CN110203908B - Method for preparing graphene by using biomass pyrolysis oil and product - Google Patents
Method for preparing graphene by using biomass pyrolysis oil and product Download PDFInfo
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Abstract
The invention belongs to the field of biomass utilization, and discloses a method for preparing graphene by using biomass pyrolysis oil and a product. Mixing biomass pyrolysis oil and organic matters to obtain a mixed solution, and then placing the mixed solution on a metal foil; mechanically pressurizing the metal foil attached with the mixed solution under the condition of air isolation, simultaneously heating the metal foil to 300-400 ℃ and preserving heat for a preset time, and then heating the metal foil to 800-1200 ℃ and preserving heat for a preset time to enable the biomass pyrolysis oil to generate a pyrolysis reaction to generate graphene; and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal foil. According to the invention, by utilizing the characteristic that the biomass pyrolysis oil is easy to deposit carbon and coke, the biomass pyrolysis oil is placed on the metal foil and is subjected to heating and pressurizing treatment to prepare the graphene material, so that high-value utilization of the biomass pyrolysis oil is realized.
Description
Technical Field
The invention belongs to the field of biomass utilization, and particularly relates to a method for preparing graphene by using biomass pyrolysis oil and a product.
Background
With the development of society, a great amount of agricultural and forestry wastes and domestic wastes are urgently needed to be subjected to harmless treatment. Meanwhile, agricultural and forestry wastes and urban domestic wastes are important components of biomass energy in China, and the high-grade utilization of the biomass energy not only can alleviate the problem of energy shortage in China, but also can effectively improve the problem of environmental pollution. Biomass pyrolysis oil is a condensable liquid produced by pyrolysis of biomass,it has a density of about 1130kg/m3～1200kg/m3Compared with 300kg/m of the original material3Compared with the prior art, the density of the biomass pyrolysis oil is greatly improved, so that the biomass pyrolysis oil is more convenient to store and transport than the raw materials.
The high-grade utilization of the biomass pyrolysis oil belongs to a part which is very important in the high-grade utilization of biomass, and is also a part which is very important in the utilization of renewable energy sources. Currently, most processes for the conversion utilization of biomass pyrolysis oil involve the thermal treatment of the biomass pyrolysis oil. For example, gasification, catalytic cracking, hydroconversion, esterification, and combustion of biomass pyrolysis oil all require rapid heating of the biomass pyrolysis oil first to accelerate the conversion of the biomass pyrolysis oil. Due to the characteristics of complex components, poor thermal stability and the like, the biomass pyrolysis oil is easy to generate carbon deposition under a heated condition, so the carbon deposition is an important challenge in the thermal conversion and utilization of the biomass pyrolysis oil. For example, in the catalytic cracking or hydrogenation upgrading process of the biomass pyrolysis oil, the formation of carbon deposition can block a reactor, cover the active site of the catalyst or fill the pore structure of the catalyst to inactivate the catalyst, and reduce the utilization rate of organic components in the biomass pyrolysis oil; at the downstream of the biomass gasification reaction system, carbon deposition or coking is easy to block a pipeline, so that operation accidents are caused, and the maintenance cost is increased; in the combustion process, the biomass pyrolysis oil is polymerized to form carbon deposition before entering a boiler for combustion, so that the problems of nozzle blockage and the like can be caused.
On the other hand, carbon materials are indispensable functional materials in our production and living. Among them, graphene is receiving attention due to its excellent properties, but the current production of graphene has problems of high production cost, complex operation steps, etc. How to prepare the functional carbon material by utilizing the characteristic of carbon deposition in the thermal conversion process of the biomass pyrolysis oil is an important way for realizing high-value utilization of the biomass pyrolysis oil.
