A method for preparing a porous thin layer of graphene-like

Abstract

The present invention relates to a method for preparing a porous thin-layer graphene-like material, comprising the following steps: (1) pretreatment of raw oil: using a coking liquid product obtained by delayed coking of catalytic oil slurry or residual oil as the pretreated raw oil, the raw oil is subjected to distillation cutting and solvent extraction to obtain a distillate oil aromatics extraction oil; (2) reactant treatment: the distillate oil aromatics extraction oil is mixed with an organic solvent, a template agent is added for dispersion, the organic solvent is evaporated from the obtained solid-liquid mixture, and a template agent powder with a surface coated with the distillate oil aromatics extraction oil is obtained; (3) preparation of a porous thin-layer graphene-like material: the template agent powder is calcined, and the calcined product is subjected to acid washing to remove the template agent to obtain a porous thin-layer graphene-like material. The graphene material prepared by the method has a high degree of homogeneity in morphology, a relatively thin number of layers, and a shell-type curled shape, which is of great significance for the high added value utilization of inferior heavy oil rich in polycyclic aromatic hydrocarbons such as catalytic oil slurry.

Description

Technical Field

[0001] The invention belongs to the cross field of petrochemical industry and carbon nanomaterial science, and in particular relates to a method for preparing porous thin-layer graphene-like materials based on different fractions of catalytic oil slurry or residual oil after delayed coking treatment. Background Art

[0002] Graphene is a new type of two-dimensional nanomaterial. Due to its excellent performance, it has attracted widespread attention from academia and industry. Graphene materials are usually prepared in the form of lamellar powders and thin films. The industry usually uses graphite as a carbon source to prepare powdered graphene, but this method usually requires the preparation of an intermediate state of graphite oxide, followed by ultrasonic exfoliation, and the use of a strong reducing agent to prepare layered graphene; this method requires a large amount of strong oxidizing agents and strong reducing agents, and the process steps are complicated. The industry also uses monomers such as methane to prepare high-purity thin-film graphene through vapor deposition. Although the latter has a higher purity, it has a high cost and low yield due to the high cost of the carbon source and high energy consumption of the process equipment. Therefore, it is necessary to develop a process method with a wide range of carbon sources, simple and easy-to-operate processes, and the ability to reduce the amount of strong oxidizing agents and strong reducing agents.

[0003] To address the above problems, researchers have used various methods to prepare graphene materials with different morphologies.

[0004] Chinese application CN106185890A discloses a method for preparing porous graphene, which uses coal tar as raw material and ammonium inorganic salt as pore-forming agent, and carbonizes the porous graphene material within a certain temperature range under an inert atmosphere.

[0005] Chinese application CN105236394A discloses a method for preparing interconnected graphene nanosheets, using coal tar dissolved in N,N-dimethylformamide as a raw carbon material, nano-magnesium oxide as a template, and KOH as a pore-forming agent to finally synthesize graphene nanosheets.

[0006] Chinese patent CN105502363B discloses a method for producing wrinkled graphene nanosheets, which uses petroleum asphalt as a carbon source, nano-magnesium oxide as a template, and potassium hydroxide as an activator. The carbonization and activation are carried out under inert atmosphere conditions in a tubular furnace to directly obtain porous graphene materials for supercapacitors.

[0007] Chinese patent CN105502363B discloses a method for preparing honeycomb porous carbon, using coal tar as a carbon source, melamine as a soft template, and potassium hydroxide as an activator, heating and carbonizing and activating under inert atmosphere conditions in a tubular furnace to prepare a graphene-like material with a honeycomb structure.

