JPS5887192A - Treatment of heavy oil - Google Patents

Abstract

PURPOSE:To obtain heart cut in a high proportion and to enable heavy oil to be efficiently treated with less hydrogen consumption, by thermally cracking heavy oil, distilling cracked oil to separate each fraction, and subjecting only the residue to hydrogenolysis. CONSTITUTION:Heavy oil contg. asphaltene such as topping residue or vacuum distillation residue of crude oil is thermally cracked. The resulting thermally cracked oil is distilled by means of topping or vacuum distillation to obtain naphtha, kerosine and gas oil. Then distillation residue is subjected to hydrogenolysis in the presence of a catalyst at 350-450 deg.C and at a pressure of 50- 200kg/cm<2>G. Since hydrogenolysis of light fractions in the thermally cracked oil is avoided in this process, the formation of gas component or naphtha is inhibited and hence the yield of the heart cut can be increased. Hydrogen consumption in the hydrogenolysis can be greatly reduced. The deterioration of the catalyst in the hydrogenolysis can be inhibited.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating heavy oil L2, specifically, by thermally decomposing heavy oil, distilling it to separate it into each fraction, and hydrocracking only the residual oil. The present invention relates to a highly efficient process for processing heavy oil, which has a high yield of middle distillates, and low hydrogen consumption.

In recent years, there has been a global trend toward heavier crude oil, but demand for petroleum products is increasingly showing a direction toward lighter crude oil.

For this reason, it is becoming increasingly important to use various methods for converting heavy oil into high-value light oil such as gasoline, kerosene, and diesel oil, such as catalytic cracking, thermal cracking, and hydrocracking. However, all of these processing methods have advantages and disadvantages, and none of them is practically satisfactory. In other words, C1 in catalytic cracking
Atmospheric steaming soda residue hIt oil.

Heavy oils such as vacuum distillation residue oil are difficult to process because they produce a lot of coke, and although the ratio of 1 to 1 gasoline fraction in the produced oil is large, it is difficult to obtain middle distillates equivalent to kerosene and light oil. There is an imbalance where the ratio is very small. On the other hand, in thermal decomposition, the produced MI+ becomes unsaturated and the resulting middle distillate 4-1
Post-treatment is required, and the storage stability of heavy oil is poor.
The IJ ratio of light oil is also small. Furthermore, specific hydrogen cracking has the disadvantage that it is economically disadvantageous because the hydrogen consumption hχ is large, and that the yield of middle distillates is not sufficient.

How to eliminate these drawbacks and 1. The heavy oil was heated in the presence of hydrogen to reduce the heat content ML, and then the total heat content W1 of the oil obtained was
A method for dispensing 1 h of hydrogen as it is
No. 2444) has been proposed, but this block J'f1
In , even the light oil produced by thermal decomposition is hydrogenated, resulting in excessive decomposition of the produced oil, resulting in a large amount of hydrogen consumption and a large amount of naphtha produced.

The present invention aims to overcome the drawbacks of the above-mentioned conventional methods and to provide an excellent method for treating heavy oil with a high yield of middle distillates and low hydrogen consumption. In this method, asphaltene-containing asphaltene-containing oil is heat-free, the resulting pyrolysis oil is distilled to separate each fraction, and the residual oil of the distillation is then subjected to hydrogen bisection.
31 (methods) for producing heavy oil.

Raw material oils to which the method of the present invention can be applied include:
Heavy oil containing asphaltene, such as atmospheric distillation of crude oil, Ri fh oil, vacuum distillation residue 1 oil, especially heavy residue 11
It is. Of course, the method of the present invention is 11, light chain 1° heavy gas oil, contact amount? It can also be applied to the hydrogenation of distillate oils such as +'i'' residual oil and 1-pressure distilled gas oil, but it is also applicable to the hydrogenation of distillate oils such as residual oil and 1-pressure distilled gas oil.
When used with IN, its true value is demonstrated in cattle.

In the method of the present invention, the above-mentioned asphaltene-containing heavy oil is used as a raw material oil and is first thermally decomposed.

Methods of thermal decomposition ← 1. There are various methods, and there are no particular restrictions, and the appropriate method should be selected depending on the type of raw material oil and other conditions! ] is good, but a method called visbreaking is generally preferred. Concrete ``V: 1-5 cannot be determined as a condition, but ``1; ↑ is a gain of 400-480°
C2 good"; l, < P, 'J', 42 (1~4
60°C, pressure 1-40k! 〆y4G.

Preferably 5-20 71G, oil residence time 2-30
minutes, preferably 2 to 5 to 20 minutes. Also,
6- During this thermal decomposition, steam, hydrogen, or diluent oil may be added to the reaction system.

In the method of the present invention, after the above thermal decomposition, it is necessary to separate the hot N oil obtained by this thermal decomposition into a residual oil and each fraction by distilling it. Distillation at this time can be carried out using different methods depending on the purpose, but usually atmospheric distillation,
Vacuum distillation or the like may be used. The residual force to be separated by distillation may be determined as appropriate, but generally the boiling point is 543°C.
It is preferable to distill off the following fractions and use those having a boiling point of 545°C or higher as residual oil.

"C" for distillate cracked by distillation here, naphza, lamp h
11. Used as light oil. You can also use these as is or blend them to create a mellow taste.
I'll'! It can also be used as a product gas oil, but it is desirable that the combustible oil fraction be hydrogenated.

The phantom oil fraction produced by the above-mentioned thermal separation contains a large amount of silica, and its storage stability and smoke point are poor. There is no problem when blending a small amount, but when used without blending, sludge is generated, and when roasted on a stove = 4
− There is a drawback that soot may be generated.

