KR20230071410A - Petroleum-based impregnated pitch manufacturing method and petroleum-based impregnated pitch manufactured using the same - Google Patents

Abstract

The present invention is a method for producing petroleum-based impregnated pitch in which mixed petroleum-based raw materials are subjected to any one or more of heat treatment, pressure treatment, and halogen gas treatment using a high-temperature thin-film distillation apparatus to obtain impregnated pitch, It is possible to produce petroleum-based impregnated pitch having a high yield and softening point for improved efficiency.

Description

Petroleum-based impregnated pitch manufacturing method and petroleum-based impregnated pitch manufactured using the method {Petroleum-based impregnated pitch manufacturing method and petroleum-based impregnated pitch manufactured using the same}

The present invention relates to a method for manufacturing petroleum-based impregnated pitch, and more particularly, to a method for manufacturing petroleum-based impregnated pitch capable of obtaining impregnated pitch in high yield using a specific petroleum-based raw material, and to a petroleum-based impregnated pitch produced through the same will be.

BACKGROUND OF THE INVENTION Here, background art related to the present disclosure is provided, and they are not necessarily meant to be prior art.

In general, petroleum-based low-grade raw materials (PFO, NCB-Oil, FCC-DO, VR, etc.) are obtained as by-products of the petroleum refining process, and are mostly used as fuel for ships and power plants at low prices due to their low utility value, but are rich in aromatic compounds. Since it contains , it is easy to form a carbon structure, so various high value-added application researches are being conducted.

Impregnated pitch is a raw material for impregnation processing to increase density and strength in the manufacture of artificial graphite-based refractories and carbon moldings, and has a lower viscosity (high flowability), lower molecular weight distribution, and lower quinoline insoluble content (QI, quinoline) than binder pitch. It refers to pitch having components that are not soluble in

Binder pitch is used as a raw material in the manufacture of artificial graphite, carbon molded body, graphite molded body, etc., and is mixed with coke or carbon powder to improve bonding strength, such as injection, extrusion, molding press molding and cold isostatic pressing, HIP A molded body can be manufactured by a method such as molding.

When a carbon molded body (live electrode body, green body) manufactured (molded) from coke or graphite powder and binder pitch is heat-treated, some organic materials are vaporized to create micropores inside the molded body, and these micropores have excellent electrical conductivity. And it adversely affects the physical properties of electrodes and materials for high temperatures that require mechanical strength. Therefore, when a carbon molded article is manufactured through a process of reducing pores through several impregnation and re-carbonization processes using binder pitch and impregnation pitch, a carbon molded article having desirable physical properties can be manufactured.

Conventionally, coal-based raw materials such as coal tar have been widely used as raw materials for producing pitch for impregnation. Patent Document 1 (Korean Patent Registration No. 1988-0001542) discloses a method for producing improved coal tar pitch having a low solids content by oxidizing coal tar distillate at high temperature using air or oxygen, and information on the resulting coal tar pitch for impregnation. is presenting However, pitch for impregnation manufactured based on coal-based raw materials such as coal tar has a problem in that it exhibits a high QI value.

On the other hand, conventional petroleum-based pitch may have a lower QI value than coal-tar (coal-based) pitch, but due to the low carbonization yield (carbon yield, fixed carbon, coking value, carbon residue, caking value, fixed carbon, etc.), the impregnation process It is difficult to apply. Patent Document 2 (Korean Registered Patent No. 10-1916392) is a high-quality petroleum-based material having a significantly lower QI value than existing coal-based raw materials by manufacturing impregnated pitch using a heat treatment-based pitch polymerization method designed based on changes in process conditions of temperature and pressure. The contents of manufacturing the impregnated pitch are presented. However, petroleum-based raw materials contain high aliphatic components and have a high low-boiling component ratio compared to coal-based raw materials, and thus have a problem of showing a low yield during heat treatment (sintering, carbonization, etc.) at high temperatures.

The present invention is to provide a petroleum-based impregnated pitch manufacturing method that can obtain impregnated pitch in high yield using a specific petroleum-based raw material in order to solve the above problems, and a petroleum-based impregnated pitch produced through this.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned will be clearly understood by those skilled in the art from the description below.

