CN108404867B - Lignin-based carbon magnetic nano material, preparation method and application in methyl orange adsorption - Google Patents
Lignin-based carbon magnetic nano material, preparation method and application in methyl orange adsorption Download PDFInfo
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Abstract
The invention belongs to the technical field of adsorbent materials, and discloses a lignin-based carbon magnetic nano material, a preparation method thereof and application thereof in adsorption of methyl orange. The preparation method comprises the following steps: dissolving ferrous sulfate and ferric chloride in water, preheating, dropwise adding ammonia water and hydrogen peroxide, and curing for 1-3 h at the temperature of 70-90 ℃; adding a lignin solution and short-chain alcohol into the system, and stirring for 1-3 h under heat preservation; separating and drying; carbonizing at 500-650 ℃ for 3-4 h under inert atmosphere, cooling, and crushing to obtain the lignin-based carbon magnetic nano material. The method takes lignin with rich sources as a carbon supply source, has low price, reduces the production cost of the magnetic material, and accords with the strategy of green sustainable development; the prepared lignin-based carbon magnetic nano material has the advantages of uniform particle size, large carbon loading amount and strong methyl orange adsorption capacity by synchronously combining high-temperature carbonization and high-temperature reforming, and can be used for adsorbing methyl orange.
Description
Technical Field
The invention belongs to the technical field of adsorbent materials, and particularly relates to a lignin-based carbon magnetic nano material, a preparation method thereof and application thereof in methyl orange adsorption.
Background
In recent years, studies on carbon nanomaterials have been actively conducted, and carbon nanomaterials having various shapes have been increasingly developed. The carbon nano material is widely applied to various fields of reinforced fibers, heat and electricity conducting materials, stealth materials, hydrogen storage materials, electrode materials, supercapacitors, adsorption materials and water purification catalytic carriers, and has excellent hardness, optical characteristics, heat resistance, radiation resistance, chemical resistance, electric conductivity, surface and interface characteristics and the like.
The magnetic material has excellent magnetic properties, and is widely applied to the fields of magnetofluid, targeted medical treatment, adsorption separation, nuclear magnetic resonance, trace detection and the like. At present, a great deal of research work is carried out by scientific and technical workers at home and abroad.
Preparation of Fe by Xuan et al3O4Adding aniline into the nano particles, and initiating aniline molecules to polymerize on the surfaces of the nano particles through an initiator to prepare Fe3O4Polyaniline magnetic composite microsphere. The microsphere has a blueberry shape, and has special application in the field of catalysis after the surface is coated with a layer of gold nanoparticles. Bhaunik et al utilizes pyrrole monomer to polymerize in aqueous solution by easy oxidation, and then pyrrole is polymerized in Fe3O4The prepared magnetic particles can completely adsorb Cr (VI) in a 200 mg/L Cr (VI) solution with the pH value of 2, Zhu and the like copolymerize methyl acrylate solution containing nano iron oxide particles and styrene to obtain the styrene-acrylic resin-coated magnetic nano microspheres, and the prepared high-molecular magnetic microspheres are uniformly distributed, and the magnetic microsphere coupling primer chain can be used for separating a probe of VEGF nucleic acid.
The carbon material and the magnetic material are combined through a physical or chemical method, the magnetic property and the carbon material property are simultaneously endowed to the new material, and the magnetic material can be applied to the fields of targeted medicine, catalysis, magnetic separation and the like, but the research of combining the magnetic material and the carbon material is rarely reported at present.
Lignin is the second largest biomass material on earth. Statistically, more than 5000 million tons of industrial lignin are produced globally by the pulp and paper industry every year. In natural biomass materials, lignin has a high molecular carbon content and is a good carbon source. Research shows that the carbon material prepared from the lignin can be used as an electrode material, a super capacitor, a device material and the like. However, the main way of using lignin at home and abroad is burning so far, and a small part of lignin is used as an industrial dispersant after being modified. The method is only low-value utilization, causes huge waste on lignin resources, is difficult to relieve the contradiction of resource shortage, and is not beneficial to the sustainable development of the society. At present, no research report for preparing carbon magnetic nano materials by using lignin as a carbon supply source exists.
