CN115974058B - Preparation method and system of graphene - Google Patents
Preparation method and system of graphene Download PDFInfo
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- CN115974058B CN115974058B CN202310128088.4A CN202310128088A CN115974058B CN 115974058 B CN115974058 B CN 115974058B CN 202310128088 A CN202310128088 A CN 202310128088A CN 115974058 B CN115974058 B CN 115974058B
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Abstract
The invention relates to the technical field of graphene preparation, in particular to a preparation method and system of graphene. Firstly, carrying out primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product, then carrying out secondary pyrolysis and condensation on part of active carbon to obtain graphite carbon, a second oil phase product and a second gas phase product, introducing the first gas phase product and the second gas phase product into the residual active carbon to carry out gas phase deposition to obtain active carbon and first mixed gas carrying graphene, then carrying out pyrolysis on plastic waste to obtain an oil gas product, and finally introducing the oil gas product into the graphite carbon to carry out gas phase deposition to obtain graphite carbon carrying graphene and second mixed gas carrying graphene, so that graphene can be obtained based on the active carbon carrying graphene, the graphite carbon carrying graphene and the second mixed gas. Therefore, the scheme of the invention not only can realize changing waste into valuables, but also can save fossil resources utilized by the traditional graphene preparation technology.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a preparation method and system of graphene.
Background
Current carbon dioxide emissions face a dramatically increasing challenge, and carbon fixation, carbon neutralization strategies are becoming an important direction for technological development in the field of material chemistry. Graphene is a two-dimensional carbon nanomaterial that has been used in the fields of energy, semiconductors, catalysis, medical treatment, and the like due to its high electron mobility, high thermal conductivity, and excellent permeability.
With the rapid development of economy, agriculture and light industry produce about several hundred million tons of different kinds of biomass waste and plastic waste each year, which is mainly achieved by an inefficient utilization manner of direct combustion, which not only causes great waste of biomass waste and plastic waste, but also brings about serious environmental pollution.
Based on this, it is needed to propose a system for preparing graphene from cheap biomass waste and plastic waste, which can change waste into valuable and save fossil resources utilized by the conventional graphene preparation technology.
Disclosure of Invention
The invention provides a preparation method and a preparation system of graphene, which can change waste into valuable and save fossil resources utilized by the traditional graphene preparation technology.
In a first aspect, an embodiment of the present invention provides a method for preparing graphene, including:
Carrying out primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product;
performing secondary pyrolysis and condensation on part of the activated carbon to obtain graphite carbon, a second oil phase product and a second gas phase product;
introducing the first gas-phase product and the second gas-phase product into the residual active carbon for gas-phase deposition to obtain graphene-loaded active carbon and a first mixed gas;
pyrolyzing the plastic waste to obtain an oil gas product;
introducing the oil gas product into the graphite carbon for vapor deposition to obtain graphene-loaded graphite carbon and a second mixed gas; wherein the second mixed gas comprises hydrogen;
and obtaining graphene based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas.
In a second aspect, an embodiment of the present invention provides a graphene preparation system, including:
the first pyrolysis condensing assembly is used for performing primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product;
the second pyrolysis condensing assembly is connected with the first pyrolysis condensing assembly and is used for carrying out secondary pyrolysis and condensation on part of the activated carbon so as to obtain graphite carbon, a second oil phase product and a second gas phase product;
The first vapor deposition furnace is respectively connected with the first pyrolysis condensing assembly and the second pyrolysis condensing assembly, the first vapor deposition furnace stores residual activated carbon, and is used for receiving the first vapor product and the second vapor product, and performing vapor deposition on the residual activated carbon to obtain graphene-loaded activated carbon and a first mixed gas;
the third pyrolysis furnace is used for pyrolyzing the plastic waste to obtain an oil gas product;
the second vapor deposition furnace is respectively connected with the second pyrolysis condensing assembly and the third pyrolysis furnace and is used for receiving the graphite carbon and the oil gas product so as to obtain graphite carbon loaded with graphene and second mixed gas by vapor deposition of the oil gas product in the graphite carbon; wherein the second mixed gas comprises hydrogen;
and obtaining graphene based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas.
According to the preparation method and the preparation system of the graphene, firstly, biomass waste is subjected to primary pyrolysis and condensation to obtain active carbon, a first oil phase product and a first gas phase product, then, part of the active carbon is subjected to secondary pyrolysis and condensation to obtain graphite carbon, a second oil phase product and a second gas phase product, the first gas phase product and the second gas phase product are introduced into residual active carbon to be subjected to gas phase deposition to obtain active carbon and first mixed gas of the graphene, then, plastic waste is subjected to pyrolysis to obtain an oil gas product, and finally, the oil gas product is introduced into the graphite carbon to be subjected to gas phase deposition to obtain graphite carbon and second mixed gas of the graphene, so that the graphene can be obtained based on the active carbon of the graphene, the graphite carbon of the graphene and the second mixed gas. Therefore, the technical scheme is that the graphene is prepared by taking cheap biomass waste and plastic waste as raw materials, so that waste is turned into wealth, and fossil resources utilized by the traditional graphene preparation technology can be saved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are some embodiments of the invention and that other drawings may be obtained based on these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation method of graphene according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for preparing graphene according to another embodiment of the present disclosure;
fig. 3 is a schematic structural diagram of a graphene preparation system according to an embodiment of the present disclosure;
fig. 4 is a schematic structural diagram of a graphene preparation system according to another embodiment of the present disclosure.
