KR101593808B1 - Method for preparing isotropic pitch - Google Patents

Abstract

The present invention relates to a method for producing an isotropic pitch, and more particularly, to a method for producing an isotropic pitch including a step of pretreating a petroleum hydrocarbon through a radical crosslinking reaction. According to an embodiment of the present invention, the flowability of the petroleum hydrocarbon may be improved through a process for producing an isotropic pitch including a step of pretreating the petroleum hydrocarbon through a radical crosslinking reaction, thereby suppressing the formation of the infusible component , A high softening point and an isotropic pitch of high carbonization yield can be produced with high yield.

Description

[0001] METHOD FOR PREPARING ISOTROPIC PITCH [0002]

The present invention relates to a method for producing an isotropic pitch, and more particularly, to a method for producing an isotropic pitch including a step of pretreating a petroleum hydrocarbon through a radical crosslinking reaction.

Carbon materials such as carbon fiber have a carbon content of 95% or more, and various uses of materials using various properties of carbon have been developed and produced. All hydrocarbon compounds generally known as raw materials for carbon materials can be used, but usually suitable hydrocarbon materials are selected depending on the requirements of the final product and the manufacturing cost.

As a typical carbon material, carbon fibers are classified into PAN (polyacrylonitrile), cellulose, pitch, and phenol resin based on the raw material. Among them, the pitch carbon fibers are classified into three types depending on the type of pitch, which is a precursor, ) Pitch-based carbon fibers and isotropic pitch-based carbon fibers.

The liquid crystal pitch-based carbon fibers are produced by using optically anisotropic liquid crystal pitch as a precursor, and isotropic pitch-based carbon fibers are produced by using optically isotropic isotropic pitch as a precursor. The mechanical properties of the carbon fiber indicate that general properties of low strength and low elasticity are exhibited by isotropic pitch based carbon fibers when the liquid crystal pitch carbon fibers generally show high strength and high elasticity.

However, since the application range of liquid crystal pitch-based carbon fibers is limited, such as ultra-high temperature materials, production of isotropic pitches for producing general-purpose carbon fibers is further demanded.

In recent years, researches are being actively conducted to utilize oil refining residues having a low elastic modulus and heat and electric conductivity at an isotropic pitch for carbon fibers at low cost. Among them, FCC-DO (fluidized catalytic cracking-decent oil) or PFO (pyrolysed fuel oil) as a raw material of petroleum hydrocarbon has a high degree of aromatization, a low content of sulfur and an incompatible component, needle coke, and artificial graphite.

However, when such raw materials of petroleum hydrocarbons are used without any pretreatment, there arises a problem that it is difficult to inhibit the generation of the infusible components and secure a high pitch yield. Therefore, in order to improve the physical properties of the carbon material, which is the final product, research on the raw material and the manufacturing process is further needed.

Korean Patent Registration No. 10-0244912 discloses a method of producing a high softening point optical isotropic pitch by using a petroleum hydrocarbon as a halogen and a halogenated compound as a prior art. In the prior art, alkyl group charge reaction of petroleum hydrocarbons is initiated by substitution and condensation of halogen at 231 to 300 ° C. However, since this pretreatment process proceeds at a high temperature of 230 ° C. or higher, It is expected that the reaction stability due to the distillation reaction of the scaffold residue is lowered and the low molecular weight cyclic hydrocarbon is lost and also the halogenated acid which is a strong acid is generated as a byproduct of the reaction.

(Prior art 1) Korean Patent Registration No. 10-0244912

Under such technical background, the present inventors have developed a process for producing an isotropic pitch that includes a step of pretreating a petroleum hydrocarbon through a radical crosslinking reaction.

Accordingly, an object of the present invention is to provide a pretreatment method of a petroleum hydrocarbon for improving the physical properties of a carbonaceous material produced by suppressing the formation of an infusible component and securing a high carbonization yield. The petroleum hydrocarbon, peroxide, And a step of heat treating the mixed mixture by charging an oxidizing gas to the resulting mixture to thereby improve the viscosity and molecular weight of the petroleum hydrocarbon.

According to an aspect of the present invention, there is provided a method of preparing a fuel cell, comprising the steps of: pre-treating a mixture of a petroleum hydrocarbon and a peroxide compound with an oxidizing gas; Treating the pretreated petroleum hydrocarbons; And removing the low boiling point material from the result of the step.

