirring the mixture for 20 to 30min by using a glass rod, standing and swelling the mixture for 3 to 4h, placing the No. 1 beaker into a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving the mixture for 40 to 60min under the conditions that the temperature is 85 to 95 ℃ and the rotating speed is 300 to 500r/min, then dripping hydrochloric acid with the mass of 0.3 to 0.5 times of that of polyvinyl alcohol and the mass fraction of 20 to 30 percent into the No. 1 beaker, heating, stirring and mixing the mixture for 40 to 60min under the conditions that the temperature is 85 to 95 ℃ and the rotating speed is 300 to 500r/min, then adding crotonaldehyde with the mass of 0.3 to 0.5 times of that of polyvinyl alcohol and an acetaldehyde solution with the mass of 0.3 to 0.5 times of that of polyvinyl alcohol into the No. 1 beaker, heating, stirring and reacting the mixture for 3 to 5h under the conditions that the temperature is 85 to 95 ℃ and the rotating speed is 300 to 500r/min, then dripping sodium hydroxide solution with the mass fraction of 20 to 30 percent into the No. 1 beaker to regulate the pH value to 8.6 to 8.9, adding urea with the mass of 0.1-0.2 times that of the polyvinyl alcohol into a No. 1 beaker, and stirring and mixing for 30-50 min under the condition that the rotating speed is 600-800 r/min to obtain modified polyvinyl alcohol liquid; mixing peach gum and water according to a mass ratio of 1: 30-1: placing the No. 2 beaker in a No. 2 beaker, stirring for 20-30 min by using a glass rod, standing and swelling for 3-4 h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 40-60 min under the conditions that the temperature is 85-95 ℃ and the rotating speed is 300-500 r/min to obtain peach gum solution; mixing calcium-based montmorillonite and water according to a mass ratio of 1: 10-1: 20, placing the No. 3 beaker in a water bath, heating, stirring and mixing for 30-50 min at the temperature of 50-60 ℃ and at the rotating speed of 400-600 r/min, adding sodium carbonate which is 0.2-0.3 times of the mass of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 2-3 h at the constant temperature under the conditions of the temperature of 55 ℃ and the rotating speed of 400-600 r/min, then adding octadecyl trimethyl ammonium chloride which is 0.4-0.5 times of the mass of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 2-3 h at the constant temperature of 85 ℃ and the rotating speed of 400-600 r/min to obtain a mixed solution, placing the mixed solution in a baking oven, and drying to constant weight under the temperature of 105-110 ℃ to obtain modified montmorillonite; placing corn straws in an oven, drying to constant weight at 105-110 ℃ to obtain dried corn straws, then placing the dried corn straws in a crusher to crush the dried corn straws, and sieving the crushed corn straws with a 20-mesh sieve to obtain corn straw powder; according to the weight parts, 20-30 parts of corn straw powder, 5-8 parts of vinasse, 5-8 parts of mushroom dregs, 5-8 parts of cow dung and 20-30 parts of deionized water are placed in a fermentation kettle, mixed fermentation is carried out for 5-8 days at the temperature of 30-35 ℃ to obtain a fermentation mixed solution, the fermentation mixed solution is filtered to obtain a filter cake, the filter cake is placed in a drying oven and dried to constant weight at the temperature of 105-110 ℃ to obtain a dried filter cake, the filter cake is placed in a ball mill for ball milling, a 40-mesh sieve is used to obtain a ball grinding material, the ball grinding material is placed in a carbonization furnace, nitrogen is filled into the furnace at the speed of 60-90 mL/min, the temperature is increased to 450-650 ℃ at the temperature increasing speed of 8-10 ℃/min, and the carbonization time is 2-3 hours to obtain the carbonization material; according to the weight parts, sequentially taking 30-40 parts of modified polyvinyl alcohol solution, 50-60 parts of carbonized material, 20-30 parts of peach gum solution, 5-8 parts of glutaraldehyde solution with the mass fraction of 20-30% and 5-8 parts of hydrochloric acid with the mass fraction of 20-30%, placing the modified polyvinyl alcohol solution and the peach gum solution in a three-neck flask, placing the three-neck flask in a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing for 30-50 min at a constant temperature under the conditions that the temperature is 50-60 ℃ and the rotating speed is 300-500 r/min, sequentially adding 20-30% of hydrochloric acid, 20-30% of glutaraldehyde solution with the mass fraction and the carbonized material into the