US20200032153A1

US20200032153A1 - Method for Producing HydroCarbon-Based Synthetic Fuel By Adding Water to Hyrocarbon-Based Fuel Oil

Info

Publication number: US20200032153A1
Application number: US16/337,824
Authority: US
Inventors: Fumio Aoki
Original assignee: Tristarhco Co Ltd
Current assignee: Tristarhco Co Ltd
Priority date: 2016-09-30
Filing date: 2017-09-28
Publication date: 2020-01-30
Also published as: JPWO2018062345A1; WO2018062345A1; TW201827582A; JP6995373B2

Abstract

In a method of producing a hydrocarbon-based synthetic fuel by adding water to a base oil, it is intended to increase a ratio of the synthetic fuel to a hydrocarbon-based fuel as the base oil, more significantly than ever before. Specifically, provided is a method of producing a hydrocarbon-based synthetic fuel oil having a volume greater than that of a hydrocarbon-based base fuel oil, by adding water to the hydrocarbon-based base fuel oil, wherein a first-order hydrocarbon-based synthetic fuel oil produced by the production method is used as a base fuel oil for producing a second-order hydrocarbon-based synthetic fuel oil, or this process is repeated plural times in sequence, thereby producing a hydrocarbon-based synthetic fuel having a high water addition rate.

Description

TECHNICAL FIELD

The present invention relates to a method of producing a hydrocarbon-based synthetic fuel equivalent to a hydrocarbon-based base fuel oil by adding water to the base oil.

BACKGROUND ART

Recently, it has been some time since environmental problems became an important issue on a global basis, and, as one countermeasure, technical developments regarding solar power generation, wind power generation and the like have been actively conducted. However, before achievement of full transition to such renewable energy, it is necessary to meticulously use traditional fossil fuel involved with a depletion problem, and conduct technical developments from many angles, such as developments regarding internal combustion engines and burning plants/facilities having less energy loss, and improvement of fossil fuel itself in terms of a calorific property or a combustion property, in a parallel manner. As one of them, it has been attempted to develop a technique of mixing water to fuel oil to increase the amount of fuel oil.
Fuel obtained by employing the conventional technique of mixing water to fuel oil is regarded as environmental load-reducing fuel, because the technique is capable of significantly reducing the amount of fuel to be used, and reducing carbon dioxide (CO₂) emission by an amount corresponding to the reduced amount of fuel used. Further, fuel oil according to this technique can be expected to be completely combusted, so that there are advantageous effects of being able to fairly reduce the amount of air to be used for combustion, and thus to suppress generation of nitrogen oxides and particulate matter (PM), and reduce an environmental load due to emission gas from boilers or internal combustion engines.
As above, such fuel increased in amount by water addition is highly useful. On the other hand, generally, water and oil have difficulty in being perfectly fused together, and tend to be separated from each other after the elapse of a certain time even when they were fully blended or mixed together. Although it is not impossible to sufficiently fuse water and oil together using a conventional technique, it requires taking so much time. Thus, it is assumed that such a conventional technique is far from practical use from an economic viewpoint.
Therefore, there is a need for a technique capable of perfectly fusing water and fuel oil together, within a relatively short period of time, so as to produce a hydrocarbon-based synthetic fuel free from separation even after the elapse of a certain time since the fusion.
As one technique of increasing the amount of hydrocarbon-based fuel, JP 4682287B (Patent Document 1) proposes a water-added fuel production method which comprises: adding catalase to a mixture of fuel oil and water; stirring and mixing the catalase-added fuel oil-water mixture while bringing the mixture into contact with a natural mineral or a metal excited by a vibrational wave such as an ultrasonic wave, thereby enhancing the degree of transparency of the mixture in an emulsion state. More specifically, the Patent Document 1 discloses a method which comprises: stirring and mixing the catalase-added fuel oil-water mixture under a contact with a natural mineral or a metal excited by a vibrational wave; and to heating the stirred and mixed fuel oil-water mixture to 30° C. to 150° C., while pressurizing the mixture at 3 atm to 10 atm, to fuse the fuel and the water together, thereby enhancing the degree of transparency of the mixture in an emulsion state. In the Patent Document 1, it is described that the catalase-added fuel oil-water mixture is brought into contact with a natural mineral or a metal excited by a vibrational wave, to fragment a molecular assembly of the fuel oil and the water, and then, after stirring and mixing the fuel oil-water mixture, the stirred and mixed fuel oil-water mixture is heated and pressurized, whereby it is possible to fuse the fuel oil and the water together, and enhance the degree of transparency of a water-added fuel in an emulsion state. In the Patent Document 1, two examples, Example 1 and Example 2, are shown, and it is described that, in each of the examples, water and fuel oil were mixed in equal amount, and transparent fuel oil could be obtained by going through a fusion step. In the Patent Document 1, it is also described that this production method makes it possible to prevent an oil-water separation phenomenon in an emulsion fuel having a water addition rate of 50% or more.
The production method described in the Patent Document 1 is based on the assumption that the amount of hydrocarbon serving as a source of combustion calorie is reduced by adding water to fuel oil, and is intended to compensate for the decline in combustion calorie due to the reduction of the hydrocarbon, by increasing the content rate of hydrogen in the fuel oil by the action of catalase. That is, teaching of the Patent Document 1 is that the hydrogen content rate can be increased by using catalase to decompose hydrogen peroxide into hydrogen and oxygen, and allowing the hydrogen to remain in the fuel oil, while releasing the oxygen to the atmosphere. However, there is a limit on compensating for the decline in rate of hydrocarbon due to water addition, only by increasing the hydrogen content rate. Thus, it is difficult to expect a significant increase in amount of fuel, from the method taught by the Patent Document 1.
JP 2014-47229A (Patent Document 2) discloses a method of producing an emulsion fuel which has capability to avoid fuel oil-water separation over a long period of time without using any surfactant, and exhibits about the same equality and calorific value as those of base fuel oil, This method comprises: causing water to flow in contact with tourmaline irradiated with far-infrared rays, microwave or ultrasonic wave; causing fuel oil to flow in contact with titanium oxide balls each having an electromagnetic wave-responsive catalyst added thereto; mixing the water and the fuel oil to prepare a mixture; and applying heat and pressure to the mixture while circulating the mixture. In this Patent Document 2, it is also described that the hydrogen content rate can be increased by addition of catalase. However, the Patent Document 2 does not include any technical teaching going beyond that of the Patent Document 1.
In the research paper titled “An efficient way of producing fuel hydrocarbon from CO₂and activated water” authored by Tadayuki IMANAKA, et al., and published to the Web by J-STAGE on Aug. 29, 2015 (Non-Patent Document 1), there is disclosed a method which comprises: generating activated water by performing treatment in which water containing nanobubbles is subjected to irradiation with UV light and black light (wavelength; 350 nm to 400 nm) in the presence of a titanium dioxide catalyst; mixing this activated water with light oil; and strongly stirring the resulting mixture to produce a synthetic oil. In the method described in this research paper, the activated water is mixed with light oil by a special mixture serving as a reaction tank, such that the resulting mixture is brought into collision with a wall of the mixer, and the mixture is circulated to repeat the collision. In this process, carbon dioxide is supplied to an upper space of the mixer serving as a reaction tank. In the method described in the Non-Patent Document 1, a cloudy emulsion is generated in the above process. Subsequently, when this emulsion is statically stored (left at rest), the emulsion is separated into two phases consisting of an oil phase and a water phase. Then, oil equivalent to light oil can be obtained from the oil phase. The research paper of the Non-Patent Document 1 reports that, with respect to the light oil used as base oil, light oil increased in amount by 5 to 10 volume % was obtained through the method disclosed therein. In the method described in the Non-Patent Document 1, carbon dioxide is supplied to the upper space of the mixer. This is understood as a technique of compensating for carbon which became deficient due to water addition, by decomposition of carbon dioxide.

PRIOR ART PUBLICATIONS

Parent Document

Parent Document 1: JP 4682287B
Patent Document 2: JP 2014-47229A

Non-Patent Document

Non-Patent Document 1: Tadayuki IMANAKA, et al., “An efficient way of producing fuel hydrocarbon from CO₂and activated water”, J-STAGE, published to the Web on Aug. 29, 2015
Non-Patent Document 2: Shinobu KODA, “Chemical Application of Cavitation; Sonochemistry (Application of Cavitation Induced by Ultrasound)”, Journal of the Institute of Electronics, Information and Communication Engineers of JAPAN, Vol J89-A, No. 9 (2006)
Non-Patent Document 3: Keiji YASUDA, “Decomposition of Chemical Compounds by Ultrasound and Development of Sonochemical Reactor”, “THE CHEMICAL TIMES”, published by Kanto Chemical Co., In, Apr. 1, 2009 Non-Patent Document 4: Yoshiteru MIZUKOSHI, “Basis of Ultrasonic Waves”, presentation material for “Monodzukuri Basic Course (34th Technical Seminar)” held on Feb. 20, 2013 at the Creation-Core Higashiosaka

SUMMARY OF INVENTION

Technical Problem

Although the methods described in the above heretofore-known documents might be able to achieve a certain level of increase rate with respect to fuel oil used as base oil, there is a limit on the level of increase rate. For example, in the method described in the Non-Patent Document 1, the increase rate is no more than 10 volume %, and in the methods described in the Patent Documents 1 and 2, an achievable of the increase rate is only about 20 volume %.
The present invention addresses the above conventional problem, and an object thereof is to provide a method of producing a hydrocarbon-based synthetic fuel by adding water to base oil, wherein the method is capable of significantly increasing the ratio of the synthetic fuel to a hydrocarbon-based fuel serving as the base oil.
It is another object of the present invention to provide a method capable of producing a hydrocarbon-based synthetic fuel which has a composition and physical properties substantially identical to or approximate to those of a base fuel oil (i.e., fuel before water addition) and exhibits properties equal to those of the base fuel oil in terms of oil-water separation, in a significantly increased amount as compared to the amount of the base fuel oil.

