CN110745808A - Method for preparing foam carbon based on heavy tar generated by pyrolysis of rich coal - Google Patents
Method for preparing foam carbon based on heavy tar generated by pyrolysis of rich coal Download PDFInfo
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- CN110745808A CN110745808A CN201911225567.8A CN201911225567A CN110745808A CN 110745808 A CN110745808 A CN 110745808A CN 201911225567 A CN201911225567 A CN 201911225567A CN 110745808 A CN110745808 A CN 110745808A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The method relates to a method for preparing foam carbon based on coal-rich tar serving as a raw material. The method solves the problem that heavy tar is difficult to utilize in the pyrolysis process of the oil-rich coal, applies the low-temperature plasma modified foam carbon material to the quenching and tempering process of the oil-rich coal pyrolysis tar, innovating the conversion idea of the oil-rich coal, and realizing clean, efficient and gradient utilization of the oil-rich coal. The method uses a self-foaming method to prepare the foam carbon, does not need the step of oxidation and solidification of the primary foam carbon, shortens the production period of the foam carbon, reduces the production cost, has simple process and is convenient for production. The method introduces a low-temperature plasma auxiliary technology to foam the foam carbon material, improves the surface performance of the material, and does not change the inherent performance of a matrix; the method has universal adaptability to the processed materials and can process the materials with more complex shapes; low reaction environment temperature, simple process, convenient operation and no pollution.
Description
Technical Field
The invention relates to a method for preparing foam carbon, belongs to the technical field of coal chemical industry, and particularly relates to a method for preparing foam carbon by taking heavy tar as a raw material based on pyrolysis of rich coal.
Background
Oil-rich coal pyrolysis tar is a viscous liquid mixture, and many researchers separate coal tar into fractions of different boiling points: the boiling point is less than 170 ℃ and is light oil, the boiling point is 170-210 ℃ and is phenol oil, the boiling point is 210-230 ℃ and is naphthalene oil, the boiling point is 230-300 ℃ and is wash oil, the boiling point is 300-360 ℃ and is anthracene oil, and the boiling point is more than 360 ℃ and is heavy oil. Wherein the heavy oil (heavy residue after distillation of the coal tar) accounts for more than 55 percent (mass fraction) of the total amount of the coal tar, is not efficiently utilized basically, and does not embody and play important values thereof. The heavy tar is a complex mixture composed of polycyclic aromatic hydrocarbons, and compared with graphite asphalt, the heavy tar has the characteristics of low molecular weight, high aromaticity and polymerization degree, high carbon content, relatively low content of heteroatoms and metals and the like, and is a high-quality precursor for synthesizing functional carbon materials.
The carbon foam is a three-dimensional light functional carbon material consisting of porous bubbles and pore walls, which is obtained by taking a carbon-rich substance as a precursor through the processes of foaming, curing, carbonizing, graphitizing and the like. In order to prepare the foam carbon with high mechanical strength and high thermal conductivity, the heavy tar which is difficult to utilize in the pyrolysis process of the oil-rich coal is selected as a precursor to prepare the foam carbon with a highly ordered graphite structure, and the foam carbon is applied to the oil extraction process of the oil-rich coal pyrolysis to increase the yield of the tar.
Disclosure of Invention
The following presents a simplified summary of one or more aspects in order to provide a basic understanding of such aspects; this summary is not an extensive overview of all contemplated aspects, and is intended to neither identify key or critical elements of all aspects nor delineate the scope of any or all aspects; its sole purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description that is presented later;
the invention mainly aims to solve the technical problems in the prior art and provides a method for preparing foam carbon by using heavy tar as a raw material based on pyrolysis of rich coal; the method comprises the steps of taking coal tar in the process of pyrolyzing the rich coal as a raw material, firstly extracting light oil to obtain heavy tar, then purifying quinoline insoluble substances in the heavy tar to obtain a purified heavy tar-based foam carbon precursor, and preparing a foam carbon material by using low-temperature plasma and adopting a self-foaming method, so that the utilization rate of the heavy tar is improved.