The present invention provides a petroleum-based impregnated pitch manufacturing method for obtaining impregnated pitch through at least one treatment of heat treatment, pressure treatment, and halogen gas treatment using a mixed petroleum-based raw material using a high-temperature thin film distillation apparatus.

In addition, the mixed petroleum-based raw materials include pyrolyzed fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene cracker bottom oil (EBO), vacuum residue , VR), at least one first petroleum-based raw material selected from the group consisting of de-asphalted oil (DAO), atmospheric residue (AR), and heavy aromatic oil; And at least one second petroleum-based raw material selected from the group consisting of FCC-DO (Fluid catalytic cracking decant oil) and RFCC-DO (Residue fluid catalytic cracking decant oil).

In addition, the mixed petroleum-based raw material is characterized by including 70 to 90 wt% of the first petroleum-based raw material and 10 to 30 wt% of the second petroleum-based raw material.

In addition, the heat treatment is characterized in that it is a method of treating for 1 hour to 3 hours at 360 ℃ to 390 ℃ under normal pressure conditions in an inert gas atmosphere.

The pressure treatment is characterized in that it is a method of treatment at 370 ° C. to 400 ° C. for 150 to 200 minutes under conditions of 20 to 30 Bar under an inert gas atmosphere.

The halogen gas treatment is characterized by treating 5 to 15% of halogen gas at 160 to 200 ° C. for 50 to 80 minutes.

When using the impregnated pitch manufacturing method according to the present invention, it is possible to manufacture impregnated pitch having a high yield and softening point for improving the efficiency of the impregnation process from petroleum-based raw materials. Therefore, when the impregnation process is applied to the carbon molded body using the impregnation pitch according to the present invention, micropores inside the molded body can be significantly reduced, and a carbon molded body having excellent electrical conductivity and mechanical strength can be manufactured.

All technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art unless otherwise specified. Also throughout this specification and claims, the terms "comprise", "comprising", and "comprising", unless stated otherwise, are meant to include a stated object, step or group of objects, and steps, and any other It is not intended to exclude an object, step or group of objects or steps.

Prior to describing the present invention in detail below, it is understood that the terms used herein are intended to describe specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the appended claims. shall.

On the other hand, various embodiments of the present invention can be combined with any other embodiments unless clearly indicated to the contrary. Any feature indicated as being particularly desirable or advantageous may be combined with any other features and characteristics indicated as being particularly desirable or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

Petroleum-based impregnated pitch manufacturing method according to an embodiment of the present invention is a petroleum-based raw material using pyrolyzed fuel oil (PFO), naphtha cracking bottom oil (NCB), and ethylene cracker bottom oil (EBO), vacuum residue (VR), de-asphalted oil (DAO), atmospheric residue (AR), FCC-DO (Fluid catalytic cracking decant oil), RFCC It is characterized in that it is manufactured using a mixed petroleum-based raw material in which at least two or more kinds from the group consisting of -DO (residue fluid catalytic cracking decant oil) and heavy aromatic oil are mixed.

The mixed petroleum-based raw material is preferably pyrolyzed fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene cracker bottom oil (EBO), vacuum residue ( At least one type of primary petroleum oil selected from the group consisting of vacuum residue (VR), de-asphalted oil (DAO), atmospheric residue (AR), and heavy aromatic oil. Raw material; and at least one second petroleum-based raw material selected from the group consisting of FCC-DO (Fluid catalytic cracking decant oil) and RFCC-DO (Residue fluid catalytic cracking decant oil).

The mixed petroleum-based raw material includes 70 to 90 wt% of the first petroleum-based raw material and 10 to 30 wt% of the second petroleum-based raw material. Most preferably, it is good to include pyrolyzed fuel oil (PFO) as the first petroleum-based raw material, and FCC-DO (Fluid catalytic cracking decant oil) as the second petroleum-based raw material.

