KR20070010828A - High quality asphalt containing pitch and preparing method thereof - Google Patents

Abstract

Provided are high quality asphalt having improved wax content and resilience at a low temperature, and a preparation method thereof utilizing a solvent deasphalting process(SDA) to overcome disadvantages which are generated by using vacuum residue(VR). The high quality asphalt is prepared by blending a first vacuum residue(VR) produced by a vacuum distillation unit and a first petroleum refining fraction containing BC; inputting the blend into a solvent deasphalting process to produce deasphalted oil and petroleum pitch; and blending the petroleum pitch with a second vacuum residue(VR) and a second BC for use in penetration index control. The mixing ratio of the VR to the BC ranges 10-90:90-10 by weight. The BC and the second BC are selected from a group consisting of AR, HCVGO, and SLO.

Description

High quality asphalt containing pitch and preparing method

1 is a schematic process diagram of producing direct current asphalt using a reduced pressure residue produced in a conventional vacuum distillation column,

Figure 2 is a schematic process diagram of producing high-quality asphalt by mixing the petroleum pitch produced in the solvent deasphalting apparatus with a hard blended oil according to the present invention.

* Description of the symbols for the main parts of the drawings *

CDU (Crude Distillation Unit): Atmospheric Distillation Process

VDU (Vacuum Distillation Unit): vacuum distillation process

HDC (Hydrocracking): Hydrocracking Process

Fluid Catalytic Cracking (FCC): Fluidized Bed Catalytic Cracking Process

Atmospheric Residue (AR): Atmospheric Residue

VGO (Vacuum Gas Oil): Decompressed gas oil

VR (Vacuum Residue): Decompression residue

Solvent DeAsphalting (SDA): Solvent Deasphalting Process

DeAsphalted Oil (DAO): Deasphalted Oil

Pitch: Oil Pitch

HCVGO (Heart Cut Vacuum Gas Oil): Heavy Pressure Gas Oil

SLO (Slurry Oil): Slurry Oil

The present invention relates to a high-quality asphalt containing a petroleum pitch as a by-product generated in the solvent deasphalting process and a manufacturing method thereof, and more specifically, to solvent deasphalting by mixing atmospheric residue and petroleum oil similar to the atmospheric residue. The present invention relates to a high quality asphalt with improved wax content and low temperature elongation (Ductility After Thin Film Oven Test) by mixing a petroleum pitch controlled by chemical components obtained using a device with a conventional vacuum residue.

Asphalt manufacturing method using a conventional vacuum distillation unit (VDU), as shown in Figure 1, the atmospheric residual oil (Atmospheric Residue, AR) produced in a crude distillation unit (CDU) It is a method of producing asphalt directly by separating the vacuum residual residue (Vacuum Residue, VR) by adjusting the penetration into the vacuum distillation process.

Asphalt produced in this way is used as a road pavement material, the main properties that should be considered at this time include penetration, penetration index, softening point, viscosity, wax content, low temperature elongation after thin film heating. Penetration is a measure of asphalt's hardness, which is the most fundamental property of asphalt to be used as a pavement material. In addition, properties considered mainly in evaluating the quality of asphalt are wax content and low temperature elongation after thin film heating. As the wax content is lower, the higher the low-temperature elongation value after thin film heating is, the better the asphalt quality is.

In the case of directly producing vacuum residue (VR) as asphalt, the crude oil group suitable for asphalt production is selectively combined and put into the atmospheric distillation tower (CDU), and then the separation temperature of the vacuum residue (VR) is controlled in the vacuum distillation process (VDU). It is produced so as to have an appropriate penetration degree, and thus the other major physical properties are dependent on the crude oil injected into the CDU. In this case, in order to produce high-quality asphalt with low wax content and high elongation at low temperature after thin film heating, the crude oil group treated in the atmospheric distillation column should be selected accordingly. You have a problem that can make it worse.