Reference numerals:
1-a first pyrolysis condensing unit;
11-a first stirring tank;
12-a first pyrolysis furnace;
13-a first condenser;
2-a second pyrolysis condensing assembly;
21-a water washing device;
22-a second stirring tank;
23-a second pyrolysis furnace;
24-a second condenser;
3-a first vapor deposition furnace;
4-a third pyrolysis furnace;
5-a second vapor deposition furnace;
6-a purifying device;
71-a first pickling device;
72-a reduction pyrolysis furnace;
81-a second pickling device;
82-separation means;
91-an electrochemical stripping device;
92-combustion device.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing graphene from biomass waste and plastic waste, the method comprising:
step 101, performing primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product;
102, performing secondary pyrolysis and condensation on part of the activated carbon to obtain graphite carbon, a second oil phase product and a second gas phase product;
step 103, introducing the first gas-phase product and the second gas-phase product into the residual active carbon for gas-phase deposition to obtain graphene-loaded active carbon and a first mixed gas;
Step 104, pyrolyzing the plastic waste to obtain an oil gas product;
step 105, introducing an oil gas product into graphite carbon for vapor deposition to obtain graphene-loaded graphite carbon and a second mixed gas; wherein the second mixed gas comprises hydrogen;
and 106, obtaining graphene based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas.
In this embodiment, first, biomass waste is pyrolyzed and condensed for one time to obtain activated carbon, a first oil phase product and a first gas phase product, then, part of the activated carbon is pyrolyzed and condensed for the second time to obtain graphite carbon, a second oil phase product and a second gas phase product, the first gas phase product and the second gas phase product are introduced into the residual activated carbon to be vapor deposited to obtain graphene-loaded activated carbon and a first mixed gas, then, plastic waste is pyrolyzed to obtain an oil gas product, and finally, the oil gas product is introduced into the graphite carbon to be vapor deposited to obtain graphene-loaded graphite carbon and a second mixed gas, so that graphene can be obtained based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas. Therefore, the technical scheme is that the graphene is prepared by taking cheap biomass waste and plastic waste as raw materials, so that waste is turned into wealth, and fossil resources utilized by the traditional graphene preparation technology can be saved.
Each step is described in turn.
For step 101:
in one embodiment of the present invention, before step 101, the method may specifically include:
and drying the biomass waste.
In this embodiment, the biomass waste is baked to remove moisture in the biomass waste, so that the yield of the solid phase product, the yield of the oil phase product and the yield of the gas phase product of the biomass waste can be accurately calculated.
In some embodiments, the drying conditions may be drying in an oven at 105-110 ℃ until the weight is no longer changed, and the drying conditions are not limited in this example of the present invention.
In one embodiment of the present invention, step 101 may specifically include:
adding biomass waste into an activating agent for impregnation;
under the inert gas atmosphere, performing primary pyrolysis on the impregnated biomass waste to obtain activated carbon and first pyrolysis gas;
condensing the first pyrolysis gas to obtain a first oil phase product and a first gas phase product.
In this embodiment, the biomass waste is added into the activator to be impregnated, so that the activated carbon obtained by performing primary pyrolysis on the impregnated biomass waste has higher porosity.
In some embodiments, biomass waste includes, but is not limited to, forestry biomass represented by pine and birch chips and agriculture and forestry biomass represented by straw and stalk, and the type of biomass waste is not limited in this example of the invention.
In some embodiments, the activators include, but are not limited to, sodium hydroxide and potassium hydroxide, and the examples of the invention herein are not limited to activators.
In some embodiments, the conditions of the primary pyrolysis may be raised to 400 to 600 ℃ at a rate of 10 to 50 ℃/min and maintained for 40 to 70min, and the present examples are not limited herein.
In some embodiments, the inert gas may be nitrogen, argon, or helium, and the inert gas is not limited in this example of the invention. Under the inert gas atmosphere, the biomass waste can be prevented from generating more carbon dioxide and carbon monoxide during pyrolysis, so that the pyrolysis is facilitated to obtain more activated carbon.
In some embodiments, the condensing mode may be a condensing device using a single refrigerant such as liquid nitrogen or other mixed refrigerants as a cold source, and the condensing mode is not limited in this embodiment of the present invention.
In some embodiments, the first pyrolysis gas may be divided into two types, condensable gas and non-condensable gas, after condensing the first pyrolysis gas, the condensable gas will be collected in the form of bio-oil (i.e. first oil phase product), and the remaining non-condensable gas is mainly hydrogen, carbon monoxide, carbon dioxide, methane and other small carbon containing gasesThe molecules predominate (i.e., the first gaseous product). Wherein the small carbon-containing molecule may be C 2 H 2 、C 3 H 3 And C 6 H 12 Etc.
For step 102:
in one embodiment of the present invention, step 102 may specifically include:
washing the activated carbon with water;
adding a catalyst into the activated carbon after water washing to obtain catalyst-loaded activated carbon; the catalyst comprises transition metal salt, target nitrate and target metal oxide, wherein the transition metal salt is used for promoting graphitization of the activated carbon and dehydrogenation of the oil gas product, the target nitrate is used for promoting gasification reaction of plastic waste, and the target metal oxide is used for serving as a carrier of the catalyst and promoting reaction of obtaining a second mixed gas from the oil gas product;
performing secondary pyrolysis on part of the activated carbon loaded with the catalyst in an inert gas atmosphere to obtain graphite carbon loaded with the catalyst and second pyrolysis gas;
Condensing the second pyrolysis gas to obtain a second oil phase product and a second gas phase product.
