Disclosure of Invention
In order to achieve the above purpose, the present invention provides a surface modification method of biomass carbon material, which aims to solve the defects of the prior art.
The invention discloses a surface modification method of a biomass carbon material, which is characterized in that biomass is used as a raw material, the biomass carbon material is treated by low-temperature plasma discharge, and the surface modified biomass carbon material is prepared, and the method specifically comprises the following steps:
step 1: drying, crushing and sieving biomass to obtain biomass powder;
step 2: isolating the biomass powder from air, and performing pyrolysis to obtain a biomass carbon material; controlling cracking parameters: heating from room temperature to a cracking temperature of 800-1200 ℃ at a heating rate of 5-15 ℃/min, and then preserving heat for 2-4 h;
and step 3: ball milling the biomass carbon material for 3-6 h at a ball milling rotating speed of 200-600 rpm;
and 4, step 4: and placing the ball-milled biomass carbon material in a reaction cavity in low-temperature plasma, vacuumizing until the air pressure is stabilized at 30-60Pa, introducing inert gas, discharging the low-temperature plasma in the inert atmosphere, and performing surface treatment on the ball-milled biomass carbon material for 15-60 min to obtain the surface-modified biomass carbon material.
The power of the low-temperature plasma discharge is 50-300W.
The inert gas is nitrogen or argon.
The biomass carbon material is used as a catalyst to activate persulfate so as to degrade organic pollutants in a water body.
The invention has the beneficial effects that: the preparation method is simple, mild in condition, green and environment-friendly, is easy for large-scale production, and is beneficial to popularization and application. The prepared biomass carbon material is used as a catalyst, can effectively activate persulfate in a water body for degrading organic pollutants, and has a good catalytic degradation effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
Drying, crushing and sieving the camellia oleifera shells to obtain biomass powder; carrying out anaerobic pyrolysis on the biomass powder at 800 ℃, heating the biomass powder from room temperature to a preset pyrolysis temperature at a heating rate of 5 ℃/min, and carrying out heat preservation for 2h after heating to the preset pyrolysis temperature to obtain a biomass carbon material; performing ball milling treatment on the biomass carbon material, wherein the ball milling rotation speed is 200rpm, and the ball milling time is 3 h; and placing the ball-milled biomass carbon material in a reaction cavity in low-temperature plasma, vacuumizing until the air pressure is stabilized at 30Pa, introducing nitrogen, and performing low-temperature plasma discharge treatment for 15min at the discharge power of 50w to obtain the surface-treated biomass carbon material.
The biomass carbon material after surface treatment is applied to the treatment of tetracycline-containing wastewater, and a comparison test is carried out:
100ml of tetracycline wastewater with the concentration of 20mg/L is respectively placed in three beakers, and the three beakers are placed in a bath kettle to be continuously stirred at room temperature, wherein the temperature is always kept at 30 ℃, and the stirring speed is 400 rmp.
0.1g of oxone was added to each of three beakers containing tetracycline wastewater, and then 40mg of untreated biomass carbon material, ball-milled biomass carbon material, and ball-milled and plasma-discharged biomass carbon material were added thereto.
2.5ml of the solution was sampled at a constant time interval under conditions of 30 ℃ and a stirring speed of 400rmp, the obtained sample was filtered, and the obtained clear solution was immediately added to a methanol solution to quench and terminate the reaction.
Experiments show that: after quenching and reaction termination after 75min, the degradation rates of tetracycline are respectively 52.2% (biomass carbon material without ball milling before treatment), 51.1% (biomass carbon material after ball milling treatment) and 73.5% (biomass carbon material after plasma discharge treatment), which indicates that the biomass carbon material after plasma discharge treatment has significant effect in treating wastewater containing tetracycline.