According to an embodiment of the present invention, the flowability of the petroleum hydrocarbon may be improved through a process for producing an isotropic pitch including a step of pretreating the petroleum hydrocarbon through a radical crosslinking reaction, thereby suppressing the formation of the infusible component , A high softening point and an isotropic pitch of high carbonization yield can be produced with high yield.

Figure 1 shows a flow of a method in which an isotropic pitch is produced in accordance with an embodiment of the present invention.
Figure 2 shows the results of radical crosslinking of pretreated petroleum hydrocarbons according to one embodiment of the present invention.
3 is a schematic view of a reactor according to an embodiment of the present invention.
Figure 4 illustrates the change in heat treated petroleum hydrocarbons according to one embodiment of the present invention.

Certain terms are hereby defined for convenience in order to facilitate a better understanding of the present invention. Unless otherwise defined herein, scientific and technical terms used in the present invention shall have the meanings commonly understood by one of ordinary skill in the art. Also, unless the context clearly indicates otherwise, the singular form of the term also includes plural forms thereof, and plural forms of the term should be understood as including its singular form.

Furthermore, the term "and / or" as used throughout this specification includes any and all combinations of any of the listed items. The word " comprise "and / or" comprising "as used herein specify the presence of stated shapes, numbers, steps, operations, elements, elements, and / , But does not preclude the presence or addition of other features, numbers, operations, elements, elements and / or groups.

Also, terms including ordinal numbers such as first, second, etc. may be used to describe various elements, but the constituent elements are not limited by such terms. These terms are used only to distinguish one component from another.

According to an aspect of the present invention, there is provided a method for producing a petroleum-based hydrocarbon, comprising the steps of: (a) pre-treating an oxidizing gas into a mixture of a petroleum hydrocarbon and a peroxide compound; (b) heat treating the pretreated petroleum hydrocarbons; And (c) obtaining an isotropic pitch by removing low boiling points from the result of step (b) (see FIG. 1).

First, step (a) of pre-treating an oxidizing gas with a mixed mixture of the petroleum hydrocarbon and the peroxide compound will be described in detail.

According to one embodiment of the present invention, the petroleum hydrocarbon used as a carbon source for producing an isotropic pitch may have an API (American Petroleum Institute) specific gravity less than 34. [ The specific gravity of the API is a value indicating the specific gravity of the crude oil. In general, when the API specific gravity is 34 or more, it is classified as light crude oil. When the API specific gravity is 24 to 34, middle crude oil, If it is 24 or less, it is classified as heavy crude oil.

In one embodiment, the petroleum hydrocarbon is selected from the group consisting of middle crude oil, heavy crude oil, naphtha cracking residues, pyrolyzed fuel oil (PFO) And may include at least one selected from catalytic cracking-decant oil (FCC-DO).

Here, the residual oil of naphtha cracking bottom oil (NCB oil) may include pyrolyzed fuel oil (PFO). The pyrolysis fuel oil (PFO) is produced at the bottom of a naphtha cracking center (NCC) and has a high degree of aromatization and a rich resin content.

The pyrolysis fuel oil (PFO) contains various aromatic hydrocarbons, and about 25 to 35% of naphthalene and / or methylnaphthalene derivatives are contained therein. Examples of the naphthalene and / or methylnaphthalene derivatives include ethylbenzene, 1-ethenyl-3-methylbenzene, indene, 1-ethyl- 1-ethyl-3-methylbenzene, 1-methylethylbenzene, 2-ethyl-1,3-dimethylbenzene, propylbenzene, Methyl-4- (2-propenyl) benzene, 1,1a, 6,6a- tetrahydro-cyclopropane (1,1a, 6,6- , 6a-tetrahydro-cycloprop [a] indene, 2-ethyl-1H-indene, 1-methyl- Dimethyl-1H-indene, 1-methyl-9H-Fluorene, 1,7-dimethyl naphthalene, 2-methylindene, 4,4'-dimethylbiphenyl, naphthalene, 4-methyl-1,1'-biphenyl (4- methyl-1,1'-biphenyl, anthracene, 2-methylnaphthalene, Or 1-methylnaphthalene, but the present invention is not limited thereto.

In one embodiment, the method may further comprise removing the low boiling point product from the petroleum hydrocarbon before the step (a). Since most of the low-boiling point volatiles do not participate in the reaction, they are unsuitable for use as raw materials for carbon materials. The low-boiling point water may be at least one selected from, for example, C ₄ to C ₂₀ hydrocarbons.