Solution to Technical Problem

In order to achieve the above object, there is provided a method of producing a hydrocarbon-based synthetic fuel oil having a volume greater than that of a hydrocarbon-based base fuel oil, by addition of water to the hydrocarbon-based base fuel oil, wherein a process of using a first-order hydrocarbon-based synthetic fuel oil produced in a first cycle of the production method, as a base fuel oil for producing a second-order hydrocarbon-based synthetic fuel oil, the process being carried out one or more times to produce a hydrocarbon-based synthetic fuel oil having a high water addition rate.
Specifically, according to a first aspect of the present invention, there is provided a hydrocarbon-based synthetic fuel oil production method which comprises:

a) an activated water generation step of subjecting water to activation treatment to generate activated water;
b) a stirring and mixing step of adding the activated water to a hydrocarbon-based base fuel oil used as a primary base fuel oil, and stirring and mixing the resulting mixture under a reactive environment for a given time period;
c) a fusion step of fusing together the hydrocarbon-based base fuel oil and the activated water after undergoing the stirring and mixing step, under a reactive environment; and
d) a first-order hydrocarbon-based synthetic fuel oil collection step of collecting a hydrocarbon-based synthetic fuel oil obtained from the mixture after undergoing the fusion step, as a first-order hydrocarbon-based synthetic fuel oil,
wherein a cycle of the steps b), c) and d) is performed using the first-order hydrocarbon-based synthetic fuel oil as a secondary base fuel oil, to collect a second-order hydrocarbon-based synthetic fuel oil, the cycle of the steps b), c) and d) being carried out one or more times, using a hydrocarbon-based synthetic fuel oil obtained in a preceding process, as a base fuel oil for a succeeding process, thereby producing a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O), and has a volume greater than that of the primary base fuel oil and a composition substantially identical to or approximate to that of the primary base fuel oil.

According to another aspect of the present invention, there is provided a hydrocarbon-based synthetic fuel oil production method which comprises:

a) an activated water generation step of subjecting water to activation treatment to generate activated water;
b) a stirring and mixing step of adding the activated water to the hydrocarbon-based base fuel oil used as a primary base fuel oil, and stirring and mixing the resulting mixture under a reactive environment for a given time period;
c) a fusion step of fusing together the hydrocarbon-based base fuel oil and the activated water after undergoing the stirring and mixing step, under a reactive environment;
d) an oil-water separation step of statically holding the mixture after undergoing the fusion step to cause the mixture to undergo phase separation to form an upper oil layer comprised of a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O) and has a composition substantially identical to or approximate to that of the primary base fuel oil, and a lower water layer; and
e) a first-order hydrocarbon-based synthetic fuel oil collection step of collecting the hydrocarbon-based synthetic fuel oil of the upper oil layer, as a first-order hydrocarbon-based synthetic fuel oil,
wherein
f) the stirring and mixing step and the fusion step are performed over a time period during which a volume of the first-order hydrocarbon-based synthetic fuel oil obtained in the first-order hydrocarbon-based synthetic fuel oil collection step becomes greater than a volume of the hydrocarbon-based base fuel oil used as the primary base fuel oil; and
g) a cycle of the steps b), c) d), e) and f) is performed using the first-order hydrocarbon-based synthetic fuel oil as a secondary base fuel oil, to collect a second-order hydrocarbon-based synthetic fuel oil, the cycle of the steps b), c) d), e) and f) being carried out one or more, using a hydrocarbon-based synthetic fuel oil obtained in a preceding process, as a base fuel oil for a succeeding process, to produce a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O), and has a volume greater than that of the primary base fuel oil and a composition substantially identical to or approximate to that of the primary base fuel oil.

Preferably, in the method according to the present invention, the activated water is activated such that it includes hotspots arising from microbubbles. Preferably, the activated water generation step is carried out by heating water to a temperature ranging from 35° C. to 45° C., while applying a voltage to the water, and, radiating an ultrasonic wave to the water. More preferably, the voltage application is performed by radiating an ultrasonic wave to tourmaline immersed in the water to bring the tourmaline into an excited state. Preferably, in the case where the activated water includes hotspots arising from microbubbles, the water contains a substance effective in holding the hotspots arising from microbubbles.
Preferably, the hotspots arising from microbubbles are generated by radiating, to the water, an ultrasonic wave having a frequency different from a frequency of the ultrasonic wave which is radiated to the tourmaline. Preferably, in the method according to the first or second aspect of the present invention, the reactive environment in the stirring and mixing step is formed by adding catalase to the water and then stirring the water while radiating an ultrasonic wave to the water. More preferably, the stirring is performed to create strong waves on a surface of the mixture of the water and the base fuel oil. Preferably, in the method according to the first or second aspect of the present invention, the reactive environment in the stirring and mixing step is formed by adding photocatalyst to the water and then stirring the water while radiating ultraviolet light to the water.
A synthetic fuel oil produced by the method of the present invention is a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O) and has a composition and physical properties substantially identical or equal to or approximate to those of a base fuel oil. For example, in a case where the base fuel oil is light oil for use as diesel fuel, it is possible to obtain a remarkable result that the synthetic fuel oil is produced as light oil equivalent to the base light oil. A synthetic light oil produced by the present invention is substantially free of water (H₂O), and it has been ascertained that no oil-water separation occurs even after long-term storage.
In a case where the base fuel oil is A-Class heavy oil, the method of the present invention also can produce heavy oil substantially identical or equal to or approximate to the A-Class heavy oil.
As above, despite the addition of the water to the base fuel oil, the resulting synthetic fuel is substantially free of water (H₂O) and has a composition and physical properties substantially identical to or approximate to those of the base fuel oil. For achieving this, it may not be necessary to introduce, from the outside, carbon for creating hydrocarbon as a combustible component. As a specific means to take in carbon, it is conceivable to take in carbon dioxide in surrounding air through a liquid surface of the mixture of the base fuel oil and the water, and decompose the carbon dioxide to utilize the resulting carbon as at least a large part of carbon necessary for a reaction for producing the synthetic fuel. In this regard, in a case where the stirring and mixing step is performed in a space opened to the atmosphere, it is effective that, in the stirring and mixing step, the mixture of the base fuel oil and the water is recirculated to create strong waves on a liquid surface of the mixture. In a case where a surrounding area of a site for performing the stirring and mixing step is a closed space, the amount of carbon dioxide to be taken in from surrounding air becomes insufficient. However, it has been ascertained that, even in this situation, an intended synthetic fuel can be obtained by adding carbon to the mixture of the base fuel oil and the water. As carbon to be added, it is possible to use charcoal obtained by carbonizing wood. It is also possible to advantageously use a carbon powder used in industrial applications. Alternatively, carbon monoxide gas or carbon dioxide gas may be added and then decomposed in the same manner as that for carbon dioxide gas taken in from surrounding air, and resulting carbon may be used to produce a synthetic fuel.
It is also assumed that hydrogen necessary for creating hydrocarbon as a combustible component is obtained by decomposition of molecules of the activated water. In the method of the present invention, water molecules are activated to include hotspots arising from microbubbles. It has been ascertained that hydrogen necessary for the reaction can be obtained by adding at least one selected from the group consisting of catalase, sodium hydroxide and an aqueous hydrogen peroxide solution, to water including such activated molecules, and stirring the resulting mixture.
It is considered that there is no particular limit in terms of the amount of the water to be added to the base fuel oil. However, if the amount of the water to be added to the base fuel oil is excessively increased, the reaction time necessary for producing a synthetic fuel having a desired composition is prolonged to an extent that the method is deemed as impractical. The inventor of the present invention has ascertained that, even when the water is mixed with the base fuel oil in a ratio by volume of about 1 with respect of 1 of the base fuel oil, a desired synthetic fuel can be produced in a sufficiently short period of time. When the ratio of the water to be added is less than the above value, a desired result can be obtained within a shorter period of time. Thus, preferably, in the method of the present invention, a mixing ratio by volume of the water to the base fuel oil is set to about 1 or less with respect to 1 of base fuel oil.
Preferably, in the method of the present invention, the stirring and mixing step includes: putting only the base fuel oil into a stirring and mixing tank; and then adding and mixing the water after undergoing a water activation step and an additive input step, to and with the base fuel oil in increments of a given amount, while stirring the base fuel oil. In this case, the mixture is intensely stirred to create strong waves on a liquid surface. This advantageously enables carbon dioxide in air to be taken in the mixture.
Preferably, the method of the present invention is implemented using an apparatus comprising: a stirring and mixing tank having a cylindrical portion; and at least one injection pipe for putting the water after undergoing the water activation step and the additive input step, into the stirring and mixing tank by means of injection or the like, wherein an injection direction of the water from the injection pipe is set to have a given angle with respect to a diametrical line of the cylindrical portion.
In the method according to the above embodiment of the present invention using the apparatus provided with the at least one injection pipe in the stirring and mixing tank having the cylindrical portion, the given angle is preferably in the range of about 40 degrees to about 50 degrees, particularly about 45 degrees. In a case where a plurality of the injection pipes are provided, the given angle in each of the injection pipes is preferably set to a specific angle, e.g., about 45 degrees, falling within the range of about 40 degrees to about 50 degrees. From a viewpoint of creating strong waves on the liquid surface in the stirring and mixing tank as mentioned above, an injection port of the injection pipe is preferably disposed at a position upwardly away from the liquid surface by at least about 8 cm, preferably 10 cm or more, to inject the activated water onto the liquid surface in the form of a high-speed jet.
Preferably, in the above embodiment, the injection pipe has a protruding portion protruding inside the stifling and mixing tank.
In this case, the protruding portion preferably has a length of about 10 cm.
In one preferred embodiment of the present invention, catalase may be added by 0.04 to 0.05% in terms of a ratio by weight thereof to the water, in the additive input step.
In another preferred embodiment of the present invention, the water activation step may include activating the water such that an ORP (Oxidation-Reduction Potential) value thereof falls within the range of 160 mV to-200 mV.
In yet another preferred embodiment of the present invention, the water activation step may include: keeping tourmaline or a copper ion generating material in contact with the water; and, in this state, alternately radiating first and second ultrasonic waves each having a respective one of a frequency of 10 kHz to 60 kHz and a frequency of 200 kHz or more, to the water, or the tourmaline or the copper ion generating material, thereby activating the water by electrical energy radiated from the tourmaline or copper ions radiated from the copper ion generating material.
In still another preferred embodiment of the present invention, the fusion step may be performed under a pressurization condition set at about 0.3 MPa or more and a heating condition set in the range of about 40° C. to about 80° C.
In yet still another preferred embodiment of the present invention, the stirring and mixing step may be performed using an OHR (Original Hydrodynamic Reaction) mixer.

