CN114455572B - Method for preparing high length-diameter ratio carbon nano tube by taking waste liquid oil as carbon source - Google Patents
Method for preparing high length-diameter ratio carbon nano tube by taking waste liquid oil as carbon source Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002699 waste material Substances 0.000 title claims abstract description 65
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 57
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000001681 protective effect Effects 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000010453 quartz Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005507 spraying Methods 0.000 claims abstract description 22
- 239000007952 growth promoter Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 41
- 235000019198 oils Nutrition 0.000 claims description 41
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 20
- 229930192474 thiophene Natural products 0.000 claims description 10
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000008157 edible vegetable oil Substances 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 239000010775 animal oil Substances 0.000 claims description 2
- 239000010828 animal waste Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000000630 rising effect Effects 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000010808 liquid waste Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
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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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of carbon nanotube preparation, and particularly discloses a method for preparing a carbon nanotube with a high length-diameter ratio by taking waste liquid oil as a carbon source. The method for preparing the carbon nano tube with high length-diameter ratio by taking the waste liquid oil as a carbon source comprises the following steps: (1) Mixing the waste liquid oil with a catalyst and a growth promoter to obtain a mixed raw material; (2) Spraying the mixed raw materials and the protective gas into a quartz tube through a sprayer, putting the quartz tube into a double-furnace system for reaction, collecting a product after the reaction is finished, and cleaning to obtain the carbon nano tube with high length-diameter ratio. The carbon nano tube prepared from the waste liquid oil by adopting the method provided by the invention has higher length-diameter ratio and higher carbon conversion rate.
Description
Technical Field
The invention relates to the technical field of carbon nanotube preparation, in particular to a method for preparing carbon nanotubes with high length-diameter ratio by taking waste liquid oil as a carbon source.
Background
Waste oils are those oils which are purified from crude oil or which are synthetic and which have been used to be contaminated with physical or chemical impurities. In short, waste oil is oil that has been used. The domestic common swill-cooked dirty oil is a typical waste edible oil, and the lubricating oil after being lubricated is one of waste oils in industry, and belongs to waste mineral oil.
The people eat the food as the sky, a large amount of waste edible oil can be produced in the catering industry in China every year, and the waste oil can be used for preparing biodiesel at present, but the existing popularization degree is insufficient, the domestic production and use chain is not sound, and the cost is still a margin for reduction. For waste mineral oil produced in industry, the liquid waste belongs to toxic and harmful substances, and belongs to dangerous waste according to national dangerous waste list regulations. The methods of utilizing and disposing of waste mineral oil mainly include recycling, incineration disposal and landfill disposal. The main index of the recycled product of the waste mineral oil is detected, so that the quality of the recycled product is ensured; the nation encourages the comprehensive utilization of heat energy by incineration; the waste mineral oil which cannot be recycled or incinerated should be safely disposed of in landfills.
The waste oil grows year by year in yield, and under the condition that the requirement of basic recovery cannot be met, the phenomenon that the waste oil is seriously damaged by disordered discharge to the environment can occur, so that the finding out of a better recovery mode is of great significance in environmental protection. In order to benefit from such waste materials, in addition to the means currently existing, the present invention proposes another possible advantageous use of waste liquid oils as starting material for the synthesis of Carbon Nanotubes (CNT).
The carbon nanotube is a large molecule with a nano-scale diameter rolled up by a hexagonal honeycomb-shaped graphite plane obtained by combining one carbon atom with three other carbon atoms, is hollow and light, and has excellent electrical conductivity, thermal conductivity and mechanical strength. Carbon nanotubes have been attracting attention as fillers for various polymer composites due to these excellent physical properties, and a large amount of research and development is being conducted on polymer composites using carbon nanotubes on a commercial scale. At present, the carbon source of the carbon nano tube is aromatic substances such as toluene or low molecular weight hydrocarbons fractionated in petroleum industry such as acetylene, ethanol and the like, the source is not easy to obtain, and the carbon nano tube is not easy to transport as a gaseous carbon source and has a certain explosion risk, so that a large number of carbon nano tubes are limited to be put on line.
Carbon nanotubes, a potentially versatile material, are an economical and environmentally friendly option for industrial scale production using abundant waste materials. Based on the development status, the invention utilizes the waste liquid oil as a carbon source to prepare the carbon nanotubes, and can prepare the carbon nanotubes with length-diameter ratio and high yield according to the regulation and control of the growth mode and the condition of the specific carbon nanotubes. The method has high efficiency of the preparation process and high quality of the product, provides an effective way for the industrialized preparation of the high-quality carbon nano tube, and has important significance for the development of the field of the carbon nano tube and the recovery of waste oil.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides a method for preparing carbon nanotubes with high length-diameter ratio by taking waste liquid oil as a carbon source.
