JPH06279763A - Reforming of heavy oil - Google Patents

Abstract

PURPOSE:To convert a heavy oil into a low-bolding oil of lower viscosity by contacting and reacting the heavy oil with high-temperature water containing supercritical water in a reactor. CONSTITUTION:The charging rate of water in the reactor is 10vol.% or above, and the reaction temperature is 300-500 deg.C. For instance, the apparatus shown in Fig. is composed of a reaction vessel 1 (of a capacity of 50ml), a flange 2, a heater 3, a thermocouple 4, a pressure transducer 5, a temperature controller 6 and a recorder 7. Oil sand is used as the heavy oil, it is washed with toluene, the sand is filtered off, and the filtrate is stripped of the toluene to obtain an oil sands oil sample. This is introduced into the vessel 1, deionized water is introduced at a charging rate of 10vol.% or above preferably 15-70mol.%, and the vessel 2 is sealed with the flange 2. If necessary, in addition to the deionized water, an alkali solution or a catalyst may be added to the vessel 1. The entire mixture is heated up to 300-500 deg.C, and then slowly cooled by stopping the heating. Thus, the oil sands having a viscosity of 25000 cp or higher at 30 deg.C is converted into a low-boiling oil having a viscosity of 5-35 cp at 30 deg.C in a yield of 85-90%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reforming heavy oil such as oil sand, heavy crude oil and vacuum residue oil.

[0002]

2. Description of the Related Art Oil sands (including tar sand oil, bitumen, etc.) have large reserves worldwide and are being developed as valuable hydrocarbon sources next to petroleum.
Since reforming and refining are difficult, hydrorefining methods, thermal decomposition methods, catalytic cracking methods, solvent extraction methods, etc. have been tried so far. There were problems such as low rates.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for reforming heavy oil, which is simple in method, has a very small amount of by-products such as coke, and has a high liquid yield.

[0004]

In order to solve the above problems, the present inventor has adopted a means of utilizing high temperature hot water containing supercritical water for reforming heavy oil.

That is, according to the present invention, a heavy oil is modified by contacting and reacting the heavy oil with high temperature hot water containing supercritical water in a reactor to lighten the oil to a lower viscosity oil. It provides a quality method.

The filling rate of water in the reactor directly influences the magnitude of pressure in the reactor as described later and is related to the viscosity of the obtained oil, and is appropriately selected according to the purpose. However, it is usually 10% by volume or more, preferably 15 to 70%.
It can be appropriately selected within the range of volume%. The reaction temperature is usually preferably 300 to 500 ° C. The water used may be pure water or, if necessary, additives such as an alkaline solution and a catalyst.

[0007]

In the present invention, light oil having an arbitrary viscosity can be reformed in a short time according to the filling rate of water in the reactor, and by-products such as coke are compared with the conventional method. Can be extremely reduced.

[0008]

The present invention will be described more specifically below with reference to the illustrated embodiments. (Example 1)

Using the apparatus shown in FIG. 1, an oil sand produced in Athabasca, Canada was modified. Figure 1
1 is a reaction vessel (volume 50 ml), 2 is a flange, 3 is a heater, 4 is a thermocouple, 5 is a pressure converter, 6 is a temperature controller, and 7 is a recorder.

The oil sand from Athabasca has a viscosity of 25,000 cp or more (30 ° C.) and a specific gravity of 1.004.
(15/4 ° C), ash content 3.4% by weight, asphaltene 2
The content was 1.79% by weight, marten 74.71% by weight, and benzene insoluble content 3.50% by weight. This oil sand was first washed with toluene, separated and filtered from sand, and then toluene was removed to obtain an oil sand oil sample.

First, 5 g of this oil sand oil sample was filled in the reaction vessel 1, and pure water was added to the reaction vessel 1 in a volume of 50 ml of 20% by volume (10 g), 30% by volume (15 g), 40% by volume.
Volume% (20g), 50volume% (25g), 60volume%
After changing to (30 g) and filling the reaction vessel 1 and sealing with the flange 2, after heating up to 400 ° C. (reaction time: 0 hour), heating was stopped and gradually cooled (see FIG. 2).

As a result, the yield is 85 to 90% and the viscosity is about 5 to 5.
It was confirmed that the oil was lightened to 35 cp (30 ° C). The relationship between the filling rate of water and the pressure in this experiment is shown in FIG.
Fig. 4 shows the relationship between pressure and viscosity, and Fig. 5 and Fig. 6 show the molecular weight distribution of this reaction product. Further, FIG. 7 shows the relationship between the pressure and the gas generation amount.

