CN112090399A - Biological modified micron magnetic charcoal adsorbent and preparation method and application thereof - Google Patents
Biological modified micron magnetic charcoal adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a biological modified micron magnetic charcoal adsorbent and a preparation method and application thereof, belonging to the field of charcoal materials. According to the invention, corn straw biomass is used as a raw material, biologically treated corn straw is obtained through fermentation, then anaerobic pyrolysis is carried out to prepare biologically modified biochar, then the magnetism is given through a method of fusing nano ferroferric oxide and the biologically modified biochar through ethanol, the biologically modified magnetic biochar is obtained through vacuum drying, the particle size fraction of an adsorbent is further reduced through a mechanical ball milling process, and finally the biologically modified micron magnetic biochar adsorbent is prepared. The method has the advantages of low cost, simple and convenient operation, high treatment efficiency, easy recovery, no secondary pollution and the like, realizes the resource utilization of the biomass, and can be applied to the removal of heavy metals in industrial and agricultural wastewater.
Description
Technical Field
The invention belongs to the field of biochar materials, and particularly relates to a biologically modified micron magnetic biochar adsorbent as well as a preparation method and application thereof.
Background
Heavy metal pollution of water bodies becomes an increasingly serious environmental problem, and not only is aquatic ecological environment damaged, but also human health is damaged through a food chain. Therefore, it is very important to find an efficient and environment-friendly method for treating the wastewater containing Cd and other toxic heavy metals to ensure that the wastewater reaches the discharge standard. The adsorption method is one of the main methods for treating heavy metal wastewater, and has the advantages of high efficiency, simplicity, convenience, high selectivity and the like. The development of cheap and efficient water treatment adsorbing materials is an important direction for sewage treatment, and the separation, regeneration and secondary pollution of the adsorbing agent are problems which are urgently needed to be solved in the treatment of heavy metal wastewater by an adsorption method.
The biochar has the characteristics of rich carbon, porous structure, large specific surface area and the like, is an economic and environment-friendly heavy metal adsorbent, but has poor adsorption capacity without modification, and has the problems of unstable adsorption, difficulty in separation or regeneration and the like, so that the application of the biochar is limited. Common modification methods are physical, chemical and biological methods.
The biological modification of the biochar is to utilize a biological pretreated biomass raw material to prepare the biochar through digestion or bacterial conversion treatment. It has been found that biological modification can change the oxidation-reduction potential and pH value of raw material, so as to increase the pH, specific surface area, Cation Exchange Capacity (CEC), hydrophobicity and surface negative charge of modified biochar, thereby improving its adsorption capacity to heavy metal. But the biological modification can not solve the problem that the separation and regeneration of the biochar in the heavy metal wastewater treatment are difficult.
Iron oxide has outstanding adsorption capacity and large specific surface area, and is widely researched at present. The magnetic modification is a common biochar chemical modification means, and researches show that the adsorbent is subjected to surface modification by using magnetic iron oxide, so that the heavy metal ions in the wastewater can be quickly and efficiently adsorbed and removed, and meanwhile, the adsorbent can be conveniently recycled, is good in reusability and shows good application prospects. The invention patent with the application number of 201610360584.2 discloses a preparation method of magnetic chaff biochar for removing lead and cadmium in water body, which uses FeCl3And FeCl2Dissolving in HCl solution, mixing with biochar and ammonia water solution, and precipitating to obtain magnetic rice husk biochar. The invention patent with the application number of 201910745086.3 discloses a preparation method and application of a biochar/iron oxide composite material, and iron oxide particles are loaded on the surface of the biochar by adopting a coprecipitation method. The coprecipitation method has certain defects, including the problems that the preparation steps are too complicated, the required chemical agent amount is large, the redundant waste liquid has secondary pollution and the like.
At present, the modification methods of the biochar are reported more, but the single modification method is mainly used. Meanwhile, the technology for preparing the novel magnetic biochar adsorbent and applying the adsorbent to cadmium-polluted wastewater treatment does not exist, wherein the adsorption quantity is improved, the problems of difficult separation and regeneration, coprecipitation defects and the like are solved, and various modification methods are coupled.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a coupling biological modification and magnetic modification method, wherein a mechanochemical method is used for preparing a micron magnetic biochar adsorbent for removing cadmium in sewage.