Example 2
Drying, crushing and screening passion fruit shells to obtain biomass powder; carrying out anaerobic pyrolysis on the biomass powder at 900 ℃, heating the biomass powder from room temperature to a preset pyrolysis temperature at a heating rate of 7 ℃/min, and carrying out heat preservation for 2.5h after heating to the preset pyrolysis temperature to obtain a biomass carbon material; performing ball milling treatment on the biomass carbon material, wherein the ball milling rotation speed is 300rpm, and the ball milling time is 3.5 h; placing the ball-milled biomass carbon material in a reaction cavity in low-temperature plasma, vacuumizing until the air pressure is stabilized at 35Pa, introducing nitrogen, and performing low-temperature plasma discharge treatment for 30min to obtain the biomass carbon material rich in surface defects; the power of the low-temperature plasma discharge was 100 w.
The biomass carbon material after surface treatment is applied to the treatment of tetracycline-containing wastewater, and a comparison test is carried out:
100ml of tetracycline wastewater with the concentration of 20mg/L is respectively placed in three beakers, and the three beakers are placed in a bath kettle to be continuously stirred at room temperature, wherein the temperature is always kept at 30 ℃, and the stirring speed is 400 rmp.
0.1g of oxone was added to each of three beakers containing tetracycline wastewater, and then 40mg of untreated biomass carbon material, ball-milled biomass carbon material, and ball-milled and plasma-discharged biomass carbon material were added thereto.
2.5ml of the solution was sampled at a constant time interval under conditions of 30 ℃ and a stirring speed of 400rmp, the obtained sample was filtered, and the obtained clear solution was immediately added to a methanol solution to quench and terminate the reaction.
Experiments show that: after quenching and reaction termination after 75min, the degradation rates of tetracycline are 67.4% (biomass carbon material without ball milling), 66.6% (biomass carbon material subjected to ball milling) and 87.2% (biomass carbon material subjected to plasma discharge treatment), respectively, which indicates that the effect of the biomass carbon material subjected to plasma discharge treatment on tetracycline-containing wastewater treatment is remarkable.
Example 3
Drying, crushing and sieving the peanut shells to obtain biomass powder; carrying out anaerobic pyrolysis on the biomass powder at 1000 ℃, heating the biomass powder from room temperature to a preset pyrolysis temperature at a heating rate of 10 ℃/min, and carrying out heat preservation for 3h after heating to the preset pyrolysis temperature to obtain a biomass carbon material; performing ball milling treatment on the biomass carbon material, wherein the ball milling rotation speed is 400rpm, and the ball milling time is 4 h; placing the ball-milled biomass carbon material in a reaction cavity in low-temperature plasma, vacuumizing until the air pressure is stabilized at 40Pa, introducing nitrogen, and performing low-temperature plasma discharge treatment for 40min to obtain the biomass carbon material rich in surface defects; the power of the low-temperature plasma discharge was 150 w.
The biomass carbon material after surface treatment is applied to the treatment of tetracycline-containing wastewater, and a comparison test is carried out:
100ml of tetracycline wastewater with the concentration of 20mg/L is respectively placed in three beakers, and the three beakers are placed in a bath kettle to be continuously stirred at room temperature, wherein the temperature is always kept at 30 ℃, and the stirring speed is 400 rmp.
0.1g of oxone was added to each of three beakers containing tetracycline wastewater, and then 40mg of untreated biomass carbon material, ball-milled biomass carbon material, and ball-milled and plasma-discharged biomass carbon material were added thereto.
2.5ml of the solution was sampled at a constant time interval under conditions of 30 ℃ and a stirring speed of 400rmp, the obtained sample was filtered, and the obtained clear solution was immediately added to a methanol solution to quench and terminate the reaction.
Experiments show that: after quenching and reaction termination after 75min, the degradation rates of tetracycline are respectively 75.9% (biomass carbon material without ball milling), 75.5% (biomass carbon material subjected to ball milling) and 95.1% (biomass carbon material subjected to plasma discharge treatment), which indicates that the biomass carbon material subjected to plasma discharge treatment has a remarkable effect in treating wastewater containing tetracycline.