[0008] At present, in addition to the conventional use of graphite or graphite oxide, the preparation method of graphene-like powders mostly uses carbon sources with high carbon content such as petroleum asphalt or coal asphalt in the development of carbon sources. Since these oil-based carbon sources are rich in aromatic structural units, they are easy to form carbon materials with graphite-like structures during the carbonization process. However, since these carbon sources contain a certain amount of asphaltene and colloid, and the ash and metal content are also high, the prepared carbon materials are mostly presented in the material morphology of porous carbon, and it is difficult to form a thin layer of graphene-like materials; the illustrations presented in the relevant patents are difficult to see the overall carbon material morphology. If a thin layer of graphene material is to be prepared, this type of raw material needs to be pretreated, resulting in a complex process and high cost, which is not conducive to commercial application. Summary of the invention

[0009] Based on the above, the purpose of the present invention is to provide a method for preparing a porous thin layer graphene-like material, using the distillate oil aromatic extracted oil collected from the coking liquid as a carbon source and a method for preparing a porous thin layer curly graphene-like material based on a metal oxide hard template as a skeleton. The preparation method is simple, the raw material source is wide, the application prospect is good and it is easy to industrialize.

[0010] To this end, the present invention provides a method for preparing a porous thin layer of graphene-like material, characterized in that it comprises the following steps:

[0011] (1) Raw oil pretreatment: The coking liquid product obtained by delayed coking of catalytic oil slurry or residual oil is used as the pretreated raw oil. The raw oil is subjected to distillation cutting and solvent extraction to obtain distillate oil and aromatics extracted oil;

[0012] (2) reactant treatment: mixing the distillate oil aromatic extract with an organic solvent, adding a template agent to disperse the mixture, and removing the organic solvent from the obtained solid-liquid mixture by rotary evaporation to obtain a template agent powder with the distillate oil aromatic extract oil coated on the surface;

[0013] (3) Preparation of porous thin-layer graphene-like materials: The template powder is calcined, and the template is removed from the calcined product by acid washing to obtain a porous thin-layer graphene-like material.

[0014] The method for preparing the porous thin-layer curled graphene of the present invention preferably comprises the following steps: in step (1), the crude oil is first distilled and cut and then subjected to solvent extraction, or the crude oil is first subjected to solvent extraction and then distilled and cut.

[0015] The method for preparing porous thin-layer curled graphene described in the present invention is preferably as follows: when the crude oil is first distilled and cut and then solvent extracted, the volume ratio of the distillate oil obtained by distillation and cutting of the crude oil to the extractant during the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90°C; when the crude oil is first solvent extracted and then distilled and cut, the volume ratio of the crude oil to the extractant during the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90°C.

[0016] The method for preparing the porous thin-layer curled graphene of the present invention is preferably characterized in that: the distillation cutting is to cut a fraction with a temperature of >350°C or >500°C.

[0017] The method for preparing the porous thin-layer curled graphene of the present invention is preferably that the composition of the distillate oil aromatic extracted oil is a distillation range>350°C, an aromatic content>80%, or a distillation range>500°C, an aromatic content>80%.

[0018] The method for preparing the porous thin-layer curled graphene of the present invention is preferably: the solvent extraction uses a polar organic solvent or a non-polar organic solvent, further preferably uses a polar organic solvent, and further preferably uses a furfural solvent.

[0019] The method for preparing the porous thin-layer curled graphene of the present invention is preferably as follows: the calcination adopts programmed temperature increase, heating to 700-900°C at 5-10°C / min in an inert atmosphere, maintaining for 1-2h, and then cooling to room temperature.

[0020] The method for preparing the porous thin layer curled graphene of the present invention is preferably as follows: before the calcination is heated to 700-900°C in an inert atmosphere, the temperature is first raised to 300°C at 5°C / min and maintained for 30 minutes.

[0021] The method for preparing the porous thin layer curled graphene of the present invention is preferably characterized in that: the inert atmosphere is nitrogen or argon.

[0022] The method for preparing the porous thin-layer curled graphene of the present invention is preferably as follows: the volume ratio of the distillate oil aromatic extracted oil to the organic solvent is 4:1-6:1, and the mass ratio of the distillate oil aromatic extracted oil to the template is 1:3-1:5.

[0023] The method for preparing the porous thin-layer curled graphene of the present invention is preferably as follows: the template is a metal oxide, and the metal oxide is magnesium oxide, iron oxide or zinc oxide; and the organic solvent is selected from at least one of toluene and carbon tetrachloride.

