CN111439741B - Method for improving atmospheric pyrolysis carbonization carbon formation rate of ethylene tar and application thereof - Google Patents
Method for improving atmospheric pyrolysis carbonization carbon formation rate of ethylene tar and application thereof Download PDFInfo
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- CN111439741B CN111439741B CN202010476847.2A CN202010476847A CN111439741B CN 111439741 B CN111439741 B CN 111439741B CN 202010476847 A CN202010476847 A CN 202010476847A CN 111439741 B CN111439741 B CN 111439741B
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Abstract
The invention belongs to the technical field of ethylene tar waste recycling, and particularly relates to a method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar and application thereof. The method comprises the following steps: (1) mixing ethylene tar and a chemical product containing unsaturated olefin or aromatic hydrocarbon, adding a catalyst for thermal polymerization, carrying out a primary reaction under a heating condition, and after the reaction is finished, heating to continue the reaction to obtain a carbonized precursor. (2) And (2) carrying out pyrolysis carbonization on the precursor obtained in the step (1) to obtain the carbon material. According to the invention, through the polycondensation reaction between the ethylene tar and waste chemical products such as 2-vinylpyridine, deoiled asphalt, waste lubricating oil residue oil, FCC (fluid catalytic cracking) settled slurry oil residue, vacuum residue oil, medical intermediate waste residue and the like, the chemical waste can be converted into a solid precursor, so that the chemical waste is recycled, and the char formation rate of the ethylene tar can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of ethylene tar waste recycling, and particularly relates to a method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
China is a big country for producing ethylene tar, and the byproduct quantity of the ethylene tar in China reaches 1.70-2.57 multiplied by 10 by 2016 years6t/a. The ethylene tar is a high-temperature condensation product of an ethylene cracking raw material in a steam cracking process, has high carbon-hydrogen ratio and low ash content and heavy metal content, and contains extremely complex components including various alkanes, aromatic hydrocarbons and aromatic olefins. Therefore, the ethylene tar contains a large amount of components with active groups, and the coking and the blockage of pipelines are easily caused in industry. It is for this reason that the use of ethylene tar is limited. The ethylene tar can be used for extracting naphthalene in industryAnd methylnaphthalene, synthetic petroleum resin, aromatic hydrocarbon solvent oil, fuel oil, carbon fiber, carbon black and the like, but the required amount is very low, and most of the ethylene tar in China is used as fuel at present.
Patent document No. 201510743427.5 discloses a method for preparing porous carbon from ethylene tar. The method comprises the steps of pretreating ethylene tar, removing light components in the ethylene tar by using n-heptane reflux, carrying out preoxidation to obtain a precursor of the porous carbon material, and finally carrying out carbonization and acid washing by using a template method to obtain the porous carbon material. It can be seen that this patent only utilizes a portion of the ethylene tar, where the light components are not effectively utilized.
Patent document No. 201710548840.5 discloses a method for preparing petroleum resin by thermal polymerization of diolefin and a method for producing petroleum resin by mixed carbon copolymerization and five-carbon nine-thermal polymerization. It can be seen that this patent also utilizes only a portion of the components of the ethylene tar as feed.
Disclosure of Invention
The invention further researches and discovers that: at present, the main reason that only part of components in the ethylene tar can be utilized when the ethylene tar is recycled is that the char yield of the directly carbonized ethylene tar is very low. Aiming at the problems, the invention provides a method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar and application thereof.
The invention aims to provide a method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar.
The second purpose of the invention is to provide the application of the method for improving the carbonization rate of ethylene tar by atmospheric pyrolysis.
In order to realize the purpose, the invention discloses the following technical scheme:
the invention discloses a method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar, which comprises the following steps:
(1) mixing ethylene tar and a chemical product containing unsaturated olefin or aromatic hydrocarbon, adding a catalyst for thermal polymerization, carrying out a primary reaction under a heating condition, and after the reaction is finished, heating to continue the reaction to obtain a carbonized precursor.
(2) And (2) carrying out pyrolysis carbonization on the precursor obtained in the step (1) to obtain the carbon material.
