CN113368841A - Method for preparing magnetic multi-effect adsorbent by utilizing enzymolysis residues through dry method - Google Patents
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Abstract
The invention provides a method for preparing a magnetic multi-effect adsorbent by using enzymolysis residues as raw materials, which comprises the following steps: washing the enzymolysis residue raw material to be neutral and drying; then uniformly mixing the magnetic nanoparticles with the magnetic nanoparticles according to the weight ratio of 5: 1-1: 5, and preheating for 1-5 hours at 80-120 ℃; and transferring the mixture into a ball milling tank for mechanical ball milling for 1-5 hours at room temperature. And finally, opening the treated ball milling tank, taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues. The magnetic multi-effect adsorbent can be applied to adsorbing pollutants in wastewater, wherein the pollutants are anionic dyes, cationic dyes and heavy metal ions. The preparation method is simple to operate, low in cost, easy to collect and high in yield, and the prepared magnetic adsorbent realizes effective adsorption of anionic fuel, cationic dye and heavy metal ions, and has important practical application value and wide market prospect.
Description
Technical Field
The invention belongs to the field of materials, relates to high-value reutilization of wood fiber biomass, and particularly relates to a method for preparing a magnetic adsorbent by taking enzymolysis residues as a raw material and application of the magnetic adsorbent.
Background
The development of the industry is changing day by day, the pollution challenge is increased, and the increasingly serious water pollution becomes a prominent problem threatening the development of human life and social economy. Since industrial waste water contains organic dyes and heavy metal ions, and these pollutants are difficult to self-degrade in natural environment, they pose potential threats to environment and human health if not treated (Ecological indicator 2015,48, 282-reservoir 291; Science of the total environment 2015, 1591-reservoir 103). The waste water adsorbent is an effective way for solving the problem by comprehensively considering the aspects of removal efficiency, cost, operation simplicity and the like.
The technology for preparing the cellulosic ethanol by taking the lignocellulose as the raw material has the advantages of not competing with the people for grains and grains for land, being beneficial to carbon peak reaching and carbon neutralization and the like, and has great development and popularization prospects. The technology not only prepares the cellulosic ethanol, but also produces enzymolysis residues rich in lignin. The enzymolysis residue is rich in lignin, and rich functional groups are reserved due to the fact that the structure of the enzymolysis residue is damaged to a relatively small degree, and the method has a development and application prospect. At present, the removal of organic or inorganic pollutants in wastewater by using lignin-based adsorbents is also reported in many cases. The invention patent application 201910482720.9 discloses a method for preparing lignin adsorbent by irradiation grafting. The invention patent application 202010596146.2 discloses a preparation method of an alkali lignin composite adsorption material. The invention patent CN 201711180164.7 discloses a lignin-based polyphenylamine adsorption material and a preparation method thereof. The technical scheme adopts reagents such as tannic acid or formaldehyde, and the like, or has the problems of high price or harm to human bodies, complex method, complex operation, difficult collection and the like.
Meanwhile, the magnetic adsorbent has the characteristics of easy collection and the like, so that the magnetic adsorbent is widely concerned by researchers. Wherein Altaf et al (Journal of cleaning production,2021, 278: 123960) synthesizes zirconium lanthanum @ Fe at 180 ℃ by using ultrapure water containing 0.45g of lanthanum nitrate as a liquid phase3O4The composite magnetic adsorbent of (1). Hu et al (Chemosphere, 2020, 246: 125757) encapsulate lignin in magnetic Fe in the presence of ethylene glycol3O4And preparing the composite magnetic lignin adsorbent. Wang et al (Industrial crop production, 2019, 127: 110-118) used p-toluenesulfonic acid as curing agent to synthesize a lignosulfonate/phenolic compound in emulsion polymerization and encapsulate Fe3O4Adsorption balls of the particles. However, the preparation processes of the lignin magnetic adsorbents are all realized in a liquid environment, and the problems of high reagent consumption, low yield, complicated solid-liquid separation operation, environmental pollution and the like exist. At present, no report exists for preparing the relevant lignin adsorbent in a loading manner under a dry environment.