In order to achieve the purpose, corn straws are biologically modified through fermentation liquor, biologically modified biochar is prepared through a slow pyrolysis method, nano ferroferric oxide is used for magnetizing the biologically modified biochar, and micron magnetic biochar microspheres are further obtained through a ball milling method.
The invention adopts the following specific technical scheme:
a preparation method of a biological modified micron magnetic charcoal adsorbent specifically comprises the following steps:
(1) washing fresh corn stalks with distilled water for three times, cutting the washed fresh corn stalks into 2-3cm long corn stalks, and performing fermentation treatment for 30 days by using a fermentation microbial inoculum to obtain biologically treated corn stalks;
(2) drying the biologically treated corn straw until the biologically treated corn straw is completely dried, crushing and sieving to obtain biologically treated corn straw powder biomass;
(3) placing the prepared corn straw powder biomass in a tubular furnace protected by nitrogen, pyrolyzing the biomass to be carbonized at the temperature of 300-500 ℃, cooling, crushing and sieving to obtain the corn straw biological modified charcoal;
(4) mixing the prepared corn straw biological modified biochar with nano ferroferric oxide according to a mass ratio of 1: 1, mixing according to a solid-liquid ratio of 1: 10 adding an organic solvent ethanol, carrying out ultrasonic treatment on the mixed substance to prevent the nano ferroferric oxide from agglomerating, and then carrying out magnetic stirring to fully mix the nano ferroferric oxide and the nano ferroferric oxide;
(5) centrifuging the obtained mixture, pouring out supernatant, washing residual solid for multiple times by using distilled water, taking out the solid matter, and performing vacuum freezing at the temperature of-20 to-l 0 ℃ until the solid matter is completely dried to obtain the biological modified magnetic biochar material;
(6) and (3) performing mechanical ball milling and crushing treatment on the magnetic biochar material for 30-120min to obtain the biological modified micron magnetic biochar adsorbent.
Preferably, the composition and proportion of the fermentation inoculum in the step (1) are as follows: 0.5 percent of beer yeast, 0.2 percent of calcium carbonate and 0.1 percent of sodium chloride;
preferably, the drying temperature in the step (2) is 65 ℃, and the crushed materials are sieved by a 2mm sieve;
preferably, in the step (3), the mixture is heated to a constant temperature at a heating rate of 10 ℃/min, pyrolyzed for 2 hours, naturally cooled to room temperature, ground and then sieved by a 0.5 mm sieve;
preferably, the ultrasonic treatment time in the step (4) is 2 hours, and the magnetic stirring time is 4 hours;
preferably, the pyrolysis temperature in step (6) is 500 ℃; the mechanical ball milling and crushing treatment time in the step 4) is 120 min.
The invention also aims to provide an application of the biological modified micron magnetic biochar adsorbent in any scheme, namely, the biological modified micron magnetic biochar adsorbent is added into cadmium wastewater to form a mixed system, and the adsorbent is recovered after the mixed system is oscillated for 4 hours.
Preferably, the concentration of cadmium ions in the wastewater is 0.5-100mg/L, and the pH is 7.0.
Preferably, the dosage of the adsorbent is 2 g/L.
Preferably, the step of recovering the adsorbent comprises: and under the action of the magnet, performing solid-liquid separation and recovery on the adsorbent in the wastewater within 30 s.