Another disadvantage of directly producing high-quality asphalt vacuum residues (VGO) is the hydrocracking unit (HDG) produced by vacuum gas (VGO) produced together with the vacuum residue (VR) in a vacuum distillation tower (VDU). And because it is used as a raw material of high-addition process such as Fluid Catalytic Cracking Unit (FCC), when operating a reduced pressure distillation tower to secure asphalt quality, the quality of relatively expensive reduced gas oil can be lowered or the yield can be lowered. Is the point. As a related patent, US Patent Publication No. 2004-163996 discloses a method for producing asphalt from a vacuum residue or an atmospheric residue.

On the other hand, in the case of direct production of vacuum residue from asphalt, the chemical structure of atmospheric pressure residue and vacuum residue are saturated, aromatic, resin, asphaltenes (Saturate), aromatic (Resin) Asphaltene), it is known that the lower the wax content, the lower the saturated content, and the lower the elongation after thin film heating, the smaller the saturated and asphaltene content and the higher the aromatic and resin content are. In the case of the vacuum distillation process (VDU), the vacuum gas oil (VGO) and the vacuum residue oil are distinguished from each other by the separation temperature. Therefore, in terms of chemical structure, the aromatic and resins are selectively decompressed to improve low temperature elongation after wax content and thin film heating. It is difficult to increase the residual oil and the chemical structure of the vacuum residue is dependent on crude oil.

Thus, in the present invention, to overcome the disadvantages that occur when producing the high-quality asphalt as a vacuum residue as described above, using a deasphalting process (SDA) to produce a chemical composition controlled petroleum pitch after the existing vacuum residue and similar By mixing the light petroleum oil was able to produce high-quality asphalt with excellent low temperature elongation after wax content and thin film heating, the present invention was completed based on this.

Accordingly, an object of the present invention is to provide a high quality asphalt with excellent low temperature elongation after wax content and thin film heating.

Another object of the present invention to provide a method for producing the high quality asphalt.

The high-quality asphalt of the present invention for achieving the above object includes a petroleum pitch obtained by combining the first reduced residue oil (VR) and the first petroleum oil in a solvent deasphalting process (SDA).

In the high-quality asphalt for achieving another object of the present invention is a method for producing asphalt by producing a vacuum residue (VR) from an atmospheric pressure distillation process (CDU), and a vacuum distillation process (VDU), the vacuum distillation process ( VDU) is prepared by including a petroleum pitch obtained by inputting a mixture of a reduced pressure residue oil produced from VDU) and a petroleum oil that is harder than the reduced pressure residue and has a higher aromatic and resin content in a solvent deasphalting process (SDA).

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

As described above, the conventional method for producing asphalt produces a direct asphalt by using the vacuum gas oil and the vacuum residue produced in the vacuum distillation tower by distilling the atmospheric residual oil produced in the atmospheric distillation column under reduced pressure. Referring to FIG. 1, the reduced pressure gas oil (VGO) is highly added to kerosene and gasoline through a hydrocracking process and a fluid catalytic cracking process. It is produced directly from asphalt.

On the other hand, the asphalt according to the present invention is mixed with the first petroleum oil containing the atmospheric residue produced in the atmospheric distillation tower and the first reduced residue oil (VR) produced in the reduced pressure distillation tower and added to the solvent deasphalting process (SDA) Include the oil pitch obtained. More preferably, the petroleum pitch and the second reduced residue oil (VR) and / or the second petroleum oil are mixed in order to control the penetration. The asphalt thus obtained has characteristics of excellent low temperature elongation properties after wax and thin film heating.

2 is a process diagram showing an embodiment of manufacturing a high-quality asphalt according to the present invention, referring to this, solvent dehydration by properly mixing the first petroleum oil containing the first reduced residue oil and atmospheric pressure residue oil produced in a vacuum distillation tower Into the asphalt process (SDA), and deasphalted oil and petroleum pitch are produced therefrom, the deasphalted oil is highly added through hydrocracking reaction process and fluidized bed catalyst reaction process, and the petroleum pitch is reduced to the second reduced residue oil ( VR) and the second petroleum oil for penetration control can be prepared according to the present invention.

The mixing ratio of the first petroleum fraction to the first reduced residue oil is preferably 10 to 90% by weight, and if the ratio is less than 10% by weight, the effects of aromatics and resins contained in the first petroleum fraction are less than 90% by weight. If it exceeds%, the hard oil in the petroleum pitch increases due to the operation characteristics of the deasphalting process, which tends to adversely affect the asphalt quality.

