WO2017094105A1

WO2017094105A1 - Method for increasing amount of hydrocarbon oil, and device therefor

Info

Publication number: WO2017094105A1
Application number: PCT/JP2015/083739
Authority: WO
Inventors: 馨中村
Original assignee: 株式会社ロイヤルコーポレーション
Priority date: 2015-12-01
Filing date: 2015-12-01
Publication date: 2017-06-08

Abstract

The purpose of the present invention is to provide a method for increasing the amount of a hydrocarbon oil by using carbon dioxide, and a device therefor. One embodiment of the present invention provides a hydrocarbon oil amount increase method that involves: a step for producing a catalyst suspension by stirring and mixing water and zeolite or a zeolite-like substance by air bubbling; a step for producing active water by filtering the catalyst suspension through a filter having an aperture of 10μm or less; and a step for contacting a liquid mixture of the active water, alcohol and a hydrocarbon oil with a gas or aqueous solution that contains carbon dioxide. This embodiment of the present invention also provides a device therefor.

Description

Method and apparatus for increasing the amount of hydrocarbon oil

This invention relates to a method for increasing the amount of hydrocarbon oil and its apparatus.

In recent years, the global warming problem due to carbon dioxide emissions has become serious, and the increase in the use of fossil fuels has spurred the emission of carbon dioxide.

As an invention for improving the fuel efficiency of fuel hydrocarbons, there is one described in Patent Document 1 by the present inventor. The invention disclosed in Patent Document 1 provides a fuel production method and apparatus for producing fuel oil by reacting an enzyme water prepared by mixing a natural plant complex enzyme with water with oil. In the invention of Patent Document 1, active water prepared by mixing natural plant complex enzyme with water is reacted with oil, and the reacted water also functions as fuel by hydrolysis reaction of the raw material oil by the enzyme. For this reason, according to the invention of Patent Document 1, it is possible to improve the fuel efficiency, to easily suppress the generation of harmful substances, and to produce a stable fuel oil.

In Patent Document 2, active water produced by stirring and mixing water and enzyme by bubbling air is mixed with raw material oil and methanol to produce an emulsion, and the emulsion is brought into contact with carbon dioxide. An invention for increasing the amount of hydrocarbon oil is disclosed.

JP 2012-72199 A International Publication No. 2015/147322

Contributing to the incorporation of carbon dioxide as a carbon source of hydrocarbon oils in technologies for increasing the amount of hydrocarbon oils at room temperature and normal pressure using gas or liquid containing carbon dioxide as raw materials without the need for high-temperature and high-pressure conditions or the addition of hydrogen There is a need for a technique for increasing the amount of active oxygen species to increase the amount of hydrocarbon oil more efficiently.

The present invention provides a method and apparatus for increasing the amount of hydrocarbon oil according to the following embodiment.
[1] Stirring and mixing zeolite or zeolite-like substance and water by bubbling air to produce a catalyst suspension;
Filtering the catalyst suspension with a filter having an aperture of 10 μm or less to generate active water;
A method of increasing the amount of hydrocarbon oil, the method comprising contacting the mixture of active water, alcohol, and hydrocarbon oil with a gas or an aqueous solution containing carbon dioxide.
[2] The method for increasing the amount of hydrocarbon oil according to [1], wherein the amount of active oxygen species per unit volume of the active water is greater than the amount of active oxygen species per unit volume of the catalyst suspension.
[3] A catalyst mixing tank that stirs and mixes zeolite or a zeolite-like substance and water by bubbling air to form a catalyst suspension;
A filter having an opening of 10 μm or less for filtering the catalyst suspension to generate active water;
An apparatus for increasing the amount of hydrocarbon oil, comprising: an oil mixing tank in which the mixture of the active water, alcohol, and hydrocarbon oil is brought into contact with a gas containing carbon dioxide or an aqueous solution.
[4] The hydrocarbon oil increasing device according to [3], wherein the amount of active oxygen species per unit volume of the active water is larger than the amount of active oxygen species per unit volume of the catalyst suspension.

According to the present invention, the amount of hydrocarbon oil can be increased more efficiently using carbon dioxide, which is one of the causes of global warming, as a raw material.

It is a block diagram of the active water production | generation apparatus which produces | generates active water. It is a block diagram of a homogeneous mixing apparatus. It is a block diagram which shows the structure of an oil mixing tank. It is explanatory drawing explaining the structure of a stirrer. It is a longitudinal cross-sectional view which shows the inside of a stirrer. It is explanatory drawing explaining the structure of a pulse filter and a precision filter. It is a longitudinal cross-sectional view of a Newton separation tank. It is a longitudinal cross-sectional view which shows the stirrer of another Example. It is a graph which shows the measurement result of CLA-CL of one Example. It is a graph which shows the measurement result of CLA-CL of one Example. It is a graph which shows the measurement result of CLA-CL of one Example. It is a graph which shows the measurement result of CLA-CL of one Example. It is a graph which shows the measurement result of the light absorbency of one Example. It is a graph which shows the measurement result of CLA-CL of one Example. It is a graph which shows the measurement result of CLA-CL of one Example.

In the present invention, first, a catalyst suspension is prepared by stirring and mixing water and zeolite or a zeolite-like substance, and the catalyst suspension is filtered through a filter having an opening of 10 μm or less to generate active water. The amount of active oxygen species contributing to the generation of carbon radical species from carbon dioxide, which is the carbon source of the hydrocarbon oil, is greater in the active water after filtration than in the catalyst suspension. And hydrocarbon oil is increased by making the mixed solution of activated water, alcohol, and the raw material hydrocarbon oil contact the gas containing carbon dioxide, or aqueous solution (carbonated water).

Here, it is considered that the metal contained in the pores of the zeolite or the zeolite-like substance acts as a catalyst and contributes to activating air or oxygen and generating reactive oxygen species (ROS) in water. The reactive oxygen species include at least one of superoxide anion radical (O ₂ ⁻ ), hydroxy radical, hydrogen peroxide (H ₂ O ₂ ), and singlet oxygen. Also, a known synthetic zeolite can be used as the zeolite-like substance, such as CDS-1 (cylindrically double saw-edged zeolite) (for example, JP-A Nos. 2004-339044 and 2005-145773), PLS-1 Synthetic zeolite such as (pentagonal-cylinder layered silicate) (for example, JP-A-2008-162878) may be used.