By means of the scheme, the invention has the following advantages: (1) according to the invention, corn straws are biologically modified, so that the oxidation-reduction potential and the pH value of the corn straws are changed, and the adsorption capacity of biochar is improved; (2) according to the biological modified micron magnetic charcoal adsorbent, the nanometer ferroferric oxide and the biological modified charcoal are magnetized by a method of fusing ethanol, the preparation method belongs to a mechanochemical magnetizing method, chemical agents required in a hydrothermal coprecipitation method are greatly reduced, and no redundant waste liquid is generated in the preparation process; (3) the biological modified micron magnetic charcoal adsorbent has strong magnetism, and can separate the adsorbent adsorbing pollutants from waste water by magnetic force, thereby realizing the recovery and regeneration of the adsorbent and avoiding secondary pollution; (4) the biologically modified micron magnetic biochar adsorbent reduces the particle size fraction of the adsorbent by a mechanical ball milling technology, obviously increases the specific surface area of the biochar and oxygen-containing functional groups on the surface, and improves the adsorption capacity to cadmium; (5) the biological modified micron magnetic biochar adsorbent provided by the invention takes corn straws as raw materials, the preparation method and the operation process are simple, the resource utilization of agricultural wastes is realized, and the biological modified micron magnetic biochar adsorbent has good environmental benefits and social benefits.
Drawings
FIG. 1 is a flow chart of the preparation method of the biologically modified micron magnetic biochar adsorbent in example 1;
FIG. 2 shows the effect of the bio-modified micron magnetic charcoal adsorbent prepared at different pyrolysis temperatures in example 1 on removing cadmium ions from water;
FIG. 3 is the isothermal adsorption curve of the application of the biologically modified micro magnetic biochar adsorbent prepared at different ball milling times to the water cadmium removal experiment described in example 2;
fig. 4 is a scanning electron micrograph of the bio-modified micro magnetic biochar adsorbent prepared at different ball milling times as described in example 2.
Detailed Description
The present invention is further described in detail below by specific examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the scope of the present invention in any way.
Comparative example
Meanwhile, taking fresh corn straws, cutting the fresh corn straws into small sections with the size of 2-3cm, drying the small sections at 65 ℃ until the small sections are completely dried, then placing the corn straws in a tubular furnace, and preparing the biochar by adopting one-step slow pyrolysis. The pyrolysis condition is that the temperature is raised to 500 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, and the temperature is naturally reduced to the room temperature after 2 hours of pyrolysis. The fired biochar was removed, ground and passed through a 0.5 mm sieve (designated BC 500). Further, mixing BC500 and nano ferroferric oxide according to a mass ratio of 1: 1, mixing according to a solid-liquid ratio of 1: 10, adding an organic solvent ethanol, carrying out ultrasonic treatment on the mixed substance for 2h to prevent the nano ferroferric oxide from agglomerating, then carrying out magnetic stirring for 4h, centrifuging to remove supernatant, washing residual solids for multiple times by using distilled water, and carrying out vacuum freezing on the solid substances at the temperature of-20 to-l 0 ℃ until the solid substances are completely dried to obtain the magnetic biochar material (marked as BCM 500).
Example 1
As shown in fig. 1, a method for preparing a biological modified micron magnetic biochar adsorbent comprises the following steps:
(1) washing fresh corn stalks with distilled water for three times, cutting into 2-3cm long, mixing 0.5% of beer yeast, 0.2% of calcium carbonate and 0.1% of sodium chloride, and performing fermentation treatment for 30 days to obtain biologically treated corn stalks;
(2) drying the biologically treated corn straw at 65 ℃ until the biologically treated corn straw is completely dried, crushing the corn straw, and sieving the crushed corn straw to obtain a 2mm sieve to obtain biologically treated corn straw powder biomass;
(3) placing the prepared corn straw powder biomass in a nitrogen-protected tubular furnace, heating to a constant temperature of 300-500 ℃ at a heating rate of 10 ℃/min, pyrolyzing at the constant temperature for 2 hours, naturally cooling to room temperature, grinding, and sieving with a 0.5 mm sieve to obtain corn straw biologically modified biochar;
(4) mixing the prepared corn straw biological modified biochar with nano ferroferric oxide according to a mass ratio of 1: 1, mixing according to a solid-liquid ratio of 1: 10, adding an organic solvent ethanol, carrying out ultrasonic treatment on the mixed substance for 2 hours to prevent the nano ferroferric oxide from agglomerating, and then carrying out magnetic stirring for 4 hours to fully mix the nano ferroferric oxide and the mixed substance;
(5) centrifuging the obtained mixture, pouring out supernatant, washing residual solid for multiple times by using distilled water, taking out the solid matter, and freezing the solid matter in vacuum at the temperature of between 20 ℃ below zero and 0 ℃ below zero until the solid matter is completely dried to obtain the biological modified magnetic biochar material.