Disclosure of Invention
In view of the above-mentioned disadvantages and/or needs for improvement of the prior art, the present invention provides a method and product for preparing graphene from biomass pyrolysis oil, wherein a graphene material having excellent properties can be prepared by subjecting a metal foil to which the biomass pyrolysis oil is attached to a heating and pressurizing treatment, and thus the method and product are particularly suitable for applications such as biomass utilization.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing graphene using biomass pyrolysis oil, the method including the steps of:
(a) mixing biomass pyrolysis oil to be treated with organic matters to obtain a mixed solution, and then placing the mixed solution on a metal foil;
(b) mechanically pressurizing the metal foil attached with the mixed solution under the condition of air isolation, simultaneously heating the metal foil to 300-400 ℃ and preserving heat for a preset time, and then heating the metal foil to 800-1200 ℃ and preserving heat for a preset time to enable the biomass pyrolysis oil to be treated to generate a pyrolysis reaction to generate graphene;
(c) and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal foil.
Further preferably, in the step (a), the biomass pyrolysis oil and the organic matter are mixed in a mass ratio of 19:1 to 17: 3.
As a further preference, in step (a), the organic is an organic containing a carbonyl group, a furan ring or an aldehyde group.
Further preferably, in the step (a), the metal foil is a Ni foil, a Cu foil, an Fe foil, a CuNi alloy foil, or a FeCu alloy foil.
More preferably, in the step (b), the temperature is maintained for 5 to 10min after the heating to 300 to 400 ℃, and then the temperature is maintained for 5 to 20min after the heating to 800 to 1200 ℃.
Further preferably, in the step (b), the metal foil is controlled to rotate while being mechanically pressurized, so that the mixed solution is ensured to form a thin film on the surface of the metal foil.
Further preferably, in the step (b), the metal foil is rotated at a rotation speed of 60 to 120 r/min.
Further preferably, in the step (b), the target pressure of the mechanical pressurization is 1 to 5 kPa.
As a further preference, in step (b), nitrogen, argon or hydrogen is passed in for air exclusion.
According to another aspect of the present invention, there is provided graphene prepared using the above method.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. according to the invention, the biomass pyrolysis oil and the organic matter are mixed and placed on the metal foil for heating and pressurizing treatment, so that the lignin-derived component in the biomass pyrolysis oil, such as an aromatic structure polymer, and the organic matter undergo copolymerization reaction at 300-400 ℃, a large amount of amorphous carbon is generated through coking, and then graphene is generated at 800-1200 ℃, thereby realizing high-valued utilization of the biomass pyrolysis oil;
2. meanwhile, the organic matter containing carbonyl, furan rings or aldehyde groups is selected, and the biomass pyrolysis oil and the organic matter are mixed according to the mass ratio of 19: 1-17: 3, so that the coking amount of the biomass pyrolysis oil can be effectively increased, and the yield of graphene is increased;
3. in addition, the metal foil is controlled to rotate at the rotating speed of 60 r/min-120 r/min, so that the mixed liquid containing the biomass pyrolysis oil can form a nano-scale uniform film on the surface of the metal foil, the number of layers of the prepared graphene is reduced, and the graphene material with excellent performance is obtained.
Drawings
FIG. 1 is a process flow diagram for preparing graphene by using biomass pyrolysis oil provided by the invention;
FIG. 2 is a comparison graph of coking characteristics of biomass pyrolysis oil and a mixed solution of biomass pyrolysis oil and furfural at different temperatures;
fig. 3 is a raman spectrum of graphene prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing graphene from biomass pyrolysis oil, including the following steps:
(a) mixing biomass pyrolysis oil to be treated with organic matters to obtain a mixed solution, and then placing the mixed solution on a metal foil;
(b) mechanically pressurizing the metal foil attached with the mixed solution under the condition of air isolation, simultaneously heating the metal foil to 300-400 ℃ and preserving heat for a preset time, and then heating the metal foil to 800-1200 ℃ and preserving heat for a preset time to enable the biomass pyrolysis oil to be treated to generate a pyrolysis reaction to generate graphene;
(c) and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal foil.