three-neck flask, stirring and mixing for 10-12 h under the conditions that the temperature is 28-38 ℃ and the rotating speed is 250-300 r/min to obtain mixed slurry, filtering the mixed slurry to obtain filter residue, washing deionized water for 5-6 days, changing deionized water every 10-12 h, and then carrying out vacuum drying on the washed filter residue for 3-5 h at room temperature to obtain pretreated biochar; according to the weight parts, 10-20 parts of modified montmorillonite, 60-80 parts of organic solvent, 20-30 parts of deionized water, 10-20 parts of pretreated biochar, 8-10 parts of ethyl orthosilicate and 5-8 parts of phospholipid are sequentially taken, the modified montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 40-60 min at the frequency of 55-75 ℃, then the deionized water is added into the No. 4 beaker, the biochar and the phospholipid are pretreated, stirring and mixing are carried out for 40-60 min at the rotating speed of 300-500 r/min, then the ethyl orthosilicate is dropwise added into the No. 4 beaker, and stirring is carried out for 48h under the rotating speed of 300-500 r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is any one of xylene, pentane, hexane, dichlorobenzene or dichloromethane. The phospholipid is any one of soybean phospholipid, yolk phospholipid or milk phospholipid.
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 50 is placed in a No. 1 beaker, stirred by a glass rod for 30min, kept stand and swelled for 4h, then the No. 1 beaker is placed in a digital display speed measurement constant temperature magnetic stirrer, heated, stirred and dissolved for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, hydrochloric acid with the mass fraction of 30 percent which is 0.5 time of the mass of polyvinyl alcohol is then dripped in the No. 1 beaker, heated, stirred and mixed for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, crotonaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol and acetaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol are then added in the No. 1 beaker, heated, stirred and reacted for 5h under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, then sodium hydroxide solution with the mass fraction of 30 percent is dripped in the No. 1 beaker to adjust the pH value to 8.9, then urea with the mass fraction of the polyvinyl alcohol is added in the No. 1 beaker, and the rotating speed is 800r/min, stirring and mixing for 50min to obtain modified polyvinyl alcohol solution; mixing peach gum and water according to a mass ratio of 1: placing the No. 2 beaker in a No. 2 beaker, stirring for 30min by a glass rod, standing and swelling for 4h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min to obtain peach gum solution; mixing calcium-based montmorillonite and water according to a mass ratio of 1: 20, placing the No. 3 beaker in a water bath, heating, stirring and mixing for 50min at the temperature of 60 ℃ and the rotating speed of 600r/min, then adding sodium carbonate with the mass of 0.3 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 55 ℃ and the rotating speed of 600r/min, then adding octadecyl trimethyl ammonium chloride with the mass of 0.5 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 85 ℃ and the rotating speed of 600r/min to obtain a mixed solution, then placing the mixed solution in a baking oven, and drying to constant weight under the temperature of 110 ℃ to obtain modified montmorillonite; placing corn stalks in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain dried corn stalks, then placing the dried corn stalks in a crusher to crush the dried corn stalks, and sieving the crushed corn stalks through a 20-mesh sieve to obtain corn stalk powder; according to the weight parts, placing 30 parts of corn straw powder, 8 parts of vinasse, 8 parts of bacterial residues, 8 parts of cow dung and 30 parts of deionized water in a fermentation kettle, mixing and fermenting for 8 days at the temperature of 35 ℃ to obtain a fermentation mixed solution, filtering the fermentation mixed solution to obtain a filter cake, then placing the filter cake in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake, then placing the filter cake in a ball mill for ball milling, sieving by a 40-mesh sieve to obtain a ball grinding material, then placing the ball grinding material in a carbonization furnace, introducing nitrogen into the furnace at the speed of 90mL/min, heating to 650 ℃ at the heating speed of 10 ℃/min, and carbonizing for 3 hours to obtain a carbonized material; taking 40 parts of modified polyvinyl alcohol liquid, 60 