Method for producing impregnated pitch from petroleum-based raw material and impregnated pitch produced thereby

Abstract

The present invention relates to a method for producing an impregnated pitch from a petroleum-based raw material and to an impregnated pitch produced using the same, and when the method for producing an impregnated pitch according to the present invention is used, it is possible to produce an impregnated pitch having a high carbonization yield (40 wt % or more) and low quinoline insoluble matter (QI, 2% or less) for improving efficiency of an impregnation process from a petroleum-based raw material. Therefore, when an impregnation process is applied to a carbon compact by using the impregnated pitch according to the present invention, it is possible to remarkably reduce micropores inside the carbon compact, and to produce a carbon compact having physical properties such as excellent electrical conductivity and mechanical strength.

Claims

1. A method for producing an impregnated pitch comprising the following steps: heat-treating a petroleum-based raw material in an inert gas atmosphere under the pressure of 1040 bar (step 1); heat-treating the petroleum-based raw material which had been heat-treated in step 1 at normal pressure (step 2); and distillating the petroleum-based raw material which had been heat-treated in step 2 under reduced pressure (step 3).

2. The method for producing an impregnated pitch according to claim 1, wherein the heat-treatment in step 1 is performed in a temperature range of 300 C. to 450 C.

3. The method for producing an impregnated pitch according to claim 1, wherein the heat-treatment in step 1 is performed for 0.510 hours.

4. The method for producing an impregnated pitch according to claim 1, wherein the heat-treatment in step 2 is performed in a temperature range of 300 C. to 450 C.

5. The method for producing an impregnated pitch according to claim 1, wherein the heat-treatment in step 2 is performed for 0.510 hours.

6. The method for producing an impregnated pitch according to claim 1, wherein the distillation under reduced pressure in step 3 is performed in a temperature range of 100 C. to 250 C.

7. The method for producing an impregnated pitch according to claim 1, wherein the distillation under reduced pressure in step 3 is performed for 0.510 hours.

8. The method for producing an impregnated pitch according to claim 1, wherein the inert gas is one or more gases selected from the group consisting of nitrogen, helium, neon or argon.

9. The method for producing an impregnated pitch according to claim 1, wherein the petroleum-based raw material is one or more materials selected from the group consisting of pyrolyzed fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene cracker bottom oil (EBO), vacuum residue (VR), de-asphalted oil (DAO), atmospheric residue (AR), FCC-DO (fluid catalytic cracking decant oil), RFCC-DO (residue fluid catalytic cracking decant oil) and heavy aromatic oil.

Description

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) Hereinafter, the present invention is described in detail.

(2) The present invention provides a method for producing an impregnated pitch comprising the following steps:

(3) heat-treating a petroleum-based raw material in an inert gas atmosphere under the pressure of 1040 bar (step 1);

(4) heat-treating the petroleum-based raw material which had been heat-treated in step 1 at normal pressure (step 2); and

(5) distillating the petroleum-based raw material which had been heat-treated in step 2 under reduced pressure (step 3).

(6) Hereinafter, the method for producing an impregnated pitch is described in more detail step by step.

(7) First, step 1 is to heat-treat a petroleum-based raw material in an inert gas atmosphere under a high-pressure condition.

(8) The purpose of this step is to induce cracking of a petroleum-based low grade raw material component. The petroleum-based low grade raw material used as a raw material in this invention is a mixture composed of polyaromatic hydrocarbons, so that it is easy to generate insoluble matters having cokes and crystals in a high temperature heat treatment process. Therefore, in order to inhibit the production of quinoline insoluble matter (QI) in the pitch which is a target product of the present invention, cracking of the components forming a petroleum-based low grade raw material is induced via pressurized heat-treatment in this step.

(9) The petroleum-based raw material above is exemplified by pyrolyzed fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene cracker bottom oil (EBO), vacuum residue (VR), de-asphalted oil (DAO), atmospheric residue (AR), FCC-DO (fluid catalytic cracking decant oil), RFCC-DO (residue fluid catalytic cracking decant oil) and heavy aromatic oil, and any conventional petroleum-based raw material generally used in this field can be used without limitation.

(10) In this step, the inert gas is exemplified by be nitrogen, helium, neon or argon, and any conventional inert gas generally used in this field can be used without limitation.

(11) In this step, the pressure condition is preferably between 10 bar and 40 bar, but it can be adjusted between 5 bar and 60 bar according to the purpose of the pitch and the kind of the raw material.

(12) In this step, the heat treatment can be performed at the temperature between 300 C. and 450 C. and preferably performed at the temperature between 350 C. and 400 C.

(13) In this step, the heat treatment can be performed for 0.510 hours, preferably performed for 18 hours, and more preferably performed for 15 hours.

(14) Next, step 2 is to heat-treat the petroleum-based raw material heat-treated in step 1 once again at normal pressure.

