WO2018062345A1

WO2018062345A1 - Method for producing hydrocarbon-based synthetic fuel by adding water to hydrocarbon-based fuel oil

Info

Publication number: WO2018062345A1
Application number: PCT/JP2017/035109
Authority: WO
Inventors: 青木　文男
Original assignee: 株式会社Ｔｒｉｓｔａｒｈｃｏ
Priority date: 2016-09-30
Filing date: 2017-09-28
Publication date: 2018-04-05
Also published as: TW201827582A; JP6995373B2; JPWO2018062345A1; US20200032153A1

Abstract

Provided is a method for producing a hydrocarbon-based synthetic fuel by adding water to a source oil, wherein the proportion of synthetic fuel to the hydrocarbon-based fuel that serves as the source oil is dramatically increased in comparison with conventional methods. A method for producing a hydrocarbon-based synthetic fuel oil, the method comprising adding water to a hydrocarbon-based fuel source oil and producing a hydrocarbon-based synthetic fuel oil of a volume greater than the volume of the hydrocarbon-based fuel source oil, wherein the hydrocarbon-based synthetic fuel oil produced by said production method is used as fuel source oil in the next production of hydrocarbon-based synthetic fuel oil, and a hydrocarbon-based synthetic fuel having a high proportion of added water is produced by repeating the same step several times in succession.

Description

Method for producing hydrocarbon-based synthetic fuel by adding water to hydrocarbon-based fuel oil

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

In recent years, environmental problems have become an important issue globally, and technological developments such as solar power and wind power generation have been actively promoted as countermeasures. However, until it becomes possible to completely shift to such renewable energy, the conventional fossil fuel including the problem of depletion is carefully used, and the development of internal combustion engines and combustion facilities with little energy loss, In order to obtain fossil fuel with excellent heat generation and combustion characteristics, fossil fuel itself needs to be improved in parallel, such as improving fossil fuel itself. One of these is to mix water with fuel oil. Attempts have been made to develop a method for increasing the amount of fuel oil.

In the conventional method of mixing water with fuel oil, by using this method, the amount of fuel used is greatly reduced, and CO ₂ (carbon dioxide) emissions are reduced by the amount of fuel reduction. It is considered a fuel that can reduce the load. In addition, according to this method, since complete combustion of the fuel oil is expected, the amount of air used for combustion can be considerably reduced, and accordingly, generation of nitrogen oxides and particulate matter (PM) can also be suppressed. There is an effect of reducing the environmental load caused by the gas discharged from the boiler or the internal combustion engine.
As described above, the fuel increased by adding water is very useful, but in general, water and oil are difficult to completely fuse, and even after mixing, they will be separated over time. Tend. Moreover, even if it is not impossible to perform the fusion sufficiently, it takes a very long time, and it is predicted that it is far from practical use from an economic point of view.
Therefore, water and fuel oil can be fused in a short time so that a hydrocarbon-based synthetic fuel that does not separate even when time passes can be produced. Is desired.

As a technique for increasing the amount of hydrocarbon fuels, natural minerals are obtained by adding catalase to a mixture of fuel oil and water, and then exciting the mixture of fuel oil and water containing catalase with vibration waves such as ultrasonic waves. Alternatively, Japanese Patent No. 4682287 (Patent Document 1) proposes a method for producing a hydrolyzed fuel that increases the transparency of an emulsion state of a mixed solution by contacting with metal, stirring, and mixing. More specifically, Patent Document 1 describes a mixture of fuel oil and water to which catalase has been added while agitating and mixing natural ore or metal in a vibration wave excitation state in contact with the mixture, and further mixing the fuel oil and water that have been agitated and mixed. A method is disclosed in which the liquid is heated to 30 ° C. to 150 ° C. and pressurized at 3 to 10 atm to fuse the fuel and water to increase the transparency of the mixture in the emulsion state. In Patent Document 1, fuel oil and water to which catalase is added are brought into contact with natural minerals or metals excited by vibration waves to subdivide the molecular aggregate of fuel oil and water, and then fuel oil and water. It is described that the fuel oil and water that have been stirred and mixed can be mixed by heating and pressurizing to increase the transparency of the emulsion state of the hydrolyzed fuel. Patent Document 1 describes two examples, Example 1 and Example 2. In any of these Examples, water and fuel oil are mixed in equal amounts and undergo a fusion process. Shows that a transparent fuel oil was obtained. Patent Document 1 states that this manufacturing method can prevent an oil-water separation phenomenon in an emulsion fuel having a hydrolysis rate of 50% or more.

The manufacturing method described in Patent Document 1 is based on the premise that hydrocarbons that are the source of combustion calories are reduced by adding water to fuel oil. By the action of catalase, the hydrogen content of fuel oil is increased to compensate. That is, it is possible to increase the ratio of hydrogen contained by catalase by decomposing hydrogen peroxide into hydrogen and oxygen, releasing oxygen into the atmosphere as gas, and leaving hydrogen in the fuel oil. Is the teaching. However, there is a limit to compensate for the decrease in the hydrocarbon ratio due to water addition only by increasing the hydrogen content ratio, and the method taught in Patent Document 1 cannot be expected to significantly increase the amount of fuel.

Japanese Patent Laid-Open No. 2014-47229 (Patent Document 2) discloses an emulsion fuel having the same quality and calorific value as a raw fuel oil without using a surfactant and without separating fuel oil and water over a long period of time. A method by which can be produced is disclosed. In this method, water is made to come into contact with tourmaline irradiated with far-infrared ray microwaves or ultrasonic waves, and fuel oil is made to come into contact with titanium oxide balls to which an electromagnetic wave-responsive catalyst is applied. It consists of mixing water and fuel oil and applying heat and pressure while circulating the mixture. This Patent Document 2 also describes that the hydrogen content is increased by the addition of catalase. However, Patent Document 2 does not include technical teaching beyond Patent Document 1.

A paper titled “An efficient way of producing fuel hydrocarbon from CO ₂ and activated water” by Tadayuki Imanaka et al. Published on the web on August 29, 2015 by J-STAGE (Non-Patent Document 1) In the presence of a titanium dioxide catalyst, UV light and black light (wavelength 350 nm to 400 nm) are irradiated to generate activated water, and this activated water is mixed with light oil to make it stronger. A method for producing synthetic oil by stirring is disclosed. In the method described in this paper, active water is mixed with light oil by a special mixer serving as a reaction layer, the mixed solution collides with the wall of the mixer, and the mixed solution is circulated so that the collision is repeated. In this process, carbon dioxide is supplied to the upper space of the mixer, which is the reaction layer. According to the method described in Non-Patent Document 1, a cloudy emulsion is generated in the above-described process. And when this emulsion is left still, an emulsion will be phase-separated into two phases, an oil phase and an aqueous phase, and oil equivalent to light oil can be obtained from an oil phase part. The paper of Non-Patent Document 1 reports that light oil increased by 5 to 10% by volume with respect to light oil used as the base oil was obtained by the method disclosed herein. In the method described in Non-Patent Document 1, since carbon dioxide is supplied to the upper space of the mixer, it is understood that the carbon deficient due to the addition of water is supplemented by the decomposition of the carbon dioxide.

Japanese Patent No. 4682287 JP 2014-47229 A

In the method described in the above-mentioned publicly known literature, a certain amount of increase can be achieved with respect to the fuel oil used as the base oil, but the extent of the increase is limited. For example, in the method described in Non-Patent Document 1, as described in the document, the increase is only about 10% by volume. In the methods described in

Patent Documents

1 and 2, the increase is only about twice. Not achieved.
The present invention addresses this problem in the prior art, and can add water to the base oil, which can dramatically increase the ratio of the synthetic fuel to the hydrocarbon-based fuel that is the base oil. An object of the present invention is to provide a method for producing a hydrocarbon-based synthetic fuel.
Another object of the present invention is that the composition and physical characteristics are substantially the same as or close to those of the fuel base oil that is the fuel before water addition, from the viewpoint of oil-water separation. Provides a method for producing a hydrocarbon-based synthetic fuel oil that can produce a hydrocarbon-based synthetic fuel oil having characteristics equivalent to those of the fuel base oil in a significantly increased amount compared to the amount of the fuel base oil. It is to be.