parts of carbonized material, 30 parts of peach gum liquid, 8 parts of glutaraldehyde solution with the mass fraction of 30% and 8 parts of hydrochloric acid with the mass fraction of 30%, placing the modified polyvinyl alcohol liquid and the peach gum liquid in a three-neck flask, placing the three-neck flask in a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing for 50min at the constant temperature under the conditions that the temperature is 60 ℃ and the rotating speed is 500r/min, sequentially adding the hydrochloric acid with the mass fraction of 30% and the glutaraldehyde solution with the mass fraction of 30% and the carbonized material in the three-neck flask, stirring and mixing for 12h under the conditions that the temperature is 38 ℃ and the rotating speed is 300r/min to obtain mixed slurry, filtering the mixed slurry to obtain filter residue, washing the filter residue with deionized water for 6 days, replacing the deionized water every 12h, then drying the washed filter residue under vacuum at room temperature for 5h, obtaining pretreated biochar; according to the weight parts, 20 parts of modified montmorillonite, 80 parts of organic solvent, 30 parts of deionized water, 20 parts of pretreated biochar, 10 parts of ethyl orthosilicate and 8 parts of phospholipid are sequentially taken, the modified montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 60min at the frequency of 75 ℃, then the deionized water is added into the No. 4 beaker, the biochar and the phospholipid are pretreated, stirring and mixing are carried out for 60min at the rotating speed of 500r/min, then the ethyl orthosilicate is dropwise added into the No. 4 beaker, and stirring is carried out continuously for 48h at the rotating speed of 500r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is xylene. The phospholipid is soybean phospholipid.
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 50 is placed in a No. 1 beaker, stirred by a glass rod for 30min, kept stand and swelled for 4h, then the No. 1 beaker is placed in a digital display speed measurement constant temperature magnetic stirrer, heated, stirred and dissolved for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, hydrochloric acid with the mass fraction of 30 percent which is 0.5 time of the mass of polyvinyl alcohol is then dripped in the No. 1 beaker, heated, stirred and mixed for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, crotonaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol and acetaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol are then added in the No. 1 beaker, heated, stirred and reacted for 5h under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, then sodium hydroxide solution with the mass fraction of 30 percent is dripped in the No. 1 beaker to adjust the pH value to 8.9, then urea with the mass fraction of the polyvinyl alcohol is added in the No. 1 beaker, and the rotating speed is 800r/min, stirring and mixing for 50min to obtain modified polyvinyl alcohol solution; mixing peach gum and water according to a mass ratio of 1: placing the No. 2 beaker in a No. 2 beaker, stirring for 30min by a glass rod, standing and swelling for 4h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min to obtain peach gum solution; mixing calcium-based montmorillonite and water according to a mass ratio of 1: 20, placing the No. 3 beaker in a water bath, heating, stirring and mixing for 50min at the temperature of 60 ℃ and the rotating speed of 600r/min, then adding sodium carbonate with the mass of 0.3 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 55 ℃ and the rotating speed of 600r/min, then adding octadecyl trimethyl ammonium chloride with the mass of 0.5 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 85 ℃ and the rotating speed of 600r/min to obtain a mixed solution, then placing the mixed solution in a baking oven, and drying to constant weight under the temperature of 110 ℃ to obtain modified montmorillonite; placing corn stalks in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain dried corn stalks, then placing the dried corn stalks in a crusher to crush the dried corn stalks, and sieving the crushed corn stalks through a 20-mesh sieve to obtain corn stalk powder; according to the weight parts, placing 30 parts of corn straw powder, 8 parts of bacterial residues, 8 parts of cow dung and 30 parts of deionized water into a fermentation kettle, mixing and fermenting for 8 days at the temperature of 35 ℃ to obtain a fermentation mixed solution, filtering the fermentation mixed solution to obtain a filter cake, then placing