As the natural zeolite, any kind of zeolite such as borohydrite, mordenite, clinoptilolite, ZSM-5 may be used, and ferrierites are preferably used. Natural ferrierites are cationic minerals with an orthorhombic structure. When the main cation species are magnesium, sodium or potassium, ferrierite-Mg, ferrierite-Na, ferrierite-K, etc. Is done. Natural ferrierite often contains calcium and other minerals as cations, and any cation can be mounted by substitution. Here, some ferrilites of natural zeolite exhibit CO ₂ adsorption ability (for example, sodium-substituted ferrilite) and are used for CO ₂ concentration (Reference Document 1 below). A greater effect can be expected by using such a material having the ability to concentrate CO _{2 in} the above-mentioned reaction for generating the CO ₂ -derived carbon radical species.
(Reference 1) Pulido, A., Nachtigall, P., Zukal, A., Dominguez, I., and Cejka, J. (2009) Adsorption of CO2 on Sodium-Exchanged Ferrierites: The Bridged CO2 Complexes Formed between Two Extraframework Cations J. Phys. Chem. C, 2009, 113 (7), pp 2928-2935

The method for increasing the amount of hydrocarbon oil according to the present invention comprises: (i) a step of stirring and mixing soot zeolite or zeolite-like substance and water by bubbling air; and (ii) opening the catalyst suspension. (Or pore diameter) a step of producing active water by filtering with a filter of 10 μm or less; and (iii) a mixture of active water, alcohol, and raw material hydrocarbon oil into a gas containing carbon dioxide or an aqueous solution (carbonated water) A step of contacting.

In the present invention, the reaction formulas in the steps (i) to (iii) are represented by the following formulas (1) and (2).
CO ₂ + H ₂ O + C _n H _{2n + 2} → C _{n + 1} H _{2n + 4} + 3 / 2O ₂ (1)
CH ₃ OH + C _n H _{2n + 2} → C _{n + 1} H _{2n + 4} + H ₂ O (2)
The above formulas (1) and (2) involving carbon dioxide are expressed by the following chain reaction.
CO ₂ + 2H ₂ O → CH ₃ OH + 3 / 2O ₂ (3)

For example, water and zeolite (or a zeolite-like substance) are mixed with air for 24 to 72 hours at room temperature and normal pressure so that the reactions represented by the above formulas (1) and (2) are performed at normal temperature and normal pressure. It is preferable to produce active water by stirring and mixing. However, the stirring and mixing time may be appropriately changed depending on the state of the raw material water. Here, the bubbling of air is to generate a large amount of minute air bubbles having a diameter of several μm to several hundred μm and to stir and mix the solution by the bubbles. Note that oxygen may be used instead of air.

In the present invention, the hydrocarbon oil is mainly composed of hydrocarbons and is liquid under normal temperature and normal pressure (for example, temperature of 15 degrees and 1 atmosphere), and has the chemical formula C _n H _{2n + 2} or C _{n + 1} H _{2n + 4} (Chain saturated hydrocarbon). n is 1 to 40, preferably 1 to 20. Such hydrocarbon oils include heavy oil, light oil (eg n = 10 to 20), gasoline (eg n = 4 to 10), naphtha, kerosene (eg n = 10 to 15), kerosene (eg n = 9 to 15) and the like, but are not limited thereto.

An apparatus for increasing the amount of hydrocarbon oil according to an embodiment of the present invention includes an active water generating apparatus 1 that generates active water from zeolite or a zeolite-like substance and water, and the active water, alcohol, and raw material hydrocarbon oil. And a fuel oil production apparatus 2 for producing fuel oil.

FIG. 1 is a schematic configuration diagram of an active water generator 1 that generates active water used for increasing the amount of hydrocarbon oil according to an embodiment of the present invention. The active water generating apparatus 1 includes a blower pump that sends air to one or more catalyst mixing tanks 11 (11a to 11d), one or more filters 12 (12a to 12b), a stabilization tank 14, and a catalyst mixing tank 11. 15, a pump P for moving the liquid between the tanks, and a filter F for removing impurities and the like when the liquid moves. In addition, the active water production | generation apparatus 1 may further be provided with the ventilation | gas_treatment process tank which carries out the ventilation | gas_treatment of the catalyst suspension from the catalyst mixing tank 11d with oxygen.

The catalyst mixing tanks 11a to 11d are provided in two lines at the top and bottom in the drawing, and both systems are connected by a pump P and a filter F in the order of the

catalyst mixing tanks

11a, 11b, 11c, and 11d. In addition, the number of the catalyst mixing tanks 11 may be one, or may be two or more. Alternatively, the catalyst mixing tanks 11 may be provided in one system or in two systems or more instead of two systems. Further, the

filters

12a and 12b may be one common to each system, or may be provided for each system.

In the catalyst mixing tank 11, water and zeolite or zeolite-like substance are supplied at a predetermined ratio (for example, 1000 liters of water, 500 g of zeolite, etc.), and these are 24 to 72 by bubbling of air supplied from the blower pump 15. Stir and mix for hours. In the catalyst mixing tank 11, an enzyme powder (for example, EP-10) may be further added. Although tap water may be used as water, soft water, ion exchange water, or pure water is preferably used.

The ratio of water to zeolite or zeolite-like substance is 5% (weight ratio) of zeolite or zeolite-like substance to 95% (weight ratio) of water, preferably zeolite or zeolite-like substance to 99% (weight ratio) of water. The zeolite or zeolite-like substance may be 0.05% (weight ratio) with respect to 1% (weight ratio) of the substance, more preferably 99.95% (weight ratio) of water.

In addition, when an enzyme is added to the catalyst mixing tank 11, it does not matter whether the enzyme is derived from an animal, a plant, or a microorganism. The enzyme is preferably made of lipase as a main raw material, and is composed of lipase and cellulase, more preferably 98% (weight ratio) of lipase and 2% (weight ratio) of cellulase.

The mixed water (catalyst suspension) of water and zeolite or zeolite-like substance in the catalyst mixing tank 11a is moved to the next catalyst mixing tank 11b by the pump P after a predetermined time has elapsed. During this movement, impurities are removed by the filter F. And in the catalyst mixing tank 11b, it stirs and mixes by bubbling of the air supplied from the blower pump 15 again. This is repeated up to the catalyst mixing tank 11d. The total stirring time in the catalyst mixing tanks 11a to 11d is about 24 to 72 hours.

The catalyst suspension stirred and mixed in the catalyst mixing tank 11d is sent to the

filters

12a and 12b. The

filters

12a and 12b are filters having openings (pore diameters) of 10 μm or less, and filter the catalyst suspension sent from the catalyst mixing tank 11d. Here, the catalyst suspension filtered through the filter 12 is referred to as active water.

The catalyst suspension (that is, active water) filtered in the

filters

12a and 12b is transferred to the stabilization tank 14, and alcohol is added to the active water in the stabilization tank 14. The alcohol can be, for example, methanol or ethanol, and methanol is preferably used. The mixing ratio of the alcohol is preferably about 5% to 20% (weight ratio) of methanol with respect to the active water. The role of the alcohol added to the active water is mainly the role of helping to mix water and oil and the role of being consumed in the initial reaction of increasing hydrocarbon oil.

The active water to which alcohol has been added in the stabilization tank 14 is taken out from the stabilization tank 14 by the pump P. At that time, one or more filters F further remove impurities, zeolites or zeolite-like substances. The extracted activated water is transferred to an appropriate container or stored in the activated water tank 22 of the fuel oil production apparatus 2 shown in FIG.