Further, in the step (a), the organic matter is an organic matter containing carbonyl, furan rings or aldehyde groups, and the biomass pyrolysis oil to be treated and the organic matter are mixed in a mass ratio of 19: 1-17: 3, so that the production cost can be reduced on the premise of improving the coking amount, the organic matter and lignin-derived components (aromatic structure polymers) in the biomass pyrolysis oil undergo copolymerization reaction in the heating process, more amorphous carbon is generated through coking, and the yield of graphene is improved, fig. 2 is a coking characteristic comparison graph of the biomass pyrolysis oil and mixed liquid of the biomass pyrolysis oil and furfural at different temperatures, and it can be known from fig. 2 that the coking yield is obviously improved after furfural is added;
the metal foil is a Ni foil, a Cu foil, an Fe foil, a CuNi alloy foil or a FeCu alloy foil, and the metal foil is preferably a Ni foil because metal nickel has a good catalytic performance.
Further, in the step (b), heating to 300-400 ℃, then preserving heat for 5-10 min, wherein the coking rate of the biomass pyrolysis oil is highest at the temperature, the biomass pyrolysis oil can be completely coked to generate a large amount of amorphous carbon after preserving heat for a period of time, and then preserving heat for 5-20 min at 800-1200 ℃, so that sufficient growth time is provided for the amorphous carbon to generate graphene on the surface of the metal foil, and the quality of the graphene is improved;
the biomass pyrolysis oil has the characteristics of high viscosity and poor fluidity, the metal foil is controlled to rotate while mechanical pressurization is carried out, a uniform film can be formed on the surface of the metal foil by mixed liquid containing the biomass pyrolysis oil to be treated, the number of prepared graphene layers is ensured to be small, the adding volume of the biomass pyrolysis oil is determined according to the area of the metal foil and the target thickness of the film, the pressure of the mechanical pressurization is controlled within the range of 1 kPa-5 kPa, the rotating speed of the metal foil is controlled to be 60 r/min-120 r/min, a good pressurization effect can be obtained, the biomass pyrolysis oil can be ensured to be adsorbed on the surface of the metal foil and form a nano-level film, graphene with few layers can be obtained, and the phenomenon that the thickness of the oil film is too thin and the yield of the graphene is too low can be avoided.
The following will further describe the method and product for preparing graphene by using biomass pyrolysis oil according to the present invention with reference to specific embodiments.
Example 1
(a) Mixing biomass pyrolysis oil and furfural in a mass ratio of 9:1 to obtain a mixed solution, and then placing the mixed solution on a metal Ni foil;
(b) pressurizing the metal Ni foil attached with the mixed solution to 5kPa under the condition of air isolation, controlling the rotating speed of the metal Ni foil to be 60r/min, simultaneously heating the metal Ni foil to 350 ℃ by adopting a heating device, preserving heat for 5min, then heating the metal Ni foil to 1000 ℃ and preserving heat for 10min, so that the biomass pyrolysis oil generates pyrolysis reaction to generate graphene;
(c) and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal Ni foil.
Fig. 3 is a raman spectrum of the prepared graphene, and it can be seen from the ratio of 2D peak/G peak in the graph that the graphene can be prepared by the method provided by the present invention, and the yield of the graphene is about 4%.
Example 2
(a) Mixing biomass pyrolysis oil and furan at a mass ratio of 19:1 to obtain a mixed solution, and then placing the mixed solution on a metal Cu foil;
(b) pressurizing the metal Cu foil attached with the mixed solution to 1kPa under the condition of air isolation, controlling the rotating speed of the metal Cu foil to be 120r/min, simultaneously heating the metal Cu foil to 400 ℃ by adopting a heating device, preserving heat for 10min, then heating the metal Cu foil to 800 ℃ and preserving heat for 20min, and enabling the biomass pyrolysis oil to generate a pyrolysis reaction to generate graphene;
(c) and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal Cu foil.
