Method for increasing liquid hydrocarbon

Abstract

To provide a method for increasing liquid hydrocarbon from oxygen and carbon dioxide.SOLUTION: A method for synthesizing liquid hydrocarbon HC for reducing carbon dioxide and water W to carbon monoxide and hydrogen through a photocatalyst in a reaction tank 1 storing the water W in a state of being mixed with the liquid hydrocarbon HC, and synthesizing the liquid hydrocarbon HC by chemical reaction of the monoxide and the hydrogen through a photocatalyst, includes: supplying mixed gas M of the carbon dioxide and air A from the bottom part and / or the side part of the reaction tank 1, supplying each of the carbon dioxide and the air A from the bottom part and the side part of the reaction tank 1, or supplying each of the carbon dioxide and the air A from the side part and the bottom part of the reaction tank 1, thereby bonding constitutional units of each of the reaction tanks 1 achieving each operation by contact of the mixed gas M to pass through the layer of the liquid hydrocarbon HC synthesized on the upper side of the water W with air bubbles, and contact of the mixed gas M with the upper side interface of the layer, in a state of being communicated with each other in a vertical direction through a hollow pipe 7.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a method for reducing carbon dioxide and water to carbon monoxide and hydrogen in water via a photocatalyst, and synthesizing and increasing the production of liquid hydrocarbons through a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst. [Background technology]

[0002] The synthesis of liquid hydrocarbons by reducing carbon dioxide in water has already been proposed in the prior art.

[0003] For example, Patent Document 1 proposes a method of producing liquid hydrocarbons by supplying oxygen to water containing carbon dioxide in a photoelectrochemical cell and reducing the carbon dioxide (page 81, lines 4-21).

[0004] That is, the photocatalyst in Patent Document 1 is premised on a photoelectrochemical cell, and on the premise that fuel is produced from liquid hydrocarbons or the like at the cathode (Claims 2, 77, 79).

[0005] Therefore, in Patent Document 1, reduction of carbon dioxide and water by pure photocatalysis is not realized. In fact, Patent Document 1 does not achieve activation of oxygen by irradiating water with ultraviolet light (in this respect, it is clearly different from Patent Document 2).

[0006] The inventors of the present application are involved in a method and apparatus for producing liquid hydrocarbons, as shown in Patent Document 2, which is premised on supplying oxygen to water containing dissolved carbon dioxide, generating oxygen nanobubbles, and reducing the carbon dioxide and water to carbon monoxide and hydrogen via a photocatalyst in the presence of active oxygen generated from the nanobubbles by irradiation with ultraviolet light.

[0007] However, in the case of Patent Document 2, the configuration is not necessarily simple in that it is essential to generate oxygen nanobubbles and generate active oxygen by irradiating with ultraviolet light.

[0008] In Patent Documents 1 and 2, when liquid hydrocarbons are produced via a photocatalyst, a layer of liquid hydrocarbons is produced in an area above water.

[0009] In such a case, contact with the air above containing carbon dioxide is realized, and in this case, the reduction efficiency of carbon dioxide in the water depends on the concentration of carbon dioxide gas contained in the air.

