CN115991468A - Preparation method of porous thin-layer graphene-like material - Google Patents
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Abstract
The invention relates to a preparation method of a pore-rich thin layer graphene, which comprises the following steps: the method comprises the following steps of (1) pretreatment of raw oil: taking a coking liquid recovery product obtained by carrying out delayed coking treatment on catalytic slurry oil or residual oil as a pretreatment raw oil, and carrying out distillation cutting and solvent extraction on the raw oil to obtain distillate aromatic extraction oil; (2) reactant treatment: mixing the distillate aromatic extract oil with an organic solvent, adding a template agent for dispersion, and rotationally evaporating the organic solvent from the obtained solid-liquid mixture to obtain template agent powder of the surface-coated distillate aromatic extract oil; (3) preparation of a pore-rich thin layer graphene-like material: and calcining the template agent powder, and removing the template agent from the calcined product by acid washing to obtain the pore-rich thin-layer graphene-like material. The graphene material prepared by the method has the advantages of high uniformity of morphology, thinner layer number and shell-type curled shape, and is particularly of great significance for high value-added utilization of inferior heavy oil rich in polycyclic aromatic hydrocarbon such as catalytic slurry oil.
Description
Technical Field
The invention belongs to the field of petrochemical industry and carbon nanomaterial science intersection, and particularly relates to a method for preparing porous thin-layer graphene based on different fractions after catalytic slurry oil or residual oil delayed coking treatment.
Background
Graphene is a novel two-dimensional nanomaterial, and is widely focused in academia and industry because of its excellent properties. The graphene material is usually prepared in a lamellar powder and lamellar film form, graphite is usually adopted as a carbon source in the industry to prepare powdery graphene, but the method usually needs to prepare a graphite oxide intermediate state, then ultrasonic stripping is carried out, and the lamellar graphene is prepared by using a strong reducing agent; the method requires a large amount of strong oxidizing agent and strong reducing agent, and the process steps are complex. The industry also uses monomers like methane to prepare high purity film graphene by vapor deposition, which, despite higher purity, is costly in terms of carbon sources, high energy consumption in process equipment, and thus higher cost and lower yield. Therefore, it is necessary to develop a process method which has a wide source of carbon source, is simple and easy to operate, and can reduce the consumption of strong oxidizing agent and strong reducing agent.
In order to solve the problems, researchers adopt various methods to prepare graphene materials with different morphologies.
Chinese application CN106185890a discloses a preparation method of porous graphene-like material, which uses coal pitch as raw material, ammonium inorganic salt as pore-forming agent, and carbonizing treatment in inert atmosphere at a certain temperature range.
Chinese application CN105236394a discloses a method for preparing interconnected graphene nanoplatelets, which uses coal tar dissolved in N, N-dimethylformamide as an original carbon material, uses nano magnesium oxide as a template, and KOH as a pore-forming agent, and finally synthesizes the graphene nanoplatelets.
Chinese patent CN105502363B discloses a method for preparing a wrinkled graphene nano-sheet, which uses petroleum asphalt as a carbon source, nano-magnesia as a template, and potassium hydroxide as an activator, and the porous graphene material for the supercapacitor is directly obtained by heating, carbonizing and activating under the inert atmosphere condition in a tube furnace.
Chinese patent CN105502363B discloses a preparation method of honeycomb porous carbon, which uses coal pitch as carbon source, melamine as soft template, potassium hydroxide as activator, and heating, carbonizing and activating under inert atmosphere in a tube furnace to prepare graphene-like material with honeycomb structure.