(15) The purpose of this step is to induce polymerization of aromatic components of the petroleum-based raw material and to discharge volatile components and non-reactive components such as paraffins having a low boiling point. In this step, the reaction is induced at normal pressure, so that all the gas generated in the course of the heat treatment is discharged out of the reactor. At this time, the normal pressure indicates a range of atmospheric pressure generally used, more particularly a pressure in the range of 1 bar10%. In addition, the pressure range is not limited to the above and this step can be performed at atmospheric condition of the ambient environment in which the method according to the present invention is conducted.

(16) In this step, the heat treatment can be performed at the temperature between 300 C. and 450 C. and preferably performed at the temperature between 350 C. and 400 C.

(17) In this step, the heat treatment can be performed for 0.510 hours, preferably performed for 18 hours, and more preferably performed for 15 hours.

(18) Finally, step 3 is to distillate the petroleum-based raw material heat-treated in step 2 under reduced pressure.

(19) This step is a step of controlling the carbonization yield and the QI value of the intermediate pitch produced in step 2. The carbonization yield of the final impregnated pitch can be increased by removing volatile components of the intermediate pitch produced in step 2. The reason for performing the distillation under the reduced pressure condition lower than the pressure in step 2 and the temperature condition lower than the temperature in step 2 is to suppress the generation of QI and to induce the discharge of volatile components in the pitch. If the reaction is induced at a temperature higher than the temperature proposed in step 2, QI would be generated due to the polymerization reaction of the hydrocarbon components in the pitch.

(20) In this step, the pressure condition is approximately 0.08 hPa, preferably 0.010.1 hPa, and more preferably 0.011.00 hPa.

(21) In this step, the distillation under reduced pressure can be performed at the temperature between 100 C. and 250 C. and preferably performed at the temperature between 150 C. and 200 C.

(22) In this step, the distillation under reduced pressure can be performed for 0.510 hours, preferably performed for 18 hours, and more preferably performed for 15 hours.

(23) The present invention also provides an impregnated pitch prepared by the method for producing an impregnated pitch of the present invention.

(24) At this time, the impregnated pitch can have a QI value of 5% or less, a QI value of 3% or less, a QI value of 2% or less, a QI value of 1.5% or less, a QI value of 1.0% or less, a QI value of 0.5% or less, a QI value of 0.3% or less, a QI value of 0.2% or less, a QI value of 0.1% or less, a QI value of 0.05% or less, and a QI value of 0.01% or less.

(25) In addition, the impregnated pitch can have a carbonization yield of 40%45%, preferably a carbonization yield of 45%50%, and more preferably a carbonization yield of 50%55%.

(26) The impregnated pitch prepared according to the method for producing an impregnated pitch of the present invention has as low QI as 2% or less and as high carbonization yield as 40% or more, so that when a carbon compact is prepared by using the impregnated pitch of the present invention, it is possible to reduce micropores inside the carbon compact, and to produce a carbon compact having physical properties such as excellent electrical conductivity and mechanical strength.

(27) Practical and presently preferred embodiments of the present invention are illustrative as shown in the following Examples.

(28) However, it will be appreciated that those skilled in the art, on consideration of this disclosure, may make modifications and improvements within the spirit and scope of the present invention.

Example 1: Preparation of Impregnated Pitch Using the Method According to the Present Invention 1

(29) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(30) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(31) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(32) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 457 g of a impregnated pitch was obtained.

Example 2: Preparation of Impregnated Pitch Using the Method According to the Present Invention 2

(33) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(34) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 330 C. under the pressure of 15 bar for 3 hours.

(35) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(36) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 482 g of a impregnated pitch was obtained.

Example 3: Preparation of Impregnated Pitch Using the Method According to the Present Invention 3

(37) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(38) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 410 C. under the pressure of 15 bar for 3 hours.

(39) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(40) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 429 g of a impregnated pitch was obtained.

Example 4: Preparation of Impregnated Pitch Using the Method According to the Present Invention 4

(41) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(42) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 1 hour.

(43) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(44) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 487 g of a impregnated pitch was obtained.

Example 5: Preparation of Impregnated Pitch Using the Method According to the Present Invention 5

(45) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(46) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 5 hours.

(47) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 330 C. under the pressure of 1 bar for 3 hours.

(48) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 446 g of a impregnated pitch was obtained.

Example 6: Preparation of Impregnated Pitch Using the Method According to the Present Invention 6

(49) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(50) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours. Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 330 C. under the pressure of 1 bar for 3 hours.

(51) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 490 g of a impregnated pitch was obtained.

Example 7: Preparation of Impregnated Pitch Using the Method According to the Present Invention 7

(52) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(53) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(54) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 410 C. under the pressure of 1 bar for 3 hours.

(55) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 440 g of a impregnated pitch was obtained.

Example 8: Preparation of Impregnated Pitch Using the Method According to the Present Invention 8

(56) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(57) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(58) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 1 hour.

(59) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 475 g of a impregnated pitch was obtained.

Example 9: Preparation of Impregnated Pitch Using the Method According to the Present Invention 9

(60) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(61) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(62) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 5 hours.

