JP7428453B1 - Method and apparatus for synthesizing liquid hydrocarbons - Google Patents

Abstract

The present invention provides a method and apparatus for efficiently producing liquid hydrocarbons from oxygen and carbon dioxide in water. [Solution] Carbon dioxide and water W are converted into carbon monoxide and water via a photocatalyst in a reaction tank 1 containing water W in which carbon dioxide is dissolved and mixed with liquid hydrocarbon HC. A method and apparatus for reducing hydrogen to hydrogen and further synthesizing the liquid hydrocarbon HC by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, the method and apparatus comprising: It is synthesized in an area above water W by supplying a mixed gas M of carbon dioxide and air A from the reactor 1, or by supplying carbon dioxide and air A from the bottom and sides of the reaction tank 1, respectively. The object is achieved by contacting the gas bubbles by the gas mixture M passing through the layer of liquid hydrocarbon HC, and contacting the upper interface of the layer with the gas mixture M of carbon dioxide and air A. A method and apparatus for synthesizing liquid hydrocarbon HC. [Selection diagram] Figure 2

Description

The present invention provides a method and apparatus for reducing carbon dioxide and water to carbon monoxide and hydrogen in water via a photocatalyst, and synthesizing liquid hydrocarbons by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst. The target is

The synthesis of liquid hydrocarbons by reducing carbon dioxide in water has already been proposed in the prior art.

For example, Patent Document 1 proposes a method of producing liquid hydrocarbons by supplying oxygen to water containing carbon dioxide and reducing carbon dioxide in a photoelectrochemical cell (page 81, lines 4-21).

That is, the photocatalyst in Patent Document 1 is based on a photoelectrochemical cell, and is based on the premise that a fuel using liquid hydrocarbon or the like is generated at the cathode (Claims 2, 77, 79).

Therefore, in Patent Document 1, reduction of carbon dioxide and water by pure photocatalyst is not realized.
In fact, in Patent Document 1, activation of oxygen by irradiating water with ultraviolet rays is not realized (in this point, it is clearly different from the case of Patent Document 2).

As shown in Patent Document 2, the inventors of the present application supply oxygen to water in which carbon dioxide is dissolved and generate oxygen nanobubbles, and the presence of active oxygen generated from the nanobubbles by irradiation with ultraviolet rays. Below, a method and apparatus for producing liquid hydrocarbons are proposed, which are based on reducing carbon dioxide and water to carbon monoxide and hydrogen via a photocatalyst.

However, in the case of Patent Document 2, the configuration is not necessarily simple in that the generation of oxygen nanobubbles and the generation of active oxygen by irradiation with ultraviolet rays are essential.

In Patent Documents 1 and 2, when liquid hydrocarbons are generated via a photocatalyst, a layer of liquid hydrocarbons is generated in a region above water.

In such a case, a state of contact with the upper air containing carbon dioxide is realized, but in that case, the reduction efficiency of carbon dioxide in the water is influenced by the concentration of carbon dioxide gas contained in the air.

However, in the conventional techniques such as Patent Documents 1 and 2, the basic idea is to efficiently generate liquid hydrocarbons by adjusting the concentration of carbon dioxide in the air that contacts the upper interface where liquid hydrocarbons exist. Not proposed at all.

WO2010/042196 A1 Patent No. 6440742

An object of the present invention is to provide a method and apparatus for extremely efficiently producing liquid hydrocarbons through a photocatalyst for water in which oxygen and carbon dioxide are dissolved.