In the present invention, the petroleum oil that can be blended into the vacuum residue as a raw material of the solvent deasphalting process and the final mixing process is a heavy cut gas oil produced in a vacuum distillation process in addition to the above-mentioned atmospheric residue oil (Heart Cut Vacuum Gas Oil, HCVGO). ) And one or more slurry oils (SLO) produced in the fluidized bed catalyst reaction process.

According to the present invention, the penetration of the petroleum pitch produced from the solvent deasphalting process is similar (almost the same) as that of the vacuum residue to produce asphalt by itself or mixed with vacuum residue and / or petroleum oil. It is necessary to operate the solvent deasphalting process to have a slightly lower value. In order to compensate for the penetration of the mixed asphalt produced below the specification, it is possible to adjust the penetration by partially mixing harder oil than the vacuum residue oil such as atmospheric residue oil, heavy pressure gas oil, and / or slurry oil. .

Normally, as the solvent used in the solvent deasphalting process, a normal or isoparaffinic solvent having about 3 to 6 carbon atoms is mainly used, but in order to control the penetration of petroleum pitch in the present invention, a 3 to 4 carbon paraffin solvent is used. Or a mixed solvent thereof is preferable, and the yield of the petroleum pitch varies depending on the ratio of the vacuum residue and the atmospheric residue as raw materials and the operating conditions, and generally falls in the range of about 10 to 90% by volume. The higher the yield of petroleum pitch, the softer semi-finished product with high penetration of pitch is produced, and generally the properties of deasphalted oil are excellent. The lower the carbon number of the solvent, the higher the operating temperature of the solvent deasphalting process, the higher the yield of petroleum pitch, which may increase the absolute content of aromatics and resins. It is very important to control the yield of petroleum pitch appropriately according to the raw material characteristics of solvent deasphalting process because the increase of minutes may adversely affect the low temperature elongation due to the accelerated oxidation reaction during low temperature elongation measurement after thin film heating.

According to the present invention, in the solvent deasphalting process, the petroleum pitch extraction pressure is preferably 30 to 46 kg / cm 2 g, and the extraction temperature is 43 to 93 ° C. for normal propane and 115 to 150 for normal butane / isobutane. Operation at ℃ is preferred in terms of low temperature elongation and wax improvement after thin film heating.

Table 1 below is a representative property of the deasphalted oil and petroleum pitch produced through the solvent-solvent asphalt process by mixing the properties of the atmospheric residue and the decompressed residue oil supplied. As shown in Table 1, the petroleum pitch has the advantage of less wax component because the content of the saturated water is less than the residual oil residue, and has the advantage of increasing the elongation at low temperature after heating the thin film because of the high content of aromatic and resin. Since the solvent used in the solvent deasphalting process is paraffinic, the chemically affinity saturates in the raw material are separated through the deasphalted oil, and the aromatic and resin components, which are relatively incompatible, are not dissolved in the solvent and petroleum pitch Because to go to.

Therefore, according to the present invention, by using not only the atmospheric residue oil but also other petroleum products rich in aromatics and resins as a raw material along with the reduced pressure residue, the saturates are removed in the form of deasphalted oil and the aromatics and resins are moved to the petroleum pitch. Wax content in asphalt properties and thin oil can be produced to improve the low temperature elongation after thin film heating.

General Characteristics of AR, VR, DAO, and Pitch in Solvent Deasphalting Process AR VR DAO Pitch Nitrogen, wt% 0.27 0.42 0.06 0.52 Sulfur, wt% 3.21 4.87 2.20 4.99 Nickel / vanadium, wppm 24.3 / 71 46.8 / 135.8 Trace / Trace 45.2 / 136.9 Distillation, D2887 IBP 297 454 266 5% 365 514 339 30% 463 597 438 50% 535 647 488 70% 623 699 539 90% 604 95% 633 FBP 750+ 750+ 699 Recovered,% 91.7 83.0 100.0 Specific Gravity, 15/4 0.9757 1.0293 0.9177 1.0514 Conradson carbon residue, wt% 10.73 23.34 0.99 25.68 Chemical Composition Saturate Aromatic Resin Asphaltene  4.5 61.8 13.7 20.0  0.7 66.4 15.2 17.7