In addition to the conventional graphite or graphite oxide, the current preparation method of the graphene-like powder mostly adopts carbon sources with larger carbon content such as petroleum asphalt or coal asphalt in the development of carbon sources, and the oil-based carbon sources are rich in aromatic hydrocarbon structural units, so that carbon materials with graphite-like structures are easy to form in the carbonization process. However, because the carbon source contains asphaltene and colloid with certain components, the ash content and the metal content are also higher, and most of the prepared carbon material is presented in the shape of porous carbon material, and is difficult to form a thin-layer graphene-like material; the graphic representation presented in the related patent is difficult to see the overall carbon material morphology, and if a thin-layer graphene material is to be prepared, pretreatment is required for the raw materials, so that the process is complex, the cost is high, and the commercialized application is not facilitated.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a thin layer graphene-like material rich in pores, which takes distillate oil aromatic hydrocarbon extracted oil obtained from coking liquid as a carbon source and takes a metal oxide hard template as a framework. The preparation method is simple, wide in raw material sources, good in application prospect and easy for industrial production.
Therefore, the invention provides a preparation method of a pore-rich thin layer graphene, which is characterized by comprising the following steps of:
(1) Pretreatment of raw oil: taking a coking liquid recovery product obtained by carrying out delayed coking treatment on catalytic slurry oil or residual oil as a pretreatment raw oil, and carrying out distillation cutting and solvent extraction on the raw oil to obtain distillate aromatic extraction oil;
(2) Reactant treatment: mixing the distillate aromatic extract oil with an organic solvent, adding a template agent for dispersion, and rotationally evaporating the organic solvent from the obtained solid-liquid mixture to obtain template agent powder of the surface-coated distillate aromatic extract oil;
(3) Preparing a pore-rich thin layer graphene-like material: and calcining the template agent powder, and removing the template agent from the calcined product by acid washing to obtain the pore-rich thin-layer graphene-like material.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: in the step (1), the raw oil is distilled and cut first and then extracted by a solvent, or the raw oil is distilled and cut first and then extracted by the solvent.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: when raw oil is distilled, cut and then subjected to solvent extraction, the volume ratio of distillate oil obtained by the distillation, cut and the extractant in the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90 ℃; when the raw oil is subjected to solvent extraction and then distillation cutting, the volume ratio of the raw oil to the extractant in the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90 ℃.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the distillation cut is to cut a fraction >350 ℃ or >500 ℃.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the distillate aromatic extract oil has a distillation range of >350 ℃ and an aromatic content of >80%, or a distillation range of >500 ℃ and an aromatic content of >80%.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the solvent extraction is carried out by using a polar organic solvent or a nonpolar organic solvent, preferably a polar organic solvent, and more preferably a furfural solvent.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the calcination adopts temperature programming, and is heated to 700-900 ℃ at 5-10 ℃/min in inert atmosphere, kept for 1-2 h, and then cooled to room temperature.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the calcination is heated to 300 ℃ at 5 ℃/min before being heated to 700-900 ℃ in inert atmosphere, and is kept for 30min.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the inert atmosphere is nitrogen or argon.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the volume ratio of the distillate aromatic extract oil to the organic solvent is 4:1-6:1, and the mass ratio of the distillate aromatic extract oil to the template agent is 1:3-1:5.
The preparation method of the pore-rich thin layer curled graphene, disclosed by the invention, comprises the following steps of: the template agent is metal oxide, and the metal oxide is magnesium oxide, ferric oxide or zinc oxide; the organic solvent is selected from at least one of toluene and carbon tetrachloride.
The invention is thatThe preparation method of the pore-rich thin layer curled graphene comprises the following steps: the porous thin layer graphene-like material is of a three-dimensional coiled structure and has specific surface area>550m 2 Per g, total pore volume>2cm 3 /g, average pore diameter>15nm。
Specifically, the preparation method of the pore-rich thin layer curled graphene comprises the following steps:
(1) The coking liquid recovery product obtained by treating catalytic slurry oil or residual oil through a delayed coking process is used as a pretreatment oil raw material, fraction cutting is carried out through distillation, and the cut fraction oil is extracted and enriched with aromatic hydrocarbon through an extractant to obtain fraction oil aromatic hydrocarbon enriched oil (namely fraction oil aromatic hydrocarbon extracted oil) which is in a solid sticky state at normal temperature.
