JPS6035090A - Method for treating heavy mineral oil - Google Patents

Abstract

PURPOSE:To obtain adventageously high-grade gas oil, deasphalted oil, etc., by hydrogenating heavy mineral oil to recover light distillates, thermally cracking the residual oil to recover gas oil distillate and deasphalting the residue with a small quantity of a low-molecular solvent. CONSTITUTION:Hydrogen 8 is mixed with heavy mineral oil 1 contg. residual oil and the mixture is introduced into a hydrogenator 4 and hydrogenated in the presence of a hydrogenation catalyst at 300-480 deg.C under a hydrogen pressure of 50-200kg/cm<2>. After hydrogen 7 and a light distillate component 12 are recovered in a gas-liquid separating device 6 and a distillation column 10, the residue is introduced into a croacker 15 and thermally cracked at 350-550 deg.C under a pressure of atmospheric pressure to 200kg/cm<2>, and a gas oil distillate, etc. 19 are recovered in a distillation stage 18. The residual oil is introduced into a solvent-deasphalting device 21 and a low-molecular solvent 22 such as propane, butane or pentane in a quantity of 1-6 times by volume that of the residual oil is added thereto to carry out a deasphating treatment, whereby deasphalted oil 27 and deasphalted asphalt 28 can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing heavy mineral oil, and is aimed at converting heavy mineral oil containing a large amount of asphaltenes, sulfur, and mineral elements into light oil with less impurities such as summer metals in a high yield. Regarding how to get minutes.

Heavy mineral oils such as atmospheric residual oil or vacuum residual oil contain asphaltenes (components that are insoluble in heptane and soluble in toluene),
Since it contains a large amount of impurities such as sulfur and donor metals, its use is limited. In addition, due to recent developments in crude oil, there is even a tendency for the yield of these heavy mineral oils to become even better.

In view of this fact, there is a strong need to develop a process that can process A-quality mineral oil and recycle it into high-value-added light synthetic fuel oil, thereby reducing the amount of high-quality fuel oil used for conversion. It is requested.

Treatment methods for such heavy mineral oil include hydrodesulfurization method, hydrodesulfurization method, catalytic cracking method, coking method, and bath bath method.
Some processes, such as the pyrolysis method, isothermal partial oxidation method, or thermal decomposition method, or a combination of these methods, are already known. These processes produce the desired product,
For example, it is mainly carried out depending on whether the target product is gas, fuel, oil, coke, etc. Each process has its own features that suit its purpose, but it also has some drawbacks and still has areas to improve. For example, in order to obtain low-sulfur fuel oil using the hydrodesulfurization method, harsh conditions such as high temperature and high pressure and equipment that can withstand such conditions are required.Moreover, the catalyst must be damaged due to carbon anastomosis and base metals, so the operation is difficult. Season 1t11 and light female oil yield are limited. Part 1
Similar problems such as catalyst poisoning, difficult operating methods, and limitations on feedstock oil have been raised in the LTL catalytic cracking process.

Furthermore, the deasphalting method is one of the processes that can obtain high-quality light fuel oil at a high yield, but on the other hand, it requires large-sized equipment and has low operating costs.

The conventional solvent deasphalting method will be explained in some detail below.

Conventionally, the deasphalting solvent used is an alkane or alkene hydrocarbon having 2 to 7 carbon atoms, or a mixture thereof, or a petroleum fraction such as petroleum oil, kerosene, or light oil that does not contain olefins or aromatic hydrocarbons. It is being By selecting these solvents, it is possible to arbitrarily change the yield, properties, operating conditions, etc. of the deasphalted oil to some extent. for example,
If a high-grade deasphalted oil is desired, using propane as a solvent will yield the desired high-grade deasphalted oil, albeit in a low yield.
In order to obtain inferior deasphalted oil in high yield, a solvent with a higher molecular weight such as pentane or hebutane is usually used.

In addition, from the perspective of equipment operation, when using a low molecular weight solvent such as propane, the deasphalting operation is performed at a relatively low temperature range of 50 to 90°C, but A 6 to 10 times larger amount of solvent is required, and further enlargement of the apparatus is unavoidable. On the other hand, when using a solvent with a crystalline molecular weight, such as heptane, the amount of the solvent is relatively small, 2 to 4 times the amount of the deasphalted feedstock, and the scale of the equipment is smaller than in the case of propane.

However, the operating mL degree is high, around 150 to 220°C, and the operating cost is high.

