KR101966886B1 - Manufacturing method of high purity pitch from pyrolysis fuel oil - Google Patents

Abstract

The present invention relates to a method for producing a pitch using pyrolysis fuel oil (PFO), and more particularly, to a method for producing a high purity pitch with high carbonization yield and softening.
According to the present invention as described above, the pyrolysis fuel oil is gradually heated to heat treatment, and the pitch produced by the solvent extraction method is extracted, thereby effectively removing the light oil component and significantly increasing the degree of polymerization with respect to the aromatic ring. In addition, there is an effect of providing a high purity pitch with high hydrocarbon yield and softening point.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a high-purity pitch based on pyrolysis fuel oil,

The present invention relates to a method for producing pitch using pyrolysis fuel oil (PFO), and more particularly, to a method for producing a high purity pitch with high carbonization yield and softening point.

In domestic NCC (Naphthacracking center), Naphtha is used as raw material to produce C4, C5 and BTX including ethylene, propylene and butadiene which are basic raw materials of various materials by high temperature pyrolysis method at 780 ~ 850 ℃. Pyrolysis residues, which are proprietary components, are consumed as fuel. Pyrolysis residues used as fuel are known to have combustion heat of about 10,000 kcal / kg, similar to Bunker C oil. There is a price difference depending on oil price fluctuation but it is known to be about 3 to 5 dollars per ton. At present, about 900,000 tons / year of pyrolysis residue is produced in Korea, and the components of these pyrolysis residues may be slightly different depending on the manufacturing process of NCC, but about 20 to 30% of naphthalene / methylnaphthalene compound And aromatic compounds of 70 to 80% of them are mixed together. Therefore, it is expected that there will be no problem in securing the intermediate raw material if the pitch is manufactured by utilizing the pyrolysis fuel oil. Especially, in the case of pyrolysis residual oil, since naphtha is used as a base raw material, the impurity content is small and unreacted components can be utilized as fuel Have

Such pyrolysis fuel oil is currently used as a roadway packaging material or a raw material oil, but has a high aromatization degree and a small amount of impurities such as sulfur, which is advantageous as a raw material for a carbon material rather than a furnace. Based on this, it is possible to manufacture carbon fiber with high strength and elasticity, and the produced carbon material can obtain a high added value, so that a suitable raw material It is known as one.

Mesophase picth, which is used as a precursor of carbon fiber or needle coke, can be obtained by heat treatment of pitch for raw materials. However, such pitch for raw materials is not limited to quinoline, so-called quinoline insoluble particles, ash component. Quinoline insoluble matter (QI) having a size of about 0.2 to about 2.0 mu m remained unremoved can affect the physical properties of coke and carbon products produced therefrom. They adhere to the surface of mesophase spheres, which are carbonized precursors, to inhibit mesophase growth and coalescence, thereby inhibiting the growth of anisotropic textures. As a result, the coefficient of thermal expansion (CTE) of the prepared needle-shaped coke may increase, or the radioactivity, strength, and elastic modulus of the carbon fiber may be adversely affected. Therefore, it is necessary to minimize quinoline insolubles content in addition to ash components from raw materials in order to produce carbon products such as needle-like coke and carbon fiber. The beta-resin component is a substance that helps the formation and growth of the mesophase, which is a precursor of carbonization, and the mesophase generation and growth are better as the content is larger. It is possible to increase the beta-resin / QI weight ratio of the pitch raw material by recovering a lot of beta-resin or removing quinoline insoluble matter (QI). At this time, a high purity pitch favorable for mesophase generation and growth can be obtained.

An object of the present invention is to provide a method for producing a high purity pitch material by using pyrolysis fuel oil (PFO). It is another object of the present invention to provide a method for utilizing pyrolysis residual oil (PFO), which is a by-product of naphtha cracking, as a raw material for a carbon material.

In order to achieve the above object, the present invention provides a method for producing a high purity pitch based on pyrolysis fuel oil (PFO). The manufacturing method of the high-purity pitch based on the pyrolysis fuel oil (PFO) includes a step of producing pitch by heat-treating the pyrolysis fuel oil and a step of increasing the purity of the produced pitch by a solvent extraction method.

The pitch manufacturing step is characterized in that the temperature is gradually increased to perform the heat treatment. The heat treatment is characterized in that the temperature raising rate is 1 to 20 占 폚 per minute at a temperature range of 100 to 600 占 폚.

Also, the pitch manufacturing step is performed under a gas condition selected from at least one inert gas such as nitrogen and argon.

The solvent extraction method is characterized in that the pitch produced in the step of pitch production is added to a solvent at a temperature of 20 to 200 캜.

According to the present invention, the pyrolysis fuel oil is gradually heated to heat treatment, and the pitch produced by the solvent extraction method is extracted, thereby effectively removing the light oil component and significantly increasing the degree of polymerization with respect to the aromatic ring. In addition, there is an effect of providing a high purity pitch with high hydrocarbon yield and softening point.

According to the present invention, since pyrolysis residual oil (PFO) uses naphtha as a base material, it has an advantage that the impurity content is small and unreacted components can be utilized as fuel.

According to the present invention, by providing a method of producing a high purity pitch by using pyrolysis fuel oil, it is possible to produce a pitch that depends on most of the imports from abroad for domestic production. Also, the produced high purity pitch can be applied to the anode material technology, which is a fuel cell of a hybrid automobile and a hydrogen automobile.

1 shows thermogravimetric analysis (TGA) results of a high purity pitch based on pyrolysis fuel oil (PFO) according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

A method for producing a high purity pitch based on Pyrolysis Fuel Oil (PFO) according to an embodiment of the present invention includes a step of producing a pitch by heat-treating pyrolysis fuel oil (PFO) .