The method uses the waste liquid oil as a carbon source, and opens up a way for recycling the liquid waste and obtaining the product with high added value. Research shows that the carbon nano tube prepared by the catalyst selection and the additive amount growth promoter has high carbon conversion rate and higher length-diameter ratio.
The invention solves the problems by the following technical proposal:
a method for preparing high length-diameter ratio carbon nano tubes by taking waste liquid oil as a carbon source comprises the following steps:
(1) Mixing the waste liquid oil with a catalyst and a growth promoter to obtain a mixed raw material;
(2) Spraying the mixed raw materials and protective gas into a quartz tube through a sprayer, and putting into a double-furnace system
And (3) carrying out a reaction, collecting a product after the reaction is finished, and cleaning to obtain the carbon nano tube with high length-diameter ratio.
Preferably, the waste liquid oil is one or more of waste edible vegetable oil, edible vegetable blend oil, waste animal oil, waste mineral oil and waste lubricating oil.
Preferably, the waste liquid oil is a waste liquid oil having a viscosity of not more than 100cP at room temperature.
Preferably, the catalyst in the step (1) is one or more of compounds containing iron, nickel, cobalt and manganese.
Preferably, the addition amount of the catalyst in the step (1) is 0.5-10 wt% of the amount of the waste liquid oil.
Preferably, the growth promoter in step (1) is thiophene.
In the process of a great deal of experimental study, the inventor surprisingly found that thiophene is used as a growth promoter in the invention, and the length-diameter ratio of the carbon nano tube prepared by the invention can be greatly improved.
Preferably, the addition amount of the growth promoter in the step (1) is 5-15 wt% of the amount of the waste liquid oil.
Preferably, in the step (2), the mixed raw material and the protective gas are sprayed into the quartz tube through a sprayer, and the flow rate of the mixed raw material sprayed into the quartz tube is controlled to be 0.5-10 ml/h.
Preferably, in the step (2), the mixed raw material and the shielding gas are sprayed into the quartz tube through a sprayer, and the flow rate of the shielding gas sprayed into the quartz tube is controlled to be 1-10 ml/h.
Preferably, the reaction conditions of the twin furnace system in step (2) are: the temperature of the furnace 1 is 300-500 ℃, the reaction is carried out for 0.5-1.5 h, and the heating rate is 3-10 ℃/min; the temperature of the furnace 2 is 700-1000 ℃, the reaction is carried out for 1-2 hours, and the heating rate is 3-10 ℃/min.
The beneficial effects are that: (1) The preparation method has the advantages of simple preparation process, high carbon conversion rate, remarkably improved carbon conversion rate compared with the traditional toluene (31%), xylene (28%) and benzene (20%), and potential of industrial production; (2) The invention has a certain environmental protection significance in liquid waste recovery, and provides a new idea for carbon source selection of carbon nanotubes; (3) The carbon nano tube prepared by the invention has higher length-diameter ratio.
Drawings
Fig. 1 is a scanning electron microscope of a carbon nanotube sample prepared in example 1.
Fig. 2 is a transmission electron microscope of the carbon nanotube sample prepared in example 1.
Fig. 3 shows the result of raman spectroscopy analysis of the carbon nanotube sample prepared in example 1, with ID/ig=0.74.
Description of the embodiments
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
Examples
(1) Taking waste paraffin oil with the viscosity of 80cP, adding 5 wt% of ferrocene and 10 wt% of growth promoter thiophene into a container together to obtain a mixed raw material;
(2) The container is connected with a protective atmosphere pipeline to an adjustable high-pressure sprayer, and the sprayer is mixed
Spraying the raw materials and the protective gas into a quartz tube, and putting the quartz tube and the protective gas into a double-furnace system for reaction; wherein the liquid spraying speed is 2ml/h, the protective atmosphere is nitrogen, and the spraying speed is 5ml/min; setting the temperature of a double furnace: the temperature of the furnace 1 is 400 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; the temperature of the furnace 2 is 800 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; after the reaction is finished, the tube is naturally cooled to room temperature, and the generated product is obtained from a collecting device; and (3) putting the obtained product into 1M hydrochloric acid solution for ultrasonic cleaning, standing for 12 hours, filtering and separating, washing the solid until the pH value is neutral, and then putting into 100 ℃ for drying for 8 hours to obtain the carbon nano tube with high length-diameter ratio.