In this embodiment, the activated carbon is first washed with water for washing away the activator on the surface of the activated carbon, because the activator may hinder graphitization of the activated carbon; and secondly, the catalyst is added into the activated carbon, so that graphitization of the activated carbon can be facilitated, gasification reaction of plastic waste can be promoted, and dehydrogenation of oil gas products of the plastic waste can be promoted.
In some embodiments, the transition metal includes, but is not limited to, fe, co, ni, etc., and the present examples are not limited thereto.
In some embodiments, the target nitrate includes but is not limited to nitrate of elements such as La, mo, ce, etc., and the mode of the target nitrate is not limited in this example.
In some embodiments, the target metal oxide includes, but is not limited to, al 2 O 3 Metal oxides such as MgO, caO, etc., in which the embodiment of the invention is aimed atThe metal oxide is not limited.
It is understood that after the secondary pyrolysis is carried out on the active carbon with partial supported catalyst, metal salts or metal oxides in the catalyst can be changed into metal simple substances and metal oxides, so that the subsequent acid washing is facilitated.
In some embodiments, the conditions of the secondary pyrolysis may be raised to 750 to 850 ℃ at a rate of 5 to 15 ℃/min and maintained for 40 to 70min, and the inventive examples herein are not limited to the conditions of the secondary pyrolysis.
It should be noted that the inert gas and the condensation are the same as those in step 101, and the second oil phase product and the first oil phase product are the same in kind, and the second gas phase product and the first gas phase product are the same in kind.
For step 103:
in one embodiment of the present invention, step 103 may specifically include:
sequentially introducing alkali liquor and a molecular sieve into the first gas-phase product and the second gas-phase product to purify the first gas-phase product and the second gas-phase product;
and introducing the purified first gas-phase product and the purified second gas-phase product into the residual activated carbon loaded with the catalyst for vapor deposition to obtain the activated carbon loaded with the catalyst and the graphene and the first mixed gas.
In this embodiment, since the first gas phase product and the second gas phase product contain carbon dioxide, the carbon dioxide reacts with the activated carbon to obtain carbon monoxide during the vapor deposition, and thus part of the activated carbon is consumed, and for this purpose, the alkali solution and the molecular sieve are sequentially introduced into the first gas phase product and the second gas phase product to remove (i.e. purify) the carbon dioxide in the first gas phase product and the second gas phase product.
In some embodiments, the conditions of vapor deposition may be elevated to 900 to 950 ℃ at a rate of 10 to 20 ℃/min and maintained for 30 to 50min, and the inventive examples herein are not limited to the conditions of vapor deposition.
In some embodiments, the first mixed gas may include hydrogen, carbon monoxide, etc., as vapor deposition is the deposition of small carbon-containing molecules in the first and second vapor products. However, the hydrogen may react with the activated carbon to obtain methane during vapor deposition, and the methane may be deposited on the surface of the activated carbon, so the first mixed gas may not include the hydrogen.
For step 104:
in some embodiments, the plastic waste includes, but is not limited to, agricultural mulch, medical waste, and agricultural greenhouses, where the present examples are not limited in the type of plastic waste
In some embodiments, the pyrolysis mode of the plastic waste can be that the temperature is raised to 600-900 ℃ at the speed of 10-30 ℃/min and maintained for 40-70 min, and the pyrolysis condition of the plastic waste is not limited in the embodiment of the invention.
In some embodiments, the hydrocarbon product comprises a hydrocarbon-containing polymer, and the examples herein are not limited to hydrocarbon products.
For step 105:
in one embodiment of the present invention, step 105 may specifically include:
and introducing the oil gas product into the graphite carbon loaded with the catalyst for vapor deposition to obtain the graphite carbon loaded with the catalyst and graphene and a second mixed gas.
In this embodiment, since the catalyst is supported in the graphite carbon, when the vapor deposition is performed by introducing the oil gas product into the catalyst-supported graphite carbon, the introduction of the catalyst is beneficial to promoting the dehydrogenation of the oil gas product, promoting the gasification reaction of the plastic waste, and promoting the reaction of obtaining the second mixed gas from the oil gas product.
In some embodiments, the conditions of vapor deposition may be the same as those of step 103, and will not be described here. Of course, the conditions for vapor deposition may be different from step 103, for example, the conditions for vapor deposition of step 105 may be to raise the temperature to 850-950 ℃ at a rate of 10-15 ℃/min and hold for 30-60 min.
In some embodiments, the hydrocarbon product comprises a hydrocarbon-containing polymer, and the examples herein are not limited to hydrocarbon products.
In some embodiments, the second gas mixture mainly includes hydrogen, where the proportion of hydrogen in the second gas mixture is about 70-80%, and the embodiment of the present invention does not limit the second gas mixture.
For step 106:
since graphene is supported on activated carbon and graphite carbon, graphene can be obtained by means of hydrogen in the second mixed gas, for a specific method, see below.