Disclosure of Invention
Aiming at the current situations that the preparation method of the magnetic adsorbent in the prior art is complex in operation and high in cost, the invention provides a method for preparing a magnetic multi-effect adsorbent by using enzymolysis residues as raw materials. The method is simple, not only is low in cost, easy to collect and high in yield, but also the prepared magnetic adsorbent realizes effective adsorption on anionic fuel, cationic dye and heavy metal ions, and has important practical application value and wide market prospect.
The technical scheme of the invention is as follows:
the method for preparing the magnetic multi-effect adsorbent by utilizing the enzymolysis residues by the dry method comprises the following steps:
(1) and (3) washing the enzymolysis residue raw material to be neutral, drying, and storing for later use under the condition of normal-temperature drying environment.
(2) Uniformly mixing the enzymolysis residues obtained in the step (1) with the magnetic nanoparticles according to a weight ratio of 5: 1-1: 5, and preheating for 1-5 hours at a temperature of 80-120 ℃ to soften the enzymolysis residues to a certain extent to obtain a pretreated material. Wherein the lignin content of the enzymolysis residue raw material is not less than 60%. The enzymolysis residue is the enzymolysis residue of a wood fiber biomass raw material, and the wood fiber raw material is one or more of xylose residue, corncob, bagasse, corn straw, rice straw, reed straw and wheat straw. The magnetic nano particles are Fe3O4Nanoparticles, Co3O4Nanoparticles, NiO nanoparticles and Mn3O4One or more of the nanoparticles.
(3) And (3) transferring the pretreated material obtained in the step (2) into a ball milling tank, then placing the ball milling tank into a planetary ball mill, and mechanically milling for 1-5 hours at room temperature. Wherein, the revolution speed of the mechanical ball milling is 30-80 r/min, and the rotation speed is 200-600 r/min. If the rotating speed is too slow, the reaction is insufficient, and the using effect of the prepared adsorbent is influenced; but if the rotational speed is too fast, unnecessary power consumption is increased. Ball milling is a commonly used dry physical mixing method. However, in the application, the chemical bonding of the magnetic nanoparticles and the enzymolysis residues is realized on the basis of physical mixing through the double processes of preheating and mechanical pressure grinding before ball milling, so that the magnetic nanoparticles and the enzymolysis residues are tightly connected and compounded and cannot be dispersed in a solution. (FIG. 8).
(4) And (4) opening the ball milling tank treated in the step (3), taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues. The magnetic multi-effect adsorbent prepared by the application realizes the chemical bonding of the magnetic nanoparticles and the enzymolysis residues, and can stably exist in water without disintegration, so that unexpected technical effects are generated. On the other hand, the lignin contained in the enzymolysis residues plays a major role in the adsorption process. Firstly, abundant groups contained in lignin molecules may form strong electrostatic attraction with pollutant ions; secondly, carboxyl, carbonyl, methoxyl and the like in lignin molecules also have a certain function of electron reduction, so that the degradation of pollutant ions is accelerated. Meanwhile, residual cellulose in the enzymolysis residues can also be complexed with pollutant particles, so that the adsorption effect is further promoted. The use of the magnetic particles can separate the prepared adsorbent from the wastewater under the condition of an external magnetic field, and the adsorbent is easy to recover and reuse. The application of the magnetic multi-effect adsorbent is to adsorb pollutants in wastewater, wherein the pollutants are anionic dyes, cationic dyes and heavy metal ions. Wherein the dosage of the magnetic multi-effect adsorbent is 0.01-0.1wt% of the weight of the wastewater; the concentrations of anionic dye, cationic dye or heavy metal ions in the wastewater are all less than or equal to 1 g/L. And after the wastewater is adsorbed, the magnetic multi-effect adsorbent is magnetically collected, then the adsorbate is eluted by using a solvent, lignin is removed by using an alkali solution, and then magnetic particles can be obtained through magnetic recovery and used for preparing the magnetic multi-effect adsorbent again.
