JP2003277771A - Oil reforming equipment having water-oil separation mean - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reform an oil by a high-temperature high-pressure water, and to separate a water-oil mixture generated from a reforming unit into water and an oil for utilizing the oil for a petroleum refining plant, a power plant and the like. <P>SOLUTION: A water-oil mixture 4 obtained from a reforming unit 1 for subjecting a high-temperature high-pressure water 2 and an oil 3 to hydrothermal reaction for reforming is emulsified. A flocculant 8 and ferromagnetic material particles 9 are added to the emulsion to form a magnetic flock 10. The magnetic flock consisting of the oil and the magnetic material is separated from water by magnetic separation and recovered. Accordingly, a hardly separable water-oil mixture generated after hydrothermal reaction can be separated into water and an oil, so that the recycling of water and the discharge of water can be facilitated and the separated oil can be recycled. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil reformer method, and more particularly to an oil reformer for hydrothermally treating heavy oil for reforming.

[0002]

2. Description of the Related Art In oil refining, heavy oil such as residual oil and residue produced after taking out gas and light oil (naphtha, gasoline, kerosene, light oil) contains a large amount of sulfur, nitrogen and metal. This heavy oil can be commercialized by taking out as useful light components or removing sulfur as possible by hydrorefining or catalytic reforming in the petroleum refining process. The resulting catalyst is poisoned by sulfur and metals contained in heavy oil, which makes it difficult to use for a long time. Heavy oil is blended and commercialized as heavy oil, but when heavy oil is used as a fuel, sulfur oxides are generated by combustion, sulfuric acid is generated when the temperature drops, and metals form molten salts by combustion. However, these substances cause metal corrosion. Therefore, it is difficult to convert heavy oil into fuel, which is required in terms of effective use of oil and inexpensive fuel supply.

As described above, in heavy oil, it is required to remove sulfur and metals, and as one means therefor, there is an oil reforming method utilizing a hydrothermal reaction. 374 ℃ or above, 25M
High-temperature high-pressure water of Pa or more, that is, supercritical water, easily dissolves an organic substance such as oil that is insoluble in water, and also acts as a solvent that causes an oxidation and hydrolysis reaction. Utilizing this property, the heavy oil is lightened, and the generated gas and light oil are used as fuel (for example, JP 2000-10985 A).
No. 0), a method of taking out harmful substances such as sulfur in oil (for example, JP 2001-050010 A) and the like are known.

In these techniques, a technique of using a lightened fuel as a fuel for a boiler or a gas turbine is shown. In addition, the residue after reforming, that is, heavy oil and water that have not been lightened, is separated into water and oil, water is used as drainage or reused water, and heavy oil is returned to the reformer. There is. However, it is known that supercritically treated oil and water are mixed at the molecular level, and it is reported that the produced water and oil molecular clusters are miniaturized to about 20 Å (for example, USPatent5800).
No. 576).

Such a water-oil mixed liquid does not separate even if a conventional water-oil separator having a specific gravity is provided, or even if it is left standing for a long period of one day to several weeks, and even if a centrifugal separator is used. More than 30% of the weight remains in the form of a water-oil emulsion and is difficult to separate. It is of course impossible to separate water and oil in a continuous treatment system, and the produced water phase also contains an oil emulsion, which makes reuse difficult and cannot be discharged as waste water. Further, when the reforming utilizing the hydrothermal reaction is applied to the petroleum refining process, there is a problem that the water cannot be separated from the reformed oil and that the performance of the refining device is deteriorated by introducing the water into the refining device. .

[0006]

As described above, there is still no method for efficiently separating water-oil in the hydrothermally-treated reformate in a short time. An object of the present invention is to provide a technique that enables continuous water-oil separation in a fuel system such as a boiler or a gas turbine, or in a petroleum refining process, and makes a reformer practical.

[0007]

The present invention provides an oil reformer having a reactor for hydrothermally reacting supercritical water or subcritical water with oil to reform the oil. An oil emulsion converter for stirring the mixture of the modified oil and water to convert it into an oil emulsion, and adding an aggregating agent and magnetic particles to the oil emulsion obtained by the oil emulsion converter to stir the oil and the magnetic particles. And a magnetic separation device that magnetically separates the flocs from water containing the flocs formed by the floc formation device and recovers oil from the water. It is in an oil reformer.

The present invention produces magnetic flocs from an oil emulsion and separates water and oil by magnetic separation. Specifically, the water-oil mixture after hydrothermal reaction treatment is used to remove the oil phase that is separable by the conventional method or to emulsify it, and add flocculant and magnetic particles to the remaining oil emulsion to form magnetic flocs. However, the magnetic flocs are magnetically separated. As a result, the oil can be removed and the water content in the oil can be proposed to reuse the oil.