Note that the hydroprocessing of kerosene by thermal decomposition can be carried out using ice fields as a sub-phase, and the methods normally used for the hydrogenation of kerosene can be used as is. For example, using a medium containing 41 cobalt and molybdenum in alumina, 20 to 50 klAX! ,
It can be carried out at 510-570°C.

In the method of the present invention ((J-1) remaining i'i after the second distillation operation
``I oil is subjected to hydrogen specific decomposition.Here, without distilling the heat component W oil, the entire amount is directly subjected to hydrogen hydrogen for 16 minutes. As the hydrogen content is converted to naphtha and naphtha, the efficiency of middle distillates such as kerosene and gas oil decreases17, and the amount of hydrogen that is extinguished becomes very large, which is undesirable.In contrast, the present invention As in the method of
If the middle distillate is separated and only the residual oil is hydrocracked, hydrogen consumption can be saved and the yield of the middle distillate can be improved as a result.

A wide range of reaction conditions can be employed, including the reaction conditions conventionally employed for hydrogenation 4], but usually the temperature is 350-45
0"C, preferably 380-420°C9 pressure 50-2
00 kickcl G, preferably 100-180k
iffl G rLiquid space time velocity (L HS V) 0
．． 1-1.0hr-'.

Preferably 0.2-0.6 hr-'', hydrogen/oil 20
It should range from 0 to s o o o Nm'-Hydrogen/Kt-Oil.

In addition, the catalyst used for this specific hydrogen decomposition can include known catalysts for hydrogen decomposition of six yuzu, but preferred ones include Y-type zeolite and an inorganic oxide mainly composed of alumina. Examples include catalysts in which metals from group 1B of the periodic table and metals from group 1Vllll of the periodic table are supported on a mixed pressed body. Details of this catalyst can be found in Japanese Patent Application No. 56-8501.
<As stated in the Specification No. 5.

According to the method of the present invention, since the light components in the pyrolysis oil are not hydrocracked, the production of gas components and naphtha components can be suppressed and the yield of middle distillates can be increased. Furthermore, the amount of hydrogen consumed during hydrocracking can be greatly reduced. Furthermore, by using the above-mentioned catalyst, it is possible to carry out hydrogenolysis with high activity for a long period of time with little catalyst deterioration.
Moreover, the obtained hydrocracked oil is of good quality and has a high yield of light oil.

Therefore, the method of the present invention can be effectively utilized in the field of petroleum refining.

Next, the present invention will be explained in more detail with reference to Examples.
°C) 0.963. Sulfur content: 59 wt%, light oil fraction: 4.
Owt%, reduction 1] E411 fraction 36 wt%, residue Mb 60. Owt%), reaction section volume 104C1f
The residence time of the liquid was 15 minutes in the pyrolysis device a, which was made of a stainless steel tube of 150 mm, and the pressure was 15 k section ηI G .

Minutes Nlr Temperature: 445°C
'r was done. Next, the generated pyrolysis oil was subjected to an atmospheric distillation apparatus to separate it into noses, naphtha, kerosene, gas oil, and residual oil (boiling point 343°C or higher). Here, for the kerosene backing, 4.25 wt nickel on the alumina carrier
% 7- Tungsten 17. Using a catalyst supported with Owt%,
550'C, 40kicn, T, HSV 1. Ohr
The hydrogenation treatment was carried out under -' conditions. Furthermore, this residual oil is made of 60% US YF zeolite and 40% alumina.
nickel as active metal on a support consisting of 4.25 wt%
wt%.

Tungsten 17. Using a catalyst supported with Owt%,
Reaction temperature 410°C or 400°C, L HS V
Q, 5hr-”.

Sitting reaction pressure 150 kg/cJ a, hydrogen/oil 200O
Hydrogenolysis was carried out at Nrn/kt. The yield and properties of the produced oil are shown in Table 1. Table 2 shows the properties of the oil produced at each stage.

Comparative Examples 1 and 2 Using the same atmospheric distillation residue oil as in Examples 1 and 2 above, it was immediately subjected to hydrocracking using the same catalyst and conditions as in Example 1.2 without thermally decomposing it.

The results are shown in Table 1.

8- Table 1 Hydrogen consumption dHydrogen in kerosene fraction obtained by hydrocracking and thermal cracking of residual oil (total amount of hydrogen consumed in both treatments) is obtained by hydrocracking vacuum gas oil and residual oil among thermally cracked oils.

Total M-'4i Example 1 of pyrolysis oil obtained without
The hydrogenation portion 8't was carried out using the same M medium and column (4) as in 2.

The results are shown in Table 3.

Edict 6 table

Claims (4)

[Claims] (1) Asphaltene-containing heavy oil is distilled to separate the thermally cracked oil into each fraction, and then the residual oil of the distillation is hydrocracked. How to process quality oil. (2) The conditions for thermal decomposition are temperature 400-480°C, pressure 1
A method according to claim 1, wherein βG is ~40 and oil residence time is from 2 to 60 minutes. (3) The method according to claim 1, wherein the residual oil has a boiling point of 543°C or higher. (4) Hydrogenolysis is carried out using a carrier made of a mixture of Y-type zeolite and an inorganic oxide mainly composed of alumina as a solvent, which supports all the metals of Group VI B and Group Ⅰ of the periodic table. temperature 650-450°C, LIE force 50-20
0 kg/cnfG, liquid spacetime NFIj a1~to
br-".Hydrogen/oil conversion 200~ro000 Nj+f'-hydrogen/KL
- Conventional process according to claim 1, carried out under oil conditions.