CN114772578B - Method for converting vinasse into carbon quantum dots and capacitance carbon - Google Patents
Method for converting vinasse into carbon quantum dots and capacitance carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 41
- 238000002791 soaking Methods 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000012265 solid product Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000004108 freeze drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
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- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
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- 239000003990 capacitor Substances 0.000 abstract description 21
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- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
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- C01B32/342—Preparation characterised by non-gaseous activating agents
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention belongs to the technical field of treatment of vinasse, and particularly relates to a method for converting vinasse into carbon quantum dots and capacitance carbon and the capacitance carbon. The method for converting the vinasse into the carbon quantum dots and the capacitance carbon comprises the following steps: (1) dispersing vinasse in water to obtain vinasse dispersion liquid; (2) Carrying out hydrothermal reaction on the vinasse dispersion liquid to obtain a hydrothermal reaction liquid; (3) Carrying out solid-liquid separation on the hydrothermal reaction liquid, and respectively collecting liquid and solid, wherein the liquid contains carbon quantum dots; (4) Modifying the solid product obtained by the treatment in the step (3) by adopting KOH; (5) Calcining the solid product treated in the step (4), soaking in acid liquor, washing with water and drying to obtain the capacitor carbon. By adopting the method, the distillers' grains can be recycled, and the novel carbon materials such as carbon quantum dots, capacitance carbon and the like can be prepared, so that the problem of environmental pollution is solved, and a novel approach is provided for the preparation of the novel carbon materials.
Description
Technical Field
The invention belongs to the technical field of treatment of vinasse, and particularly relates to a method for converting vinasse into carbon quantum dots and capacitance carbon and the capacitance carbon.
Background
The carbon dot is used as a novel nano carbon material with the particle size smaller than 10nm, has excellent optical characteristics, stable electric and chemical properties, is very friendly to the environment and has low toxicity. The method is widely used in the fields of photoelectric devices, biological imaging and catalytic sensing at present, has wide application prospect and is popular with home and abroad scientists.
The capacitor carbon is the most mainstream electrode material of the supercapacitor due to the advantages of wide sources, reproducibility, high specific surface area, low cost, high conductivity and the like.
Distillers' grains are by-products produced in the process of brewing wine by biomass such as rice, wheat, sorghum and the like. Contains a large amount of organic pollutants, has high acidity and is easy to be spoiled. If not treated effectively, serious environmental pollution is caused. However, because the distillers ' grains contain abundant substances such as cellulose, lignin and protein, if the distillers ' grains can be effectively developed and utilized, the pollution of the waste distillers ' grains to the environment can be reduced, the resource waste is avoided, and the obvious economic benefit can be created.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a method for converting vinasse into carbon quantum dots and capacitance carbon and the capacitance carbon, which are used for solving or relieving the problems of environmental pollution and/or resource waste caused by waste of vinasse in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions: a method for converting distillers' grains into carbon quantum dots and capacitive carbon, comprising the steps of: (1) dispersing vinasse in water to obtain vinasse dispersion liquid; (2) Carrying out a hydrothermal reaction on the vinasse dispersion liquid to obtain a hydrothermal reaction liquid; (3) Carrying out solid-liquid separation on the hydrothermal reaction liquid, and respectively collecting liquid and solid, wherein the liquid contains the carbon quantum dots; (4) Modifying the solid product obtained by the treatment in the step (3) by adopting KOH; (5) And (3) calcining the solid product treated in the step (4), soaking in acid liquor, washing with water and drying to obtain the capacitor carbon.
Preferably, the vinasse dispersion is prepared by immersing, drying and crushing vinasse, and then re-dispersing the vinasse in water.