In order to solve the above problems, the basic configuration of the present invention is as follows:
(1) Carbon dioxide and water are monoxidized via a photocatalyst in a reaction tank containing water in which continuously supplied carbon dioxide is dissolved and mixed with liquid hydrocarbons. A method of reducing the liquid hydrocarbon to carbon and hydrogen, and further synthesizing the liquid hydrocarbon by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst , the method comprising: produced in the upper region of the reactor by supplying bubbles of a mixture of carbon dioxide and air, or by supplying carbon dioxide bubbles and air bubbles from the bottom and sides of the reactor, respectively. A method for synthesizing liquid hydrocarbons, wherein the upper interface of a layer of liquid hydrocarbons is maintained in contact with a mixed gas of carbon dioxide and air that has passed through the layer;
(2) In a reaction tank containing water mixed with liquid hydrocarbons, carbon dioxide, which is continuously supplied at the bottom and/or side of the reaction tank, is added to the water via a photocatalyst. An apparatus for reducing carbon monoxide and hydrogen within the reactor, and further synthesizing liquid hydrocarbons in a layered manner in an upper region of the reaction tank by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, A photocatalyst means having the photocatalyst is provided in the reaction tank , and is connected to a supply source of the mixed gas of carbon dioxide and air at the bottom and/or side of the reaction tank, or a liquid hydrocarbon synthesis apparatus connected to a carbon dioxide supply source and an air supply source at the bottom and side of the reaction tank, respectively ;
Consisting of

By the method of basic configuration (1) and the device of basic configuration (2), in the liquid hydrocarbon layer generated in the region above the water in the reaction tank, a mixed gas of carbon dioxide and air passes through. By contacting the carbon dioxide and maintaining the contact state with the gas mixture of carbon dioxide and air at the upper interface of the layer, extremely efficient reduction of carbon dioxide and further synthesis of liquid hydrocarbons can be realized.
That is, the efficient synthesis is made possible by both the step of allowing the gas bubbles of the mixed gas to pass through the layer while being in contact with the entire surface of the bubbles, and the step of maintaining the contact state at the upper interface. However, the former effect in particular becomes more pronounced as the synthesis of liquid hydrocarbons proceeds sequentially and the layer in the upper region becomes larger.
Although the basic configurations (1) and (2) are based on the assumption that carbon dioxide is continuously supplied, the above effect naturally occurs when a mixed gas of carbon dioxide and air is supplied. are doing.
Even if the gas mixture is not the above, if carbon dioxide bubbles and air bubbles are supplied from the bottom and side of the reactor, respectively, the bubbles will be considerably reduced by the time they pass through the layer. Since a mixed gas of carbon dioxide and air is generated at a ratio of , the above effect can be achieved.

The method of basic configuration (1) and the device of (2) are extremely simple compared to the configuration using electrodes in Patent Document 1, and moreover, they generate fuel by pure photocatalytic reaction without the need for voltage application. A liquid hydrocarbon can be obtained.

In the case of the method of basic configuration (1) and the device of basic configuration (2), the mixed gas of carbon dioxide and air or air is supplied, and the air contains oxygen. , a simple configuration is realized in that the supply of oxygen and the formation of nanobubbles of oxygen are not indispensable as in Patent Document 2.

As described above, the present invention, which is based on the method of basic configuration (1) and the device of basic configuration (2), can realize extremely efficient production of liquid hydrocarbons despite its simple configuration. .
Incidentally, the configuration of Patent Document 2 also includes a configuration in which carbon dioxide is reduced in the presence of active oxygen generated from separately prepared liquid hydrocarbon and oxygen nanobubbles. When the condition is maintained for, for example, 24 hours, the rate at which liquid hydrocarbons are further synthesized is usually 10 to 15% (paragraph [0029]). If the concentration of carbon dioxide in the contacting air is adjusted within the range of 430 ppm to 2000 ppm, the proportion of liquid hydrocarbons further synthesized can be 20 to 30%.

FIG. 2 is a block diagram showing a method of basic configuration (1). FIG. 3 is a schematic diagram showing the configuration of the device of basic configuration (2), in which (a) shows an embodiment that employs a supply source of a gas mixture of carbon dioxide and air and adjusts the amount of air to be mixed; (b) shows an embodiment in which an air supply source is employed, the air is supplied above the reaction tank, and the supply amount is adjusted.