As described above, the low-boiling point water can be removed from the petroleum hydrocarbon beforehand, but the low boiling point water can be removed by the step (c). In addition, the low-boiling point water may be removed through the continuous heat treatment in the step (c).

In one embodiment, the peroxide-based compound serves as a radical initiator. The peroxide compound preferably generates a radical, preferably a hydroxyl radical, through a homogeneous decomposition reaction under the pretreatment conditions of the step (a).

The peroxide-based compound may be any compound containing at least one peroxide group. The peroxide compound includes mono-or bis-peroxide.

The peroxide compound may be present in the form of a mixture with the petroleum-based hydrocarbon as a mixture, and may be provided as a mixture, but may be provided as an inorganic support such as clay or silica, a polymeric support such as EPDM or any mixture of the supports have. For example, as will be described later, the peroxide compound can be used by being supported on the beads filled in the reactor into which the petroleum hydrocarbon is charged and the oxidizing gas is charged.

When the peroxide compound is mixed with the petroleum hydrocarbon to provide the mixture, the peroxide compound may be dispersed in the petroleum hydrocarbon.

Examples of the peroxide compound include, but are not limited to, hydroperoxide compounds, alkyl peroxide compounds, cyclic peroxide compounds, acyl peroxide compounds, ketone peroxide compounds, alkyl acyl peroxide compound, And more specifically, dicumylperoxide (DCP), hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like. t-butyl hydroperoxide, methylethylketone peroxide, and any mixture thereof.

In one embodiment, the mixture in step (a) may be produced by mixing 5 to 50 parts by weight of the peroxide compound per 100 parts by weight of the petroleum hydrocarbon.

Here, when the peroxide compound is mixed at less than 5 parts by weight per 100 parts by weight of the petroleum hydrocarbon, the amount of radicals generated as a result of the pretreatment in the step (a) is small and the desired viscosity of the petroleum hydrocarbon It may be difficult to obtain the effect of improving the molecular weight. On the other hand, when the peroxide compound is mixed in an amount of more than 50 parts by weight per 100 parts by weight of the petroleum hydrocarbon, a sufficient amount of radicals may be produced as a result of the pretreatment in the step (a), but rather an excessive radical crosslinking reaction And an insoluble component (for example, a quinoline insoluble (QI)) may be generated by oxidation of the petroleum hydrocarbon.

In one embodiment, the oxidizing gas used in step (a) may be at least one selected from oxygen, ozone, and air. In another embodiment, the oxidizing gas may be charged with at least one inert gas selected from nitrogen, helium, neon, and argon.

At this time, the oxidizing gas partial pressure selected from the range of 5 g / m ² to 100 g / m ^2, preferably 10 g / m ² to 50 g / m ² on a mixed gas of the oxidizing gas and the inert gas .

Here, when the oxidizing gas (or the mixed gas of the oxidizing gas and the inert gas) is charged into the petroleum hydrocarbon at a partial pressure of less than 5 g / m ² , the radicals generated as a result of the pretreatment in the step (a) The effect of improving the viscosity and molecular weight of the petroleum hydrocarbons may be difficult to obtain. On the other hand, when the oxidizing gas (or the mixed gas of the oxidizing gas and the inert gas) is charged into the petroleum hydrocarbon at a partial pressure exceeding 100 g / m ² , sufficient radicals are obtained as a result of the pretreatment in the step (a) But may cause an oxidation reaction, and an insoluble component (for example, a quinoline insoluble (QI)) may be generated due to the oxidation of the petroleum hydrocarbons.

In one embodiment, the pretreatment of step (a) may be performed at a temperature selected from the range of 50 to 200 ° C. If the pretreatment temperature is less than 50 ° C, it may be impossible for the peroxide compound to generate radicals, preferably hydroxyl radicals, through the homogeneous decomposition reaction regardless of whether the oxidizing gas is charged or not . On the other hand, when the pretreatment temperature is higher than 200 ° C, termination of the radical crosslinking reaction may occur and it may be difficult to obtain the desired viscosity and molecular weight improving effect of the petroleum hydrocarbon.

The pretreatment of step (a) may be performed simultaneously with the charging of the oxidizing gas into the mixture, but may be performed after the charging of the oxidizing gas with the mixture is completed.

