CN112265981B - Method for preparing carbon nano tube by lignin nano micelle - Google Patents
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- CN112265981B CN112265981B CN202011149494.1A CN202011149494A CN112265981B CN 112265981 B CN112265981 B CN 112265981B CN 202011149494 A CN202011149494 A CN 202011149494A CN 112265981 B CN112265981 B CN 112265981B
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- C01B32/00—Carbon; Compounds thereof
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention discloses a method for preparing carbon nano-tubes by lignin nano-micelles, which comprises the following steps: (1) preparing lignin @ catalyst nano micelles by taking lignin, a catalyst, an organic solvent and pure water as raw materials; (2) pyrolyzing the lignin @ catalyst nano micelle in a protective atmosphere; (3) and carrying out acid treatment on the pyrolysis product to obtain the purified lignin-based carbon nanotube. According to the invention, the catalyst and lignin are prepared into the lignin @ catalyst nano micelle, the catalyst forms nano particles in the micelle, and the nano particles are dispersed in the lignin very uniformly, so that the prepared lignin-based carbon nano tube has small size and is distributed uniformly. The invention utilizes industrial waste lignin as a carbon source, adopts a catalytic pyrolysis method to prepare the carbon nano tube with high performance and high value, and can become an important way for high-value utilization of lignin. The preparation method has the advantages of rich raw material sources, simple process and low cost, and has good development prospect in the field of high-value utilization of lignin.
Description
Technical Field
The invention belongs to the field of high-value utilization of lignin, and particularly relates to a method for preparing a carbon nano tube by using a lignin nano micelle.
Background
Lignin is a cheap, readily available and renewable resource, and has received much attention in the preparation of lignin-based carbon fibers and lignin-based carbon nanofibers [1], but reports on the preparation of carbon nanotubes using lignin as a carbon source are rare. Liaoning university Liaohao, Jiangchune et al [2] take lignin extracted from corn stalks and hay as a biomass-based carbon source, and take porous anodic alumina as a template to prepare a lignin-based carbon nanotube, wherein the diameter of the carbon nanotube is about 200nm, and the size of the carbon nanotube is larger.
[1]W.Fang,S.Yang,X.Wang,T.Yuan,R.Sun.Manufacture and application of lignin-based carbon fibers(LCFs)and lignin-based carbon nanofibers(LCNFs)[J].Green Chemistry,2017,19:1794–1827.
[2] Liaoning university 2014, Liaoning university.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a brand-new method for preparing carbon nanotubes by using lignin nano micelles, can effectively solve the problems that a catalyst is difficult to disperse uniformly in lignin, and the prepared carbon nanotubes have large size, and has rich raw material sources, simple preparation process and good development prospect in the field of high-value utilization of lignin.
A method for preparing carbon nanotubes by lignin nano-micelles comprises the following specific steps:
(1) preparing lignin @ catalyst nano micelles by taking lignin, a catalyst, an organic solvent and pure water as raw materials;
(2) pyrolyzing the lignin @ catalyst nano micelle in a protective atmosphere;
(3) and carrying out acid treatment on the pyrolysis product to obtain the purified lignin-based carbon nanotube.
The method comprises the steps of (1) adding lignin and a catalyst into an organic solvent, stirring until the lignin and the catalyst are completely dissolved and uniformly dispersed, then dropwise adding pure water while stirring, volatilizing or dialyzing to remove the organic solvent, and freeze-drying to constant weight to obtain the lignin @ catalyst nano micelle.
The method comprises the steps of (1) dropwise adding pure water with the volume of 1-10 times, preferably 2-8 times, and more preferably 3-4 times of that of the organic solvent while stirring (the dropwise adding speed of the water is 0.1-10mL/min, preferably 1-3 mL/min); the weight volume concentration of the lignin in the organic solvent is 0.01-20 g/100 mL; preferably 0.1 to 10g/100mL, and more preferably 0.5 to 5g/100 mL.
According to the method, the mass ratio of the catalyst to the lignin is 1: 1000-1: 5; preferably 5:1000 to 1:10, and more preferably 1:100 to 8: 100.
According to the method, after the pure water is dripped, the organic solvent is removed by adopting a dialysis or volatilization mode, preferably dialysis is carried out for 24-48h, and freeze drying is carried out to prepare the lignin @ catalyst nano micelle.
The method, wherein the lignin comprises: one or more of enzymatic lignin, ethanolic lignin, alkaline lignin, kraft lignin, and organo-lignin.