Disclosure of Invention
In order to overcome the defects and shortcomings of low-value utilization of lignin in the prior art, the invention mainly aims to provide a preparation method of a lignin-based carbon magnetic nano material. The method takes lignin as a carbon supply source and Fe3O4The lignin-based carbon magnetic nano material is obtained by combining preparation, the added value of lignin is improved, the application range of the lignin is expanded, the resource utilization of the lignin is realized, and the realization of the strategic target of sustainable development is promoted.
The invention also aims to provide the lignin-based carbon magnetic nanomaterial prepared by the method.
The invention further aims to provide application of the lignin-based carbon magnetic nanomaterial in methyl orange adsorption.
The purpose of the invention is realized by the following scheme:
a preparation method of lignin-based carbon magnetic nano-materials comprises the following steps: dissolving ferrous sulfate and ferric chloride in water, preheating, dropwise adding ammonia water and hydrogen peroxide, and curing for 1-3 h at the temperature of 70-90 ℃; adding a lignin solution and short-chain alcohol into the system, and stirring for 1-3 h under heat preservation; separating and drying; carbonizing at 500-650 ℃ for 3-4 h under inert atmosphere, cooling, and crushing to obtain the lignin-based carbon magnetic nano material.
In the method, the dosage formula of each component is as follows, and the components are calculated by mass parts: 2-5 parts of lignin, 10-25 parts of short-chain alcohol, 2.5-5 parts of ferrous sulfate, 3-6 parts of ferric chloride, 10-20 parts of ammonia water and 1-5 parts of hydrogen peroxide.
The lignin can be industrial lignin, such as at least one of alkali lignin, sodium lignosulfonate, enzymatic lignin, calcium lignosulfonate, and sulfonated alkali lignin.
The short-chain alcohol can be at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol; ethanol is preferred.
The temperature for the heat preservation curing is more preferably 80 ℃.
The time for the heat preservation and curing is more preferably 3 hours.
The concentration of the aqueous ammonia used is preferably 25%.
The concentration of hydrogen peroxide used is preferably 35%.
The ammonia and hydrogen peroxide are preferably added sequentially.
The dropping speed is preferably 1 drop/second.
The concentration of the lignin solution is preferably 10-30 wt%, and more preferably 20 wt%.
The time for stirring under heat preservation is preferably 2 h.
The lignin solution, short chain alcohol is preferably added dropwise to the system. More preferably, the lignin solution and the short-chain alcohol are added dropwise to the system at the same time.
The separation can be carried out by using a magnet to obtain magnetic particles.
The material obtained by the separation can be washed by ethanol.
The drying temperature is preferably 50-70 ℃, and more preferably 60 ℃.
The material of the invention takes lignin with rich sources as a carbon supply source, has low price, not only reduces the production cost of the magnetic material, but also conforms to the strategy of green sustainable development
The invention also provides the lignin-based carbon magnetic nano material prepared by the method. The material has the advantages of uniform particle size, large carbon loading capacity and strong methyl orange adsorption capacity.
The method of the invention combines high temperature carbonization and high temperature reforming synchronously, improves the magnetism of the material while obtaining the carbon material, and more importantly, regulates and controls the particle size of the magnetic nano material, improves the adsorption performance of the magnetic nano material on methyl orange, and can be used for adsorbing the methyl orange.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the industrial lignin molecule is in a space network structure, and the molecular skeleton of the industrial lignin molecule contains polyfunctional groups, so that firm combination can be easily formed on the surface of the magnetic nanoparticles, and the functionalization of the nanoparticles is facilitated; (2) by adjusting the carbonization temperature, active functional groups such as hydroxyl, carboxyl and the like are still reserved on the surface of the carbonized lignin, and the carbonized lignin has larger specific surface area and good adsorption performance; (3) the invention not only utilizes the residual functional groups after lignin molecules are carbonized to adsorb methyl orange, but also utilizes Fe prepared by a precipitation method3O4Inorganic O contained in the particles2-、OH-The strong polar ions form strong electrostatic interaction with the polar groups in the methyl orange. Lignin and Fe3O4The particles have synergistic effect, so that the adsorption performance of the particles on methyl orange is further improved; (4) the polarity of the solution is adjusted by short-chain alcohol, the characteristic that the solubility of industrial lignin is reduced in a nonpolar solvent is utilized, the coating amount of the lignin on the surface of the magnetic particles is reasonably increased, and the application performance of the lignin-based magnetic nano material is improved; (5) by the high-temperature carbonization process, the lattice structure of the magnetic particles is reformed while the carbon material is obtained, and the magnetism of the material is greatly improved; (6) the industrial lignin has rich source and low cost. The carbon magnetic nano material is prepared from the industrial lignin, so that the production cost of magnetic particles is greatly reduced, renewable resources are effectively utilized, and the carbon magnetic nano material has the advantages of environmental protection.
