Method for preparing carbon material precursor through vacuum residue dehydrogenation

Abstract

The invention discloses a method for preparing a carbon material precursor through vacuum residue dehydrogenation. The method comprises the following steps: by taking petroleum residual oil as raw material oil, firstly adding oxide nanoparticles into the raw material oil, treating under an electric field and / or a magnetic field, and then extracting the petroleum residual oil by utilizing an extracting agent, so as to obtain deoiled asphalt, namely a carbon material precursor; the extraction agent comprises an organic hydrocarbon solvent and a carrying agent; the carrying agent is prepared from one or more of isooctyl phosphate, tri (4-nonylphenyl) phosphite, tri-p-tolyl phosphate, 2, 2, 2-trifluoroethanol and 2-propylaniline, and the carrying agent is prepared from one or more of isooctyl phosphate, tri (4-nonylphenyl) phosphite, tri-p-tolyl phosphate, 2, 2, 2-trifluoroethanol and 2-propylaniline. When the method is used for producing the carbon material precursor, the carbonization rate of the target product deoiled asphalt is high, the deoiled asphalt is a high-quality raw material for preparing the carbon material precursor, and the additional value of the deoiled asphalt product is increased.

Description

Technical Field

[0001] The present invention belongs to the field of carbon material preparation, and particularly relates to a method for preparing a carbon material precursor by dehydrogenating vacuum residue. Background Art

[0002] Carbon materials are non-metallic materials with excellent properties such as corrosion resistance, heat and moisture resistance, and mechanical strength. Their excellent properties have promoted the rapid development of carbon materials, and they are showing a broad application prospect in many fields such as aerospace, energy, and environmental protection. However, the manufacturing process of carbon materials is complex and the equipment operation is difficult, resulting in a long cycle, high cost, and poor performance stability of the products, which greatly limits the further development of carbon materials. Therefore, the research on low-cost and high-performance carbon materials has attracted the widespread attention of countries around the world. Therefore, developing a carbon material precursor with excellent comprehensive performance is the key to developing low-cost and high-performance carbon materials.

[0003] Most high-performance carbon material precursors are coal tar pitch. As a cheap carbonaceous precursor, coal has the advantages of high carbon content, good fluidity, and high porosity, and can be used to prepare a variety of advanced carbon-based materials. However, the residual carbon rate of coal tar pitch is relatively low, and a large amount of volatile components are generated during carbonization, resulting in a large number of pores in the carbon material, which will inevitably have a great impact on the performance of the carbon material, causing the density of the carbon material to decrease, the mechanical strength to decrease, the resistivity to increase, the conductivity to become poor, and the oxidation resistance to become low.

[0004] CN101624730A discloses a production process method of coal tar pitch-based carbon fiber. The method uses coal tar pitch as a raw material, and prepares a carbon material precursor by catalytic hydrogenation treatment of coal tar pitch and then polycondensation. However, the production process of the carbon material precursor of this method is complex, the production cost is high, and the impurities in the product are not easy to separate, resulting in a high ash content and a low residual carbon rate in the target product, and a low carbon content in the carbon material precursor. Summary of the Invention

[0005] Aiming at the problems existing in the prior art, the present invention provides a method for preparing a carbon material precursor by dehydrogenating vacuum residue. When this method is used to produce a carbon material precursor, the carbonization rate of the target product, deoiled asphalt, is relatively high, which is a high-quality raw material for preparing a carbon material precursor and increases the added value of the deoiled asphalt product.

[0006] The present invention provides a method for preparing a carbon material precursor by dehydrogenating vacuum residue. The method includes:

[0007] Using petroleum resid as the raw material oil, first add oxide nanoparticles to the raw material oil and treat it under an electric field and / or a magnetic field, and then extract the petroleum resid with an extractant. The deoiled asphalt obtained is the carbon material precursor; the extractant includes an organic hydrocarbon solvent and a carrier; preferably, the petroleum resid contains a carrier; the carrier in the extractant and the carrier in the raw material oil are each independently selected from one or more of isooctyl phosphate, tris(4-nonylphenyl) phosphite, triphenyl phosphate, 2,2,2-trifluoroethanol, 2-propylaniline, and preferably triphenyl phosphate.

[0008] According to the present invention, the addition amount of the carrier in the extractant accounts for 0.5 wt% to 2 wt% of the mass of the petroleum resid. As a non-limiting example, the proportion of the addition amount of the carrier in the extractant to the mass of the petroleum resid can be any point value in the following ranges: 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, etc.