In order to achieve the above object, a method according to the present invention comprises adding hydrocarbon to a hydrocarbon-based fuel base oil to produce a hydrocarbon-based synthetic fuel oil having a volume larger than the volume of the hydrocarbon-based fuel base oil. In the method for producing fuel oil, the hydrocarbon-based synthetic fuel oil produced by the production method is used as a fuel base oil in the production of the next hydrocarbon-based synthetic fuel oil, and the same steps are sequentially repeated a plurality of times. Thus, a hydrocarbon-based synthetic fuel having a high water addition ratio is produced.
That is, the method for producing a hydrocarbon-based synthetic fuel oil according to one aspect of the present invention includes:
a) An activated water generating step of performing an activation treatment on water to generate activated activated water;
b) an agitation and mixing step of adding the activated water to a hydrocarbon-based fuel base oil that is initially used as a fuel base oil, and stirring and mixing for a predetermined time under a reactive environment;
c) a fusion step of fusing the hydrocarbon fuel base oil and the activated water that have undergone the stirring and mixing step under a reactive environment;
d) a primary produced hydrocarbon fuel oil collecting step for collecting a hydrocarbon produced fuel obtained from the mixture obtained through the fusion step as a primary produced hydrocarbon fuel oil;
And then
The primary product hydrocarbon fuel oil is used as a secondary fuel base oil, and the steps b), c) and d) are performed to collect the secondary product hydrocarbon fuel oil. System fuel oil is sequentially used as the fuel base oil, and the process of steps b), c) and d) is repeated a plurality of times, so that water (H ₂ O) having a volume larger than that of the initial fuel base oil is obtained. It does not substantially contain, but includes producing a multi-generation hydrocarbon-based synthetic fuel oil composed of a hydrocarbon-based fuel oil having a composition that is substantially equivalent to or close to that of the corresponding initial fuel base oil. .

A method for producing a hydrocarbon-based synthetic fuel oil according to another aspect of the present invention includes:
a) An activated water generating step of performing an activation treatment on water to generate activated activated water;
b) an agitation and mixing step of adding the activated water to a hydrocarbon-based fuel base oil that is initially used as a fuel base oil, and stirring and mixing for a predetermined time under a reactive environment;
c) a fusion step of fusing the hydrocarbon fuel base oil and the activated water that have undergone the stirring and mixing step under a reactive environment;
d) A hydrocarbon system having a composition that is not substantially contained in water (H ₂ O) and is substantially equivalent to or close to the initial fuel base oil by allowing the mixed solution that has undergone the fusion step to stand. An oil-water separation step for phase separation into an upper oil layer made of fuel oil and a lower water layer;
e) a primary produced hydrocarbon fuel oil collecting step for collecting the hydrocarbon fuel oil in the upper oil layer as a primary produced hydrocarbon fuel oil;
Including
f) The stirring and mixing step and the fusion step are the steps of the hydrocarbon-based fuel base oil in which the volume of the primary-generated hydrocarbon fuel oil obtained by the primary-generation hydrocarbon-based fuel oil collecting step is used as the initial fuel base oil. To be performed over a period of time greater than the volume, then
g) Using the primary product hydrocarbon fuel oil as a secondary fuel base oil, collecting the secondary product hydrocarbon fuel oil by performing the above steps b) c) d) e) f) The obtained hydrocarbon-based fuel oil is sequentially used as a fuel base oil, and the process of the above steps b), c), d), e) and f) is repeated a plurality of times. A multi-generation hydrocarbon-based synthetic fuel comprising a hydrocarbon-based fuel oil having a composition substantially free of water (H ₂ O) and substantially equivalent to or close to the original fuel base oil Including producing oil.

In the method of the present invention, the activated water preferably contains microbubble hot spots. Moreover, it is preferable that an activated water production | generation process is performed by irradiating an ultrasonic wave to this water in the state which heated up water to the temperature of the range of 35 to 45 degreeC, and applied the voltage. Furthermore, the voltage is preferably applied by irradiating tourmaline immersed in water with ultrasonic waves to bring the tourmaline into an excited state. When the activated water contains microbubble hot spots, it is preferable that a substance effective to retain the microbubble hot spots is added to the activated water.

It is preferable that the generation of hot spots of microbubbles is performed by irradiating water with ultrasonic waves having a frequency different from the frequency of ultrasonic waves irradiated to tourmaline. The reactive environment in the stirring and mixing step can be formed by stirring water while irradiating water to which catalase has been added. Stirring is preferably performed so as to generate a strong wave at the liquid level of the mixture of water and fuel base oil. Furthermore, the reactive environment in the stirring and mixing step can be formed by adding a photocatalyst to water and stirring while irradiating with ultraviolet light.

The fuel oil produced by the method of the present invention is a hydrocarbon-based synthetic fuel oil that is substantially free of water (H ₂ O) and is substantially the same as or close to the fuel base oil. It has a composition and a physical characteristic to do. For example, when the fuel base oil is a light oil used as a diesel fuel, a surprising result is obtained that the resultant synthetic fuel oil is a light oil equivalent to the light oil that is the base oil. Since the light oil produced by the present invention does not substantially contain water (H ₂ O), it has been confirmed that oil-water separation does not occur even when stored for a long period of time.
Similarly, according to the method of the present invention, when the fuel base oil is A heavy oil, it is possible to produce heavy oil that is substantially equivalent to or close to the A heavy oil.

Despite the addition of water to the fuel base oil, the synthetic fuel is substantially free of water (H ₂ O) and is substantially the same as or close to the fuel base oil. In order to achieve physical properties, it is necessary to incorporate carbon from the outside to generate hydrocarbons that are combustible components. For this purpose, carbon dioxide in ambient air is taken in from the liquid level of the mixture of the fuel base oil and water, and the carbon dioxide is decomposed and used for the reaction for generating the synthetic fuel. It is conceivable to obtain at least the majority of the carbon required. For this purpose, when the agitation and mixing step is performed in an open space to the atmosphere, the mixture is circulated in the agitation and mixing step so as to generate a strong wave at the liquid level of the mixture of fuel base oil and water. It is effective. If the surrounding area where the stirring and mixing process is performed is a closed space, the amount of carbon dioxide taken in from the ambient air is insufficient, but under such circumstances, carbon is added to the fuel base oil and water mixture. It was confirmed that the intended synthetic fuel can be obtained by addition. As carbon to be added, charcoal obtained by carbonizing wood can be used. In addition, powdered carbon used for industrial applications can also be used advantageously. Further, carbon monoxide gas or carbon dioxide gas may be added and decomposed in the same manner as in the case of carbon dioxide taken from the air, and used for the production of synthetic fuel.
Moreover, it is estimated that hydrogen required for the production | generation of the hydrocarbon which is a combustible component is obtained by decomposition | disassembly of the activated water molecule. Water molecules are activated to include microbubble hot spots in the method of the present invention, and water containing the activated water molecules is added to at least one of catalase, sodium hydroxide, and hydrogen peroxide aqueous solution. It has been confirmed that the hydrogen necessary for the reaction can be obtained by stirring with one added.

The amount of water added to the fuel base oil is not particularly limited, but if the amount of water added to the fuel base oil is too large, the reaction time required to produce a synthetic fuel having the desired composition will be excessive. There is a concern that it will become impractical. The inventor of the present invention has confirmed that a desired synthetic fuel can be produced in a sufficiently short time even when water is mixed at a ratio of about 1 to the fuel base oil 1 by volume ratio. When the amount of water added is less than this, the desired result can be obtained in a shorter time. Therefore, in the present invention, the mixing ratio of the fuel base oil and water is preferably about 1 or less with respect to the fuel base oil 1 in terms of volume ratio.

In the method of the present invention, in the agitation and mixing step, first, only the fuel base oil is charged into the agitation and mixing tank, and the water after the water activation step and the additive addition step is added and mixed in predetermined amounts while stirring. Is preferred. In this case, it is preferable to vigorously stir so as to generate a strong wave on the liquid surface in order to take carbon dioxide in the air into the liquid.

In the method of the present invention, an apparatus having a stirring and mixing tank having a cylindrical portion, and at least one injection pipe for introducing water that has undergone a water activation step and an additive addition step into the tank by a method such as injection. It is preferable that the water jet direction of the jet pipe has a predetermined angle with respect to the diameter line of the cylindrical portion.