[0024] The method for preparing the porous thin layer curled graphene of the present invention is preferably: the porous thin layer graphene-like material is a three-dimensional curled structure with a specific surface area of ​​>550m 2 / g, total pore volume>2cm 3 / g, average pore size>15nm.

[0025] Specifically, the method for preparing the porous thin layer curled graphene of the present invention comprises the following steps:

[0026] (1) The coking liquid product obtained by treating catalytic oil slurry or residual oil through a delayed coking process is used as the pre-treated oil raw material, and the fractions are cut by distillation. The cut fractions are extracted and enriched with aromatics by an extractant to obtain a fraction oil aromatic-enriched oil (i.e., a fraction oil aromatic-extracted oil), which is solid and viscous at room temperature.

[0027] (2) The obtained distillate oil aromatic extracted oil is mixed with an organic solvent, a template is added for dispersion, and the organic solvent is removed by rotary evaporation of the solid-liquid mixture to obtain a template powder with the distillate oil aromatic extracted oil coated on the surface.

[0028] (3) The powder is calcined, and the template agent is removed from the calcined product by acid washing to obtain a porous thin layer curled graphene material.

[0029] In step (1) of the present invention, the distillation cutting and solvent extraction process steps can be adjusted in order, first the coking liquid is subjected to extraction with an extractant to obtain aromatics-enriched oil, and then distilled and cut to obtain distillate oil aromatics-enriched oil. Since the coking liquid contains less than 1% asphaltene, the solvent extraction process for extracting aromatics can obviously obtain liquid level stratification of saturated and aromatic parts, so the extraction process first does not affect the composition of the final product. Patent CN111500316A mentions that the furfural extraction tower is used in industry to extract and cut the distillate in one step to obtain heavy aromatic components. The pretreatment process method of this patent can also be applied to the industrial device mentioned in the above patent for treatment.

[0030] In step (2) of the present invention, the obtained distillate aromatic extracted oil is solid and viscous at room temperature, and needs to be mixed with an organic solvent, and then a template is added for dispersion. The liquid phase is mixed with the solid template to ensure that the aromatics are evenly coated on the surface of the template, and a graphene-like carbon material with uniform morphology can be formed in the calcination stage.

[0031] In step (3) of the present invention, the temperature is raised to 700-900°C at 5-10°C / min in an inert atmosphere, maintained for 1-2 hours, and then cooled to room temperature to take out the product. Considering that the aromatic component will liquefy and flow at high temperature, it is preferred to first raise the temperature to 300°C at 5°C / min and maintain for 30 minutes before raising the temperature to 700-900°C in an inert atmosphere to ensure that the aromatic can be evenly covered on the template.

[0032] The present invention uses coking liquid rich in aromatics and asphaltene <1% as raw oil, separates the aromatic oil >350℃ or >500℃ as the carbon source, uses organic solvent as a dispersing aid, and uses metal oxide as the attachment skeleton and pore-forming agent for the high-temperature carbonization growth of aromatics, and obtains a porous thin layer curly graphene-like material through high-temperature carbonization. The prepared graphene-like material has a specific surface area of ​​592-730m2 without any secondary pore-forming treatment. 2 / g, the average pore size is between 15 and 22 nm, and the total pore volume is between 2.24 and 3.76 cm 3 / g, and the morphology presents a curled porous thin layer structure.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] First, the sources of coking liquid are wide, and different fractions can be cut and selected according to the needs of refineries, which broadens the carbon source pathway for preparing graphene-like carbon materials. In addition, since the raw materials contain almost no asphaltene and have a very low colloid content, the graphene material formed by carbonization has a thinner layer, a clear interface, and a high degree of graphitization.

[0035] Second, the preparation process is simple. It uses the principle of template forming to prepare porous graphene-like powder materials with fewer layers through carbonization heating;

[0036] 3. The metal oxide particle template used is a hard template and can be removed directly with dilute acid.

[0037] 4. The graphene material prepared by this method has a high specific surface area, uniform pore size distribution, and very thin layers, and has a wide range of applications in catalysis, adsorption, supercapacitors and other fields.