Drawings
FIG. 1 is an IR spectrum of a lignin-based carbon magnetic nanomaterial prepared in example 1.
Fig. 2 is an XRD pattern of the lignin-based carbon magnetic nanomaterial prepared in example 1.
Fig. 3 is a Raman spectrum of the lignin-based carbon magnetic nanomaterial prepared in example 1.
Fig. 4 is an SEM image of the lignin-based carbon magnetic nanomaterial prepared in example 1.
Fig. 5 is a hysteresis chart of the lignin-based carbon magnetic nanomaterial prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
Example 1
Dissolving 2.5g ferrous sulfate and 3g ferric chloride in 100m L water, transferring into a four-neck flask, heating to 80 deg.C under mechanical stirring, and sequentially and slowly adding 10g 25% ammonia water solution and 1g 35% H solution2O2The dropping speed was 1 drop/second. After the dropwise addition, the mixture is cured for 1 hour at the temperature of 80 ℃. Dissolving 2g of alkali lignin into 10g of aqueous solution, then dripping the aqueous solution and 10g of absolute ethyl alcohol into the reaction system simultaneously at the dripping speed of 1 drop/second, and keeping the temperature and stirring for 2 hours after dripping. Finally, magnetic particles are separated by a permanent magnet, washed three times by ethanol and dried in vacuum at 60 ℃. Taking the dried product in N2Carbonizing at 550 ℃ for 3h in the atmosphere, cooling and grinding to obtain the lignin-based carbon magnetic nanoparticles. The average particle diameter of the prepared lignin-based carbon magnetic nanoparticles is about 140nm, and the BET specific surface area is 252m2/g。
Adding 0.1g of lignin-based carbon magnetic nanoparticles into a methyl orange solution with the concentration of 100m L being 0.1 g/L, placing the mixture on a shaking table with a fixed shaking speed at 25 ℃, shaking for adsorption, magnetically separating the nanoparticles for 5min in an external magnetic field after adsorption is finished, taking supernatant, measuring the pH to be 2.0 by adopting ultraviolet absorption spectroscopy, and taking a commercially available lignin adsorbent as a comparative example material, wherein the saturated adsorption capacity of the commercially available lignin adsorbent to the methyl orange under the same conditions is only 25.3 mg/g.
Example 2
Dissolving 5g of ferrous sulfate and 6g of ferric chloride in 100m of L-water, transferring the mixture into a four-neck flask, heating the mixture to 70 ℃ under mechanical stirring, and sequentially and slowly dropping 20g of 25% ammonia water solution and 5g of 35% H2O2The dropping speed was 1 drop/second. After the dropwise addition, the mixture is cured for 3 hours under the condition of heat preservation. Dissolving 5g of sodium lignosulfonate into 50g of aqueous solution, and then simultaneously dripping the aqueous solution and 25g of methanol into the reaction system at the dripping speed of 1 drop/second, wherein the dripping is finishedThen stirring for 1h under the condition of heat preservation. Finally, magnetic particles are separated by a permanent magnet, washed three times by ethanol and dried in vacuum at 50 ℃. Taking the dried product in N2Carbonizing at 500 deg.C for 4h in atmosphere, cooling, and grinding to obtain lignin-based carbon magnetic nanoparticles. The average particle diameter of the prepared lignin-based carbon magnetic nanoparticles is about 160nm, and the BET specific surface area is 231m2/g。
Adding 0.1g of lignin-based carbon magnetic nanoparticles into a methyl orange solution with the concentration of 100m L being 0.1 g/L, placing the mixture on a shaking table with a fixed shaking speed at 25 ℃, shaking for adsorption, magnetically separating the nanoparticles for 5min in an external magnetic field after adsorption is finished, taking supernatant, measuring the pH to be 2.0 by adopting ultraviolet absorption spectroscopy, and taking a commercially available lignin adsorbent as a comparative example material, wherein the saturated adsorption capacity of the commercially available lignin adsorbent to the methyl orange under the same conditions is only 25.3 mg/g.