Examples
(1) Taking waste palm oil with the viscosity of 30cP, adding 3wt% of ferrocene and 5wt% of growth promoter thiophene into a container together to obtain a mixed raw material;
(2) The container is connected with a protective atmosphere pipeline to an adjustable high-pressure sprayer, and the sprayer is mixed
Spraying the raw materials and the protective gas into a quartz tube, and putting the quartz tube and the protective gas into a double-furnace system for reaction; wherein the liquid spraying speed is 3ml/h, the protective atmosphere is nitrogen, and the spraying speed is 5ml/min; setting the temperature of a double furnace: the temperature of the furnace 1 is 350 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; the temperature of the furnace 2 is 750 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; after the reaction is finished, the tube is naturally cooled to room temperature, and the generated product is obtained from a collecting device; and (3) putting the obtained product into 1M hydrochloric acid solution for ultrasonic cleaning, standing for 12 hours, filtering and separating, washing the solid until the pH value is neutral, and then putting into 100 ℃ for drying for 8 hours to obtain the carbon nano tube with high length-diameter ratio.
Examples
(1) Taking waste engine oil with the viscosity of 40cP, adding 3wt% of ferrocene and 12 wt% of growth promoter thiophene into a container together to obtain a mixed raw material;
(2) The container is connected with a protective atmosphere pipeline to an adjustable high-pressure sprayer, and the sprayer is mixed
Spraying the raw materials and the protective gas into a quartz tube, and putting the quartz tube and the protective gas into a double-furnace system for reaction; wherein the liquid spraying speed is 4ml/h, the protective atmosphere is nitrogen, and the spraying speed is 5ml/min; setting the temperature of a double furnace: the temperature of the furnace 1 is 500 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; the temperature of the furnace 2 is 900 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; after the reaction is finished, the tube is naturally cooled to room temperature, and the generated product is obtained from a collecting device; and (3) putting the obtained product into 1M hydrochloric acid solution for ultrasonic cleaning, standing for 12 hours, filtering and separating, washing the solid until the pH value is neutral, and then putting into 100 ℃ for drying for 8 hours to obtain the carbon nano tube with high length-diameter ratio.
Examples
(1) Taking waste coconut oil with the viscosity of 40cP, adding 6wt% of nickel dichloride, 2 wt% of ferrocene and 10 wt% of growth promoter thiophene into a container together to obtain a mixed raw material;
(2) The container is connected with a protective atmosphere pipeline to an adjustable high-pressure sprayer, and the sprayer is mixed
Spraying the raw materials and the protective gas into a quartz tube, and putting the quartz tube and the protective gas into a double-furnace system for reaction; wherein the liquid spraying speed is 4ml/h, the protective atmosphere is nitrogen, and the spraying speed is 5ml/min; setting the temperature of a double furnace: the temperature of the furnace 1 is 450 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1.5h; furnace 2 temperature is 850 ℃, heating speed is 5 ℃/min, and reaction is carried out for 1.5h; after the reaction is finished, the tube is naturally cooled to room temperature, and the generated product is obtained from a collecting device; and (3) putting the obtained product into 1M hydrochloric acid solution for ultrasonic cleaning, standing for 12 hours, filtering and separating, washing the solid until the pH value is neutral, and then putting into 100 ℃ for drying for 8 hours to obtain the carbon nano tube with high length-diameter ratio.
Examples
(1) Taking waste paraffin oil with the viscosity of 80cP, adding 3 wt% of nickel dichloride, 2 wt% of ferrocene and 10 wt% of growth promoter thiophene into a container together to obtain a mixed raw material;
(2) The container is connected with a protective atmosphere pipeline to an adjustable high-pressure sprayer, and the sprayer is mixed
Spraying the raw materials and the protective gas into a quartz tube, and putting the quartz tube and the protective gas into a double-furnace system for reaction; wherein the liquid spraying speed is 2ml/h, the protective atmosphere is nitrogen, and the spraying speed is 5ml/min; setting the temperature of a double furnace: the temperature of the furnace 1 is 400 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; the temperature of the furnace 2 is 800 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; after the reaction is finished, the tube is naturally cooled to room temperature, and the generated product is obtained from a collecting device; and (3) putting the obtained product into 1M hydrochloric acid solution for ultrasonic cleaning, standing for 12 hours, filtering and separating, washing the solid until the pH value is neutral, and then putting into 100 ℃ for drying for 8 hours to obtain the carbon nano tube with high length-diameter ratio.
Comparative example 1
(1) Taking waste paraffin oil with the viscosity of 80cP and 5 wt% ferrocene, and adding the waste paraffin oil and the 5 wt% ferrocene into a container to obtain a mixed raw material;
(2) The container is connected with a protective atmosphere pipeline to an adjustable high-pressure sprayer, and the sprayer is mixed
Spraying the raw materials and the protective gas into a quartz tube, and putting the quartz tube and the protective gas into a double-furnace system for reaction; wherein the liquid spraying speed is 2ml/h, the protective atmosphere is nitrogen, and the spraying speed is 5ml/min; setting the temperature of a double furnace: the temperature of the furnace 1 is 400 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; the temperature of the furnace 2 is 800 ℃, the temperature rising speed is 5 ℃/min, and the reaction is carried out for 1h; after the reaction is finished, the tube is naturally cooled to room temperature, and the generated product is obtained from a collecting device; and (3) putting the obtained product into 1M hydrochloric acid solution for ultrasonic cleaning, standing for 12 hours, filtering and separating, washing the solid until the pH value is neutral, and then putting into 100 ℃ for drying for 8 hours to obtain the carbon nano tube with high length-diameter ratio.