According to the present invention, water can be removed from the reformed oil after the hydrothermal treatment and sent to the downstream process, and it can be applied to a petroleum refining plant.

Further, since heavy oil and water can be separated and used for reuse and re-reaction, the fuel use efficiency can be improved and the fuel can be used as fuel for power generation equipment.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the accompanying drawings, but the present invention is not limited to the embodiments.

(Embodiment 1) FIG. 1 shows an embodiment of the oil reforming apparatus of the present invention. The water-oil mixture 4 produced by the reactor 1 for reacting the heavy oil 3 and the high-temperature high-pressure water 2 to reform the oil is sent to the emulsifying device 5. In the emulsification device 5, it is possible to effectively perform further aggregation processing.
Oil and water are mixed and the whole is emulsified. The emulsifying means can be an in-line mixer, a static mixer, a liquid cyclone, and various other means.

The emulsion 6 is sent to the coagulation tank 7, where the coagulant 8 and the ferromagnetic particles 9 are added and stirred. Flocculant 8
As a salt of iron or aluminum, for example, ferric sulfate, ferrous chloride, polyaluminum chloride or the like is added to cause aggregation. At the same time, ferromagnetic particles 9 such as magnetite (ferrous tetroxide) are added and stirred, whereby emulsion particles and magnetic particles are aggregated to form flocs 10.

The intermediate treatment liquid 11 containing the flocs 10 is sent to the magnetic separator 12. A rotary filtration membrane 13 is installed in the magnetic separator 12 to obtain filtered treated water 14. The flocs deposited on the rotary filtration membrane 13 are peeled off by the washing water in the washing device 14 and fall near the cylindrical rotary body 15. Inside the rotating cylindrical body 15, the magnetic field generating means 1
6 is provided to attract the flocs magnetically. The magnetic field generating means 16 can be various means such as a permanent magnet, an electromagnet, a superconducting bulk magnet and the like. Flock is a rotating cylinder 15
The surface is carried and scraped off by the separated oil recovery plate 17,
It is collected in the separated oil tank 18. Moisture drops due to scraping in the atmosphere, so that the water content of the separated oil can be lowered. Of course, a method of mixing the recovered separated oil 19 with the heavy oil 3 in order to return it to the reformer can also be used.

(Embodiment 2) FIG. 2 shows an embodiment in which the petroleum reforming apparatus of the present invention is applied to a petroleum refining process. The structure from the reactor 1 to the magnetic separator 12 is the same as the structure shown in the first embodiment. However, the water-oil mixture sent from the reactor 1 is retained in the liquid separator 28, the lightening oil 29 is separated, and the remaining water-oil mixture 4 is sent to the emulsification device 5.

In the petroleum refining process, the crude oil 21 is distilled by the atmospheric distillation unit 22, and the gas fraction 23, the naphtha fraction 24, the kerosene fraction 25, and the gas oil fraction 26 are taken out. The residual oil after distillation is
Usually, treatments such as reforming and desulfurization are carried out by hydrorefining using a catalyst, but the catalyst is poisoned because it contains a large amount of metals and sulfur. Therefore, the heavy oil 3 which is a distillation residual oil is treated with high temperature and high pressure water in the reactor 1 to remove harmful substances and lighten a part.

A lightened oil 29 is separated from the produced reformed intermediate oil 27, and hydrogen 31 is separated in a hydrorefining unit 30.
And refined oil 32 is obtained. The water-oil mixture 4 is separated by the magnetic separator 12 into treated water 20 and separated oil 19. Since the separated oil 19 is reformed again, after the magnetic particles are separated through the solid-liquid separator 43, the separated oil 19 is mixed with the heavy oil 3 and sent to the reactor 1. Since the treated water 20 does not contain oil, it may be drained or reused. With the configuration of this embodiment, the catalyst of the hydrorefining apparatus can have a long life, the running cost can be reduced, and the waste can be reduced.

(Embodiment 3) FIG. 3 shows an embodiment in which the petroleum reformer of the present invention is applied to a power plant. In order to burn inexpensive heavy oil and use it in a power plant, it is necessary to remove harmful substances such as sulfur and metals that cause corrosion of equipment materials. Therefore, the configuration in which the petroleum reformer of the present invention is installed in the fuel system is effective. In this embodiment, the structure from the reactor 1 to the magnetic separator 12 is the same as the structure shown in the second embodiment.

The heavy oil 3 as a fuel is reformed, the lightened oil is taken out by the liquid separator 28, and burned by the combustor 33. The gas 37 generated by burning oil with the air compressed by the compressor 35 drives the gas turbine 38. The gas turbine 38 rotates a generator 39 and supplies electricity. The exhaust gas 40 is sent to the exhaust heat recovery boiler 41, and the high temperature high pressure water 2 is generated from the water 42. On the other hand, the oil 19 separated by the magnetic separator 12 is mixed with the heavy oil 3 and recycled to the reformer 1.