As shown in the block diagram of Fig. 1, the basic configuration (1) consists of a reaction tank containing dissolved carbon dioxide that is continuously supplied and containing W in a mixed state with liquid hydrocarbon HC. 1, reduce carbon dioxide and water to carbon monoxide and hydrogen via a photocatalyst, and further synthesize the liquid hydrocarbon HC by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst. The method includes supplying bubbles of the mixed gas M of carbon dioxide and air A from the bottom and/or side of the reaction tank , or supplying bubbles of carbon dioxide and air from the bottom and the side of the reaction tank, respectively. By supplying bubbles of air A, the upper interface of the layer of liquid hydrocarbon HC generated in the upper region of the reaction tank 1 is brought into contact with the mixed gas M of carbon dioxide and air A that has passed through the layer. This is a method for synthesizing liquid hydrocarbon HC while maintaining a contact state.

As shown in the schematic diagram of FIG. 2, the device with the basic configuration (2) uses a photocatalyst in the reaction tank 1 containing water W in a mixed state with liquid hydrocarbon HC . Carbon dioxide, which is continuously supplied at the bottom and/or side , is reduced to carbon monoxide and hydrogen in water, and further reduced by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst. An apparatus for synthesizing liquid hydrocarbon HC in a layered manner in the upper region of a reaction tank 1, comprising a photocatalyst means having the photocatalyst in the reaction tank 1, and /or connected to the supply source 2 of the mixed gas M of carbon dioxide and air A at the side, or supply of the carbon dioxide supply 3 and air A at the bottom and side of the reaction tank 1, respectively; This is a liquid hydrocarbon HC synthesis device connected to a source 4 .

In the basic configurations (1) and (2), when bubbles of mixed gas M of carbon dioxide and air A are supplied, and when bubbles of carbon dioxide and air A are supplied, the bubbles of carbon dioxide and the bubbles of air A are supplied to the bottom and side of the reaction tank 1, respectively. However , in consideration of efficient synthesis of liquid hydrocarbon HC, the former is often adopted.

Basic configurations (1) and (2) are based on the technical premise of continuous supply of carbon dioxide to generate liquid hydrocarbon HC, but as already pointed out in the effect section, the liquid in the upper region Contact between the layer of hydrocarbon HC and a mixed gas M of carbon dioxide and air A passing through the layer, and further contact between the upper interface of water W where liquid hydrocarbon HC is generated and carbon dioxide and air A. Regarding the reason why the reduction reaction is promoted by contact with the mixed gas M, the following technical matters can be presumed.

Regarding carbon dioxide dissolved in water, if radical water, that is, activated water that is susceptible to chemical reactions, is formed by a photocatalyst on water, the following reduction due to the radicalization occurs: The reactions are proceeding sequentially.
_CO2 + _H2O →CO+ _H2 + _O2 ...(1)
That is, in the above equation (1), the reduction reaction is shown sequentially from the left side to the right side, but if we focus on the individual reactions, we can see that some carbon monoxide molecules are oxidized and changed to carbon dioxide molecules. Although there are reverse reactions that occur, the overall result is that a reaction proceeds in which carbon dioxide molecules are reduced to carbon monoxide molecules.

Following the reaction equation (1) above, the following reaction equation proceeds to further produce liquid hydrocarbon HC due to the radicalization in radical water.
(2n+1) _H2 +nCO→ _{CnH2n +2} + _nH2O ...(2)
Therefore, the layer of liquid hydrocarbon HC formed by C _n H _2n+2 in the upper region of the water W is derived from the reaction formula (2) above.
In addition, since the carbon number n is the same as the carbon number of the liquid hydrocarbon HC that has been blended in advance and is in a mixed state with radical water, the liquid hydrocarbon HC that is blended in advance is called a mold. .
However, the reason why the carbon number n of the liquid hydrocarbon HC that is further synthesized is the same as the carbon number of the liquid hydrocarbon HC that is the template is not completely elucidated.

In the case of reaction formulas (1) and (2), carbon dioxide is in the stage of passing through a layer of liquid hydrocarbon HC and is generating a mixed gas M with air A, and above the layer The carbon dioxide that generates air A and mixed gas M has an affinity for liquid hydrocarbon HC, which is a non-polar liquid, so it permeates through the layer of liquid hydrocarbon HC and further penetrates into the lower region. Even if the water W is a polar liquid, it migrates to the water W side and dissolves because it is easily dissolved in the water W.