The water activated by the active water generator 1 (active water) undergoes reactions of reaction formulas (1) and (2) when raw material oil (hydrocarbon oil) is added in the reaction step even at room temperature. It has been activated. Further, as will be described in detail later, the amount of active oxygen species in the active water is increased by filtering with the filter 12 having an opening of 10 μm or less as compared with the case of not filtering with the filter 12.

FIG. 2 shows a configuration diagram of the fuel oil production apparatus 2. The fuel oil production apparatus 2 includes a raw material oil tank 21 as an oil storage unit that stores a raw material hydrocarbon oil, an active water tank 22 as an active water storage unit that stores active water, and one or a plurality of oil mixing tanks 23. The control panel 24, the pulse applying unit 25, the Newton separation tank 26, the separation tank 27, the precision filter unit 28, the completed tank 29, and the drainage tank 30.

The raw material oil tank 21 is a tank for storing oil as a raw material, and the required amount of raw material hydrocarbon oil is poured into the oil mixing tank 23 through the pipe R in a necessary amount. The hydrocarbon oil as the raw material can be, for example, A heavy oil, B heavy oil, C heavy oil, light oil, kerosene and the like.

The active water tank 22 is a tank for storing the active water purified by the active water generator 1, and the stored active water is poured into the oil mixing tank 23 through the pipe R in a necessary amount.

The carbon dioxide supply unit 31 includes a cylinder or tank filled with gaseous carbon dioxide or water in which carbon dioxide is dissolved (carbonated water), and supplies gaseous carbon dioxide or carbonated water to the oil mixing tank 23. The concentration of carbon dioxide supplied to the oil mixing tank 23 exceeds the atmospheric carbon dioxide concentration (about 0.03 to 0.04%, 300 to 400 ppm). This is good because more carbon dioxide is used. For example, the concentration of gaseous carbon dioxide (or carbonated water) supplied from the carbon dioxide supply unit 31 is 90% or more, preferably 99% or more, and more preferably 99.5% or more. The carbon dioxide supply unit 31 may be a cylinder filled with carbon dioxide, or recovers carbon dioxide from combustion gas generated at a large-scale source of carbon dioxide such as a power plant, a steel mill, or an oil plant. The apparatus itself or an apparatus for supplying carbon dioxide recovered by the apparatus may be used.

The oil mixing tank 23 mixes and stirs the raw material hydrocarbon oil supplied from the raw material oil tank 21 and the active water supplied from the active water tank 22, and supplies the mixed liquid to the carbon dioxide supplied from the carbon dioxide supply unit 31. This is a tank that produces an increased amount of hydrocarbon oil (referred to as “fuel oil”) by being brought into contact with a gas or an aqueous solution containing. In the oil mixing tank 23, active oxygen species (including at least one of O ₂ ⁻ , hydroxy radicals, H ₂ O ₂ , and singlet oxygen) in active water are mainly carbon dioxide (and bicarbonate ions). , Carbonate ions, and carbon dioxide-derived ions) to generate carbon radical species, and the carbon radical species react with the hydrocarbon oil as a raw material to extend the carbon chain of the hydrocarbon oil.

The ratio (weight ratio) of the raw material hydrocarbon oil to the active water in the oil mixing tank 23 may be appropriately adjusted depending on the type of the raw material hydrocarbon oil. For example, A heavy oil 60%, active water 40%, light oil 70% The ratio is preferably 30% and 30% of active water, or 70% of kerosene and 30% of active water, but may be appropriately adjusted depending on the properties of the hydrocarbon oil as a raw material. Carbon dioxide may be supplied to the oil mixing tank 23 after the hydrocarbon oil and the active water are sufficiently stirred and mixed to obtain an emulsified mixed liquid, or the hydrocarbon oil and the active water are stirred. Carbon dioxide may be supplied during mixing so that the reaction with carbon dioxide proceeds faster.

The control panel 24 is a control unit that controls each unit of the fuel oil production apparatus 2 and executes various controls such as ON / OFF of power supply. The pulse applying unit 25 vibrates the fuel oil produced in the oil mixing tank 23 to make it easy to remove residues. Residues include water that has not reacted completely, impurities in heavy oil, and the like.

The Newton separation tank 26 stores the fuel oil, drops the residue downward by gravity, and extracts the fuel oil remaining above.

The separation tank 27 further separates residue from the fuel oil. The precision filter unit 28 removes residue from the fuel oil with a filter. The completed tank 29 stores the completed fuel oil. The drainage tank 30 stores the drainage containing the residue generated in the pulse applying unit 25 and the Newton separation tank 26.

FIG. 3 is a configuration diagram showing the configuration of the oil mixing tank 23. The oil mixing tank 23 is provided with a substantially cylindrical stirring space 40, and a stirrer 43 (43L, 43R) and a pump 44 (44L, 44R) are provided in the stirring space 40. In the stirrer 43, the left stirrer 43L in the drawing is provided below the stirring space 40, and the right stirrer 43R in the drawing is provided above the stirring space 40, and each of them is distributed vertically and horizontally. Has been. Each stirrer 43 is connected to a pump 44 (44L, 44R), from which raw material hydrocarbon oil and activated water, or a mixture thereof is supplied. In addition, a vent pipe (or pump) 45 is connected to each stirrer 43, and carbon dioxide (or carbonated water) is supplied from the carbon dioxide supply unit 31 into the stirrer 43.

The pump 44L is connected to a pipe with the suction port 41L disposed above, and the pump 44L sends the raw hydrocarbon oil and active water or a mixture thereof to the stirrer 43L, and the fuel in the stirring space 40 Hydrocarbon oil and activated water, and carbon dioxide (or carbonated water) or a mixture thereof are circulated substantially evenly.

The pump 44R is connected to a pipe having a suction port 41R disposed below, and the pump 44L sends the raw hydrocarbon oil and active water or a mixture thereof to the stirrer 43L. The raw material hydrocarbon oil and active water, or a mixture thereof are circulated substantially evenly. The

pumps

44L and 44R are preferably 30 to 40 pressure pumps.

FIG. 4 is an explanatory diagram for explaining the configuration of the stirrer 43. The stirrer 43 is made of a hollow metal, and is mainly composed of a substantially cylindrical head 51, an inverted conical body 59 that follows the head 51, and a rear end 60 below the head 51. . A cylindrical central shaft 53 is provided at the center of the upper surface of the head 51. The central shaft 53 is provided with an inflow hole 53a (see FIG. 5) penetrating in the vertical direction, and raw material hydrocarbon oil and active water or a mixture thereof flows from the inflow hole 53a.

A part of the side surface of the head 51 is provided with an inlet 57 into which raw material hydrocarbon oil and active water or a mixture thereof flows. The inflow port 57 is a hole penetrating from the outside to the inside, and is surrounded by a cylindrical connecting cover 55. A thread groove 56 is provided on the inner surface of the connection cover 55 so that a pipe connected to the pump 44 is attached.

