CN111039272A - Nano carbon microsphere and controllable preparation method and application thereof - Google Patents
Nano carbon microsphere and controllable preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 85
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920005610 lignin Polymers 0.000 claims abstract description 60
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 24
- 239000001923 methylcellulose Substances 0.000 claims abstract description 24
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 23
- 235000010981 methylcellulose Nutrition 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002077 nanosphere Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- -1 polytetrafluoroethylene Polymers 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 239000002028 Biomass Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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Abstract
The invention belongs to the technical field of papermaking industrial waste utilization, and discloses a nano carbon microsphere and a controllable preparation method and application thereof. The controllable preparation method of the nano carbon microsphere comprises the following steps: (1) dispersing a mixture of lignin and methylcellulose in a strong alkali solution to obtain a precursor solution; (2) carrying out hydrothermal carbonization reaction on the precursor solution to obtain nano carbon microspheres; the temperature of the hydrothermal carbonization reaction is 140-240 ℃. The method is simple, utilizes the paper making waste lignin to synthesize the nano carbon microspheres in one step, realizes the utilization of resources and can realize the synthesis with controllable particle size. The invention applies the nano carbon microspheres to remove the heavy metal Cr (VI) in the environment, and the removal rate is high.
Description
Technical Field
The invention belongs to the technical field of waste utilization in the papermaking industry, and particularly relates to a controllable prepared nano carbon microsphere as well as a preparation method and application thereof. The nano carbon microsphere is used for removing environmental heavy metal ions, particularly Cr (VI).
Background
The paper industry causes numerous environmental pollution, with lignin and hemicellulose being the major solid waste contaminants in the paper industry. Lignin is a natural organic high molecular compound, widely present in plants, and is a reinforcing system in the plant skeleton, which is more than half fiber and less than cellulose, and is synthesized in the earth by photosynthesis of plants by about 500 million tons every year. The paper industry generates about 5000 million tons of industrial lignin wastes every year, only a small part of the industrial lignin wastes is effectively utilized, and most of industrial waste lignin is discharged into rivers or burnt in the paper industry in developing countries, so that the environment is seriously polluted.
The nano carbon microsphere is a nano material which attracts attention in recent years, and has wide application in the fields of energy, catalysis, biology, environment and the like. The raw materials for preparing the carbon nano material in the early stage mainly comprise mesophase pitch, polycyclic aromatic hydrocarbon and the like; with the development of green chemical technology in recent years, the requirement of zero emission of carbon dioxide can be realized by adopting biomass as a raw material, and the biomass can be changed into valuables to realize the maximization of resource utilization, so that the synthesis of the nano carbon material by adopting the biomass becomes a recent research hotspot.
Currently, commonly used biomass raw materials mainly adopt glucose and fructose, while lignin which is a biomass waste in the paper industry is recycled, and related researches on recycling of lignin are less. According to the current situation, the method for recycling and fully developing and utilizing the lignin of the biomass waste in the paper industry has good environmental, economic and social benefits, so that the method for preparing the nano carbon microspheres by utilizing the lignin and changing waste into valuable is applied to environmental pollution treatment and has important development value and application prospect.
Disclosure of Invention
The invention aims to solve the problem of improper treatment of lignin which is a waste in the paper industry at present, and provides a method for synthesizing nano carbon microspheres by utilizing waste, which is green, energy-saving and capable of changing waste into valuables.
Another object of the present invention is to provide the nanocarbon microspheres obtained by the above method. The invention can control and synthesize the carbon microspheres with different diameters by adjusting the factors such as the hydrothermal temperature, the hydrothermal time and the like.
The invention also aims to provide application of the nano carbon microsphere. The nano carbon microsphere is used for removing metal ions in the environment, particularly removing Cr (VI).
The purpose of the invention is realized by the following technical scheme:
a controllable preparation method of nano carbon microspheres comprises the following steps:
(1) dispersing a mixture of lignin and methylcellulose in a strong alkali solution to obtain a precursor solution;
(2) carrying out hydrothermal carbonization reaction on the precursor solution to obtain nano carbon microspheres; the temperature of the hydrothermal carbonization reaction is 140-240 ℃. The time of the hydrothermal carbonization reaction is 18-24 h.
The concentration of the strong alkali solution in the step (1) is 0.5-2 mol/L; the mass of the lignin and the methyl cellulose is 3 to 15 percent of that of the strong alkali. The content of lignin in the mixture is 70-80 wt%. The dispersing refers to stirring for 10-24 hours. The strong base is more than one of sodium hydroxide or potassium hydroxide. The mixture of lignin and methylcellulose is prepared from papermaking waste.
In the step (2), when the temperature of the hydrothermal carbonization reaction is 140-160 ℃, the diameter of the obtained nano carbon microsphere is nano-scale and is less than or equal to 600 nm; the diameter of the nano carbon microsphere obtained at 180-240 ℃ is micron-sized, and is not less than 1um and not more than 7 um.
The nano carbon microspheres are used for removing heavy metal ions in the environment, such as Cr (VI); the removal rate of the environmental heavy metal ions Cr (VI) is close to 95 percent when the concentration is 5.0mg/L and the pH value is 2.0.