the filter cake into a drying oven, drying the filter cake to constant weight at the temperature of 110 ℃ to obtain a dried filter cake, then placing the filter cake into a ball mill for ball milling, sieving by a 40-mesh sieve to obtain a ball grinding material, then placing the ball grinding material into a carbonization furnace, filling nitrogen into the furnace at the speed of 90mL/min, heating to 650 ℃ at the heating rate of 10 ℃/min, and carbonizing for 3 hours to obtain a carbonized material; taking 40 parts of modified polyvinyl alcohol liquid, 60 parts of carbonized material, 30 parts of peach gum liquid, 8 parts of glutaraldehyde solution with the mass fraction of 30% and 8 parts of hydrochloric acid with the mass fraction of 30%, placing the modified polyvinyl alcohol liquid and the peach gum liquid in a three-neck flask, placing the three-neck flask in a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing for 50min at the constant temperature under the conditions that the temperature is 60 ℃ and the rotating speed is 500r/min, sequentially adding the hydrochloric acid with the mass fraction of 30% and the glutaraldehyde solution with the mass fraction of 30% and the carbonized material in the three-neck flask, stirring and mixing for 12h under the conditions that the temperature is 38 ℃ and the rotating speed is 300r/min to obtain mixed slurry, filtering the mixed slurry to obtain filter residue, washing the filter residue with deionized water for 6 days, replacing the deionized water every 12h, then drying the washed filter residue under vacuum at room temperature for 5h, obtaining pretreated biochar; according to the weight parts, 20 parts of modified montmorillonite, 80 parts of organic solvent, 30 parts of deionized water, 20 parts of pretreated biochar, 10 parts of ethyl orthosilicate and 8 parts of phospholipid are sequentially taken, the modified montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 60min at the frequency of 75 ℃, then the deionized water is added into the No. 4 beaker, the biochar and the phospholipid are pretreated, stirring and mixing are carried out for 60min at the rotating speed of 500r/min, then the ethyl orthosilicate is dropwise added into the No. 4 beaker, and stirring is carried out continuously for 48h at the rotating speed of 500r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is xylene. The phospholipid is soybean phospholipid.
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 50 is placed in a No. 1 beaker, stirred by a glass rod for 30min, kept stand and swelled for 4h, then the No. 1 beaker is placed in a digital display speed measurement constant temperature magnetic stirrer, heated, stirred and dissolved for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, hydrochloric acid with the mass fraction of 30 percent which is 0.5 time of the mass of polyvinyl alcohol is then dripped in the No. 1 beaker, heated, stirred and mixed for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, crotonaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol and acetaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol are then added in the No. 1 beaker, heated, stirred and reacted for 5h under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, then sodium hydroxide solution with the mass fraction of 30 percent is dripped in the No. 1 beaker to adjust the pH value to 8.9, then urea with the mass fraction of the polyvinyl alcohol is added in the No. 1 beaker, and the rotating speed is 800r/min, stirring and mixing for 50min to obtain modified polyvinyl alcohol solution; mixing peach gum and water according to a mass ratio of 1: placing the No. 2 beaker in a No. 2 beaker, stirring for 30min by a glass rod, standing and swelling for 4h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min to obtain peach gum solution; mixing calcium-based montmorillonite and water according to a mass ratio of 1: 20, placing the No. 3 beaker in a water bath, heating, stirring and mixing for 50min at the temperature of 60 ℃ and the rotating speed of 600r/min, then adding sodium carbonate with the mass of 0.3 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 55 ℃ and the rotating speed of 600r/min, then adding octadecyl trimethyl ammonium chloride with the mass of 0.5 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 85 ℃ and the rotating speed of 600r/min to obtain a mixed solution, then placing the mixed solution in a baking oven, and drying to constant weight under the temperature of 110 ℃ to obtain modified montmorillonite; placing corn stalks in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain dried corn stalks, then placing the dried corn stalks in a crusher to crush the dried corn stalks, and sieving the crushed corn stalks through a 20-mesh sieve to obtain corn stalk powder; according to the weight parts, placing 30 parts of corn straw powder, 8 parts of vinasse, 8 parts of cow dung and 30 parts of deionized water into a fermentation kettle, mixing and fermenting for 8 days at the temperature of 35 ℃ to obtain a fermentation mixed solution, filtering the fermentation mixed solution to obtain a filter cake, then placing the filter cake into a drying oven, drying the filter cake to constant weight at the temperature of 110 ℃ to obtain a dried filter cake, then placing the filter cake into a ball mill for ball milling, sieving by a 40-mesh sieve to obtain a ball grinding material, then placing the ball grinding material into a carbonization furnace, filling nitrogen into the furnace at the speed of 90mL/min, heating to 650 ℃ at the heating rate of 10 ℃/min, and carbonizing for 3 hours to obtain a carbonization material; taking 40 parts of modified polyvinyl alcohol liquid, 60 parts of carbonized material, 30 parts of peach gum liquid, 8 parts of glutaraldehyde solution with the mass fraction of 30% and 8 parts of hydrochloric acid with the mass fraction of 30%, placing the modified polyvinyl alcohol liquid and the peach gum liquid in a three-neck flask, placing the three-neck flask in a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing for 50min at the constant temperature under the conditions that the temperature is 60 ℃ and the rotating speed is 500r/min, sequentially adding the hydrochloric acid with the mass fraction of 30% and the glutaraldehyde solution with the mass fraction of 30% and the carbonized material in the three-neck flask, stirring and mixing for 12h under the conditions that the temperature is 38 ℃ and the rotating speed is 300r/min to obtain mixed slurry, filtering the mixed slurry to obtain filter residue, washing the filter residue with deionized water for 6 days, replacing the deionized water every 12h, then drying the washed filter residue under vacuum at room temperature for 5h, obtaining pretreated biochar; according to the weight parts, 20 parts of modified montmorillonite, 80 parts of organic solvent, 30 parts of deionized water, 20 parts of pretreated biochar, 10 parts of ethyl orthosilicate and 8 parts of phospholipid are sequentially taken, the modified montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 60min at the frequency of 75 ℃, then the deionized water is added into the No. 4 beaker, the biochar and the phospholipid are pretreated, stirring and mixing are carried out for 60min at the rotating speed of 500r/min, then the ethyl orthosilicate is dropwise added into the No. 4 beaker, and stirring is carried out continuously for 48h at the rotating speed of 500r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is xylene. The phospholipid is soybean phospholipid.
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 50 is placed in a No. 1 beaker, stirred by a glass rod for 30min, kept stand and swelled for 4h, then the No. 1 beaker is placed in a digital display speed measurement constant temperature magnetic stirrer, heated, stirred and dissolved for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, hydrochloric acid with the mass fraction of 30 percent which is 0.5 time of the mass of polyvinyl alcohol is then dripped in the No. 1 beaker, heated, stirred and mixed for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, crotonaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol and acetaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol are then added in the No. 1 beaker, heated, stirred and reacted for 5h under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, then sodium hydroxide solution with the mass fraction of 30 percent is dripped in the No. 1 beaker to adjust the pH value to 8.9, then urea with the mass fraction of the polyvinyl alcohol is added in the No. 1 beaker, and the rotating speed is 800r/min, stirring and mixing for 50min to obtain modified polyvinyl alcohol solution; mixing peach gum and water according to a mass ratio of 1: placing the No. 2 beaker in a No. 2 beaker, stirring for 30min by a glass rod, standing and swelling for 4h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min to obtain peach gum solution; mixing calcium-based montmorillonite and water according to a mass ratio of 1: 20, placing the No. 3 beaker in a water bath, heating, stirring and mixing for 50min at the temperature of 60 ℃ and the rotating speed of 600r/min, then