(2) And (3) mixing the obtained distillate aromatic extract oil with an organic solvent, adding a template agent for dispersion, and rotationally evaporating the solid-liquid mixture to obtain the organic solvent to obtain template agent powder of the surface-coated distillate aromatic extract oil.
(3) And (3) calcining the powder, and removing the template agent from the calcined product by acid washing to obtain the pore-rich thin-layer curled graphene material.
In the step (1), the sequence of the distillation cutting and solvent extraction process steps can be adjusted, the coking liquid is firstly collected and extracted by an extracting agent to obtain aromatic enriched oil, and then the distillate aromatic enriched oil is obtained by distillation cutting. Because the coking liquid contains less than 1% of asphaltene, the liquid level layering of saturated and aromatic components can be obviously obtained by the solvent extraction and extraction process, so that the composition of a final product is not influenced by the extraction process, the extraction and the fraction cutting are carried out by adopting a furfural extraction tower one-step method in the industry in the patent CN111500316A to obtain heavy aromatic components, and the pretreatment process of the method can be also suitable for treatment by adopting an industrial device in the patent.
In the step (2), the obtained distillate aromatic hydrocarbon extract oil is solid and viscous at normal temperature, and needs to be mixed with an organic solvent, then template agents are added for dispersion, and liquid phase and a solid template are mixed, so that the aromatic hydrocarbon can be uniformly coated on the surface of the template agents, and a graphene-like carbon material with uniform morphology can be formed in the calcination stage.
In the step (3), the temperature is raised to 700-900 ℃ at 5-10 ℃/min in an inert atmosphere, the temperature is kept for 1-2 h, and then the product is cooled to room temperature and taken out. Considering that the aromatic hydrocarbon component can liquefy and flow at high temperature, the temperature is preferably raised to 300 ℃ at 5 ℃/min before the temperature is raised to 700-900 ℃ in an inert atmosphere, and the temperature is kept for 30min, so that the aromatic hydrocarbon can be uniformly covered on the template agent.
The invention is rich in aromatic hydrocarbon and asphaltene<1% of coking liquid is taken as raw oil, and separated>350 ℃ or>Aromatic hydrocarbon oil at 500 ℃ is used as a carbon source, an organic solvent is used as a dispersing auxiliary, a metal oxide is used as an adhesion framework and a pore-forming agent for high-temperature carbonization growth of aromatic hydrocarbon, and the porous thin-layer curled graphene-like material is prepared through high-temperature carbonization. The specific surface area of the prepared graphene-like material is 592-730 m without any secondary pore-forming treatment 2 Between/g, the average pore diameter is 15-22 nm, and the total pore volume is 2.24-3.76 cm 3 Between/g, the morphology presents a coiled porous lamellar structure.
Compared with the prior art, the invention has the following beneficial effects:
1. the coking liquid has wide sources, and different fractions can be cut and selected according to the refinery requirement, so that the carbon source path for preparing the graphene-like carbon material is widened; in addition, because the raw materials hardly contain asphaltene and have low colloid content, the carbonized graphene material has the advantages of thinner layer number, clear interface and high graphitizable degree;
2. the preparation process is simple, and the porous graphene-like powder material with fewer layers is prepared by carbonization and heating by using the template molding principle;
3. the metal oxide particle template used belongs to a hard template, and can be removed by directly using dilute acid.
4. The graphene material prepared by the method has the advantages of high specific surface area, uniform pore size distribution, very thin layer number and wide application in the fields of catalysis, adsorption, super capacitors and the like.
In summary, the invention takes the aromatic hydrocarbon component of the distillate oil of the coking liquid as a raw material, takes the nano metal oxide as a template agent, and prepares the thin-layer graphene-like material with a porous structure by self-assembling oil molecules at high temperature to form carbon. The method has the advantages of uniform raw material components, low price, wide sources, simple raw material pretreatment process, and thinner layer number of the prepared graphite-like material, and has good market prospect.