[0010] Considering the operating conditions of such reduction efficiency, the applicant has already filed Patent Application No. 2022-192688 for the following synthesis method and synthesis apparatus in order to overcome the problems of the prior art (hereinafter, the synthesis method based on said application will be abbreviated as "Prior Application Synthesis Method (1)" and the synthesis apparatus based on said application will be abbreviated as "Prior Application Synthesis Apparatus (2)"). (1) A method for increasing the production of liquid hydrocarbons, comprising: reducing carbon dioxide and water to carbon monoxide and hydrogen via a photocatalyst in a reaction vessel containing water in which carbon dioxide, which is continuously supplied, is dissolved and mixed with liquid hydrocarbons; and further synthesizing the liquid hydrocarbons by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst; supplying bubbles of the mixed gas of carbon dioxide and air from the bottom and / or side of the reaction vessel, or supplying bubbles of carbon dioxide and air from the bottom and side of the reaction vessel, respectively, so that the upper interface of a layer of liquid hydrocarbons produced in an upper region of the reaction vessel is maintained in contact with the mixed gas of carbon dioxide and air that has passed through the layer; and arranging the constituent units by this method for synthesizing liquid hydrocarbons in succession in a plurality of stages in the vertical direction, and connecting the reservoirs of the constituent units in the vertical direction via a pipe through which the mixed gas flows. (2) An apparatus for reducing carbon dioxide, which is continuously supplied to the bottom and / or side of a reaction vessel containing water mixed with liquid hydrocarbons, to carbon monoxide and hydrogen in the water via a photocatalyst, and further synthesizing liquid hydrocarbons in layers in the upper region of the reaction vessel through a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, wherein the reaction vessel is provided with photocatalytic means having the photocatalyst, and each component unit of a liquid hydrocarbon synthesis apparatus is connected to a supply source of a mixed gas of carbon dioxide and air at the bottom and / or side of the reaction vessel, or to an oxygen supply source and an air supply source at the bottom and side of the reaction vessel, respectively, or to a carbon dioxide supply source and an air supply source at the side and bottom of the reaction vessel, respectively, and the mixed gas flows upward through pipes that vertically connect the water reservoirs of each component unit. The synthesis method (1) and synthesis apparatus (2) of the prior application can realize the production of liquid hydrocarbons in an extremely efficient manner. However, the synthesis method (1) and the synthesis apparatus (2) of the prior application do not envisage a configuration that increases the quantity of liquid hydrocarbons produced. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] WO2010 / 042196 A1 [Patent Document 2] Patent No. 6440742 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention provides a highly efficient method for producing liquid hydrocarbons through photocatalysis of water containing dissolved oxygen and carbon dioxide. For each reactor The object of the present invention is to provide a method for increasing the production of liquid hydrocarbons based on structural units. [Means for solving the problem]

[0013] In order to solve the above problems, the basic configuration of the present invention is as follows. A method for synthesizing liquid hydrocarbons, comprising reducing carbon dioxide and water to carbon monoxide and hydrogen via a photocatalyst in a reaction vessel containing water in which continuously supplied carbon dioxide is dissolved and which is mixed with liquid hydrocarbons, and further synthesizing the liquid hydrocarbons by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, wherein bubbles of the mixed gas of carbon dioxide and air are supplied from the bottom and / or side of the reaction vessel, or bubbles of carbon dioxide and air are supplied from the bottom and side of the reaction vessel, respectively, thereby maintaining the upper interface of a layer of liquid hydrocarbons produced in an upper region of the reaction vessel in contact with the mixed gas of carbon dioxide and air which has passed through the layer. Do each For each reactor The structural units are arranged in multiple rows in the vertical direction, and each Reactor The mixed gas flows hollow Up and down through the pipe In a connected state A method for increasing the production of bound liquid hydrocarbons. [Effects of the Invention]

[0014] Each of the basic configuration Reactor In this case, a layer of liquid hydrocarbons is formed above the water. of By contacting the passing carbon dioxide with the mixed gas of carbon dioxide and air and maintaining a state of contact between the upper interface of the layer and the mixed gas of carbon dioxide and air, it is possible to realize extremely efficient reduction of carbon dioxide and further synthesis of liquid hydrocarbons. That is, the efficient synthesis is made possible by both the stage in which the bubbles of the mixed gas pass through the layer while contacting the entire surface of the bubbles, and the stage in which the contact state is maintained at the upper interface. In particular, the effect of the former stage becomes more pronounced as the synthesis of liquid hydrocarbons progresses and the layer in the upper region becomes larger. each ReactorIn the above, it is assumed that carbon dioxide is continuously supplied, but when a mixed gas of carbon dioxide and air is supplied, the above effect is naturally produced. Even if carbon dioxide and air are supplied from the bottom and side of the reaction tank, respectively, rather than from the side and bottom of the reaction tank, the above-mentioned effect can be achieved because a considerable proportion of the bubbles will produce a mixed gas of carbon dioxide and air by the time they pass through the layer.

[0015] Each in the basic configuration Reactor As with the prior application synthesis method (1) and prior application synthesis apparatus (2), this is extremely simple compared to the configuration employing electrodes in Patent Document 1, and does not require the application of voltage, and liquid hydrocarbons that can be used as fuel can be obtained purely by a photocatalytic reaction.