Preferably, the water immersion comprises the steps of: adding distilled grain into deionized water, stirring and dispersing to obtain distilled grain water immersion liquid; the drying comprises the following steps: placing the vinasse water immersion liquid in a vacuum oven, heating and drying to obtain vinasse powder; the crushing comprises the following steps: placing the vinasse powder into a pulverizer for pulverizing, and sieving to obtain millimeter-sized vinasse powder; adding the millimeter-grade vinasse powder into deionized water, and performing ultrasonic dispersion to obtain the vinasse dispersion liquid.
Preferably, when water is immersed, the stirring and dispersing time is 24-36 hours; the drying temperature is 110-120 ℃; in the process of preparing the millimeter-grade vinasse powder, the aperture of a screen mesh adopted by the sieving is 100-150 meshes.
Preferably, the hydrothermal reaction is carried out under microwave conditions.
Preferably, the temperature of the hydrothermal reaction is 180-220 ℃ and the reaction time is 10-30 min.
Preferably, the hydrothermal reaction comprises the steps of: and (3) placing the vinasse dispersion liquid obtained through the treatment in the step (1) in a microwave reaction tube, and placing the mixture in a microwave synthesizer for hydrothermal reaction after ultrasonic mixing is uniform.
Preferably, the method further comprises the steps of freeze-drying, grinding and dissolving the liquid obtained in the step (3) in a solvent.
Preferably, the freeze drying temperature is-75 to-85 ℃, and the freeze drying time is 20 to 25 hours.
Preferably, the solid-liquid separation in the step (3) is a centrifugal treatment, the rotational speed of the centrifugal treatment is 7500-8500 r/min, and the centrifugal time is 5-15 min.
Preferably, the step (4) includes: A. adding the solid product obtained in the step (3) into KOH solution, and carrying out ultrasonic treatment and soaking; B. and C, carrying out solid-liquid separation on the solution obtained by the treatment in the step A, and washing, centrifuging, filtering and vacuum drying the separated solid.
Preferably, in the step A, the concentration of the KOH solution is 550-650 g/L, and the soaking time is 22-26 h.
Preferably, the calcination in step (4) is performed under an argon atmosphere, the calcination temperature is 650-750 ℃ and the calcination time is 2-3 h.
Preferably, the acid soaking in the step (5) specifically comprises: and soaking the calcined product by adopting hydrochloric acid.
Preferably, the concentration of the hydrochloric acid is 10%, and the soaking time is 20-25 h.
The invention also provides a capacitor carbon, which adopts the following technical scheme: the capacitor carbon is prepared by adopting the method.
The beneficial effects are that:
the method can recycle the distilled grain, and prepares and obtains the novel carbon materials such as carbon quantum dots, capacitance carbon and the like by taking the distilled grain as a carbon source, thereby solving the problem of environmental pollution, providing a novel path for preparing the novel carbon materials and realizing the recycling.
The invention takes the vinasse as a matrix, and prepares two novel carbon materials by a simple microwave-assisted hydrothermal method, the preparation process is quick and simple, the raw materials are easy to obtain, the cost is low, the method is green and environment-friendly, the biomass characteristics of the waste vinasse are effectively utilized, the waste of resources is reduced, and the method is an advanced method for recycling the vinasse and rapidly preparing the carbon materials.
The carbon quantum dot (blue light) prepared by the method for converting the vinasse into the carbon quantum dot and the capacitance carbon has excellent fluorescence characteristic and good water solubility, and can be used in the fields of biological imaging, photoelectric devices, light-emitting devices and the like. The prepared capacitor carbon has a porous structure and good capacitance performance, and can be used in the fields of super capacitors and the like.
Heteroatoms such as N, O, S contained in the vinasse can be inevitably remained in the carbon material in the biomass pyrolysis process, and the capacitor carbon prepared by the method for converting the vinasse into the carbon quantum dots and the capacitor carbon can form self-doping atoms to provide pseudo-capacitance or enhance the conductivity of the carbon material.