In order to solve the problems, the scheme of the invention is as follows:
a method for preparing carbon foam comprises the following steps:
separating the rich-oil coal pyrolysis tar to remove light oil, and purifying the residual heavy tar to obtain a heavy tar foam carbon precursor;
carrying out self-foaming treatment on the carbon precursor by using a low-temperature plasma generator to obtain a carbon foam primary body;
and carbonizing the foam carbon primary body in a tubular carbonization furnace to obtain the foam carbon.
Preferably, in the above method for preparing carbon foam, the obtaining of the heavy tar-based carbon foam precursor specifically comprises:
and (3) diluting and dissolving the heavy tar after the light oil is extracted by using the coking wash oil as a solvent, and removing quinoline by adopting a centrifugal separation method to obtain a purified heavy tar-based foam carbon precursor.
Preferably, in the above method for preparing carbon foam, the purified heavy tar precursor is placed in a low-temperature plasma generator for self-foaming treatment and modification, the low-temperature plasma baking power is 30-90W, and N is selected as the foaming atmosphere2、Ar、O2And air, wherein the foaming time is 10-30min, and the gas flux is 40-100 mL/min.
Preferably, in the preparation method of the carbon foam, nitrogen is introduced for protection during the carbonization treatment of the carbon foam primary body, the carbonization temperature is 300-600 ℃, the carbonization time is 1-4h, and the carbonization temperature rise rate is 30-50 ℃/s.
Therefore, compared with the prior art, the invention has the following advantages:
(1) according to the invention, the functional foam carbon material is constructed by taking the heavy tar obtained after pyrolysis and purification of the oil-rich coal as a precursor, so that the problem that the heavy tar is difficult to utilize in the pyrolysis process of the oil-rich coal is solved, and the prepared foam carbon is applied to the conditioning of the heavy tar in the oil-rich coal pyrolysis oil extraction process, so that the conversion idea of the oil-rich coal is created, and the clean, efficient and gradient utilization of the oil-rich coal is realized.
(2) The invention uses the self-foaming method to prepare the foam carbon, does not need the step of oxidation and solidification of the primary foam carbon, shortens the production period of the foam carbon, reduces the production cost, has simple process and is convenient for production.
(3) The invention introduces the low-temperature plasma technology to assist the foaming process to prepare the novel foam carbon material, and the inherent performance of the matrix is not changed while the surface performance of the material is improved; the method has universal adaptability to the processed materials and can process the materials with more complex shapes; low reaction environment temperature, simple process, convenient operation and no pollution.
Detailed Description
Examples
In the embodiment, the coking wash oil with wide source and low cost is selected as a solvent, and QI in the coal tar is separated and removed by a solvent-centrifugation method.
The process for preparing the carbon foam by using the heavy tar in the pyrolysis process of the rich coal as the raw material, provided by the embodiment, comprises the following specific steps:
the method comprises the following steps: coal tar is collected for later use through pyrolysis of oil-rich coal;
step two: weighing a certain amount of coal tar, placing the coal tar in a small 100mL beaker, and adding proper washing oil to dilute the coal tar; putting the beaker filled with the mixed tar into a constant-temperature water bath kettle which is preheated to a specified temperature, and stirring for several minutes to fully dilute and dissolve the components of the coal tar; taking out after keeping the temperature for 30min, and transferring the mixed tar in the small beaker into a centrifugal test tube; the centrifugal tube is provided with a heat insulation sleeve, after heat insulation measures are taken, the centrifugal tube is placed into a centrifugal machine with set rotating speed and centrifugal time, the centrifugal machine is started, and separation operation is started; after the centrifugation is finished, slowly removing the supernatant coal tar clear liquid in the centrifuge tube by using a suction tube, discarding heavy quinoline insoluble residues deposited at the bottom of the centrifuge tube, and drying the extracted coal tar to obtain a heavy tar-based carbonaceous precursor;
step three: grinding the heavy tar base precursor obtained in the step two, and sieving the ground heavy tar base precursor with a 60-mesh sieve for later use;
step four, placing the ground heavy tar precursor in the step three into a low-temperature plasma generator, ① selecting the foaming power of 30W, 60W and 90W respectively for low-temperature plasma, screening the optimal foaming power of low-temperature plasma, selecting the optimal low-temperature plasma power in ①, and selecting N for ② foaming background gas respectively2、Ar、O2The optimal gas flux is selected from 40mL/min, 60mL/min, 80mL/min and 100mL/min in ③, the optimal gas flux is selected from ④, the low-temperature plasma foaming time is respectively selected from 10min, 15min, 25min and 30min, and the optimal foaming time is selected.
