JP2021134242A - Method and apparatus for refining mineral oil - Google Patents

Abstract

To provide a method and an apparatus that effectively and inexpensively remove impurities of mineral oil.SOLUTION: A mineral oil refining apparatus comprises: a water activation device for generating active oxygen in water; a mineral oil mixing device for mixing mineral oil with water in which the active oxygen has been generated; and a mineral oil separating device for separating the mixture liquid into water, impurities, and mineral oil.SELECTED DRAWING: Figure 1

Description

The present invention relates to the refining of mineral oils such as heavy oils.

The following patent documents disclose a technique for removing metal impurities and the like from petroleum using supercritical water.

Special Table 2018-534396

Mineral oils, especially heavy oils, have a high content of sulfur and ash impurities, and in recent years, it has been desired to remove such impurities effectively and at low cost in order to cope with the environmental load. Since the technique described in the patent document uses supercritical water, large-scale equipment is required and it is considered that a considerable cost is required. On the other hand, it is an object of the present invention to provide a method and an apparatus capable of removing impurities of mineral oil effectively and at low cost.

In the present invention, active oxygen is generated in water, mineral oil is mixed with the water in which the active oxygen is generated, the mixed solution is separated into water, impurities and mineral oil, and the separated mineral oil is used. This is a method for refining mineral oil to be recovered.

Further, the present invention comprises a water activating device that generates active oxygen in water, a mineral oil mixing device that mixes mineral oil in the water in which the active oxygen is generated, and water, impurities, and mineral oil while maintaining the mixed solution. It is a mineral oil refining device provided with a mineral oil separating device for separating the oil.

According to the present invention, since active oxygen is generated in water to purify mineral oil, impurities of mineral oil can be effectively and inexpensively removed.

It is a basic block diagram of an example of the mineral oil refining apparatus by this invention. It is a schematic diagram which shows the state which the mixed liquid of mineral oil and water is naturally separated into mineral oil, water, and an impurity. (A), (b) and (c) are water before mixing, volume of mineral oil, volume of mixed solution of water and mineral oil, water after the mixed solution is separated into mineral oil and water, respectively. It is a schematic diagram which shows the volume of mineral oil. It is a basic block diagram of another example of a mineral oil refining apparatus. It is a basic block diagram of another example of a mineral oil refining apparatus.

FIG. 1 is a basic configuration diagram of an example of a mineral oil refining apparatus according to the present invention.
The mineral oil refining device 1 keeps the water activating device 10 that generates active oxygen in water, the mineral oil mixing device 11 that mixes mineral oil with the water in which the active oxygen is generated, and the mixed solution in a stationary state. It is provided with a mineral oil separating device 12 that naturally separates water, impurities, and mineral oil.

The mineral oil supplied to the mineral oil mixing device 11 is not particularly limited, and heavy oil, light oil, kerosene and the like can be used. In particular, heavy oil has a high content of sulfur and ash impurities, and the present invention has a special effect on removing such impurities.

To briefly explain mineral oil, heavy oil is classified into A, B, and C. Heavy oil A (No. 1) has an average carbon number of hydrocarbon molecules of about 16.3 (standard deviation 3.8) and sulfur content. Is 0.5% or less, and the ash content mass is 0.05% or less. Heavy oil B has an average carbon number of hydrocarbon molecules of about 17.1 (standard deviation 3.0), a sulfur content of 3% or less, and an ash content of 0.05% or less. Heavy oil C (No. 1) has an average carbon number of about 20.2 (standard deviation 4.9), a sulfur content of 3.5% or less, and an ash content of 0.1% or less.
According to the present invention, for example, it is possible to remove the sulfur content weight of the heavy fuel oil A to 0.1% or less, which is particularly effective.
It is also possible to remove fine coagulated substances by further filtering the heavy oil after removing impurities with a mineral oil refiner with an appropriate filter. By such filtering, higher quality mineral oil can be obtained.
Further, light oil has an average carbon number of hydrocarbon molecules of about 17.0 (standard deviation 2.7) and a sulfur content mass of 10 ppm or less. Kerosene has an average carbon number of carbonized water molecules of about 12.9 (standard deviation 1.6) and a sulfur content mass of 8 ppm or less. The present invention can remove sulfur and ash impurities from such light oil and kerosene.

The water activation device 10 may be configured as a photocatalyst device that generates active oxygen in water by the action of a photocatalyst, for example. In the photocatalyst device, a photocatalyst in which fine particles of a photocatalyst active substance such as titanium oxide or tungsten oxide are fixed on a carrier such as porous ceramic or zeolite is sealed in a transparent pipe, and the photocatalyst is irradiated with ultraviolet rays from a UV lamp or the like. It can be configured as follows. In this case, if water is passed through the pipe, active oxygen is generated in the water by the action of the photocatalyst.