Further, the position of the inlet 57 and the direction of the connecting cover 55 are, as shown in the AA cross-sectional view of FIG. 4B, eccentric from the center of the stirrer 43 toward the inner periphery, Active water or a mixture of active water and oil flows in. As a result, the hydrocarbon oil or the like of the raw material that has flowed in from the inlet 57 is efficiently rotated about the cylindrical central shaft 53.
As shown in the BB cross-sectional view of FIG. 5, a plurality of pins 63 are provided inside the stirrer 43 along the inner periphery. The plurality of pins 63 are arranged with a gap so as not to cross each other. For example, it is preferable to provide 55 to 80 0.03 mm pins with an interval of about 10 mm.

A discharge hole 61 is provided in the rear end portion 60 of the stirrer 43. The stirrer 43 configured as described above can efficiently stir oil and active water to cause a decomposition reaction. More specifically, the raw material hydrocarbon oil and active water flowing in from the inlet 57, or a mixture thereof, rotates around the central shaft 53 and gradually decreases in radius of rotation toward the discharge hole 61. Move to. In that case, it agitates with the some pin 63 provided in the inside. Further, by rotating in a tornado shape, a negative pressure is generated in the vicinity of the lower portion of the central shaft 53, whereby the raw material hydrocarbon oil and active water or a mixture thereof flows from the inflow hole 53a. That is, the stirrer 43L shown in FIG. 3 takes in oil mainly from the inlet port 41L through the inlet port 57 by the pump 44L and takes in the active water mainly from the inlet hole 53a and stirs it. On the other hand, the stirrer 43R mainly takes in active water sucked from the suction port 41R from the inlet 57 by the pump 44R and takes in oil mainly from the inlet hole 53a and stirs. With this stirrer 43, the active water and oil collide with each other in a strong water pressure, and the mixture is stirred to promote the reaction of the reaction formula (1).

When the oil mixing tank 23 equipped with the stirrer 43 is stirred for a predetermined time (for example, about 15 to 20 minutes), the oil and the enzyme that are moved in a stirrer shape in the stirrer 43 and stirred are 300 to 500 times. The contact is repeated, the hydrolysis reaction is promoted, the molecular structure is reduced, and the specific gravity is also reduced.

FIG. 6A is a perspective view of the pulse filter 70 provided in the pulse applying unit 25. The pulse filter 70 is provided between the two line mixers, and allows the fuel oil to pass through holes formed between the grid-like partitions 71. The pulse applying unit 25 (particularly the partition 71) is formed of a ceramic fired body.

The partition 71 is gently twisted in a screw shape inside, and vibrates the fuel oil that has flowed in, thereby promoting the reaction. As a result, it is possible to easily remove impurities.

FIG. 6B is a perspective view of the precision filter 80 provided in the precision filter section 28. This precision filter 80 is provided with a filter 81 extending radially from the center around a cylindrical tube portion 82 formed of a mesh-like material. Impurities can be removed by allowing the fuel oil to pass through the filter 81 from the outer periphery toward the cylindrical portion 82.

Since the filters 81 are provided radially, the fuel oil can pass through the entire plate-like surface 81b from the base side 81a to the tip side 81c, as shown in the partially enlarged plan view of FIG. . For this reason, even if impurities accumulate on the base portion side 81a and become difficult to pass, the fuel oil can be passed through the plate-like surface 81b without any problem and removed.

FIG. 7 shows a longitudinal sectional view of a Newton separation tank 26 as a contact tank according to the present invention. The Newton separation tank 26 is mainly composed of an inclined plate 96 provided in the vicinity of the bottom, and a plurality of high-level plates 92 and low-level plates 93 provided alternately above the upper plate, and a liquid inlet 91 is provided at the front stage and the rear stage. Is provided with a liquid discharge port 95. The high plate 92 is provided with a space between the lower end and the inclined plate 96, and is configured so that the fuel oil can move back and forth. The lower plate 93 has an upper end formed lower than the high plate 92 and can overflow the upper portion of the stored fuel oil and move it to the adjacent storage section. The lower plate 93 is provided with a movable plate 94 at the lower end, and is configured such that the lower end of the movable plate 94 contacts the inclined plate 96. The high level plate 92 and the low level plate 93 are alternately arranged in this order, and are configured such that the lower ends are successively shortened in accordance with the inclination of the inclined plate 96.

With this configuration, the fuel oil that has flowed into the first reservoir 90a from the liquid inlet 91 is refined with impurities accumulated downward, and the fuel oil is generated according to the reaction formulas (1) and (2). It overflows to the next second reservoir 90b. The fuel oil that has been cleaned by repeating this from the first reservoir 90 a to the fourth reservoir 90 d is discharged from the liquid outlet 95.

Impurities precipitated in the reservoirs 90a to 90d move downward along the inclined plate 96. At this time, the movable plate 94 is opened to allow impurities to move downward. Since the movable plate 94 does not open in the reverse direction, impurities do not flow backward.

Impurities that have moved downward along the inclined plate 96 move from the collection opening 97 to the collection unit 98 via the valve 99a and are collected in the collection unit 98. The valve 99a is opened / closed intermittently, and is opened and collected in the collection unit 98 and closed when a certain amount of residue is accumulated. At this time, the gas is exhausted from an exhaust valve 99c provided near the upper portion of the recovery unit 98. The impurities collected in the collection unit 98 may be taken out from the collection valve 99b and discarded.

The stirrer 43 may be a different type of stirrer 43A as shown in FIG. The stirrer 43A is not provided with a discharge hole at the rear end portion 60. A central pipe 54 is provided instead of the central shaft 53 of the above-described embodiment. The center pipe 54 has a cylindrical shape having a hollow portion 67 therein, and its upper end 67a functions as a fuel oil discharge port. The stirrer 43A configured in this manner rotates the active water and oil flowing in from the inlet 57, moves downward in a tornado shape while reducing the rotation radius, and moves from the lower end to the upper end of the center pipe 54. It is discharged from the upper end. This stirrer 43A can also exhibit the same effects as the stirrer 43 of the above-described embodiment.

Through the above-described active water generating apparatus 1, fuel oil producing apparatus 2, Newton separation tank 26, etc., the reaction according to the reaction formulas (1) and (2) can be performed to generate fuel oil.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[1] Method for Quantitative Evaluation of Active Oxygen Species Using a catalyst suspension obtained by stirring and mixing zeolite or a zeolite-like substance and water by bubbling air as a catalyst, it was mixed with hydrocarbon oil and alcohol as raw materials. It is considered that the generation of active oxygen species continuously occurs in the solution, and the active oxygen species promotes the generation of carbon radical species from carbon dioxide, which contributes to an increase in hydrocarbon oil. That is, the generation of reactive oxygen species is one of the rate-limiting steps of the reaction. Therefore, in this example, the active oxygen species continuously generated in the catalyst suspension were quantitatively examined.

