Method for improving combustibility of oil containing large amount of aromatic component, and method for producing internal combustion engine fuel

Abstract

To provide a novel method for using flame-retardant oil containing a large amount of flame-retardant aromatic components, such as waste tire oil, as an internal combustion engine fuel.SOLUTION: A method for producing an internal combustion engine fuel comprises: a mixing step of mixing flame-retardant oil containing a large amount of flame-retardant aromatic components with blending oil selected from the group consisting of light oil and kerosene; and a radical generation treatment step of generating hydroperoxy radicals in the blending oil.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for improving the combustibility of oils containing a large amount of flame-retardant aromatic components, such as waste tire recycled oil recycled from waste tires (hereinafter also referred to as "flame-retardant oil"). The present invention also relates to a method for producing an internal combustion engine fuel using the method.

Background Art

[0002] Technologies related to the recycling of waste tires have attracted attention from the perspective of effective utilization of resources. When the high-temperature gas generated during the pyrolysis of waste tires is cooled and condensed, a liquid oil component can be obtained as waste tire oil. Since the obtained waste tire oil contains a large amount of flame-retardant aromatic components (for example, about 76%, see Table 2 in the examples), its combustion characteristics are low, and thus it cannot be directly used as a fuel for internal combustion engines such as diesel. When used as a fuel for an internal combustion engine, it is necessary to mix it with an oil having good combustion characteristics containing a large amount of unsaturated fatty acids and / or short-chain alkanes (hereinafter referred to as "blending oil" in this specification) to reduce the ratio of flame-retardant aromatic components in the fuel.

[0003] On the other hand, in order to effectively utilize waste tire oil, for example, Patent Document 1 discloses a method for pyrolyzing waste tires that can control the flash point of waste tire oil.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Although Patent Document 1 describes controlling the flash point of waste tire oil, the resulting waste tire oil still contains a large amount of flame-retardant aromatic components. When used as an internal combustion engine fuel, it was necessary to mix a large amount of blending oil. And blending oils with good combustion characteristics are costly, which has been a problem for using waste tire oil as an internal combustion engine fuel. The present invention solves such problems and provides a new method for using a flame-retardant oil containing a large amount of flame-retardant aromatic components such as waste tire oil as an internal combustion engine fuel.

Means for Solving the Problems

[0006] The inventor of the present invention conducted studies to solve the above problems and found that by performing a radical generation treatment on the blending oil, the combustion characteristics of the flame-retardant oil can be greatly improved even when the mixing ratio of the blending oil is low. The inventor believes that this is because by performing a radical generation treatment on the blending oil, hydroperoxy radicals are generated, making the low-temperature oxidation reaction likely to occur, thereby improving the combustion characteristics.

[0007] That is, the present invention is a method for producing an internal combustion engine fuel including a mixing step of mixing a flame-retardant oil containing a large amount of flame-retardant aromatic components and a blending oil selected from the group consisting of vegetable oil, light oil, and kerosene, which includes a radical generation treatment step of generating hydroperoxy radicals in the blending oil.

[0008] In the present invention, in the mixing step, it is preferable to contain the blending oil in an amount of 25% by volume or less based on the total amount, more preferably 20% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less. Also, it is preferable to contain 1% by volume or more, preferably 3% by volume or more, and more preferably 5% by volume or more. Also, a radical generation treatment step may be performed on the blending oil in advance before the mixing step, or a radical generation treatment step may be performed on the mixed oil after the mixing step.

[0009] The radical generation treatment step is preferably a step of treating the blending oil by one or more methods selected from the group consisting of mixing treatment with ozone and / or hydrogen peroxide, magnetic field treatment, electrolysis treatment, heat treatment, ultraviolet treatment, and catalyst treatment.

[0010] Another aspect of the present invention is a method for improving the combustibility of a flame-retardant oil containing 40% by volume or more of a flame-retardant aromatic component, including a step of mixing the blending oil subjected to radical generation treatment with the flame-retardant oil, wherein the mixing amount of the blending oil is 1 to 25% by volume based on the total amount.

[0011] Another aspect of the present invention is a method for improving the combustibility of a flame-retardant oil containing 40% by volume or more of a flame-retardant aromatic component, including a step of mixing the blending oil with the oil, and a treatment step of subjecting the mixed mixture to radical treatment, wherein the mixing amount of the blending oil is 1 to 25% by volume based on the total amount.