In one embodiment of the present invention, step 106 may specifically include:
acid washing is carried out on the supported catalyst and the active carbon of the graphene, so that the active carbon of the supported graphene is obtained;
introducing part of the second mixed gas into the graphene-loaded activated carbon after acid washing to perform a reduction reaction to obtain graphene and a third mixed gas; the third mixed gas comprises methane, and is used for continuing to be introduced into the activated carbon with the residual supported catalyst for vapor deposition after purification;
and obtaining graphene based on the residual second mixed gas and the graphene-loaded graphite carbon.
In the embodiment, the active carbon carrying the catalyst and the graphene is firstly pickled, and metal simple substances and metal oxides in the catalyst can be cleaned before the reduction reaction, so that the graphene with higher purity can be obtained later; and secondly, introducing part of the second mixed gas into the graphene-loaded activated carbon after acid washing for reduction reaction, so that the activated carbon can react with hydrogen to obtain methane, and graphene and a third mixed gas are obtained.
In some embodiments, the acid used for pickling may be dilute hydrochloric acid or dilute sulfuric acid, and the acid used for pickling is not limited in this example.
In one embodiment of the invention, the temperature of the reduction reaction is 370-400 ℃.
In this embodiment, the temperature range of the reduction reaction between the hydrogen and the activated carbon is approximately 370 to 400 ℃, and the temperature range of the reduction reaction between the hydrogen and the graphene is approximately 470 to 520 ℃, so in order to obtain high-purity graphene, it is necessary to control the temperature to remove the hydrogen in the second mixed gas to remove the activated carbon, and at the same time, the graphene cannot be removed.
In one embodiment of the present invention, the step of obtaining graphene based on the remaining second mixed gas and the graphene-loaded graphite carbon may specifically include:
carrying out acid washing on the graphene carbon loaded with the catalyst to obtain graphene-loaded graphite carbon;
separating graphite carbon loaded with graphene after acid washing to obtain graphite carbon and graphene;
and obtaining graphene based on the residual second mixed gas and the graphite carbon.
In this embodiment, the graphene-loaded graphite carbon is obtained by acid washing the graphene-loaded graphite carbon with the catalyst, then the graphene-loaded graphite carbon after acid washing is separated to obtain the graphene carbon and graphene, and finally the graphene can be obtained based on the remaining second mixed gas and the graphene carbon. Therefore, the scheme can fully convert the graphene-loaded graphite carbon into graphene.
In some embodiments, the acid used for pickling may be dilute hydrochloric acid or dilute sulfuric acid, and the acid used for pickling is not limited in this example.
In one embodiment of the present invention, the step of separating graphene-loaded graphite carbon after acid washing may specifically include:
and (3) dissolving the graphite carbon loaded with the graphene after acid washing into a liquid with the density of 0.9-1.1 g/mL so as to separate by utilizing a gravity sedimentation method.
In the present embodiment, since both graphene and graphitic carbon are powdery particles, the inventors creatively found that both can be dissolved in a target liquid to be separated by the density difference of both. Through a lot of experiments, the inventor finds that graphite carbon loaded with graphene after acid washing can be dissolved in liquid with the density of 0.9-1.1 g/mL so as to be separated by utilizing a gravity sedimentation method.
In some embodiments, the target liquid may be water.
In one embodiment of the present invention, the step of obtaining graphene based on the remaining second mixed gas and graphite carbon may specifically include:
adding an adhesive into graphite carbon to obtain a graphite rod;
and under the inert gas atmosphere, carrying out electrochemical stripping on the graphite rod by utilizing the residual second mixed gas to obtain the graphene.
In this embodiment, graphene can be obtained by converting graphite carbon into a graphite rod and electrochemically stripping the graphite rod with the remaining second mixture.
Specifically, in a closed container, a graphite rod is used as a cathode, a graphite crucible is used as an anode, molten sodium chloride is used as an electrolyte, argon and the rest of second mixed gas are continuously introduced, the temperature needs to reach the melting point of sodium chloride (for example, the temperature can be 900 ℃), 35A direct current is applied to a reaction system, and the graphite rod is gradually peeled off in the reaction process, so that fluffy graphene can be peeled off from the graphite rod and fall into sodium chloride. Because the density of the graphene is less than that of sodium chloride, the graphene floats on the surface of molten sodium chloride, and then the graphene is extracted and collected.
If pure hydrogen is used for electrochemical stripping of the graphite rod, the pure hydrogen may explode when in use, and the hydrogen concentration of the second mixed gas is 70-80%, so that the explosion does not occur. Meanwhile, the consumption of pure hydrogen is saved when the second mixed gas is introduced.
In one embodiment of the present invention, after step 105, the method may specifically further include:
Combusting the first oil phase product and the second oil phase product to obtain pyrolysis gas;
sequentially introducing pyrolysis gas into alkali liquor and a molecular sieve to purify the pyrolysis gas;
introducing the purified pyrolysis gas into the residual active carbon for vapor deposition;
the heat generated by the combustion is provided for the reactions of primary pyrolysis, secondary pyrolysis, pyrolysis of plastic waste and vapor deposition.
In this embodiment, by combusting the first oil phase product and the second oil phase product, the pyrolysis gas obtained by the combustion can be continuously purified and introduced into the remaining activated carbon for vapor deposition, so that more graphene can be obtained, and a large amount of heat generated by the combustion can be provided for the reactions of primary pyrolysis, secondary pyrolysis, pyrolysis of plastic waste and vapor deposition, so that the input of energy sources is saved.