[0009] According to the present invention, the addition amount of the carrier in the raw material oil accounts for 0.5 wt% to 3 wt% of the mass of the petroleum resid. As a non-limiting example, the proportion of the addition amount of the carrier in the extractant to the mass of the petroleum resid can be any point value in the following ranges: 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, etc.

[0010] According to the present invention, the oxide nanoparticles include at least one of iron oxide and zinc oxide. The particle size of the oxide nanoparticles is 100 to 400 nm. Preferably, the particle size of the nano iron oxide particles is 150 nm to 300 nm; the particle size of the nano zinc oxide particles is 200 nm to 400 nm. Further, the mass ratio of the addition amount of the oxide nanoparticles to the raw material oil is 0.2 to 0.7:1000.

[0011] According to the present invention, the treatment time of the raw material oil added with oxide nanoparticles under an electric field and / or a magnetic field is 5 to 15 min. The electric field used is a direct current electric field, and the electric field strength is 2000 V / cm to 10000 kV / cm; the magnetic field used is a constant magnetic field, and the magnetic field strength is 0.1 T to 2 T.

[0012] According to the present invention, the petroleum resid is the residue obtained by atmospheric or vacuum distillation of crude oil. The properties of the petroleum resid are as follows: the asphaltene content is 4.2 wt% to 10 wt%; the 10% distillation point ≥ 500 °C, preferably 500 to 530 °C, the softening point is 25 to 45 °C, and the carbon residue value is 10 wt% to 20 wt%. Preferably, the petroleum resid is preferably vacuum resid.

[0013] According to the present invention, the organic hydrocarbon solvent is an organic hydrocarbon having 3 to 5 carbon atoms. The organic hydrocarbon is an alkane and / or an alcohol. Preferably, the organic hydrocarbon solvent includes at least one of propane, butane, pentane, and isopropyl alcohol. The mass ratio of the added amount of the organic hydrocarbon solvent to the petroleum resid (agent-oil ratio) is 3 to 8:1.

[0014] According to the present invention, preferably, the extraction process is carried out in an extraction column. The operating pressure of the extraction is 3.8 to 8.0 MPa; the temperature of the extraction is 50 to 190 °C. A constant pressure and temperature reduction operation mode is adopted in the extraction column. The temperature ranges at various parts of the extraction column are as follows: 70 to 190 °C at the top of the column, 60 to 180 °C in the middle of the column, and 50 to 170 °C at the bottom of the column. Preferably, it is 140 to 190 °C at the top of the column, 130 to 180 °C in the middle of the column, and 120 to 170 °C at the bottom of the column. Preferably, the temperature at various parts of the extraction column: the temperature at the top of the column is at least 10 to 20 °C higher than that in the middle of the column; the temperature in the middle of the column is at least 10 to 20 °C higher than that at the bottom of the column.

[0015] According to the present invention, preferably, the feedstock oil can be preheated before entering the extraction column, and the feedstock oil is preheated to 120 to 180 °C.

[0016] According to the present invention, the operation process of the extraction is as follows: the extractant enters the column from the bottom and flows upward, and the treated petroleum resid enters the column from the middle of the column and flows downward. The petroleum resid and the extractant are in countercurrent contact in the column. The residue raffinate is discharged from the bottom of the column, and the extract is discharged from the upper part of the column; the raffinate is the target product.

[0017] According to the present invention, preferably, the yield of the raffinate is controlled to be 15 wt% to 30 wt%.

[0018] Compared with the prior art, the main advantages of the present invention are as follows:

[0019] The present invention provides a method for preparing deoiled asphalt suitable as a carbon material precursor by solvent deasphalting. Through pretreatment of the test raw materials in the early stage and the combined action of an extractant containing a specific content of a carrier, the aggregation of asphaltenes is promoted in advance, the asphaltene content in the deoiled asphalt is increased, and the residual carbon value of the deoiled asphalt is increased;

[0020] Preferably, by adding a small amount of carrier to both the feedstock oil and the extractant, the yield of deasphalted oil is increased, and the light components entering the deoiled asphalt are reduced. Among them, the carrier will leave the device together with the deoiled asphalt, does not need to be recovered, does not increase the process flow, and with the dual action of raw material pretreatment and the addition of a small amount of carrier, the carbonization rate of the deoiled asphalt is increased, which is a high-quality raw material for preparing carbon material precursors, and the added value of the deoiled asphalt product is increased.

[0021] The present invention uses petroleum residue extract to produce a carbon material precursor, which improves the added value of the extraction residue. Moreover, the extraction residue produced by the present invention has the advantages of low volatile component content and high residual carbon rate. Detailed implementation mode

[0022] The present invention will be further described in detail below in conjunction with embodiments, but the present invention is not limited to these embodiments.