Advantages of the Invention

[0012] According to the present invention, a new method for using a flame-retardant oil containing a large amount of a flame-retardant aromatic component such as waste tire oil as an internal combustion engine fuel can be provided. Specifically, by performing radical generation treatment on the blending oil, the combustion characteristics of the flame-retardant oil can be improved even when the mixing ratio of the blending oil is low, and it can be used as an internal combustion engine fuel compatible with conventional internal combustion engines.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Embodiment for Carrying Out the Invention

[0014] Hereinafter, the present invention will be described in more detail, but the scope of the invention is not limited only to the specific forms.

[0015] One embodiment of the present invention is a method for producing an internal combustion engine fuel, including a mixing step of mixing a flame-retardant oil containing a large amount of flame-retardant aromatic components and a blending oil selected from the group consisting of vegetable oil, light oil, and kerosene, and a radical generation treatment step of generating hydroperoxy radicals in the blending oil.

[0016] <Mixing step> The mixing step is a step of mixing the flame-retardant oil and the blending oil. The flame-retardant oil contains a large amount of flame-retardant aromatic components and is typically waste tire oil. Since the flame-retardant oil contains a large amount of flame-retardant aromatic components, it is difficult to use it as an internal combustion engine fuel by itself. The content of the flame-retardant aromatic components in the flame-retardant oil may usually be 40% by volume or more, may be 50% by volume or more, may be 60% by volume or more, and may be 70% by volume or more. The content of the flame-retardant aromatic components in the flame-retardant oil is usually 100% by volume or less and may be 90% by volume or less.

[0017] The blending oil is selected from the group consisting of vegetable oil, light oil, and kerosene. Examples of the vegetable oil include, but are not limited to, palm oil, soybean oil, rapeseed oil, sunflower oil, palm kernel oil, cottonseed oil, peanut oil, olive oil, coconut oil, corn oil, and pongamia oil. From the viewpoint of facilitating the occurrence of low-temperature oxidation reaction, it is preferable to contain a large amount of unsaturated fatty acids and / or short-chain alkanes.

[0018] In the blending process, it is preferable that the blending oil is contained in an amount of 25% by volume or less, more preferably 20% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less, based on the total amount of the blending oil and the flame retardant oil. Also, it is preferably contained in an amount of 1% by volume or more, more preferably 3% by volume or more, and still more preferably 5% by volume or more.

[0019] <Radical treatment process> The radical treatment process is a process of generating hydroperoxy radicals in the blending oil. By subjecting the blending oil to radical generation treatment, hydroperoxy radicals are generated, making it easier to cause a low-temperature oxidation reaction.

[0020] The radical treatment is not particularly limited as long as it can generate hydroperoxy radicals in the blending oil, but it is preferably selected from a mixed treatment with ozone and / or hydrogen peroxide, magnetic field treatment, electrolytic treatment, heat treatment, ultraviolet treatment, and catalytic treatment. These methods may be used alone or in combination of two or more. For example, when using light oil as the blending oil, hydroperoxy radicals can be generated by performing heat treatment at a temperature below the flash point temperature after ozone treatment. In the case of vegetable oil containing a large amount of unsaturated fatty acids, hydroperoxy radicals can be generated only by heat treatment. Also, ultraviolet treatment and catalytic treatment can be combined as appropriate.

[0021] The mixing amounts of ozone and hydrogen peroxide in the mixed treatment with ozone and / or hydrogen peroxide are not particularly limited, but since it is difficult to dissolve in the recycled oil, it is necessary to dissolve it using a stirrer such as a mixer. Magnetic field treatment generates hydroperoxy radicals by applying a magnetic field with a magnetic field generator or a strong magnet to cause an oxidation-reduction reaction. Electrolytic treatment generates hydroperoxy radicals by applying a voltage or potential according to a conventional method to cause an oxidation-reduction reaction. The heat treatment may be performed at a temperature below the flash point of the blending oil. The heating time is appropriately set according to the type of blending oil used. For the ultraviolet treatment, the blending oil may be irradiated with ultraviolet rays by using an existing ultraviolet irradiation device. The irradiation time is appropriately set according to the type of blending oil used. For the catalyst treatment, existing catalysts used to promote the reaction, such as copper, iron, manganese, chromium, nickel, cobalt, etc., can be used.

[0022] In the radical generation step, the peroxide value (POV) of the blending oil after radical treatment is preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 15 or less.