In addition, the first gas phase product, the second gas phase product, the third mixed gas and the pyrolysis gas obtained by the scheme contain more waste heat, so that the gases are purified and then are introduced into the activated carbon for vapor deposition, and energy sources and heating cost can be saved.
Referring to fig. 2, another embodiment of the present invention provides a method for preparing graphene from biomass waste and plastic waste, the method comprising:
Step 201, adding biomass waste into an activating agent for impregnation;
step 202, performing primary pyrolysis on the impregnated biomass waste in an inert gas atmosphere to obtain activated carbon and first pyrolysis gas;
step 203, condensing the first pyrolysis gas to obtain a first oil phase product and a first gas phase product;
step 204, washing the activated carbon with water;
step 205, adding a catalyst into the activated carbon after water washing to obtain catalyst-loaded activated carbon;
step 206, performing secondary pyrolysis on part of the activated carbon loaded with the catalyst in an inert gas atmosphere to obtain graphite carbon loaded with the catalyst and second pyrolysis gas;
step 207, condensing the second pyrolysis gas to obtain a second oil phase product and a second gas phase product;
step 208, sequentially introducing alkali liquor and a molecular sieve into the first gas-phase product and the second gas-phase product to purify the first gas-phase product and the second gas-phase product;
step 209, introducing the purified first gas-phase product and the purified second gas-phase product into the residual activated carbon loaded with the catalyst for vapor deposition to obtain the activated carbon loaded with the catalyst and graphene and a first mixed gas;
step 210, pyrolyzing plastic waste to obtain an oil gas product;
Step 211, introducing an oil gas product into the graphite carbon loaded with the catalyst for vapor deposition to obtain the graphite carbon loaded with the catalyst and graphene and a second mixed gas;
step 212, carrying out acid washing on the graphene carbon loaded with the catalyst and graphene to obtain graphene-loaded graphite carbon;
213, dissolving graphite carbon loaded with graphene after acid washing in liquid with the density of 0.9-1.1 g/mL, and separating by utilizing a gravity sedimentation method to obtain graphite carbon and graphene;
step 214, adding an adhesive into graphite carbon to obtain a graphite rod;
and 215, carrying out electrochemical stripping on the graphite rod by using the residual second mixed gas in an inert gas atmosphere to obtain the graphene.
Referring to fig. 3, an embodiment of the present invention provides a graphene preparation system, which includes:
the first pyrolysis condensing assembly 1 is used for performing primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product;
the second pyrolysis condensing assembly 2 is connected with the first pyrolysis condensing assembly 1, and the second pyrolysis condensing assembly 2 is used for performing secondary pyrolysis and condensation on part of the activated carbon so as to obtain graphite carbon, a second oil phase product and a second gas phase product;
The first vapor deposition furnace 3 is respectively connected with the first pyrolysis condensing assembly 1 and the second pyrolysis condensing assembly 2, the first vapor deposition furnace 3 stores residual active carbon, and the first vapor deposition furnace 3 is used for receiving the first vapor product and the second vapor product and performing vapor deposition on the residual active carbon to obtain graphene-loaded active carbon and a first mixed gas;
a third pyrolysis furnace 4 for pyrolyzing the plastic waste to obtain oil gas products;
the second vapor deposition furnace 5 is respectively connected with the second pyrolysis condensing assembly 2 and the third pyrolysis furnace 4, and the second vapor deposition furnace 5 is used for receiving graphite carbon and oil gas products so as to obtain graphite carbon loaded with graphene and second mixed gas by vapor deposition of the oil gas products in the graphite carbon; wherein the second mixed gas comprises hydrogen;
and obtaining graphene based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas.
In this embodiment, first, biomass waste is pyrolyzed and condensed for one time to obtain activated carbon, a first oil phase product and a first gas phase product, then, part of the activated carbon is pyrolyzed and condensed for the second time to obtain graphite carbon, a second oil phase product and a second gas phase product, the first gas phase product and the second gas phase product are introduced into the residual activated carbon to be vapor deposited to obtain graphene-loaded activated carbon and a first mixed gas, then, plastic waste is pyrolyzed to obtain an oil gas product, and finally, the oil gas product is introduced into the graphite carbon to be vapor deposited to obtain graphene-loaded graphite carbon and a second mixed gas, so that graphene can be obtained based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas. Therefore, the technical scheme is that the graphene is prepared by taking cheap biomass waste and plastic waste as raw materials, so that waste is turned into wealth, and fossil resources utilized by the traditional graphene preparation technology can be saved.
In one embodiment of the present invention, the system further includes:
and a drying device (not shown in the figure) for drying the biomass waste.
In this embodiment, the biomass waste is baked to remove moisture in the biomass waste, so that the yield of the solid phase product, the yield of the oil phase product and the yield of the gas phase product of the biomass waste can be accurately calculated.
Referring to fig. 4, in one embodiment of the present invention, a first pyrolysis condensing unit 1 includes:
a first stirring tank 11 for stirring the biomass waste and the activator;
the first pyrolysis furnace 12 is connected with the first stirring pool 11, and the first pyrolysis furnace 12 is used for carrying out primary pyrolysis on the stirred biomass waste under the inert gas atmosphere to obtain activated carbon and first pyrolysis gas;
the first condenser 13 is connected with the first pyrolysis furnace 12, and the first condenser 13 is used for condensing the first pyrolysis gas to obtain a first oil phase product and a first gas phase product.