The capacitor carbon prepared by the method for converting the vinasse into the carbon quantum dots and the capacitor carbon has stable cycle characteristics; at a current density of 1A/g, the capacitance of the capacitor carbon can reach 98.2F/g.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Wherein:
FIG. 1 is a fluorescence spectrum of a carbon quantum dot according to embodiment 1 of the present invention;
FIG. 2 is an ultraviolet-visible absorption spectrum of the carbon quantum dots provided in inventive example 1;
FIG. 3 is an X-ray diffraction chart of the carbon quantum dots provided in inventive example 1;
fig. 4 is a graph of the carbon quantum dot solution provided in the embodiment 1 of the invention under irradiation of an ultraviolet lamp;
FIG. 5 is a scanning electron micrograph of the capacitive charcoal provided in inventive example 1;
FIG. 6 is a constant current charge-discharge curve of the capacitor carbon provided in example 1 of the present invention;
FIG. 7 is a cyclic voltammogram of the capacitive carbons provided in inventive example 1 and comparative examples 1-6.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention provides a method for converting vinasse into carbon quantum dots and capacitance carbon aiming at the problems of environmental pollution and/or resource waste caused by the existing waste vinasse, so as to realize the recycling of the vinasse and avoid or improve the problems caused by the vinasse.
The method for converting the vinasse into the carbon quantum dots and the capacitance carbon comprises the following steps: (1) dispersing vinasse in water to obtain vinasse dispersion liquid; (2) Carrying out hydrothermal reaction on the vinasse dispersion liquid to obtain a hydrothermal reaction liquid; (3) Carrying out solid-liquid separation on the hydrothermal reaction liquid, and respectively collecting liquid and solid, wherein the liquid contains carbon quantum dots; (4) Modifying the solid product obtained by the treatment in the step (3) by adopting KOH; (5) Calcining the solid product treated in the step (4), soaking in acid liquor, washing with water and drying to obtain the capacitor carbon.
In a preferred embodiment of the present invention, the distillers ' grains dispersion is obtained by immersing, drying and pulverizing distillers ' grains, and then re-dispersing the distillers ' grains in water.
In a preferred embodiment of the invention, the water immersion comprises the steps of: adding the vinasse into deionized water, stirring and dispersing to obtain vinasse water immersion liquid. Water-soluble impurities in the vinasse can be removed by carrying out water leaching treatment on the vinasse.
In a preferred embodiment of the invention, the drying comprises the steps of: placing the distilled grain water immersed solution into a vacuum oven, heating and drying to obtain distilled grain powder; the water contained in the distiller's grains after water immersion can be removed by drying.
In a preferred embodiment of the invention, the comminution comprises the steps of: placing distiller's grains powder into pulverizer, pulverizing, and sieving to obtain millimeter-sized distiller's grains powder (to make distiller's grains sufficiently refined).
In the preferred embodiment of the invention, the millimeter-sized distillers 'grains powder is added into deionized water, and the distillers' grains powder is dispersed by ultrasonic (the millimeter-sized distillers 'grains powder is fully dispersed in the deionized water), thus obtaining the distillers' grains dispersion liquid.
In a preferred embodiment of the present invention, the stirring and dispersing time is 24 to 36 hours (e.g., 24 hours, 30 hours or 36 hours) while water immersion, the drying temperature is 110 to 120 ℃ (e.g., 110 ℃, 115 ℃ or 120 ℃), and the mesh size of the screen used for sieving when preparing the millimeter-sized distillers' grains powder is 100 to 150 mesh (e.g., 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh or 150 mesh).
In a preferred embodiment of the invention, the hydrothermal reaction is carried out under microwave conditions.
In a preferred embodiment of the present invention, the hydrothermal reaction is carried out at a temperature of 180 to 220 ℃ (e.g., 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃) for a reaction time of 10 to 30 minutes (e.g., 10 minutes, 20 minutes or 30 minutes).