Effect of Invention

The method of the present invention makes it possible to obtain a hydrocarbon-based synthetic fuel oil which is less likely to cause or free from causing oil-water separation after being synthesized or fused once. Further, by repeating the cycle of the steps, using a synthetic fuel oil obtained in the previous cycle as a base oil for the current cycle, it becomes possible to efficiently produce a hydrocarbon-based synthetic fuel oil having a high water addition rate. The synthetic fuel oil produced by the method of the present invention is substantially free of water (H₂O) and has a composition and physical properties substantially identical to or approximate to those of the base fuel oil, as mentioned above.
Further, the hydrocarbon-based synthetic fuel oil of the present invention is equal to or superior to existing fuel oils, in terms of a calorific value per unit quantum, and has an advantageous effect of being less likely to cause degradation or corrosion of a combustion chamber, an exhaust pipe or the like after combustion, as compared to the existing fuel oils. Furthermore, the synthetic fuel oil of the present invention can achieve advantageous effects of: being excellent in perfect combustibility; being less likely to generate carbon monoxide; and being low in amount of emission of carbon monoxide.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a process chart of a synthetic fuel oil production method according to one embodiment of the present invention.

FIG. 2 is a diagram depicting the overall configuration of a production apparatus capable of implementing the synthetic fuel oil production method according to the one embodiment.

FIG. 3 is a diagram depicting the structure of an injection pipe for injection to a reaction tank, in a stirring device usable in the production apparatus in FIG. 2.

FIG. 4 is a schematic diagram depicting one example of an ionization device usable in the production apparatus in FIG. 2.

FIG. 5 is a chart presenting a result of GC-MS analysis regarding a hydrocarbon-based synthetic fuel oil obtained in one example using light oil as base oil.

FIG. 6 is a chart presenting a result of GC-MS analysis regarding a synthetic fuel obtained in another example using light oil as base oil.

FIG. 7 is a chart presenting a result of GC-MS analysis regarding the light oil used as base oil.

FIG. 8 is a chart presenting a result of GC-MS analysis regarding yet another synthetic fuel obtained in yet another example using A-heavy oil as base oil.

FIG. 9 is a chart presenting a result of GC-MS analysis regarding the A-heavy oil used as base oil.