This is attributed to the fact that the above-mentioned dissolution promotes the reaction formula by reduction of the above-mentioned (1), and as a result, the synthetic reaction of formula (2) is also promoted.
As far as we pay attention to the reaction formulas (1) and (2) above, the higher the concentration of the liquid hydrocarbon HC which can be adjusted above the interface, the higher the reaction formulas (1) and (2) above. This is how it is promoted.

However, according to the experience of the inventors, the reactions of equations (1) and (2) above are not accelerated as the concentration of carbon dioxide is higher, and the carbon dioxide above the interface has a predetermined concentration. It has been found that if it exceeds the limit, the production of liquid hydrocarbon HC may actually decrease.

At present, the exact reason why the efficiency of synthesizing liquid hydrocarbon HC decreases when the concentration of carbon dioxide exceeds a predetermined value is not clear at present.
However, it can be estimated that the function of the photocatalyst in the reaction formulas (1) and (2) above is rather reduced when the concentration of carbon dioxide exceeds a predetermined concentration.

The appropriate concentration of carbon dioxide at the upper interface depends on the content of carbon dioxide contained in the water, but in most cases, the appropriate concentration of carbon dioxide can be set in the numerical range of 430 ppm to 2000 ppm. can.

In the basic configurations (1) and (2), which assume continuous supply of carbon dioxide, a mixed gas M of carbon dioxide and air A is supplied from the bottom and/or side of the reaction tank 1 , or a carbon dioxide By supplying carbon from the bottom of the reaction vessel 1 and supplying air A from the side of the reaction vessel 1 , it is possible to achieve the concentration of carbon dioxide in the appropriate numerical range as described above.

In the case of the configuration of Patent Document 2 in which oxygen nanobubbles are essential, it was assumed that the temperature in the reaction tank 1 is preferably room temperature of 40°C, and particularly preferably 30°C (paragraph [0028]) .
On the other hand, in the case of basic configurations (1) and (2), the water temperature includes all cases of natural state, cooling, and heating; has no significant effect on the synthesis efficiency.

The basis for this is that the photocatalyst that acts through the reduction reaction in formula (1) and the synthesis reaction of liquid hydrocarbon HC in formula (2) locally causes molecules to vibrate locally in water at an order of magnitude higher than thermal vibrations. It is understood that the thermal vibrations that affect the water temperature have little effect on the molecular motion.

The reduction reaction of formula (1) is preferably in a calm state.
In such a case, as in basic configurations (1) and (2), when bubbles of air A or a gas mixture M of carbon dioxide and air A are raised into water W, the equation (1) above is Although there is a fear that the peaceful state may be disrupted, which may interfere with the reduction reaction, in reality, such disruption has not occurred.

The reason for this is that due to the rise of the bubbles, no oscillating state or turbulent flow state that would impede the reduction reaction is formed in the water W, so the reduction reaction and the rise of the bubbles are The two are fully compatible.
In fact, even in the case of the prior art in which bubbles are not supplied by air A or a mixed gas M of carbon dioxide and air A, the above-mentioned (( 1) No particular problem occurred in the reduction reaction of formula.

In the basic configuration (1), an embodiment is adopted in which the supply amount of air A that is mixed or supplied at the bottom and/or the side is adjusted, and in the basic configuration (2), the As shown in FIG. 2(a), an embodiment characterized in that a supply amount adjustment device 5 for the air A being mixed or supplied at the bottom and/or the side is provided can be adopted.
However, FIG. 2(a) shows a case where a supply amount adjusting device 5 for air A before being mixed is employed.

In the case of these embodiments, the synthesis efficiency of liquid hydrocarbon HC is adjusted by adjusting the amount of supplied carbon dioxide, air A, or mixed gas M of carbon dioxide and air A, and moreover, the synthesis efficiency of liquid hydrocarbon HC is adjusted to 430 ppm. A preferred carbon dioxide concentration of ˜2000 ppm can be set.