Impregnated pitch is obtained by subjecting the mixed petroleum-based raw material to at least one of heat treatment, pressure treatment, and halogen gas treatment. Heat treatment and halogen gas treatment are performed in a reactor, and pressure treatment is performed in an autoclave. Subsequently, when the softening point is low, high-temperature (240 ° C. to 270 ° C.) thin film distillation using a high-temperature thin-film distillation apparatus can be performed to obtain impregnated pitch with an increased softening point. Preferably, high-temperature thin-film distillation after halogen gas treatment and heat treatment can increase the softening point while yield is high.

The high-temperature thin-film distillation apparatus includes a raw material inlet at the top of which liquid mixed petroleum-based raw material flows, and a cylindrical housing in which a rotating shaft is installed in the inner center; a heater for heating the inside of the housing; a driving motor generating a driving force to rotate the rotating shaft; a distribution plate installed inside the housing to distribute and transfer the liquid raw material introduced into the housing toward the inner circumferential surface of the housing; and a scraper assembly installed inside the housing to form a thin film from the liquid raw material flowing down along the inner circumferential surface of the housing while rotating corresponding to the rotating shaft.

The heat treatment is a method of treating at 360° C. to 390° C. for 1 hour to 3 hours under normal pressure conditions under an inert gas atmosphere. Preferably, heat treatment is performed at 370°C to 380°C.

The pressure treatment is a method of treating for 150 to 200 minutes at 370 ° C to 400 ° C under conditions of 20 to 30 Bar under an inert gas atmosphere. The inert gas includes nitrogen (N ₂ ), helium (He), neon (Ne), argon (Ar), and a mixed component gas thereof, preferably argon gas.

The halogen gas treatment is a method of treating 5 to 15% of halogen gas at 160 to 200 ° C. for 50 to 80 minutes. The halogen gas includes fluorine, chlorine, bromine, iodine, and mixtures thereof, and preferably includes chlorine gas.

Examples and experimental examples

(1) Preparation of mixed petroleum-based raw materials

Petroleum-based raw materials mixed in a composition (weight ratio) as shown in Table 1 below were prepared.

Petroleum raw material PFO FCC-DO mix 1 100 - mix 2 90 10 mix 3 80 20 mix 4 70 30 mix 5 50 50

(2) heat treatment

The yield and softening point of the impregnated pitch obtained by heat-treating the mixed petroleum-based raw material under the same conditions as shown in Table 2 below are shown in Table 2 below. As shown in Table 2 below, the yield decreased as the reaction temperature increased, and the softening point tended to increase. In addition, the higher the ratio of slurry oil, the higher the yield and the lower the softening point.

Petroleum raw material heat treatment reaction temperature
(℃) reaction time
(h) transference number
(%) softening point
(℃) 1-1 mix 1 390 One 38.7 101 1-2 mix 2 360 One 41.7 59 1-3 mix 2 370 One 37.4 78 1-4 mix 2 380 One 35.2 86 1-5 mix 2 390 One 32.9 124 1-6 mix 3 360 One 44.5 53 1-7 mix 3 370 One 44.8 58 1-8 mix 3 380 One 41.4 78 1-9 mix 3 390 One 37.2 101 1-10 mix 4 360 One 52.1 35 1-11 mix 4 370 One 49.8 51 1-12 mix 4 380 One 48.3 57 1-13 mix 4 390 One 43.9 60

(3) Heat treatment after pressure treatment

The yield, softening point and carbonization yield of impregnated pitch obtained by treatment at 25 bar and 390 ° C. for 3 hours under an inert gas (N ₂ ) atmosphere and then heat treatment at 390 ° C. for 1 hour or 3 hours are shown in Table 3 below.

Petroleum raw material heat treatment time
(h) transference number
(%) softening point
(℃) carbonization yield
(%) 2-1 mix 2 One 54.9 40 - 2-2 mix 3 3 51.8 95 32.63 2-3 mix 4 One 62.1 44 -

(4) Pressure treatment, heat treatment after halogen gas treatment

Yield, softening point and carbonization yield of impregnated pitch obtained by treatment at 25 bar and 390 ° C for 3 hours under an inert gas (N ₂ ) atmosphere, treatment with 10% chlorine gas at 165 ° C for 1 hour, and heat treatment at 390 ° C for 3 hours are shown in Table 4 below.