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Example 1

The raw material obtained by mixing the atmospheric residue oil (AR) and the vacuum residue oil (VR) having the properties shown in Table 1 above at a volume ratio of 18: 11 is deasphalted oil and petroleum under the conditions of Table 2 in the solvent deasphalting process. The results of the pitch are shown in Table 3 below. The characteristics of the asphalt prepared by mixing the heavy pressure residue oil in order to control the penetration of the obtained petroleum pitch are shown in Table 4 below.

As shown in Table 4, when the asphalt is manufactured using petroleum pitch, the aromatic and resin contents are higher and the saturation content is smaller than the asphalt produced by the vacuum residue produced in the conventional vacuum distillation tower, and thus the wax content and the thin film are low. After heating, it was possible to produce high-quality asphalt with increased low temperature elongation. In addition, since the penetration is about 6 lower than the decompression residue oil, the asphalt using petroleum pitch has a lower elongation after heating the thin film.

Conditions for Solvent Deasphalting Process: 61% Pitch Feed AR / VR (18/11 vol.) Solvent Propane Pitch Yield, wt% 61 Pressure, kg / ㎠g 45.7 Asphaltene separator temperature, ℃ 83

Characteristics of source and product by solvent deasphalting: 61% pitch Source DAO Pitch Specific gravity, 15/4 0.9888 0.9177 1.0514 API Gravity 11.60 22.69 3.08 Nitrogen, wppm 0.34 0.06 0.52 Sulfur, wt% 3.84 2.20 4.99 CCR, wt% 15.86 0.99 25.68 Nickel / vanadium, wppm 33.5 / 93.2 Trace / Trace 45.2 / 136.9 D2887, ℃ IBP 291 266 5% 376 339 30% 512 438 50% 588 488 70% 660 539 90% 604 95% 633 FBP 750+ 699 Recovery,% 88.7 100.0

VR vs. pitch mixed asphalt: 61% pitch VR (asphalt) Pitch-mixed asphalt Breakdown of high quality asphalt Mixed ratio, vol.% VR pitch HCVGO  100   82.3 17.7 Pen Number, 25mm at 25 ℃ 70 64 60 to 80 Softening Point, ℃ 48.2 48.6 Min 47 Viscosity at 60 ° C., Pa · s 213 221 Min 180 Wax, wt% 1.87 1.49 Max 1.8 Low temperature elongation at 15 ℃, cm 63 105 Min 100 Chemical Composition Saturate Aromatic Resin Asphaltene 4.5 61.8 13.7 20.0 2.3 66.9 14.1 16.8

Example 2

The raw material obtained by mixing the atmospheric residue oil (AR) and the vacuum residue oil (VR) having the properties shown in Table 1 at a volume ratio of 18:11 in a solvent deasphalting process under desulphurized oil and petroleum pitch under the conditions of Table 5 below. The produced results are shown in Table 6 below. The properties of the asphalt prepared by mixing the obtained petroleum pitch with a vacuum residue oil and partially mixed with a heavy vacuum residue oil to control the penetration.

As can be seen in Table 7 below, the asphalt prepared using the petroleum pitch compared to the asphalt produced by the residue under reduced pressure under the same intrusion degree it can be confirmed that the low temperature elongation excellent after thin film heating.

Solvent deasphalting process conditions: 70% pitch Feed AR / VR (18/11 vol.) Solvent Propane Pitch Yield, wt% 70 Pressure, kg / ㎠g 45.7 Asphaltene separator temperature, ℃ 88

Source and product properties by solvent deasphalting: 70% pitch Source DAO Pitch Specific gravity, 15/4 0.9888 0.9089 1.0385 API Gravity 11.60 24.18 4.75 Nitrogen, wppm 0.34 0.07 0.48 Sulfur, wt% 3.84 2.03 4.70 CCR, wt% 15.86 0.29 23.13 Nickel / vanadium, wppm 33.5 / 93.2 Trace / Trace 40.5 / 129.4 D2887, ℃ IBP 291 259 5% 376 332 30% 512 428 50% 588 475 70% 660 523 90% 591 95% 623 FBP 750+ 699 Recovery,% 88.7 99.5