The nano carbon microspheres are used for removing heavy metal Cr (VI) in water, the pH value is less than or equal to 3, and the temperature is between normal temperature and 70 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the method utilizes the lignin of the papermaking waste to synthesize the nano carbon microspheres in one step, thereby realizing the utilization of resources;
(2) the invention basically realizes green pollution-free treatment of solid waste, changes waste into valuable, and the synthesized nano carbon microspheres have better application prospect in the field of environmental pollution treatment.
(3) The whole preparation engineering process is simple, and the preparation of the carbon nanospheres can realize the controllable synthesis of the particle size (300 nm-6 um).
(4) The invention applies the nano carbon microspheres to remove heavy metal Cr (VI) in the environment, and the removal rate is close to 95 percent.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the nanocarbon microspheres prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the nanocarbon microspheres prepared in example 5;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the nanocarbon microspheres prepared in example 9;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the nanocarbon microspheres prepared in example 13;
FIG. 5 is a graph showing the change of the removal rate of heavy metal Cr (VI) with pH and ionic strength;
FIG. 6 shows the adsorption amount of heavy metal Cr (VI) with temperature and initial concentration; q. q.seIs the adsorption capacity; c0Is the original Cr (VI) concentration.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Dispersing 0.2g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 0.5M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) and transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 160 ℃, preserving heat for 24h, naturally cooling to room temperature, carrying out centrifugal separation, washing with deionized water for 5 times, and drying to obtain the nano carbon microspheres (200-500 nm) to be prepared.
The SEM image of the nanocarbon microsphere prepared in this example is shown in fig. 1, and it is apparent that the maximum diameter of the prepared nanocarbon microsphere is about 500nm and there is almost no impurity when the synthesis condition is 160 ℃.
Example 2
(1) Dispersing 0.5g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 0.5M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) and transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting the precursor solution into an oven, heating to 160 ℃, preserving the temperature for 20h, naturally cooling to room temperature, performing centrifugal separation, and drying to obtain the nano carbon microspheres to be prepared. The morphology of the carbon nanospheres prepared in this example is similar to that of example 1.
Example 3
(1) Dispersing 1.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 1.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, stirring uniformly, then putting the precursor solution into an oven, heating to 160 ℃, preserving the temperature for 22h, carrying out centrifugal separation, washing for 5 times by deionized water, and drying to obtain the nano carbon microspheres to be prepared. The morphology of the carbon nanospheres prepared in this example is similar to that of example 1.
Example 4
(1) Dispersing 2.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 160 ℃, preserving heat for 24h, centrifugally separating, washing with deionized water for 5 times, and drying to obtain the nano carbon microspheres to be prepared. The morphology of the carbon nanospheres prepared in this example is similar to that of example 1.
Example 5
(1) Dispersing 0.2g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 0.5M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 180 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by deionized water, and drying to obtain the nano carbon microsphere (about 2.0um) to be prepared.
The SEM image of the carbon microsphere prepared in this example is shown in fig. 2, and it is obvious that the diameter of the micron-sized carbon microsphere prepared by increasing the lignin concentration is about 2.0um under the synthesis condition of 180 ℃.
Example 6
(1) Dispersing 0.5g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 0.5M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 180 ℃, preserving heat for 20h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-sized carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 5.
Example 7
(1) Dispersing 1.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 1.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 180 ℃, preserving heat for 22h, centrifugally separating, washing with deionized water for 5 times, and drying to obtain the micron-sized carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 5.
Example 8
(1) Dispersing 2.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 180 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-sized carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 5.
Example 9
(1) Dispersing 0.5g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 0.5M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 220 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by deionized water, and drying to obtain the micron-scale carbon microspheres (about 4.0um) to be prepared.
The SEM image of the carbon microsphere prepared in this example is shown in fig. 3, and it is apparent that the diameter of the prepared micron-sized carbon microsphere is about 4.0um under the synthesis condition of 220 ℃.
Example 10
(1) Dispersing 1.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 1.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 220 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-scale carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 9.
Example 11
(1) Dispersing 1.5g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 220 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-scale carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 9.
Example 12
(1) Dispersing 2.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 220 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-scale carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 9.
Example 13
(1) Dispersing 1.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 1.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 240 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by deionized water, and drying to obtain the micron-scale carbon microspheres (about 6.0um) to be prepared.
The SEM image of the carbon microsphere prepared in this example is shown in fig. 4, and it is apparent that the diameter of the prepared micron-sized carbon microsphere is about 6.0um under the synthesis condition of 240 ℃.
Example 14
(1) Dispersing 1.5g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) and transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 240 ℃, preserving the temperature for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-scale carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 13.
Example 15
(1) Dispersing 2.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) and transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 240 ℃, preserving the temperature for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-scale carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 13.
Example 16
(1) Dispersing 3.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) and transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 260 ℃, preserving heat for 24h, carrying out centrifugal separation, washing for 5 times by using deionized water, and drying to obtain the micron-scale carbon microspheres to be prepared. The morphology of the carbon microspheres prepared in this example was similar to that of example 13.