The invention has the beneficial effects that:
(1) the magnetic multi-effect adsorbent is prepared by mixing industrial waste, namely enzymolysis residues, serving as a raw material with magnetic nanoparticles in a dry method and then performing mechanical ball milling, and has the advantages of low price and easiness in obtaining of the raw material, simplicity and convenience in operation, environmental friendliness and easiness in separation and recovery.
(2) The preparation method of the magnetic multi-effect adsorbent realizes the thermal bonding of the magnetic nano particles and the enzymolysis residues through a mechanical ball milling method, so that the magnetic nano particles and the enzymolysis residues are connected and compounded tightly, and cannot be dispersed in a solution, thereby generating unexpected technical effects.
(3) The magnetic multi-effect adsorbent provided by the invention is simple in preparation method, the surface aperture of enzymolysis residue particles is increased, and the adsorption effect is excellent. The adsorption capacity to the cationic dye methylene blue can exceed 500mg/g, the adsorption capacity to the anionic dye Congo red can exceed 500mg/g, and the adsorption capacity to the hexavalent chromium ion can exceed 30mg/g, so that a sustainable strategy of treating wastes with wastes is realized, and the method has important social significance.
Drawings
FIG. 1 is a graph showing the adsorption effect of the magnetic adsorbent prepared in example 1 of the present application on the cationic dye methylene blue.
Fig. 2 is a graph showing the actual response of the magnetic adsorbent prepared in example 1 of the present application under the action of a magnet.
Fig. 3 is a graph showing the adsorption effect of the adsorbent loaded with nonmagnetic nanoparticles prepared in example 2 of the present application on methylene blue.
Fig. 4 is a graph showing the adsorption effect of the magnetic adsorbent prepared in example 3 of the present application on the anionic dye congo red.
Fig. 5 is a scanning electron microscope image of the magnetic adsorbent prepared in example 3 of the present application.
Fig. 6 is a transmission electron microscope image of the magnetic adsorbent prepared in example 3 of the present application.
FIG. 7 is a hysteresis loop diagram of a magnetic adsorbent prepared in example 4 of the present application.
FIG. 8 is an XPS O-1s narrow spectrum of a magnetic adsorbent prepared in example 4 of the present application.
FIG. 9 is a graph showing the effect of the magnetic adsorbent prepared in example 5 of the present application on the adsorption of hexavalent chromium ions.
FIG. 10 is a graph showing the adsorption effect of the magnetic adsorbent prepared in example 5 of the present application on a mixed solution of the cationic dye methylene blue, the anionic dye congo red and hexavalent chromium ions at 90mg/L (before the adsorption treatment in the left side, after the adsorption treatment in the right side).
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the method for preparing the magnetic multi-effect adsorbent by utilizing the enzymolysis residues through the dry method and the application thereof comprise the following specific steps:
step 1: and (3) centrifugally washing the corncob enzymolysis residues with the lignin content of 86% to be neutral by using distilled water, drying, and storing for later use under the normal-temperature drying environment condition.
Step 2: taking the obtained enzymolysis residue and Co3O4The ratio of the nano particles is 5:1, in the mass ratio ofPreheating for 3 hours at the temperature of 100 ℃ to obtain the pretreated material.
And step 3: and transferring the treated materials into a ball milling tank, placing the ball milling tank into a planetary ball mill, and performing mechanical ball milling for 5 hours at the speed of revolution of 80 revolutions per minute and rotation of 300 revolutions per minute.
And 4, step 4: and opening the ball milling tank after treatment, taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues.
And 5: and (3) taking 30mg of the prepared magnetic multi-effect adsorbent, and testing the adsorption effect of methylene blue with the concentration of 50-800 mg/L under the conditions that the temperature is 25 ℃, the pH value is 7 and the adsorption treatment time is 2 hours.