For quantitative evaluation of reactive oxygen species generated by the action of enzyme water as a catalyst, superoxide anion radicals generally catalyzed by plant-derived enzymes (Reference 2 below) and animal-derived peptides (Reference 3 below) (O 2 _^-) O ₂ is generated by the generating reaction or the photocatalyst is ^- (following reference 4 and 5) a method of observing the adopted methods utilizing renilla from chemiluminescence of luciferin analog (CLA) (CL) did. Integrated value of CLA-CL _{is, O} ^{2 -} are generated amount of correlation (proportional), as the integrated value of the CLA-CL is large, _{O 2} ^- production of also considered large.
(Reference 2) Kawano, T., Kawano, N., Hosoya, H. and Lapeyrie, F. (2001) Fungal auxin antagonist hypaphorine competitively inhibits indole-3-acetic acid-dependent superoxide generation by horseradish peroxidase. Biochemical and Biophysical Research Communications 288 (3): 546-551.
(Reference 3) Kawano, T. (2007) Prion-derived copper-binding peptide fragments catalyze the generation of superoxide anion in the presence of aromatic monoamines. International Journal of Biological Science 3 (1): 57-63.
(Reference 4) Kagenishi, T., Yokawa, K., Lin, C., Tanaka, K., Tanaka, L. and Kawano, T. (2008) Chemiluminescent and bioluminescent analysis of plant cell responses to reactive oxygen species produced by: newly developedped water conditioning apparatus equipped with titania-coated photocatalystic fibers.In: Bioluminescence and Chemiluminescence, 2008 (Eds, Kricka, LJ, Stanley, PE), World Scientific Publishing Co. Pte. Ltd., Singapore.pp. 27-30 .
(Reference 5) Lin, C., Tanaka, K., Tanaka, L. and Kawano, T. (2008) Chemiluminescent and electron spin resonance spectroscopic measurements of reactive oxygen species generated in water treated with titania-coated photocatalytic fibers. : Bioluminescence and Chemiluminescence, 2008 (Eds, Kricka, LJ, Stanley, PE), World Scientific Publishing Co. Pte. Ltd., Singapore. Pp. 225-228.

Here, as a general active oxygen species _{O 2} ^- unlikely and only generates, _{O 2} ^- derived from

hydrogen peroxide

_(H 2 _{O 2)} and _H 2 _{O 2} derived from ^- with generation of, _{O 2} It is considered that other active oxygen species such as hydroxy radicals are also generated. If the amount of O ₂ ⁻ produced is large, it is considered that the amount of other active oxygen species produced is also relatively large. For this reason, it is considered that the amount of active oxygen species generated in the catalyst suspension (or active water) can be quantitatively evaluated to some extent based on the amount of O ₂ ⁻ generated.

The specific method using the chemiluminescence of CLA is described in Reference Document 6 below. A luminometer was used for detection of CL in this method. Although CLA is a chemiluminescent probe specific for O ₂ ⁻ , it is known to react slightly with singlet oxygen ( ¹ O ₂ ).
(Reference 6) Kawano, T., et al., (1998) Salicylic acid induces extracellular superoxide generation followed by an increase in cytosolic calcium ion in tobacco suspension culture: The earliest events in salicylic acid signal transduction.Plant and Cell Physiology 39 (7): 721-730.

Therefore, in this example, a catalyst suspension was prepared in which natural zeolite and ion-exchanged water were bubbled with air for 2 days (48 hours) and mixed by stirring. In Examples 1 to 5, natural zeolite mainly containing ferrierites natural zeolite was used. To the catalyst suspension, catalase to remove hydrogen peroxide (CAT), _{O 2} ^- superoxide dismutase to remove (SOD), and is the removal reagent ¹ O ₂ 1,4-diazabicyclo [2.2.2] Samples to which octane (1,2-diazabicyclo [2.2.2] octane: DABCO) was added were prepared. The integrated value of CLA chemiluminescence (CLA-CL) (integrated time: 3 minutes, unit: rlu) was measured for each sample (FIG. 9).

In FIG. 9, “2 day bubbling” represents a sample of a catalyst suspension obtained by mixing natural zeolite and ion exchange water for 2 days, “DDW” represents a sample of only ion exchange water, and “4 kU / ml”. “CAT” represents a sample obtained by adding 4 kU / ml of CAT to the catalyst suspension, “20 kU / ml CAT” represents a sample obtained by adding 20 kU / ml of CAT to the catalyst suspension, and “5 kU / ml SOD”. Represents a sample with 5 kU / ml of SOD added to the catalyst suspension and “DABCO” represents a sample with DABCO added to the catalyst suspension.

As shown in FIG. 9, the CLA-CL integrated value of the “2-day bubbling” sample was four times or more larger than the value of the “DDW” sample containing only ion-exchanged water. From this, it was found that O ₂ ⁻ active oxygen species were generated in the catalyst suspension obtained by bubbling natural zeolite and ion-exchanged water for 2 days. In addition, CLA-CL of samples “4 kU / ml CAT” and “20 kU / ml CAT” added with CAT for removing hydrogen peroxide to the catalyst suspension and sample “DABCO” added with DABCO for removing ¹ O ₂ were added. Compared to the integrated value, the CLA-CL integrated value of the sample “5 kU / ml SOD” to which SOD that removes O ₂ ⁻ was added was greatly reduced. Therefore, this method is suitable for quantitative evaluation of O ₂ ^−. I understand that.

Here, CLA, especially _{O 2} ^- show high selectivity ^for, are known to react even to 1 _{O 2} (below Reference 7). CLA-CL is _{O 2} ^- to indicate that it is the specific detection, is effective utilization of ¹ O ₂ removal reagent such as ^DABCO, the system is long if CLA-CL of 1 _{O 2} is generated Can be quenched with DABCO (Reference 8 below). Therefore, as shown in FIG. 9, since there was no significant difference between the CLA-CL integrated value of the sample “2 day bubbling” and the CLA-CL integrated value of the sample “DABCO”, the observed CLA-CL is O ₂ ^- has been suggested to be specific for. Also, from the result of the CLA-CL integrated value of the sample “SOD” added with the O ₂ ⁻ removal enzyme SOD, it can be seen that the observed CLA-CL is specific to O ₂ ⁻ . In addition, the CLA-CL integrated value of the samples “4 kU / ml CAT” and “20 kU / ml CAT” added with CAT for removing hydrogen peroxide (H ₂ O ₂ ) is the CLA-CL integrated value of the sample “2 day bubbling”. It was not so different from the value. However, the value of the sample “20 kU / ml CAT” with the increased enzyme concentration was smaller than the value of the sample “4 kU / ml CAT”. These results, _{O 2} ^- is considered to _H 2 _{O 2} is not required upstream of the production.