(6) And (3) performing mechanical ball milling and crushing treatment on the magnetic biochar material for 60min to obtain the biological modified micron magnetic biochar adsorbent.
In this example, three different pyrolysis temperatures of 300 ℃, 400 ℃, and 500 ℃ were set to show the effects at different pyrolysis temperatures (denoted as BBCM300-60, BBCM400-60, and BBCM500-60, respectively).
The removal experiment of cadmium ions in the water body is carried out by utilizing the three biological modified micron magnetic biochar with different pyrolysis temperatures prepared by the method of the embodiment, and the specific operations are as follows:
respectively weighing 0.05g of comparative biochar and three kinds of biologically modified micron magnetic biochar prepared at the pyrolysis temperature into a 50mL centrifuge tube, adding 2g/L of adsorbent according to the set dosage, respectively adding 25mL of solution with the cadmium ion concentration of 100mg/L into the centrifuge tube, and adjusting the initial pH of the solution to 6.5 by using 0.1M hydrochloric acid and sodium hydroxide solution. And (3) placing the centrifuge tube into an oscillator, oscillating at the temperature of 25 ℃ and the rotation speed of 180rpm for 4 hours, separating the biological modified micron magnetic biochar from the water body by using a magnet after adsorption is finished, obtaining a clean water body, and calculating the adsorption amount and the removal rate.
The results of the different biochar tests are shown in figure 2. In the simulation of Cd content2+When the initial concentration of the wastewater solution is 100mg/L, when comparative corn straw biochar (BC500) and corn straw magnetic biochar (BCM500) are added, the adsorption capacities are 24.7mg/g and 31.7mg/g respectively, and the removal rates are 49.4% and 63.4%. When the biological modified micron magnetic biochar with pyrolysis temperature of 500 ℃ and ball milling time of 60min is added, the adsorption capacity reaches 41.6mg/g, and the removal rate is 83.2%. Meanwhile, the adsorption capacities of the biological modified micron magnetic biochar at the pyrolysis temperatures of 300 ℃ and 400 ℃ are respectively 25.1mg/g and 34.2mg/g, and the removal rates are respectively 50.2% and 68.4%. The cadmium adsorption capacity of the biological modified micron magnetic biochar is obviously higher than that of the original biochar, and the 500 ℃ pyrolysis temperature is expected to be the optimal temperature.
Example 2
The preparation process of biologically modified micron magnetic biochar adsorbent includes the following steps:
(1) washing fresh corn stalks with distilled water for three times, cutting into 2-3cm long, mixing 0.5% of beer yeast, 0.2% of calcium carbonate and 0.1% of sodium chloride, and performing fermentation treatment for 30 days to obtain biologically treated corn stalks;
(2) drying the biologically treated corn straw at 65 ℃ until the biologically treated corn straw is completely dried, crushing the corn straw, and sieving the crushed corn straw to obtain a 2mm sieve to obtain biologically treated corn straw powder biomass;
(3) placing the prepared corn straw powder biomass in a nitrogen-protected tubular furnace, heating to a constant temperature of 500 ℃ at a heating rate of 10 ℃/min, pyrolyzing at the temperature for 2 hours, naturally cooling to room temperature, grinding, and sieving with a 0.5 mm sieve to obtain corn straw biological modified charcoal;
(4) mixing the prepared corn straw biological modified biochar with nano ferroferric oxide according to a mass ratio of 1: 1, mixing according to a solid-liquid ratio of 1: 10, adding an organic solvent ethanol, carrying out ultrasonic treatment on the mixed substance for 2 hours to prevent the nano ferroferric oxide from agglomerating, and then carrying out magnetic stirring for 4 hours to fully mix the nano ferroferric oxide and the mixed substance;
(5) centrifuging the obtained mixture, pouring out supernatant, washing residual solid for multiple times by using distilled water, taking out the solid matter, and freezing the solid matter in vacuum at the temperature of between 20 ℃ below zero and 0 ℃ below zero until the solid matter is completely dried to obtain the biological modified magnetic biochar material.