[0038] In summary, the present invention uses the aromatic components of the coking liquid fraction as raw materials, nano-metal oxides as templates, and self-assembles oil molecules into carbon at high temperature to prepare a thin-layer graphene-like material with a porous structure. The raw material components of the method are uniform, low-priced and widely available, the raw material pretreatment process is simple, the prepared graphite-like material has a thinner layer, and has a good market prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH350-CT-M4-9 of Example 1;

[0040] Figure 2 This is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH500-CT-M4-9 of Example 2;

[0041] Figure 3This is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH500-CT-M3-7 of Example 3;

[0042] Figure 4 This is a scanning electron microscope image of the porous thin layer curled graphene-like LHJH350-CT-M5-7 of Example 4

[0043] Figure 5 The scanning electron microscope image of the porous thin layer curled graphene-like LHJH CT-350-M4-9 of Example 5 is

[0044] Figure 6 This is a scanning electron microscope image of the magnesium oxide particles used in the present invention. DETAILED DESCRIPTION

[0045] The following is a detailed description of the embodiments of the present invention: This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and process are given, but the protection scope of the present invention is not limited to the following embodiments. The experimental methods in the following embodiments without specifying specific conditions are usually carried out under conventional conditions.

[0046] The coking fraction oil is derived from the coking liquid product of Liaohe catalytic cracking slurry after delayed coking treatment. The above oil products are used as carbon sources in Examples 1-5.

[0047] The metal oxide templates are magnesium oxide and iron oxide nanoparticles, which are particles with a single particle size of 50nm-100nm and an aggregated state of 2-3μm, and are used as templates in Examples 1-5.

[0048] Example 1

[0049] The first step: crude oil pretreatment.

[0050] Weigh 500kg of coking liquid product and cut it into normal pressure fractions through a real boiling point distiller, and take the >350℃ fraction (recorded as LHJH350). Mix the cut distillate oil with furfural in a volume ratio of 1:2, and stir and mix at a water bath temperature of 60℃; transfer the mixed solution to a separatory funnel, let it stand in a 60℃ oven for 2h, and separate the lower layer of extracted oil. Transfer the lower layer of extracted oil to a rotary evaporator, slowly raise the temperature to 140℃ under a negative pressure of -0.15MPa to evaporate the furfural solvent, and obtain the distillate oil aromatic extracted oil (recorded as LHJH350-CT, where CT means extraction). The aromatic extracted oil is viscous and colloid at room temperature, and becomes a Newtonian fluid when the temperature is greater than 80℃.

[0051] Step 2: Reactant processing.

[0052] The distillate oil aromatics extracted oil obtained in step 1 is mixed with toluene solvent in a volume ratio of 4:1, so that the distillate oil aromatics extracted oil that is viscous at room temperature is fully dissolved in the toluene solvent; the distillate oil aromatics extracted oil and magnesium oxide nanoparticles are dispersed in a mass ratio of 1:4 while stirring and adding iron oxide particles, stirring for 1 hour, ultrasonicating for 30 minutes, and then stirring for 30 minutes; the obtained solid-liquid mixture is transferred to a rotary evaporator, the temperature is slowly raised to 80°C under a negative pressure of 0.15 MPa to evaporate the toluene solvent, and the powdery product is scraped out and transferred to a porcelain boat.

[0053] Step 3: Preparation of porous thin layer graphene-like materials.

[0054] The porcelain boat containing the powder in step 2 was placed in a tube furnace, heated to 300°C at 5°C / min in a nitrogen atmosphere, maintained for 30 minutes, then heated to 900°C at 5°C / min, maintained for 1 hour, and then cooled to room temperature to take out the product; the product was ground into fine powder and then removed from the template with 2 mol / L dilute hydrochloric acid, washed with deionized water until neutral, and dried to obtain a graphene-like material, which was labeled LHJH350-CT-M4-9.

[0055] Example 2

[0056] The first step: crude oil pretreatment.