In a preferred embodiment of the invention, the hydrothermal reaction comprises the steps of: and (3) filling the vinasse dispersion liquid treated in the step (1) into a microwave reaction tube, uniformly mixing by ultrasonic waves, and then placing the mixture into a microwave synthesizer for hydrothermal reaction. The method has the advantages that the vinasse is subjected to the hydrothermal reaction by adopting the microwave-assisted hydrothermal method, the hydrothermal reaction can be ensured to be carried out in a high-pressure environment, and the characteristics of the microwave method and the hydrothermal method are combined, so that the hydrothermal reaction is simpler, more mild and faster. And the prepared carbon quantum dots have better dispersibility and higher quantum yield.
In a preferred embodiment of the present invention, the method further comprises the steps of freeze-drying, grinding and dissolving the liquid obtained in step (3) in a solvent (e.g., deionized water).
In a preferred embodiment of the invention, the temperature of the freeze-drying is-75 to-85 ℃ (e.g., -75 ℃, -80 ℃ or-85 ℃), and the freeze-drying time is 20 to 25 hours (e.g., 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or 25 hours).
In a preferred embodiment of the present invention, the solid-liquid separation in the step (3) is a centrifugation treatment, the rotational speed of the centrifugation treatment is 7500-8500 r/min (for example, 7500r/min, 8000r/min or 8500 r/min), and the centrifugation time is 5-15 min (for example, 5min, 10min or 15 min).
In a preferred embodiment of the present invention, step (4) includes: A. adding the solid product obtained in the step (3) into KOH solution, and carrying out ultrasonic treatment and soaking; B. and C, carrying out solid-liquid separation on the solution obtained by the treatment in the step A, and washing, centrifuging, filtering and vacuum drying the separated solid.
In a preferred embodiment of the invention, in step A, the concentration of KOH solution is 550-650 g/L (e.g., 550g/L, 580g/L, 600g/L, 620g/L or 650 g/L) and the soaking time is 22-26 h (e.g., 22h, 23h, 24h, 25h or 26 h). If the KOH concentration is too high, the internal structure of the prepared carbon material is destroyed, micropores and mesopores are converted into macropores, and the capacitance performance is not facilitated; if the KOH concentration is too low, the activation degree is incomplete, and the pore structure of the prepared carbon material is not developed enough, and the capacitance performance is not facilitated.
In a preferred embodiment of the present invention, the calcination in step (4) is carried out under an argon atmosphere (the solid obtained by the treatment in step B is placed in a crucible) at a temperature of 650 to 750 ℃ (e.g., 650 ℃, 680 ℃, 700 ℃, 720 ℃ or 750 ℃) for a time of 2 to 3 hours (e.g., 2 hours, 2.3 hours, 2.5 hours, 2.8 hours or 3 hours). The calcining temperature and time can influence the void characteristics of the generated carbon material, and the micropore structure can be increased due to the excessively high temperature and excessively long time without utilizing the capacitance characteristic; too low a calcination temperature and too short a calcination time, the activation of pore formation is not achieved.
Preferably, the acid liquor soaking is specifically that hydrochloric acid is adopted to soak the calcined product.
More preferably, the hydrochloric acid concentration is 10% and the soaking time is 20 to 25 hours (e.g., 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or 25 hours). Wherein, 10% hydrochloric acid is used for removing unreacted and redundant KOH, the acidity is weak, if the hydrochloric acid concentration is too high or other strong acid is used, the structure of the carbon material is easily damaged, and the capacitance performance is not good.
The invention also provides the capacitor carbon, which is prepared by adopting the method for converting the vinasse into the carbon quantum dots and the capacitor carbon.
The method for converting distiller's grains into carbon quantum dots and capacitance carbon and the capacitance carbon prepared by the method are described in detail below through specific examples.