The catalyst comprises: one or more of ferrocene, nickel oxalate, cobalt oxalate, nickelocene, allylnickel, nickelocene, ferric nitrate, cobalt nitrate and nickel nitrate; one or more of ferrocene, nickelocene and cobaltocene is preferred.
The organic solvent is an organic solvent capable of dissolving lignin, and preferably comprises: one or more of N, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, dioxane, acetone, ethanol, isopropanol, ethyl acetate and alkali solution.
In the method, a one-step heating method is adopted during the pyrolysis in the step (2), the temperature is increased from the normal temperature to 600-1300 ℃, preferably 800-1000 ℃ at the speed of 5-20 ℃/min, the time is 2-12h, preferably 4-8h, and nitrogen is introduced for protection in the whole process.
The method comprises the steps of (2) heating the lignin @ catalyst nano micelle from normal temperature to 300 ℃ at the rate of 5-20 ℃/min and keeping the temperature for 1-2h, then heating to 550 ℃ at the rate of 400-20 ℃/min and keeping the temperature for 1-3h, then heating to 1300 ℃ at the rate of 600-1300 ℃ at the rate of 5-20 ℃/min and keeping the temperature for 1-6h, cooling to obtain a pyrolysis product, and introducing nitrogen for protection in the whole process.
In the method, in the step (3), the pyrolysis product is treated by dilute acid (dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid), preferably dilute HCl, and then filtered, washed by water (to remove the catalyst) and dried; adding the dried sample to concentrated H 2 SO 4 And HNO 3 And refluxing, cooling, dialyzing (removing amorphous carbon), and drying the mixed solution to obtain the purified lignin-based carbon nanotube.
Adding the pyrolysis product into dilute hydrochloric acid with the concentration of 5-20% according to the weight volume concentration of 0.1-10g/100mL, carrying out ultrasonic treatment for 1-6h, then filtering and washing, and carrying out vacuum drying at 50-90 ℃ to constant weight; adding 3/1 vol% concentrated 98% H into a dry sample according to the weight volume concentration of 0.1-10g/100mL 2 SO 4 And 65% HNO 3 The mixed solution is refluxed for 1 to 24 hours at the temperature of 120 ℃ and 140 ℃ and then usedDiluting with distilled water, cooling, dialyzing for 24-48h, and vacuum drying at 50-90 deg.C to constant weight to obtain purified lignin-based carbon nanotube.
The invention has the positive effects that:
1. firstly, the catalyst and lignin are prepared into lignin @ catalyst nano-micelles, on one hand, the catalyst forms nano-particles in the micelles, and on the other hand, the catalyst is dispersed in the lignin very uniformly, so that the prepared lignin-based carbon nano-tubes have small sizes (the diameters are not more than 20nm, preferably not more than 10nm) and are uniformly distributed.
2. The size of the carbon nano tube can be regulated and controlled by regulating and controlling the size of the lignin nano micelle.
3. The invention utilizes industrial waste lignin as a carbon source, adopts a catalytic pyrolysis method to prepare the carbon nano tube with high performance and high value, and can become an important way for high-value utilization of lignin.
4. The preparation method has the advantages of rich raw material sources, simple process and low cost, and has good development prospect in the field of high-value utilization of lignin.
Drawings
FIG. 1 is a Raman spectrum of carbon nanotubes prepared by lignin nanomicelle of example 1;
FIG. 2 is a transmission electron microscope image of carbon nanotubes prepared by lignin nanomicelles of example 1.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it.
Example 1
Adding 5g of enzymatic hydrolysis lignin powder and 0.1g of catalyst ferrocene into 50mL of N, N-dimethylformamide, stirring until the lignin and the ferrocene are completely dissolved and uniformly dispersed, then dropwise adding 200mL of pure water while stirring, wherein the dropwise adding speed of water is 1mL/min, dialyzing for 24-48h after the dropwise adding of the water is finished, removing the solvent, and freeze-drying to constant weight to obtain the lignin @ ferrocene nano micelle;
weighing about 2g of lignin @ ferrocene nano micelle in a crucible, covering the crucible with a pot cover, introducing nitrogen for 10-20 minutes, and exhausting in a tubular furnaceHeating the temperature from normal temperature to 230 ℃ at a speed of 10 ℃/min and keeping the temperature for 1h, heating the temperature to 550 ℃ at 10 ℃/min and keeping the temperature for 1h, heating the temperature to 900 ℃ at 2 ℃/min and keeping the temperature for 2h, cooling the temperature to normal temperature, and taking out the product (nitrogen protection is introduced in the whole process, N is used for protection) 2 Flow rate 200 mL/min);
carrying out ultrasonic treatment on 0.5g of pyrolysis product in 50mL of 10% dilute hydrochloric acid for 4 hours, then filtering and washing with water to remove the catalyst, and carrying out vacuum drying at 50-90 ℃ to constant weight; 0.3g of the dried sample was taken up in 50mL of concentrated H 2 SO 4 (98％)/HNO 3 (65%) (3/1 vol.%) in the mixture, reflux at 120 deg.C for 4 hr, diluting with distilled water, cooling to room temperature, dialyzing in dialysis bag for 48 hr to remove amorphous carbon, and vacuum drying at 50-90 deg.C to constant weight to obtain purified lignin-based carbon nanotubes.