[0057] Weigh 500kg of coking liquid product and cut it into normal pressure fractions through a real boiling point distiller, and take the >500℃ fraction (recorded as LHJH500). Mix the cut distillate oil with furfural in a volume ratio of 1:2, and stir and mix at a water bath temperature of 60℃; transfer the mixed solution to a separatory funnel, let it stand in an 80℃ oven for 2h, and separate the lower layer of extracted oil. Transfer the lower layer of extracted oil to a rotary evaporator, slowly raise the temperature to 140℃ under a negative pressure of -0.15MPa to evaporate the furfural solvent, and obtain the distillate oil aromatic extracted oil (recorded as LHJH500-CT). The aromatic extracted oil is viscous and colloid at room temperature, and becomes a Newtonian fluid when the temperature is greater than 80℃.

[0058] Step 2: Reactant processing.

[0059] The distillate oil aromatics extracted oil obtained in step 1 is mixed with toluene solvent in a volume ratio of 6:1, so that the distillate oil aromatics extracted oil that is viscous at room temperature is fully dissolved in the toluene solvent; the distillate oil aromatics extracted oil and magnesium oxide nanoparticles are dispersed in a mass ratio of 1:4 while stirring and adding iron oxide particles, stirring for 1 hour, ultrasonicating for 30 minutes, and then stirring for 30 minutes; the obtained solid-liquid mixture is transferred to a rotary evaporator, the temperature is slowly raised to 80°C under a negative pressure of 0.15 MPa to evaporate the toluene solvent, and the powdery product is scraped out and transferred to a porcelain boat.

[0060] Step 3: Preparation of porous thin layer graphene-like materials.

[0061] The porcelain boat containing the powder obtained in step 2 was placed in a tube furnace, heated to 300°C at 5°C / min in a nitrogen atmosphere, maintained for 30 minutes, then heated to 900°C at 5°C / min, maintained for 1 hour, and then cooled to room temperature to take out the product; the product was ground into fine powder, removed from the template with 2 mol / L dilute hydrochloric acid, washed with deionized water until neutral, and dried to obtain a graphene-like material, which was labeled LHJH500-CT-M4-9.

[0062] Example 3

[0063] The first step: crude oil pretreatment.

[0064] Weigh 500kg of coking liquid product and cut it into normal pressure fractions through a real boiling point distiller, and take the >500℃ fraction (recorded as LHJH500). Mix the cut distillate oil with furfural in a volume ratio of 1:2, and stir and mix at a water bath temperature of 60℃; transfer the mixed solution to a separatory funnel, let it stand in an 80℃ oven for 2h, and separate the lower layer of extracted oil. Transfer the lower layer of extracted oil to a rotary evaporator, slowly raise the temperature to 140℃ under a negative pressure of -0.15MPa to evaporate the furfural solvent, and obtain the distillate oil aromatic extracted oil. The aromatic extracted oil is viscous and colloid at room temperature, and becomes a Newtonian fluid when the temperature is greater than 80℃.

[0065] Step 2: Reactant processing.

[0066] The distillate oil aromatics extracted oil obtained in step 1 is mixed with toluene solvent in a volume ratio of 6:1, so that the distillate oil aromatics extracted oil that is viscous at room temperature is fully dissolved in the toluene solvent; the distillate oil aromatics extracted oil and iron oxide nanoparticles are dispersed while stirring according to a mass ratio of 1:3, and the iron oxide particles are added, stirred for 1 hour, ultrasonicated for 30 minutes, and then stirred for 30 minutes; the solid-liquid mixture is transferred to a rotary evaporator, the temperature is slowly raised to 80°C under a negative pressure of 0.15 MPa to evaporate the toluene solvent, and the powdery product is scraped out and transferred to a porcelain boat.

[0067] Step 3: Preparation of porous thin layer graphene-like materials.

[0068] The porcelain boat containing the powder obtained in step 2 was placed in a tube furnace, heated to 300°C at 5°C / min in a nitrogen atmosphere, maintained for 30 minutes, then heated to 700°C at 5°C / min, maintained for 1 hour, and then cooled to room temperature to take out the product; the product was ground into fine powder, removed from the template with 2 mol / L dilute hydrochloric acid, washed with deionized water until neutral, and dried to obtain a graphene-like material, which was labeled LHJH500-CT-M3-7.