For reference, in the case of O ₂ ⁻ production by a plant enzyme (peroxidase), H ₂ O ₂ is required as an O ₂ ⁻ precursor (upstream). It is known to be inhibited (Reference 9 below). However, this does not deny that H ₂ O ₂ and its downstream hydroxy radical are produced from O ₂ ⁻ .
(Reference 7) Nakano M, Sugioka K, Ushijima Y, Goto T. Chemiluminescence probe with Cypridina luciferin analog, 2-methyl-6-phenyl-3,7-dihydroimidazo [1,2-a] pyrazin-3-one, for reducing the ability of human granulocytes to generate O2-. Anal Biochem 1986; 159: 363-9.
(Reference 8) Yokawa K, Suzuki N, Kawano T. Ethanol-enhanced singlet oxygen-dependent chemiluminescence interferes with the monitoring of biochemical superoxide generation with a chemiluminescence probe, Cypridina luciferin analog. ITE Lett Batter New Technol Medic 2004; 5:49 -52.
(Reference 9) Kawano, T. and Muto, S. (2000) Mechanism of peroxidase actions for salicylic acid-induced generation of active oxygen species and an increase in cytosolic calcium in tobacco suspension culture. Journal of Experimental Botany 51 (345) : 685-693.

Since it is considered that other active oxygen species are generated as O ₂ ⁻ as active oxygen species, the other active oxygen species are also generated in correlation with the amount of O ₂ ⁻ generated. Conceivable.

[2] Effect of bubbling on the generation of active oxygen species In this example, the presence or absence of air bubbling when the catalyst suspension is generated by stirring and mixing affects the generation of active oxygen species. I investigated.

First, as in Example 1, natural zeolite and ion-exchanged water were stirred and mixed for 2 days (48 hours) to prepare a catalyst suspension sample. The stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling. In addition, for each of the catalyst suspension prepared by bubbling air and the catalyst suspension prepared without bubbling, Tyron, which is an O ₂ ⁻ removal reagent, and dimethyl, which is a hydroxyl radical removal reagent. Thiourea (DMTU), DABCO (1,2-diazabicyclo [2.2.2] octane) as a singlet oxygen ( ¹ O ₂ ) remover and 2,2′-bipyridine (Bipy) as a metal ion chelator ) And orthophenanthroline (o-Phe) were added respectively. Each sample was filtered using a filter having an opening of 0.2 μm. Then, as in Example 1, the integrated value of CLA chemiluminescence (measurement time: 3 minutes, unit: rlu) was measured for each sample (FIG. 10). Here, Bipy and O-Phe are chelating agents for metal ions, and remove iron ions (especially Bipy is mainly divalent iron ions) and copper ions.

In FIG. 10, “Air0.2” represents a sample of the catalyst suspension prepared by stirring and mixing by air bubbling, and “Air0.2 Tiron2.5 mM” represents the catalyst suspension prepared by stirring and mixing by air bubbling. Represents the sample added with 2.5 mM Tyrone, and “Air0.2 Bipy1 mM” represents the sample added with 1

mM

2,2′-bipyridine to the catalyst suspension prepared by stirring and mixing by air bubbling, and “Air0.2 Dabco2 .5 mM "represents a sample obtained by adding 2.5 mM of DABCO to a catalyst suspension prepared by stirring and mixing by air bubbling, and" Air0.2 to DMTU1 mM "represents a catalyst suspension prepared by stirring and mixing by air bubbling. DMTU represents a sample added with 1 mM, and “Air0.2 o-Phe1 mM (1% EtOH)” represents a sample obtained by adding orthophenanthroline to a catalyst suspension prepared by stirring and mixing by bubbling air. In FIG. 10, “w / o Air0.2” represents a sample of the catalyst suspension prepared without bubbling, and “w / o Air0.2 Tiron2.5 mM” represents the catalyst suspension prepared without bubbling. “W / o Air0.2 Bipy1 mM” represents a sample in which 1 mM of 2,2′-bipyridine was added to a catalyst suspension prepared without bubbling. "O Air0.2 Dabco2.5mM" represents a sample prepared by adding 2.5mM DABCO to a catalyst suspension prepared without bubbling, and "w / o Air0.2 DMTU1mM" represents a catalyst suspension prepared without bubbling. Represents a sample added with 1 mM DMTU, and “w / o Air0.2 o-Phe1mM (1% EtOH)” represents a sample obtained by adding orthophenanthroline to a catalyst suspension prepared without bubbling.

As shown in FIG. 10, since the CLA-CL integrated value of the sample “Air0.2” is larger than the value of the sample “w / o Air0.2”, stirring and mixing by air bubbling generates O ₂ ⁻ . I found it to improve. At the same time, the stirring and mixing of the bubbling air, O ₂ ^- with product is improved, and it is considered that the increase also generates other reactive oxygen species, as by bubbling air, O ₂ ^- in addition to hydroxy radicals and the like The production amount of other active oxygen species is also improved.

In addition, as shown in FIG. 10, samples “Air0.2 Tiron2.5 mM” and “w / o Air0.2 Tiron2.5 mM” to which Tyrone, which is an O ₂ ⁻ removal reagent different from the SOD of Example 1, was added. It was found that the CLA-CL integrated values of the samples “Air0.2 DMTU1 mM” and “w / o Air0.2 DMTU1 mM” to which DMTU, which is a hydroxyl radical removal reagent, was added, were relatively low. This result provides further confirmation that O ₂ ⁻ is produced in the catalyst suspension, as in Example 7, and the reaction is catalyzed by the catalyst suspension leading to O ₂ ⁻ production. It was found that radical generation may have occurred. DMTU inhibits the generation of hydroxy radicals. However, since high concentrations of DMTU were used in this example, various intermediates of reactive oxygen species related to the generation of O ₂ ⁻ may be removed. As a result, it is considered that the CLA-CL integrated values of the samples “Air0.2 DMTU1 mM” and “w / o Air0.2 DMTU1 mM” to which DMTU was added were reduced.

[3] Effect of aeration treatment with oxygen on catalyst suspension In this example, the influence of aeration treatment with oxygen on the catalyst suspension was examined.

First, as in Example 1, natural zeolite and ion-exchanged water were stirred and mixed by air bubbling for 2 days (48 hours) to prepare a catalyst suspension, and a sample filtered through a filter having an opening of 0.2 μm was prepared. Got ready. The filtered sample was aerated with oxygen (O ₂ ), carbon dioxide (CO ₂ ), and nitrogen (N ₂ ) gas for 10 seconds, and then the CLA-CL integrated value (integrated time 3 minutes) for each sample. , Unit: rlu) was measured (FIG. 11). In the aeration treatment, the catalyst suspension filtered through a filter was stirred and mixed by bubbling oxygen, carbon dioxide, and nitrogen, respectively. The purity of oxygen (O ₂ ), carbon dioxide (CO ₂ ), and nitrogen (N ₂ ) gases used for the aeration treatment is 99.9% or more.

In FIG. 11, “2 day bubbling” is a sample not subjected to aeration treatment, “2 day bubbling + O _{2 10} sec” is a sample aerated with oxygen, “2 day bubbling + CO _{2 10} sec” is a sample aerated with carbon dioxide, “2 day bubbling + N _{2 10} sec” represents a sample that has been aerated with nitrogen.