In one embodiment, the pretreatment time of step (a) may be performed for a time period selected from the range of 5 minutes to 120 minutes, preferably 5 minutes to 30 minutes. If the pretreatment time is less than 5 minutes, it may be difficult to obtain the desired viscosity and molecular weight improving effect of the petroleum hydrocarbon because the amount of radicals generated as a result of the pretreatment in the step (a) is small. On the other hand, if the pretreatment time exceeds 120 minutes, solidification due to agglomeration between petroleum hydrocarbons may be caused by an excessive radical crosslinking reaction.

When the petroleum hydrocarbons and / or the solidified petroleum hydrocarbons containing an incompatible component are provided in a heat treatment step to be described later, the yield of final pitch and the yield of carbonization can be drastically reduced. Also, when the petroleum hydrocarbons in which sufficient modification (viscosity and molecular weight improvement) are not achieved in the heat treatment step to be described later, it may be difficult to obtain the aimed pitch yield and carbonation yield increasing effect.

According to the above-mentioned conditions, when the pretreatment is started in the step (a), a hydroxyl radical is formed by the reaction of the peroxide compound and the oxidizing gas in the mixture.

Wherein the hydroxyl radical forms a radical while removing the hydrogen atoms in the alkyl group of the petroleum hydrocarbon molecule and the radical initiates a crosslinking reaction and the petroleum hydrocarbon molecules cross- The viscosity and the molecular weight of the hydrocarbon are improved.

Here, the cross-linked hydrocarbon molecule has a sigma bond between the ring structure and the ring structure, and thus has a three-dimensional structure as compared with the two-dimensional ring structure. The sigma bond rotates 360 °, which means that the fluidity of the molecule has increased. In the case of conventional cyclic hydrocarbons, when heated, they aggregate to form solid matter such as coke by aromatic interactions due to van der Waals force, whereas cross-linked hydrocarbon molecules have a structure that is intermolecular steric hindrance steric hinderance) is induced, so that the coagulation phenomenon can be prevented.

Therefore, the improvement of the molecular fluidity of the crosslinked hydrocarbon suppresses the formation of an immiscible component (for example, quinoline insoluble (QI)) upon oxidation of the petroleum hydrocarbon (see FIG. 2).

In one embodiment, the mixture produced by mixing the petroleum hydrocarbon and the peroxide compound is injected into a reactor filled with a bead, and is contacted with the oxidizing gas charged in the reactor (See FIG. 3).

Non-limiting examples of the beads include glass, pyrex, quartz, silica or silicon carbide.

That is, the two-phase mixture produced by mixing the petroleum hydrocarbon and the peroxide compound is injected into a reactor filled with solid phase beads, and the gas phase ) Of oxidizing gas.

Therefore, in order to efficiently improve the viscosity and the molecular weight of the petroleum hydrocarbon, it is necessary to widen the contact area between the mixture and the oxidizing gas, which can be achieved by the beads filled in the reactor.

At this time, the injection direction of the mixture in the reactor and the charging direction of the oxidizing gas in the reactor may be con-ncurrent or counter-current.

For example, the mixture may be lowered in the reactor along the direction of gravity by being injected from the upper part of the reactor toward the lower part, and the oxidizing gas is charged into the reactor from the lower part of the reactor, Lt; RTI ID = 0.0 > diffusion < / RTI >

Here, the beads filled in the reactor serve to reduce the moving speed of the mixture and the oxidizing gas, and to maximize the contact area between the mixture and the oxidizing gas by widening the diffusion direction.

Maximizing the contact area of the mixture with the oxidizing gas is necessary to complete the radical crosslinking reaction between the petroleum hydrocarbon molecules within a short time.

That is, the method of improving the viscosity and molecular weight of petroleum hydrocarbons according to one embodiment of the present invention is different from the condensation reaction, and when the radical crosslinking reaction time between the petroleum hydrocarbon molecules is prolonged, excessive radical crosslinking reaction is caused (For example, a quinoline insoluble (QI)) may be generated due to the oxidation of the petroleum hydrocarbons.

Therefore, it is important to induce the radical crosslinking reaction between the petroleum hydrocarbon molecules contained in the mixture to be completed within a shortest possible time in order to obtain the effect of improving the viscosity and molecular weight of the petroleum hydrocarbon as the object of the present invention.