adding sodium carbonate with the mass of 0.3 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 55 ℃ and the rotating speed of 600r/min, then adding octadecyl trimethyl ammonium chloride with the mass of 0.5 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 85 ℃ and the rotating speed of 600r/min to obtain a mixed solution, then placing the mixed solution in a baking oven, and drying to constant weight under the temperature of 110 ℃ to obtain modified montmorillonite; placing corn stalks in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain dried corn stalks, then placing the dried corn stalks in a crusher to crush the dried corn stalks, and sieving the crushed corn stalks through a 20-mesh sieve to obtain corn stalk powder; according to the weight parts, placing 30 parts of corn straw powder, 8 parts of vinasse, 8 parts of bacterial residues, 8 parts of cow dung and 30 parts of deionized water in a fermentation kettle, mixing and fermenting for 8 days at the temperature of 35 ℃ to obtain a fermentation mixed solution, filtering the fermentation mixed solution to obtain a filter cake, then placing the filter cake in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake, then placing the filter cake in a ball mill for ball milling, sieving by a 40-mesh sieve to obtain a ball grinding material, then placing the ball grinding material in a carbonization furnace, introducing nitrogen into the furnace at the speed of 90mL/min, heating to 650 ℃ at the heating speed of 10 ℃/min, and carbonizing for 3 hours to obtain a carbonized material; according to the weight parts, 20 parts of modified montmorillonite, 80 parts of organic solvent, 30 parts of deionized water, 20 parts of carbonized material, 10 parts of ethyl orthosilicate and 8 parts of phospholipid are sequentially taken, the modified montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 60min under the condition that the frequency is 75 ℃, then the deionized water, the carbonized material and the phospholipid are added into the No. 4 beaker, the mixture is stirred and mixed for 60min under the condition that the rotating speed is 500r/min, then the ethyl orthosilicate is added into the No. 4 beaker in a dropwise mode, and the mixture is continuously stirred for 48h under the condition that the rotating speed is 500r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is xylene. The phospholipid is soybean phospholipid.
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 50 is placed in a No. 1 beaker, stirred by a glass rod for 30min, kept stand and swelled for 4h, then the No. 1 beaker is placed in a digital display speed measurement constant temperature magnetic stirrer, heated, stirred and dissolved for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, hydrochloric acid with the mass fraction of 30 percent which is 0.5 time of the mass of polyvinyl alcohol is then dripped in the No. 1 beaker, heated, stirred and mixed for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, crotonaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol and acetaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol are then added in the No. 1 beaker, heated, stirred and reacted for 5h under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, then sodium hydroxide solution with the mass fraction of 30 percent is dripped in the No. 1 beaker to adjust the pH value to 8.9, then urea with the mass fraction of the polyvinyl alcohol is added in the No. 1 beaker, and the rotating speed is 800r/min, stirring and mixing for 50min to obtain modified polyvinyl alcohol solution; mixing peach gum and water according to a mass ratio of 1: placing the No. 2 beaker in a No. 2 beaker, stirring for 30min by a glass rod, standing and swelling for 4h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min to obtain peach gum solution; placing corn stalks in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain dried corn stalks, then placing the dried corn stalks in a crusher to crush the dried corn stalks, and sieving the crushed corn stalks through a 20-mesh sieve to obtain corn stalk powder; according to the weight parts, placing 30 parts of corn straw powder, 8 parts of vinasse, 8 parts of bacterial residues, 8 parts of cow dung and 30 parts of deionized water in a fermentation kettle, mixing and fermenting for 8 days at the temperature of 35 ℃ to obtain a fermentation mixed solution, filtering the fermentation mixed solution to obtain a filter cake, then placing the filter cake in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake, then placing the filter cake in a ball mill for ball