[0023] Before the mixing step, a radical generation treatment step may be performed on the blending oil in advance, or after the mixing step, a radical generation treatment step may be performed on the mixed oil.

[0024] The outline of the apparatus used in the method for manufacturing an internal combustion engine fuel according to this embodiment is shown in FIG. 1. In the waste tire oil tank 9, waste tire oil is stored as a fire-resistant oil. As the blending oil to be mixed with the waste tire oil, vegetable oil is stored in the blending oil tank 1A and light oil is stored in the blending oil tank 1B. There may be one blending oil tank, but in the case of one tank, it becomes a batch type in which the blending oil is radical-treated and then mixed with the waste tire oil. From the viewpoint of the production efficiency of the internal combustion engine fuel, it is preferable to have two or more blending oil tanks. In the case of having two or more blending oil tanks, the types of blending oil in the tanks may be the same or different.

[0025] ​The blending oil tank 1A is provided with a heater 2A and can heat the vegetable oil stored therein. While appropriately setting the heating temperature and heating time according to the type of vegetable oil and heating it, oxygen is supplied and mixed by an air compressor 3, and stirred by a stirrer 5A, thereby performing radical generation treatment on the vegetable oil to generate hydroperoxy radicals. At this time, the POV of the vegetable oil is adjusted to be about 10 to 18, preferably about 12 to 15.

[0026] In addition, the blending oil tank 1A may be provided with an ultraviolet ray generating device (not shown) for performing radical generation treatment on the upper part or side part of the tank, or an oxidation catalyst (not shown) such as copper, iron, manganese, chromium, nickel, cobalt, etc. may be arranged in the tank. When arranging the oxidation catalyst at a predetermined position, it is preferable to control the temperature so that the blending oil convects in the tank.

[0027] The blending oil tank 1B is provided with a heater 2B and can heat the light oil stored therein. At this time, since the flash point of the light oil is about 50°C, it is necessary to pay attention not to raise the temperature of the light oil too much by heating. While heating, ozone is supplied and mixed by an ozone generating device 4, and stirred by a stirrer 5B, thereby performing radical generation treatment on the light oil to generate hydroperoxy radicals. At this time, the POV of the light oil is adjusted to be about 10 to 18, preferably about 12 to 15.

[0028] In addition, the blending oil tank 1B may be provided with an ultraviolet ray generating device (not shown) for performing radical generation treatment on the upper part or side part of the tank, or an oxidation catalyst (not shown) such as copper, iron, manganese, chromium, nickel, cobalt, etc. may be arranged in the tank. When arranging the oxidation catalyst at a predetermined position, it is preferable to control the temperature so that the blending oil convects in the tank.

[0029] The blended oil subjected to radical generation treatment is mixed with the waste tire oil in the waste tire oil tank 9. The amount of the blended oil at this time is preferably 1 to 25% by volume or less, particularly preferably 5 to 10% by volume, based on the amount of the waste tire oil. The mixed blended oil and waste tire oil are stirred by a stirrer 5C and sent to an internal combustion engine such as a diesel engine.

[0030] The mixing of the blended oil and the waste tire oil may be carried out by batch processing. However, by providing flow meters (not shown) in the respective lines from the blended oil tank and the waste tire oil tank and adjusting the respective flow rates, the fuel for the internal combustion engine can be produced continuously.

Example

[0031] Hereinafter, the present embodiment will be described in more detail with reference to examples, but the scope of the present invention is not limited by this description.

[0032] <Confirmation of heat generation by low-temperature oxidation reaction> Waste tire oil 1 having the following Table 1 components (unit: %) was prepared. Next, commercially available light oil was mixed with waste tire oil 1 so as to be 5% of the whole, and mixed oil 1 (POV of the mixed oil after magnetic treatment = 12) subjected to magnetic treatment was prepared. The components of the mixed oil 1 are shown in Table 1.

[0033]

Table 1

[0034] Regarding the mixed oil 1 and the waste tire oil 1 shown in Table 1, the combustion characteristics were confirmed by a fuel oil ignition fuel property test apparatus (FCA). The results are shown in Figure 2. From Figure 2, it was confirmed that the blended oil 1 generated heat due to the low-temperature oxidation reaction as shown by the dashed line. Also, when measuring the low-temperature maximum heat generation rate (maximum ROHR), the waste tire oil 1 was 0.31, while the blended oil 1 was 0.59. Further, when measuring the cumulative heat generation rate, the waste tire oil 1 was 4.90, while the blended oil 1 was 6.99. From the above, it can be understood that the combustibility of the blended oil 1 was improved and the main combustion was promoted.