[0016] Each of the above Reactor In the case of (1), a mixed gas of carbon dioxide and air is supplied, or carbon dioxide and air are supplied, and oxygen is contained in the air. Therefore, unlike Patent Document 2, the supply of oxygen and the formation of nanobubbles of the oxygen are not essential, and a simple configuration is realized.

[0017] In this way, each of the above Reactor The basic configuration employing the above is simple, as in the case of the synthesis method (1) and synthesis apparatus (2) of the prior application, yet can realize extremely efficient production of liquid hydrocarbons. Incidentally, the configuration of Patent Document 2 also includes a configuration in which carbon dioxide is reduced in the presence of activated oxygen generated from nanobubbles of separately prepared liquid hydrocarbons and oxygen. However, when such a mixed state is left for, for example, 24 hours, the rate at which liquid hydrocarbons are further synthesized is usually 10 to 15% (paragraph

[0029] ). ReactorIn this case, by adjusting the carbon dioxide concentration of the air in contact with the liquid hydrocarbons to within the range of 430 ppm to 2000 ppm, the proportion of liquid hydrocarbons further synthesized can be set to 20 to 30%. These Each reaction vessel In addition to the effect of Reactor By stacking multiple layers vertically, each Reactor The effects of the above can be superimposed. Specifically, the contact area between the supplied mixed gas or air and water can be increased by stacking, which in turn can increase the production of liquid hydrocarbons.

[0018] Furthermore, in the basic configuration, when synthesizing a predetermined liquid hydrocarbon, a considerable amount of carbon dioxide is required and a considerable amount of oxygen is emitted, as will be described later. However, as a result, the carbon dioxide emitted in the various production processes is consumed and oxygen is produced, which contributes to improving the living environment in the same way as the action of plants. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 2 is a block diagram showing the operation of each reaction vessel in the basic configuration. [Figure 2] 1A and 1B are schematic diagrams of the reaction tanks and the apparatus integrated with the reaction tanks of an apparatus corresponding to the case where the basic configuration is actually put into practice, in which (a) shows an embodiment in which a supply source of a mixed gas of carbon dioxide and air is connected to the bottom and / or side of the reaction tank (the upper side of (a) shows a case where connection is made at the bottom, and the lower side shows a case where connection is made at the bottom and side, but a configuration where connection is made at the side is also naturally adoptable), and the amount of mixed air is adjusted; (b) shows an embodiment in which the carbon dioxide and air supply sources are connected to the bottom and side of the reaction tank, respectively, and air is supplied above the reaction tank with the supply amount adjusted; and (c) shows an embodiment in which the carbon dioxide and air supply sources are connected to the side and bottom of the reaction tank, respectively, and air is supplied above the reaction tank with the supply amount adjusted. [Figure 3]1 is a block diagram showing a basic configuration of the method, in which the arrows indicate the flow direction of a mixed gas of carbon dioxide and air. DETAILED DESCRIPTION OF THE INVENTION

[0020] As shown in the block diagrams of Figures 1 and 3, the basic configuration of this method is as follows: in a reaction vessel 1 containing water W in which carbon dioxide, which is continuously supplied and dissolved and which is mixed with liquid hydrocarbons (HC), carbon dioxide and water W are reduced to carbon monoxide and hydrogen via a photocatalyst; and the carbon monoxide and hydrogen are further reacted via the photocatalyst to synthesize the liquid hydrocarbons (HC), Reactor 1 a method for synthesizing liquid hydrocarbons (HC), wherein bubbles of the mixed gas M of carbon dioxide and air A or bubbles of air A are supplied from the bottom and / or side of the reaction vessel (1), so that the upper interface of the layer of liquid hydrocarbons (HC) produced in the upper region of the reaction vessel (1) is kept in contact with the mixed gas M of carbon dioxide and air A that has passed through the layer. Do each Reactor 1 per The structural units are stacked in multiple layers in the vertical direction, and each Reactor 1, The mixed gas M is flowing hollow pipe 7 via Connected in a vertically connected state This is a method for increasing the production of liquid hydrocarbons (HC).