[0023] In the present invention, the petroleum residue used in each example is vacuum residue, and its properties are as follows: the 10% distillation point is 520 °C, the softening point is 36 °C, the asphaltene content is 4.5 wt%, and the residual carbon value is 18.4 wt%.

[0024] In the present invention, the residual carbon value is tested by the petroleum product residual carbon determination method of GB / T17144-1997.

[0025] In the present invention, % is the mass percentage unless otherwise specified.

[0026] Example 1

[0027] Using a batch solvent deasphalting device, take 1.0 kg of vacuum residue, and add 0.5 g of nano-ferric oxide (particle size 200 nm) at 165 °C. After mixing evenly, the feed oil enters the solvent deasphalting device (extraction tower) through an electric field with a strength of 6000 V / cm within 10 minutes. Pentane is used as the solvent, and the solvent-to-oil ratio is 5:1. No carrier is added to the feed oil. 2-propylaniline is added as a carrier to the extractant, and the addition amount of the carrier accounts for 0.5 wt% of the petroleum residue. The extraction conditions are as follows: the extraction pressure is 4 MPa; the top temperature of the tower is 185 °C, the middle temperature of the tower is 175 °C, the bottom temperature of the tower is 160 °C, and fractional distillation is carried out under the operating conditions of constant pressure and temperature reduction, and a total of 80 wt% of the extraction liquid is withdrawn. The residual carbon value of the 20 wt% raffinate residue at the bottom of the tower is measured, and the residual carbon value is 48 wt%.

[0028] Example 2

[0029] Using a batch solvent deasphalting device, take 1.0 kg of vacuum residue, slowly and evenly add the carrier tris(4-nonylphenyl) phosphite at 165 °C, and the addition amount accounts for 1.5 wt% of the petroleum residue, and then add 0.5 g of nano-ferric oxide (particle size 200 nm). After mixing evenly, the feed oil enters the solvent deasphalting device (extraction tower) through an electric field with a strength of 6000 V / cm within 10 minutes. Pentane is used as the solvent, and the solvent-to-oil ratio is 5:1. In addition, 2,2,2-trifluoroethanol accounting for 0.5 wt% of the petroleum residue is also added to the extractant. The extraction conditions are as follows: the extraction pressure is 4 MPa; the top temperature of the tower is 185 °C, the middle temperature of the tower is 175 °C, the bottom temperature of the tower is 160 °C, and fractional distillation is carried out under the operating conditions of constant pressure and temperature reduction, and a total of 80 wt% of the extraction liquid is withdrawn. The residual carbon value of the 20 wt% raffinate residue at the bottom of the tower is measured, and the residual carbon value is 57 wt%.

[0030] Example 3

[0031] Using a batch solvent deasphalting unit, 1.0 kg of vacuum residue was slowly and evenly added with a carrier agent, tris(4-nonylphenyl)phosphite, at 165°C (0.5 wt% of the residue). 0.5 g of nano-iron oxide (200 nm particle size) was then added. After thorough mixing, the crude oil was subjected to an electric field at 6000 V / cm over 10 minutes before entering the solvent deasphalting unit (extraction tower). Pentane was used as the solvent, with a solvent-to-oil ratio of 5:1. In addition, 2,2,2-trifluoroethanol (1 wt% of the residue) was added to the extractant. Extraction conditions were: extraction pressure of 4 MPa; tower top temperature of 185°C, tower mid-temperature of 175°C, and tower bottom temperature of 160°C. Fractional distillation was performed under constant pressure and cooling conditions, yielding a total of 80 wt% of the extract. The carbon content of the 20 wt% raffinate at the bottom of the tower was measured and found to be 69 wt%.

[0032] Example 4

[0033] Using a batch solvent deasphalting unit, 1.0 kg of vacuum residue was slowly and evenly added with a carrier agent, tri-p-tolyl phosphate, at 165°C (0.5 wt% of the residue). 0.2 g of nano-zinc oxide (400 nm particle size) was then added. After thorough mixing, the crude oil passed through a 0.5 T constant magnetic field over 15 minutes and entered the solvent deasphalting unit (extraction column). Pentane was used as the solvent, and the solvent-to-oil ratio was 5:1. 2,2,2-trifluoroethanol (3 wt% of the residue) was also added to the extractant. Extraction conditions were: extraction pressure of 4 MPa; tower top temperature of 185°C, tower mid-temperature of 175°C, and tower bottom temperature of 160°C. Fractional distillation was performed under constant pressure and cooling conditions, yielding a total of 80 wt% of the extract. The carbon content of the 20 wt% raffinate at the bottom of the tower was measured and found to be 78 wt%.