DESCRIPTION OF EMBODIMENTS

With reference to the drawings, a hydrocarbon-based synthetic fuel oil production method according to the present invention will now be described based on one embodiment thereof.
It should be noted that an overall configuration, individual detailed configurations and numerical values in the synthetic fuel production method described in the following embodiment and examples are not meant to be construed in a limiting sense, but various changes and modifications may be made therein within the spirit and scope of the present invention, i.e., within configurations and dimensions capable of fulfilling the same function.
One embodiment of the present invention will be described based on FIGS. 1, 2 and 3. FIG. 1 is a flowchart of a process regarding the method according to this embodiment, to be performed in the following production apparatus. FIG. 2 is a diagram depicting the overall configuration of a production apparatus capable of implementing the synthetic fuel production method according to this embodiment, and FIG. 3 is a diagram depicting the structure of an injection pipe for performing water injection to a reaction tank of the production apparatus in FIG. 2.
Referring to FIG. 2, the synthetic fuel production apparatus 1 according to this embodiment comprises a base oil improving tank 2, a water refining tank 3, a reaction accelerator injection unit 4, a reaction tank 5, a statically-storing tank 6, and a product receiving tank 7. This apparatus 1 can be outlined as follows. Base fuel oil is subjected to pretreatment in the base oil improving tank 2, and water is subjected to activation treatment in the water refining tank 3. Then, an additive is put into a given tank from the reaction accelerator injection unit 4. Further, the base fuel oil and the water are stirred, mixed and fused together in the reaction tank 5. Then, after removing unwanted residues such as scum, and, optionally, as needed, performing phase separation between an oil phase and a water phase, in the statically-storing tank 6, a hydrocarbon-based synthetic fuel oil as a product is introduced into the product receiving tank 7 from the statically-storing tank 6.
The base oil improving tank 2 is a tank for subjecting base fuel oil to pretreatment prior to the mixing. The base fuel oil is supplied from another base oil tank 201. This base oil improving tank is intended to set the temperature of the base oil to a value appropriate to the mixing. The base fuel oil is supplied from the base oil tank 201 to the base oil improving tank 2. Then, the base fuel oil is heated up to a given temperature by a first heater 8 provided in the base oil improving tank 2, and controlled at the given temperature by a first thermocouple (T).
In order to improve the degree of uniformity in oil temperature, the base fuel oil within the base oil improving tank 2 may be circulated according to a first pump such that it is extracted from the base oil improving tank 2, and re-put into the base oil improving tank 2 via a header pipe 202. Further, the pretreatment may include fragmenting molecules of the base fuel oil using a catalyst.
The water refining tank 3 is configured to perform a water activation step (activated water generation step). Preferably, water to be used in the method according to the present invention is soft water. Thus, water is preferably supplied from a water softening device 301. This water refining tank 3 is intended to keep the temperature of the water at a value appropriate to the mixing, and fragment molecules of the water to reach an active level to form activated water including hotspots arising from microbubbles. The water supplied to the water refining tank 3 is heated up to a given temperature by a second heater 8 provided in the water refining tank 3, and controlled at the given temperature by a second thermocouple (T). The level of activation can be measured using an ORP (Oxidation-Reduction Potential) meter. The water refining tank 3 is provided with an ultrasonic wave generator 10 at the bottom thereof. The ultrasonic wave generator 10 is operable to radiate an ultrasonic wave to the water to thereby fragment a molecular assembly of the water. In this process, it is desirable to alternately radiate two types of ultrasonic waves having different wavelength. Specifically, it is desirable to alternately radiate a first ultrasonic wave having a frequency of 10 kHz to 60 kHz and a second ultrasonic wave having a frequency of 200 kHz or more. This provides improved efficiency of the activation.
Further, in the water refining tank 3, tourmaline or a copper ion generating material is preferably used as a catalyst 9. During radiation of the ultrasonic wave from the ultrasonic wave generator 10, the catalyst 9 is kept in contact with the water, so that it is possible to improve efficiency of the activation by electrical energy radiated from the catalyst 9. Further, an ultrasonic wave may be radiated to the catalyst 9, such as tourmaline or a copper ion generating material, immersed in the water contained in the water refining tank 3, to promote action of the catalyst.
In order to uniformly activate the water, the water within the water refining tank 3 may be circulated according to a second pump such that it is extracted toward a header pipe 302 and returned to the water refining tank 3 from the header pipe 302. In this case, the water is extracted from a lower portion of the water refining tank, and, after being pressurized by the second pump re-injected from an upper portion of the water refining tank via the header pipe 302. The above structure makes it possible to achieve uniformity in temperature and activation of the water.
The activation of the water may be performed by plasma arc water treatment configured to generate a discharge between two electrodes connected to a high-voltage transformer to thereby cause dissociation and ionization of the water. In the case where the water is activated by the plasma arc water treatment, the plasma arc water treatment can be performed by a plasma arc water treatment unit provided in a circulation path of the water at a position between the water refining tank 3 and the second pump 11. Further, in the plasma arc water treatment, alumina can be suitably used as the catalyst 9.
In the present invention, the application of electrical energy and the plasma arc water treatment will be collectively or generically referred to as “electrical stimulus”.
The reaction accelerator injection unit 4 is provided as a means to put an additive as a reaction accelerator into the water refining tank 3 or the reaction tank 5. The additive is a substance capable of decomposing hydrogen peroxide into hydrogen and oxygen, and releasing the oxygen to the atmosphere in the form of gas. Based on this function, it is possible to increase a hydrogen content ratio in a resulting synthetic fuel oil to prevent lowering of the calorific value of the synthetic fuel oil. As the additive, it is possible to use catalase, sodium hydroxide, an aqueous hydrogen peroxide solution or the like. The input amount of the additive needs to be finely adjusted. In the case where catalase is added, the addition amount of catalase is preferably in the range of 0.04% to 0.05%, in terms of a ratio by weight thereof to the water. If the addition amount of catalase is less than 0.04%, it becomes impossible to sufficiently bring out an intended effect. On the other hand, if the addition amount is greater than 0.05%, it becomes impossible to ensure sufficient dissolution, leading to an increase in scum and thus deterioration in quality of a resulting synthetic fuel oil.
The reaction tank 5 is provided as a means to perform a stirring and mixing step and a fusion step. The base fuel oil is supplied from the base oil improving tank 2 to an upper portion of a reaction tank container 13. The water is supplied from the water refining tank 3 to a lateral side of the container 13 of the reaction tank 5 via an injection pipe 14. A mixture of the base fuel oil and the water is circulated according to a third pump such that it is extracted from a discharge port 15 of the container 13 of the reaction tank 5, and re-put into the container 13 of the reaction tank 5 via an OHR (Original Hydrodynamic Reaction) mixer 12, a header pipe 502 and the injection pipe 14, in a pressurized state. The OHR mixer 12 is provided as a means to efficiently mix a plurality of materials together. This reaction tank 5 undergoes a pressure of about 3 to 9 atm during the fusion step, so that it is necessary to have a structure capable withstanding a higher pressure as compared to the remaining tanks. The reaction tank 5 is provided with a third heater 8 at a vertically intermediate position thereof. The mixture of the base fuel oil and the water is controlled at a given temperature by the third heater 8.
The statically-storing tank 6 is a tank for temporarily storing a product liquid after the fusion step. In this statically-storing tank 6, impurities generated from the additive and others, such as scum, are precipitated. A synthetic fuel oil in which the base fuel oil and the water are perfectly fused together and the impurities are separated from each other through static storage in the statically-storing tank 6, and the synthetic fuel oil as a supernatant is supplied to the product receiving tank 7. The additive is included in the impurities, so that the impurities are returned to the reaction tank 5. A residence time period in the statically-storing tank is preferably set to about one hour. In a case where the product liquid after the fusion step contains water, the product liquid is subjected to phase separation in the statically-storing tank 6 to form an upper oil phase and a lower water phase, and a synthesis oil as the upper oil phase is extracted as a product into the product receiving tank 7.
The product receiving tank 7 is a tank for storing the synthetic fuel oil produced as a product. The produced synthetic fuel oil is supplied from the product receiving tank 7 to a product storage tank 701, when it is accumulated to a certain amount.
Next, with reference to FIG. 1, a basic process in the synthetic fuel production method according to the present invention will be described. This method is divided into a process for treating water (water treating process) and a process for treating base fuel oil (base fuel oil treating process). The water treating process comprises a water activation step and an additive input step. The base fuel oil treating process comprises a base oil improving step and an additive input step. The activated water after undergoing the water activation step and the additive input step and the base fuel oil after undergoing the base oil improving step and the additive input step are stirred and mixed together in a stirring and mixing step, and the resulting mixture is produced as a first-order synthetic oil through a fusion step. When needed, a filtration step is performed before extraction of the first-order synthetic oil
The water activation step is performed in the water refining tank 3. In this step, a water molecule assembly is fragmented to reach an active level. By fragmenting molecules of the water to reach the active level, it becomes possible to improve compatibility with molecules of the base fuel oil to thereby enable a larger amount of water to be used for producing a synthetic fuel. Specifically, water is put into the water refining tank 3, and an ultrasonic wave is radiated from the ultrasonic wave generator 10 to the water, so that the water is vibrated at a high frequency to promote fragmentation of the water molecules. The fragmentation of the water molecules can be promoted by alternately radiating two types of ultrasonic waves having different frequencies. For example, the two types of ultrasonic waves may have a frequency of 10 kHz to 60 kHz and a frequency of 200 kHz or more, respectively, to facilitate the molecular fragmentation. Further, in the case where the ultrasonic wave generator 10 is used, it is effective that an electrical stimulus is applied to the water by additionally using, as the catalyst, tourmaline or a copper ion generating material. By operating the ultrasonic wave generator 10 while immersing such a catalytic material in the water, an electrical stimulus can be applied to the water to form hotspots arising from microbubbles in the water, so that it is possible to increase the degree of activation of the water. In this case, the ultrasonic waves are preferably radiated such that they hit the catalytic material such as tourmaline or a copper ion generating material.
The level of activation caused by radiation of the ultrasonic waves can be ascertained by measuring ORP (Oxidation-Reduction Potential) (mv). An ORP value of the water to be obtained by radiating the ultrasonic waves thereto is preferably from 160 mV to −790 mV, more preferably from 30 mV to −600 mV. For comparison, an ORP value of normal tap water is from 700 mV to 500 mV.
Additionally by radiation the ultrasonic waves, oxygen is released from the water to improve the hydrogen content ratio in the water.
For example, in a case where 200 L of water is brought into contact with tourmaline so as to reform the water, it is desirable to inject water from a pipe at a flow rate of 20 L/min to 50 L/min. While a reaction time period may be suitably set to about 1 hour, the same activation effect can be obtained even when it is set in the range of 20 minutes to 1 day.
Next, the additive input step will be described. The additive input step is intended to add the additive stored in the reaction accelerator injection unit 4, to the water refining tank 3 or the reaction tank 5, to thereby increase the hydrogen content ratio in the water.
As the additive, it is possible to use one or more selected from the group consisting of catalase, sodium hydroxide and an aqueous hydrogen peroxide solution. The input amount of the additive needs to be finely adjusted. In the case of using catalase, the addition amount of catalase is preferably from 0.04% to 0.05%, in terms of a ratio by weight thereof to the water, as mentioned above. If the addition amount is less than 0.04%, it becomes impossible to sufficiently bring out an intended effect. On the other hand, if the addition amount is greater than 0.05%, it becomes impossible to ensure sufficient dissolution, leading to an increase in scum and thus deterioration in fuel quality.
With regard to sodium hydroxide, the intended effect as an additive can be sufficiently brought out by adding it in an amount of 0.001 weight % to 0.1 weight %, with respect to 100 weight % of the water. With regard to an aqueous hydrogen peroxide solution, the intended effect as an additive can be sufficiently brought out by adding it in an amount of 0.001 weight % to 0.1 weight %, with respect to 100 weight % of the water.
Next, the stirring and mixing step will be described. In the stirring and mixing step, the water after being activated in the water refining tank 3 and subjected to input of the additive is mixed with the base fuel oil. First of all, only the base fuel oil is put into the reaction tank 5. This base fuel oil is circulated through the OHR mixer 12 of the reaction tank 5. By circulating the base fuel oil through the OHR mixer 12, molecules of the base fuel oil are also homogenized, so that the base fuel oil is more likely to be fused with the water. When the circulation is almost completed, the activated water is put into the reaction tank 5 from the water refining tank 3 little by little. This is intended to enable the water to be possibly homogeneously dispersed with respect to the base fuel oil. The activated water supplied from the water refining tank 3 is pressurized by the second pump 11 of the water refining tank 3, and mixed with the base fuel oil extracted from the discharge port 15 of the reaction tank 5, and the resulting mixture is pressurized by the third pump 11 of the reaction tank 5, and further subjected to mixing by the OHR mixer 12. Preferably, the OHR mixer 12 is operated to apply a pressure of 3 atm (0.3 MPa) or more and a temperature of 40° C. to 80° C. Thus, respective pressures of the second and third pumps 11 of the water refining tank 3 and the reaction tank 5 are set in a manner suited to the pressure of the OHR mixer 12, and respective warming levels of the second and third heaters 8 of the water refining tank 3 and the reaction tank 5 are also set in a manner suited to the temperature of the OHR mixer 12. The activated water and the base fuel oil mixed by the OHR mixer 12 are re-put into the reaction tank 5 from the injection pipe 14 via the header pipe 502.
Efficiency and quality of the mixing varies depending on an angle of the injection pipe 14 with respect to the reaction tank 5, and a protruding amount of the injection pipe 14 toward an inside of the reaction tank 5.
For example, in the case where 100 L of the activated water is mixed with 100 L of the base fuel oil, the mixture of the activated water and the base fuel oil is preferably circulated through a pipe having a nominal diameter of 15 A to 50 A at a flow rate of 20 L/min to 50 L/min. A mixing time period may be set in the range of about 5 minutes to about 1 hour.
Next, the fusion step will be described. The fusion step is performed after completion of the input of the activated water from the water refining tank 3 into the reaction tank 5, and achieved by circulating the mixture of the activated water and the base fuel oil through the OHR mixer 12. Preferably, the pressure and the temperature during the fusion step are set, respectively, to 3 atm (0.3 MPa) or more and in the range of 40° C. to 80° C., as with the stirring and mixing step. In this fusion step, by circulating the mixture of the activated water and the base fuel oil through the OHR mixer 12 for a sufficient period of time, it is possible to promote fusion between the activated water and the base fuel oil to produce a hydrocarbon-based synthetic fuel oil free from a risk of separation.
For example, in a case where 100 L of the activated water is fused with 100 L of the base fuel oil, the pressure to be applied to the mixture is preferably set to 0.3 MPa (3 atm) or more. The temperature may be 70° C. or less. It is most effective that the pressure and the temperature are set, respectively, to 0.9 MPa and 50° C. It is appropriate to set the reaction time period to fall within the range of 20 minutes to 60 minutes after reaching the above pressure and temperature.
Next, the filtration step will be described. The filtration step is intended to separate, from a fully produced synthetic fuel, scum-like substances arising from solidification of components of an enzyme used during the production process, or other components. The technique using the statically-storing tank 6 is based on an idea of statically storing produced substances to separate them from each other due to a difference in specific gravity. Specifically, substances having relatively large specific gravities, such as scum, are accumulated on the bottom, and the synthetic fuel having a relatively small specific gravity gathers as a supernatant layer. The synthetic fuel as the supernatant layer is send to the product receiving tank 7 to obtain a hydrocarbon-based synthetic fuel oil as a product. The residence time period of the mixture in the statically-storing tank 6 is desirably set to 1 hour or more.
Alternatively, the produced substances may be enabled to pass through a filtration filter to separate scum or the like from the synthetic fuel. As the filtration filter, it is possible to use a filter having a pore size of about 10 to 30 μm. It is preferable to enable the produced substances to pass through the filtration filter at a temperature of 40° C. or less. Further, a passing speed (flow rate) is preferably set in the range of about 20 to 50 L/min when a pipe has a nominal diameter of 20 A to 50 A, wherein a lower passing speed is more preferable. The number of times of passing through the filtration filter may be one or more.
By performing the above steps in the above manner, it becomes possible to enable the activated water and the base fuel oil to be fully mixed and fused together to produce a hydrocarbon-based synthetic oil which is free of water-oil separation ever after the elapse of a certain time. Further, it becomes possible to realize fusion of the activated water and the base fuel oil within a relatively short period of time.
As presented in FIG. 1, a cycle of the above steps can be repeated using the obtained first-order synthetic fuel oil as a base fuel oil to produce a second-order synthetic fuel oil. In the same manner, the cycle can be repeated n-times (where n is an integer of 2 or more) in sequence, using a synthetic fuel oil obtained in a previous cycle, as a base fuel oil for the current cycle, to produce a n-th-order synthetic fuel oil. The n-th-order synthetic fuel oil produced by the method according to the present invention has a significantly high water addition rate.
With reference to FIG. 3, another example of the synthetic fuel production apparatus capable of implementing the method according to the present invention will be described. In the following description, description about the same element or component as that in the aforementioned production apparatus will be omitted.
FIG. 3 is a diagram depicting the structure of an injection pipe for injection to the reaction tank 5, usable in the production apparatus. FIG. 3(a) is a top plan view for explaining a positional relationship between the reaction tank 5 and the injection pipe 14. FIG. 3(b) is a side view of the reaction tank 5.
In connection with the above embodiment, the steps for production of the synthetic fuel have been described. Among them, it is important how to circulate the mixture of the activated water and the base fuel oil, in the stirring and mixing step and the fusion step. Basically, in the apparatus depicted in FIG. 2, the circulation is performed by enabling the mixture extracted from the discharge port 15 of the reaction tank 5 to be re-put into the reaction tank 5 from the lateral side of the upper portion of the reaction tank 5 via the pump the OHR mixer 12 and the injection pipe 14, in the form of a jet flow. In this circulation process, it is ideal that all of the mixture is evenly circulated. However, if a way to re-put the mixture into the reaction tank 5 is not adequate, only part of the mixture is circulated in a larger amount but the remaining part is not sufficiently circulated, leading to a problem that the entire mixture is not evenly formed as a synthetic fuel oil, or it takes a lot of time for evenly forming the entire mixture as a synthetic fuel oil.
Therefore, the inventor of the present invention made a study on the relationship between the reaction tank 5 and the injection pipe 14 for re-putting the mixture into the reaction tank 5. As depicted in FIG. 3(b), the reaction tank 5 in this example has a circular cylindrical upper portion, and a conical lower portion. As depicted in FIG. 3(a), four injection pipes 14 are attached to a lateral wall of the upper portion of the reaction tank 5, and arranged so as to inject the mixture of the activated water and the base fuel oil into the reaction tank 5 from four directions, respectively. An angle of a longitudinal direction of each of the injection pipes 14 with respect to a diametrical line of the cylindrical upper portion of the reaction tank 5 passing through a central axis of the cylindrical upper portion of the reaction tank 5 and an attached point at which the injection pipe 14 is attached to the cylindrical portion of the reaction tank 5 is defined as an attachment angle or injection direction of the injection pipe 14. Then, under the condition that the attachment angle is changed in the range of 0 degree to 90 degrees, a time required for the fusion and quality of a resulting synthetic fuel were checked. In FIG. 3(c), an injection pipe 14 a 1 is attached such that the attachment angle becomes 0 degree. Similarly, injection pipes 14 a 2, 14 a 3, 14 a 4 are attached while an angle with respect to an axis of the injection pipe 14 a 1 is gradually increased in increments of 15 degrees. A test was conducted by changing the angle in increments of 15 degrees. As a result, it was ascertained that, when the angle with respect to the axis is 45 degrees, the time required for the fusion is minimized, and a resulting synthetic fuel has good quality. This result shows that the attachment angle of each of the injection pipes 14 is preferable set in the range of about 40 to 50 degrees with respect to the diametrical line.
Further, a protruding amount of each of the injection pipes 14 toward an inside of a reaction tank 5 having a diameter of 60 cm, as depicted in FIG. 3(d), a time required for the fusion and quality of a resulting synthetic fuel were checked. In FIG. 3(d), an injection pipe 14 b 1 is attached such that the protruding amount becomes 0. Similarly, injection pipes 14 b 2, 14 b 3, 14 b 4 are attached while the protruding amount is gradually increased. The protruding amount was increased in increments of 10 cm. As a result, it was ascertained that, when the protruding amount is 10 cm, the time required for the fusion is minimized, and a resulting synthetic fuel has good quality. Further, in case of using a reaction tank having a larger size, it is preferable to increase the protruding amount of the injection pipe, and/or increase the number of injection pipes, according to the diameter of the reaction tank.
Considering the above, for the input of the mixture from the injection pipe 14 into the reaction tank 5, the attachment angle with respect to the diametrical line of the cylindrical portion of the reaction tank 5 is optimally set to 45 degrees, and the protruding amount of the injection pipe 14 toward the inside of the reaction tank 5 is optimally set to 10 cm. By attaching the injection pipe at a given angle with respect to the diametrical line of the cylindrical portion, it becomes possible to create a natural vortex within the reaction tank. This also makes it possible to effectively perform the mixing. Further, by setting the protruding amount of the injection pipe 14 toward the inside of the reaction tank 5 to a given amount, it becomes possible to avoid a situation where the circulated mixture gathers only around an outer peripheral region or a central region of the mixture in the reaction tank 5. The injection pipe 14 is disposed at a position upwardly away from a liquid surface in the reaction tank 5, preferably by at least 8 cm, more preferably by at least 10 cm, and preferably configured to inject the mixture therefrom at a high speed.
By adjusting the arrangement of the injection pipes 14 with respect to the reaction tank 5 in the above manner, it becomes possible to enable the activated water and the base fuel oil to be fully mixed together to produce a hydrocarbon-based fuel oil which is free of water-oil separation ever after the elapse of a certain time. Further, it becomes possible to perform fusion between the activation water and the base fuel oil within a relatively short period of time.
With reference to FIG. 4, yet another example of the synthetic fuel production apparatus capable of implementing the method according to the present invention will be described.
FIG. 4 is a schematic diagram depicting one example of a plasma arc treatment unit usable in the production apparatus capable of implementing the method according to the present invention. This plasma arc water treatment unit 20 comprises a first electrode 21 (indicated by the hexagonal dotted-line in FIG. 4) disposed in a central region of the unit, and a plurality of (in FIG. 4, twelve) second electrode 22 arranged to surround the first, central, electrode 21, wherein the first and second electrodes 21, 22 are connected to a high-voltage transformer (not depicted). Upon supplying electric power to the first and second electrodes, an arc discharge is generated between the first and second electrodes. In the production apparatus 1 depicted in FIG. 2, the plasma arc water treatment unit 20 is installed between the water refining tank 3 and the second pump and the water from the water refining tank is sent to pass through the plasma arc water treatment unit 20, so that it becomes possible to activate water by plasma arc water treatment. Preferred examples of the plasma arc water treatment unit may include a plasma arc water treatment unit used in Ultra U-MAN manufactured by Nippon Risuiken, K. K.