[0021] Each corresponding to the actual implementation of the basic configuration Reaction vessel 1 and the vessel that is integrated with the reaction vessel 1 As shown in the schematic diagrams of Figures 2(a), (b), and (c), the apparatus is an apparatus in which carbon dioxide continuously supplied into a reaction vessel 1 containing water W in a mixed state with liquid hydrocarbons HC is reduced to carbon monoxide and hydrogen in the water via a photocatalyst, and liquid hydrocarbons HC are further synthesized in a layered form in the upper region of the reaction vessel 1 by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst, and a photocatalytic means in the reaction vessel 1 and a supply source of a mixed gas M of the carbon dioxide and air A at the bottom and / or side of the reaction vessel 1 are provided. 2 or Carbon dioxide sources 3 and Air A source 4 The system consists of a liquid hydrocarbon HC synthesis unit connected to the

[0022] Basic configuration (1) Reactor 1 In the above, both cases are encompassed: a case in which bubbles of a mixed gas M of carbon dioxide and air A are supplied from the bottom and / or side of the reaction tank 1; and a case in which carbon dioxide bubbles and air A bubbles are supplied from the bottom and side of the reaction tank 1, respectively, without being mixed with carbon dioxide, or from the side and bottom of the reaction tank 1, respectively. However, usually, in consideration of efficient synthesis of liquid hydrocarbons HC, a configuration in which mixed bubbles M are supplied from the beginning is often adopted. Below are the basic configurations: Reactor 1 The technical features of the embodiments will be specifically described below.

[0023] Each reactor 1 In the above, the continuous supply of carbon dioxide for the production of liquid hydrocarbons (HC) is a technical premise, but as already pointed out in the section on effects, the following technical points can be inferred as the basis for the promotion of the reduction reaction due to contact between the layer of liquid hydrocarbons (HC) in the upper region and the mixed gas M of carbon dioxide and air A passing through the layer, and further due to contact between the upper interface of water W in which liquid hydrocarbons (HC) are produced and the mixed gas M of carbon dioxide and air A.

[0024] When carbon dioxide dissolved in water is photocatalyzed to form radical water, i.e., activated water that is prone to chemical reactions, the following reaction formula can be assumed with a considerable degree of probability for the reduction reaction caused by the radicalization: nCO2+(2n + 1) H2O → nCO+(2n + 1)H2+(3n + 1 / 2)O2···(1) That is, in the above formula (1), the reduction reaction proceeds sequentially from left to right. When focusing on the individual reactions, there is a reverse reaction in which carbon monoxide molecules are oxidized and converted into carbon dioxide molecules. However, overall, the reaction proceeds in which carbon dioxide molecules are sequentially reduced to carbon monoxide molecules.

[0025] Following the reaction formula (1) above, the following reaction formula can be assumed with a considerable probability as a reaction formula for further producing the following liquid hydrocarbons HC due to the radicalization in radical water. (2n+1)H2+nCO→C n H 2n+2 +nH2O (2) Therefore, C generated in the upper region of water W n H 2n+2 The liquid hydrocarbon HC layer is derived from the reaction formula (2) above. The carbon number n is the same as the carbon number of the liquid hydrocarbons HC that are blended in advance and are mixed with the radical water, and therefore the liquid hydrocarbons HC that are blended in advance are called templates or, alternatively, seed oils. 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 has not yet been fully elucidated.

[0026] According to the above-mentioned assumed formulas (1) and (2), 1 mole of liquid hydrocarbon C n H 2n+2 When synthesizing, n moles of carbon dioxide are consumed and (3n+1) / 2 moles of oxygen are produced. Therefore, n = 14, and 10 moles of liquid hydrocarbon C 14 H 30 When synthesizing this compound, 140 moles, or 6,160 g, of carbon dioxide are required, and 215 moles, or 6,880 g of oxygen, are produced. On a weight basis, this means that 3.1 times as much carbon dioxide is consumed and 3.5 times as much oxygen is released. That is, even in the above-mentioned assumed case, when synthesizing a predetermined amount of liquid hydrocarbon, several times as much carbon dioxide is consumed and several times as much oxygen is generated. However, such consumption of carbon dioxide and generation of oxygen can contribute to the improvement of the living environment in the same way as plants, since it is possible to consume the carbon dioxide generated industrially and realize the production of oxygen. However, when carbon dioxide is supplied and consumed in a natural environment, a method can also be adopted in which mushrooms are cultivated and the carbon dioxide generated by the mushrooms is supplied and consumed.