In the method of the invention according to the above embodiment using an apparatus with at least one injection tube in a stirred mixing tank having a cylindrical portion, the predetermined angle is about 40 degrees to about 50 degrees, in particular about 45 degrees. Preferably, when multiple spray tubes are provided, the predetermined angle in all the spray tubes is a specific angle in the range of about 40 degrees to about 50 degrees, for example, about 45 degrees. It is preferable to do so. In order to generate the above-described strong ripples on the liquid level in the stirring and mixing tank, the discharge port of the injection pipe is positioned at least 8 cm, preferably 10 cm or more above the liquid level, and activated water is used as a high-speed jet. Is preferably sprayed onto the liquid surface.

In the above aspect of the present invention, it is preferable that the injection pipe has a projecting portion that projects into the stirring and mixing tank tank.

In this case, the length of the protrusion is preferably about 10 cm.

In one embodiment of the present invention, in the additive addition step, it is preferable to add catalase in a weight ratio of 0.04 to 0.05% with respect to water.

In still another aspect of the present invention, it is preferable that the water activated in the water activation step described above has an ORP of 160 mV to −200 mV.

In a preferred embodiment of the present invention, the water activation step maintains the tourmaline or copper ion generating material in contact with water, and the water or the tourmaline or copper ion generating material is 10 KHz to 60 KHz. Until then, two frequency ultrasonic waves of 200 KHz or higher are alternately irradiated, and water is activated by electrical energy radiated from the tourmaline or copper ions radiated from the copper ion generating material.

In a further preferred embodiment of the present invention, the pressure applied in the fusion step is 0.3 MPa or more, and the heating temperature is in the range from 40 ° C to 80 ° C.

In a further preferred embodiment of the present invention, an OHR mixer can be used in the stirring and mixing step.

According to the present invention, by the above-described method, it is possible to obtain a hydrocarbon-based synthetic fuel oil that is difficult to be separated into water and oil after being synthesized, or hardly separated. Further, by using the obtained synthetic fuel oil as a base oil, adding water thereto, and further repeating the same steps, a hydrocarbon-based synthetic fuel oil having a high water content can be efficiently produced. As described above, the synthetic fuel oil produced by the method of the present invention is substantially free of water (H ₂ O) and is substantially the same as or close to the fuel base oil. It will have composition and physical properties.
Further, the hydrocarbon-based synthetic fuel oil of the present invention has a calorific value per unit amount equal to or higher than that of the existing fuel oil, and compared with the existing fuel oil, the combustion chamber and exhaust after combustion. There is an effect that there is little deterioration and corrosion of a pipe etc. Furthermore, the synthetic fuel oil of the present invention is excellent in complete combustibility, and it is difficult to produce carbon monoxide, and the effects such as low carbon monoxide emission are achieved.

It is process drawing of the manufacturing method of the synthetic fuel oil which concerns on this invention. It is a whole block diagram of the manufacturing apparatus used for the manufacturing method of the synthetic fuel oil which concerns on this invention. It is a structural diagram of the injection tube to the reaction tank of the stirring apparatus which can be used for the manufacturing apparatus of FIG. It is the schematic of an example of the ionization apparatus which can be used for the manufacturing apparatus of FIG. It is a chart which shows the result of the GC-MS analysis about the hydrocarbon type | system | group synthetic fuel oil obtained by using the method which concerns on one Example of this invention as a base oil. It is a chart which shows the result of the GC-MS analysis about the other synthetic fuel obtained by using the light oil as base oil by the method which concerns on one Example of this invention. 4 is a chart showing the results of GC-MS analysis of light oil used as base oil in one example of the present invention. It is a chart which shows the result of the GC-MS analysis about the other synthetic fuel obtained by using A heavy oil as a base oil by the method which concerns on the other Example of this invention. FIG. 9 is a chart showing GC-MS analysis results for A heavy oil used as base oil in the example shown in FIG. 8.

An embodiment of a method for producing a hydrocarbon-based synthetic fuel oil according to the present invention will be described below with reference to the drawings.
It should be noted that the overall configuration of the synthetic fuel production method shown in this example, the configuration of each detail, and the numerical values are not limited to the embodiments and examples described below, but are based on the technical idea of the present invention. It can be changed within the range, that is, within the range of the shape and size that can exhibit the same effect.

An embodiment of the present invention will be described with reference to FIGS. 1, 2, and 3. FIG. 1 is a flow diagram of a method according to an embodiment of the present invention performed using a manufacturing apparatus according to the present invention. FIG. 2 is an overall configuration diagram of a manufacturing apparatus used in the synthetic fuel manufacturing method according to the present invention, and FIG. 3 is a structural diagram of an injection pipe for performing water injection into a reaction tank of the manufacturing apparatus according to the present invention. It is.
Referring to FIG. 2, in one embodiment of the present invention, the synthetic fuel production apparatus 1 includes a base oil improvement tank 2, a purified water tank 3, a reaction accelerator injection unit 4, a reaction tank 5, a stationary tank 6, and a product receiving tank. 7 is composed. The outline of the apparatus 1 will be described. The fuel base oil is pretreated in the base oil improvement tank 2, the water is activated in the purified water tank 3, and the additive is supplied from the reaction accelerator injection unit 4 to a predetermined tank. throw into. Further, the fuel tank oil and water are stirred and mixed and fused in the reaction tank 5, and unnecessary residues such as scum are removed in the stationary tank 6. If necessary, the oil phase and the water phase are phase-separated. Then, hydrocarbon synthetic fuel oil as a product is introduced from the stationary tank 6 to the product receiving tank 7.

The base oil improvement tank 2 is a tank that performs a process before the fuel oil is mixed. The fuel base oil is supplied from another base oil tank 201. This base oil improvement tank is intended to make the temperature of the oil suitable for mixing. After the fuel base oil is supplied from the base oil tank 201 to the base oil improvement tank 2, it is heated by the heater 8 provided in the base oil improvement tank 2, and is managed at a predetermined temperature by the thermocouple (T).
In order to increase the uniformity of the oil temperature, the fuel base oil in the base oil improvement tank 2 is circulated by being taken out of the base oil improvement tank 2 by the pump 11 and reintroducing into the tank through the header pipe 202. May be. Further, oil molecules may be subdivided as a pretreatment using a catalyst.

The purified water tank 3 performs a water activation process. The water used in the method of the present invention is preferably soft water, and therefore water is preferably supplied from the water softening device 301. The purpose of the purified water tank 3 is to maintain the temperature of the water at a temperature suitable for mixing, and to subdivide the water molecules to an active level to obtain activated water containing microbubble spots. The water supplied to the purified water tank 3 is heated by a heater 8 provided in the purified water tank 3 and is controlled at a predetermined temperature by a thermocouple (T). The degree of activation can be measured by an ORP (oxidation / reduction potential) meter. An ultrasonic generator 10 is provided at the bottom of the purified water tank 3, and the water molecular aggregate can be subdivided by irradiating the ultrasonic wave from the ultrasonic generator 10. In this case, it is preferable to irradiate ultrasonic waves of two types of wavelengths alternately. Specifically, ultrasonic waves of 10 kHz to 60 kHz and ultrasonic waves of 200 kHz or higher are alternately applied. By doing so, the efficiency of activation is improved.

Furthermore, in the purified water tank 3, it is preferable to use tourmaline or a copper ion generating material as the catalyst 9. When the ultrasonic wave is irradiated from the ultrasonic wave generation unit 10, the efficiency of activation can be improved by bringing the catalyst 9 into contact with water by the electric energy radiated from the catalyst 9. Further, the action of the catalyst can be promoted by irradiating the catalyst 9 such as tourmaline or copper ion generating material immersed in the purified water tank 3 with ultrasonic waves.

The water may be circulated by taking out the water in the tank to the header 302 by the pump 11 and returning it again from the header 302 into the purified water tank 3 so that the activation is performed uniformly. In this case, water is drawn from the bottom of the tank, pressure is applied by the pump 11, and water is re-injected from the top of the tank through the header pipe 302. By setting it as such a structure, the temperature and activation of water can be performed equally.

The activation of water can also be performed by plasma arc treatment of water configured to generate a discharge between electrodes connected to a high-voltage transformer and dissociate and ionize water by this discharge. When water is activated by plasma arc treatment, for example, the treatment can be performed by installing a plasma arc treatment apparatus between the purified water tank 3 and the pump 11 in the water circulation path. Moreover, when performing a plasma arc process, aluminum can be used suitably as the catalyst 9.
In the present invention, the above-described application of electrical energy and plasma arc treatment of water are collectively referred to as “electrical stimulation”.