The pitch manufacturing step is characterized in that the temperature is gradually increased to perform the heat treatment. The heat treatment is preferably carried out at a temperature ranging from 100 to 600 ° C and a temperature rising rate ranging from 1 to 20 ° C per minute. As described above, the temperature is gradually raised to heat treatment to remove the light oil component.

If the heat treatment temperature is lower than 100 ° C, the reaction temperature is too low to sufficiently remove the hard oil contained in the thermal cracking fuel oil, which is not preferable for producing a high purity pitch. If the heat treatment temperature is 600 ° C or higher, high temperature carbonization is performed to form an anisotropic coke This is not desirable for producing a high purity pitch by acting as a quinoline insoluble component.

If the rate of temperature rise is less than 1 ° C per minute, the reaction takes a long time, which is not economical and is not preferable. If the rate of temperature increase is more than 20 ° C per minute, the reaction time is reduced, It is not preferable to produce the pyrolysis fuel oil-based high purity pitch to be invented in this study because the light oil fraction in the pyrolysis fuel oil to be removed can not be sufficiently removed and the quality of the pitch can be lowered.

The pitch manufacturing step is characterized in that it is performed under inert gas conditions such as nitrogen and argon.

The solvent extraction method is characterized in that the pitch produced in the pitch manufacturing step is added to a solvent at a temperature of 20 to 200 캜. The reason why the pitch is immersed in a solvent is to remove the insolubility of the produced pitch to increase the purity of the pitch. The bath temperature can be selected according to the vaporization temperature of the solvent used.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.

Example  1. Pyrolysis Fuel Oil, PFO ) -Based high purity pitch

1-1 Pyrolysis Fuel Oil ( PFO ) Is heat-treated to produce a pitch Pitch manufacturing stage

 1000 g of pyrolysis fuel oil (PFO) was prepared in the vessel, and the pyrolysis fuel oil in the glass reactor was maintained at 300 DEG C for 1 hour and then the temperature was raised at a rate of 2 DEG C / min. In order to prevent local overheating of the viscous heavy specimens during the heat treatment, the stainless steel stirrer was rotated at 300 rpm and stirred, and 2 L / min of nitrogen was flowed near the bottom of the reactor. After maintaining at 360 ° C for 3 hours, the sample was cooled by slow cooling and a pitch was prepared.

≪ RTI ID = 0.0 > 1-2 < / RTI > solvent extraction method to increase the purity of the prepared pitch

The pyrolysis fuel oil-based pitch obtained by the heat treatment in 1-1 above was added to a quinoline solution at 75 ° C. and then filtered under reduced pressure to obtain a sample dissolved in quinoline. Then, the toluene solution was heated to 130 ° C. and filtered under reduced pressure to obtain toluene insoluble Min to produce a high purity pitch based on pyrolysis fuel oil.

Comparative Example  One.

A pyrolysis fuel oil-based pitch was prepared by the method of Example 1 except for the step 1-2.

Measurement example  One.

Thermogravimetric analysis (TGA) was conducted to observe the carbonization yield of the pitch based on the pyrolysis fuel oil of Example 1 and Comparative Example 1, and the results are shown in FIG. 1 and Table 1.

According to the above results, it can be confirmed that the carbonization yield in Comparative Example 1 is 53%, that in Example 1, the carbonization yield is about 83%, and the carbonization yield is very stable at high temperature and excellent in thermal stability. This indicates that unreacted low molecular weight components were effectively removed in the high purity pitch production process based on the pyrolysis fuel oil.

Condition TI
(%) QI
(%) Carbon yield
(%) Softening point
(° C) Comparative Example  One > 49.5 ≪ 1.0 53 177.3 Experimental Example  One > 99.9 ≪ 0.1 83 230.0

Measurement example  2.

In order to observe the quinoline insolubles (QI) of the pitch based on the pyrolysis fuel oil prepared in Example 1 and Comparative Example 1, QI analysis was performed according to ASTM D 2318, and the results are shown in Table 1.

According to the above results, the QI value of Example 1 is lower than 0.1, which is lower than the QI value, which is the quinoline insoluble matter value that can lower the physical properties of the coke and carbon product produced from the pitch as in the ash of Comparative Example 1, Has a low value. From these analysis results, it can be confirmed that the high purity pitch based on the pyrolysis fuel oil was produced by minimizing the quinoline insolubles content through the above high purity pitch production method.

Experimental Example  3.

The softening point of the pitch based on the pyrolysis fuel oil prepared in Example 1 and Comparative Example 1 was measured according to ASTM D3104 using a softening point measuring device (Mattler toledo, DP90). The results are shown in Table 1.

According to the above results, the softening point of Comparative Example 1 is 177.3 ° C and that of Example 1 has a softening point of 230.0 ° C, whereby the unreacted or low-reacted low molecular weight component through the pyrolysis fuel oil-based high- It can be confirmed that it has been removed.

Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (6)

(1) a pitch producing step of producing a pitch by heat-treating pyrolysis fuel oil (PFO);
(2) primary solvent extraction of the prepared pitch with quinoline; And
(3) a step of secondary solvent extraction of the extracted solvent-extracted pitch with toluene,
In the pitch manufacturing step of (1), the temperature is gradually increased to heat treatment
Wherein the heat treatment is carried out at a temperature ranging from 300 to 400 DEG C and a temperature rising rate ranging from 1 to 20 DEG C per minute,
The step of producing pitch in the step (1) is performed in nitrogen which is an inert gas,
The temperature of the quinoline in step (2) is 70 to 80 占 폚,
Wherein the step (3) of extracting the secondary solvent with toluene comprises adding toluene at 130 ° C. delete delete delete delete delete

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