[0027] In the case of the above reaction formulas (1) and (2), the carbon dioxide that is passing through the layer of liquid hydrocarbons HC and is generating mixed gas M with air A, and the carbon dioxide that is generating mixed gas M with air A above the layer, permeate the layer of liquid hydrocarbons HC because of its affinity for liquid hydrocarbons HC, which are non-polar liquids, and further, because it is easily soluble in water W, even though water W in the lower region is a polar liquid, it migrates to the side of water W and dissolves therein.

[0028] The dissolution promotes the reduction reaction of the formula (1), which in turn promotes the synthesis reaction of the formula (2). As far as the reaction formulas (1) and (2) are concerned, the higher the concentration of liquid hydrocarbons HC, which can be freely adjusted above the interface, the more the reactions of the formulas (1) and (2) are promoted.

[0029] However, according to the experience of the inventors, it has been found that the higher the concentration of carbon dioxide, the more the reactions of the above formulas (1) and (2) are not promoted, and that when the concentration of carbon dioxide above the interface exceeds a certain level, the generation of liquid hydrocarbons HC may actually decrease.

[0030] The exact reason why the efficiency of synthesis of liquid hydrocarbons HC decreases when the carbon dioxide concentration exceeds a certain value is not clear at present. However, it can be assumed that the function of the photocatalyst in the reaction formulas (1) and (2) above will actually decrease if the carbon dioxide concentration exceeds a certain level.

[0031] The appropriate concentration of carbon dioxide at the upper interface depends on the amount of carbon dioxide contained in the water, but in most cases, the appropriate carbon dioxide concentration can be set within the range of 430 ppm to 2000 ppm.

[0032] In the basic configuration that assumes a continuous supply of carbon dioxide, the carbon dioxide concentration in the appropriate numerical range as described above can be achieved by supplying a mixed gas M of carbon dioxide and air A or by supplying air A.

[0033] 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 vessel 1 would preferably be room temperature, 40°C, and more preferably 30°C (paragraph

[0028] ). In response to this, Reactor 1 In this case, the water temperature includes the natural state, the case where it is cooled, and the case where it is heated, but the water temperature does not have a significant effect on the synthesis efficiency of liquid hydrocarbons HC.

[0034] The basis for this is understood to be that the photocatalyst, which acts through the reduction reaction of the formula (1) and the synthesis reaction of liquid hydrocarbon HC of the formula (2), locally causes molecular vibrations in the water at frequencies orders of magnitude greater than thermal vibrations, and that thermal vibrations, which affect the water temperature, have almost no effect on the molecular motions.

[0035] The reduction reaction of the above formula (1) is preferably carried out in a calm state. In such cases, Reactor 1 As described above, when bubbles of air A or a mixed gas M of carbon dioxide and air A are raised into water W, there is a concern that the calm state may be disrupted, causing problems in the reduction reaction of the above formula (1). However, in reality, no such disruption has occurred.

[0036] The reason for this is that the rising of the bubbles does not create a vibration or turbulent state in the water W that would interfere with the reduction reaction, so the reduction reaction and the rising of the bubbles can be fully achieved. In fact, even in the case of the prior art in which bubbles of air A or a mixed gas M of carbon dioxide and air A are not supplied, the movement of the continuously supplied carbon dioxide bubbles does not cause any particular hindrance to the reduction reaction of the above formula (1).

[0037] Each of the basic configuration In the case of reactor 1 The embodiment can adopt an embodiment in which the supply amount of air A being mixed or supplied at the bottom and / or side is adjusted, and in this case, as a corresponding device, a supply amount adjustment device 4 for air A being mixed or supplied at the bottom and / or side is adopted, as shown in Figure 2(a). However, FIG. 2(a) shows a case where a supply amount adjusting device 4 for the air A before mixing is employed.

[0038] In the case of the above embodiment, by adjusting the supply amount of carbon dioxide, or air A, or mixed gas M of carbon dioxide and air A, it is possible to adjust the synthesis efficiency of liquid hydrocarbons HC and set a preferable carbon dioxide concentration of 430 ppm to 2000 ppm.