The reaction accelerator injecting section 4 is for introducing an additive into the purified water tank 3 or the reaction tank 5 as a reaction accelerator. The additive is a substance that achieves the action of decomposing hydrogen peroxide into hydrogen and oxygen and releasing the oxygen into the atmosphere as a gas. By this action, the hydrogen content ratio of the produced fuel oil can be increased to prevent the calorific value from decreasing. As an additive, catalase, sodium hydroxide, aqueous hydrogen peroxide solution or the like can be used. It is necessary to finely adjust the amount of additive added. When catalase is added, the amount of catalase added is preferably 0.04% to 0.05% by weight with respect to water. If the amount of catalase added is less than 0.04% by weight, the effect is weak, and if it exceeds 0.05%, it will not dissolve sufficiently and will increase the scum, which will lower the quality of the fuel oil produced. .

The reaction vessel 5 is for performing a stirring and mixing step and a fusion step. The fuel base oil is supplied from the base oil improvement tank 2 to the upper part of the reaction tank container 13. Water is supplied from the purified water tank 3 to the side surface of the container 13 of the reaction tank 5 through the injection pipe 14. The mixed liquid of oil and water is taken out from the discharge port 15 of the container 13 of the reaction tank 5 by the pump 11, and in a pressurized state, passes through the OHR mixer 12 and reacts through the header pipe 502 and the injection pipe 14. It is circulated inside the container 13 of the tank 5. The OHR mixer 12 is for efficiently mixing a plurality of substances. Since this reaction tank 5 acts on a pressure of about 3 to 9 atm when used in the fusion process, it needs to have a structure that can withstand a higher pressure than other tanks. There is a heater 8 in the middle of the tank, and the mixture of oil and water is managed at a predetermined temperature by the heater 8.

The stationary tank 6 is a tank that temporarily stores the product solution after the fusion process. In this tank 6, scum generated by additives and the like is precipitated. The synthetic fuel oil in which the oil and water are completely integrated and the impurities are separated by being left in the stationary tank 6, and the synthetic fuel oil as a supernatant is supplied to the product receiving tank 7. The impurities include additives, and these impurities are returned to the reaction vessel 5. The residence time in the stationary tank 6 is preferably about 1 hour. When the product solution after the fusion step contains water, the product solution is phase-separated into an upper oil phase and a lower water phase in the stationary tank 6, and the synthetic oil in the upper oil phase is used as a product. It is taken out into the product receiving tank 7.

The product receiving tank 7 is a tank for storing synthetic fuel oil produced as a product. The produced synthetic fuel oil is supplied from the product receiving tank 7 to the product storage tank 701 at a stage where it is gathered to some extent.

Next, a basic process in the method for producing a synthetic fuel according to the present invention will be described with reference to FIG. This method is divided into a process for treating water and a process for treating fuel base oil. The process for treating water includes a water activation process and an additive charging process. The process of processing the fuel base oil includes a base oil improving process and an additive charging process. The activated water that has undergone the water activation process and additive feeding process and the fuel base oil that has undergone the base oil improvement process and additive feeding process are agitated and mixed in the agitation and mixing process, and the primary production synthetic oil is produced through the fusion process. Is done. If necessary, a filtration step is performed before removal of the primary synthetic oil.

The activation process is performed in the purified water tank 3. In this step, the water molecule aggregate is subdivided to the active level. By subdividing the water to the active level, the affinity with the fuel base oil molecules is improved, and more water can be used for the production of synthetic fuel. Water is put into the purified water tank 3, and ultrasonic waves are irradiated to the water by the ultrasonic wave generation unit 10, and the water is vibrated at a high frequency, thereby promoting the fragmentation of water molecules. Ultrasonic irradiation can promote subdivision of water by alternately irradiating ultrasonic waves having two different frequencies. For example, the frequency of the ultrasonic waves can be further subdivided by using two types of frequencies of 10 KHz to 60 KHz and 200 KHz or more. Moreover, when using the ultrasonic wave generation part 10, it is effective to give an electrical stimulus to water using a substance such as tourmaline or a copper ion generating material as a catalyst. By operating the ultrasonic wave generator 10 in a state where such a catalyst material is immersed in water, electrical stimulation is given to the water, and microbubble hot spots are formed in the water. The degree of conversion can be increased. In this case, it is preferable to perform ultrasonic irradiation so that the ultrasonic wave strikes a catalyst material such as tourmaline or a copper ion generating material.

The degree of activation by irradiating with ultrasonic waves can be confirmed by measuring ORP (redox potential) (mv). The ORP of water obtained by irradiating with ultrasonic waves is preferably 160 mV to -790 mV, more preferably 30 mV to -600 mV. Incidentally, the normal tap water ORP is 700 mV to 500 mV.
Moreover, by irradiating ultrasonic waves, oxygen is released from water, and the hydrogen content ratio of water is improved.
For example, in the case where tourmaline and water are brought into contact with each other in order to reform 200 L of water, it is desirable to eject water from the pipe toward the tourmaline at a flow rate of 20 L / min to 50 L / min. The reaction time is suitably about 1 hour, but the effect can be obtained even from 20 minutes to 1 day.

Next, the additive charging process will be described. The additive charging step is to increase the hydrogen content ratio of water by adding the additive stored in the reaction accelerator injecting unit 4 to the purified water tank 3 or the reaction tank 5.
As the additive, one or more of catalase, sodium hydroxide, and hydrogen peroxide aqueous solution are used. It is necessary to finely adjust the amount of additive added. As described above, when catalase is used, the amount of catalase added is preferably 0.04% to 0.05% by weight with respect to water. If it is less than 0.04%, the effect is weak, and if it is more than 0.05%, it does not dissolve sufficiently, so that the scum is increased and the quality of the fuel is lowered.
Sodium hydroxide is sufficiently effective as an additive when added in an amount of 0.001 to 0.1% by weight based on water. In the case of an aqueous hydrogen peroxide solution, the addition of 0.001% to 0.1% by weight with respect to water can sufficiently exhibit the effect as an additive.

Next, the stirring and mixing step will be described. In the stirring and mixing step, the water after being activated in the purified water tank 3 and charged with the additive is mixed with the fuel base oil. First, only the fuel base oil is charged into the reaction tank 5. This base fuel oil is circulated through the OHR mixer 12 in the reaction vessel 5. By passing through the OHR mixer 12, the molecules of the fuel base oil are made uniform and are easily fused with water. When the circulation is completed to some extent, the activated water is poured from the purified water tank 3 into the reaction tank 5 little by little. This is because water is dispersed as uniformly as possible in the fuel base oil. The activated water supplied from the purified water tank 3 is pressurized by the pump 11 of the purified water tank 3, mixed with the fuel base oil taken out from the discharge port 15 of the reaction tank 5, and pressurized by the pump 11 of the reaction tank 5. And mixed by the OHR mixer 12. The pressure of the OHR mixer 12 is preferably 3 atm (0.3 MPa) or more, and the temperature is preferably 40 ° C. to 80 ° C. Therefore, the pressure of the pump 11 of the purified water tank 3 and the reaction tank 5 is set to a pressure corresponding to that, and the heating of the heater 8 of the purified water tank 3 and the reaction tank 5 is also set to the pressure. The activated water and the fuel base oil mixed in the OHR mixer 12 are reintroduced into the reaction tank 5 from the injection pipe 14 through the header pipe 502. Depending on the angle of the injection pipe 14 with respect to the reaction tank 5 and the amount of protrusion inside the reaction tank 5, the efficiency and quality of mixing change.
For example, when 100 L of activated water is mixed with 100 L of fuel base oil, the mixture of the activated water and fuel base oil is circulated through a pipe having a pipe size of 15 A to 50 A at a flow rate of 20 L / min to 50 L / min. It is preferable to make it. The mixing time can be about 5 minutes to 1 hour.

Next, the fusion process will be described. In the fusion process, the input of the activated water from the purified water tank 3 to the reaction tank 5 is completed, and the fusion process is performed by circulating the mixture of the activated water and the fuel base oil through the OHR mixer 12. Is done. In this case, the pressure is preferably 3 atm (0.3 MPa) or more, which is the same as in the stirring and mixing step, and the temperature is preferably 40 ° C to 80 ° C. In this step, the mixture of activated water and fuel base oil is passed through the OHR mixer 12 for a sufficient period of time, so that the activated water and the oil are fused and the hydrocarbon-based synthetic fuel oil that is not likely to be separated. Can be obtained.
For example, when the activated water 100L is fused with the fuel base oil 100L, it is desirable that the pressure applied to the mixed liquid is 0.3 MPa (3 atm) or more. The temperature may be 70 ° C. or lower. It is most effective that the pressure applied in the fusion process is 0.9 MPa and the temperature is 50 ° C. The reaction time is suitably 20 to 60 minutes after reaching the pressure and temperature.