Drawings
FIG. 1 is a scanning electron microscope image of a porous thin layer curled graphene-like LHJH350-CT-M4-9 of example 1;
FIG. 2 is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH500-CT-M4-9 of example 2;
FIG. 3 is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH500-CT-M3-7 of example 3;
FIG. 4 is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH350-CT-M5-7 of example 4
FIG. 5 is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH CT-350-M4-9 of example 5
FIG. 6 is a scanning electron microscope image of magnesium oxide particles used in the present invention.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The coking distillate oil is derived from coking liquid products obtained after delayed coking treatment of Liaohe catalytic cracking slurry oil, and the oil is used as a carbon source in examples 1-5.
The metal oxide template agent is magnesium oxide and ferric oxide nano particles, which are single particles with the particle diameter of 50nm-100nm, the agglomeration state is 2-3 mu m, and the metal oxide template agent is used as the template agent in the embodiment 1-5.
Example 1
The first step: pretreatment of raw oil.
500kg of the coking liquid yield was weighed and subjected to atmospheric pressure fraction cutting by means of a true boiling point distiller, and a fraction of >350℃was taken (denoted LHJH 350). Mixing the cut distillate oil with furfural according to the volume ratio of 1:2, and stirring and uniformly mixing at the water bath temperature of 60 ℃; transferring the uniformly mixed solution into a separating funnel, standing for 2 hours in a 60 ℃ oven, separating the lower layer, and extracting oil. Transferring the lower layer extract oil to a rotary evaporator, slowly heating to 140 ℃ under negative pressure of-0.15 MPa to evaporate furfural solvent, and obtaining distillate aromatic extract oil (denoted as LHJH350-CT, wherein CT means extraction). The aromatic hydrocarbon extract oil is sticky colloid at normal temperature, and is Newtonian fluid after the temperature is higher than 80 ℃.
And a second step of: reactant treatment.
Stirring and mixing the distillate aromatic extract oil obtained in the first step with toluene solvent according to a volume ratio of 4:1, so that the distillate aromatic extract oil which is sticky at normal temperature is fully dissolved in the toluene solvent; adding ferric oxide particles according to the mass ratio of the distillate aromatic extract oil to the magnesium oxide nano particles of 1:4 while stirring for dispersion, stirring for 1h, carrying out ultrasonic treatment for 30min, and stirring for 30min; transferring the obtained solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under the negative pressure of 0.15MPa to evaporate the toluene solvent, scraping out the powdery product and transferring to a porcelain boat.
And a third step of: and (3) preparing the pore-rich thin layer graphene-like material.
Placing the porcelain boat containing the powder in the second step into a tube furnace, heating to 300 ℃ at 5 ℃/min in a nitrogen atmosphere, keeping for 30min, heating to 900 ℃ at 5 ℃/min, keeping for 1h, and cooling to room temperature and taking out a product; grinding the product into fine powder, washing the fine powder to be neutral through a dilute hydrochloric acid stripper plate with the concentration of 2mol/L and deionized water, and drying the fine powder to obtain the graphene-like material, wherein the graphene-like material is marked as LHJH350-CT-M4-9.
Example 2
The first step: pretreatment of raw oil.
500kg of a coking liquid yield was weighed and subjected to atmospheric pressure fraction cutting by means of a true boiling point distiller, and a fraction of >500℃was taken (denoted LHJH 500). Mixing the cut distillate oil with furfural according to the volume ratio of 1:2, and stirring and uniformly mixing at the water bath temperature of 60 ℃; transferring the uniformly mixed solution into a separating funnel, standing for 2 hours in an oven at 80 ℃, and separating the lower layer to extract oil. Transferring the lower layer extract oil to a rotary evaporator, slowly heating to 140 ℃ under negative pressure of-0.15 MPa to evaporate furfural solvent, and obtaining distillate aromatic hydrocarbon extract oil (recorded as LHJH 500-CT). The aromatic hydrocarbon extract oil is sticky colloid at normal temperature, and is Newtonian fluid after the temperature is higher than 80 ℃.
And a second step of: reactant treatment.