Fig. 1 is a raman spectrum of the lignin-based carbon nanotube obtained in example 1. As can be seen from FIG. 1, it is at 1372cm -1 (peak D) and 1605cm -1 Two strong vibration peaks exist around the (G peak), the former is attributed to the defect peak in amorphous carbon and graphite sheet layer, and the latter is attributed to sp in graphite sheet layer 2 Vibration of the carbon in the hybrid state. The intensity of the G peak is obviously higher than that of the D peak, which shows that the graphitization degree of the carbon nano tube is higher.
FIG. 2 is a transmission electron micrograph of the lignin-based carbon nanotube obtained in example 1. As can be seen from fig. 2, the average diameter of the carbon nanotubes is about 3.5 nm.
Example 2
The amount of the catalyst ferrocene is 0.2g, and the process steps and other process parameters are the same as those of the example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 4.1nm as measured by transmission electron microscopy.
Example 3
The amount of the catalyst ferrocene is 0.8g, and the process steps and other process parameters are the same as those of the example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 5.6nm as measured by transmission electron microscopy.
Example 4
The catalyst is selected from cobaltocene, and the process steps and other process parameters are the same as those in example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 4.5nm as measured by transmission electron microscopy.
Example 5
The catalyst is selected from ferric nitrate, and the process steps and other process parameters are the same as those of example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 8.4nm as measured by transmission electron microscopy.
Example 6
The lignin is selected as alkali lignin, and the process steps and other process parameters are the same as those in example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 7.2nm as measured by transmission electron microscopy.
Example 7
The lignin is selected as kraft lignin, and the process steps and other process parameters are the same as in example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 4.1nm as measured by transmission electron microscopy.
Example 8
The pyrolysis final temperature was taken as 600 ℃ and the process steps and other process parameters were the same as in example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 5.6nm as measured by transmission electron microscopy.
Example 9
The pyrolysis final temperature was taken to be 1100 ℃ and the process steps and other process parameters were the same as in example 1. The purified lignin-based carbon nanotubes were obtained and had an average diameter of about 3.2nm as measured by transmission electron microscopy.
Comparative example
Uniformly mixing 5g of enzymatic hydrolysis lignin and 0.1g of catalyst ferrocene;
the subsequent process steps and other process parameters were the same as in example 1. The purified lignin-based carbon nanotubes are obtained, and the average diameter of the lignin-based carbon nanotubes is about 40-50nm through transmission electron microscope test.
Claims (15)
1. A method for preparing carbon nanotubes by lignin nano-micelles is characterized by comprising the following specific steps:
(1) preparing lignin @ catalyst nano-micelle by taking lignin, a catalyst, an organic solvent and pure water as raw materials;
(2) pyrolyzing the lignin @ catalyst nano micelle in a protective atmosphere;
(3) treating the pyrolysis product with acid to obtain a purified lignin-based carbon nanotube;
adding lignin and a catalyst into an organic solvent, stirring until the lignin and the catalyst are completely dissolved and uniformly dispersed, then dropwise adding pure water while stirring, volatilizing or dialyzing to remove the organic solvent, and freeze-drying to obtain the lignin @ catalyst nano micelle;
dropwise adding pure water with the volume of 1-10 times that of the organic solvent while stirring, wherein the dropwise adding speed of the water is 0.1-10 mL/min;
the weight volume concentration of the lignin in the organic solvent is 0.01-20 g/100 mL.
2. The method of claim 1,
dropwise adding pure water with the volume 2-8 times that of the organic solvent while stirring, wherein the dropwise adding speed of the water is 1-3mL/min, and the weight volume concentration of the lignin in the organic solvent is 0.1-10g/100 mL.
3. The method of claim 1,
and (2) dropwise adding pure water with the volume 3-4 times that of the organic solvent while stirring, wherein the weight volume concentration of the lignin in the organic solvent is 0.5-5g/100 mL.