Example 3
Dissolving 3g of ferrous sulfate and 5g of ferric chloride in 100m of L-water, transferring the mixture into a four-neck flask, heating the mixture to 90 ℃ under mechanical stirring, and sequentially and slowly dropping 15g of 25% ammonia water solution and 3g of H2O2The dropping speed was 1 drop/second. After the dropwise addition, the mixture is cured for 2 hours under the condition of heat preservation. Dissolving 4g of enzymatic hydrolysis lignin into 13g of aqueous solution, then dripping the aqueous solution and 20g of n-propanol into the reaction system at the same time, wherein the dripping speed is 1 drop/second, and stirring for 3 hours under heat preservation after dripping. Finally, magnetic particles are separated by a permanent magnet, washed three times by ethanol and dried in vacuum at 70 ℃. Taking the dried product in N2Carbonizing at 650 deg.C for 3.5h in atmosphere, cooling, and grinding to obtain lignin-based carbon magnetic nanoparticles. The average particle diameter of the prepared lignin-based carbon magnetic nanoparticles is about 145nm, and the BET specific surface area is 259m2/g。
Adding 0.1g of lignin-based carbon magnetic nanoparticles into a methyl orange solution with the concentration of 100m L being 0.1 g/L, placing the mixture on a shaking table with a fixed shaking speed at 25 ℃, shaking for adsorption, magnetically separating the nanoparticles for 5min in an external magnetic field after adsorption is finished, taking supernatant, measuring the pH to be 2.0 by adopting ultraviolet absorption spectroscopy, and taking a commercially available lignin adsorbent as a comparative example material, wherein the saturated adsorption capacity of the commercially available lignin adsorbent on methyl orange under the same conditions is only 25.3 mg/g.
Example 4
Dissolving 2.5g ferrous sulfate and 5g ferric chloride in 100m L water, transferring into a four-neck flask, heating to 85 deg.C under mechanical stirring, and sequentially and slowly adding 10g 25% ammonia water solution and 4g 35% H solution2O2The dropping speed was 1 drop/second. After the dropwise addition, the mixture is cured for 1 hour under the condition of heat preservation. Dissolving 3g of calcium lignosulphonate into 15g of aqueous solution, then simultaneously dripping the aqueous solution and 15g of isopropanol into the reaction system at the dripping speed of 1 drop/second, and keeping the temperature and stirring for 2 hours after dripping. Finally, magnetic particles are separated by a permanent magnet, washed three times by ethanol and dried in vacuum at 50 ℃. Taking the dried product in N2Carbonizing at 600 deg.C for 3h in atmosphere, cooling, and grinding to obtain lignin-based carbon magnetic nanoparticles. The average particle diameter of the prepared lignin-based carbon magnetic nanoparticles is about 155nm, and the BET specific surface area is 222m2/g。
Adding 0.1g of lignin-based carbon magnetic nanoparticles into a methyl orange solution with the concentration of 100m L being 0.1 g/L, placing the mixture on a shaking table with a fixed shaking speed at 25 ℃, shaking for adsorption, magnetically separating the nanoparticles for 5min in an external magnetic field after adsorption is finished, taking supernatant, measuring the pH to be 2.0 by adopting ultraviolet absorption spectroscopy, and taking a commercially available lignin adsorbent as a comparative example material, wherein the saturated adsorption capacity of the commercially available lignin adsorbent on methyl orange under the same conditions is only 25.3 mg/g.