[0034] Comparative Example 1

[0035] Using a batch solvent deasphalting unit, 1.0 kg of vacuum residue was extracted. The crude oil was subjected to an electric field of 6000 V / cm over a 10-minute period before entering the solvent deasphalting unit (extraction tower). Pentane was used as the solvent, and the solvent-to-oil ratio was 5:1. No carrier was added. Extraction conditions were: extraction pressure of 4 MPa; tower top temperature of 185°C, tower mid-temperature of 175°C, and tower bottom temperature of 160°C. Fractional distillation was performed under constant pressure and cooling conditions, yielding a total of 80 wt% of extract. The carbon content of the 20 wt% raffinate at the bottom of the tower was measured and found to be 35 wt%.

[0036] Comparative Example 2

[0037] Same as Example 1, except that the feedstock oil does not pass through the electric field, but the feedstock oil preheated with silica is directly fed into the solvent deasphalting unit. Other conditions are the same as in Example 1. Fractionation is carried out under constant pressure and temperature reduction operation conditions, and a total of 80 wt% of the extract is withdrawn. The carbon residue value of the 20 wt% raffinate residue at the bottom of the column is measured, and the carbon residue value is 40 wt%.

[0038] Comparative Example 3

[0039] An intermittent solvent deasphalting unit is used. 1.0 kg of vacuum residue is taken, and 0.5 g of nano-silica (particle size 200 nm) is added at 165 °C. After mixing evenly, the feedstock oil enters the solvent deasphalting unit (extraction column) through an electric field with a strength of 6000 V / cm within 10 min. Pentane is used as the solvent, and the solvent-to-oil ratio is 5:1. In addition, nonylphenol polyoxyethylene ether NP-10 accounting for 0.5 wt% of the mass of the feedstock oil is added to the extractant. The extraction conditions are: the extraction pressure is 4 MPa; the top temperature of the column is 185 °C, the middle temperature of the column is 175 °C, the bottom temperature of the column is 160 °C, and fractionation is carried out under constant pressure and temperature reduction operation conditions, and a total of 80 wt% of the extract is withdrawn. The carbon residue value of the 20 wt% raffinate residue at the bottom of the column is measured, and the carbon residue value is 43 wt%.

[0040] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing a carbon material precursor by dehydrogenating vacuum residue, comprising: Using petroleum residue as the raw material oil, first add oxide nanoparticles to the raw material oil and treat it under an electric field and / or a magnetic field, and then use an extractant to extract the petroleum residue to obtain the deoiled asphalt, which is the carbon material precursor; The extractant includes an organic hydrocarbon solvent and a carrier; preferably, the petroleum residue contains a carrier; The carrier in the extractant and the carrier in the raw material oil are each independently selected from one or more of isooctyl phosphate, tris(4-nonylphenyl) phosphite, trip-tolyl phosphate, 2,2,2-trifluoroethanol, and 2-propylaniline.

2. The method according to claim 1, wherein The addition amount of the carrier in the extractant accounts for 0.5 wt% to 2 wt% of the mass of the petroleum residue.

3. The method according to claim 1, wherein The addition amount of the carrier in the raw material oil accounts for 0.5 wt% to 3 wt% of the mass of the petroleum residue.

4. The method according to claim 1, wherein The oxide nanoparticles include at least one of iron oxide and zinc oxide.

5. The method according to claim 1 or 4, characterized in that, The particle size of the oxide nanoparticles is 100 to 400 nm; preferably, the particle size of the nano iron oxide particles is 150 nm to 300 nm; the particle size of the nano zinc oxide particles is 200 nm to 400 nm; And / or, the mass ratio of the addition amount of the oxide nanoparticles to the raw material oil is 0.2 to 0.7:1000.

6. The method according to claim 1, wherein The treatment time of the raw material oil added with oxide nanoparticles under an electric field and / or a magnetic field is 5 to 15 min.

7. The method according to claim 1, wherein The electric field used is a direct current electric field, and the electric field strength is 2000 V / cm to 10000 V / cm.

8. The method according to claim 1, characterized in that The magnetic field used is a constant magnetic field, and the magnetic field strength is 0.1 T to 2 T.

9. The method according to claim 1, wherein The petroleum residue is the residue obtained by the atmospheric or vacuum distillation of crude oil; the properties of the petroleum residue are: the asphaltene content is 4.2 wt% to 10 wt%; the 10% distillation point ≥ 500 °C, preferably 500 to 530 °C, the softening point is 25 to 45 °C, and the carbon residue value is 10 wt% to 20 wt%.

10. The method according to claim 1, characterized in that, Control the raffinate yield to be 15 wt% to 30 wt%.