EXAMPLES

[Formation of Activated Water]

(Preparation of Tourmaline and Catalase)

Tourmaline produced in Estado de Tocantins, Brazil, and having a particle size of 20 mm to 80 mm was purchased from New Wave SA. Further, catalase (trade name “Leonet F-35”) was purchased from Nagase ChemteX Corporation. These tourmaline and catalase were used in the following examples.

(Example of Formation of Activated Water)

As water for forming activated water, tap water as soft water was used. 3 kg of tourmaline was immersed in 20 L of water at normal temperatures, and an ultrasonic wave having a frequency of 30 kHz to 40 kHz and an ultrasonic wave having a frequency of 200 kHz to 600 kHz are radiated, respectively, to the tourmaline and the water, for 20 minutes. In the following examples, the frequency of the ultrasonic wave to be radiated to the tourmaline and the frequency of the ultrasonic wave to be radiated to the water were set, respectively, to 35 kHz and 400 kHz. After the elapse of 20 minutes, the water was heated up to a temperature of 43° C. using a heater, while the ultrasonic wave radiation was continued and the water was recirculated according to a pump. When the water temperature reached 43° C., the heating by the heater and the the ultrasonic wave radiation were stopped. At this point of time, ORP was about −790 mV, and pH was 8 to 9. Further, hotspots arising from microbubbles were formed in the water. Thus, the water was considered to be activated.
In the above operation, as a substance for maintaining hotspots arising from microbubbles, Ryukyu limestone consisting mainly of calcium carbonate was preliminarily mixed in the tourmaline. In the activated water preparation step, when ORP of the water is stabilized at a negative value, and pH of the water becomes 8 to 9, the activation can be considered to be completed.
Here, the term “microbubble” means tiny air bubbles generated by a local pressure variation when the ultrasonic wave is radiated to the water.
The research paper titled “Chemical Application of Cavitation; Sonochemistry (Application of Cavitation Induced by Ultrasound)” authored by Shinobu KODA, School of Engineering, Graduate School of Engineer, Nagoya University, and presented in Journal of the Institute of Electronics, Information and Communication Engineers of JAPAN, Vol J89-A, No. 9 (2006) (Non-Patent Document 2), the research paper titled “Decomposition of Chemical Compounds by Ultrasound and Development of Sonochemical Reactor” authored by Keiji YASUDA, School of Engineering, Graduate School of Engineer, Nagoya University, and presented in “THE CHEMICAL TIMES”, published by Kanto Chemical Co., In, Apr. 1, 2009 (Non-Patent Document 3), and the presentation material for “Monodzukuri Basic Course (34th Technical Seminar)” held on Feb. 20, 2013 at the Creation-Core Higashiosaka, by Yoshiteru MIZUKOSHI, Institute for Materials Research, Tohoku University (Non-Patent Document 4), sonochemistry based on radiating a strong ultrasonic wave to liquid to create a state in which tiny air bubbles are generated in the liquid, i.e., a cavitation state, to cause decomposition of liquid molecules is discussed in detail. According to descriptions of these Non-Patent Documents, tiny air bubbles, i.e., microbubbles, generated by an ultrasonic wave expand to about several ten p.m after several cycles and subsequently rapidly contract by a quasi-adiabatic compression process. As a result, during the contraction, the inside of each air bubble reaches a temperature of 5000 K to several tens of thousand K, and a pressure of one thousand several hundred atm. This high-temperature and high-pressure local field is referred to as a hotspot, and understood as an origin of a chemical action by cavitation.