Example 5
Dissolving 5g of ferrous sulfate and 6g of ferric chloride in 100m of L-water, transferring the mixture into a four-neck flask, heating the mixture to 75 ℃ under mechanical stirring, and slowly and sequentially dropping 20g of 25% ammonia water solution and 2g of 35% H2O2The dropping speed was 1 drop/second. After the dropwise addition, the mixture is cured for 3 hours under the condition of heat preservation. Dissolving 5g of sulfonated alkali lignin into 50g of water solution, then simultaneously dripping the water solution and 25g of n-butyl alcohol into the reaction system at the dripping speed of 1 drop/second, and keeping the temperature and stirring for 1 hour after the dripping is finished. Finally, magnetic particles are separated by a permanent magnet, washed three times by ethanol and dried in vacuum at 70 ℃. Taking the dried product in N2In an atmosphere of 5Carbonizing at 50 deg.C for 3.5h, cooling, and grinding to obtain lignin-based carbon magnetic nanoparticles. The average particle diameter of the prepared lignin-based carbon magnetic nanoparticles is about 125nm, and the BET specific surface area is 301m2/g。
Adding 0.1g of lignin-based carbon magnetic nanoparticles into a methyl orange solution with the concentration of 100m L being 0.1 g/L, placing the mixture on a shaking table with a fixed shaking speed at 25 ℃, shaking for adsorption, magnetically separating the nanoparticles for 5min in an external magnetic field after adsorption is finished, taking supernatant, measuring the pH to be 2.0 by adopting ultraviolet absorption spectroscopy, and taking a commercially available lignin adsorbent as a comparative example material, wherein the saturated adsorption capacity of the commercially available lignin adsorbent on methyl orange under the same conditions is only 25.3 mg/g.
Example 6
Dissolving 4g of ferrous sulfate and 5g of ferric chloride in 100m of L-water, transferring the mixture into a four-neck flask, heating the mixture to 70 ℃ under mechanical stirring, and sequentially and slowly dropping 12g of 25% ammonia water solution and 1g of 35% H2O2The dropping speed was 1 drop/second. After the dropwise addition, the mixture is cured for 1 hour under the condition of heat preservation. Dissolving 3g of alkali lignin into 10g of water solution, then simultaneously dripping the water solution and 15g of isobutanol into the reaction system at the dripping speed of 1 drop/second, and stirring for 3 hours under heat preservation after dripping. Finally, magnetic particles are separated by a permanent magnet, washed three times by ethanol and dried in vacuum at 50 ℃. Taking the dried product in N2Carbonizing at 500 deg.C for 4h in atmosphere, cooling, and grinding to obtain lignin-based carbon magnetic nanoparticles. The average particle diameter of the prepared lignin-based carbon magnetic nanoparticles is about 168nm, and the BET specific surface area is 199m2/g。
Adding 0.1g of lignin-based carbon magnetic nanoparticles into a methyl orange solution with the concentration of 100m L being 0.1 g/L, placing the mixture on a shaking table with a fixed shaking speed at 25 ℃, shaking for adsorption, magnetically separating the nanoparticles for 5min in an external magnetic field after adsorption is finished, taking supernatant, measuring the pH to be 2.0 by adopting ultraviolet absorption spectroscopy, and taking a commercially available lignin adsorbent as a comparative example material, wherein the saturated adsorption capacity of the commercially available lignin adsorbent on methyl orange under the same conditions is only 25.3 mg/g.
Table 1 below is an elemental analysis of the lignin-based carbon magnetic nanomaterial prepared in example 1. As can be seen from table 1, the product of example 1 contains elements N, H, S in addition to Fe and C, which indicates that after proper high-temperature carbonization, the nanomaterial can retain more active functional groups, which is beneficial to subsequent modification or adsorption of organic substances.
TABLE 1 elemental content (/ wt%) of the product of example 1
FIG. 1 is an IR spectrum of the product of example 1. Wherein, 3400cm-1Is at-OH absorption peak, 2380cm-1The peak at the position is C-O stretching vibration peak, 1203cm-1Is located at a C-C stretching vibration peak and 1720cm-1Located at the stretching vibration peak of Fe-O, 560cm-1Has a peak of Fe3O4Characteristic absorption peak of (1). The infrared spectrum shows that after high-temperature treatment, Fe3O4The crystal structure of the carbon magnetic material is more regular, certain functional groups can still be reserved in the molecules of the lignin after the lignin is carbonized at a proper temperature, and strong chemical bond combination exists between the carbon material and the Fe oxide, so that the prepared carbon magnetic material has a firmer structure.