Further, in the step (1), the chemical products containing unsaturated olefin or aromatic hydrocarbon include any one of 2-vinylpyridine, deoiled asphalt, waste lubricating oil residue oil, FCC settled slurry oil residue oil, vacuum residue oil, medical intermediate waste residue, and the like, and by the polycondensation reaction between these waste chemical products and ethylene tar, not only the chemical wastes can be converted into solid precursors, so that the chemical wastes can be recycled, but also the char formation rate of the ethylene tar can be effectively improved.
Further, in the step (1), the mass ratio of the ethylene tar, the chemical product containing unsaturated olefin or aromatic hydrocarbon and the acid catalyst is 1: 0.6-3: 0.01-0.1.
Further, in the step (1), the catalyst comprises: p-toluenesulfonic acid, cyclopentadien, cyclohexanone peroxide, and the like. These species initiate the polymerization reaction and can increase the reaction rate.
Further, in the step (1), the conditions of the preliminary reaction are as follows: the reaction is carried out for 30-120min under the temperature of 120 ℃ and 180 ℃ (preferably 150 ℃). The reaction is a curing step, i.e. the preliminary olefin-aromatic hydrocarbon is polymerized into a chain polymer.
Further, in the step (1), the conditions for raising the temperature to continue the reaction are as follows: the reaction is carried out at 240 ℃ and 300 ℃ (preferably 270 ℃) for 60-240 min. The reaction is pre-oxidation and non-melting treatment, further improves the degree of contact of the raw materials and increases the yield of the subsequent carbonization reaction.
Further, in the step (2), the pyrolysis carbonization is carried out under a protective atmosphere, the pyrolysis temperature is 400-800 ℃, the time is 2-8h, and the carbonization is preferably carried out at 500 ℃ for 5 h.
Further, the method for improving the atmospheric pressure carbon forming rate of the plastic solid waste further comprises the step of activating the carbon material obtained in the step (2).
Further, the activation method comprises the following steps: the carbon material is mixed with an activating agent and then activated for 60-180min (preferably 100min) at the temperature of 650-850 ℃ under the condition of protective atmosphere, so as to obtain the activated carbon.
Further, the activator is a commonly used alkaline activator, such as any one of potassium hydroxide, sodium hydroxide, potassium carbonate, and the like.
Further, the protective atmosphere is nitrogen, and the gas flow is controlled to be 50-150ml/min (preferably 100 ml/min).
The invention further discloses application of the method for improving the atmospheric pyrolysis carbonization carbon formation rate of the ethylene tar in chemical waste treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention directly adopts untreated ethylene tar as a part of raw materials, and modifies the ethylene tar into a precursor with high molecular weight or ultrahigh molecular weight after carrying out thermal polymerization reaction on chemical byproducts containing unsaturated olefin or aromatic hydrocarbon, thereby obviously improving the char forming rate of the ethylene tar under the normal pressure pyrolysis condition.
(2) The method provided by the invention not only improves the char yield of the ethylene tar under the condition of normal pressure pyrolysis, but also can convert the liquid ethylene tar at normal temperature into solid state, and is more convenient for storage, transportation and feeding of raw materials when being used as a carbonization raw material.
(3) The method provided by the invention can simultaneously utilize the chemical wastes such as 2-vinylpyridine, deoiled asphalt, waste lubricating oil residual oil, FCC (fluid catalytic cracking) settling slurry residual oil, vacuum residual oil, medical intermediate waste residue and the like, so that the chemical wastes are subjected to resource treatment.
(4) The method provided by the invention breaks through the technical bottleneck that only the ethylene tar component can be selectively utilized in the prior art, can realize the indiscriminate utilization of the components of the ethylene tar, and obviously improves the utilization rate and the treatment efficiency of the ethylene tar.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Aiming at the problems that only part of components in ethylene tar can be utilized when the ethylene tar is recycled at present and the carbonization rate of carbonized ethylene tar is low, the invention provides a method for improving the carbonization rate of ethylene tar through atmospheric pyrolysis and carbonization, and the invention is further explained by combining with a specific embodiment.