Stirring and mixing the distillate aromatic extract oil obtained in the first step with toluene solvent according to a volume ratio of 6:1, so that the distillate aromatic extract oil which is sticky at normal temperature is fully dissolved in the toluene solvent; adding ferric oxide particles according to the mass ratio of the distillate aromatic extract oil to the magnesium oxide nano particles of 1:4 while stirring for dispersion, stirring for 1h, carrying out ultrasonic treatment for 30min, and stirring for 30min; transferring the obtained solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under the negative pressure of 0.15MPa to evaporate the toluene solvent, scraping out the powdery product and transferring to a porcelain boat.
And a third step of: and (3) preparing the pore-rich thin layer graphene-like material.
Placing the porcelain boat containing the powder obtained in the step two into a tube furnace, heating to 300 ℃ at 5 ℃/min in a nitrogen atmosphere, keeping for 30min, heating to 900 ℃ at 5 ℃/min, keeping for 1h, cooling to room temperature, and taking out a product; grinding the product into fine powder, washing the fine powder to be neutral through a dilute hydrochloric acid stripper plate with the concentration of 2mol/L and deionized water, and drying the fine powder to obtain the graphene-like material, wherein the graphene-like material is marked as LHJH500-CT-M4-9.
Example 3
The first step: pretreatment of raw oil.
500kg of a coking liquid yield was weighed and subjected to atmospheric pressure fraction cutting by means of a true boiling point distiller, and a fraction of >500℃was taken (denoted LHJH 500). Mixing the cut distillate oil with furfural according to the volume ratio of 1:2, and stirring and uniformly mixing at the water bath temperature of 60 ℃; transferring the uniformly mixed solution into a separating funnel, standing for 2 hours in an oven at 80 ℃, and separating the lower layer to extract oil. Transferring the lower layer extract oil to a rotary evaporator, slowly rising to 140 ℃ under negative pressure of-0.15 MPa, and evaporating the furfural solvent to obtain distillate aromatic hydrocarbon extract oil. The aromatic hydrocarbon extract oil is sticky colloid at normal temperature, and is Newtonian fluid after the temperature is higher than 80 ℃.
And a second step of: reactant treatment.
Stirring and mixing the distillate aromatic extract oil obtained in the first step with toluene solvent according to a volume ratio of 6:1, so that the distillate aromatic extract oil which is sticky at normal temperature is fully dissolved in the toluene solvent; adding ferric oxide particles according to the mass ratio of the distillate aromatic extract oil to the ferric oxide nanoparticles of 1:3 while stirring for dispersion, stirring for 1h, carrying out ultrasonic treatment for 30min, and stirring for 30min; transferring the solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under the negative pressure of 0.15MPa to evaporate the toluene solvent, scraping out the powdery product and transferring the powdery product to a porcelain boat.
And a third step of: and (3) preparing the pore-rich thin layer graphene-like material.
Placing the porcelain boat containing the powder obtained in the step two into a tube furnace, heating to 300 ℃ at 5 ℃/min in a nitrogen atmosphere, keeping for 30min, heating to 700 ℃ at 5 ℃/min, keeping for 1h, and cooling to room temperature and taking out a product; grinding the product into fine powder, washing the fine powder to be neutral through a dilute hydrochloric acid stripper plate with the concentration of 2mol/L and deionized water, and drying the fine powder to obtain the graphene-like material, wherein the graphene-like material is marked as LHJH500-CT-M3-7.
Example 4
The first step: and (5) pretreatment of raw materials.
500kg of the coking liquid yield was weighed and subjected to atmospheric pressure fraction cutting by means of a true boiling point distiller, and a fraction of >350℃was taken (denoted LHJH 350). Mixing the cut distillate oil with furfural according to the volume ratio of 1:2, and stirring and uniformly mixing at the water bath temperature of 60 ℃; transferring the uniformly mixed solution into a separating funnel, standing for 2 hours in a 60 ℃ oven, separating the lower layer, and extracting oil. Transferring the lower layer extract oil to a rotary evaporator, slowly heating to 140 ℃ under negative pressure of-0.15 MPa to evaporate the furfural solvent, and obtaining distillate aromatic hydrocarbon extract oil (recorded as LHJH 350-CT). The aromatic hydrocarbon extract oil is sticky colloid at normal temperature, and is Newtonian fluid after the temperature is higher than 80 ℃.