(6) And (3) mechanically ball-milling and crushing the magnetic biochar material for 30-120min to obtain the biological modified micron magnetic biochar adsorbent.
In this example, three different sets of mechanical ball milling times (30min, 60min, 120min) were set to show the effects of the different ball milling times (denoted as BBCM500-30, BBCM500-60, BBCM500-120, respectively).
The isothermal adsorption experiment is carried out by using the three biologically modified micron magnetic charcoal adsorbents with different ball milling times, which are prepared by the method of the embodiment, and the specific operations are as follows:
respectively weighing 0.05g of comparative biochar and biologically modified micron magnetic biochar adsorbent prepared at three pyrolysis temperatures into 50mL centrifuge tubes, adding 25mL of solution containing 1, 5, 10, 25, 50, 75, 100, 150 and 200mg/L of cadmium ions into each set of centrifuge tube according to the set addition dose of the adsorbent of 2g/L, and adjusting the initial pH value of the solution to 6.5 by using 0.1M dilute hydrochloric acid and dilute sodium hydroxide solution. And (3) placing the centrifugal tube into an oscillator, oscillating at the temperature of 25 ℃ and the rotating speed of 180rpm for 4 hours, separating the biological modified micron magnetic biochar from the water body by using a magnet after adsorption is finished, measuring the concentration of cadmium in the equilibrium liquid, and calculating the adsorption amount and the removal rate.
The results of the adsorption isotherms of the biologically modified micro-magnetic biochar adsorbents prepared at different mechanical ball milling times are shown in fig. 3. All the adsorption processes of the biochar to the cadmium are suitable for Langmuir isotherms, and the correlation coefficient R of a fitting curve2Greater than 0.98. Using Langmuir isotherm equation Ce/Qe＝1/(bQm)+Ce/QmThe maximum adsorption amount was calculated. Wherein the maximum adsorption capacity of the comparative corn straw biochar is 25.9mg/g, and the maximum adsorption capacity of the biological modified micron magnetic biochar processed by ball milling for 30min, 60min and 120min is 34.0mg/g, 40.2mg/g and 52.1mg/g respectively. Therefore, the proper extension of the mechanical ball milling time is beneficial to improving the cadmium removal effect of the biological modified micron magnetic biochar, and the optimal ball milling time is 120 min.
Scanning electron microscope analysis was performed on the biologically modified micro magnetic biochar adsorbent prepared in this example. Fig. 4 shows Scanning Electron Microscopy (SEM) analysis images of raw corn stover biochar and biologically modified micro-magnetic biochar prepared by ball milling for 30min, 60min, 120 min. It can be found that the original corn straws are smooth and have the appearance characteristics of large aperture, the surface layer of the biological modified micron magnetic biochar is relatively rough and shows heterogeneity, and a large amount of Fe can be seen3O4The nano-particles are loaded on the surface of the biochar particles. As can be seen from FIG. 4, BBCM500-120 is micronized magnetic biochar with a denser mesoporous surface layer and more uniform Fe3O4And (4) distributing the nanoparticles. The rich ferrite functional groups and the huge specific surface area on the surface of the BBCM500-120 are beneficial to improving the cadmium adsorption performance, so that the mechanical ball milling for 120min is the optimal ball milling time.