milling, sieving by a 40-mesh sieve to obtain a ball grinding material, then placing the ball grinding material in a carbonization furnace, introducing nitrogen into the furnace at the speed of 90mL/min, heating to 650 ℃ at the heating speed of 10 ℃/min, and carbonizing for 3 hours to obtain a carbonized material; taking 40 parts of modified polyvinyl alcohol liquid, 60 parts of carbonized material, 30 parts of peach gum liquid, 8 parts of glutaraldehyde solution with the mass fraction of 30% and 8 parts of hydrochloric acid with the mass fraction of 30%, placing the modified polyvinyl alcohol liquid and the peach gum liquid in a three-neck flask, placing the three-neck flask in a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing for 50min at the constant temperature under the conditions that the temperature is 60 ℃ and the rotating speed is 500r/min, sequentially adding the hydrochloric acid with the mass fraction of 30% and the glutaraldehyde solution with the mass fraction of 30% and the carbonized material in the three-neck flask, stirring and mixing for 12h under the conditions that the temperature is 38 ℃ and the rotating speed is 300r/min to obtain mixed slurry, filtering the mixed slurry to obtain filter residue, washing the filter residue with deionized water for 6 days, replacing the deionized water every 12h, then drying the washed filter residue under vacuum at room temperature for 5h, obtaining pretreated biochar; according to the weight parts, 20 parts of montmorillonite, 80 parts of organic solvent, 30 parts of deionized water, 20 parts of pretreated biochar, 10 parts of ethyl orthosilicate and 8 parts of phospholipid are sequentially taken, the montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 60min at the frequency of 75 ℃, then the deionized water is added into the No. 4 beaker, the biochar and the phospholipid are pretreated, stirring and mixing are carried out for 60min at the rotating speed of 500r/min, then the ethyl orthosilicate is dropwise added into the No. 4 beaker, and stirring is carried out for 48h at the rotating speed of 500r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is xylene. The phospholipid is soybean phospholipid.
Mixing polyvinyl alcohol and water according to a mass ratio of 1: 50 is placed in a No. 1 beaker, stirred by a glass rod for 30min, kept stand and swelled for 4h, then the No. 1 beaker is placed in a digital display speed measurement constant temperature magnetic stirrer, heated, stirred and dissolved for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, hydrochloric acid with the mass fraction of 30 percent which is 0.5 time of the mass of polyvinyl alcohol is then dripped in the No. 1 beaker, heated, stirred and mixed for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, crotonaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol and acetaldehyde with the mass fraction of 0.5 time of the mass of the polyvinyl alcohol are then added in the No. 1 beaker, heated, stirred and reacted for 5h under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min, then sodium hydroxide solution with the mass fraction of 30 percent is dripped in the No. 1 beaker to adjust the pH value to 8.9, then urea with the mass fraction of the polyvinyl alcohol is added in the No. 1 beaker, and the rotating speed is 800r/min, stirring and mixing for 50min to obtain modified polyvinyl alcohol solution; mixing peach gum and water according to a mass ratio of 1: placing the No. 2 beaker in a No. 2 beaker, stirring for 30min by a glass rod, standing and swelling for 4h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, and heating, stirring and dissolving for 60min under the conditions that the temperature is 95 ℃ and the rotating speed is 500r/min to obtain peach gum solution; mixing calcium-based montmorillonite and water according to a mass ratio of 1: 20, placing the No. 3 beaker in a water bath, heating, stirring and mixing for 50min at the temperature of 60 ℃ and the rotating speed of 600r/min, then adding sodium carbonate with the mass of 0.3 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 55 ℃ and the rotating speed of 600r/min, then adding octadecyl trimethyl ammonium chloride with the mass of 0.5 time that of the calcium-based montmorillonite into the No. 3 beaker, stirring and reacting for 3h at the constant temperature of 85 ℃ and the rotating speed of 600r/min to obtain a mixed solution, then placing the mixed solution in a baking oven, and drying to constant weight under the temperature of 110 ℃ to obtain modified montmorillonite; placing corn stalks