Next, the filtration process will be described. The filtration step is a step of separating the scum-like product from the coagulation of the components of the enzyme and other components when the enzyme is used at the time of production from the completely produced synthetic fuel. The method using the stationary tank 6 is a method in which the product is allowed to stand and the specific gravity is separated. Scum, which has a relatively high specific gravity, accumulates at the bottom, and synthetic fuel collects in the upper layer because of its low specific gravity. By sending the upper layer synthetic fuel to the product receiving tank 7, a hydrocarbon-based synthetic fuel oil as a product can be obtained. The mixed liquid residence time in the stationary tank 6 is desirably 1 hour or longer.
Moreover, synthetic fuel and scum can also be separated by passing through a filtration filter. A filtration filter having a size of about 10 μm to 30 μm is used. The temperature for passing through the filtration filter is preferably 40 ° C. or less, and the passage time is preferably about 20 L / min to 50 L / min when passing through a pipe having a pipe size of 20 A to 50 A, but the speed is more moderate. desirable. The number of passes through the filtration filter can be one or more.

In this way, by performing the above-described steps, it is possible to produce a hydrocarbon-based synthetic oil that is thoroughly mixed and united with water and does not separate over time. Moreover, it becomes possible to perform the fusion process of the activated water and the fuel base oil in a short time.
As shown in FIG. 1, by using the obtained primary production synthetic fuel oil as a fuel base oil and repeating the same steps, a secondary production synthetic fuel oil can be produced. Thereafter, in the same manner, it is possible to produce a multi-generation synthetic fuel oil by repeating the process of using the obtained synthetic oil as a base oil a plurality of times. Such a multi-generation synthetic fuel oil produced by the method of the present invention has a very high water content.

Another embodiment of the present invention will be described with reference to FIG. In the following description, the description of the same parts as those of the above-described embodiment is omitted. FIG. 3 is a view showing the structure of a liquid injection pipe to the reaction vessel 5 that can be used in the production apparatus according to the present invention. FIG. 3A is a view seen from above for showing the positional relationship between the reaction vessel 5 and the injection pipe 14. FIG. 3B is a side view of the reaction vessel 5.

In connection with the above-mentioned embodiment, although each process for synthetic fuel manufacture was demonstrated, in each process, the mixing liquid of activated water and a fuel base oil performed by a stirring mixing process and a fusion process is carried out. Circulation is important. In the apparatus shown in FIG. 2, basically, the mixture is extracted from the discharge port 15 of the reaction tank 5 from the pump 11 and the OHR mixer 12 through the injection pipe 14 and from the upper side surface of the reaction tank 5. Then, it is carried out by charging the reaction vessel 5 again in an injection state. In this circulation process, it is ideal that all of the mixed solution is circulated evenly. However, if the recharging method into the reaction tank 5 is not appropriate, only a part of the mixed solution is circulated more and the other part is not circulated so much, and the whole is not a uniform synthetic fuel oil. There is a concern that the time until it becomes uniform becomes very long.

Therefore, the inventor of the present invention examined the relationship between the injection tube 14 for recharging the mixture into the reaction vessel 5 and the reaction vessel 5. As shown in FIG. 3B, the reaction vessel 5 has a cylindrical body at the top and a cone at the bottom. Four injection pipes 14 are arranged on the upper side surface, and the oil / water mixture can be injected into the reaction tank 5 from four directions as shown in FIG. As shown in FIG. 3 (c), the angle in the length direction of the injection tube 14 with respect to the diameter line connecting the central axis of the cylindrical portion of the reaction vessel 5 and the attachment point where the injection tube 14 is attached to the reaction vessel 5, The mounting angle or the injection direction of the injection pipe 14 was determined. Then, the time required for the fusion and the quality of the generated synthetic fuel oil were examined when the mounting angle was changed from 0 degrees to 90 degrees. In FIG.3 (c), the case where an attachment angle is 0 degree | times is the injection pipe 14a1. Below, the angles from 14a2, 14a3, 14a4 and the axis were increased by 15 degrees. In this way, as a result of examining and examining by changing the angle every 15 degrees, when the angle from the axis is 45 degrees, the time required for the fusion is shortest, and the quality of the generated synthetic combustion is good. Was confirmed. From this result, it can be seen that the mounting angle of the injection tube 14 is preferably in the range of about 40 degrees to about 50 degrees with respect to the above-described diameter line.

Next, as shown in FIG. 3 (d), the amount of protrusion of the injection tube 14 into the reaction vessel 5 having a diameter of 60 cm, the time required for fusion, and the quality of the generated synthetic fuel oil were examined. In FIG.3 (d), when the protrusion amount is 0, it is the injection pipe 14b1. Below, the amount of protrusion was increased to 14b2, 14b3, 14b4. The amount of protrusion was examined by changing by 10 cm. As a result, it was found that when the protrusion amount was 10 cm, the time required for fusion was the shortest and the quality of the produced synthetic fuel oil was good. When a larger reaction tank is used, it is preferable to increase the protruding amount of the injection pipe according to the diameter of the reaction tank, and it is desirable to increase the number of injection pipes.

From the above, the mixture is injected into the reaction vessel 5 through the injection tube 14 at an angle of 45 degrees with respect to the diameter line of the cylinder. In the case of the reaction vessel 5 having a diameter of 60 cm, the reaction of the injection tube 14 is performed. It may be considered that 10 cm is optimal for the amount of protrusion into the tank 5. By providing an angle with respect to the diametrical axis of the cylinder, a natural vortex can be created in the vessel. Therefore, mixing can be performed efficiently. Further, by setting the amount of protrusion of the injection tube 14 into the reaction tank 5 to a predetermined amount, it is possible to avoid the mixture that has circulated around the circumference of the mixture or only near the center. It is preferable that the injection tube 14 is disposed so as to be located at least 8 cm, preferably at least 10 cm above the liquid level in the reaction vessel 5, and the mixture is injected from the injection tube 14 at a high speed.

In this way, by adjusting the arrangement of the injection pipe 14 with respect to the reaction vessel 5, the activated water and the fuel base oil are completely mixed and united so that they do not separate over time. Fuel oil can be produced. Moreover, the fusion process of activated water and fuel oil can be performed in a short time.

Still another embodiment of the present invention will be described with reference to FIG.
FIG. 4 is a schematic diagram showing an example of a plasma arc processing apparatus that can be used as an activation apparatus of a manufacturing apparatus according to the present invention. The plasma arc processing apparatus 20 is arranged so as to surround the center electrode and an electrode 21 (shown by a hexagon in the figure) each connected to a high voltage transformer (not shown). A plurality of (in the figure, 12) electrodes 22 are provided. By supplying power to the electrodes, arc discharge occurs between the electrodes. In the purified water tank 3 in the production apparatus 1 shown in FIG. 2, a plasma arc treatment apparatus 20 is installed between the purified water tank 3 and the pump 11, and water from the purified water tank is passed through the plasma arc treatment apparatus 20. Thus, water can be activated by plasma arc treatment. As such a plasma arc processing apparatus, for example, a plasma arc processing apparatus used for Ultra U-MAN manufactured by Nippon Risuiken Co., Ltd. can be preferably used.