[0069] Example 4

[0070] The first step: raw material pretreatment.

[0071] Weigh 500kg of coking liquid product and cut it into atmospheric fractions through a real boiling point distiller, and take the >350℃ fraction (recorded as LHJH350). Mix the cut distillate oil with furfural in a volume ratio of 1:2, and stir and mix at a water bath temperature of 60℃; transfer the mixed solution to a separatory funnel, let it stand in a 60℃ oven for 2h, and separate the lower layer of extracted oil. Transfer the lower layer of extracted oil to a rotary evaporator, slowly raise the temperature to 140℃ under a negative pressure of -0.15MPa to evaporate the furfural solvent, and obtain the distillate oil aromatic extracted oil (recorded as LHJH350-CT). The aromatic extracted oil is viscous and colloid at room temperature, and becomes a Newtonian fluid when the temperature is greater than 80℃.

[0072] Step 2: Reactant processing.

[0073] The distillate oil aromatics extracted oil obtained in step 1 is mixed with toluene solvent in a volume ratio of 4:1, so that the distillate oil aromatics extracted oil that is viscous at room temperature is fully dissolved in the toluene solvent; the distillate oil aromatics extracted oil and magnesium oxide nanoparticles are dispersed in a mass ratio of 1:3 while stirring and adding iron oxide particles, stirring for 1 hour, ultrasonicating for 30 minutes, and then stirring for 30 minutes; the solid-liquid mixture is transferred to a rotary evaporator, the temperature is slowly raised to 80°C under a negative pressure of -0.15 MPa to evaporate the toluene solvent, and the powdery product is scraped out and transferred to a porcelain boat.

[0074] Step 3: Preparation of porous thin layer graphene-like materials.

[0075] The porcelain boat containing the powder obtained in step 2 was placed in a tube furnace, heated to 900°C at 10°C / min in a nitrogen atmosphere, maintained for 2 hours, and then cooled to room temperature to take out the product; the product was ground into fine powder and then removed from the template with 2 mol / L dilute hydrochloric acid, washed with deionized water until neutral, and dried to obtain a graphene-like material, which was labeled LHJH350-CT-M3-9.

[0076] Example 5

[0077] The first step: crude oil pretreatment.

[0078] Weigh 500kg of coking liquid product and mix it with furfural in a volume ratio of 1:3, stir and mix at a water bath temperature of 60°C; transfer the resulting mixed solution to a separatory funnel, let it stand in a 60°C oven for 2 hours, and separate the lower layer of extracted oil. Transfer the lower layer of extracted oil to a rotary evaporator, slowly raise the temperature to 140°C under a negative pressure of -0.15MPa to evaporate the furfural solvent, and obtain the coking liquid aromatics extracted oil. Cut the extracted oil into atmospheric fractions using a real boiling point distiller, and take the >350°C fraction as the fraction oil aromatics extracted oil (recorded as LHJHCT-350).

[0079] Step 2: Reactant processing.

[0080] The distillate oil aromatics extracted oil obtained in step 1 is mixed with toluene solvent in a volume ratio of 4:1, so that the distillate oil aromatics extracted oil that is viscous at room temperature is fully dissolved in the toluene solvent; the distillate oil aromatics extracted oil and magnesium oxide nanoparticles are dispersed in a mass ratio of 1:4 while stirring and adding iron oxide particles, stirring for 1 hour, ultrasonicating for 30 minutes, and then stirring for 30 minutes; the solid-liquid mixture is transferred to a rotary evaporator, the temperature is slowly raised to 80°C under a negative pressure of -0.15 MPa to evaporate the toluene solvent, and the powdery product is scraped out and transferred to a porcelain boat.

[0081] Step 3: Preparation of porous thin layer graphene-like materials.

[0082] The porcelain boat containing the powder obtained in step 2 was placed in a tube furnace, heated to 700°C at 10°C / min in a nitrogen atmosphere, maintained for 2 hours, and then cooled to room temperature to take out the product; the product was ground into fine powder and then removed from the template with 2 mol / L dilute hydrochloric acid, washed with deionized water until neutral, and dried to obtain a graphene-like material, which was labeled LHJH CT-350-M4-7.