[0039] Each of the basic configuration Reactor 1 In this case, an embodiment can be adopted in which air A is supplied to the upper side of the upper interface and the amount of air supplied is adjusted. In this case, an apparatus corresponding to this embodiment employs an air supply source 3 and a supply amount adjusting device 4 above the reaction tank 1, as shown in Figure 2(b).

[0040] In the above embodiment, the supply amount of the mixed gas M of carbon dioxide and air A or the air A is kept constant, and by adjusting the supply amount of the air A supplied above the water W surface, it is possible to adjust the synthesis efficiency of the liquid hydrocarbons HC and set a preferable carbon dioxide concentration of 430 ppm to 2000 ppm.

[0041] In the case of the embodiment of adjusting the supply amount, each of the basic components In the case of reactor 1,In this case, a configuration can be adopted in which the carbon dioxide concentration is measured above the upper interface, and in this case, as shown in Figures 2(a), (b), and (c), a device for measuring the carbon dioxide concentration 5 is provided above the reaction tank 1, thereby accurately setting the carbon dioxide concentration.

[0042] Each of the basic configuration Reactor 1 In the above, an embodiment can be adopted in which a resistance element for slowing down the movement speed of bubbles is provided in the layer of liquid hydrocarbons HC, and as a corresponding device in this case, one or more filters are installed in the reaction tank 1. In the above embodiment, the time it takes for the bubbles to reach the bottom layer of the liquid hydrocarbons HC is extended, thereby increasing the chances of the reactions (1) and (2) occurring. Each of the basic configuration Reactor 1 In the above, an embodiment can be adopted in which the concentration of carbon dioxide in the mixed gas M to be supplied is adjusted in advance, or the layer of carbon dioxide and air A to be supplied is adjusted in advance, so that the concentration of carbon dioxide in the mixed gas M is 430 ppm to 2000 ppm.As an apparatus corresponding to this case, a shield plate is provided on the upper side of the reaction tank 1 to block the rise of the mixed gas M of carbon dioxide and air A. In the above embodiment, the concentration of carbon dioxide in the mixed gas M with air A is set to a concentration significantly higher than 430 ppm, which is approximately equal to the atmospheric pressure, throughout the entire region of the reaction tank 1, and the reaction formulas (1) and (2) can be efficiently promoted. In particular, when a configuration is adopted in which a predetermined gap is provided between multiple shielding plates and the size of the gap can be adjusted, the concentration can be appropriately selected by adjusting the gap.

[0043] Each of the basic configuration Reactor 1 In the above, an embodiment can be adopted in which oxygen-containing water W in which nanobubbles have been formed by ultrasonic vibration is supplied to the bottom and / or side of the reaction tank 1, and a corresponding device in this case is a water tank equipped with an ultrasonic vibration device, and a supply tank for oxygen in which nanobubbles have been formed is connected to the bottom and / or side of the reaction tank 1.

[0044] In the case of the above embodiment, oxygen nanobubbles are formed in advance by ultrasonic vibration and then supplied into the reaction vessel 1, thereby making it possible to improve the synthesis efficiency of liquid hydrocarbons HC, and at the same time, since no ultrasonic vibrations are generated in the reaction vessel 1, the reduction reaction of (1) above can be realized in a calm state.

[0045] Each of the basic configuration Reactor 1 In the embodiment, water containing carbon dioxide and / or air A in which nanobubbles have been formed by ultrasonic vibration is supplied to the bottom and / or side of the reaction tank 1, and a corresponding device can be configured to connect a supply tank for carbon dioxide and / or air A in which nanobubbles have been formed in water W equipped with an ultrasonic vibration device to the bottom and / or side of the reaction tank 1.

[0046] In the above embodiment, the nanobubbled carbon dioxide and / or air A is activated, and the efficiency of synthesis of liquid hydrocarbons HC can be improved.