Example 3
(a) Mixing biomass pyrolysis oil and acetaldehyde in a mass ratio of 17:3 to obtain a mixed solution, and then placing the mixed solution on a metal FeCu foil;
(b) pressurizing the metal FeCu foil attached with the mixed solution to 2.5kPa under the condition of air isolation, controlling the rotating speed of the metal FeCu foil to be 90r/min, simultaneously heating the metal FeCu foil to 300 ℃ by adopting a heating device and preserving heat for 8min, and then heating the metal FeCu foil to 1200 ℃ and preserving heat for 5min so that the biomass pyrolysis oil generates a pyrolysis reaction to generate graphene;
(c) and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal FeCu foil.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A method for preparing graphene by using biomass pyrolysis oil is characterized by comprising the following steps:
(a) mixing biomass pyrolysis oil to be treated with organic matters to obtain a mixed solution, and then placing the mixed solution on a metal foil; wherein the organic matter is an organic matter containing carbonyl, furan rings or aldehyde groups;
(b) under the condition of air isolation, mechanically pressurizing the metal foil attached with the mixed liquid, heating the metal foil to 300-400 ℃ and preserving heat for a preset time, then heating the metal foil to 800-1200 ℃ and preserving heat for a preset time to enable the biomass pyrolysis oil to be treated to generate pyrolysis reaction to generate graphene, and controlling the metal foil to rotate while mechanically pressurizing so as to ensure that the mixed liquid forms a film on the surface of the metal foil, wherein the rotating speed of the metal foil is 60-120 r/min, and the target pressure of the mechanical pressurization is 1-5 kPa;
(c) and after the pyrolysis reaction is finished, separating the prepared graphene from the surface of the metal foil so as to prepare the required graphene.
2. The method for preparing graphene by using biomass pyrolysis oil as claimed in claim 1, wherein in the step (a), the biomass pyrolysis oil to be treated is mixed with organic matters in a mass ratio of 19:1 to 17: 3.
3. The method for preparing graphene using biomass pyrolysis oil as claimed in claim 1, wherein in the step (a), the metal foil is a Ni foil, a Cu foil, an Fe foil, a CuNi alloy foil or a FeCu alloy foil.
4. The method for preparing graphene from biomass pyrolysis oil as claimed in any one of claims 1 to 3, wherein in the step (b), the temperature is kept for 5min to 10min after the heating is carried out to 300 ℃ to 400 ℃, and then the temperature is kept for 5min to 20min after the heating is carried out to 800 ℃ to 1200 ℃.
5. The method for preparing graphene by using biomass pyrolysis oil as claimed in claim 1, wherein in the step (b), nitrogen, argon or hydrogen is introduced for air exclusion.
6. Graphene prepared by the method according to any one of claims 1 to 5.
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| CN102800774A (en) * | 2011-05-27 | 2012-11-28 | 浦项工科大学校产学协力团 | Method of preparing carbon thin film, and electronic device and electrochemical devices each including the carbon thin film |
| CN107531487A (en) * | 2015-04-13 | 2018-01-02 | 科廷大学 | Produce the method and system of solid carbonaceous material |
| CN108163841A (en) * | 2018-01-17 | 2018-06-15 | 华中科技大学 | A kind of method that graphene is prepared using tar |
| CN109666494A (en) * | 2019-01-24 | 2019-04-23 | 华中科技大学 | A kind of biomass pyrolysis oil prepares the method and product of spongy Carbon Materials |
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| US20170113936A1 (en) * | 2013-06-05 | 2017-04-27 | The United States Of America As Represented By The Secretary Of Agriculture | Methods for Synthesizing Graphene from a Lignin Source |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102800774A (en) * | 2011-05-27 | 2012-11-28 | 浦项工科大学校产学协力团 | Method of preparing carbon thin film, and electronic device and electrochemical devices each including the carbon thin film |
| CN107531487A (en) * | 2015-04-13 | 2018-01-02 | 科廷大学 | Produce the method and system of solid carbonaceous material |
| CN108163841A (en) * | 2018-01-17 | 2018-06-15 | 华中科技大学 | A kind of method that graphene is prepared using tar |
| CN109666494A (en) * | 2019-01-24 | 2019-04-23 | 华中科技大学 | A kind of biomass pyrolysis oil prepares the method and product of spongy Carbon Materials |
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