(63) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 1 hour, and as a result 444 g of a impregnated pitch was obtained.

Example 10: Preparation of Impregnated Pitch Using the Method According to the Present Invention 10

(64) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(65) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(66) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(67) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 170 C. under the pressure of 0.08 hPa for 1 hour, and as a result 474 g of a impregnated pitch was obtained.

Example 11: Preparation of Impregnated Pitch Using the Method According to the Present Invention 11

(68) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(69) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(70) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(71) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 230 C. under the pressure of 0.08 hPa for 1 hour, and as a result 451 g of a impregnated pitch was obtained.

Example 12: Preparation of Impregnated Pitch Using the Method According to the Present Invention 12

(72) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(73) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(74) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(75) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for 2 hours, and as a result 452 g of a impregnated pitch was obtained.

Example 13: Preparation of Impregnated Pitch Using the Method According to the Present Invention 13

(76) An impregnated pitch was prepared using the method according to the present invention comprising the following steps 1, 2 and 3.

(77) Step 1: 1000 g of pyrolyzed fuel oil (PFO), a petroleum-based low grade raw material, was loaded in an autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 15 bar for 3 hours.

(78) Step 2: The pyrolyzed fuel oil (PFO) heat-treated in step 1 was loaded in the autoclave reactor, followed by heat-treatment at 370 C. under the pressure of 1 bar for 3 hours.

(79) Step 3: The pyrolyzed fuel oil (PFO) heat-treated in step 2 was loaded in a thin layer distillation (TLD) reactor, followed by distillation under reduced pressure at 200 C. under the pressure of 0.08 hPa for minutes, and as a result 470 g of a impregnated pitch was obtained.

(80) Pressure, temperature and time conditions of each step of Examples 13 are summarized in Table 1 below.

(81) TABLE-US-00001 TABLE 1 Step 2 Step 3 Step 1 (normal (reduced (pressurization) pressure) pressure) pressure temperature time pressure temperature time pressure temperature time (Bar) ( C.) (H) (Bar) ( C.) (H) (Bar) ( C.) (H) Example 15 370 3 1 370 3 0 200 1 1 Example 330 3 370 3 200 1 2 Example 410 3 370 3 200 1 3 Example 370 1 370 3 200 1 4 Example 370 5 370 3 200 1 5 Example 370 3 330 3 200 1 6 Example 370 3 410 3 200 1 7 Example 370 3 370 1 200 1 8 Example 370 3 370 5 200 1 9 Example 370 3 370 3 170 1 10 Example 370 3 370 3 230 1 11 Example 370 3 370 3 200 2 12 Example 370 3 370 3 200 0.5 13

Experimental Example 1: Analysis of Physical Properties of Impregnated Pitches According to the Present Invention

(82) The physical properties of the impregnated pitches prepared in Examples 113 according to the present invention were analyzed.

(83) 1. Analysis of Quinoline Insoluble Matter (QI) of the Impregnated Pitches Prepared in Examples 113

(84) QI values of the impregnated pitches prepared in Examples 113 were measured based on ASTM D2318.

(85) 2. Analysis of Carbonization Yield of the Impregnated Pitches Prepared in Examples 113

(86) Carbonization yields of the impregnated pitches prepared in Examples 113 were calculated based on ASTM D4530.

(87) The measured QI value and carbonization yield of each impregnated pitch are shown in Table 2.

(88) TABLE-US-00002 TABLE 2 Step 2 Step 3 Step 1 (normal (reduced (pressurization) pressure) pressure) carbonization pressure temperature time pressure temperature time pressure temperature time QI yield (Bar) ( C.) (H) (Bar) ( C.) (H) (Bar) ( C.) (H) (%) (%) Example 15 370 3 1 370 3 0 200 1 0.00 51.3 1 Example 330 3 370 3 200 1 0.01 48.2 2 Example 410 3 370 3 200 1 1.54 54.6 3 Example 370 1 370 3 200 1 0.00 47.9 4 Example 370 5 370 3 200 1 0.52 52.1 5 Example 370 3 330 3 200 1 0.05 47.4 6 Example 370 3 410 3 200 1 1.89 53.1 7 Example 370 3 370 1 200 1 0.00 49.1 8 Example 370 3 370 5 200 1 0.78 52.6 9 Example 370 3 370 3 170 1 0.00 49.3 10 Example 370 3 370 3 230 1 0.11 51.9 11 Example 370 3 370 3 200 2 0.15 51.7 12 Example 370 3 370 3 200 0.5 0.00 49.7 13

(89) As shown in Table 2, the impregnated pitches prepared in every example according to the method of the present invention demonstrated a low QI value (2% or less) and a high carbonization yield (45% or more).

(90) Therefore, when an impregnated pitch is prepared from a petroleum-based raw material using the method for producing an impregnated pitch according to the present invention, it is possible to produce an W impregnated pitch having a low QI value and a high carbonization yield at the same time.