In the basic configuration (1), an embodiment is adopted in which air A is sent above the upper interface and the amount of air A is adjusted, and in the basic configuration (2), an embodiment is adopted in which the air A is sent above the upper interface and the amount of air A is adjusted. ), an embodiment characterized in that an air supply source 4 and a supply amount adjusting device 5 are provided above the reaction tank 1 can be adopted.

In these embodiments, by keeping the supply amount of the mixed gas M of carbon dioxide and air A constant or the air A, and adjusting the supply amount of the air A above the water W surface, The synthesis efficiency of liquid hydrocarbon HC can be adjusted and a preferred carbon dioxide concentration of 430 ppm to 2000 ppm can be set.

In the case of the above two embodiments of adjusting the supply amount, a configuration is adopted in which the concentration of carbon dioxide is measured above the upper interface in the basic configuration (1). In configuration (2), as shown in FIGS. 2(a) and 2(b), if a configuration is adopted in which a carbon dioxide concentration measuring instrument 6 is provided above the reaction tank 1, accurate carbon dioxide concentration can be obtained. can be set.

In the basic configuration (1), an embodiment is adopted in which a resistance element is provided in the layer of liquid hydrocarbon HC to moderate the moving speed of bubbles, and in the basic configuration (2), these In the case of the embodiment, when the bubbles pass through the layer of liquid hydrocarbon HC, the bubbles generate a gas mixture M of carbon dioxide and air A in a considerable proportion, and the bubbles as described above generate a gas mixture M of carbon dioxide and air A in a considerable proportion. As a result of the relaxation of the migration speed of the liquid hydrocarbon HC, the synthesis efficiency of the liquid hydrocarbon HC can be promoted by increasing the contact time between the liquid hydrocarbon HC and the gas bubbles in the mixed state.
In addition, when the resistance element and the filter are provided in water W below the layer of liquid hydrocarbon HC, bubbles of the air A supplied without generating the mixed gas M and carbon dioxide It can promote mixing with air bubbles.

In the basic configuration (1), an embodiment characterized in that water W containing oxygen that forms nanobubbles by ultrasonic vibration is supplied to the bottom and/or side of the reaction tank 1. The basic configuration (2) is characterized in that an oxygen supply tank in which nanobubbles are formed in a water tank equipped with an ultrasonic vibration device is connected to the bottom and/or side of the reaction tank 1. An embodiment may be adopted.

In the case of these embodiments, by forming oxygen nanobubbles in advance by ultrasonic vibration and then supplying the nanobubbles into the reaction tank 1, it is possible to improve the synthesis efficiency of liquid hydrocarbon HC. On the other hand, since vibrations due to ultrasonic waves are not generated in the reaction tank 1, the reduction reaction described in (1) above can be achieved in a calm state.

In the basic configuration (1), an embodiment characterized in that carbon dioxide and/or air A forming nanobubbles by ultrasonic vibration is supplied to the bottom and/or side of the reaction tank 1. In basic configuration (2), a supply tank for carbon dioxide and/or air A in which nanobubbles have been formed is connected to the bottom and/or side of reaction tank 1 in a water tank equipped with an ultrasonic vibration device. It is possible to adopt an embodiment characterized in that:

In these embodiments, nanobubble carbon dioxide and/or air A are activated, and the synthesis efficiency of liquid hydrocarbon HC can be improved.

Specifically, nanobubbles reduce the volume of bubbles caused by carbon dioxide and/or air A, thereby reducing the speed of movement in water W, and the air A being supplied without being mixed with carbon dioxide. Not only is it easy to create a mixed state of carbon dioxide in which HC is separately supplied, but also the rate at which the liquid hydrocarbon HC moves through the layer decreases and the period during which the layer is in contact with the mixed gas M increases, so that the It can help improve synthesis efficiency.

Moreover, since the ultrasonic vibration is realized outside the reaction tank 1, the reduction reaction of the above formula (1) can be realized in a calm state, as in the case of the oxygen nanobubbles.