As described above, there are differences in the selection of solvent, yield of deasphalted oil, pouring conditions, operating conditions, equipment scale, etc., and each has its advantages and disadvantages. However, since solvents are generally selected based on the yield of deaspendable oil, low molecular dehydrogenation is not currently used except in special cases such as lubricating oil manufacturing processes. .

In addition, the combination of thermal decomposition treatment and solvent deasphalting treatment is also possible.
This method has been proposed in Publications No. 54-22445 and No. 57-11590. In this case, although it is recognized that the deasphalting efficiency is the same and the amount of metals in the deasphalted oil is reduced, on the other hand, the asphaltene content in the pyrolyzed oil and the amount of pyrolysis gas generated increase the pyrolysis rate. As a result, the total yield of deasphalted oil and pyrolyzed gas oil in the subsequent solvent deasphalting process decreases, and the yield of as7alt 5-ate in the deasphalting process decreases. is recognized, and the thermal decomposition treatment mark is restricted.

In addition, the combination of hydrogenation contact treatment and bath agent deasphalting treatment is also possible.
jf458-17793 publication and concave 58-26391
It is proposed in the publication. However, in this method,
The problem is that it is difficult to obtain deasphalted oil with low metal and asphaltene content unless a solvent with a relatively large molecular weight such as hexane or heptane is used and a high bath agent ratio is employed. If a solvent with a large molecular weight is used or a solvent ratio is used, a problem arises in that the operating cost of the solvent deasphalting step becomes high.

The inventors of the present invention have continued to conduct intensive studies aimed at solving the above-mentioned various problems encountered in the treatment of highly prized mineral oils, and as a result, they have arrived at the present invention, which is highly effective.

That is, the present invention deals with direct heating of mineral oil containing distillation residue (1) in the presence of a hydrogenation catalyst at a reaction temperature of about 600 to 480°C and a hydrogen pressure of about 5.
0-20〇6-1 was hydrogenated with 9/Cn1' (gauge), (11)
This hydrotreated product (at least 1611 of
9/cm” (gauge) and then filtrated.
+1 During this thermal decomposition treatment, at least a part is propane,
Using butane, pentane or a mixture of these two as a solvent and solvent/solvent deasphalting treatment raw oil ratio (volume)
The present invention provides a method for treating straight roasted oil, characterized in that it is subjected to solvent deasphalting treatment under conditions of about 1 to 6.

The present invention exhibits a synergistic effect by combining hydrogenation treatment, thermal decomposition treatment, and solvent deasphalting process to solve the problems of the prior art and to derive new effects.

According to the method of the present invention, it is possible to use a low molecular weight solvent such as propane in the solvent deasphalting treatment at a solubility ratio of 41 (volume ratio to feedstock oil) that is comparable to that of a conventional high molecular weight solvent. It is possible to obtain high-quality deasphalted oil with low content of asphaltenes, sulfur, and heavy metals at a high yield.In addition, there are problems such as the scale and operating cost of the deasphalting equipment. resolved at the same time. In addition, as impurities such as sulfur and heavy metals are removed in the solvent deasphalting process, the load on desulfurization and demetalization in the first hydrotreating process is reduced, allowing for operation under milder conditions. This makes it possible to significantly extend the life of the catalyst.

Furthermore, according to the method of the present invention, even if the hydrotreated oil is subjected to thermal cracking treatment and solvent deasphalting treatment, the total yield of deasphalted oil and pyrolyzed light oil for the same amount of heavy metals is simply The amount of waste treated with solvent deasphalting also increases significantly, an effect that could not be predicted from the conventional technology. Furthermore, by carrying out the hydrogenation treatment in the first step, there is also the effect that the thermal decomposition conditions in the second step are not subject to the severe restrictions as in the prior art.

Next, the configuration of the present invention will be specifically explained.

Examples of the heavy 11 fuel oil to be used in the present invention include crude oil, prefixed crude oil, atmospheric residue oil or vacuum residue oil of crude oil, deasphalted asphalt, or high-boiling fractions from oil sands and oil joules. These heavy mineral oils contain sulfur,
Contains large amounts of impurities such as nitrogen, heavy metals, and asphaltene.

These heavy mineral oils undergo a first step of hydrotreating using an industrially used hydrotreating catalyst. Hydrotreating catalysts include activated alumina, silica-alumina and silica-magnesia catalysts with substantially low decomposition function, and nicohalto-molybdenum, nickel-molybdenum, nickel-tungsten or platinum catalysts. A catalyst supporting a hydrogenation metal component consisting of a Group 1 and/or Group Ⅰ metal or metal compound is used.