According to the test result, the adsorption capacity of the magnetic multi-effect adsorbent prepared by the enzymolysis residue dry method to methylene blue for 2h can reach 560 +/-10 mg/g (figure 1), and the effective adsorption to cationic dye methylene blue is realized. As can be seen from FIG. 1, as the initial concentration of methylene blue was increased from 50mg/L to 800mg/L, the amount adsorbed was increased from 49. + -.2 mg/g to 560. + -.10 mg/g. This is probably because the higher the probability of contact between the adsorbent and methylene blue, the greater the force between the adsorbent and the adsorbent contact surface, and therefore the greater the amount of adsorption. In addition, since the adsorbent has a sensitive response to the magnet, the recovery operation of the adsorbent is simple and the recovery rate is good (fig. 2).
Example 2 (comparative example, without addition of magnetic nanoparticles):
a method for preparing a multi-effect adsorbent by utilizing an enzymolysis residue dry method and application thereof comprise the following specific steps:
step 1: and (3) centrifugally washing the corncob enzymolysis residues with the lignin content of 89% to be neutral by using distilled water, drying, and storing for later use under the normal-temperature drying environment condition.
Step 2: and (3) adding the obtained enzymolysis residues into a ball milling tank, and preheating for 3 hours at the temperature of 100 ℃ to obtain a pretreated material.
And step 3: and transferring the treated materials into a ball milling tank, placing the ball milling tank into a planetary ball mill, and performing mechanical ball milling for 5 hours at the speed of revolution of 80 revolutions per minute and rotation of 300 revolutions per minute.
And 4, step 4: and opening the ball milling tank after treatment, taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues.
And 5: and (3) taking 30mg of the prepared adsorbent, and carrying out an adsorption effect test on methylene blue with the concentration of 50-800 mg/L under the conditions that the temperature is 25 ℃, the pH value is 7 and the adsorption treatment time is 2 hours.
According to the test result, the adsorbent prepared by the enzymolysis residue dry method can achieve 480 +/-10 mg/g (figure 3) of adsorption capacity for 2h of methylene blue, and the effective adsorption of the cationic dye methylene blue is realized. But the adsorption effect is inferior to that of the mixed magnetic nano particles, and the magnetic nano particles have no responsiveness to the magnet and are difficult to collect.
Example 3:
the method for preparing the magnetic multi-effect adsorbent by utilizing the enzymolysis residues through the dry method and the application thereof comprise the following specific steps:
step 1: and (3) centrifugally washing the wheat straw enzymolysis residues with the lignin content of 81% to be neutral by using distilled water, drying, and storing for later use under the condition of normal-temperature drying environment.
Step 2: taking the obtained enzymolysis residues and NiO nano particles in a ratio of 1: 4, and preheating for 5 hours at the temperature of 80 ℃ to obtain the pretreated material.
And step 3: adding the pretreated materials into a ball milling tank, then placing the ball milling tank into a planetary ball mill, and performing mechanical ball milling for 4 hours at the speed of revolution of 60 revolutions per minute and rotation of 200 revolutions per minute;
and 4, step 4: and opening the ball milling tank after treatment, taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues.
And 5: and (3) taking 30mg of the prepared magnetic multi-effect adsorbent, and testing the adsorption effect of Congo red with the concentration of 50-800 mg/L under the conditions that the temperature is 25 ℃, the pH is 6 and the adsorption time is 8 h.
According to the test result, the adsorption capacity of the magnetic multi-effect adsorbent prepared by the dry method by utilizing the enzymolysis residues to Congo red for 2h can reach 560 +/-10 mg/g (figure 4), the effective adsorption to the anionic dye Congo red is realized, the magnetic multi-effect adsorbent has sensitive responsiveness to a magnet, and the collection condition is good.
The prepared magnetic multi-effect adsorbent particles are characterized by a scanning electron microscope, as shown in fig. 5. As can be seen from fig. 5, a plurality of porous structures are formed on the surface of the magnetic multi-effect adsorbent, which illustrates that the magnetic nanoparticles play an important role in perforating the surface of the enzymolysis residue particles during the ball milling process, so that the surface aperture and the specific surface area of the enzymolysis residue particles are improved.