In the basic configuration (1), it is possible to adopt an embodiment characterized in that the concentration of carbon dioxide in the mixed gas is 430 ppm to 2000 ppm.
Corresponding to such an embodiment, the basic configuration (2) is characterized in that a shielding plate is provided above the reaction tank 1 to shield the rise of the mixed gas M of carbon dioxide and air A. An embodiment can be adopted.
In the case of such an embodiment, the concentration of carbon dioxide in the mixed gas M of carbon dioxide and air A above the interface of the liquid hydrocarbon HC is set to a considerably higher concentration than 430 ppm, which is approximately equal to that at atmospheric pressure. can do.
In particular, when a configuration is adopted in which a predetermined gap is provided between a plurality of shielding plates and the degree of the gap can be adjusted, the concentration can be appropriately selected by adjusting the gap. be able to.

In the basic configuration (1), it is possible to adopt an embodiment in which the dissolved oxygen is irradiated with ultraviolet rays, and in the basic configuration (2), the dissolved oxygen in the reaction tank is irradiated with ultraviolet rays. An embodiment characterized in that it includes an ultraviolet irradiation device can be adopted.
In these embodiments,
When at least a portion of the dissolved oxygen is activated by irradiation with ultraviolet rays, the efficiency of reducing carbon dioxide can be significantly improved compared to the case where it is not activated.

The basis for this is that hydrogen peroxide (H ₂ O ₂ ) is generated by activation of dissolved oxygen, and as a result, efficient reduction of carbon dioxide can be assumed by the chemical formula below. .
CO ₂ +H ₂ O ₂ →CO + H ₂ +3O ₂ /2 (3)

Hereinafter, description will be made based on examples.

Example 1 is characterized in that the liquid hydrocarbon HC and the water W in a mixed state flow into the reaction tank 1 in the basic configuration (1).

Due to these characteristics, in the reaction tank 1, frequent contact between the liquid hydrocarbon HC flowing into the reaction tank 1 and bubbles caused by the mixed gas M of carbon dioxide and air A is realized, and the liquid hydrocarbon HC flows into the reaction tank 1. This is attributed to the fact that the synthesis efficiency is further promoted.

Example 2 is characterized in that, in basic configuration (2), the reaction tank 1 is provided with a supply device that supplies water W, and a receiving tank that receives the supply of liquid hydrocarbon HC from the reaction tank 1. There is.

Due to these features, in the device of basic configuration (2), continuous and efficient production of liquid hydrocarbon HC can be realized.

In the present invention, which is based on the method of basic configuration (1) and the apparatus of basic configuration (2), the entire surface of the bubbles due to the mixed gas of carbon dioxide and air in the layer where liquid hydrocarbons are generated is It has the great advantage of being able to efficiently generate liquid hydrocarbons through contact with the gas mixture of carbon dioxide and air at the upper interface of the layer, and has great industrial value. is enormous.

W Water A Air HC Liquid hydrocarbon (abbreviation for hydrocarbon)
M Mixed gas of carbon dioxide and air 1 Reaction tank 2 Source of mixed gas of carbon dioxide and air
3 Sources of carbon dioxide
4 Air supply source
5 Supply amount adjustment device 6 Carbon dioxide concentration measuring device

Claims (21)