Figure 2 is the XRD pattern of the product of example 1. Wherein, the peaks at the incident angles 2 θ of 30 °, 37 °, 58 ° and 62 ° are all Fe3O4The absorption peak at an incident angle 2 θ of 12 ° is a diffraction peak of elemental carbon. XRD spectrogram shows that Fe with regular structure can be obtained after high-temperature treatment3O4The crystal of (4).
FIG. 3 is a Raman spectrum of the product of example 1. As can be seen from the figure, the ratio ID/IG is higher, which indicates that the carbon graphitization degree is higher after high-temperature carbonization, thereby being beneficial to subsequent application.
FIG. 4 is an SEM image of the product of example 1. It is obvious from the figure that after high temperature, the carbon magnetic nano material has regular shape, is close to spherical, has uniform particle size, large specific surface area and good adsorption performance.
Fig. 5 is a hysteresis chart of the product of example 1 when T is 300K. It can be seen from the figure that the product of example 1 exhibits better superparamagnetic characteristic when T is 300K, and has a saturation magnetization of 15.6emu/g and good magnetic responsiveness. This provides an important prerequisite for subsequent applications.
The product properties of the other examples were the same as in example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of lignin-based carbon magnetic nano-materials is characterized by comprising the following steps: dissolving ferrous sulfate and ferric chloride in water, preheating, dropwise adding ammonia water and hydrogen peroxide, and curing for 1-3 h at the temperature of 70-90 ℃; adding a lignin solution and short-chain alcohol into the system, and stirring for 1-3 h under heat preservation; separating and drying; carbonizing at 500-650 ℃ for 3-4 h under an inert atmosphere, cooling, and crushing to obtain a lignin-based carbon magnetic nano material;
the dosage formula of each component is as follows, and the components are calculated by mass parts: 2-5 parts of lignin, 10-25 parts of short-chain alcohol, 2.5-5 parts of ferrous sulfate, 3-6 parts of ferric chloride, 10-20 parts of ammonia water and 1-5 parts of hydrogen peroxide;
the short-chain alcohol is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.
2. The method for preparing the lignin-based carbon magnetic nanomaterial according to claim 1, wherein the lignin-based carbon magnetic nanomaterial comprises: the lignin is industrial lignin, and comprises at least one of alkali lignin, sodium lignosulphonate, enzymatic lignin, calcium lignosulphonate and sulfonated alkali lignin.
3. The method for preparing the lignin-based carbon magnetic nanomaterial according to claim 1, wherein the lignin-based carbon magnetic nanomaterial comprises: the temperature for heat preservation and curing is 80 ℃; the time for heat preservation and curing is 3 hours.
4. The method for preparing the lignin-based carbon magnetic nanomaterial according to claim 1, wherein the lignin-based carbon magnetic nanomaterial comprises: the concentration of the ammonia water is 25 wt%; the concentration of hydrogen peroxide used was 35 wt%.
5. The method for preparing the lignin-based carbon magnetic nanomaterial according to claim 1, wherein the lignin-based carbon magnetic nanomaterial comprises: the concentration of the lignin solution is 10-30 wt%; the time for stirring is 2 h.
6. The method for preparing the lignin-based carbon magnetic nanomaterial according to claim 1, wherein the lignin-based carbon magnetic nanomaterial comprises: the drying temperature is 50-70 ℃.
7. A lignin-based carbon magnetic nanomaterial characterized by being obtained by the preparation method according to any one of claims 1 to 6.
8. The application of the lignin-based carbon magnetic nanomaterial of claim 7 in adsorption of methyl orange.
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| CN101497028A (en) * | 2009-01-16 | 2009-08-05 | 中国矿业大学(北京) | Method for preparing magnetic active carbon and the magnetic active carbon |
| CN101642699A (en) * | 2009-08-06 | 2010-02-10 | 浙江大学 | Method for preparing magnetic biological carbon adsorbing material and usage thereof |
| CN103599737A (en) * | 2013-11-20 | 2014-02-26 | 北京化工大学 | Magnetic nano material with carbon shell layer and preparation method thereof |
| CN105777428A (en) * | 2016-03-18 | 2016-07-20 | 常州大学 | Technology for preparing biological charcoal applicable to southern and northern rice regions |
| CN106622239A (en) * | 2016-12-13 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | Lignin-based heterogeneous fenton catalyst and preparation method thereof |
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