And a second step of: reactant treatment.
Stirring and mixing the distillate aromatic extract oil obtained in the first step with toluene solvent according to a volume ratio of 4:1, so that the distillate aromatic extract oil which is sticky at normal temperature is fully dissolved in the toluene solvent; adding ferric oxide particles according to the mass ratio of the distillate aromatic extract oil to the magnesium oxide nano particles of 1:3 while stirring for dispersion, stirring for 1h, carrying out ultrasonic treatment for 30min, and stirring for 30min; transferring the solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under negative pressure of-0.15 MPa to evaporate the toluene solvent, scraping out the powdery product and transferring to a porcelain boat.
And a third step of: and (3) preparing the pore-rich thin layer graphene-like material.
Placing the porcelain boat containing the powder obtained in the step two into a tube furnace, heating to 900 ℃ at 10 ℃/min in a nitrogen atmosphere, keeping for 2 hours, cooling to room temperature, and taking out a product; grinding the product into fine powder, washing the fine powder to be neutral through a dilute hydrochloric acid stripper plate with the concentration of 2mol/L and deionized water, and drying the fine powder to obtain the graphene-like material, wherein the graphene-like material is marked as LHJH350-CT-M3-9.
Example 5
The first step: pretreatment of raw oil.
Weighing 500kg of coking liquid recovery product, mixing with furfural according to a volume ratio of 1:3, and stirring and uniformly mixing at a water bath temperature of 60 ℃; the obtained mixed solution is transferred to a separating funnel, and is kept stand in a baking oven at 60 ℃ for 2 hours, and the lower layer is separated and the oil is extracted. Transferring the lower layer extract oil to a rotary evaporator, slowly rising to 140 ℃ under negative pressure of-0.15 MPa, and evaporating the furfural solvent to obtain the coking liquid aromatic hydrocarbon extract oil. The extract was cut by a true boiling point distiller at atmospheric pressure, and a fraction >350 ℃ was taken as the distillate aromatic extract (denoted LHJHCT-350).
And a second step of: reactant treatment.
Stirring and mixing the distillate aromatic extract oil obtained in the step one with toluene solvent according to the volume ratio of 4:1, so that the distillate aromatic extract oil which is sticky at normal temperature is fully dissolved in the toluene solvent; adding ferric oxide particles according to the mass ratio of the distillate aromatic extract oil to the magnesium oxide nano particles of 1:4 while stirring for dispersion, stirring for 1h, carrying out ultrasonic treatment for 30min, and stirring for 30min; transferring the solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under negative pressure of-0.15 MPa to evaporate the toluene solvent, scraping out the powdery product and transferring to a porcelain boat.
And a third step of: and (3) preparing the porous thin-layer graphene-like material.
Placing the porcelain boat containing the powder obtained in the step two into a tube furnace, heating to 700 ℃ at 10 ℃/min in a nitrogen atmosphere, keeping for 2 hours, cooling to room temperature, and taking out a product; grinding the product into fine powder, washing the fine powder to be neutral through a dilute hydrochloric acid stripper plate with the concentration of 2mol/L and deionized water, and drying the fine powder to obtain the graphene-like material, wherein the graphene-like material is marked as LHJH CT-350-M4-7.
The results of analysis of the properties of the fractions obtained in examples 1 to 5 are shown in Table 1. The results of the pore structure of the porous thin layer rolled graphene-like material obtained in examples 1 to 5 are shown in Table 2. The morphology of the porous thin-layer curled graphene-like material obtained in examples 1-5 is characterized, and the results are shown in fig. 1-5. As can be seen from Table 2 and FIGS. 1 to 3, the graphene-like material prepared by the present invention has a specific surface area of 592-730 m without any secondary pore-forming treatment 2 Between/g, the average pore diameter is 15-22 nm, and the total pore volume is 2.24-3.76 cm 3 Between/g, the morphology presents a coiled porous lamellar structure.