The water supplied to the photocatalyst device is, for example, pure water (ultrapure water) treated with an RO membrane, but carbon dioxide and oxygen are dissolved before being supplied to the photocatalyst device. The carbon dioxide and oxygen may be naturally dissolved in the air. Alternatively, it may be dissolved in a high concentration by another method or contained as bubbles.

The mineral oil mixing device 11 is a device that mixes mineral oil with water at a predetermined ratio of, for example, 1: 1. The mineral oil mixing device 11 may be configured such that a measuring pump or the like is provided in each of the pipeline led from the water tank and the pipeline led from the mineral oil tank, and these pipelines are merged on the downstream side thereof. .. Further, the mineral oil mixing device 11 may further provide a tank for storing a mixed liquid of water and mineral oil, and the mixed liquid may be agitated there for a certain period of time.

The mineral oil separation device 12 is a tank for storing a mixed liquid of water and mineral oil, and after the mixed liquid naturally separates into water, impurities and mineral oil over time, the portion of the mineral oil is recovered. It is configured to be possible. Alternatively, the mineral oil and water may be separated by centrifugation. There is no particular limitation on how to take out the mineral oil after separation, but the mineral oil may be left by draining heavy water and impurities from the bottom of the tank. Since water and mineral oil have different specific gravities, it is possible to centrifuge water, impurities, and mineral oil.

Next, the basic operation of the mineral oil refining apparatus 1 will be described.
The water supplied to the photocatalyst device contains carbon dioxide and oxygen, and a part of this water is decomposed by the action of the photocatalyst to generate so-called active oxygen. Active oxygen is, for example, OH radical and exhibits a very strong oxidizing action. The impurities are unspecified compounds containing sulfur, carbon and minerals. Then, such impurities cause some chemical reaction in the environment where active oxygen is present, and aggregate and separate from mineral oil or water. It is difficult to specify the chemical reaction at this time, but as a phenomenon, the mineral oil and water are naturally separated in the tank of the mineral oil separation device 12, and some of the impurities are at the boundary between the mineral oil and water. It has been confirmed that it floats and some of the other minerals are precipitated at the bottom. Impurities floating at the boundary between mineral oil and water are organic impurities (soot, etc.), and impurities precipitated at the bottom are inorganic impurities.
FIG. 2 is a schematic view showing a state in which the mixed liquid is naturally separated into mineral oil, water, and impurities in the mineral oil separation device. In this way, mineral oil, water, and impurities are naturally separated into layers.

As described above, according to the present invention, active oxygen is generated in water to purify mineral oil, but if a photocatalyst or cavitation as described later is used as a means for producing active oxygen in water, the active oxygen is very high. It can be continuously produced at low cost, and as a result, impurities in mineral oil can be removed effectively and at low cost.

Further, in the mineral oil refining apparatus 1, carbon dioxide contained in water is reduced by the action of active oxygen to generate carbon monoxide, and the carbon monoxide reacts with the molecules of mineral oil to produce a new mineral. It also produces oil, that is, increases the amount of mineral oil.
In the mineral oil mixing device 11, the water in which the reaction is occurring and the mineral oil are mixed, and the mineral oil synthesized here further extends the chain structure by the reaction with hydrogen and carbon monoxide. To go. At this time, a large number of template mineral oils are present in the surrounding area. Therefore, the elongation of the chain structure of the mineral oil seems to stop substantially when it reaches the same length as the template mineral oil. It is considered that this is because there are so many template mineral oils that even if the locking structure of a very small part of them is stretched, it is difficult to observe it. By such a reaction, a mineral oil having substantially the same composition as the template mineral oil is synthesized. At this time, the amount of mineral oil in the mixed solution naturally increases, and the amount of water naturally decreases. Experiments have confirmed that this increase in mineral oil reaches about 10% under ideal conditions.

In the mineral oil separating device 12, a mixed liquid of mineral oil and water is stored in a tank and kept in a stationary state. Then, the mixed solution naturally separates into mineral oil and water over time. By recovering the mineral oil after natural separation in this way, a high-quality mineral oil with few impurities can be obtained.

Further, the volume change of water and mineral oil in the reaction will be described with reference to a schematic diagram.
3 (a), (b), and (c) show the volume of water before mixing, the volume of mineral oil, the volume of the mixed solution of water and mineral oil, and the volume of the mixed solution after the mixed solution is separated into mineral oil and water, respectively. It is a schematic diagram which shows the volume of water and mineral oil.
When water of the same volume and mineral oil (mineral oil: water = 10:10) are mixed as shown in FIG. 3 (a), a mixed solution in which the volumes are simply combined as shown in FIG. 3 (b). (Volume 20). After the mineral oil is synthesized, the mixed solution is separated into two layers of mineral oil and water with the passage of time as shown in FIG. 3 (c). At this time, the amount of mineral oil is naturally increasing and the amount of water is naturally decreasing (for example, mineral oil: water = 11: 9).