To this end, the packing density of the beads in the reactor may be asymmetric. The diffusion rate in the gas phase within a certain space is faster than the diffusion rate in the solid phase or the liquid phase. Thus, the degree of filling of the beads in the reactor may be different across the height direction of the reactor in order to balance diffusion rates between the different phases and to maximize the contact area.

For example, the packing density of the beads in the reactor may be lowered from the upper portion to the lower portion of the reactor. Accordingly, the mixture is injected into the reactor at a high packing density of the beads, and the oxidizing gas can be charged to a low packing density of the beads in the reactor.

At this time, as the mixture injected into the region (upper portion) of the reactor having a relatively dense packing density of beads flows in the gravity direction, the filling density of the relatively less dense beads after being appropriately diffused in the reactor The branch may be contacted with the oxidizing gas charged into the region (lower portion) of the reactor.

In order to control the packing density of the beads in the reactor, beads having a non-uniform diameter may be used. For example, the diameter of the beads filled in the reactor may be reduced from the top to the bottom of the reactor. On the contrary, the diameters of the beads filled in the reactor may become larger from the upper portion to the lower portion of the reactor.

The adjustment of the above-described injection or filling directions of the different phases, the filling density of the beads and / or the diameters of the beads described above can be achieved by balancing the diffusion rates between the different phases, And for the purpose of the present invention, it may be possible to set it as opposed to that described above.

As described above, the pretreatment of step (a) may be performed in the reactor. After the pretreatment is completed, unreacted gas and byproducts are removed from the reaction system, and the petroleum hydrocarbon is heat-treated in step (b) .

Hereinafter, the step (b) will be described in detail.

The step (b) is a step of condensing the pretreated petroleum hydrocarbons according to the step (a). More specifically, in the condensation step, naphthenic hydrocarbons are converted into aromatic hydrocarbons by heat treatment, and cracking of the aliphatic hydrocarbons is performed to increase the carbonization yield 4).

The heat treatment in step (b) may be performed at a temperature selected from the range of 340 ° C or higher, preferably 340 ° C to 400 ° C, more preferably 360 ° C to 380 ° C. Referring to the heat treatment condition of the step (b), the step (b) is clearly distinguished from the pretreatment of the step (a). That is, the pretreatment in the step (a) is a step of inducing a radical crosslinking reaction for modifying the petroleum hydrocarbon (viscosity and molecular weight), and the step (b) is a step for condensing the pretreated petroleum hydrocarbon . Therefore, the present invention is characterized in that the pretreatment temperature is kept lower than the heat treatment temperature in the step (b) to suppress the condensation between the petroleum hydrocarbons in the step (a).

If the heat treatment step is not accompanied by the step (b), the carbonization yield may be less than 40%, and if the heat treatment temperature is less than 340 ° C, the carbonization yield of the pitch may be less than 50% . On the other hand, when the heat treatment temperature is 340 ° C or higher, the carbonization yield of the pitch can be maintained at 50% or higher, and when the heat treatment temperature is 360 ° C, the pitch carbonization yield can reach 70%. That is, as the heat treatment temperature is increased, the carbonization yield of the pitch tends to increase. On the other hand, when the heat treatment temperature exceeds 400 ° C, the condensation reaction by the rapid cracking and / Termination and / or reactant loss can occur.

In one embodiment, the heat treatment time in step (b) may be performed for a selected time in the range of 5 minutes to 10 hours. When the heat treatment time is less than 5 minutes, the condensation reaction between the pretreated petroleum hydrocarbons is difficult to occur sufficiently. When the heat treatment time exceeds 10 hours, the condensation reaction between the petroleum hydrocarbons during the condensation reaction The possibility of causing a solidification phenomenon may increase.

As described above, the petroleum hydrocarbon preprocessed through the step (a) may be condensed by being heat-treated in the step (b). If the low boiling point product is used in a state in which the low boiling point product is not removed from the petroleum hydrocarbon before the step (a), or if it is used in an incompletely removed state, the low boiling point product is removed from the product of the step (b) .

Hereinafter, the step (c) will be described in detail.

The step (c) is a step of removing the low-boiling point product by distilling the resultant of the step (b) at a high temperature. More specifically, the step (c) includes: a first heat treatment step of collecting and removing low-boiling point substances in the vapor phase; And a second heat treatment step of controlling the softening point of the final product to a temperature selected from the range of 250 to 320 ° C. The first heat treatment step and the second heat treatment step may be performed sequentially.