Meanwhile, the prepared magnetic multi-effect adsorbent particles are characterized by adopting a transmission electron microscope, as shown in fig. 6. As can be seen from FIG. 6, the magnetic multi-effect adsorbent is still in an intact state, and the magnetic particles and the enzymolysis residues are kept in a combined state. The magnetic multi-effect adsorbent prepared by the method can stably exist in a solution environment, maintains the tight combination of the magnetic particles and the enzymolysis residues, and also shows that certain bonding connection exists between the magnetic particles and the enzymolysis residues, but not simple physical combination.
Example 4:
the method for preparing the magnetic multi-effect adsorbent by utilizing the enzymolysis residues through the dry method and the application thereof comprise the following specific steps:
step 1: centrifugally washing the xylose residue enzymolysis residues with the lignin content of 68% to neutrality by using distilled water, drying, and storing for later use under the condition of normal-temperature drying environment.
Step 2: taking the obtained enzymolysis residue and Fe3O4The ratio of the nano particles is 4: 3, and preheating for 1.1 hours at the temperature of 120 ℃ to obtain the pretreated material.
And step 3: and adding the pretreated materials into a ball milling tank, then placing the ball milling tank into a planetary ball mill, and performing mechanical ball milling for 1 hour at the speed of revolution of 75 revolutions per minute and rotation of 580 revolutions per minute.
And 4, step 4: and opening the ball milling tank after treatment, taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues.
The adsorbent particles prepared in this example have sensitive responsiveness to the magnet, the collection condition is good, and the hysteresis loop is shown in fig. 7. As can be seen from FIG. 7, Fe3O4Both nanoparticles and magnetic adsorbents exhibit excellent superparamagnetism; wherein, Fe3O4The saturation magnetization of the nano particles is 60-80 emu/g, and the saturation magnetization of the magnetic adsorbent is 10-30 emu/g, which shows that the enzymolysis residues do not have magnetic response and are Fe loaded by the enzymolysis residues3O4The nanoparticles impart this property to the adsorbent.
As can be seen from fig. 8, the adsorbent particles obtained in this example have a micro-shift relative to the magnetic particles, which confirms that the enzymatic residues in the adsorbent chemically react with the magnetic particles, rather than simply physically mix and coat. In the narrow spectrum of O1s, O-1 represents the O-Fe peak, and O-2 belongs to the same Fe3O4The nano particles and the xylose residue enzymolysis residues, wherein O-C represented by O-3 mainly comes from lignin in the xylose residue enzymolysis residues. The shift in O-2 among these peaks further illustrates Fe3O4Effectively chemically bonding with enzymolysis residues, and O-3 plays a main role in adsorption.
Example 5:
the method for preparing the magnetic multi-effect adsorbent by utilizing the enzymolysis residues through the dry method and the application thereof comprise the following specific steps:
step 1: and (3) centrifugally washing the corn straw enzymolysis residues with the lignin content of 61% to be neutral by using distilled water, drying, and storing for later use under the normal-temperature drying environment condition.
Step 2: mixing the obtained enzymolysis residues with Fe3O4The ratio of the nano particles is 1: 1, and preheating for 2.5 hours at the temperature of 100 ℃ to obtain the pretreated material.
And step 3: and transferring the treated materials into a ball milling tank, then placing the ball milling tank into a planetary ball mill, and performing mechanical ball milling for 2 hours at the speed of revolution of 35 revolutions per minute and rotation of 400 revolutions per minute.
And 4, step 4: and opening the ball milling tank after treatment, taking out materials in the tank, sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues.
And 5: taking 30mg of the prepared magnetic multi-effect adsorbent, and respectively testing the adsorption effect of potassium dichromate with the concentration of 20-600 mg/L under the conditions of temperature of 25 ℃, pH of 5 and adsorption time of 8 h; the mixed adsorption effect test was carried out on methylene blue, congo red and hexavalent chromium ions (wherein the ion concentration was 30mg/L respectively) at a mixed concentration of 90mg/L under the conditions of a temperature of 25 ℃, a pH of 6 and an adsorption time of 8 h.