Comparative example 1 differs from example 1 in that no growth promoter thiophene was added.
As can be seen from the aspect ratio and the carbon conversion rate data of the carbon nanotubes in table 1, the aspect ratio of the carbon nanotubes prepared by the method of the invention is more than 4000, and the carbon conversion rate is more than 40% by taking the waste liquid oil as a raw material; this illustrates: the carbon nano tube prepared from the waste liquid oil by adopting the method has higher length-diameter ratio and higher carbon conversion rate; the carbon conversion rate is far higher than that of the carbon nano tube prepared by adopting the traditional toluene (31%), xylene (28%) and benzene (20%); the obvious technical effect is achieved.
From the carbon conversion data of example 5 and example 1, it can be seen that the carbon conversion of example 5 is much higher than that of example 1; this illustrates: the method prepares the carbon nano tube by taking the waste liquid oil as a raw material, and takes the nickel dichloride and the ferrocene as catalysts, so that the carbon conversion rate of the prepared carbon nano tube is obviously higher than that of other catalysts.
As can be seen from the aspect ratios of the carbon nanotubes of comparative example 1 and example 1, the aspect ratio of the carbon nanotubes prepared in comparative example 1 is much smaller than that of example 1; this illustrates: in the process of preparing the carbon nano tube by using the waste liquid oil as a raw material, thiophene is added as a growth promoter, so that the length-diameter ratio of the prepared carbon nano tube can be greatly improved.
Claims (7)
1. The method for preparing the carbon nano tube with the high length-diameter ratio by taking the waste liquid oil as a carbon source is characterized by comprising the following steps of:
(1) Mixing the waste liquid oil with a catalyst and a growth promoter to obtain a mixed raw material;
(2) Spraying the mixed raw materials and protective gas into a quartz tube through a sprayer, putting the quartz tube into a double-furnace system for reaction, collecting a product after the reaction is finished, and cleaning to obtain the carbon nano tube with high length-diameter ratio;
the growth promoter in the step (1) is thiophene;
The catalyst in the step (1) consists of nickel dichloride and ferrocene;
the waste liquid oil is one or more of waste edible vegetable oil, waste animal oil and waste paraffin oil.
2. The method for preparing high aspect ratio carbon nanotubes from waste liquid oil as carbon source of claim 1, wherein the waste liquid oil is waste liquid oil with a viscosity of not more than 100cP at room temperature.
3. The method for preparing carbon nanotubes with high length-diameter ratio by using waste liquid oil as carbon source according to claim 1, wherein the catalyst in the step (1) is added in an amount of 0.5-10 wt% of the amount of the waste liquid oil.
4. The method for preparing carbon nanotubes with high length-diameter ratio by using waste liquid oil as carbon source according to claim 1, wherein the addition amount of the growth promoter in the step (1) is 5-15 wt% of the amount of the waste liquid oil.
5. The method for preparing carbon nanotubes with high aspect ratio by using waste liquid oil as carbon source according to claim 1, wherein the step (2) comprises spraying the mixed raw material and the protective gas into the quartz tube by a sprayer, and controlling the flow rate of the mixed raw material sprayed into the quartz tube to be 0.5-10 ml/h.
6. The method for preparing carbon nanotubes with high length-diameter ratio by using waste liquid oil as a carbon source according to claim 1, wherein the step (2) is to spray the mixed raw material and the shielding gas into a quartz tube through a sprayer, and the flow rate of the shielding gas sprayed into the quartz tube is controlled to be 1-10 ml/h.
7. The method for preparing carbon nanotubes with high aspect ratio by using waste liquid oil as carbon source according to claim 1, wherein the reaction conditions of the double furnace system in the step (2) are as follows: the temperature of the furnace 1 is 300-500 ℃, the reaction is carried out for 0.5-1.5 h, and the heating rate is 3-10 ℃/min; the temperature of the furnace 2 is 700-1000 ℃, the reaction is carried out for 1-2 hours, and the heating rate is 3-10 ℃/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1678523A (en) * | 2002-06-24 | 2005-10-05 | 原子能委员会 | Method and device for depositing carbon nanotubes or nitrogen-doped carbon nanotubes by means of pyrolysis |
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