The conditions for the hydrogen treatment step include a reaction temperature of approximately 300℃.
~480'C1 reaction pressure approximately 50-20'Okg/c♂
(gauge) preferably about 75-150119/C♂ (gauge), liquid air bending speed about 9-01-1ona, preferably about 0.2-411RS
Also, hydrogen/oil conversion, Il/1J100~2,0OOON/
The values of each area of are adopted respectively. Hydrogen home 4 above! The material is preferably selected so that asphaltene content does not increase significantly during the subsequent pyrolysis treatment. De-fi
It is preferable that the & ratio is about 80 to 98% when it is about 60% or more, or the metal removal rate is about 60% or more, especially about 50 to 95%. In the second step of thermal decomposition treatment, a commonly used reactor such as a tubular reactor or a soaker drum is used.

Further, the pyrolyzed hydrogen or steam may or may not coexist, and there is no particular restriction. When thermally decomposed in the coexistence of water vapor, about 1 to 50%
ωt %, preferably about 1 to 10 ωt % water vapor is added. Further, hydrogen is used in an amount of about 10 to 2,000 times the total volume of hydrogen coexisting, preferably about 10 to 100 times the amount of hydrogen. The thermal decomposition conditions are approximately 350 to 550 for one reactor.
"C1 preferably about 680-50〇10- °C1 decomposition pressure at normal pressure -200kg 7cm" (gauge), water LI7) preferably about 10-509/cm" (gauge) in the absence of gas , if present, preferably about 10 to 150 9/C♂, and the residence time in the reactor is in the range of 10 seconds to 10 hours, preferably several minutes to several tens of minutes. Thermal decomposition rate (reduction rate of fractions of 482°C or higher in treated feedstock oil) is approximately 3 to 70%.
, particularly preferably about 5 to 40%.

Furthermore, the thermal decomposition treatment conditions in the second step can also be varied depending on the hydrogenation treatment conditions in the first step. That is, as the severity of the hydrogen treatment conditions increases, for example as the treatment temperature increases and the liquid hourly space velocity decreases, the thermal decomposition in the second step can be performed under milder conditions. Treatment under mild conditions does not impair the properties of the combination of the present invention in the final solvent deasphalting step.

The deasphalting equipment used in the third step of solvent deasphalting treatment is a contact tower type;
A mixer-settler type or a hydrocyclone type can be used, and there are no particular restrictions.

Propane, butane, pentane or a mixture thereof is used as the deasphalting solvent. In order to maximize the effects of the present invention, low molecular weight propane and butane are preferred;
The amount used is about 1 to 6 times the volume of the raw material oil, preferably 1 to 4 times the volume. If the amount of solvent used is too large, the operating cost will be high, and if the amount used is too small, the deasphalting process will not be carried out successfully. The deasphalting temperature is in the range below the critical temperature of the solvent used, for example when propane is used5.
In the range of 0-90℃, and the pressure is about 5-1509/C
♂ (gauge), preferably about 15-60Jc9/cm”
(gauge) area values are respectively adopted. In the case of butane, 100-140℃, about 5-150 kg 7c
m” (gauge), 150-190℃ for pentane
, about 5 to 150 Jc97 cm'' (gauge) is preferred.

S1 The oil that does not contain large amounts of asphaltone and heavy metals, such as pyrolyzed light oil or deasphalted oil obtained from each of the first, second and third steps of the present invention, is subjected to catalytic cracking alone or in combination. It is consumed after processing such as hydrogenation, page break, etc., or without processing. The deasphalted asphalt obtained from the third step, the solvent deasphalting step, is used as a base material for oil, paving asphalt, needle coke, binder pitch, etc., and is supplied to a coker, a partial asphaltizer, and the like.

In addition, atmospheric distillation equipment and vacuum distillation equipment are installed between each process, that is, between the first and second processes, and between the second and third processes, to recover light oil and reduce the burden of processing in the next process. It can also be reduced.

Next, the process diagrams (1) and (1) of the present invention are shown in FIGS. 1 and 2.
2) will be further explained. However, the present invention is not limited thereto.