In the following examples: the distilled spirit vinasse is from a Shanxi Fenjiu group feed factory, KOH and hydrochloric acid are provided by Tianjin light complex technology development limited company; the vacuum oven model is GZX-9140MBE, which is from Shanghai Boxun Co., ltd; the microwave synthesizer model number Monowave300, from Austrian An Dongpa (China) Inc.; the centrifuge (TG 16) is provided by the Ministry of national instruments, inc. of the Ministry of China; the model of the ultralow temperature preservation box is DW-86W100, and comes from Qingdao sea special electric appliance Co., ltd; the model of the vacuum freeze dryer is FD-1D-80, which is obtained from Beijing Bo Yikang laboratory instruments Co.
Example 1
The method for converting distiller's grains into carbon quantum dots and capacitance carbon in the embodiment comprises the following steps:
(1) Dispersing vinasse in water to obtain vinasse dispersion liquid: a. soaking in water, adding distiller's grains into deionized water, stirring and dispersing to obtain distiller's grains water soaking liquid; b. drying, soaking for 24 hours, placing the distilled grain water soaking solution into a vacuum oven, heating to 110 ℃, and drying to obtain distilled grain powder; c. crushing, namely putting the vinasse powder into a crusher for crushing, and sieving (the aperture of a screen is 100 meshes) to obtain millimeter-sized vinasse powder; d. adding millimeter-sized vinasse powder into deionized water, and performing ultrasonic dispersion to obtain vinasse dispersion liquid.
(2) Carrying out hydrothermal reaction on the vinasse dispersion liquid to obtain a hydrothermal reaction liquid: placing the vinasse dispersion liquid in a microwave reaction tube, uniformly mixing by ultrasonic waves, and placing in a microwave synthesizer for hydrothermal reaction; wherein the temperature of the hydrothermal reaction is 180 ℃ and the reaction time is 10min.
(3) Carrying out solid-liquid separation (centrifuging at 8000r/min for 10 min) on the hydrothermal reaction liquid, and respectively collecting liquid (supernatant, brown yellow) and solid (black), wherein the liquid contains carbon quantum dots; the brown yellow supernatant is freeze-dried (the freeze-drying temperature is-80 ℃ and the freeze-drying time is 24 hours), and the solid product obtained after freeze-drying is collected, ground into powder and dissolved in a solvent to obtain the carbon quantum dot (solution) of the embodiment.
(4) Modification of the solid product (black solid) obtained by the treatment in step (3) with KOH: A. adding the solid product obtained in the step (3) into a KOH solution with the concentration of 600g/L, performing ultrasonic dispersion, and soaking for 24 hours; B. and C, carrying out solid-liquid separation on the solution obtained by the treatment in the step A, and washing, centrifuging, filtering and vacuum drying the separated solid.
(5) Calcining, soaking in acid liquor, washing in water, centrifuging and drying the solid product treated in the step (4) to obtain the capacitance carbon: placing the solid product obtained in the step (4) in a crucible, and calcining in an argon atmosphere at 750 ℃ for 2 hours; and then, placing the calcined product into hydrochloric acid with the concentration of 10% to be soaked for 24 hours, washing with water, centrifuging, filtering and drying to obtain the capacitor carbon of the embodiment.
Example 2
The only difference from example 1 is that the temperature of the hydrothermal reaction is 220℃and the remainder remains the same as in example 1.
Example 3
The only difference from example 1 is that the hydrothermal reaction time is 20min, the remainder remaining the same as in example 1.
Example 4
The only difference from example 1 is that the hydrothermal reaction time is 30min, the remainder remaining the same as in example 1.