Carbon dioxide and water are converted into carbon monoxide and hydrogen via a photocatalyst in a reaction tank containing water in which continuously supplied carbon dioxide is dissolved and mixed with liquid hydrocarbons. A method of further synthesizing the liquid hydrocarbon by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, in which the carbon dioxide and the hydrogen are further synthesized from the bottom and/or side of the reaction tank. Liquid carbonization is produced in the upper region of the reactor by supplying bubbles of a gas mixture with air or by supplying carbon dioxide bubbles and air bubbles from the bottom and sides of the reactor, respectively. A method for synthesizing liquid hydrocarbons, wherein the upper interface of a hydrogen layer maintains contact with a gas mixture of carbon dioxide and air that has passed through the layer. 2. The method for synthesizing liquid hydrocarbons according to claim 1, wherein the amount of air mixed or supplied at the bottom and/or the side is adjusted. The method for synthesizing liquid hydrocarbons according to claim 1, characterized in that air is sent above the upper interface and the amount of air sent is adjusted. 4. The method for synthesizing liquid hydrocarbons according to claim 2, wherein the concentration of carbon dioxide is measured above the upper interface. 4. The method for synthesizing liquid hydrocarbons according to claim 1, further comprising a resistance element in the layer of liquid hydrocarbons for moderating the moving speed of bubbles. Any one of claims 1, 2, and 3, characterized in that water containing oxygen forming nanobubbles by ultrasonic vibration is supplied to the bottom and/or side of the reaction tank. The method for synthesizing liquid hydrocarbons described in . According to any one of claims 1, 2 and 3, characterized in that carbon dioxide and/or air forming nanobubbles by ultrasonic vibration is supplied to the bottom and/or side of the reaction tank. A method of synthesizing the liquid hydrocarbons described. 4. The method for synthesizing liquid hydrocarbons according to claim 1, wherein the concentration of carbon dioxide in the mixed gas is 430 ppm to 2000 ppm. 4. The method for synthesizing liquid hydrocarbons according to claim 1, wherein dissolved oxygen is irradiated with ultraviolet rays. 4. The method for synthesizing liquid hydrocarbons according to claim 1, wherein the liquid hydrocarbon and the water in a mixed state flow into a reaction tank. Carbon dioxide, which is continuously supplied at the bottom and/or side of the reaction tank via a photocatalyst in a reaction tank containing water mixed with liquid hydrocarbons, is added to the water. An apparatus for reducing carbon monoxide and hydrogen and further synthesizing liquid hydrocarbons in a layered manner in an upper region of a reaction tank by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, the apparatus comprising: a photocatalyst means having the photocatalyst in the reaction tank , and connected to a supply source of the mixed gas of carbon dioxide and air at the bottom and/or side of the reaction tank, or the reaction tank A liquid hydrocarbon synthesis apparatus connected to a source of carbon dioxide and a source of air at the bottom and side, respectively . 12. The liquid hydrocarbon synthesis apparatus according to claim 11, further comprising a supply amount adjusting device for the air being mixed or supplied at the bottom and/or the side. 13. The liquid hydrocarbon synthesis apparatus according to claim 12, further comprising an air supply source and a supply amount adjusting device above the reaction tank. 14. The liquid hydrocarbon synthesis apparatus according to claim 12, further comprising a carbon dioxide concentration measuring device above the reaction tank. 14. The liquid hydrocarbon synthesis apparatus according to claim 11, wherein one or more filters are installed in the liquid hydrocarbon layer. Any one of claims 11, 12, and 13, characterized in that a supply tank of oxygen in which nanobubbles are formed in a water tank equipped with an ultrasonic vibration device is connected to the bottom and/or side of the reaction tank. The liquid hydrocarbon synthesis apparatus described in . Claims 11, 12, 13 characterized in that a supply tank for carbon dioxide and/or air in which nanobubbles are formed in a water tank equipped with an ultrasonic vibration device is connected to the bottom and/or side of the reaction tank. The liquid hydrocarbon synthesis apparatus according to any one of the above. Synthesis of liquid hydrocarbons according to any one of claims 11, 12, and 13, characterized in that a shielding plate is provided above the reaction tank to shield the rise of the mixed gas of carbon dioxide and air. Device. 19. The liquid hydrocarbon synthesis apparatus according to claim 18, wherein a predetermined gap is provided between the plurality of shielding plates, and the degree of the gap can be adjusted. 14. The liquid hydrocarbon synthesis apparatus according to claim 11, further comprising an ultraviolet irradiation device for irradiating dissolved oxygen in the reaction tank. 14. The reactor according to claim 11, further comprising a supply device for supplying water to the reaction tank, and a receiving tank for receiving supply of liquid hydrocarbons from the reaction tank. Liquid hydrocarbon synthesis equipment.

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