Step five, placing the foam carbon obtained in the step four into a carbonization furnace after cooling, introducing nitrogen for protection, selecting the optimal foaming power and foaming gas in the step four, selecting the carbonization temperature of ③ to be 300, 400, 500 and 600 ℃, screening the optimal carbonization temperature according to the performance of the obtained foam carbon, selecting the optimal foaming power and foaming gas in the step four, selecting the optimal carbonization temperature in ③ and the carbonization time of ④ to be 1, 2, 3 and 4 hours respectively, screening the optimal carbonization time according to the performance of the obtained foam carbon, selecting the optimal foaming power and foaming gas in the step four, selecting the optimal carbonization temperature in ③ and the optimal carbonization time in ④ and the temperature rise rate of ⑤ to be 30, 40 and 50 ℃/s, screening the optimal carbonization temperature rise rate according to the performance of the obtained foam carbon, finally screening the initially optimal preparation conditions of the foam carbon, and obtaining the foam carbon under the optimal conditions, wherein embodiment examples 1 to 5 are used for preparing the foam carbon under different parameters, and the influence of the different parameters on the performance of the foam carbon is researched, and the concrete steps are as follows.
Example 1:
obtaining coal tar through pyrolysis of oil-rich coal, weighing a certain amount of coal tar, placing the coal tar in a small 100mL beaker, and adding a certain amount of wash oil to dilute the coal tar according to requirements. And (3) putting the beaker filled with the mixed tar into a constant-temperature water bath kettle which is preheated to a specified temperature, and stirring for several minutes to fully dilute and dissolve the coal tar component. Taking out after keeping the temperature for 30min, and immediately transferring the mixed tar in the small beaker into a centrifugal test tube. The centrifugal tube is provided with a heat insulation sleeve, after heat insulation measures are taken, the centrifugal tube is placed into a centrifuge with set rotating speed and centrifugal time, the centrifuge is started, and centrifugal separation operation is started. After the centrifugation is finished, the supernatant coal tar clear liquid in the centrifuge tube is slowly removed by a suction tube, and heavy quinoline insoluble residues deposited at the bottom of the centrifuge tube are discarded to obtain a purified heavy tar precursor. Grinding and purifying the heavy tar precursor, and sieving with a 60-mesh sieve for later use. And putting the ground purified heavy tar precursor into a low-temperature plasma generator. The low-temperature plasma roasting power is respectively selected from 30W, 60W and 90W, the foaming precursor is taken out to be carbonized to obtain the foam carbon, and the optimal foaming power is selected through characterization analysis.
Example 2:
the cleaned heavy tar precursor ground in example 1 was placed in a low temperature plasma generator. Selecting the optimal foaming power in example 1, and respectively introducing N into the low-temperature plasma generator2、Ar、O2And air. Other conditions were exactly the same as in example 1. And taking out the foaming precursor for carbonization to obtain the foam carbon, and selecting the optimal foaming gas through characterization analysis.
Example 3:
the cleaned heavy tar precursor ground in example 1 was placed in a low temperature plasma generator. The foaming stage was exactly the same as in examples 1 and 2. The carbonization temperatures were 300, 400, 500, and 600 ℃ respectively, and the other conditions were exactly the same as in examples 1 and 2. And finally, taking out the foam carbon, cooling to room temperature, and selecting the optimal carbonization temperature through characterization analysis.