With this configuration, it is possible to use heavy oil as a fuel for a power plant, reduce fuel cost, and at the same time generate high temperature and high pressure water used for reforming by exhaust heat to improve plant efficiency. .

[0021]

According to the present invention, in heavy oil reforming utilizing a hydrothermal reaction, water-oil separation can be efficiently realized from a fuel in which water and oil are mixed. The separated water and oil are easy to reuse and dispose, and the problem regarding the treatment of the water-oil mixture, which has been a problem for realizing the hydrothermal reaction reforming, can be solved. If the present invention is applied to an oil refining plant or a power generation plant, effective use of heavy oil and reduction of plant operating cost can be realized.

[Brief description of drawings]

FIG. 1 is a schematic view showing an embodiment of an oil reforming apparatus of the present invention.

FIG. 2 is a schematic diagram showing an embodiment of an oil refining plant to which the present invention is applied.

FIG. 3 is a schematic diagram showing an embodiment of a power plant to which the present invention is applied.

[Explanation of Codes] 1 ... Reactor, 2 ... High-temperature high-pressure water, 3 ... Heavy oil, 4 ... Water-oil mixture, 5 ... Emulsifying device, 6 ... Oil emulsion,
7 ... Flocculant tank, 8 ... Flocculant, 9 ... Ferromagnetic particles, 10 ... Flock, 11 ... Intermediate treatment liquid, 12 ... Magnetic separator, 13 ...
Rotating filtration membrane, 14 ... Washing device, 15 ... Rotating cylinder, 16
... magnetic field generating means, 17 ... separated oil recovery plate, 18 ... separated oil tank, 19 ... separated oil, 20 ... treated water, 21 ... crude oil, 22
… Atmospheric distillation device, 23… Gas fraction, 24… Naphtha fraction,
25 ... Kerosene fraction, 26 ... Light oil fraction, 27 ... Modified intermediate oil,
28 ... Liquid separator, 29 ... Light oil, 30 ... Hydrorefining equipment, 31 ... Hydrogen, 32 ... Refined oil, 33 ... Combustor, 34
... Air, 35 ... Compressor, 36 ... Compressed air, 37 ... Combustion gas, 38 ... Gas turbine, 39 ... Generator, 40 ... Exhaust gas, 41 ... Exhaust heat recovery boiler, 42 ... Water, 43 ... Solid-liquid separator.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01D 21/01 101 B01D 21/01 101A B01J 3/00 B01J 3/00 A B03C 1/00 B03C 1/00 A C10G 9/00 C10G 9/00 29/06 29/06 29/12 29/12 29/16 29/16 32/02 32/02 B 33/02 33/02 F23K 5/08 F23K 5/08 C ( 72) Inventor Shinichi Inage, 7-2-1, Omika-cho, Hitachi-shi, Ibaraki Co., Ltd., Hitachi, Ltd., Electric Power & Electrical Development Laboratory (72) Inventor Hiromi Koizumi 7-2-1, Omika-cho, Hitachi-shi, Ibaraki Hitachi, Ltd., Electric Power and Electrical Development Laboratory (72) Inventor Akinori Hayashi 7-2-1, Omika-cho, Hitachi City, Ibaraki Prefecture, Ltd. Hitachi, Ltd. Electric Power and Electrical Development Laboratory (72) Inventor Norihide Saho Tsuchiura, Ibaraki Prefecture 502 Jinritsu-cho Machinery Research Institute Co., Ltd. (72) Inventor Naoshi Isogami 502 Jinritsu-cho, Tsuchiura City, Ibaraki Prefecture F-term inside Hiritsu Works Machinery Research Institute Co., Ltd. (reference) 3K068 AA11 AB12 AB37 4D015 BA04 BA08 BB09 BB16 CA20 DA04 DA13 DA16 DA17 DA37 EA40 4H029 AA11 DA02 DA06 DA07 DA14

Claims (4)

[Claims] 1. An oil reformer having a reactor for hydrothermally reacting supercritical water or subcritical water with oil to reform the oil, and a mixture of the reformed oil and water produced in the reactor. An emulsifying device for stirring and converting the oil into an oil emulsion, and a floc forming device for adding a flocculant and magnetic particles to the oil emulsion obtained by the emulsifying device and stirring to form flocs containing oil and magnetic particles. An oil reforming device comprising: a magnetic separation device that magnetically separates the flocs from water containing the flocs formed by the floc forming device and recovers oil from the water. 2. A petroleum refining plant comprising the oil reforming apparatus according to claim 1 in a process. 3. A combustion device comprising the oil reforming device according to claim 1 in a fuel system. 4. A power plant comprising the oil reforming apparatus according to claim 1 in a fuel system.