In this embodiment, by stirring the biomass waste and the activator, the activated carbon obtained by performing primary pyrolysis on the biomass waste after stirring is facilitated to have higher porosity.
With continued reference to fig. 4, in one embodiment of the present invention, the second pyrolytic condensing unit 2 comprises:
the water washing device 21 is connected with the first pyrolysis furnace 12, and the water washing device 21 is used for washing the activated carbon;
the second stirring pool 22 is connected with the water washing device 21, and the second stirring pool 22 is used for stirring the activated carbon after water washing and the catalyst to obtain catalyst-loaded activated carbon; the catalyst comprises transition metal salt, target nitrate and target metal oxide, wherein the transition metal salt is used for promoting graphitization of the activated carbon and dehydrogenation of the oil gas product, the target nitrate is used for promoting gasification reaction of plastic waste, and the target metal oxide is used for serving as a carrier of the catalyst and promoting reaction of obtaining a second mixed gas from the oil gas product;
the second pyrolysis furnace 23 is respectively connected with the second stirring pool 22 and the second vapor deposition furnace 5, and the second pyrolysis furnace 23 is used for carrying out secondary pyrolysis on part of the catalyst-loaded activated carbon in an inert gas atmosphere to obtain catalyst-loaded graphite carbon and second pyrolysis gas;
and the second condenser 24 is connected with the second pyrolysis furnace 23, and the second condenser 24 is used for condensing the second pyrolysis gas to obtain a second oil phase product and a second gas phase product.
In this embodiment, the activated carbon is first washed with water for washing away the activator on the surface of the activated carbon, because the activator may hinder graphitization of the activated carbon; and secondly, the catalyst is added into the activated carbon, so that graphitization of the activated carbon can be facilitated, gasification reaction of plastic waste can be promoted, and dehydrogenation of oil gas products of the plastic waste can be promoted.
It should be noted that the inert gas and the condensation manner in the second pyrolysis condensation unit 2 are the same as those in the first pyrolysis condensation unit 1, the second oil phase product and the first oil phase product are the same in kind, and the second gas phase product and the first gas phase product are the same in kind.
With continued reference to fig. 4, in one embodiment of the present invention, the system further includes:
the purification device 6 is respectively connected with the first condenser 13, the second condenser 24 and the first vapor deposition furnace 3, the purification device 6 is provided with alkali liquor and a molecular sieve, the purification device 6 is used for sequentially introducing the first vapor product and the second vapor product into the alkali liquor and the molecular sieve so as to purify the first vapor product and the second vapor product, and the purified first vapor product and second vapor product are introduced into the first vapor deposition furnace 3 so as to obtain the activated carbon and the first mixed gas of the supported catalyst and the graphene.
In this embodiment, since the first gas phase product and the second gas phase product contain carbon dioxide, the carbon dioxide reacts with the activated carbon to obtain carbon monoxide during the vapor deposition, and thus part of the activated carbon is consumed, and for this purpose, the alkali solution and the molecular sieve are sequentially introduced into the first gas phase product and the second gas phase product to remove (i.e. purify) the carbon dioxide in the first gas phase product and the second gas phase product.
In some embodiments, the vapor deposition condition of the first vapor deposition furnace 3 may be that the temperature is raised to 900 to 950 ℃ at a rate of 10 to 20 ℃/min and maintained for 30 to 50min, and the vapor deposition condition of the first vapor deposition furnace 3 is not limited in this embodiment of the present invention.
With continued reference to fig. 4, in one embodiment of the present invention, the system further includes:
the first acid washing device 71 is connected with the first vapor deposition furnace 3, and the first acid washing device 71 is used for carrying out acid washing on the supported catalyst and the active carbon of the graphene to obtain the active carbon of the supported graphene;
the reduction pyrolysis furnace 72 is respectively connected with the first acid cleaning device 71 and the purification device 6, and the reduction pyrolysis furnace 72 is used for receiving part of the second mixed gas and the graphene-loaded activated carbon after acid cleaning so as to perform reduction reaction on the graphene-loaded activated carbon after acid cleaning by using part of the second mixed gas to obtain graphene and a third mixed gas; wherein the temperature of the reduction reaction is 370-400 ℃, the third mixed gas comprises methane, and the third mixed gas is used for continuing to be introduced into the active carbon with the residual supported catalyst for vapor deposition after purification;
And obtaining graphene based on the residual second mixed gas and the graphene-loaded graphite carbon.
In the present embodiment, since graphene is supported on activated carbon and graphite carbon, graphene can be obtained by means of hydrogen in the second mixed gas. Specifically, the active carbon carrying the catalyst and the graphene is firstly subjected to acid washing, and metal simple substances and metal oxides in the catalyst can be washed away before reduction reaction, so that the graphene with higher purity can be obtained later; and secondly, introducing part of the second mixed gas into the graphene-loaded activated carbon after acid washing for reduction reaction, so that the activated carbon can react with hydrogen to obtain methane, and graphene and a third mixed gas are obtained.