The fluorescence spectra of the carbon quantum dots prepared in examples 1-4 are shown in figure 1, and under 365nm excitation, the emission peak is 442nm, and the carbon quantum dots belong to blue fluorescence carbon dots;
the ultraviolet-visible absorption spectrum of the carbon quantum dot prepared in example 1 is shown in fig. 2, and the absorption peak in fig. 2 is located in the 280nm region (remark: the ultraviolet-visible spectrum of the carbon quantum dot prepared in examples 2-4 is basically consistent with that in fig. 2);
the X-ray diffraction spectrum of the carbon quantum dot prepared in example 1 is shown in fig. 3, and when the diffraction angle 2θ is 21 °, a peak appears, and the diffraction peak corresponds to the (002) plane of the graphite structure, which indicates that carbon in the prepared carbon dot is amorphous carbon;
the image of the carbon quantum dot solution prepared in example 1 under irradiation of an ultraviolet lamp is shown in fig. 4, and the image can be obtained from fig. 4, and under irradiation of 365nm, the carbon quantum dot solution emits blue fluorescence;
FIG. 5 is a scanning electron micrograph of the capacitive carbon prepared in example 1, which shows that the capacitive carbon is porous and has a particle size of millimeter;
FIG. 6 is a constant current charge-discharge curve of the capacitor charcoal prepared in example 1, calculated to have a capacitance of 98.2F/g at a current density of 1A/g.
Comparative example 1
This comparative example differs from the method of example 1 of converting distillers grains into carbon quantum dots and capacitive carbon only in that: in the step (4), the KOH solution with the concentration of the activating agent KOH of 500 g/L; the remainder remained the same as in example 1.
Comparative example 2
This comparative example differs from the method of example 1 of converting distillers grains into carbon quantum dots and capacitive carbon only in that: in the step (4), the KOH solution with the concentration of the activating agent KOH of 700 g/L; the remainder remained the same as in example 1.
Comparative example 3
This comparative example differs from the method of example 1 of converting distillers grains into carbon quantum dots and capacitive carbon only in that: in the step (5), the calcination temperature is 600 ℃; the remainder remained the same as in example 1.
Comparative example 4
This comparative example differs from the method of example 1 of converting distillers grains into carbon quantum dots and capacitive carbon only in that: in the step (5), the calcination temperature is 800 ℃; the remainder remained the same as in example 1.
Comparative example 5
This comparative example differs from the method of example 1 of converting distillers grains into carbon quantum dots and capacitive carbon only in that: in the step (5), the calcination time is 1h; the remainder remained the same as in example 1.
Comparative example 6
This comparative example differs from the method of example 1 of converting distillers grains into carbon quantum dots and capacitive carbon only in that: in the step (5), the calcination time is 4 hours; the remainder remained the same as in example 1.
Experimental example
The cyclic voltammograms of the capacitive carbons prepared in example 1 and comparative examples 1 to 6 were tested and the test results are shown in fig. 7.
As can be seen from FIG. 7, the capacitor charcoal prepared in example 1 has a rectangular shape with a larger rectangular area at a scan rate of 50mV/s, compared with comparative examples 1-6, indicating that the better capacitor charcoal has stable cycle characteristics.
Remarks: (1) In fig. 7, since the overlap ratio of the cyclic voltammograms of comparative example 1 and comparative example 4 is large, the curves of the respective tables of comparative examples 1 and 4 are not easily recognized from fig. 7;
(2) In fig. 7, the cyclic voltammograms (upper half of the curve) of corresponding example 1, comparative example 4 (the curve overlap with comparative example 1 is large and not easily recognized), comparative example 5, comparative example 2, comparative example 3, and comparative example 6 are arranged in this order from the top.