[Formation of activated water]
(Preparation of tourmaline and catalase)
A tourmaline with a particle size of 20mm to 80mm from Tocantin, Brazil was purchased from New Wave. Furthermore, a catalase with the trade name “Leonette F-35” was purchased from Nagase ChemteX Corporation. These tourmalines and catalases were used in the following preparation examples and examples.
(Example of formation of active water)
Tap water which is soft water was used as water for forming active water. 3 kg of tourmaline is immersed in 20 liters of water at room temperature, and ultrasonic waves with a frequency of 30 kHz to 40 kHz are irradiated to tourmaline, and ultrasonic waves with a frequency of 200 kHz to 600 kHz are irradiated to water for 20 minutes. In the following production examples and examples, the frequency of ultrasonic waves irradiated to tourmaline was 35 kHz, and the frequency of ultrasonic waves irradiated to water was 400 kHz. After the elapse of 20 minutes, the ultrasonic irradiation was continued, and the temperature was raised to a water temperature of 43 ° C. using a heater while circulating water with a pump. When the water temperature reached 43 ° C., water circulation, heating by the heater and ultrasonic irradiation were stopped. At this time, the ORP of water was about −790 mV, the pH was 8 to 9, and microbubble hot spots were formed in the water, and it was confirmed that the water was activated.
In the above-described operation, Ryukyu limestone containing calcium carbonate as a main component was previously mixed in tourmaline as a substance for maintaining the hot spot of microbubbles. In the above-mentioned preparation step of the activated water, if the ORP of water is stabilized in a negative tendency and the pH becomes 8 to 9, it may be considered that the activation is completed.

Here, microbubbles mean microbubbles generated by local pressure fluctuation when water is irradiated with ultrasonic waves. Shinobu Koda from the Graduate School of Engineering, Nagoya University J89-ANo. 9 (2006), a paper titled “Chemical application of cavitation: Application of cavitation Induced by Ultrasound,” published by Kanto Chemical Co., Ltd. on April 1, 2009 "THE CHEMICAL TIMES" announced by Keiji Yasuda, Graduate School of Engineering, Nagoya University "Decomposition of Chemical Compounds by Ultrasound and Development of Sonochemical Reactor" " And a presentation material (Non-Patent Document 3) and “Manufacturing Basic Course (34th Technology Seminar)” held on February 20, 2013 by Toshi University Katsuaki Mizukoshi 4) is a state in which minute bubbles are generated in the liquid by irradiating the liquid with strong ultrasonic waves, that is, a cavitation state Sonochemistry, which is based on the generation of liquid molecules and the decomposition of liquid molecules, is discussed in detail.According to these non-patent literature descriptions, bubbles or microbubbles generated by ultrasonic waves are approximately in several cycles. It expands to a size of about several tens of μm, and then suddenly contracts by a quasi-adiabatic compression process. Local fields are called hot spots and are understood to be the origin of cavitation chemistry.

[Production of primary production synthetic fuel oil]
(Primary fuel oil production example 1)
A primary synthetic fuel oil using A heavy oil as a base oil was produced by the following method.
First, a tourmaline container with a volume of 25 liters equipped with a part for accommodating tourmaline, an ultrasonic generator (35 kHz ultrasonic transducer), and a thermometer and connected with a circulation pump (24 liters / minute × 0.5 Mpa). 3kg and 20 liters of tap water were added (a small-sized tourmaline ore imported from New Wave Co., Ltd.) To this water, 20 ml of catalase (Leonet F-35 manufactured by Nagase ChemteX Corporation) was added. Next, the ultrasonic vibrator was actuated, and water circulation was started by a circulation pump while irradiating tourmaline and water under the conditions described in “Formation example 1 of activated water”. The set temperature of the 3 kW line heater provided in the water circulation path was set to 40 ° C., and the circulation was continued for 1 hour from the time when it was confirmed that the temperature of the water in the container became 40 ° C. or higher. After 1 hour, when the redox potential of water in the container was measured with an ORP meter, it was 12 mV, and it was confirmed that the water was activated.

Next, 20 liters of commercially available A heavy oil (Type 1 No. 1 A heavy oil purchased from Fujikosan Co., Ltd.) was placed in a 25 liter container equipped with a thermometer and connected to a circulation pump, as in the above container. Circulation of heavy oil A was started by a circulation pump. The set temperature of the 3 kW line heater provided in the circulation path of A heavy oil was set to 40 ° C., and the circulation was continued for 1 hour from the time when it was confirmed that the temperature of the A heavy oil in the container became 40 ° C. or higher.

The activated water and A heavy oil thus obtained were mixed and stirred as follows, and then the mixed solution was heated and applied with pressure to be fused. That is, in addition to a thermometer, a 1 kW heating heater and a rotary vane type stirrer were provided, and an open system container having a volume of 25 liters opened to the atmosphere, and 10 liters of activated water was obtained. 10 liters of heavy oil was added. The container had a configuration in which a circulation pump and a mixing mixer (OHR mixer manufactured by OHR Fluid Engineering Laboratory Co., Ltd.) were connected. In the container containing the activated water and A heavy oil, the heating heater was turned on so that the temperature of the liquid in the container was maintained at 40 ° C. Here, 10 ml of the same catalase as described above was added. After 40 minutes, the stirrer was turned on, and water and A heavy oil were mixed and stirred. Next, the circulating pump was operated, and the supply pressure to the mixing mixer was adjusted to be about 0.5 MPa, and the mixed liquid was circulated. At that time, the circulation pipe for introducing the liquid into the container from the circulation path was positioned about 8 cm above the liquid level of the mixed liquid in the container. After the mixed liquid was circulated for 1 hour, the stirrer, the circulation pump and the heating heater were stopped. The liquid thus obtained was allowed to stand for about 3 days, and then a sample was taken for analysis. The amount of the sample collected was 20 liters, and it was confirmed that the sample was a synthetic fuel oil having the characteristics shown in Table 1.

(Primary fuel oil production example 2)
A synthetic fuel oil was produced in the same manner as in Production Example 1 except that a commercial diesel oil (No. 2 diesel oil purchased from JX Energy Co., Ltd. (ENEOS)) was used as the base oil instead of A heavy oil. Therefore, a sample was taken. The amount of sample collected was 20 liters.

Table 1 shows the component analysis results of the synthetic fuel oil produced in the primary synthetic fuel oil production examples 1 and 2 of the present invention. It is a mixture of water and oil, mixed one-on-one.
For comparison, the same component analysis was performed on the A heavy oil and light oil used as the base oil.
First, looking at the total calorific value and the true calorific value, it can be seen that both Example 1 and Example 2 exceed the base oil, and the effect of the present invention is obtained.
Next, when looking at the item of moisture, it can be seen that in both Production Example 1 and Production Example 2, the volume% of moisture in the synthetic fuel oil is 0.00% and substantially does not contain water. Since fuel oil and water are mixed one-to-one and fused, if sufficient fusion is not achieved, the amount of water should be detected. However, the volume% of water being 0.00% indicates that the fuel base oil and water are completely fused and not analyzed as a water component.
Thus, according to the present invention, the fuel base oil and water can be completely fused to produce a high-quality hydrocarbon-based synthetic fuel oil.

(Primary fuel oil production example 3)
A synthetic fuel was produced using an apparatus as shown in FIGS. 2 and 3 and using light oil as the base oil.
First, 150 liters of tap water was injected into a purified water tank filled with the same tourmaline as used in Production Example 1 in a portion containing tourmaline. The heater installed in the purified water tank was turned on, and the temperature was set to 40 ° C. Further, 150 ml of the same catalase used in Production Example 1 was added. Next, the circulating pump connected to the purified water tank is operated (discharge pressure 0.5 MPa), the ultrasonic generator installed in the purified water tank is operated, and the temperature of the water reaches 40 ° C. for 60 minutes, 40 ° C. After reaching the value, ultrasonic waves (frequency: 40 kHz) were irradiated to tourmaline and water for another 60 minutes. When water was introduced into the purified water tank, only one of the four injection tubes was used (three were closed), and the flow velocity at the tip of the injection tube was 3.3 m / s. It was 20 mV when the oxidation reduction potential of the water obtained by the ORP meter was measured. In this way, activated water was obtained.

Next, 150 liters of commercially available light oil (No. 2 light oil purchased from JX Energy Corporation (ENEOS)) was injected into the base oil improvement tank. Subsequently, the heater installed in the base oil improvement tank was turned on, and the temperature was set to 40 ° C. The circulation pump connected to the base oil improvement tank was operated (discharge pressure 0.3 MPa), and the diesel oil was circulated for 60 minutes until the temperature of the diesel oil reached 40 ° C., and after reaching 40 ° C. for another 60 minutes. When light oil was injected into the base oil improvement tank, only one of the four injection pipes was used (three were closed), and the flow velocity at the tip of the injection pipe was 2.0 m / s.