The result of the step (b) is a liquid phase, and the resultant product generally contains about 30 to 60% of a low boiling point relative to the total weight. A low boiling point product having a relatively low boiling point is phase-shifted to a component of a gas phase through the first heat treatment step, and the low boiling point product of the vapor phase is separated from the product of the liquid phase And stored in a liquid state (gas-liquid separation). Then, in the second heat treatment step, the result of the liquid phase is thermally treated to control the softening point of the product, from which the low-boiling point product is primarily removed, to 250 to 320 ° C, preferably 270 to 290 ° C, . In one embodiment, the second heat treatment step may be performed through a thin film distillation apparatus under vacuum conditions.

In one embodiment, the heat treatment of step (c) may be performed at a temperature selected from the range of 300 to 400 ° C. If the heat treatment temperature is less than 300 ° C, it may be difficult to sufficiently remove the low boiling point product from the result of the step (b). If the heat treatment temperature exceeds 400 ° C, rapid cracking and / Termination of the condensation reaction by the reaction and / or problems of reactant loss may occur.

In addition, the heat treatment time of the step (c) for removing the low boiling point water may be performed for a time period selected from the range of 30 minutes to 10 hours, which can be appropriately adjusted according to the degree of inclusion of the low boiling point water.

The pitch produced according to one embodiment of the present invention is optically isotropic. In addition, the incompatible component (for example, quinoline insoluble (QI)) included in the pitch may be contained in an amount of 5 wt% or less, and preferably the pitch substantially contains the incompatible component I can not.

Hereinafter, the present invention will be described in more detail with reference to Examples. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention.

Example

One. Isotropic  Manufacturing method of pitch

Example  1-4

A mixture of pyrolysis fuel oil (PFO) and hydrogen peroxide is mixed to produce a mixture. The mixture is injected into an upper part of a reactor filled with beads. Oxygen (O ₃ ) gas Was pre-treated at a partial pressure of 25.8 g / m ² or 12.9 g / m ² . The pretreatment was carried out at a temperature of 120 캜 for 15 minutes.

After the pre-treatment was completed, nitrogen gas was passed through the reactor at a flow rate of 2 L / min for a predetermined time to remove unreacted gases and by-products (low reactants). Thereafter, the pretreated pyrolysis fuel oil (PFO) was subjected to heat treatment at 360 ° C for 1 hour for condensation reaction, and then vacuum distillation was performed to remove low boiling point products to produce an isotropic pitch having a softening point of 270 to 290 ° C.

The manufacturing method according to Examples 1 to 4 is briefly summarized in Table 1 below.

Feed flow
(ml / min) Hydrogen peroxide / PFO Pretreatment temperature
(° C) ozone
(g / m ² ) Reaction temperature
(° C) Example 1 100 1/9 120 25.8 360 Example 2 50 1/9 120 12.9 360 Example 3 100 1/5 120 25.8 360 Example 4 50 1/5 120 25.8 360

Comparative Example  1-3

In Comparative Example 1, pyrolysis fuel oil (PFO) was injected into the reactor and then pretreated in a nitrogen atmosphere at 120 ° C for 10 minutes. After the pretreatment, the isotropic pitch was prepared in the same manner as in Example. Comparative Example 2 was carried out in the same manner as in Example except that ozone (O ₃ ) gas was not charged into the reactor. In Comparative Example 3, all reactions except the condensation reaction temperature (330 ° C) were carried out in the same manner as in Example.

The manufacturing method according to Comparative Examples 1 to 3 is briefly summarized in Table 2 below.

Feed flow
(ml / min) Hydrogen peroxide / PFO Pretreatment temperature
(° C) ozone
(g / m ² ) Reaction temperature
(° C) Comparative Example 1 100 0 120 0 360 Comparative Example 2 100 1/9 120 0 360 Comparative Example 3 100 1/5 120 25.8 330

2. Manufactured Isotropic  Evaluation of physical properties of pitch

The measurement results of the QI content, the hydrocarbon yield, the pitch softening point and the pitch yield of the isotropic pitches obtained in Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 3 below.