As shown in FIG. 11, the value of the sample “2 day bubbling + O _{2 10} sec” aerated with oxygen is more significant (7-8) than the CLA-CL integrated value of the sample “2 day bubbling” that has not been aerated (7-8). Doubled). From this, it was found that the amount of O ₂ ⁻ produced can be significantly improved by subjecting the catalyst suspension to aeration treatment with oxygen, compared to the case where the catalyst suspension is not subjected to aeration treatment with oxygen. Since it is considered that other active oxygen species are generated along with the generation of O ₂ ^−, the amount of other active oxygen species produced (the amount of active oxygen species per unit volume) by oxygen aeration treatment is also aerated with oxygen. It is considered that the amount is significantly higher than the amount of the catalyst suspension before treatment (the amount of active oxygen species per unit volume).

In addition, the CLA-CL integrated value of the sample “2 day bubbling + CO _{2 10} sec” aerated with carbon dioxide is small, and the O ₂ ⁻ production activity is significantly inhibited by aeration treatment of the catalyst suspension with carbon dioxide. I understood it. This is considered to be due to the fact that the carbon component derived from carbon dioxide used for the aeration treatment reacted with O ₂ ⁻ in the catalyst suspension.

In this way, the amount of active oxygen species produced can be significantly increased (7 to 8 times) by aeration treatment with oxygen after the catalyst suspension is produced, so that active water rich in active oxygen species can be obtained. Can be used as a catalyst for increasing hydrocarbon oils.

Then, active water, alcohol, and raw material hydrocarbon oil are mixed to produce an emulsion, and the emulsion is brought into contact with a gas containing carbon dioxide or an aqueous solution (carbonated water). Carbon radical species are generated from carbon dioxide according to the amount of oxygen species, and the amount of hydrocarbon oil is increased according to the amount of carbon radical species produced. Note that the higher the concentration of carbon dioxide that is brought into contact with the emulsion, the more carbon dioxide molecules are present at the interface between the emulsion and the gas (or aqueous solution) containing carbon dioxide. It is considered that the number of carbon dioxide molecules that react with the active oxygen species increases, and as a result, the amount of carbon radical species generated also increases.

[4] Effect of Filtration on Catalyst Suspension In this example, the influence of the opening size of the filter used for the process of filtering the catalyst suspension with a filter was examined.

First, as in Example 1, natural zeolite and ion-exchanged water were stirred and mixed for 2 days (48 hours) to prepare a catalyst suspension, and samples filtered through filters with various openings were prepared. The stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling. Moreover, the filter used for filtration used what has an opening of 0.2 micrometers, 5 micrometers, 10 micrometers, and 40 micrometers. Then, CLA-CL integrated value (integrated time: 3 minutes, unit: rlu) was measured for each sample of the filtered catalyst suspension (FIG. 12). The filter used in this example is a filter for syringes (Mirex Mille (registered trademark) for HPLC (Mirex LG / LH)) manufactured by Merck Millipore, with a filter having an opening of 0.2 μm, and has an opening of 5 μm, 10 μm, and 40 μm. The filter is a nylon mesh (mesh cloth) filter.

In addition, in order to determine the optimum aperture filter, the catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water for 2 days (48 hours) with air bubbling is used for various aperture filters. Then, the absorbance (turbidity) of light having a wavelength of 600 nm was measured in the air for each sample, and the difference in turbidity was examined (FIG. 13). As in the above, filters having a mesh size of 0.2 μm, 5 μm, 10 μm, and 40 μm were used.

In FIG. 12, “DDW” is a sample containing only ion-exchanged water, “Air0.2” is a sample obtained by filtering a catalyst suspension prepared by stirring and mixing by bubbling air with a filter having an opening of 0.2 μm, and “Air5”. Is a sample obtained by filtering the catalyst suspension prepared by stirring and mixing by air bubbling with a filter having a mesh opening of 5 μm, and “Air10” is filtering the catalyst suspension prepared by stirring and mixing by air bubbling through a filter having a mesh of 10 μm. The sample “Air40” represents a sample obtained by filtering a catalyst suspension prepared by stirring and mixing by bubbling air through a filter having an opening of 40 μm. In addition, in FIG. 11, “w / o」 Air0.2 ”is a sample obtained by filtering a catalyst suspension prepared without bubbling with a filter having a mesh opening of 0.2 μm, and“ w / o Air5 ”is prepared without bubbling. A sample obtained by filtering the prepared catalyst suspension through a filter having a mesh opening of 5 μm, “w / o Air10” is a sample obtained by filtering the prepared catalyst suspension through a filter having a mesh opening of 10 μm without bubbling, “w / o Air40” Represents a sample obtained by filtering a catalyst suspension prepared without bubbling through a filter having an opening of 40 μm.

As shown in FIG. 12, the largest integrated value of CLA-CL was the sample “Air0.2” that was stirred and mixed by bubbling air for two days and filtered through a filter with an opening of 0.2 μm. It was. Further, as shown in FIG. 13, the absorbance (suspension) of the sample filtered with a filter opening of 10 μm and 40 μm hardly changed. From this, it can be seen that the size of the natural zeolite used for the sample of this measurement is approximately 10 μm or less. Then, in FIG. 12, the samples “Air10” and “w / o Air10” filtered through 10 μm, and the samples “Air40” and “w / o Air40” filtered through a filter with 40 μm openings are not filtered. It can also be said to be a suspension.

Returning to the explanation of FIG. 12, the CLA-CL integrated values of the samples “Air0.2” and “Air5” are CLA-CL integrated values of the samples “Air10” and “Air40” which can be regarded as unfiltered catalyst suspensions. Further, the CLA-CL integrated value of the sample “Air0.2” was larger than the CLA-CL integrated value of the sample “Air5”. Similar results were obtained for samples “w / o Air0.2” to “w / o Air40” prepared without bubbling.

For this reason, a filter having a small opening (preferably an opening of 10 μm or less, more preferably 0.2 μm or less) is used for a catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water. It has been found that the amount of active oxygen species in the catalyst suspension can be improved as the amount of filtration increases. In other words, the more natural zeolite with a smaller outer diameter (preferably the outer diameter is 10 μm or less, more preferably the outer diameter is 0.2 μm or less), the more active oxygen species in the catalyst suspension. It was found that can be improved. The reason for this is thought to be that zeolite or zeolite-like material having a particle size of a certain size (especially a size exceeding 10 μm) partially inhibits the reaction that generates active oxygen species in the catalyst suspension. It is done.

[5] Influence of metal ions in catalyst suspension In this example, the influence of metal ions on the reaction of generating active oxygen species catalyzed by the catalyst suspension was examined.

First, a sample was prepared by filtering a catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water for 2 days (48 hours) in the same manner as in Example 1 with a filter having an opening of 0.2 μm. The stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling. Further, 50 μM of divalent iron ions (Fe ²⁺ ) or 50 μM of trivalent iron ions (Fe ³⁺ ) were added to the filtered samples, and the CLA-CL integrated value was measured for each (FIG. 14).