Example 17
(1) Dispersing 1.0g of lignin (the content of lignin is about 76%, and the content of methylcellulose is about 24%) in 200mL of 2.0M potassium hydroxide solution, and stirring at normal temperature for 24h to obtain a precursor solution;
(2) transferring 30mL of the precursor solution to a polytetrafluoroethylene inner container with the capacity of 50mL, uniformly stirring, then putting into an oven, heating to 150 ℃, preserving heat for 24h, centrifugally separating, washing with deionized water for 5 times, and drying to obtain the nano carbon microspheres to be prepared.
Example 18 environmental heavy Metal ion Cr (VI) removal applications
The nano carbon microspheres prepared in example 1 are applied to removal of environmental heavy metal ions Cr (VI):
(1) mixing NaNO carbon microspheres (namely lignin carbon spheres) with a solution containing Cr (VI), adsorbing, wherein the concentration of the NaNO carbon microspheres is 0.1g/L, the concentration of the Cr (VI) in the solution containing Cr (VI) is 5.0mg/L, the adsorption temperature is 25 ℃, and respectively testing different ionic strengths (adding different amounts of NaNO into the solution)3，NaNO3The concentration of the nano carbon microspheres is 0.001M, 0.01M, 0.1M and the adsorption removal performance of the nano carbon microspheres to Cr (VI) under the conditions of pH (2-10). The test results are shown in fig. 5. Adsorbing and removing hexavalent chromium by the nano carbon microspheres under the conditions for 24 hours; but the adsorption lasts for 60-80 min, and the adsorption balance of the nano carbon microspheres is already achieved.
(2) Mixing nano carbon microspheres (namely lignin carbon spheres) with a solution containing Cr (VI), adsorbing, wherein the concentration of the nano carbon microspheres is 0.1g/L, and testing the adsorption removal performance of the nano carbon microspheres on the Cr (VI) under the conditions of different temperatures (25,35,45 ℃) and initial concentrations (5-110 mg/L) of Cr (VI). The test results are shown in fig. 6. Under the above conditionsRemoving hexavalent chromium by using a rice carbon microsphere for adsorption, wherein the adsorption time is 24h, the pH is 2.0, and the NaNO is3The concentrations of (A) and (B) are respectively 0.001M; but the adsorption lasts for 60-80 min, and the adsorption balance of the nano carbon microspheres is already achieved.
Fig. 5 is a graph showing the removal rate of nano carbon microspheres (i.e., lignin carbon spheres) to cr (vi) (i.e., the removal rate of heavy metal cr (vi) varies with pH and ionic strength) under different pH and ionic strength; FIG. 6 is a graph showing the adsorption capacity of nano carbon microspheres (i.e. lignin carbon spheres) to Cr (VI) at different temperatures and initial concentrations of Cr (VI) (i.e. the adsorption capacity of heavy metal Cr (VI) varies with temperature and initial concentration; q)eIs the adsorption capacity; c0Original cr (vi) concentration).
Claims (9)
1. A controllable preparation method of nano carbon microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing a mixture of lignin and methylcellulose in a strong alkali solution to obtain a precursor solution;
(2) carrying out hydrothermal carbonization reaction on the precursor solution to obtain nano carbon microspheres; the temperature of the hydrothermal carbonization reaction is 140-240 ℃.
2. The controllable preparation method of the carbon nanospheres according to claim 1, wherein: the time of the hydrothermal carbonization reaction in the step (2) is 18-24 h; the dispersing in the step (1) is stirring for 10-24 hours.
3. The controllable preparation method of the carbon nanospheres according to claim 1, wherein: the concentration of the strong alkali solution in the step (1) is 0.5-2 mol/L; in the step (1), the mass of the mixture of the lignin and the methyl cellulose is 3 to 15 percent of the mass of strong alkali;
in the step (1), the content of lignin in the mixture is 70-80 wt%.
4. The controllable preparation method of the carbon nanospheres according to claim 1, wherein: in the step (1), the strong base is more than one of sodium hydroxide or potassium hydroxide;
the mixture of lignin and methylcellulose is prepared from papermaking waste.
5. The controllable preparation method of the carbon nanospheres according to claim 1, wherein: when the temperature of the hydrothermal carbonization reaction is 140-160 ℃, the diameter of the obtained nano carbon microsphere is nano-scale and is less than or equal to 600 nm; the diameter of the nano carbon microsphere obtained at 180-240 ℃ is micron-sized, and is not less than 1um and not more than 7 um.
6. A nanocarbon microsphere obtained by the production method according to any one of claims 1 to 5.
7. The use of the nanocarbon microspheres according to claim 1, wherein: the nano carbon microspheres are used for removing heavy metal ions in the environment.
8. Use according to claim 7, characterized in that: the heavy metal is Cr (VI).
9. Use according to claim 8, characterized in that: when the nano carbon microspheres are used for removing heavy metals Cr (VI) in water, the pH value of the solution is less than or equal to 3, and the temperature is between normal temperature and 70 ℃.
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| CN104649246A (en) * | 2013-11-18 | 2015-05-27 | 湖南师范大学 | Low temperature hydrothermal preparation method of biomass carbon microsphere / nanosphere |
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