Example 4:
the cleaned heavy tar precursor ground in example 1 was placed in a low temperature plasma generator. The foaming stage was exactly the same as in examples 1 and 2. The optimal carbonization temperature and the optimal carbonization time in the embodiment 3 are selected, the optimal carbonization time and the optimal carbonization time in the embodiment 8 are respectively selected, the carbonization time is respectively selected from 1 hour, 2 hours, 3 hours and 4 hours, and other conditions are completely the same as those in the embodiments 1 and 2. And finally, taking out the foam carbon, cooling to room temperature, and selecting the optimal carbonization time through characterization analysis.
Example 5:
the cleaned heavy tar precursor ground in example 1 was placed in a low temperature plasma generator. The foaming stage was exactly the same as in examples 1 and 2. The optimal carbonization temperature in the embodiment 3 and the optimal carbonization time in the embodiment 4 are selected, the carbonization temperature rise rate is respectively selected to be 30 ℃/s, 40 ℃/s and 50 ℃/s, and other conditions are completely the same as those in the embodiments 1 and 2. And finally, taking out the foam carbon, cooling to room temperature, and selecting the optimal carbonization heating rate through characterization analysis.
TABLE 1 optimal foaming and modification conditions
| Foaming stage | Foaming power | Foaming atmosphere |
| Optimum conditions | 60W | Ar |
TABLE 2 optimal carbonization conditions
| Carbonization stage | Temperature of carbonization | Charring time | Rate of temperature rise in carbonization |
| Optimum conditions | 500℃ | 1h | 40℃/s |
TABLE 3 influence of carbon foam on the 10g of oil-rich coal pyrolysis for oil production and lightening
| Pyrolysis products | Rich oil coal (non-foam carbon) | Rich oil coal (with foam carbon) |
| Coal tar | 1.258g | 1.317g |
| Heavy component | 0.922g | 0.756g |
| Light component | 0.336g | 0.561g |
As can be seen from Table 1, the optimum conditions for preparing the carbon foam primary body in the foaming experiment in the low-temperature plasma generator are the foaming combustion power: 60W, the foaming background gas is: and Ar. As can be seen from table 2, the optimum carbonization conditions in the carbonization tube furnace were: the carbonization temperature is 500 ℃, the carbonization time is 1h, and the carbonization temperature rise rate is as follows: 40 ℃/s. As can be seen from Table 3, the tar produced by pyrolysis of 10g of the rich coal in the absence of the catalyst of the carbon foam was 1.258g, which was 0.922g for the heavy component and 0.336g for the light component. Under the catalysis of carbon foam, 10g of tar produced by pyrolysis of oil-rich coal is 1.317g, wherein the weight component is 0.756g, and the light component is 0.561 g. Under the catalytic action of the foam carbon, the yield of the coal tar is not changed greatly, and the content of light components is improved by 15.89%.
It is noted that references in the specification to "one embodiment," "an example embodiment," "some embodiments," etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic; moreover, such phrases are not necessarily referring to the same embodiment; further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to effect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described;
the previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure; various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the spirit or scope of the disclosure; thus, the disclosure is not intended to be limited to the examples and designs described herein.
Claims (3)
1. A method for preparing carbon foam is characterized by comprising the following steps:
separating the oil-rich coal tar to remove light oil and purifying the residual heavy tar to obtain a carbon precursor;
carrying out self-foaming treatment and carbonization treatment on the carbon precursor to obtain unmodified carbon foam;
and modifying the unmodified carbon foam by using low-temperature plasma to obtain the modified carbon foam.
2. The method for preparing carbon foam according to claim 1, wherein the obtaining of the carbonaceous precursor is specifically:
the coking wash oil is used as a solvent to dilute and dissolve the coal tar, heavy quinoline is removed by a centrifugal separation method, and the extracted coal tar is dried to obtain a carbonaceous precursor.
3. The method for preparing foam carbon according to claim 1, wherein the purified heavy tar precursor is placed in a low-temperature plasma generator for self-foaming treatment and modification, wherein the foaming power is 30-90W, and N is selected as the background gas2、Ar、O2And air, wherein the foaming time is 10-30min, and the gas flux is 40-100 mL/min.
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