FIG. 4 is a basic configuration diagram of another example of the mineral oil refining apparatus according to the present invention.
In this mineral oil refining device 1, the configuration of the water activating device 10 is different from the above example. That is, the water activation device 10 of this example has a configuration in which a photocatalyst device and a cavitation device are connected in series.
A cavitation device is a device that causes and activates cavitation in water. For example, the cavitation generator can be configured by providing a plurality of protrusions or orifices inside the middle portion of the conduit for pressurizing and circulating water. When water is pressure-fed into such a conduit, the water is accelerated and boiled under reduced pressure at a portion provided with a plurality of protrusions or orifices, and a steam bubble is generated. When this bubble disappears by pressurization, a high-temperature and high-pressure field is locally formed, where water is thermally decomposed to generate active oxygen.
In this example, the water activation device 10 is configured by combining the photocatalyst device and the cavitation generator. However, the water activation device 10 can also be composed of only a cavitation device.

FIG. 5 is a basic configuration diagram of another example of the mineral oil refining apparatus according to the present invention.
The mineral oil refining device 1 is characterized in that it is provided with a temperature control device 13 for keeping the water activating device 10, the mineral oil mixing device 11, and the mineral oil separating device 12 at an appropriate temperature. That is, the temperature control equipment 13 controls the temperature of water and the mixed liquid of water and mineral oil within a predetermined temperature range.
The temperature control equipment 13 may be configured as a constant temperature bath that surrounds the water activation device 10, the mineral oil mixing device 11, and the mineral oil separation device 12. Alternatively, it may be an air conditioning facility for a room space in which a water activation device 10, a mineral oil mixing device 11, and a mineral oil separating device 12 are installed.
With such a temperature control equipment 13, the temperature of the water activating device 10, the mineral oil mixing device 11, and the mineral oil separating device 12 is set to 20 to 45 degrees Celsius, preferably 30 to 40 degrees Celsius, and more preferably 37 to 38 degrees Celsius. It is good to keep it in. Generally, as the temperature rises, the activity of the photocatalyst increases, but the solubility of carbon dioxide, oxygen, etc. decreases. Further, when the temperature becomes 15 ° C. or lower, water clusters become large, so that the performance of the RO membrane (reverse osmosis membrane) deteriorates. Therefore, although the reaction occurs even at 20 to 45 degrees Celsius, 37 to 38 degrees Celsius is optimal.
The following experimental results have been obtained regarding changes in the yield of mineral oil with temperature.
When the temperature is 20 degrees Celsius, the yield of mineral oil (natural increase) is 4%, when the temperature is 25 degrees Celsius, the yield of mineral oil is 6%, when the temperature is 30 degrees Celsius, the yield of mineral oil is 8%, and the yield is 8%. The yield of mineral oil at 37-38 degrees was 10%, and the yield of mineral oil at 40 degrees Celsius was 6%.

Further, the mineral oil refining device 1 of this example further includes an oxygen supply device 14 for supplying oxygen gas to water. The oxygen supply device 14 dissolves oxygen gas in water before it is supplied to the water activation device 10. That is, in this example, active oxygen is generated after further adding oxygen to water containing carbon dioxide. In this way, active oxygen is efficiently generated, and as a result, the effect of increasing the yield of mineral oil can be obtained.

1 Mineral oil refining device 10 Water activation device 11 Mineral oil mixing device 12 Mineral oil separation device

Claims (9)

Generates active oxygen in water,
Mineral oil is mixed with the water in which the active oxygen is generated,
The mixture is separated into water, impurities and mineral oil.
A mineral oil refining method for recovering mineral oil after its natural separation. In claim 1,
A method for refining mineral oil, which comprises generating the active oxygen with a photocatalyst. In claim 1,
A method for refining mineral oil, which comprises generating the active oxygen by cavitation. In any one of claims 1 to 3,
The mineral oil refining method, wherein the mineral oil is heavy oil. In any one of claims 1 to 3,
The mineral oil refining method, wherein the mineral oil is light oil. A water activator that produces active oxygen in water,
A mineral oil mixing device that mixes mineral oil with the water in which the active oxygen is generated,
A mineral oil refining device including a mineral oil separating device that separates the mixed liquid into water, impurities, and mineral oil. In claim 6,
The water activation device is a mineral oil refining device characterized in that active oxygen is generated by a photocatalyst. In claim 6,
The water activating device is a mineral oil refining device characterized in that active oxygen is generated by cavitation. In any one of claims 6 to 8,
A mineral oil refining apparatus characterized in that the mineral oil is heavy oil.

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