With continued reference to fig. 4, in one embodiment of the present invention, the second vapor deposition furnace 5 is specifically configured to receive the catalyst-loaded graphite carbon and the oil gas product, so as to obtain the catalyst-loaded graphene carbon and the second mixed gas by vapor deposition of the oil gas product in the catalyst-loaded graphite carbon;
the system further comprises:
the second acid washing device 81 is connected with the second vapor deposition furnace 5, and the second acid washing device 81 is used for carrying out acid washing on the supported catalyst and the graphene graphite carbon to obtain the graphene-supported graphite carbon;
The separation device 82 is connected with the second acid washing device 81, and the separation device 82 is used for separating graphite carbon loaded with graphene after acid washing to obtain graphite carbon and graphene;
and obtaining graphene based on the residual second mixed gas and the graphite carbon.
In this embodiment, since the catalyst is supported in the graphite carbon, when the vapor deposition is performed by introducing the oil gas product into the catalyst-supported graphite carbon, the introduction of the catalyst is beneficial to promoting the dehydrogenation of the oil gas product, promoting the gasification reaction of the plastic waste, and promoting the reaction of obtaining the second mixed gas from the oil gas product. Specifically, the graphene-loaded graphite carbon is obtained by acid washing the graphene-loaded graphite carbon with the catalyst, then the graphene-loaded graphite carbon after acid washing is separated to obtain the graphene carbon and the graphene, and finally the graphene can be obtained based on the remaining second mixed gas and the graphene carbon. Therefore, the scheme can fully convert the graphene-loaded graphite carbon into graphene.
In some embodiments, the vapor deposition conditions of the second vapor deposition furnace 5 may be the same as those of the first vapor deposition furnace 3, and a detailed description thereof will be omitted. Of course, the vapor deposition conditions of the second vapor deposition furnace 5 may be different from those of the first vapor deposition furnace 3, for example, the vapor deposition conditions of the second vapor deposition furnace 5 may be raised to 850 to 950 ℃ at a rate of 10 to 15 ℃/min and maintained for 30 to 60 minutes.
In one embodiment of the present invention, the separation device 82 is disposed in a liquid with a density of 0.9-1.1 g/mL, and the separation device 82 is specifically configured to dissolve graphite carbon loaded with graphene after pickling in the liquid with a density of 0.9-1.1 g/mL, so as to perform separation by using a gravity sedimentation method.
In the present embodiment, since both graphene and graphitic carbon are powdery particles, the inventors creatively found that both can be dissolved in a target liquid to be separated by the density difference of both. Through a lot of experiments, the inventor finds that graphite carbon loaded with graphene after acid washing can be dissolved in liquid with the density of 0.9-1.1 g/mL so as to be separated by utilizing a gravity sedimentation method.
With continued reference to fig. 4, in one embodiment of the present invention, the system further includes:
the electrochemical stripping device 91 is connected with the separation device 82, and the electrochemical stripping device 91 is used for carrying out electrochemical stripping on the graphite rod by using the residual second mixed gas under the inert gas atmosphere to obtain graphene; wherein the graphite rod is obtained by adding a binder to graphite carbon.
In this embodiment, graphene can be obtained by converting graphite carbon into a graphite rod and electrochemically stripping the graphite rod with the remaining second mixture.
With continued reference to fig. 4, in one embodiment of the present invention, the system further includes:
the combustion device 92 is respectively connected with the first pyrolysis condensing assembly 1 and the second pyrolysis condensing assembly 2, and the combustion device 92 is used for combusting a first oil phase product and a second oil phase product to obtain pyrolysis gas; wherein, pyrolysis gas is used for letting in alkali lye and molecular sieve in proper order and letting in remaining active carbon and carry out vapor deposition, and the heat that burner 92 produced is used for providing the reaction of primary pyrolysis, secondary pyrolysis, pyrolysis and the vapor deposition of plastics discarded object.
In this embodiment, by combusting the first oil phase product and the second oil phase product, the pyrolysis gas obtained by the combustion can be continuously purified and introduced into the remaining activated carbon for vapor deposition, so that more graphene can be obtained, and a large amount of heat generated by the combustion can be provided for the reactions of primary pyrolysis, secondary pyrolysis, pyrolysis of plastic waste and vapor deposition, so that the input of energy sources is saved.