[Production Cases of First-Order Synthetic Fuel Oils]

(Production Case 1 of First-Order Synthetic Fuel Oil)

A first-order synthetic fuel oil was produced using A-Class heavy oil as the base oil in the following manner.
First of all, 3 kg of tourmaline (tourmaline ore (small size) purchased from New Wave SA, who directly imported it from a mine in Estado de Tocantins, Brazil), and 20 L of tap water were put in a 25 L container provided with a tourmaline-receiving section, an ultrasonic wave generator (35 kHz ultrasonic transducer) and a temperature gauge and connected to a circulation pump (24 L/min×0.5 MPa). 20 mL of catalase (Leonet F-35 manufactured by Nagase ChemteX Corporation) was added to the water. Then, the ultrasonic transducer was activated, and further the circulation pump was activated to start circulation of the water, while an ultrasonic wave is radiated to the tourmaline under the conditions mentioned in the “Formation of Activated Water”. A preset temperature of a 3 kW line heater provided in a circulation path of the water was set to 40° C., and the circulation was continued for one hour after confirming that the temperature of the water in the container reached 40° C. or more. After the elapse of one hour, the oxidation-reduction potential of the water in the container was measured by an ORP meter. As a result, it was 12 mV, i.e., it could be ascertained that the water had been activated.
Then, 20 L of commercially-available A-heavy oil (Class 1 (A), No. 1 heavy oil purchased from Fuji Kosan Co., Ltd.) was put in a 25 L container provided with a temperature gauge and connected to a circulation pump as with the aforementioned container. The circulation pump was activated to start circulation of the A-heavy oil. A preset temperature of a 3 kW line heater provided in a circulation path of the A-heavy oil was set to 40° C., and the circulation was continued for one hour after confirming that the temperature of the A-heave oil in the container reached 40° C. or more.
Activated water and A-heavy oil obtained in the above manner were mixed and stirred, and a resulting mixture was further fused together by applying heat and pressure thereto, in the following manner. 10 L of the activated water and 10 L of the obtained A-heavy oil were put in a 25 L, open-type container having an upper portion opened to the atmosphere, wherein the container was provided with a 1 kW warming heater and a propeller-type stirrer, in addition to a temperature gauge. The container was connected to a circulation pump and a blending mixer (OHR (Original Hydrodynamic Reaction) mixer manufactured by OHR Laboratory Corporation). In the container containing the activated water and the A-heavy oil, the warming heater was powered on to enable the temperature of the liquids in the container to be maintained at 40° C. 10 mL of the same catalase as described above was added thereto. After the elapse of 40 minutes, the stirrer was powdered on to mix and stir the activated water and the A-heavy oil. Then, the circulation pump was activated and adjusted such that a supply pressure to the blending mixer becomes about 0.5 MPa, to circulate the mixture. A circulation pipe for allowing the mixture to be put into the container from the circulation path therethrough in the above process was disposed at a position upwardly away from a surface of the mixture in the container by about 8 cm. After circulating the mixture for one hour, the stirrer, the circulation pump and the warming heater were deactivated. A liquid obtained in the above manner was statically stored for about 3 days, and an analytical sample was collected therefrom. The amount of the collected sample was 20 L, and it was ascertained that the sample is a synthetic fuel oil having properties presented in Table 1.

(Production Case 2 of First-Order Synthetic Fuel Oil)

Except that commercially-available light oil (No. 2 light oil purchased from JX Nippon Oil & Energy Corporation (ENEOS)) was used as the base oil, in place of the A-Class heavy oil, a synthetic fuel oil (first-order synthetic fuel oil 2) was produced in the same manner as that in the production Case 1, and an analytical sampler was collected therefrom. The amount of the collected sample was 20 L.
Table 1 presents a result of componential analysis of the two types of first-order synthetic fuel oils 1 and 2 produced in the above manner. Each of the first-order synthetic fuel oils 1 and 2 is obtained by mixing and fusing the activated water and the base fuel oil together at a ratio of 1:1.
For comparison, each of the A-heavy oil and the light oil used as base oil was subjected to the same componential analysis
First of all, looking at gross calorific value and net calorific value, each of the first-order synthetic fuel oils 1 and 2 is superior to the base oil, which shows that the intended effect of the present invention is brought out.
Secondly, looking at water content, in each of the first-order synthetic fuel oils 1 and 2, the volume % of the water content is 0.00%, which proves that each of the first-order synthetic fuel oils 1 and 2 is substantially free of water. Each of the first-order synthetic fuel oils 1 and 2 was obtained by mixing and fusing the activated water and the base fuel oil together at a ratio of 1:1. Thus, if sufficient fusion is not achieved, a certain amount of water should be detected. That is, the fact that the volume % of the water content is 0.00% means that the base fuel oil and the activated water were fully fused, and thereby no water component was analytically detected.
As above, the present invention makes it possible to fully fuse the base fuel oil and the activated water, and produce a high-quality hydrocarbon-based synthetic fuel oil.

	TABLE 1

	Test Result

		First-order	First-order
		synthetic	synthetic
		fuel oil	fuel oil
Test Items	Unit	Case	1	Case 2	Testing Method

Gross calorific value	J/g	45,450	45,880	JIS K2279
Net calorific value	J/g	42,440	42,690	JIS K2279
Density (15° C.)	g/cm³	0.8445	0.8283	JIS K2249-1
C (carbon content))	mass %	86.6	85.8	Elemental analyzer
H (hydrogen content)	mass %	13.3	14.1	Elemental analyzer
S (sulfur content)	mass %	0.045	0.0000	JIS K2541-6
N (nitrogen content)	mass %	0.0043	0.0003	JIS K2609
H₂O (water)	mass %	0.00	0.00	JIS K2275
Flash point	° C.	73	73	JIS K2265-3
Kinetic viscosity (50° C.)	mm²/s	2.417	3.498	JIS K2283
Pour point	° C.	−15	−10	JIS K2269
Carbon residue content	mass %	0.01	0.01	JIS K2270-2
Water content	volume %	0.00	0.00	JIS K2275
Ash content	mass %	0.000	0.000	JIS K2272
Sulfur content	mass %	0.045	0.0009	JIS K2541-6
Inorganic acid	—	neutral	neutral	JIS K2252

(Production Case 3 of First-Order Synthetic Fuel Oil)

A first-order synthetic fuel oil was produced using the apparatus depicted in FIGS. 2 and 3 and using light oil as base oil.
First of all, 150 L of tap water was poured into the refined water container having the tourmaline-receiving section packed with the same tourmaline as that used in the production of the first-order synthetic fuel oil 1. The second heater installed in the water refining tank was powered on, and a preset temperature thereof was set to 40° C. 150 mL of the same catalase as that used in the production of the first-order synthetic fuel oil 1 was added thereto. Subsequently, the second circulation pump connected to the water refining tank was activated (discharge pressure: 0.5 MPa), and the ultrasonic wave generator installed in the water refining tank was activated to radiate an ultrasonic wave (frequency: 40 kHz) to the water and the tourmaline for 60 minutes until the temperature of the water reaches 40° C., and additionally for 60 minutes after the temperature reached 40° C. In operation of putting the water into the water refining tank, only one of the four injection pipes was used (the remaining three injection pipes were closed), and the flow rate at a distal end of the injection pipe was set to 3.3 m/s. The oxidation-reduction potential of the resulting water was measured by an ORP meter. As a result, it was 20 mV. In this way, activated water was obtained.
Subsequently, 150 L of commercially-available light oil (No. 2 light oil purchased from JX Nippon Oil & Energy Corporation (ENEOS)) was poured into the base oil improving tank. Then, the first heater installed in the base oil improving tank was powered on, and a preset temperature thereof was set to 40° C. The first circulation pump connected to the base oil improving tank was activated (discharge pressure: 0.3 MPa) to circulate the light oil for 60 minutes until the temperature of the light oil reaches 40° C., and additionally for 60 minutes after the temperature reached 40° C. In operation of injecting the light oil into the base oil improving tank, only one of the four injection pipes was used (the remaining three injection pipes were closed), and the flow rate at a distal end of the injection pipe was set to 2.0 m/s.
Activated water and light oil obtained in the above manner were put into the reaction tank, and mixed and stirred. Further, the activated water and the light oil were fused together by applying heat and pressure thereto. Specifically, 75 L of the light oil in the base oil improving tank and 55 L of the activated water in the water refining tank were transferred to the reaction tank (water addition rate: 42%). 62 mL of the same catalase as that used in the production of the first-order synthetic fuel oil 1 was added thereto. Then, the third heater was powered on to enable the temperature of the liquid in the container to become 40° C. After the temperature of the liquid reached 40° C., the third circulation pump was activated and adjusted such that a supply pressure to the blending mixer becomes about 0.5 MPa, to circulate the mixture for 60 minutes. In operation of putting the mixture into the reaction tank, only one of the four injection pipes was selected and used (the remaining three injection pipes were closed), and the flow rate at a distal end of the selected injection pipe was set to 2.0 m/s. Further, the selected injection pipe was attached in such a manner as to be kept from submerging in the mixture in the reaction tank. Specifically, the selected injection pipe was disposed at a position upwardly away from a surface of the mixture in the reaction tank by about 8 cm. An analytical sampler was collected from the resulting liquid. The amount of the collected sample was 114 L.