In the process diagram (1) of FIG. 1, raw filtrate oil is sent through line 1 (13) and mixed with hydrogen gas supplied from line 8. The mixed raw material system is sent through a line 3 to a hydrotreating device 4 for the first step. Hydrogen treatment conditions The products that have undergone reactions such as hydrogenation are sent to a gas-liquid separator 6 through a line 5. In the gas-liquid separator 6, the gas is separated into a gas rich in hydrogen gas and a liquid product using four high-temperature components.

The separated gas removes impurities as necessary, passes through a circulation line 7, is mixed with hydrogen gas for replenishment from line 2, and is recycled and reused via line 8.

The liquid product is sent via line 9 to a distillation stage 10.

In the distillation step 10, a light fraction from the naphtha fraction to a gas oil fraction or a reduced lf@oil fraction is recovered out of the υ system through a line 12 by atmospheric distillation and/or vacuum distillation. The residual oil under normal pressure or the residual oil under reduced pressure is sent to the thermal separation treatment device 15 through the first lie No. 11. When performing thermal decomposition treatment in the coexistence of hydrogen or steam gas, the gas 14- is supplied from the line 13. Gases such as hydrogen sulfide generated during thermal decomposition and a portion of cracked light oil are recovered outside the system through line 16. When hydrogen gas is used, the hydrogen gas is recovered once in the line 14 and recycled and reused after removing impurities as necessary. The pyrolysis products are passed through line 17 to distillation step 1.
It is sent to Japan and subjected to atmospheric distillation and vacuum distillation. Light produced by thermal decomposition, reduced pressure from strange oil fraction; tti? IlI
Each fraction of 17 minutes is collected via line 19. The vacuum residue oil that has undergone thermal decomposition is supplied to a solvent removal device 21 through a line 20. At the same time, deasphalting #If411 for circulation use is also added from line 22 to the solvent deasphalting device.

The circulating solvent consists of the recovered solvent in line 26 obtained from the solvent recovery step 25 and the Q1 standard solvent added from line 29 for replenishment. A deasphalted oil phase and a deasphalted asphalt phase obtained from the solvent deasphalting device 21 are each passed through a line 23.
and is sent to a solvent recovery step 25 via a line 24, where the solvent is removed.

The resulting deasphalted oil and deasphalted asphalt are transferred to line 27.2.
8, respectively. The process diagram (2) in Figure 2 is IJjt
An example in which heavy oil is subjected to hydrogenation treatment in the first step, 4, and then immediately sent to the second step, pyrolysis step 15, without passing through the gas-liquid separation device, where it is treated in the coexistence of hydrogen. This is what is shown. Therefore, the hydrogen gas enrichment 18 is omitted, and the subsequent solvent deasphalting treatment step is the same as the process diagram (1) in FIG.

The features of the invention are illustrated in the above examples and comparative quantities.

Example 1 is an example of processing according to the method of the present invention. Comparative Example 1 exemplifies a combined process of conventional pyrolysis solvent deasphalting, and Comparative Example 1+12 exemplifies a combined process of hydrotreating solvent deasphalting. Reference Tari 1 is an example in which the reduced If residual oil was subjected to solvent deasphalting treatment without any pretreatment.

[Example 1] Arabin heavy atmospheric residual oil containing large amounts of asphaltone and heavy metals was mixed with a gas rich in hydrogen gas and then subjected to hydrogenation treatment in a fixed bed flow reactor.

That is, 4. Assuming that the arabin heavy atmospheric residual oil with a flow rate of 500 cc/HR was heated and pressurized and the hydrogen flow rate was 4.
63Nj! The mixture was mixed with a gas rich in hydrogen gas adjusted to have a temperature of /f (literature) and sent to reactor 6.
6N)/ノ.

In this reaction step, the above raw material mixture system is passed in a downward flow through a fixed bed υ1EjlV1 anti-L6 column filled with a cobalt-molybdenum hydrodesulfurization catalyst supported on alumina gel with effective surface soaking and pore distribution. and hydrogenated. The reaction system has a half-uniform temperature of the catalyst bed of 364°C and a reaction pressure of 12a.
ja;t/cm"('f - U) K naru X,'#
It is maintained at 14f/m.

The reaction product obtained from the reaction step is processed into a gas-liquid separation device consisting of a high-temperature separator and a low-temperature separator whose pressure is substantially the same as that of the reaction system, and a low-pressure separator whose pressure is substantially lower than that of the reaction system. The reaction product is separated into a hydrogen-rich gas and a substantially liquid reaction product. The separated hydrogen-rich gas is further processed by a bacterial amine cleaning device that separates light hydrocarbon oil) into hydrogen sulfide,
Impurities such as ammonia were removed. In order to maintain the hydrogen concentration of the gas above a certain level, a portion of the gas is discharged to the outside of the system, and the remaining gas is mixed with make-up hydrogen and recycled for use.