4. The method of claim 1,
the mass ratio of the catalyst to the lignin is 1: 1000-1: 5.
5. The method of claim 4,
the mass ratio of the catalyst to the lignin is 5:1000-1: 10.
6. The method of claim 5,
the mass ratio of the catalyst to the lignin is 1:100-8: 100.
7. The method of claim 1, wherein the dialysis is for 24 to 48 hours.
8. The method of claim 1,
the lignin comprises: one or more of enzymatic hydrolysis lignin, ethanol lignin, alkali lignin, sulfate lignin, kraft lignin and organic lignin;
the catalyst comprises: one or more of ferrocene, nickel oxalate, cobalt oxalate, nickelocene, allylnickel, nickelocene, ferric nitrate, cobalt nitrate and nickel nitrate; the organic solvent is an organic solvent capable of dissolving lignin.
9. The method of claim 8,
the catalyst comprises: one or more of ferrocene, nickelocene and cobaltocene;
the organic solvent comprises: one or more of N, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, dioxane, acetone, ethanol, isopropanol, ethyl acetate and alkali solution.
10. The method as claimed in claim 1, wherein the pyrolysis in step (2) is carried out by a one-step heating method, wherein the temperature is increased from room temperature to 600-1300 ℃ at a rate of 5-20 ℃/min for 2-12h, and nitrogen is introduced for protection.
11. The method as claimed in claim 10, wherein the pyrolysis in step (2) is carried out by a one-step heating method, wherein the temperature is raised from room temperature to 800-1000 ℃ at a rate of 5-20 ℃/min for 4-8h, and nitrogen is introduced for protection.
12. The method of claim 1,
and (2) heating the lignin @ catalyst nano micelle from the normal temperature to 300 ℃ for 1-2h at the speed of 5-20 ℃/min, then heating to 550 ℃ for 400 ℃ for 550 h at the speed of 5-20 ℃/min, keeping for 1-3h, heating to 1300 ℃ at the speed of 5-20 ℃/min, keeping for 1-6h, cooling to obtain a pyrolysis product, and introducing nitrogen for protection in the whole process.
13. The method of claim 1,
treating the pyrolysis product by dilute acid, filtering, washing with water, and drying; adding the dried sample to concentrated H 2 SO 4 And HNO 3 And refluxing, cooling, dialyzing and drying the mixed solution to obtain the purified lignin-based carbon nano tube.
14. The method of claim 13,
and (3) treating the pyrolysis product by using dilute hydrochloric acid.
15. The method of claim 1 or 13 or 14,
adding the pyrolysis product into dilute hydrochloric acid with the concentration of 5-20% according to the weight volume concentration of 0.1-10g/100mL, carrying out ultrasonic treatment for 1-6h, then filtering, washing with water, and drying; adding 3/1 vol% concentrated 98% H into a dried sample according to the weight volume concentration of 0.1-10g/100mL 2 SO 4 And 65% HNO 3 And refluxing the mixed solution at the temperature of 120 ℃ and 140 ℃ for 1-24h, then diluting the mixed solution by using distilled water, cooling the diluted solution, dialyzing the diluted solution for 24-48h, and drying the dialyzed solution to obtain the purified lignin-based carbon nanotube.
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| CN112973625B (en) * | 2021-02-05 | 2022-05-10 | 中南林业科技大学 | Lignin-based carbon nanotube and preparation method and application thereof |
| CN113307250B (en) * | 2021-04-30 | 2022-08-26 | 齐鲁工业大学 | Preparation method and application of ordered lignin carbon-carbon nanotube composite material |
| CN114914101B (en) * | 2022-06-07 | 2023-05-16 | 西南交通大学 | Porous carbon energy storage material and preparation method thereof |
| CN114920952B (en) * | 2022-06-07 | 2023-08-18 | 西南交通大学 | Lignin nanowire and preparation method and application thereof |
| CN114989448B (en) * | 2022-06-07 | 2023-04-18 | 西南交通大学 | System for regulating and controlling different lignin morphologies and regulating and controlling method thereof |
| CN114854041B (en) * | 2022-06-07 | 2023-08-22 | 西南交通大学 | Lignin nanotube and preparation method and application thereof |
| CN115650212A (en) * | 2022-11-07 | 2023-01-31 | 河南农业大学 | Method for preparing carbon nitrogen nano tube by agriculture and forestry biomass |
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| CN111634902B (en) * | 2020-06-01 | 2023-03-28 | 南京博岭节能环保研究院有限公司 | Method for preparing carbon nano tube by secondary catalytic reforming of lignin pyrolysis gas |
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