[0047] Specifically, the nanobubbles reduce the volume of the bubbles of carbon dioxide and / or air A, thereby slowing down the speed at which they move through the water W. This not only makes it easier for the air A supplied without being mixed with carbon dioxide to be mixed with separately supplied carbon dioxide, but also reduces the speed at which the liquid hydrocarbons HC move through the layer, thereby increasing the period during which the layer is in contact with the mixed gas M, thereby promoting the improvement of the synthesis efficiency.

[0048] Moreover, since the ultrasonic vibration is realized outside the reaction vessel 1, the reduction reaction of the above formula (1) can be realized in a calm state, as in the case of the oxygen nanobubbles.

[0049] Each of the basic configuration Reactor 1In the embodiment, ultraviolet light is irradiated onto the dissolved oxygen, and an ultraviolet light irradiating device for irradiating the oxygen dissolved in the reaction vessel 1 is used as the corresponding device. When the dissolved oxygen is activated by irradiation with ultraviolet light, the efficiency of carbon dioxide reduction can be significantly improved compared to when the oxygen is not activated.

[0050] The basis for this is that hydrogen peroxide (H2O2) is produced by the activation of dissolved oxygen, which results in the efficient reduction of carbon dioxide, as envisaged by the following chemical equation: CO2+H2O2→CO+H2+3O2 / 2 ···(3)

[0051] In this way, each of the basic components Reactor 1 In the above, various embodiments can be adopted, and the unique effects of each of the above features can be achieved. That is, the basic configuration realizes the effect of these characteristics by stacking multiple stages to increase the production of liquid hydrocarbons. An embodiment of the basic configuration itself will be described below. In the basic configuration, the highest position Reactor 1 In the above, an embodiment can be adopted in which carbon dioxide in the mixed gas M that has passed through the layer of liquid hydrocarbons HC has disappeared after passing through.

[0052] In the case of the above embodiment, each Reactor 1 Therefore, it is possible to realize an efficient increase in production by consuming all of the carbon dioxide supplied in the step (2) for generating liquid hydrocarbons (HC). In the basic configuration, an embodiment can be realized in which a plurality of vertically stacked layers are arranged side by side in the horizontal direction.

[0053] In such an embodiment, in addition to the increase in production due to stacking, it is possible to further promote the increase in production due to the parallel placement in the horizontal direction.

[0054] In the basic configuration, an embodiment characterized in that water W flows in the reaction tank 1 can be adopted. When the water is flowing, the bubbles of the mixed gas M, the bubbles of carbon dioxide, and the bubbles of air A all flow horizontally within the reaction vessel 1, increasing the flow distance.

[0055] Furthermore, when the bubbles flow, they are subjected to pressure from the water in the direction of flow, causing their volume to decrease, and as a result, the speed at which the liquid hydrocarbons HC rise to the bottom layer decreases, and the time it takes for them to reach the bottom layer also increases.

[0056] In this way, the increase in the travel distance and travel time of each bubble increases the chances of each bubble coming into contact with the water W, which in turn increases the amount of liquid hydrocarbons HC produced. Therefore, in the case of the above embodiment, this means that the volume of the reaction vessel 1 is substantially increased, which can further promote increased production of liquid hydrocarbons HC.

[0057] In the basic configuration, each Reactor 1 In one embodiment, carbon dioxide is supplied to all or part of the pipes connecting the two.

[0058] This feature allows the upper part of the pipe where the carbon dioxide is being supplied to Reactor 1 The mixed gas M in the above can efficiently realize each chemical reaction of (1) and the basic configuration (2) by using carbon dioxide with an appropriately high concentration. Examples will be described below. [Example]

[0059] The basic configuration of the embodiment is Each reactor 1 In this method, the liquid hydrocarbons HC and the water W in a mixed state flow into the reaction vessel 1.