TABLE 1 four component analysis of the fractions obtained in examples 1-5
| Fraction hydrocarbon composition | LHJH350 | LHJH350-CT | LHJH500 | LHJH500-CT |
| Saturated portion | 44.5 | 3.2 | 28.7 | 0.2 |
| Aromatic components | 49.3 | 85.4 | 61.9 | 82.1 |
| Colloid | 5.6 | 10.4 | 8.5 | 16.7 |
| Asphaltenes | 0.6 | 1.0 | 0.9 | 1.0 |
| Yield is good | - | 49％ | - | 65％ |
TABLE 2 pore Structure results of porous thin layer graphene-like materials obtained in examples 1-5
Comparative example 1
The first step: and (5) pretreatment of raw materials.
500kg of a coking liquid product is weighed and subjected to normal pressure fraction cutting by a true boiling point distiller, a fraction (recorded as LHJH 350) with the temperature of more than 350 ℃ is taken, and the fraction oil of the fraction is directly used as a carbon source.
And a second step of: reactant treatment.
Stirring and mixing the distillate oil obtained in the step one with toluene solvent according to a volume ratio of 4:1, adding ferric oxide particles to disperse according to a mass ratio of 1:4 while stirring, stirring for 1h, performing ultrasonic treatment for 30min, and stirring for 30min again; transferring the solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under the negative pressure of 0.15MPa to evaporate the toluene solvent, and enabling the residual product to be in a semi-viscous flowing state, wherein the template agent cannot be uniformly dispersed in distillate oil (carbon source) and cannot form solid powder. The viscous product was scraped off and applied to a porcelain boat.
And a third step of: and (3) preparing the pore-rich thin layer graphene-like material.
And (3) putting the porcelain boat obtained in the step II into a tube furnace, heating to 300 ℃ at 5 ℃/min in a nitrogen atmosphere, keeping for 30min, heating to 900 ℃ at 5 ℃/min, keeping for 1h, cooling to room temperature, taking out products, and most of the products are cracked, so that carbon powder cannot be collected.
Comparative example 2
The first step: pretreatment of raw oil.
Weighing 500kg of coking liquid recovery product, mixing with furfural according to a volume ratio of 1:3, and stirring and uniformly mixing at a water bath temperature of 60 ℃; transferring the uniformly mixed solution into a separating funnel, standing for 2 hours in a 60 ℃ oven, separating the lower layer, and extracting oil. Transferring the lower layer extract oil to a rotary evaporator, slowly rising to 140 ℃ under negative pressure of-0.15 MPa to evaporate the furfural solvent, and obtaining the coking liquid aromatic hydrocarbon extract oil as a carbon source, wherein the coking liquid aromatic hydrocarbon extract oil shows flow dynamics at normal temperature.
And a second step of: reactant treatment.
Stirring and mixing the aromatic hydrocarbon extracted oil obtained in the step one with toluene solvent according to the volume ratio of 4:1; adding ferric oxide particles to disperse while stirring according to the mass ratio of the aromatic hydrocarbon extracted oil to the magnesium oxide nanoparticles of 1:4, stirring for 1h, performing ultrasonic treatment for 30min, and stirring for 30min; transferring the solid-liquid mixture to a rotary evaporator, slowly heating to 80 ℃ under negative pressure of-0.15 MPa to evaporate the toluene solvent, scraping out a viscous product, and transferring the viscous product to a porcelain boat.
And a third step of: and (3) preparing the porous thin-layer graphene-like material.