VR vs. pitch mixed asphalt: 70% pitch VR (asphalt) Pitch-mixed asphalt Breakdown of high quality asphalt Mixed ratio, vol.% VR pitch HCVGO  100  30.0 65.5 4.5 Pen Number, 25mm at 25 ℃ 70 70 60 to 80 Softening Point, ℃ 48.2 48.0 Min 47 Viscosity at 60 ° C., Pa · s 213 194 Min 180 Wax, wt% 1.87 1.49 Max 1.8 Low temperature elongation at 15 ℃, cm 63 145+ Min 100 Chemical Composition Saturate Aromatic Resin Asphaltene  4.5 61.8 13.7 20.0  2.4 62.6 18.5 16.5

As described above, the present invention not only allows the aromatic and resin contained in the atmospheric residue and the reduced residue oil to be distributed to the petroleum pitch by appropriately adjusting the operating parameters of the deasphalting process, and thus eliminates the saturated water. Compared to the method of manufacturing asphalt using only reasons, there is an effect of improving the low temperature elongation after wax content and thin film heating.

Claims (11)

It comprises a petroleum pitch obtained by combining the first reduced residual oil (VR) and the first petroleum oil that is harder than the reduced residual oil and the sum of the aromatic and the resin is high in the solvent deasphalting process (SDA). High quality asphalt with petroleum pitch. The high-quality asphalt as set forth in claim 1, wherein the mixing ratio of the petroleum oil to the vacuum residue oil (VR) is 10 to 90% by weight. The high-quality asphalt as claimed in claim 1, wherein the asphalt further comprises a second reduced residue oil (VR), a second petroleum fraction, or a second reduced residue oil (VR) and a second petroleum fraction. The method of claim 1 or claim 3, wherein the first and second petroleum fraction is one from the group consisting of atmospheric residual oil (AR), heavy pressure gas oil (HCVGO), and slurry oil (SLO) of the fluidized bed catalytic decomposition process. High quality asphalt, characterized in that more than selected. The high-quality asphalt as set forth in claim 1, wherein the penetration of the petroleum pitch is similar (almost the same) or lower than that of the vacuum residue. In the method of producing asphalt by producing a vacuum residue (VR) from a normal pressure distillation process (CDU), and a reduced pressure distillation process (VDU), Petroleum pitch obtained by introducing a mixture of the first reduced residue oil produced from the vacuum distillation process (VDU) and the first petroleum fraction that is harder than the reduced pressure residue oil and the sum of aromatics and resin is higher in the solvent deasphalting process (SDA). Method for producing high quality asphalt containing petroleum pitch, characterized in that using. The method of claim 6, wherein the blending ratio of the first petroleum oil to the first reduced residue oil (VR) is 10 to 90% by weight. The method according to claim 6, wherein the solvent of the solvent deasphalting apparatus (SDA) is a paraffin solvent having 3 to 4 carbon atoms or a mixture thereof, and the yield of petroleum pitch is 10 to 90% by volume. The petroleum pitch extraction pressure in the solvent deasphalting process is 30 to 46kg / ㎠g, extraction temperature is 43 ~ 93 ℃ for normal propane, 115 ~ 150 ℃ for normal butane / isobutane Wherein the penetration rate of the petroleum pitch produced in the solvent deasphalting process is similar to (almost the same) or lower than that of the vacuum residue used as a raw material of the solvent deasphalting process. 7. The method of claim 6, further comprising the step of mixing a second reduced residue oil (VR), a second petroleum fraction, or a second reduced residue oil (VR) and a second petroleum fraction to a petroleum pitch. How to. The method of claim 6 or 10, wherein the first and second petroleum fraction is one from the group consisting of atmospheric residue oil (AR), heavy pressure gas oil (HCVGO), and slurry oil (SLO) of the fluidized bed catalytic decomposition process. The method characterized in that the above selection.

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