In FIG. 14, “Air0.2” represents a sample obtained by filtering a catalyst suspension prepared by stirring and mixing by bubbling, and “Air0.2 (Fe ²⁺ ) 50 μM” represents a catalyst prepared by stirring and mixing by air bubbling. The suspension is filtered and a sample to which 50 μM of divalent iron ions (Fe ²⁺ ) is added is represented. “Air0.2 (Fe ³⁺ ) 50 μM” is a filtered catalyst suspension prepared by stirring and mixing by bubbling air. 3 represents a sample to which 50 μM of trivalent iron ions (Fe ³⁺ ) is added. In FIG. 13, “w / o Air0.2” represents a sample obtained by filtering the prepared catalyst suspension without bubbling, and “w / o Air0.2 (Fe ²⁺ ) 50 μM” does not bubbling. Represents a sample to which 50 μM of divalent iron ion (Fe ²⁺ ) was added after filtering the prepared catalyst suspension, and “w / o Air0.2 (Fe ³⁺ ) 50 μM” represents the catalyst suspension prepared without bubbling. The sample is obtained by filtering the suspension and adding 50 μM of trivalent iron ions (Fe ³⁺ ).

As shown in FIG. 14, samples added with iron ions “Air0.2 (Fe ²⁺ ) 50 μM”, “Air0.2 (Fe ³⁺ ) 50 μM”, “w / o Air0.2 (Fe ²⁺ ) 50 μM ”And“ w / o Air0.2 (Fe ³⁺ ) 50 μM ”, the CLA-CL integrated value is higher than the values of the samples“ Air0.2 ”and“ w / o Air0.2 ”to which no iron ions are added. Was also small. Therefore, O ₂ ^- prevent a decrease in production activity or to reduce, by removing the iron component from the catalyst suspension, the amount of active oxygen species has been found that it is possible to prevent the reduction .

That is, by reducing the amount of active oxygen species due to the presence of iron ions, it is possible to prevent the iron ions from being contained in the active water that is finally used to increase the amount of hydrocarbon oil. In order to remove the iron ion component in the generated active water, ion exchange water or pure water may be used as water. Further, in order to remove iron ions in the active water, the flow between the

filters

12a and 12b and the stabilization tank 14 in the active water generation apparatus 1 (or between the stabilization tank 14 and the fuel oil production apparatus 2). An iron content removal unit may be provided in the road to remove iron ions from the active water generated by the

filters

12a and 12b. Further, in order to remove iron ions in the catalyst suspension, between at least one adjacent catalyst mixing tank among the catalyst mixing tanks 11a to 11d (or between the catalyst mixing tank 11d and the

filters

12a and 12b). ), An iron removing unit may be provided to remove iron ions from the catalyst suspension before being sent to the

filters

12a and 12b. As the iron removal unit, an ion exchange resin or a reverse osmosis (RO) membrane may be used, or a device that is precipitated by a chelating agent or an oxidant and precipitated or filtered may be used.

Next, a sample was prepared by filtering a catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water for 2 days (48 hours) with a filter having an opening of 0.2 μm. The stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling. Further, 50 μM of monovalent copper ions (Cu ⁺ ) or 50 μM of divalent copper ions (Cu ²⁺ ) were added to the filtered samples, and CLA-CL integrated values were measured for each (FIG. 15).

In FIG. 15, “Air0.2” represents a sample obtained by filtering the catalyst suspension prepared by stirring and mixing by air bubbling, and “Air0.2 (Cu ⁺ ) 50 μM” was prepared by stirring and mixing by air bubbling. This represents a sample in which the catalyst suspension was filtered and monovalent copper ions (Cu ⁺ ) 50 μM were added. “Air0.2 (Cu ²⁺ ) 50 μM” represents the catalyst suspension prepared by stirring and mixing by bubbling air. The sample which filtered and added 50 micromol of divalent copper ion (Cu2 ⁺ ) is represented. In FIG. 15, “w / o Air0.2” represents a sample obtained by filtering the prepared catalyst suspension without bubbling, and “w / o Air0.2 (Cu ⁺ ) 50 μM” does not bubbling. The prepared catalyst suspension is filtered and a sample to which 50 μM monovalent copper ion (Cu ⁺ ) is added is represented. “W / o Air0.2 (Cu ²⁺ ) 50 μM” is a catalyst suspension prepared without bubbling. The sample which filtered the liquid and added 50 micromol of bivalent copper ion (Cu2 ⁺ ) is represented.

As shown in FIG. 15, the CLA-CL integrated values of the samples “Air0.2 (Cu ⁺ ) 50 μM” and “Air0.2 (Cu ²⁺ ) 50 μM” added with copper ions were not added with copper ions. There was no significant difference from the value of sample “Air0.2”. In addition, the CLA-CL integrated values of the samples “w / o Air0.2 (Cu ⁺ ) 50 μM” and “w / o Air0.2 (Cu ²⁺ ) 50 μM” with copper ions added do not contain copper ions. The value of the sample “w / o Air0.2” was not significantly different. Therefore, the effect of O ₂ of copper ions ^- reduction of production activity (i.e. the amount of active oxygen species) has little, if adding metal ions to the reaction solution, rather than iron ions, copper ions is desirable I understood. Also, among the active water generating device, homogeneous mixing device, mixing device, oil mixing tank, stirrer, pulse filter, precision filter, and Newton separation tank shown in FIGS. It is preferable that the portion that comes into contact with the emulsified liquid, which is a mixed solution of active water, alcohol, and raw material hydrocarbon oil, be made of a copper member and not an iron member as much as possible.

The present invention can be used for increasing the amount of various hydrocarbon oils.

Claims

Agitating and mixing zeolite or zeolite-like material with water by bubbling air to form a catalyst suspension;
Filtering the catalyst suspension with a filter having an aperture of 10 μm or less to generate active water;
A method of increasing the amount of hydrocarbon oil, the method comprising contacting the mixture of active water, alcohol, and hydrocarbon oil with a gas or an aqueous solution containing carbon dioxide.
The method according to claim 1, wherein the amount of active oxygen species per unit volume of the active water is greater than the amount of active oxygen species per unit volume of the catalyst suspension.
A catalyst mixing tank that stirs and mixes zeolite or a zeolite-like substance and water by bubbling air to form a catalyst suspension;
A filter having an opening of 10 μm or less for filtering the catalyst suspension to generate active water;
An apparatus for increasing the amount of hydrocarbon oil, comprising: an oil mixing tank in which the mixture of the active water, alcohol, and hydrocarbon oil is brought into contact with a gas containing carbon dioxide or an aqueous solution.
The apparatus according to claim 3, wherein the amount of active oxygen species per unit volume of the active water is greater than the amount of active oxygen species per unit volume of the catalyst suspension.