[0083] The results of the property analysis of the distillate oil obtained in Examples 1-5 are listed in Table 1. The pore structure results of the porous thin layer curled graphene-like materials obtained in Examples 1-5 are listed in Table 2. The morphology of the porous thin layer curled graphene-like materials obtained in Examples 1-5 was characterized, and the results are shown in Table 2. Figure 1-5 From Table 2 and Figure 1 As can be seen from the figure, the specific surface area of ​​the graphene-like material prepared by the present invention is between 592 and 730 m2 without any secondary pore-forming treatment. 2 / g, the average pore size is between 15 and 22 nm, and the total pore volume is between 2.24 and 3.76 cm 3 / g, and the morphology presents a curled porous thin layer structure.

[0084] Table 1 Analysis of four components of the fractions obtained in Examples 1-5

[0085] Distillate hydrocarbon composition LHJH350 LHJH350-CT LHJH500 LHJH500-CT Saturated 44.5 3.2 28.7 0.2 Aroma 49.3 85.4 61.9 82.1 Gel 5.6 10.4 8.5 16.7 Asphaltene 0.6 1.0 0.9 1.0 Yield - 49％ - 65％

[0086] Table 2 Pore structure results of porous thin-layer graphene-like materials obtained in Examples 1-5

[0087]

[0088]

[0089] Comparative Example 1

[0090] The first step: raw material pretreatment.

[0091] 500 kg of the coking liquid product was weighed and cut into atmospheric pressure fractions using a real boiling point distillation apparatus, and the >350°C fraction (denoted as LHJH350) was taken, and the fraction oil was directly used as a carbon source.

[0092] Step 2: Reactant processing.

[0093] The distillate oil obtained in step 1 and the toluene solvent were mixed and dissolved in a volume ratio of 4:1, and the iron oxide particles were added and dispersed in a mass ratio of 1:4 for distillate oil and magnesium oxide nanoparticles, stirred for 1 hour, ultrasonicated for 30 minutes, and stirred for another 30 minutes; the solid-liquid mixture was transferred to a rotary evaporator, and the temperature was slowly raised to 80°C under a negative pressure of 0.15MPa to evaporate the toluene solvent. The remaining product showed a semi-viscous flow state, and the template agent could not be evenly dispersed in the distillate oil (carbon source), and could not form a solid powder. The viscous product was scraped out and applied to a porcelain boat.

[0094] Step 3: Preparation of porous thin layer graphene-like materials.

[0095] The porcelain boat obtained in step 2 was placed in a tubular furnace, heated to 300°C at 5°C / min in a nitrogen atmosphere, maintained for 30 min, then heated to 900°C at 5°C / min, maintained for 1 h, and then cooled to room temperature to take out the product. Most of the product was cracked and no carbon powder could be collected.

[0096] Comparative Example 2

[0097] The first step: crude oil pretreatment.

[0098] Weigh 500kg of coking liquid product and mix it with furfural in a volume ratio of 1:3, stir and mix at a water bath temperature of 60°C; transfer the mixed solution to a separatory funnel, let it stand in a 60°C oven for 2 hours, and separate the lower layer of extracted oil. Transfer the lower layer of extracted oil to a rotary evaporator, slowly raise the temperature to 140°C under a negative pressure of -0.15MPa to evaporate the furfural solvent, and obtain the coking liquid aromatics extracted oil as a carbon source. The coking liquid aromatics extracted oil is in a fluid state at room temperature.

[0099] Step 2: Reactant processing.

[0100] The coking liquid aromatics extracted oil obtained in step 1 is mixed with toluene solvent in a volume ratio of 4:1; the coking liquid aromatics extracted oil and magnesium oxide nanoparticles in a mass ratio of 1:4 are dispersed while stirring with iron oxide particles, stirred for 1 hour, ultrasonicated for 30 minutes, and then stirred for 30 minutes; the solid-liquid mixture is transferred to a rotary evaporator, the temperature is slowly raised to 80°C under a negative pressure of -0.15 MPa to evaporate the toluene solvent, and the viscous product is scraped out and transferred to a porcelain boat.