The liquid product distilled from the low-pressure separator is used to distill hydrocarbon oils with boiling points lower than approximately 567°C, such as sinafusa fraction, kerosene and gas oil fractions, and vacuum gas oil fractions, using atmospheric distillation equipment and vacuum distillation equipment. As a result, the vacuum residue oil shown in Table 1 was obtained at a distillation rate of 198ee/HR.

The vacuum residue of the above-mentioned hydrotreated oil is treated in a flow-through type thermal PII apparatus equipped with a front-type reactor, and then subjected to solvent deasphalting treatment using propane.

18- That is, the vacuum residual oil of the hydrotreated oil is 1540 ℃ after preheating.
It is sent to a tubular reactor with an outside diameter of about 15118 mm at a flow rate of cc/cm. The tubular reactor was heated and maintained at 440°C, and the apparent residence time in the open zone for decomposition of residual oil was approximately 15°C.
It was 5 minutes. The reaction system is maintained at a decomposition pressure of 10 to 9/C♂ (gauge).

The pyrolysis product oil leaving the reaction tube is stripped by nitrogen gas at a low pressure of 1III1ΔJ, where the pressure is substantially lower than that of the reaction system, resulting in a substantially gaseous product and a substantially liquid product. Separated. The gaseous product was further cooled by a cooler and separated into a light hydrocarbon oil mainly composed of naphtha fraction and a gaseous product mainly composed of hydrogen sulfide, methane, etc. The liquid product distilled from the low-pressure separator is then further passed through an atmospheric-pressure distillation device to distill naphtha and kerosene fractions with a boiling point of 320°C or less, resulting in a thermal cracking pressure residue oil having the notes shown in Table 1. I got it.

Approximately 259 liters of the pyrolysis atmospheric residue and 6 times the volume of liquefied propane were collected in a stainless steel pressure-resistant centrifuge tube, and the centrifuge tube was heated at 70°.
The mixture was shaken and stirred under a light beam for 30 minutes while being heated at a temperature of 100°C.

Thereafter, the deasphalted oil (l) and the deasphalted asphalt phase were centrifuged in a centrifugal separator heated and maintained at 70°C in the same manner. After extracting each phase from the centrifuge tube, the solvent was removed and dried. The yield of deasphalted oil was 7t8wt% based on the deasphalted raw material.The amount of asphaltene in the deasphalted oil was 0.2wt%.
%, the amount of heavy metals (V+N+) was 5 ppm or less, and the sulfur content was 0.66 wt%. FIG. 3 shows the relationship between the total yield of deasphalted oil and pyrolysis gas oil and heavy metals (V+N1) ii when the pyrolysis residual oil was similarly subjected to solvent deasphalting treatment at solvent ratios of 4.6: and 8.

In addition, Arabian-Bee atmospheric residual oil was hydrogenated, thermally decomposed, and solvent deasphalted in exactly the same manner as above. The only difference from the above process is that 3-fold n-pentane is used as the deasphalting solvent in the solvent deasphalting step and the treatment is carried out at 170''C.

The obtained deasphalted oil yield was 85.1 wt% based on the deasphalted raw material.
The amount of asphaltene in the deasphalted oil is o, 4wt%,
The heavy metal amount CV+NO was 8wtpyn, and the sulfur content was 0.84wtti. Figure 3 shows the total yield of deasphalted oil and pyrolysis gas oil and the amount of heavy metals (CV+Ni) when solvent deasphalting was carried out at solvent ratios of 1.0, 2.0, and 2.5.

-20' - [Comparative Example 1] The vacuum residue oil shown in Table 2 obtained from Arabian heavy atmospheric residue oil by ordinary vacuum distillation was thermally decomposed and distilled in the same manner as in Example 1, and then deasphalted solvent The solvent was deasphalted in the same manner as in Example 1 using 3 times the volume of propane and 3 times the volume of n-pentane. Comparative Example 1 and Example 1 differ only in the presence or absence of hydrogen treatment.

The results are as follows.