(Production Case 4 of First-Order Synthetic Fuel Oil)

Except that temperatures of the water refining tank, the base oil improving tank and the reaction tank were set, respectively, to higher values: 42° C., 41° C. and 44° C., and a circulation time period in the water refining tank and the base oil improving tank was set to one-half that in the production Case 3 of the first-order synthetic fuel oil (specifically, set to 60 minutes in each of the tanks), a first-order synthetic fuel oil 4 was produced in the same manner as that in the production of the first-order synthetic fuel oil 3. The oxidation-reduction potential of the water obtained in the water refining tank was measured by an ORP meter. As a result, it was 26 mV. An analytical sampler was collected from a liquid obtained in the reaction tank. An amount of the collected sample was 114 L.

(Production Case 5 of First-Order Synthetic Fuel Oil)

Except that: the A-Class heavy oil (Class 1 (A), No. 1 heavy oil purchased from Fuji Kosan Co., Ltd.) was used as the base oil; the temperature of the reaction tank was set to 36° C.; the circulation time period in each of the water refining tank and the base oil improving tank was set to 90 minutes; and the addition amount of catalase was set to 230 mL and 130 mL, respectively, for the water refining tank and the reaction chamber, the production Case 5 of first-order synthetic fuel oil was carried out in the same manner as that in the production Case 3 of the first-order synthetic fuel oil. The oxidation-reduction potential of the water obtained in the water refining tank was measured by an ORP meter. The measured value was 18 mV. An analytical sampler was collected from a liquid obtained in the reaction tank. An amount of the collected sample was 114 L.
Table 2 presents a result of componential analysis of the two types of first-order synthetic fuel oils 4 and 5 produced in the above manner.

	TABLE 2

	Test Result

		First-order	First-order
		synthetic	synthetic
		fuel oil	fuel oil
Test Item	Unit	Case	4	Case 5	Testing Method

Gross calorific value	J/g	45,950	44,400	JIS K2279
Net calorific value	J/g	42,740	41,640	JIS K2279
Density (15° C.)	g/cm³	0.8277	0.876	JIS K2249-1
C (carbon content)	mass %	85.7	87.7	Elemental analyzer
H (hydrogen content)	mass %	14.2	12.2	Elemental analyzer
S (sulfur content)	mass %	0.0008	0.51	JIS K2541-6
N (nitrogen content)	mass %	0.0002	0.033	JIS K2609
H₂O (water)	mass %	0.00	0.00	JIS K2275
Flash point	° C.	64.5	78.5	JIS K2265-3
Kinetic viscosity (50° C.)	mm²/s	3.558	2.48	JIS K2283
Pour point	° C.	−12.5	−22.5	JIS K2269
Carbon residue content	mass %	0.01	0.05	JIS K2270-2
Water content	Volume %	0.00	0.00	JIS K2275
Ash content	mass %	less than 0.001	0.004	JIS K2272
Sulfur content	mass %	0.0008	0.51	JIS K2541-6
Inorganic acid	—	neutral	neutral	JIS K2252

[Qualitative Analysis of First-Order Synthetic Fuel Oils]

The sample of the first-order synthetic fuel oil 3 obtained in the above manner using light oil as base oil was subjected to qualitative analysis based on gas chromatogram-mass spectrometry (GC-MS). An analytical sample was prepared by diluting the sample of the first-order synthetic fuel oil 3, with n-hexane 1000 times. HP-5MS (length: 30 m, inner diameter: 2.5 mm, membrane thickness: 0.25 μm) was used as a gas chromatography column, and He was used as carrier gas. An injection amount of the analytical sample was set to 1 μL, and an injection mode was set to the splitless mode. An oven temperature was held at 50° C. for 3 minutes, and then after being increased from 50° C. to 100° C. at a temperature rise rate of 5° C./min, and from 100° C. to 300° C. at a temperature rise rate of 15° C./min, held at 300° C. for 3 minutes. A GC-MS chart obtained as a result of the analysis is depicted in FIG. 5, wherein FIG. 5(a) is a TIC chromatogram, and FIG. 5(b) is a mass spectrum indicating peaks at about 18.4 min.
As to the sample of the first-order synthetic fuel oil 4 was also subjected to the same qualitative analysis. A result of the analysis is presented in FIG. 6.
For comparison, the light oil used as base oil was also subjected to the same qualitative analysis. A result of the analysis is presented in FIG. 7.
Comparing FIGS. 5, 6 and 7 with each other, it can be ascertained that a component composition of each of the first-order synthetic fuel oils 3 and 4 is well coincident with that of the base oil, although components having relatively large carbon numbers (greater than C19) tend to decrease as compared to the base oil.
The sample of the first-order synthetic fuel oil 5 obtained in the above manner using A-heavy oil as base oil was also subjected to the same qualitative analysis. A result of the analysis is presented in FIG. 8.
For comparison, the A-heavy oil used as base oil was subjected to the same qualitative analysis. A result of the analysis is presented in FIG. 9.
Comparing FIGS. 8 and 9 with each other, it can be ascertained that a component composition of the first-order synthetic fuel oil 5 is well coincident with that of the base oil.
[Properties Test of First-Order Synthetic Fuel Oils]
The samples of the first-order synthetic fuel oils 3 and 4 obtained in the above manner using light oil as base oil were subjected to properties test. Items and methods of the properties test were as follows.
Density (vibration type, 15° C.): JIS K2249
Kinetic viscosity)(30°: JIS K2283
Nitrogen quantitative analysis: JIS K2609
Sulfur content (UV fluorescence method): JIS K2541-6
Oxygen content: ASTM D5622
Light oil composition analysis (JPI method); JPI-5S-49
For comparison, the light oil used as base oil was subjected to the same properties test. A result of the analysis is presented in Table 3.
From Table 3, it is observed that the first-order synthetic fuel oils obtained in the above manner is reduced in terms of an aromatic content, and is increased in terms of a saturates content. It is considered that light oil having a relatively small aromatic content and a relatively large saturates content is desirable in view of combustion efficiency, and reduction of toxic content in exhaust gas including PM.

	TABLE 3

	Test Result

		First-order	First-order
		synthetic	synthetic	Base oil
		fuel oil	fuel oil	(light
Test Item	Unit	Case	3	Case 4	oil)

Density (15° C.)	g/cm³	0.8297	0.8279	0.8293
Kinetic viscosity (30° C.)	mm²/s	2.976	3.565	3.377
Nitrogen quantitative	ppm		2	1	2
analysis
Sulfur content	ppm	8	9	9
Oxygen content	mass %	<0.1	<0.1	<0.1
Composition analysis (JPI	volume %	80.7	80.2	76.1
method) Saturates content
Olefin content	volume %	0.0	0.0	0.0
Monocyclic aromatic	volume %	18.4	18	19.9
content
Bicyclic aromatic content	volume %	0.6	1.6	3.6
tricyclic aromatic content	volume %	0.3	0.2	0.4

[Test of Oxidative Stability of First-Order Synthetic Fuel Oils]

The samples of the first-order synthetic fuel oils in Cases 3 and 4 obtained in the above manner using light oil as base oil were subjected to oxidative stability test (test method: ASTM D2274). For comparison, the light oil used as base oil was subjected to the same oxidative stability test.
In each of the samples, an amount of sludge measured was lower than 0.1 mg/100 mL as a measurement limit.
[Driving Test using First-Order Synthetic Fuel Oil]
The sample of the first-order synthetic fuel oil 3 obtained in the above manner using light oil as base oil was subjected to the JC08 mode driving test (vehicle used: Nissan NV350, LDF-VW2E26, Vehicle mass: 1840 kg). For comparison, commercially-available light oil (JIS No. 2) was subjected to the same driving test.
A result of the driving test is presented in Table 4. For reference, the exhaust emission regulation values are put down therewith.
From Table 4, attention is focus on the point that the first-order synthetic fuel oil obtained in the above manner is low, particularly, in terms of CO₂emission, as compared to the commercially-available light oil.
42% by volume of the first-order synthetic fuel oil 3 is derived from water. From previous experimental results, a conversion ratio of the water mixed with the base oil and converted to fuel is assumed to be about 70%, and a volume ratio of a water-derived fuel to a total amount of produced fuel can be calculated by the following formula: [volume ratio of water-derived fuel]=(42×0.7)/(58+42×0.7)=34%. From this result, in the first-order synthetic fuel oil 3, it can be evaluated that 34% of the obtained fuel is not derived from petroleum. Therefore, the first-order synthetic fuel oil in Case 3 can be deemed to reduce the carbon emission amount by about 34%.

	TABLE 4

	Test Result

		First-order
		synthetic		Emission
		fuel oil		Regulation
Test Item	Unit	Case	3	Light Oil	Values

Fuel economy (FE)	Km/L	13.15	12.71	12.4
T-HC	g/kg	0.001	0.001	0.032
CO	g/kg	0.004	0.005	0.84
NOx	g/kg	0.182	0.185	0.2
PM	g/kg	0.001	0.001	0.009
CO₂	g/kg	200.1	207.0	216.0

(Production Case 6 of First-Order Synthetic Fuel Oil)

5 L of the activated water formed in the process described in the “Formation of Activated Water”, and 10 L of the commercially-available light oil (No. 2 light oil purchased from JX Nippon Oil & Energy Corporation (ENEOS)) after passing through the base oil improving tank 2 were put into the reaction tank 5 to perform the mixing, stirring and fusion steps under the same conditions as those in the production of the first-order synthetic fuel oil 2. Subsequently, a resulting mixture was transferred to the statically-storing tank 6, and statically stored therein for 1 hour. As a result, the mixture was separated into an upper oil phase and a lower water phase. Then, oil existing in the upper oil phase is extracted as a first-order synthetic fuel oil 6. The amount of the first-order synthetic fuel oil was 11 L. The amount of water remaining in the water phase was 4 L. Through this process, it could be ascertained that 1 L water in the 5 L water was converted into a synthetic fuel oil. This shows that the amount of the first-order synthetic fuel oil is increased by 10% as compared to the base oil.