[0035] <Confirmation of the Effect of Radical Generation Treatment> Waste tire oil 2 shown in Table 2 was prepared. Next, blended oil 2 in which pongamia oil (acid value: 13.8 mgKOH / g, fatty acid composition shown in Table 3 (unit is %)) was mixed with waste tire oil 2 to a total of 50% by volume, blended oil 3 in which pongamia oil was mixed with waste tire oil 2 to a total of 25% by volume, and blended oil 4 in which pongamia oil was mixed with waste tire oil 2 to a total of 10% by volume were prepared. Note that the radical generation treatment was not performed.

[0036]

Table 2

[0037]

Table 3

[0038] For blended oils 2 to 4, the combustion characteristics were confirmed using a fuel oil ignition fuel property test apparatus (FCA). The results are shown in Figure 3. From Figure 3, blended oil 2 in which pongamia oil was mixed to a total of 50% by volume and blended oil 3 in which pongamia oil was mixed to a total of 25% by volume had good combustion characteristics because a large amount of blending oil was mixed. On the other hand, for blended oil 4 in which pongamia oil was mixed to a total of 10% by volume, when measuring the low-temperature maximum heat generation rate (maximum ROHR), it was 0.31, and when measuring the cumulative heat generation rate, it was 4.92, and the combustion characteristics were at the same level as waste tire oil 1.

[0039] That is, when the blending oil is not subjected to radical generation treatment, it is necessary to increase the content of the blending oil in order to improve the combustion characteristics of the mixed oil. When the content of the blending oil is about 10%, the combustion characteristics are not improved compared with waste tire oil. On the other hand, as in the case of the mixed oil 1, even when the content of the blending oil is about 5%, it can be understood that the combustion characteristics are improved by the low-temperature oxidation reaction by subjecting the blending oil to radical generation treatment.

Industrial Applicability

[0040] According to the present invention, new uses can be imparted to the recycled oil extracted from waste tires. That is, the reuse of waste tires, which have become a social problem as industrial waste, can be promoted. Furthermore, the combustion characteristics of the flame-retardant oil can be improved. That is, a new way of using the flame-retardant oil, which was difficult to use in conventional internal combustion engines, will be opened up. The present invention greatly contributes to the reduction of the environmental load and is an invention with extremely high contribution to the SDGs.

Explanation of Signs

[0041] 1A Blending oil tank (vegetable oil) 1B Blending oil tank (light oil) 2A, 2B Heater 3 Air compressor 4 Ozone generator 5A, 5B, 5C Stirrer 6 Flow control valve with switching valve 7 Flow control valve 8 Three-way valve 9 Waste tire oil tank

Claims

1. A method for manufacturing an internal combustion engine fuel, comprising a mixing step of mixing a flame-retardant oil containing a large amount of flame-retardant aromatic components and a blending oil selected from the group consisting of light oil and kerosene. The method for manufacturing an internal combustion engine fuel includes a radical generation treatment step of generating hydroperoxy radicals in the blending oil.

2. In the mixing step, the blending oil is contained in an amount of 25% by volume or less based on the total amount. The method for manufacturing an internal combustion engine fuel according to Claim 1.

3. Before the mixing step, a radical generation treatment step is performed on the blending oil in advance. The manufacturing method according to Claim 1 or 2.

4. After the mixing step, the radical generation treatment step is performed. The manufacturing method according to Claim 1 or 2.

5. In the radical generation treatment step, the blending oil is treated by one or more methods selected from the group consisting of mixing treatment with ozone and / or hydrogen peroxide, magnetic field treatment, electrolysis treatment, heat treatment, ultraviolet treatment, and catalyst treatment. The manufacturing method according to Claim 1 or 2.

6. A method for improving the combustibility of a flame-retardant oil containing 40% by volume or more of flame-retardant aromatic components. The method includes a step of mixing the blending oil subjected to radical generation treatment and the flame-retardant oil, and the mixing amount of the blending oil is 1 to 25% by volume based on the total amount.

7. A method for improving the combustibility of a flame-retardant oil containing 40% by volume or more of flame-retardant aromatic components. The method includes a step of mixing the blending oil and the flame-retardant oil, and a treatment step of performing radical treatment on the mixed mixture. The mixing amount of the blending oil is 1 to 25% by volume based on the total amount.

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