Propane; Deasphalted oil yield 29.2 wt Deasphalted oil Oily heavy metals 1 kCV+Ni) 2 tntpprn or less Asphaltenes amount 0.05 wt 22- 21- n-Pentane; Deasphalted oil yield 70. Owt% Deasphalted oil Deasphalted oil basin type 4i (V + Ni) 20wtppm Asphaltene content 0.6wt% As is clear from comparing Example 1 and Comparative Example 1, the thermal decomposition-solvent desorption of the prior art When the hydrogenation process promoted by the present invention is carried out on 1M of asphalt treatment, a deasphalted oil of good quality can be obtained at a relatively high yield even if one portion of either propane or n-pentane is used as the solvent.

Approximately 2.5% of the conventional method uses propane as the load.
It is clear that it is economically viable even when using propane, and the present invention! Superiority is demonstrated.

In addition, the yield of deasphalted oil and pyrolyzed gas oil when solvent deasphalted with n-butane and n-pentane and heavy metals (V + Nl
) quantity relationship is shown in 1233. The conditions for de-history are as follows.

Solvent n-butane n-pentane 23- Solvent ratio 3.0 1.0 to 5.0 i 1f140'C170'C [Comparison row 2] The vacuum residue of the hydrotreated oil obtained in Example 1 was poured into a real barrel. Solvent desaturation was carried out in the same manner as in Example 1. Therefore, book tll and real 1
The difference from Blood Example 1 lies in the presence or absence of thermal decomposition treatment. The result is the following J...C.

Propane; deasphalted oil yield 72.2 wt% deasphalted oil pouring heavy metals 1iH (V+Ni) 16 wtppm annuphaltene amount 0.58 wt% sulfur content 0.67 wt% n-pentane; deasphalted oil yield 84.2 wt% flaking Oil pouring 11E metal 1ii (V + Ni) 15wtppm Asphaltene amount 0.42wt% Sulfur content 0.76wL% Other than that, propane with solvent ratio of 4.6 and 8, and n-pentane with solvent ratio of 1.2 and 2.5 Figure 3 shows the relationship between the yield of each deasphalted oil and the amount of heavy metals in the deasphalted oil when treated in the same manner.

As seen in Comparison ρ2, in the case of the conventional technology of direct solvent deasphalting without thermal cracking after hydrotreating, the deasphalted oil yield with propane at a low solvent ratio is lower than that with n-pentane at the same solvent ratio. Although the yield of deasphalted oil is about 15% lower, there is almost no difference in the properties of the deasphalted oil between the two, and there is no perceived advantage of using propane with a low solvent ratio as the deasphalted solvent. Therefore, in the case of the prior art, it is preferable and industrially advantageous to use a solvent with a higher molecular weight than n-pentane or n-heptane.

On the other hand, when thermal decomposition is carried out after hydrotreating as proposed in the invention, and solvent deasphalting is performed, the properties of the deasphalted oil change as shown in Example 1. The use of this method is a significant improvement over conventional hydrotreating-solvent deasphalting processes. In particular, when propane is used for a period of time, the effect is remarkable. That is, n
-It is much better economically and industrially to obtain a high-grade deasphalted oil using a low solvent ratio of propane than to obtain a higher-grade deasphalted oil by increasing the solvent ratio of pentane. ing.

Thus, when treating heavy mineral oil according to the method of the present invention, a relatively low molecular weight solvent such as propane, butane or n-pentane may be substituted with a lower molecular weight solvent, such as propane, butane or n-pentane, depending on the properties or yield of the desired deasphalted oil. The ratio can be arbitrarily selected, and the deasphalted oil can be obtained at a still high yield.

[Reference Example 1] Arabin heavy vacuum residue oil shown in Table 2 was solvent deasphalted using n-butane and pentane. Figure 3 shows the yield of deasphalted oil and the amount of heavy metals (V+Ni) in the deasphalted oil at that time. The cases of dereliction of records were as shown in 26-F.

Heart punishment n-butane n-pentane solvent ratio 5.0 and 7.0 1.0-5.0 temperature If 1
40'C170'C Figure 6 shows ■Solvent deasphalting treatment alone (reference column 1), ■Pyrolysis-solvent deasphalting treatment (comparison column 1), and ■Hydrogenation treatment-bath cutting deasphalting treatment (comparison t112). ■Hydrotreatment of the present invention - thermal decomposition -
Solvent Pleasure Process 4 (Example 1) and Deasphalted Oil Yield Obtained in Each Process (However, in processes that involve pyrolysis treatment, pyrolysis gas oil distilled by normal pressure or/and vacuum distillation after pyrolysis) and deasphalted oil) and heavy metals in the oil (V + N1
)ii indicates the OIA staff.