Placing the porcelain boat obtained in the second step into a tube furnace, heating to 700 ℃ at 10 ℃/min in a nitrogen atmosphere, keeping for 2 hours, cooling to room temperature, and taking out a product, wherein the product presents agglomerated carbon blocks; grinding the product into fine powder, washing the fine powder to be neutral by using 2M dilute hydrochloric acid template removal and deionized water, and drying to obtain only finely divided small carbon blocks, which are not graphene-like carbon powder.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. The preparation method of the pore-rich thin-layer graphene is characterized by comprising the following steps of:
(1) Pretreatment of raw oil: taking a coking liquid recovery product obtained by carrying out delayed coking treatment on catalytic slurry oil or residual oil as a pretreatment raw oil, and carrying out distillation cutting and solvent extraction on the raw oil to obtain distillate aromatic extraction oil;
(2) Reactant treatment: mixing the distillate aromatic extract oil with an organic solvent, adding a template agent for dispersion, and rotationally evaporating the organic solvent from the obtained solid-liquid mixture to obtain template agent powder of the surface-coated distillate aromatic extract oil;
(3) Preparing a pore-rich thin layer graphene-like material: and calcining the template agent powder, and removing the template agent from the calcined product by acid washing to obtain the pore-rich thin-layer graphene-like material.
2. The method for preparing the pore-rich thin layer curled graphene according to claim 1, wherein the method comprises the following steps: in the step (1), the raw oil is distilled and cut first and then extracted by a solvent, or the raw oil is distilled and cut first and then extracted by the solvent.
3. The method for preparing the pore-rich thin layer curled graphene according to claim 2, wherein the method comprises the following steps: when raw oil is distilled, cut and then subjected to solvent extraction, the volume ratio of distillate oil obtained by the distillation, cut and the extractant in the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90 ℃; when the raw oil is subjected to solvent extraction and then distillation cutting, the volume ratio of the raw oil to the extractant in the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90 ℃.
4. The method for preparing the pore-rich thin layer curled graphene according to claim 1, wherein the method comprises the following steps: the distillation cut is to cut a fraction >350 ℃ or >500 ℃.
5. The method for preparing the pore-rich thin layer curled graphene according to claim 4, wherein the method comprises the following steps: the distillate aromatic extract oil has a distillation range of >350 ℃ and an aromatic content of >80%, or a distillation range of >500 ℃ and an aromatic content of >80%.
6. The method for preparing the pore-rich thin layer curled graphene according to claim 1, wherein the method comprises the following steps: the solvent extraction is carried out by using a polar organic solvent or a nonpolar organic solvent, preferably a polar organic solvent, and more preferably a furfural solvent.
7. The method for preparing the pore-rich thin layer curled graphene according to claim 1, wherein the method comprises the following steps: the calcination adopts temperature programming, and is heated to 700-900 ℃ at 5-10 ℃/min in inert atmosphere, kept for 1-2 h, and then cooled to room temperature.
8. The method for preparing the pore-rich thin layer curled graphene according to claim 7, wherein the method comprises the following steps: the calcination is heated to 300 ℃ at 5 ℃/min before being heated to 700-900 ℃ in inert atmosphere, and is kept for 30min.
9. The method for preparing the pore-rich thin layer curled graphene according to claim 7, wherein the method comprises the following steps: the inert atmosphere is nitrogen or argon.
10. The method for preparing the pore-rich thin layer graphene-like material according to claim 1, wherein the method comprises the following steps: the volume ratio of the distillate aromatic extract oil to the organic solvent is 4:1-6:1, and the mass ratio of the distillate aromatic extract oil to the template agent is 1:3-1:5.
11. The method for preparing the pore-rich thin layer graphene-like material according to claim 1, wherein the method comprises the following steps: the template agent is metal oxide, and the metal oxide is magnesium oxide, ferric oxide or zinc oxide; the organic solvent is selected from at least one of toluene and carbon tetrachloride.
12. The method for preparing the pore-rich thin layer graphene-like material according to claim 1, wherein the method comprises the following steps: the porous thin layer graphene-like material is of a three-dimensional coiled structure and has specific surface area>550m 2 Per g, total pore volume>2cm 3 /g, average pore diameter>15nm。
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