Petroleum raw material heat treatment time
(h) transference number
(%) softening point
(℃) carbonization yield
(%) 3-1 mix 3 3 51.9 197 44.92 3-2 mix 5 3 62.6 135 36.40

(5) Heat treatment after halogen gas treatment

The yield, softening point, and carbonization yield of the impregnated pitch obtained by treating 10% chlorine gas at 165 ° C. for 1 hour and heat treatment at 390 ° C. for 1 hour or 3 hours are shown in Table 5 below.

Petroleum raw material heat treatment time
(h) transference number
(%) softening point
(℃) carbonization yield
(%) 4-1 mix 3 3 51.8 109.6 37.48 4-2 mix 4 One 54.9 52 - 4-3 mix 5 3 62.1 92 31.20

(6) High Temperature Thin Film Distillation (TLE)

The yield, softening point, and carbonization yield of impregnated pitch obtained by high-temperature thin-film distillation of the raw material pitch obtained by heat treatment after the heat treatment or halogen gas treatment are shown in Table 6 below. As shown in Table 6 below, it was found that the softening point was increased when high-temperature thin-film distillation was performed. In addition, it can be seen that as the ratio of the slurry oil increases, the softening point decreases and the range of yield increases, and as the reaction temperature increases, the range of variation of the softening point and yield increases.

raw pitch high temperature thin film distillation TLE temperature
(℃) TLE yield
(%) softening point
(℃) carbonization yield
(%) 5-1 1-3 240 84.7 130 31.13 5-2 250 85.7 133 34.31 5-3 260 80.9 139 32.55 5-4 270 79.5 146 32.31 5-5 1-4 240 83.9 109 27.71 5-6 250 81.8 113 29.37 5-7 260 77.4 121 30.56 5-8 270 73.9 130 29.41 5-9 1-7 240 82.2 93 21.45 5-10 250 80.0 99 27.63 5-11 260 75.7 103 26.33 5-12 270 67.9 123 30.07 5-13 4-1 240 84.87 146 33.22 5-14 250 82.52 150 33.71 5-15 260 78.35 159 37.01 5-16 270 79.90 165 37.15 5-17 4-2 240 84.28 114.3 30.42 5-18 250 82.49 121.5 30.32 5-19 260 80.12 127.6 32.58 5-20 270 72.51 150 36.03 5-21 1-12 240 83.84 91.5 27.86 5-22 250 78.09 98.8 TBD 5-23 260 72.14 107 TBD 5-24 270 68.45 116.9 TBD

The features, structures, effects, etc. illustrated in each of the above-described embodiments can be combined or modified with respect to other embodiments by those skilled in the art in the field to which the embodiments belong. Therefore, contents related to these combinations and variations should be construed as being included in the scope of the present invention.

Claims (3)

It is a petroleum-based impregnated pitch manufacturing method in which mixed petroleum-based raw materials are subjected to any one or more of heat treatment, pressure treatment, and halogen gas treatment using a high-temperature thin film distillation apparatus to obtain impregnated pitch,
The mixed petroleum-based raw materials include pyrolyzed fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene cracker bottom oil (EBO), vacuum residue, At least one first petroleum-based raw material selected from the group consisting of VR), de-asphalted oil (DAO), atmospheric residue (AR), and heavy aromatic oil; And at least one second petroleum-based raw material selected from the group consisting of FCC-DO (Fluid catalytic cracking decant oil) and RFCC-DO (Residue fluid catalytic cracking decant oil). Method for manufacturing impregnated pitch.
According to claim 1,
The mixed petroleum-based raw material comprises 70 to 90 wt% of the first petroleum-based raw material and 10 to 30 wt% of the second petroleum-based raw material.
According to claim 1,
The heat treatment is a method of treating at 360 ° C. to 390 ° C. for 1 hour to 3 hours under normal pressure conditions under an inert gas atmosphere,
The pressure treatment is a method of treating for 150 to 200 minutes at 370 ° C to 400 ° C under conditions of 20 to 30 Bar under an inert gas atmosphere,
The halogen gas treatment is a petroleum-based impregnated pitch manufacturing method, characterized in that a method of treating 5 to 15% of halogen gas at 160 to 200 ° C. for 50 to 80 minutes.