Example 1
A method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar comprises the following steps:
(1) mixing ethylene tar and 2-vinylpyridine, adding p-toluenesulfonic acid as a catalyst, uniformly mixing and stirring, placing in a heating jacket at 150 ℃ for heat preservation reaction for 50min, adjusting the temperature to 270 ℃ after the reaction is finished, and reacting for 150min to obtain a carbonized precursor, wherein the adding mass of the 2-vinylpyridine residue, the ethylene tar and the catalyst is 100g, 100g and 0.5g in sequence.
(2) And (2) when the temperature of the carbonized precursor obtained in the step (1) is reduced to 150 ℃, putting the carbonized precursor into a carbonization tube furnace, carbonizing the carbonized precursor for 5 hours at the temperature rising rate of 5K/min under the nitrogen atmosphere (with the flow rate of 100ml/min) to 500 ℃, and obtaining the carbon material after the carbonization reaction is finished.
Example 2
A method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar comprises the following steps:
(1) mixing ethylene tar with waste lubricating oil residual oil, adding dicyclopentadiene as a catalyst, uniformly mixing and stirring, placing in a heating sleeve at 180 ℃ for heat preservation reaction for 30min, adjusting the temperature to 240 ℃ after the reaction is finished, and reacting for 240min to obtain a carbonized precursor, wherein the adding mass of the ethylene tar, the waste lubricating oil residual oil and the catalyst is 100g, 60g and 0.1g in sequence.
(2) And (2) when the temperature of the carbonized precursor obtained in the step (1) is reduced to 150 ℃, putting the carbonized precursor into a carbonization tube furnace, carbonizing the carbonized precursor for 2 hours at the temperature of 800 ℃ at the heating rate of 5K/min under the nitrogen atmosphere (with the flow rate of 50ml/min), and obtaining the carbon material after the carbonization reaction is finished.
Example 3
A method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar comprises the following steps:
(1) mixing ethylene tar and FCC (fluid catalytic cracking) settled slurry oil residual oil, adding p-cyclohexanone peroxide as a catalyst, uniformly mixing and stirring, placing in a heating jacket at 120 ℃ for heat preservation reaction for 120min, adjusting the temperature to 300 ℃ after the reaction is finished, and reacting for 60min to obtain a carbonized precursor, wherein the adding mass of the ethylene tar, the FCC settled slurry oil residual oil and the catalyst is 100g, 300g and 1g in sequence.
(2) And (2) when the temperature of the carbonized precursor obtained in the step (1) is reduced to 150 ℃, putting the carbonized precursor into a carbonization tube furnace, increasing the temperature to 400 ℃ at a heating rate of 5K/min in a nitrogen atmosphere (with a flow rate of 150ml/min), and carbonizing for 8 hours to obtain the carbon material after the carbonization reaction is finished.
Example 4
The method for improving the atmospheric pyrolysis carbonization carbon formation rate of the ethylene tar is the same as the method in the example 1, and the difference is that: grinding the carbon material obtained in the step (2) and potassium hydroxide according to the mass ratio of 3:1, then activating for 100min at the temperature rising rate of 5K/min to 780 ℃ in a nitrogen atmosphere (flow rate of 100ml/min), and obtaining the activated carbon after the activation reaction is finished.
Example 5
The method for improving the atmospheric pyrolysis carbonization carbon formation rate of the ethylene tar is the same as the method in the example 2, and the difference is that: grinding the carbon material obtained in the step (2) and sodium hydroxide according to the mass ratio of 3:1, then activating for 60min at the temperature rising rate of 5K/min to 850 ℃ in a nitrogen atmosphere (flow rate of 50ml/min), and obtaining the activated carbon after the activation reaction is finished.
Example 6
The method for improving the atmospheric pyrolysis carbonization carbon formation rate of the ethylene tar is the same as the method in the example 3, and the difference is that: grinding the carbon material obtained in the step (2) and potassium carbonate according to the mass ratio of 3:1, then activating for 180min at the temperature rising rate of 5K/min to 650 ℃ in a nitrogen atmosphere (flow rate of 150ml/min), and obtaining activated carbon after the activation reaction is finished.
Example 7
A method for preparing a carbon material by atmospheric pyrolysis of ethylene tar comprises the following steps: putting ethylene tar into a carbonization tube furnace, increasing the temperature to 500 ℃ at the heating rate of 5K/min under the nitrogen atmosphere (the flow rate is 100ml/min), carbonizing for 5h, and obtaining the carbon material after the carbonization reaction is finished.