To sum up: the two carbon materials prepared by the one-step hydrothermal method are respectively blue light-emitting carbon quantum dots and capacitance carbon which can be used for super capacitors. And taking the supernatant after the hydrothermal reaction to obtain the aqueous solution of the carbon quantum dots, wherein the aqueous solution of the carbon quantum dots has strong fluorescence characteristic. And taking the precipitate after the hydrothermal reaction, and activating to obtain the capacitance carbon, wherein the capacitance carbon shows excellent capacitance performance under the optimized parameters of the invention.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for converting distillers' grains into carbon quantum dots and capacitive carbon, comprising the steps of: (1) dispersing vinasse in water to obtain vinasse dispersion liquid;
(2) Carrying out a hydrothermal reaction on the vinasse dispersion liquid to obtain a hydrothermal reaction liquid;
(3) Carrying out solid-liquid separation on the hydrothermal reaction liquid, and respectively collecting liquid and solid, wherein the liquid contains the carbon quantum dots;
(4) Modifying the solid product obtained by the treatment in the step (3) by adopting KOH;
(5) Calcining, soaking in acid liquor, washing in water and drying the solid product treated in the step (4) to obtain the capacitance carbon;
the vinasse is white spirit vinasse;
in the step (2), the hydrothermal reaction is carried out under the microwave condition, the temperature of the hydrothermal reaction is 180-220 ℃, and the reaction time is 10-30 min;
the step (4) comprises:
A. adding the solid product obtained in the step (3) into KOH solution, and carrying out ultrasonic treatment and soaking;
B. c, carrying out solid-liquid separation on the solution obtained by the treatment in the step A, and carrying out water washing, centrifugation, filtration and vacuum drying on the separated solid;
in the step A, the concentration of the KOH solution is 550-650 g/L, and the soaking time is 22-26 h;
the calcination in the step (5) is carried out under the argon atmosphere, the temperature of the calcination is 650-750 ℃, and the calcination time is 2-3 h.
2. The method of converting distillers ' grains into carbon quantum dots and capacitive carbon of claim 1, wherein the distillers ' grains dispersion is prepared by immersing distillers ' grains in water, drying, pulverizing, and then re-dispersing in water;
the water immersion comprises the following steps: adding distilled grain into deionized water, stirring and dispersing to obtain distilled grain water immersion liquid;
the drying comprises the following steps: placing the vinasse water immersion liquid in a vacuum oven, heating and drying to obtain vinasse powder;
the crushing comprises the following steps: placing the vinasse powder into a pulverizer for pulverizing, and sieving to obtain millimeter-sized vinasse powder;
adding the millimeter-grade vinasse powder into deionized water, and performing ultrasonic dispersion to obtain the vinasse dispersion liquid.
3. The method for converting distillers' grains into carbon quantum dots and capacitive carbon according to claim 2, wherein the stirring and dispersing time is 24-36 hours when immersed in water;
the drying temperature is 110-120 ℃;
in the process of preparing the millimeter-grade vinasse powder, the aperture of a screen mesh adopted by the sieving is 100-150 meshes.
4. The method of converting distillers grains to carbon quantum dots and capacitive carbon of claim 1, wherein the hydrothermal reaction comprises the steps of: and (3) placing the vinasse dispersion liquid obtained through the treatment in the step (1) in a microwave reaction tube, and placing the mixture in a microwave synthesizer for hydrothermal reaction after ultrasonic mixing is uniform.
5. The method of converting distillers grains into carbon quantum dots and capacitive carbon of claim 1, further comprising the steps of freeze-drying, milling, and dissolving the liquid obtained in step (3) in a solvent.
6. The method of claim 5, wherein the freeze-drying temperature is-75 to-85 ℃ and the freeze-drying time is 20 to 25 hours.
7. The method of converting distillers' grains into carbon quantum dots and capacitive carbon according to claim 5, wherein the solid-liquid separation in step (3) is a centrifugation process, the rotational speed of the centrifugation process is 7500-8500 r/min, and the centrifugation time is 5-15 min.
8. The method of claim 1, wherein the acid soaking in step (5) is specifically: and soaking the calcined product by adopting hydrochloric acid.
9. The method of converting distillers' grains into carbon quantum dots and capacitive carbon of claim 8, wherein the hydrochloric acid is at a concentration of 10% and the soaking time is 20-25 hours.
10. A capacitive carbon prepared by the method of any one of claims 1-9.
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| US20180291266A1 (en) * | 2016-03-11 | 2018-10-11 | Dalian University Of Technology | A carbon quantum dot synthesizing method and its application of modifying functional water purification material |
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