[0060] Due to these characteristics, in the reaction vessel 1, the liquid hydrocarbons (HC) that have flowed into the reaction vessel 1 are brought into frequent contact with bubbles of the mixed gas M of carbon dioxide and air A, which further promotes the synthesis efficiency of the liquid hydrocarbons (HC). [Industrial Applicability]

[0061] In the present invention based on the basic configuration, the liquid hydrocarbons are efficiently produced by contacting the entire surface of the bubbles with a mixed gas of carbon dioxide and air in the layer where the liquid hydrocarbons are produced, and further by contacting the mixed gas of carbon dioxide and air with the upper interface of the layer. Reactor This has the great advantage that such generation can be further enhanced by lamination, and is of great industrial value. [Explanation of symbols]

[0062] W water A. Air HC Liquid hydrocarbons (abbreviation for hydrocarbon) M: A mixture of carbon dioxide and air 1 Reaction vessel 2. Source of carbon dioxide and air mixture or source of air 3. Sources of carbon dioxide 4. Air supply source 5 Supply amount adjustment device 6. Carbon dioxide concentration measuring equipment 7 Pipe

Claims

1. 1. A method for increasing liquid hydrocarbon production, comprising: a reaction vessel containing water in which continuously supplied carbon dioxide is dissolved and which is mixed with liquid hydrocarbons, reducing carbon dioxide and water to carbon monoxide and hydrogen via a photocatalyst; and further synthesizing the liquid hydrocarbons by a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst; wherein bubbles of a mixed gas of carbon dioxide and air are supplied from the bottom and / or side of the reaction vessel, or carbon dioxide bubbles and air bubbles are supplied from the bottom and side of the reaction vessel, respectively, so that the upper interface of a layer of liquid hydrocarbons produced in an upper region of the reaction vessel is maintained in contact with the mixed gas of carbon dioxide and air which has passed through the layer; and wherein the constituent units of this method for synthesizing liquid hydrocarbons are arranged in succession in a plurality of vertical stages, and the reservoirs of the constituent units are connected in the vertical direction via pipes through which the mixed gas flows.

2. 2. The method for increasing production of liquid hydrocarbons according to claim 1, wherein carbon dioxide in the mixed gas that has passed through the layer of liquid hydrocarbons in the highest reservoir tank has disappeared after passing through.

3. 2. The method for increasing production of liquid hydrocarbons according to claim 1, wherein a plurality of multi-stage arrangements are arranged side by side in the horizontal direction.

4. 2. The method for increasing the production of liquid hydrocarbons according to claim 1, wherein water is flowing in each unit reaction vessel.

5. 2. The method for increasing liquid hydrocarbon production according to claim 1, wherein carbon dioxide is supplied to all or part of the pipe.

6. 6. The method for increasing the production of liquid hydrocarbons according to any one of claims 1, 2, 3, 4 and 5, characterized in that the amount of air mixed or supplied at the bottom and / or side of all or part of each unit reaction vessel is adjusted.

7. 6. The method for increasing liquid hydrocarbon production according to claim 1, wherein air is supplied to the upper side of the upper interface in all or part of each unit reaction vessel, and the amount of air supplied is adjusted.

8. 6. The method for increasing production of liquid hydrocarbons according to claim 1, wherein the concentration of carbon dioxide is measured above the upper interface in all or part of the reaction vessels of each unit.

9. 6. The method for increasing production of liquid hydrocarbons according to any one of claims 1, 2, 3, 4 and 5, characterized in that a resistance element for reducing the movement speed of gas bubbles is provided in the layer of liquid hydrocarbons in all or part of the reaction vessels of each unit.

10. 6. The method for increasing production of liquid hydrocarbons according to any one of claims 1 to 5, wherein oxygen-containing water in which nanobubbles have been formed by ultrasonic vibrations is supplied to the bottom and / or side of all or some of the reaction vessels in each unit.

11. 6. The method for increasing production of liquid hydrocarbons according to any one of claims 1 to 5, wherein water containing carbon dioxide and / or air in which nanobubbles have been formed by ultrasonic vibrations is supplied to the bottom and / or side of all or some of the reaction tanks in each unit.

12. 6. The method for increasing liquid hydrocarbon production according to claim 1, wherein the concentration of carbon dioxide in the mixed gas is 430 ppm to 2000 ppm in all or part of each unit reaction vessel.

13. 6. The method for increasing the production of liquid hydrocarbons according to any one of claims 1, 2, 3, 4 and 5, wherein the dissolved oxygen is irradiated with ultraviolet light in all or part of each unit reaction vessel.

14. 6. The method for increasing production of liquid hydrocarbons according to any one of claims 1 to 5, wherein the liquid hydrocarbons and the water in a mixed state flow into all or some of the reaction vessels of each unit.

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