[0101] Step 3: Preparation of porous thin layer graphene-like materials.

[0102] The porcelain boat obtained in step 2 is placed in a tubular furnace, and the temperature is raised to 700°C at 10°C / min in a nitrogen atmosphere, maintained for 2 hours, and then cooled to room temperature to take out the product, which appears to be agglomerated carbon blocks. The product is ground into fine powder and then removed from the template with 2M dilute hydrochloric acid and washed with deionized water until neutral. After drying, only finely divided small carbon blocks are obtained, which are not graphene-like carbon powder.

[0103] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a porous thin layer of graphene-like material, characterized in that: The following steps are involved: (1) Raw oil pretreatment: The coking liquid product obtained by delayed coking of catalytic oil slurry or residual oil is used as the pretreated raw oil. The raw oil is subjected to distillation, cutting and solvent extraction to obtain distillate oil and aromatics extracted oil; (2) Reactant treatment: The distillate oil aromatic extract is mixed with an organic solvent, a template is added for dispersion, and the organic solvent is removed by rotary evaporation of the obtained solid-liquid mixture to obtain a template powder with the distillate oil aromatic extract coated on the surface; (3) Preparation of porous thin-layer graphene-like materials: calcining the template powder, and removing the template from the calcined product by acid washing to obtain porous thin-layer graphene-like materials; In step (1), the crude oil is first distilled and cut and then subjected to solvent extraction, or the crude oil is first subjected to solvent extraction and then distilled and cut; When the crude oil is first distilled and cut and then solvent extracted, the volume ratio of the distillate oil obtained by distillation and cutting of the crude oil to the extractant during the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90°C; when the crude oil is first solvent extracted and then distilled and cut, the volume ratio of the crude oil to the extractant during the solvent extraction is 1.5:1-3:1, and the temperature of the solvent extraction is 60-90°C; The composition of the distillate oil aromatic extracted oil is that the distillation range is greater than 500° C. and the aromatic content is greater than 80%.

2. The method for preparing a porous thin layer of graphene-like material according to claim 1, characterized in that: The solvent extraction uses a polar organic solvent or a non-polar organic solvent.

3. The method for preparing a porous thin layer of graphene-like material according to claim 2, characterized in that: The solvent extraction uses a polar organic solvent.

4. The method for preparing a porous thin layer of graphene-like material according to claim 2, characterized in that: The solvent extraction uses furfural solvent.

5. The method for preparing a porous thin layer of graphene-like material according to claim 1, characterized in that: The calcination adopts programmed temperature increase, and the temperature is increased to 700-900° C. at 5-10° C. / min in an inert atmosphere, maintained for 1-2 hours, and then cooled to room temperature.

6. The method for preparing a porous thin layer of graphene-like material according to claim 5, characterized in that: The calcination is carried out in an inert atmosphere before the temperature is raised to 700-900° C., and then the temperature is raised to 300° C. at a rate of 5° C. / min and maintained for 30 minutes.

7. The method for preparing a porous thin layer of graphene-like material according to claim 5, characterized in that: The inert atmosphere is nitrogen or argon.

8. The method for preparing a porous thin layer of graphene-like material according to claim 1, characterized in that: The volume ratio of the distillate oil aromatic extracted oil to the organic solvent is 4:1-6:1, and the mass ratio of the distillate oil aromatic extracted oil to the template is 1:3-1:

5.

9. The method for preparing a porous thin layer of graphene-like material according to claim 1, characterized in that: The template agent is a metal oxide, and the metal oxide is magnesium oxide, iron oxide or zinc oxide; the organic solvent is selected from at least one of toluene and carbon tetrachloride.

10. The method for preparing a porous thin layer of graphene-like material according to claim 1, characterized in that: The porous thin-layer graphene-like material is a three-dimensional curled structure with a specific surface area of ​​>550 m 2 / g, total pore volume>2cm 3 / g, average pore size>15nm.

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