in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain dried corn stalks, then placing the dried corn stalks in a crusher to crush the dried corn stalks, and sieving the crushed corn stalks through a 20-mesh sieve to obtain corn stalk powder; according to the weight parts, placing 30 parts of corn straw powder, 8 parts of vinasse, 8 parts of bacterial residues, 8 parts of cow dung and 30 parts of deionized water in a fermentation kettle, mixing and fermenting for 8 days at the temperature of 35 ℃ to obtain a fermentation mixed solution, filtering the fermentation mixed solution to obtain a filter cake, then placing the filter cake in a drying oven, drying to constant weight at the temperature of 110 ℃ to obtain a dried filter cake, then placing the filter cake in a ball mill for ball milling, sieving by a 40-mesh sieve to obtain a ball grinding material, then placing the ball grinding material in a carbonization furnace, introducing nitrogen into the furnace at the speed of 90mL/min, heating to 650 ℃ at the heating speed of 10 ℃/min, and carbonizing for 3 hours to obtain a carbonized material; taking 40 parts of modified polyvinyl alcohol liquid, 60 parts of carbonized material, 30 parts of peach gum liquid, 8 parts of glutaraldehyde solution with the mass fraction of 30% and 8 parts of hydrochloric acid with the mass fraction of 30%, placing the modified polyvinyl alcohol liquid and the peach gum liquid in a three-neck flask, placing the three-neck flask in a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing for 50min at the constant temperature under the conditions that the temperature is 60 ℃ and the rotating speed is 500r/min, sequentially adding the hydrochloric acid with the mass fraction of 30% and the glutaraldehyde solution with the mass fraction of 30% and the carbonized material in the three-neck flask, stirring and mixing for 12h under the conditions that the temperature is 38 ℃ and the rotating speed is 300r/min to obtain mixed slurry, filtering the mixed slurry to obtain filter residue, washing the filter residue with deionized water for 6 days, replacing the deionized water every 12h, then drying the washed filter residue under vacuum at room temperature for 5h, obtaining pretreated biochar; according to the weight parts, 20 parts of modified montmorillonite, 80 parts of organic solvent, 30 parts of deionized water, 20 parts of pretreated biochar and 10 parts of ethyl orthosilicate are sequentially taken, the modified montmorillonite and the organic solvent are placed in a No. 4 beaker, the No. 4 beaker is placed in an ultrasonic dispersion instrument, ultrasonic mixing is carried out for 60min at the frequency of 75 ℃, then the deionized water is added into the No. 4 beaker, the biochar is pretreated, stirring and mixing are carried out for 60min at the rotating speed of 500r/min, then the ethyl orthosilicate is dropwise added into the No. 4 beaker, and stirring is carried out continuously for 48h at the rotating speed of 500r/min, so that the corn straw biochar-based composite adsorbent is obtained. The organic solvent is xylene.
Comparative example: adsorbent produced by environmental protection technology ltd, changzhou.
The charcoal adsorbents obtained in examples 1 to 6 and comparative products were subjected to performance tests, and the specific test methods were as follows:
adsorption capacity (q) of biochar to ammonia nitrogene) And the method for calculating the adsorption efficiency (eta) is as follows:
qe=(c0-ce)V/1000m (1)
η=(c0-ce)/c0×100% (2)
in the formula: q. q.seThe adsorption capacity of the biochar to ammonia nitrogen is mg/g; v is the volume of the solution, mL; m is the mass of the biochar, g; c. C0And ceRespectively the initial concentration and the equilibrium concentration of ammonia nitrogen in the solution, mg/L; eta is adsorption efficiency,%.
Specific detection results are shown in table 1:
table 1: performance test meter
Detecting content
|
Example 1
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Example 2
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Example 3
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Example 4
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Example 5
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Example 6
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Comparative example
|
qe/mg/g
|
3.89
|
2.75
|
2.78
|
2.66
|
2.72
|
2.81
|
1.82
|
η/%
|
42.3
|
35.2
|
36.5
|
30.8
|
34.3
|
37.1
|
25.4 |
The detection results in table 1 show that the corn straw biochar-based composite adsorbent has excellent adsorption efficiency on ammonia nitrogen in acidic wastewater.