As is apparent from FIG. 5, the water filling rate is 20-
At 40% by volume (gas phase atmosphere), the peak molecular weight is 3000 to 5000, and the molecular weight is entirely moved to the polymer side as the water filling rate increases. Further, as is clear from FIG. 6, the water filling rate is 50 to 60% by volume (liquid phase atmosphere).
, There is almost no change in the peak, but the distribution width tends to become narrow when the water filling rate is 60% by volume.

FIG. 8 shows the results of SFC (supercritical CO ₂ chromatography) analysis of the product oil at a water filling rate of 20 to 40% by volume. Focusing on the peaks of C _{10 to} C ₃₀ , the filling rate increases. Accordingly, the n-paraffin tends to decrease. This is consistent with the decrease on the low molecular side in FIG. Example 2 The same oil sand from Athabasca as in Example 1 was used and treated with toluene to obtain an oil sand oil sample.

5 g of this oil sand oil sample and 10
g, 15 g, and filled in the reaction container 1 respectively,
40 volume% (2
0 g) After filling and sealing with the flange 2, after heating up to 400 ° C. (reaction time: 0 hours), heating was stopped and gradually cooled (see FIG. 2).

When the viscosity of the resulting product oil was measured, the results shown in FIG. 9 were obtained. As is clear from this result, it was confirmed that even if the amount of oil sand was increased, the weight reduction could be achieved similarly. Example 3 The same oil sand from Athabasca as in Example 1 was used and treated with toluene to obtain an oil sand oil sample.

5 g of this oil sand oil sample was added to the reaction vessel 1.
Then, 40% by volume (20 g) of pure water was filled in 50 ml of the reaction vessel, and sealed with the flange 2, then 30
After heating to 0 ° C. and maintaining at this temperature for 10 hours (reaction time: 10 hours), heating was stopped and gradually cooled. As a result, the viscosity was about 1500 to 1600 cp as in Example 1.
It was confirmed that the oil (50 ° C) was lightened. The total amount of gas generated in this experiment was 59 cc, and the components were as shown in Table 1. It should be noted that Table 1 also shows the generation rate of gas components when the filling rate of pure water in Example 1 was 40% by volume (20 g).

[0018]

[Table 1]

Although the oil sand reforming treatment is described in the above embodiment, heavy oils other than oil sands, such as heavy crude oil and reduced pressure residual oil, are also lightened with a high liquid yield. It was confirmed that it was possible.

[0020]

As described in detail above, according to the present invention,
It is possible to reform heavy oil with a viscosity of about 3500 (50 ° C) into a light oil with a viscosity of about 5 to 35 (30 ° C) without using hydrogen as in the past, and to reduce coke generation. By appropriately selecting the reaction temperature and the reaction pressure, it is possible to reform into light oil having an arbitrary viscosity in a short time.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an autoclave used to carry out the method of the present invention.

FIG. 2 is a diagram showing changes over time in temperature and pressure in the method of the present invention.

FIG. 3 is a diagram showing the relationship between water filling rate and pressure in the method of the present invention.

FIG. 4 is a diagram showing the relationship between pressure and product viscosity in the method of the present invention.

FIG. 5 is a diagram showing the molecular weight distribution of the product obtained by the method of the present invention.

FIG. 6 is a diagram showing the molecular weight distribution of the product obtained by the method of the present invention.

FIG. 7 is a diagram showing the relationship between the gas generation amount and pressure obtained by the method of the present invention.

FIG. 8 is a diagram showing the results of SFC (supercritical CO ₂ chromatography) analysis of the product oil obtained by the method of the present invention.

FIG. 9 is a graph showing the relationship between the filling amount of oil sand and the viscosity in the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Reaction container 2 ... Flange 3 ... Heater 4 ... Thermocouple 5 ... Pressure converter 6 ... Temperature controller 7 ... Recorder

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yamazaki Nakamichi Ko Sagawa, Takaoka-gun, Kochi 107 Ko (72) Inventor Hisaki Makino 7-2-1, Nakayama, Aoba-ku, Sendai-shi, Miyagi Tohoku Electric Power Co., Inc. (72) Inventor Takehiko Moriya 72-1 Nakayama, Aoba-ku, Sendai City, Miyagi Prefecture, Tohoku Electric Power Co., Inc. Applied Technology Laboratory (72) Inventor Shiro Ishii 2-4-2 Daisaku Sakura City, Chiba Prefecture

Claims (4)

[Claims] 1. A method for reforming heavy oil, which comprises contacting and reacting heavy oil with high temperature hot water containing supercritical water in a reactor to lighten the oil to a lower viscosity oil. 2. The filling rate of water in the reactor is 10% by volume.
The method for reforming heavy oil according to claim 1, wherein the method is as described above. 3. The method for reforming heavy oil according to claim 1, wherein the reaction temperature is 300 to 500 ° C. 4. The method for reforming heavy oil according to claim 1, wherein the heavy oil is oil sand.