Example 8
A method for preparing a carbon material by utilizing 2-vinylpyridine atmospheric pyrolysis comprises the following steps: putting 2-vinylpyridine into a carbonization tube furnace, increasing the temperature to 500 ℃ at the heating rate of 5K/min under the nitrogen atmosphere (the flow rate is 100ml/min), carbonizing for 5h, and obtaining the carbon material after the carbonization reaction is finished.
Performance testing：
The yields of the carbon materials prepared in examples 1 to 8 were measured, and the results are shown in Table 1.
TABLE 1
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Carbonization yield/% | 42.53 | 36.97 | 45.36 | 44.19 | 38.64 | 43.83 | 13.32 | 12.34 |
As can be seen from the test results in Table 1, when ethylene tar or 2-vinylpyridine alone was used for carbonization, the char formation rate was only 13.32%, 12.34%. After the ethylene tar is modified by adopting the chemical wastes such as the 2-vinylpyridine, the waste lubricating oil residual oil and the FCC settling slurry residual oil, the char formation rate is generally up to more than 36 percent and is far higher than the char formation rate of an independent raw material and the sum of the carbonization rates of the two independent raw materials of the ethylene tar and the 2-vinylpyridine, and the char formation rate of the chemical wastes such as the ethylene tar or the 2-vinylpyridine can be obviously improved by the method disclosed by the invention.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A method for improving the atmospheric pyrolysis carbonization carbon formation rate of ethylene tar is characterized by comprising the following steps:
(1) mixing ethylene tar and a chemical product containing unsaturated olefin or aromatic hydrocarbon, adding a catalyst for thermal polymerization, carrying out a primary reaction under a heating condition, and after the reaction is finished, heating to continue the reaction to obtain a carbonized precursor;
(2) carrying out pyrolysis carbonization on the precursor obtained in the step (1) to obtain a carbon material;
the conditions for heating and continuing the reaction are as follows: reacting at the temperature of 240 ℃ and 300 ℃ for 60-240 min;
the pyrolysis carbonization is carried out under the protective atmosphere, the pyrolysis temperature is 400-800 ℃, and the time is 2-8 h;
in the step (1), the conditions of the primary reaction are as follows: reacting at the temperature of 120-180 ℃ for 30-120 min;
the catalyst comprises: any one of p-toluenesulfonic acid, cyclopentanediene and cyclohexanone peroxide.
2. The method for increasing the carbonization yield of ethylene tar in atmospheric pyrolysis as claimed in claim 1, wherein in step (1), the chemical products containing unsaturated olefins or aromatic hydrocarbons comprise any one of 2-vinylpyridine, deoiled asphalt, spent lubricating oil residue, FCC settled oil slurry residue, vacuum residue and medical intermediate residue.
3. The method for increasing the atmospheric pyrolysis carbonization yield of ethylene tar according to claim 1, wherein the reaction temperature is 150 ℃.
4. The method for increasing the atmospheric pyrolysis carbonization carbon formation rate of the ethylene tar according to claim 1, wherein in the step (1), the temperature rise is carried out under the following reaction conditions: the temperature was 270 ℃.
5. The method for increasing the carbonization rate of ethylene tar in atmospheric pyrolysis carbonization according to claim 1, wherein in the step (2), the ethylene tar is carbonized at 500 ℃ for 5 h.
6. The method for increasing the carbonization rate of ethylene tar by atmospheric pyrolysis and carbonization according to claim 1, wherein in the step (2), the protective atmosphere is nitrogen, and the gas flow is controlled to be 50-150 ml/min.
7. The method for increasing the carbonization rate of ethylene tar in atmospheric pyrolysis carbonization according to claim 6, wherein the gas flow rate is controlled to be 100 ml/min.
8. The use of the method according to any one of claims 1 to 7 for increasing the carbonization rate of ethylene tar in atmospheric pyrolysis carbonization in the treatment of chemical waste.
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| CN106672966A (en) * | 2015-11-05 | 2017-05-17 | 长春工业大学 | Preparation method of ethylene tar-based porous carbon with narrow aperture distribution |
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