Claims (10)
1. A preparation method of a biological modified micron magnetic biochar adsorbent is characterized by comprising the following steps:
(1) cleaning fresh corn straws, cutting into sections, and performing fermentation treatment by using a fermentation microbial inoculum to obtain the corn straws subjected to biological treatment;
(2) drying the biologically treated corn straws until the biologically treated corn straws are completely dried, crushing and sieving the biologically treated corn straws to obtain biologically treated corn straw powder;
(3) slowly pyrolyzing the prepared corn straw powder to be carbonized, cooling, crushing and sieving to obtain the corn straw biological modified charcoal;
(4) mixing the prepared corn straw biological modified biochar and nano ferroferric oxide at a mass ratio of 1: 1, adding an organic solvent ethanol according to a solid-liquid ratio of 1: 10, carrying out ultrasonic treatment on the mixed substance, and then carrying out magnetic stirring to fully mix the two;
(5) centrifuging the obtained mixture, pouring out supernatant, washing residual solid for multiple times by using distilled water, taking out the solid matter, and performing vacuum freezing at the temperature of-20 to-l 0 ℃ until the solid matter is completely dried to obtain the biological modified magnetic biochar material;
(6) and (3) performing mechanical ball milling and crushing treatment on the biological modified magnetic biochar material to obtain the biological modified micron magnetic biochar adsorbent.
2. The method of claim 1, wherein: the fermentation inoculum in step (1) comprises the following components in proportion: 0.5 percent of beer yeast, 0.2 percent of calcium carbonate and 0.1 percent of sodium chloride.
3. The method of claim 1, wherein: and (3) drying at 65 ℃ in the step (2), and sieving after crushing to obtain a sieve of 2 mm.
4. The method of claim 1, wherein: in the step (3), the slow pyrolysis is carried out by heating to a constant temperature at a heating rate of 10 ℃/min, and naturally cooling to room temperature after 2 hours of pyrolysis; the mesh size of the crushing and sieving is 0.5 mm.
5. The method of claim 4, wherein: the constant temperature is any temperature between 300 ℃ and 500 ℃.
6. The method of claim 1, wherein: and (4) performing mechanical ball milling and crushing treatment for 30-120min in the step (6).
7. The method of claim 1, wherein: the method comprises the following steps:
(1) cleaning fresh corn straws, cutting into 2-3cm long, and performing fermentation treatment by using a fermentation microbial inoculum to obtain biologically treated corn straws; the fermentation inoculum comprises the following components in percentage by weight: 0.5 percent of beer yeast, 0.2 percent of calcium carbonate, 0.1 percent of sodium chloride and the balance of water;
(2) drying the biologically treated corn straws at 65 ℃ until the biologically treated corn straws are completely dried, crushing the corn straws, and sieving the crushed corn straws by a 2mm sieve to obtain biologically treated corn straw powder;
(3) placing the prepared corn straw powder in a nitrogen-protected tube furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 2 hours, naturally cooling to room temperature, grinding, and sieving by a 0.5 mm sieve to obtain the corn straw biological modified charcoal;
(4) mixing the prepared corn straw biological modified biochar and nano ferroferric oxide at a mass ratio of 1: 1, adding an organic solvent ethanol according to a solid-liquid ratio of 1: 10, carrying out ultrasonic treatment on the mixture for 2 hours, and then carrying out magnetic stirring for 4 hours to fully mix the two;
(5) centrifuging the obtained mixture, pouring out supernatant, washing residual solid for multiple times by using distilled water, taking out the solid matter, and performing vacuum freezing at the temperature of-20 to-l 0 ℃ until the solid matter is completely dried to obtain the biological modified magnetic biochar material;
(6) and (3) performing mechanical ball milling and crushing treatment on the biological modified magnetic biochar material for 120min to obtain the biological modified micron magnetic biochar adsorbent.
8. The application of the biological modified micron magnetic biochar adsorbent as claimed in any one of claims 1 to 7, wherein the biological modified micron magnetic biochar adsorbent is added into cadmium-containing wastewater, oscillated at room temperature and then recovered.
9. The use of the biologically modified micron magnetic biochar adsorbent according to claim 8, wherein the dosage of the biologically modified micron magnetic biochar adsorbent is 2 g/L; the concentration of cadmium ions in the cadmium-containing wastewater is 0.5-100mg/L, and the pH value is 5.5-7.0.
10. The use of the biologically modified micron magnetic biochar adsorbent according to claim 8, wherein the oscillation time is 4 hours; the steps for recovering the biological modified micron magnetic charcoal adsorbent are as follows: and under the action of the magnet, performing solid-liquid separation and recovery on the adsorbent in the wastewater within 30 seconds.
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