QI
(%) Carbonization yield
(%) Pitch softening point
(° C) Pitch yield
(%) Example 1 0 72 280 25 Example 2 0 72 280 25 Example 3 0 72 280 34 Example 4 0.5 72 280 45 Comparative Example 1 6 73 280 19 Comparative Example 2 5 73 280 19 Comparative Example 3 4 53 280 24

It was confirmed that the isotropic pitches of the isotropic pitches obtained by the above Examples 1 to 4 and Comparative Examples 1 to 3 were all 280 ° C, which is a high softening point. In addition, it was confirmed that, except for Comparative Example 3, all of the carbonization yields were 70% or more.

However, as a result of measuring the content of QI as an immiscible component, it was confirmed that substantially all of the immiscible components in the pitch were removed in Examples 1 to 4, but according to Comparative Examples 1 to 3, the QI content 4 to 6%, and it was confirmed that a considerably large amount of the immiscible component in the pitch was not removed.

In Examples 1 to 4, the pitch yield was 25% or more, and in Examples 3 and 4, the pitch yield was 34% and 45%, respectively, which was much higher than the pitch yields of Comparative Examples 1 to 3 .

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention as set forth in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.

Claims (20)

(a) pre-treating a mixture of a petroleum hydrocarbon and a peroxide compound with an oxidizing gas;
(b) heat treating the pretreated petroleum hydrocarbons; And
(c) removing the low boiling point product from the product of step (b)
In the step (a), a hydroxyl radical is generated by the reaction of the peroxide compound and the oxidizing gas in the mixture, and the hydroxyl radical initiates the radical crosslinking reaction between the petroleum hydrocarbon ,
Method of manufacturing isotropic pitch.
The method according to claim 1,
Wherein the petroleum hydrocarbon has an API (American Petroleum Institute) specific gravity of less than 34.
The method according to claim 1,
The petroleum hydrocarbon may be at least one selected from the group consisting of middle crude oil, heavy crude oil, naphtha cracking residual oil, pyrolyzed fuel oil (PFO) and fluidized catalyst decomposition-decanter oil and a fluidized catalytic cracking-decant oil (FCC-DO).
The method according to claim 1,
Further comprising the step of removing the low-boiling point product from the petroleum hydrocarbon before the step (a).
The method according to claim 1,
The peroxide compound may be at least one selected from the group consisting of dicumylperoxide (DCP), hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide ) And methylethylketone peroxide. ≪ RTI ID = 0.0 > 11. < / RTI >
The method according to claim 1,
Wherein the mixture is produced by mixing 5 to 50 parts by weight of the peroxide compound per 100 parts by weight of the petroleum hydrocarbon.
The method according to claim 1,
Wherein the oxidizing gas is at least one selected from oxygen, ozone, and air.
8. The method of claim 7,
Wherein the oxidizing gas is charged with at least one inert gas selected from nitrogen, helium, neon and argon.
8. The method of claim 7,
Wherein the oxidizing gas is charged at a partial pressure selected from the range of 5 g / m ² to 100 g / m ² .
The method according to claim 1,
Wherein the pretreatment of step (a) is performed at a temperature selected from the range of 50 to 200 ° C.
delete The method according to claim 1,
Wherein the mixture is injected into a reactor filled with beads and brought into contact with the oxidizing gas charged in the reactor.
13. The method of claim 12,
Wherein the mixing direction of the mixture and the loading direction of the oxidizing gas are the same or opposite directions to each other.
13. The method of claim 12,
Wherein the mixture is injected from the upper part of the reactor toward the lower part and the oxidizing gas is charged from the lower part of the reactor toward the upper part.
13. The method of claim 12,
Wherein the packing density of the beads in the reactor is asymmetric.
16. The method of claim 15,
Wherein the packing density of the beads in the reactor is lowered from the upper portion to the lower portion of the reactor.
17. The method of claim 16,
Wherein the mixture is injected into the reactor at a high filling density of the beads and the oxidizing gas is charged to a low packing density of the beads in the reactor.
The method according to claim 1,
Wherein the heat treatment in step (b) is performed at a temperature selected from the range of 340 to 400 ° C.
The method according to claim 1,
Wherein the step (c) comprises at least one heat treatment step performed at a temperature selected from the range of 300 to 400 ° C.
20. The method of claim 19,
The step (c) may include: a first heat treatment step of collecting and removing the low-boiling point vapor phase; And
And a second heat treatment step of controlling the softening point of the final product to a temperature selected from the range of 250 to 320 ° C.

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