Example 4
Drying, crushing and sieving the camellia oleifera shells to obtain biomass powder; carrying out anaerobic pyrolysis on the biomass powder at 1100 ℃, heating the biomass powder from room temperature to a preset pyrolysis temperature at a heating rate of 12 ℃/min, heating the biomass powder to the preset pyrolysis temperature, and then preserving heat for 3.5h to obtain a biomass carbon material; performing ball milling treatment on the biomass carbon material, wherein the ball milling rotation speed is 500rpm, and the ball milling time is 5 h; placing the ball-milled biomass carbon material in a reaction cavity in low-temperature plasma, vacuumizing until the air pressure is stabilized at 50Pa, introducing nitrogen, and performing low-temperature plasma discharge treatment for 50min to obtain the biomass carbon material rich in surface defects; the power of the low-temperature plasma discharge was 200 w.
The biomass carbon material after surface treatment is applied to the treatment of tetracycline-containing wastewater, and a comparison test is carried out:
100ml of tetracycline wastewater with the concentration of 20mg/L is respectively placed in three beakers, and the three beakers are placed in a bath kettle to be continuously stirred at room temperature, wherein the temperature is always kept at 30 ℃, and the stirring speed is 400 rmp.
0.1g of oxone was added to each of three beakers containing tetracycline wastewater, and then 40mg of untreated biomass carbon material, ball-milled biomass carbon material, and ball-milled and plasma-discharged biomass carbon material were added thereto.
2.5ml of the solution was sampled at a constant time interval under conditions of 30 ℃ and a stirring speed of 400rmp, the obtained sample was filtered, and the obtained clear solution was immediately added to a methanol solution to quench and terminate the reaction.
Experiments show that: after quenching and reaction termination after 75min, the degradation rates of tetracycline are respectively 68.7% (biomass carbon material without ball milling), 70.1% (biomass carbon material subjected to ball milling) and 90.2% (biomass carbon material subjected to plasma discharge treatment), which indicates that the effect of the biomass carbon material subjected to plasma discharge treatment on tetracycline-containing wastewater treatment is remarkable.
Example 5
Drying, crushing and screening passion fruit shells to obtain biomass powder; carrying out anaerobic pyrolysis on the biomass powder at 1200 ℃, heating the biomass powder from room temperature to a preset pyrolysis temperature at a heating rate of 15 ℃/min, and keeping the temperature for 4h after heating to the preset pyrolysis temperature to obtain a biomass carbon material; performing ball milling treatment on the biomass carbon material, wherein the ball milling rotation speed is 600rpm, and the ball milling time is 6 hours; placing the ball-milled biomass carbon material in a reaction cavity in low-temperature plasma, vacuumizing until the air pressure is stabilized at 60Pa, introducing nitrogen, and performing low-temperature plasma discharge treatment for 60min to obtain the biomass carbon material rich in surface defects; the power of the low-temperature plasma discharge was 300 w.
The biomass carbon material after surface treatment is applied to the treatment of tetracycline-containing wastewater, and a comparison test is carried out:
100ml of tetracycline wastewater with the concentration of 20mg/L is respectively placed in three beakers, and the three beakers are placed in a bath kettle to be continuously stirred at room temperature, wherein the temperature is always kept at 30 ℃, and the stirring speed is 400 rmp.
0.1g of oxone was added to each of three beakers containing tetracycline wastewater, and then 40mg of untreated biomass carbon material, ball-milled biomass carbon material, and ball-milled and plasma-discharged biomass carbon material were added thereto.
2.5ml of the solution was sampled at a constant time interval under conditions of 30 ℃ and a stirring speed of 400rmp, the obtained sample was filtered, and the obtained clear solution was immediately added to a methanol solution to quench and terminate the reaction.
Experiments show that: after quenching and reaction termination after 75min, the degradation rates of tetracycline are 72.1% (biomass carbon material without ball milling), 70.9% (biomass carbon material subjected to ball milling) and 92.2% (biomass carbon material subjected to plasma discharge treatment), respectively, which indicates that the effect of the biomass carbon material subjected to plasma discharge treatment on tetracycline-containing wastewater treatment is remarkable.