Here, the total yield is based on the vacuum distillation residue of the Tani process.

That is, in processes (1) and (2), the total yield is based on the solvent deasphalt treated feedstock, and in processes (2) and (2), the total yield is based on the thermal #treated feedstock. Also, 01, C4, C6 in Figure 3L
Solvent 27 indicates that propane, n-butane, and n-pentane were used as molten AIJ in the deasphalting process, respectively.

As is clear from the figure, the thermal content obtained by the combined process of ■solvent deasphalting process and ■pyrolysis treatment-solvent deasphalting process is as follows: The st yield is almost the same in both cases, or rather shows a lower value in the combination process of thermal decomposition and solvent deasphalting.

On the other hand, in method ① of the present invention, even if the hydrotreated oil is subjected to pyrolysis-solvent deasphalting, the total yield of deasphalted oil and pyrolyzed light oil relative to the same content is lower than that of the hydrotreated oil. The number of cases where the solvent is simply deasphalted has increased significantly, and the behavior is completely different from that of the conventional technology.

Furthermore, it is clear that both the heavy metal content and the yield of deasphalted oil are superior to (2) solvent deasphalting treatment alone. Furthermore, the method of the present invention has a low operating temperature;
Moreover, due to the solvent deasphalting at a low solvent ratio, the amount of heavy metals is lower than that of other processes. 28-C...hydrogenation-pyrolysis-solvent deasphalting treatment (Example 1).

It is an excellent process in terms of deasphalting oil with a high total yield, deasphalting cost, yield, and quality of deasphalting oil.

[Brief explanation of drawings]

FIGS. 1 and 2 are flow sheets each showing, as a block diagram, one embodiment of the method according to the invention. In the figure, 4...hydrogenation equipment, 6...
Gas-liquid separation device, 15...Pyrolysis treatment device, 21
・・・・・・This is a solvent deasphalting device. Figure 3 shows the deasphalted oil yield (with the exception of pyrolysis In a process including treatment, it is a graph showing the relationship between the total yield of pyrolysis gas oil and deasphalted oil) and the amount of heavy metals in kernel oil. In the figure,... Solvent deasphalting treatment (Reference example 1), j.
...Thermal decomposition-solvent deasphalting treatment (Comparative Example 1), ○...
... Hydrogenation treatment - Solvent deasphalting treatment (Comparative example 2), 29
- Patent applicant: New Fuel Oil Development Technology Research Association 2,゛・,
No. 130 - Procedural amendment February 14, 1980 Kazuo Wakasugi, Director General of the Patent Office 1, Indication of the case, Patent Application No. 142485, filed in 1982, 2, Name of the invention, Process for treating heavy mineral oil 3, Amendment Patent applicant name: Sekihan Taisei Building (telephone: 582-7161) and Ganchi-
Figure 2 6 attached hereto, contents of amendment (1) On page 16, line 12 of the specification, "thermolysis solvent deasphalting" is amended to 7 "pyrolysis - solvent deasphalting." (2) “Hydrotreating solvent deasphalting” on page 16, line 13 of the specification
Corrected to a certain meeting: ``Hydrotreating - Solvent deasphalting''. (3) Does it say "thermal decomposition =" on page 23, line 6 of the specification? Correct as “pyrolysis-”. (4) What is the next sentence after the first line on page 30 of the specification? insert. ``Also, the downward arrow in Figure 3 indicates that the amount of heavy metals is less than that.'' (5) Correct as shown in the attached sheet in Figure 2.

Claims (1)

[Claims] The distilled mineral oil containing residual oil is heated in the presence of a hydrogenation catalyst at a reaction temperature of about 300-480'C1 hydrogen pressure of about 50-20
0119/Cm' (gauge), and at least 111S of this hydrogenated product was hydrogenated at a reaction temperature of about 650 to 550°C and a decomposition pressure of normal pressure to 200 kg.
cm” (gauge) and further (Ill)
At least a part of this thermal decomposition product is treated using propane, butane, pentane, or a mixture of these at a ratio of 2f/1 or more as a solvent, and the ratio of bath agent/solvent deasphalting feedstock oil (volume) is about 1.
A method for treating heavy mineral oil that is timed by solvent deasphalting treatment under the conditions of ~6.