It is noted that in the present invention, relational terms such as first and second are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the graphene is characterized by comprising the following steps of:
carrying out primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product;
performing secondary pyrolysis and condensation on part of the activated carbon to obtain graphite carbon, a second oil phase product and a second gas phase product;
introducing the first gas-phase product and the second gas-phase product into the residual active carbon for gas-phase deposition to obtain graphene-loaded active carbon and a first mixed gas;
pyrolyzing the plastic waste to obtain an oil gas product;
introducing the oil gas product into the graphite carbon for vapor deposition to obtain graphene-loaded graphite carbon and a second mixed gas; wherein the second mixed gas comprises hydrogen;
obtaining graphene based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas;
The method for performing primary pyrolysis and condensation on biomass waste to obtain activated carbon, a first oil phase product and a first gas phase product comprises the following steps:
adding biomass waste into an activating agent for impregnation;
under the inert gas atmosphere, performing primary pyrolysis on the impregnated biomass waste to obtain activated carbon and first pyrolysis gas;
condensing the first pyrolysis gas to obtain a first oil phase product and a first gas phase product;
and performing secondary pyrolysis and condensation on part of the activated carbon to obtain graphite carbon, a second oil phase product and a second gas phase product, wherein the secondary pyrolysis and condensation comprises the following steps:
washing the activated carbon with water;
adding a catalyst into the activated carbon after water washing to obtain catalyst-loaded activated carbon; wherein the catalyst comprises a transition metal salt, a target nitrate and a target metal oxide, wherein the transition metal salt is used for promoting graphitization of the activated carbon and dehydrogenation of the oil gas product, the target nitrate is used for promoting gasification reaction of the plastic waste, and the target metal oxide is used for serving as a carrier of the catalyst and promoting reaction of the oil gas product to obtain the second mixed gas;
performing secondary pyrolysis on part of the catalyst-loaded activated carbon in an inert gas atmosphere to obtain catalyst-loaded graphite carbon and second pyrolysis gas;
Condensing the second pyrolysis gas to obtain a second oil phase product and a second gas phase product;
introducing the first gas-phase product and the second gas-phase product into the remaining activated carbon for vapor deposition to obtain graphene-loaded activated carbon and a first mixed gas, wherein the method comprises the following steps of:
sequentially introducing alkali liquor and molecular sieves into the first gas-phase product and the second gas-phase product to purify the first gas-phase product and the second gas-phase product;
introducing the purified first gas-phase product and the purified second gas-phase product into the residual active carbon loaded with the catalyst to carry out gas-phase deposition to obtain active carbon loaded with the catalyst and graphene and a first mixed gas;
the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas are based on the graphene-loaded activated carbon, and graphene is obtained, and the method comprises the following steps:
acid washing is carried out on the supported catalyst and the active carbon of the graphene, so that the active carbon of the supported graphene is obtained;
introducing part of the second mixed gas into the graphene-loaded activated carbon subjected to acid washing to perform reduction reaction to obtain graphene and a third mixed gas; the temperature of the reduction reaction is 370-400 ℃, the third mixed gas comprises methane, and the third mixed gas is used for continuing to be introduced into the residual active carbon of the supported catalyst for vapor deposition after purification;
Obtaining graphene based on the residual second mixed gas and the graphene-loaded graphite carbon;
introducing the oil gas product into the graphite carbon for vapor deposition to obtain graphene-loaded graphite carbon and a second mixed gas, wherein the method comprises the following steps of:
introducing the oil gas product into the graphite carbon loaded with the catalyst for vapor deposition to obtain graphite carbon loaded with the catalyst and graphene and a second mixed gas;
the graphene obtaining method based on the remaining second mixed gas and the graphene-loaded graphite carbon comprises the following steps:
acid washing is carried out on the supported catalyst and the graphene graphite carbon to obtain the graphene-supported graphite carbon;
separating graphite carbon loaded with graphene after acid washing to obtain graphite carbon and graphene;
obtaining graphene based on the rest of the second mixed gas and the graphite carbon;
the obtaining graphene based on the remaining second mixed gas and the graphite carbon comprises the following steps:
adding an adhesive into the graphite carbon to obtain a graphite rod;
and under the inert gas atmosphere, carrying out electrochemical stripping on the graphite rod by utilizing the residual second mixed gas to obtain graphene.
2. The method of claim 1, wherein separating the graphene-loaded graphitic carbon after pickling comprises:
And (3) dissolving the graphite carbon loaded with the graphene after acid washing into a liquid with the density of 0.9-1.1 g/mL so as to separate by utilizing a gravity sedimentation method.
3. The method of any one of claims 1-2, further comprising, after said passing said hydrocarbon product into said graphitic carbon for vapor deposition:
combusting the first oil phase product and the second oil phase product to obtain pyrolysis gas;
sequentially introducing the pyrolysis gas into alkali liquor and a molecular sieve to purify the pyrolysis gas;
introducing the purified pyrolysis gas into the residual active carbon for vapor deposition;
the heat generated by the combustion is provided to the reactions of primary pyrolysis, secondary pyrolysis, pyrolysis of the plastic waste and vapor deposition.
4. A graphene preparation system, characterized in that it is based on the method according to any one of claims 1-3, comprising:
the first pyrolysis condensing assembly is used for performing primary pyrolysis and condensation on biomass waste to obtain active carbon, a first oil phase product and a first gas phase product;
the second pyrolysis condensing assembly is connected with the first pyrolysis condensing assembly and is used for carrying out secondary pyrolysis and condensation on part of the activated carbon so as to obtain graphite carbon, a second oil phase product and a second gas phase product;
The first vapor deposition furnace is respectively connected with the first pyrolysis condensing assembly and the second pyrolysis condensing assembly, the first vapor deposition furnace stores residual activated carbon, and is used for receiving the first vapor product and the second vapor product, and performing vapor deposition on the residual activated carbon to obtain graphene-loaded activated carbon and a first mixed gas;
the third pyrolysis furnace is used for pyrolyzing the plastic waste to obtain an oil gas product;
the second vapor deposition furnace is respectively connected with the second pyrolysis condensing assembly and the third pyrolysis furnace and is used for receiving the graphite carbon and the oil gas product so as to obtain graphite carbon loaded with graphene and second mixed gas by vapor deposition of the oil gas product in the graphite carbon; wherein the second mixed gas comprises hydrogen;
and obtaining graphene based on the graphene-loaded activated carbon, the graphene-loaded graphite carbon and the second mixed gas.
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