The activated water and light oil thus obtained were mixed in a reaction vessel and stirred. Further, the activated water and light oil were heated and fused by applying pressure. More specifically, 75 liters of base oil from the base oil improvement tank and 55 liters of activated water from the purified water tank were transferred to the reaction tank (hydration rate of about 42%). 65 ml of the same catalase used in Production Example 1 was added to the reaction vessel. Next, the heater was turned on so that the temperature of the liquid in the container was 40 ° C. After the liquid temperature reached 40 ° C., the circulation pump was operated, and the supply pressure to the mixing mixer was adjusted to be about 0.5 MPa, and the mixed liquid was circulated for 60 minutes. When the mixed solution was charged into the reaction tank, only one of the four injection tubes was used (three were closed), and the flow rate at the tip of the injection tube was 2.0 m / s. In addition, the injection tube was not submerged in the mixed solution in the reaction vessel. Specifically, the injection tube was positioned about 8 cm above the liquid level of the mixed liquid in the reaction tank. A sample of synthetic fuel oil for analysis was taken from the resulting liquid. The amount of sample collected was 114 liters.

(Primary fuel oil production example 4)
The temperature of the refined water tank, the base oil improvement tank, and the reaction tank is higher than that in Production Example 3, and is set to 42 ° C, 41 ° C, and 44 ° C, respectively, and the circulation time in the refined water tank and the base oil improvement tank A synthetic fuel oil was produced by carrying out the same steps as in Production Example 3 except that it was half of that in Production Example 3 (that is, 60 minutes). In addition, it was 26 mV when the oxidation reduction potential of the water obtained with the ORP meter in the purified water tank was measured. A sample of synthetic fuel oil for analysis was taken from the liquid obtained in the reaction vessel. The amount of sample collected was 114 liters.

(Primary fuel oil production example 5)
A heavy oil (type 1 No. 1 A heavy oil purchased from Fujikosan Co., Ltd.) is used as the base oil, the reaction tank temperature is set to 36 ° C., and the circulation time in the refined water tank and the base oil improvement tank is both 90 minutes. In addition, a synthetic fuel was produced in the same manner as in Production Example 3, except that the amounts of catalase added to the purified water tank and the reaction tank were 230 ml and 130 ml, respectively. In addition, it was 18 mV when the redox potential of the water obtained in the purified water tank was measured with the ORP meter. A sample of synthetic fuel oil for analysis was taken from the liquid obtained in the reaction vessel. The amount of sample collected was 114 liters.

Table 2 shows the component analysis results of the hydrocarbon-based synthetic fuel oil produced in Production Examples 4 and 5 of the present invention.

[Qualitative analysis of primary synthetic fuel oil]
A qualitative analysis by gas chromatogram mass spectrometry (GC-MS) was performed on a sample of the synthetic fuel oil obtained by the method of the present invention using light oil as the fuel base oil in Production Example 3. As an analytical sample, a sample obtained by diluting the sample obtained in Production Example 3 1000 times with n-hexane was prepared. The column was HP-5MS (length 30 m, inner diameter 2.5 mm, film thickness 0.25 μm), and the carrier gas was He. The injection amount of the analysis sample is 1 microliter, the injection method is splitless mode, the oven temperature is kept at 50 ° C. for 3 minutes, the temperature is raised from that temperature to 100 ° C. at a heating rate of 5 ° C. per minute, and from there The temperature was raised to 300 ° C. at a rate of 15 ° C. per minute and held at 300 ° C. for 3 minutes. The resulting GC-MS chart is shown in FIG. (A) is a TIC chromatogram, and (b) is a mass spectrum of a peak around 18.4 minutes.
The same qualitative analysis was performed on the synthetic fuel sample obtained in Production Example 4. The results are shown in FIG.
For comparison, the same qualitative analysis was performed on light oil used as the fuel base oil. The results are shown in FIG.
When FIG. 5 and FIG. 6 are compared with FIG. 7, the hydrocarbons obtained in Production Examples 3 and 4 have a tendency to reduce the components having a large number of carbon atoms (those larger than C19) compared to the base oil. It was confirmed that the component composition of the system synthetic fuel oil is in good agreement with the base oil.

The same qualitative analysis was performed on the sample of the primary production synthetic fuel oil obtained by the method of the present invention using A heavy oil as the base oil in Production Example 5. The results are shown in FIG.
For comparison, the same qualitative analysis was performed on heavy oil A used as the base oil. The results are shown in FIG.
8 was compared with FIG. 9, it was confirmed that the component composition of the primary synthetic fuel oil obtained in Production Example 5 was also in good agreement with that of the base oil.

[Property test of primary synthetic fuel]
A property test was conducted on samples of synthetic fuel oil obtained by the method of the present invention using light oil as a base oil in Production Examples 3 and 4. The property test items and methods were as follows.
・ Density (vibration type 15 ℃): JIS K2249
・ Kinematic viscosity (30 ℃): JIS K2283
・ Nitrogen quantitative analysis: JIS K2609
・ Sulfur content (ultraviolet fluorescence method): JIS K2541-6
・ Oxygen content: ASTM D5622
-Light oil composition analysis (JPI method): JPI-5S-49
For comparison, the same property test was performed on light oil used as base oil.
The results are shown in Table 3.
From Table 3, it can be seen that in the primary product synthetic fuel oil obtained by the method of the present invention, the aromatic content decreased and the saturated content increased compared to the base oil. A light oil with a small aromatic content and a high saturation content is desirable from the viewpoints of efficiency, toxic content of exhaust gas, and reduction of PM.

[Oxidation stability test of primary production synthetic fuel oil]
An oxidation stability test (test method: ASTM D2274) was performed on samples of the primary production synthetic fuel oil obtained by the method of the present invention using light oil as the base oil in Production Examples 3 and 4. For comparison, the same oxidative stability test was performed on light oil used as the base oil.
The measured amount of sludge was below the measurement limit of 0.1 mg / 100 ml for any sample.

[Running test with primary synthetic fuel oil]
The primary production synthetic fuel oil obtained by the method of the present invention using light oil as the fuel base oil in Production Example 3 was subjected to a JC08 mode running test (vehicle used: Nissan Motor NV350 model LDF-VW2E26 weight 1840 kg). For comparison, a similar running test was performed on a commercially available light oil (JIS No. 2).
The results are shown in Table 4. For reference, emission control values are also shown.
From Table 4, it is noted that the primary produced synthetic fuel oil obtained by the method of the present invention has a lower CO ₂ emission than that of commercially available light oil.
The primary production synthetic fuel oil obtained in Production Example 3 is 42% by volume derived from water. The conversion rate of water mixed with fuel base oil to fuel is estimated to be approximately 70% from the results of previous experiments, and the volume ratio of water-derived fuel out of the total amount of fuel produced is given by the formula [water-derived Fuel volume ratio] = (42 × 0.7) / (58 + 42 × 0.7) = 34%
It can ask for. From this, in the case of Production Example 3, it can be evaluated that 34% of the obtained fuel is not derived from petroleum. Therefore, it can be seen that the fuel obtained in Production Example 3 has reduced carbon emissions by about 34%.

(Primary fuel oil production example 6)
5 liters of activated water formed by the procedure described in “Formation of activated water” above, and commercially available diesel oil (No. 2 diesel oil purchased from JX Energy Co., Ltd. (ENEOS)) passed through the base oil improvement tank 2 10 The liter was put into the reaction vessel 5 and the mixing, stirring, and fusion steps were performed under the same conditions as in Production Example 2. Then, the produced | generated liquid mixture was moved to the stationary tank 6, and left still for 1 hour. As a result, the mixed solution was phase-separated into an upper oil phase and a lower aqueous phase. Therefore, the oil present in the upper oil phase was taken out as the primary production synthetic fuel oil. The amount of primary production synthetic fuel oil was 11 liters. The amount of water remaining in the aqueous phase was 4 liters. By this step, it was confirmed that 1 liter of 5 liters of water was converted to synthetic fuel oil. It can be seen that the synthetic fuel oil was increased by 10% compared to the base oil.