Example 1

As Example 1 of the present invention, a second-order synthetic fuel oil was produced using the first-order synthetic fuel oil Case 6 as base oil. Specifically, 10 L of the first-order synthetic fuel oil Case 6 was conditioned through the base oil improving tank 2, and then put into the reaction tank 5. Simultaneously, 5 L of the activated water formed in the process described in the “Formation of Activated Water” was put into the reaction tank 5 to perform the mixing, stirring and fusion steps under the same conditions as those in the production of the first-order synthetic fuel oil 2. Subsequently, a resulting mixture was transferred to the statically-storing tank 6, and statically stored therein for 1 hour. As a result, the mixture was separated into an upper oil phase and a lower water phase. Then, oil existing in the upper oil phase was extracted as a second-order synthetic fuel oil. The amount of the extracted second-order synthetic fuel oil was 11 L. The amount of water remaining in the water phase was 4 L. Through this process, it could be ascertained that 1 L water in the 5 L water was converted into a synthetic fuel oil. This shows that the amount of the second-order synthetic fuel oil is increased by 10% as compared to the first-order synthetic fuel oil used as base oil.
Subsequently, a third-order synthetic fuel oil was produced, using, as base oil, the second-order synthetic fuel oil obtained in the above process. Specifically, 10 L of the second-order synthetic fuel oil obtained in the above process was conditioned through the base oil improving tank 2, and then put into the reaction tank 5. Simultaneously, 5 L of the activated water formed in the process described in the “Formation of Activated Water” was put into the reaction tank 5 to perform the mixing, stirring and fusion steps under the same conditions as those in the production of the first-order synthetic fuel oil 2. Subsequently, a resulting mixture was transferred to the statically-storing tank 6, and statically stored therein for 1 hour. As a result, the mixture was separated into an upper oil phase and a lower water phase. Then, oil existing in the upper oil phase was extracted as a third-order synthetic fuel oil. The amount of the extracted third-order synthetic fuel oil was 11 L. The amount of water remaining in the water phase was 4 L. Through this process, it could be ascertained that 1 L water in the 5 L water was converted into a synthetic fuel oil. This shows that the amount of the third-order synthetic fuel oil is increased by 10% as compared to the second-order synthetic fuel oil used as base oil.
The first-order synthetic fuel oil 6 and the second-order synthetic fuel oil produced in the Example 1 were subjected to calorific value measurement and component analysis. A result of the measurement and analysis is presented in Table 5 in comparative manner with the commercially-available light oil used, as base oil, in the production Case 6 of the first-order synthetic fuel oil.

TABLE 5

			First-Order	Second-Order
			Synthetic	Synthetic	Testing
Test Item	Unit	Base Oil	Oil	Oil	Method

Calorific value	J/g	46,080	45,900	45,960	JIS K 2279
Gross calorific value
Lower calorific value	J/g	43,030	42,910	42,840
Element Analysis	mass %	86.4	86.3	86.1	Elemental
Carbon (C)					analyzer
Hydrogen (H)	mass %	13.6	13.6	13.8

The Example 1 is one example using the first-order synthetic fuel oil Case 6 as base oil. Alternatively, a second-order synthetic fuel oil can be produced using one of the first-order synthetic fuel oils 1 to 5, in the same manner as that in the Example 1.

LIST OF REFERENCE SIGNS

1: synthetic fuel production apparatus
2: base oil improving tank
3: water refining tank
4: reaction accelerator injection unit
5: reaction tank
6: statically-storing tank
7: product receiving tank
8: heater
9: catalyst
10: ultrasonic wave generator
11: pump
12: OHR mixer
13: reaction tank container
14: injection pipe
15: discharge port
20: plasma arc treatment unit
21, 22: electrode

Claims

1.-10. (canceled)

11. A method of producing a hydrocarbon-based synthetic fuel oil having a volume greater than that of a hydrocarbon-based base fuel oil, by addition of water to the hydrocarbon-based base fuel oil, the method comprising:

a) an activated water generation step of subjecting water to activation treatment to generate activated water;

b) a stirring and mixing step of adding the activated water to a hydrocarbon-based base fuel oil used as a primary base fuel oil, and stirring and mixing the resulting mixture under a reactive environment for a given time period;

c) a fusion step of fusing together the hydrocarbon-based base fuel oil and the activated water after undergoing the stirring and mixing step, under a reactive environment; and

d) a first-order hydrocarbon-based synthetic fuel oil collection step of collecting a hydrocarbon-based synthetic fuel oil obtained from the mixture after undergoing the fusion step, as a first-order hydrocarbon-based synthetic fuel oil,

wherein a cycle of the steps b), c) and d) is performed using the first-order hydrocarbon-based synthetic fuel oil as a secondary base fuel oil, to collect a second-order hydrocarbon-based synthetic fuel oil, the cycle of the steps b), c) and d) being carried out one or more times, using a hydrocarbon-based synthetic fuel oil obtained in a preceding process, as a base fuel oil for a succeeding process, thereby producing a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O), and has a volume greater than that of the primary base fuel oil and a composition substantially identical to or approximate to that of the primary base fuel oil.

12. A method of producing a hydrocarbon-based synthetic fuel oil having a volume greater than that of a hydrocarbon-based base fuel oil, by adding water to the hydrocarbon-based base fuel oil, the method comprising:

b) a stirring and mixing step of adding the activated water to the hydrocarbon-based base fuel oil used as a primary base fuel oil, and stirring and mixing the resulting mixture under a reactive environment for a given time period;

c) a fusion step of fusing together the hydrocarbon-based base fuel oil and the activated water after undergoing the stirring and mixing step, under a reactive environment;

d) an oil-water separation step of statically holding the mixture after undergoing the fusion step to cause the mixture to undergo phase separation to form an upper oil layer comprised of a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O) and has a composition substantially identical to or approximate to that of the primary base fuel oil, and a lower water layer; and

e) a first-order hydrocarbon-based synthetic fuel oil collection step of collecting the hydrocarbon-based synthetic fuel oil of the upper oil layer, as a first-order hydrocarbon-based synthetic fuel oil,

wherein

f) the stirring and mixing step and the fusion step are performed over a time period during which a volume of the first-order hydrocarbon-based synthetic fuel oil obtained in the first-order hydrocarbon-based synthetic fuel oil collection step becomes greater than a volume of the hydrocarbon-based base fuel oil used as the primary base fuel oil; and

g) a cycle of the steps b), c) d), e) and f) is performed using the first-order hydrocarbon-based synthetic fuel oil as a secondary base fuel oil, to collect a second-order hydrocarbon-based synthetic fuel oil, the cycle of the steps b), c) d), e) and f) being carried out one or more times, using a hydrocarbon-based synthetic fuel oil obtained in a preceding process as a base fuel oil for the succeeding process to produce a hydrocarbon-based synthetic fuel oil which is substantially free of water (H₂O), and has a volume greater than that of the primary base fuel oil and a composition substantially identical to or approximate to that of the primary base fuel oil.

13. The method as recited in claim 11, wherein the activated water is activated such that it includes hotspots arising from microbubbles.

14. The method as recited in claim 12, wherein the activated water is activated such that it includes hotspots arising from microbubbles.

15. The method as recited in claim 11, wherein the activated water generation step includes: heating water to a temperature ranging from 35° C. to 45° C., while applying a voltage to the water, and, in this state, radiating an ultrasonic wave to the water.

16. The method as recited in claim 12, wherein the activated water generation step includes: heating water to a temperature ranging from 35° C. to 45° C., while applying a voltage to the water, and, in this state, radiating an ultrasonic wave to the water.

17. The method as recited in claim 15, wherein the voltage application is performed by radiating an ultrasonic wave to tourmaline immersed in the water with to bring the tourmaline into an excited state.

18. The method as recited in claim 13, wherein the water contains a substance effective in holding the hotspots arising from microbubbles.

19. The method as recited in claim 14, wherein the water contains a substance effective in holding the hotspots arising from microbubbles.

20. The method as recited in claim 13, wherein the hotspots arising from microbubbles are generated by radiating, to the water, an ultrasonic wave having a frequency different from a frequency of the ultrasonic wave which is radiated to the tourmaline.

21. The method as recited in claim 14, wherein the hotspots arising from microbubbles are generated by radiating, to the water, an ultrasonic wave having a frequency different from a frequency of the ultrasonic wave which is radiated to the tourmaline.

22. The method as recited in claim 11, wherein the reactive environment in the stirring and mixing step is formed by adding catalase to the water and then stirring the water while radiating an ultrasonic wave to the water.

23. The method as recited in claim 12, wherein the reactive environment in the stirring and mixing step is formed by adding catalase to the water and then stirring the water while radiating an ultrasonic wave to the water.

24. The method as recited in claim 22, wherein the stirring is performed to create strong waves on a surface of the mixture of the water and the base fuel oil.

25. The method as recited in claim 23, wherein the stirring is performed to create strong waves on a surface of the mixture of the water and the base fuel oil.

26. The method as recited in claim 11, wherein the reactive environment in the stirring and mixing step is formed by adding photocatalyst to the water and then stirring the water while radiating ultraviolet light to the water.

27. The method as recited in claim 12, wherein the reactive environment in the stirring and mixing step is formed by adding photocatalyst to the water and then stirring the water while radiating ultraviolet light to the water.