Step 6: and 5, collecting the magnetic multi-effect adsorbent adsorbing the wastewater by using a magnetic characteristic, eluting the adsorbate by using a solvent, removing lignin by using an alkali solution, and recovering by using magnetic force to obtain magnetic particles. The magnetic particles can be used for preparing the magnetic multi-effect adsorbent again. As shown in fig. 9, the adsorption amount of the magnetic adsorbent for enzymatic hydrolysis residues obtained in the present embodiment to hexavalent chromium ions can reach 30 ± 7mg/g, and effective adsorption of hexavalent chromium ions is achieved.
As shown in fig. 10, the magnetic adsorbent for enzymolysis residues obtained in the present embodiment has a good adsorption effect on the mixed solution, wherein 75 to 95% of methylene blue, 70 to 90% of congo red, and 65 to 85% of hexavalent chromium ions are effectively removed.
In conclusion, the magnetic multi-effect adsorbent prepared by the method has excellent adsorption effect on single cationic dye, single anionic dye and single heavy metal ions, can effectively remove the pollutants in the mixed solution, and has important practical application value. Meanwhile, the magnetic multi-effect adsorbent is prepared by taking enzymolysis residues as raw materials, is low in cost, simple in preparation method and convenient to collect and recycle, realizes a sustainable strategy of treating wastes with processes of wastes against one another, and has important social significance.
Claims (8)
1. The method for preparing the magnetic multi-effect adsorbent by utilizing the enzymolysis residues by the dry method is characterized by comprising the following steps of: the method comprises the following steps:
(1) washing the enzymolysis residue raw material to be neutral and drying for later use;
(2) uniformly mixing the enzymolysis residues obtained in the step (1) with the magnetic nanoparticles according to a weight ratio of 5: 1-1: 5, and preheating for 1-5 hours at a temperature of 80-120 ℃ to obtain a pretreated material;
(3) transferring the pretreated material obtained in the step (2) into a ball milling tank, then placing the ball milling tank into a planetary ball mill, and mechanically milling for 1-5 hours at room temperature and at a proper rotating speed;
(4) and (4) opening the ball milling tank treated in the step (3), taking out materials in the tank, and sieving and separating ball milling zirconium beads to obtain the magnetic multi-effect adsorbent prepared from the enzymolysis residues.
2. The method for preparing the magnetic multi-effect adsorbent by using the enzymolysis residues in the dry method according to claim 1, which is characterized in that: the rotating speed of the mechanical ball milling in the step (3) is as follows: the revolution speed is 30-80 rpm, and the rotation speed is 200-600 rpm.
3. The method for preparing the magnetic multi-effect adsorbent by using the enzymolysis residues in the dry method according to claim 2, which is characterized in that: the lignin content of the enzymolysis residue raw material is not less than 60%.
4. The method for preparing the magnetic multi-effect adsorbent by using the enzymolysis residues in the dry method according to claim 3, which is characterized in that: the enzymolysis residue in the step (1) is the enzymolysis residue of a wood fiber biomass raw material, and the wood fiber raw material is one or more of xylose residue, corncob, bagasse, corn straw, rice straw, reed straw and wheat straw.
5. The method for preparing the magnetic multi-effect adsorbent by using the enzymolysis residues in the dry method according to claim 2, which is characterized in that: the magnetic nano particles in the step (2) are Fe3O4Nanoparticles, Co3O4Nanoparticles, NiO nanoparticlesParticles and Mn3O4One or more of the nanoparticles.
6. Use of a magnetic multi-effect adsorbent prepared according to the method of any one of claims 1 to 5, characterized in that: the adsorbent is applied to adsorbing pollutants in wastewater, wherein the pollutants are anionic dyes, cationic dyes and heavy metal ions.
7. Use of a magnetic multi-effect adsorbent prepared according to the method of claim 6, characterized in that: the addition amount of the magnetic multi-effect adsorbent is 0.01-0.1wt% of the weight of the wastewater, and the concentrations of the anionic dye, the cationic dye and the heavy metal ions in the wastewater are less than or equal to 1 g/L.
8. Use of a magnetic multi-effect adsorbent prepared according to the method of claim 6, characterized in that: and after the magnetic multi-effect adsorbent is used for adsorbing the treated wastewater, eluting adsorbates after magnetic collection, and removing lignin to obtain recovered magnetic particles.
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