[Example 1]
As an example of the present invention, the synthetic fuel oil produced in the primary fuel oil production example 6 was used as a base oil to produce a secondary synthetic fuel oil. Specifically, 10 liters of the synthetic fuel oil produced in the primary fuel oil production example 6 was adjusted through the base oil improvement tank 2 and then charged into the reaction tank 5. At the same time, 5 liters of activated water formed by the procedure described in “Formation of activated water” was charged into the reaction vessel 5 and the mixing, stirring, and fusion steps were performed under the same conditions as in Production Example 2. . Then, the produced | generated liquid mixture was moved to the stationary tank 6, and left still for 1 hour. As a result, the mixed solution was phase-separated into an upper oil phase and a lower aqueous phase. Therefore, the oil present in the upper oil phase was taken out as a secondary generated synthetic fuel oil. The amount of the secondary production synthetic fuel oil taken out was 11 liters. The amount of water remaining in the aqueous phase was 4 liters. By this step, it was confirmed that 1 liter of 5 liters of water was converted to synthetic fuel oil. It can be seen that the secondary synthetic fuel oil was increased by 10% compared to the primary synthetic fuel oil used as the base oil.

Next, the secondary synthetic fuel oil obtained by the above process was used as a base oil to produce a tertiary synthetic fuel oil. Specifically, 10 liters of the secondary synthetic fuel oil produced in the above process was adjusted through the base oil improvement tank 2 and then charged into the reaction tank 5. At the same time, 5 liters of activated water formed by the procedure described in “Formation of activated water” was charged into the reaction vessel 5 and the mixing, stirring, and fusion steps were performed under the same conditions as in Production Example 2. . Then, the produced | generated liquid mixture was moved to the stationary tank 6, and left still for 1 hour. As a result, the mixed solution was phase-separated into an upper oil phase and a lower aqueous phase. Therefore, the oil present in the upper oil phase was taken out as the tertiary production synthetic fuel oil. The amount of the tertiary production synthetic fuel oil taken out was 11 liters. The amount of water remaining in the aqueous phase was 4 liters. By this step, it was confirmed that 1 liter of 5 liters of water was converted to synthetic fuel oil. It can be seen that the amount of the tertiary generated synthetic fuel oil is increased by 10% compared to the secondary generated synthetic fuel oil used as the base oil.
The calorific value measurement and component analysis of the primary product synthetic fuel oil produced in the primary fuel oil production example 6 and the secondary product synthetic fuel oil produced in Example 1 were performed. The results are shown in Table 5 in comparison with the commercially available diesel oil used as the base oil in the primary fuel oil production example 6.

The first embodiment is an example in which the primary production synthetic fuel oil produced in the primary fuel oil production example 6 is used as the base oil, but the primary production synthetic fuel oil produced in the primary fuel oil production examples 1 to 5 is used as the base oil. As in Example 1, a synthetic fuel oil can be produced.

DESCRIPTION OF SYMBOLS 1 Synthetic fuel manufacturing apparatus 2 Original oil improvement tank 3 Purified water tank 4 Reaction promoter injection | pouring part 5 Reaction tank 6 Stationary tank 7 Product receiving tank 8 Heater 9 Catalyst 10 Ultrasonic wave generation part 11 Pump 12 OHR mixer 13 Reaction tank container 14 Injection pipe 15 Discharge port 20 Plasma

arc treatment device

21, 22 Electrode

Claims

A method for producing a hydrocarbon-based synthetic fuel oil, wherein water is added to a hydrocarbon-based fuel base oil to produce a hydrocarbon-based synthetic fuel oil having a volume larger than the volume of the hydrocarbon-based fuel base oil,
a) An activated water generating step of performing an activation treatment on water to generate activated activated water;
b) an agitation and mixing step in which the activated water is added to a hydrocarbon-based fuel base oil that is initially used as a fuel base oil and stirred and mixed for a predetermined time under a reactive environment;
c) a fusion step of fusing the hydrocarbon-based fuel base oil that has undergone the stirring and mixing step and the activated water under a reactive environment;
d) a primary produced hydrocarbon fuel oil collecting step for collecting a hydrocarbon produced fuel obtained from the mixture obtained through the fusion step as a primary produced hydrocarbon fuel;
And then
The primary product hydrocarbon fuel oil is used as a secondary fuel base oil, and the steps b), c) and d) are performed to collect the secondary product hydrocarbon fuel oil. System fuel oil is sequentially used as fuel base oil, and the process of b), c) and d) is repeated a plurality of times, so that a volume of water (H 2 O) larger than that of the original fuel base oil is increased. A multi-generation hydrocarbon-based synthetic fuel oil comprising a hydrocarbon-based fuel oil having a composition substantially not included and substantially equivalent to or close to the initial fuel base oil is produced. A method for producing a hydrocarbon-based synthetic fuel.
A method for producing a hydrocarbon-based synthetic fuel, wherein water is added to a hydrocarbon-based fuel base oil to produce a hydrocarbon-based synthetic fuel having a volume larger than the volume of the hydrocarbon-based fuel base oil,
a) An activated water generating step of performing an activation treatment on water to generate activated activated water;
b) an agitation and mixing step in which the activated water is added to a hydrocarbon-based fuel base oil that is initially used as a fuel base oil and stirred and mixed for a predetermined time under a reactive environment;
c) a fusion step of fusing the hydrocarbon-based fuel base oil that has undergone the stirring and mixing step and the activated water under a reactive environment;
d) A hydrocarbon system having a composition in which the mixture that has undergone the fusion step is allowed to stand and does not substantially contain water (H 2 O) and is substantially equivalent to or close to the initial fuel base oil. An oil-water separation step for phase separation into an upper oil layer made of fuel oil and a lower water layer;
e) a primary produced hydrocarbon fuel oil collecting step of collecting the hydrocarbon fuel oil in the upper oil layer as a primary produced hydrocarbon fuel oil;
Including
f) In the stirring and mixing step and the fusion step, the hydrocarbon-based fuel in which the volume of the primary-generated hydrocarbon-based fuel oil obtained by the primary-generated hydrocarbon-based fuel oil collecting step is used as the initial fuel base oil. Performed over a period of time greater than the volume of the base oil, then
g) The primary product hydrocarbon fuel oil is used as a secondary fuel base oil, and the steps b) c) d) e) f) are performed to collect the secondary product hydrocarbon fuel oil, and The obtained hydrocarbon-based fuel oil is sequentially used as a fuel base oil, and the process of steps b), c), d), e) and f) is repeated a plurality of times, so that it is larger than the initial fuel base oil. A multi-generation hydrocarbon-based synthesis comprising a hydrocarbon-based fuel oil having a composition substantially free of water (H 2 O) or substantially equivalent to or close to the initial fuel base oil. A method for producing a hydrocarbon-based synthetic fuel, characterized by producing a fuel oil.
A method for producing a hydrocarbon-based synthetic fuel according to claim 1 or 2,
The method for producing a hydrocarbon-based synthetic fuel, wherein the activated water that has been activated is activated so as to include a hot spot of a microbubble.
The method for producing a hydrocarbon-based synthetic fuel according to any one of claims 1 to 3, wherein the activated water generation step raises water to a temperature in the range of 35 ° C to 45 ° C. A method for producing a hydrocarbon-based synthetic fuel, which is performed by irradiating the water with ultrasonic waves in a state where a voltage is applied.
5. The method for producing a hydrocarbon-based synthetic fuel according to claim 4, wherein the voltage is applied by irradiating tourmaline immersed in water with ultrasonic waves to bring the tourmaline into an excited state. A method for producing a hydrocarbon-based synthetic fuel.
4. The method for producing a hydrocarbon-based synthetic fuel according to claim 3, wherein a substance effective to hold a microbubble hot spot is added to the water. Fuel manufacturing method.
The method for producing a hydrocarbon-based synthetic fuel according to claim 3 or 6, wherein the generation of the hot spot of the microbubble is performed by using an ultrasonic wave having a frequency different from the frequency of the ultrasonic wave irradiated on the tourmaline. A method for producing a hydrocarbon-based synthetic fuel, which is performed by irradiating the water.
The method for producing a hydrocarbon-based synthetic fuel according to any one of claims 1 to 7, wherein the reactive environment in the stirring and mixing step irradiates the water to which catalase is added with ultrasonic waves. A method for producing a hydrocarbon-based fuel, which is formed by stirring the water.
9. The method for producing a hydrocarbon-based synthetic fuel according to claim 8, wherein the agitation is performed so as to generate strong undulations in a liquid surface of a mixture of water and fuel base oil. Synthetic fuel manufacturing method.
The method for producing a hydrocarbon-based synthetic fuel according to any one of claims 1 to 9, wherein the reactive environment in the stirring and mixing step includes adding a photocatalyst to the water and generating ultraviolet light. A method for producing a hydrocarbon-based synthetic fuel, which is formed by stirring while irradiating.