Method for increasing liquid hydrocarbon

Abstract

To provide a method for increasing liquid hydrocarbon from oxygen and carbon dioxide in the water.SOLUTION: A method and device 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, include 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, or supplying each of the carbon dioxide and the air A from one and the other side of the bottom part and the side part of the reaction tank 1, thereby achieving the problem by contact of the mixed gas M to pass through the layer of the liquid hydrocarbon HC on the upper side of the water W with air bubbles, contact of the upper side interface of the layer with the mixed gas M of the carbon dioxide and the air A, and flow of the water W.SELECTED DRAWING: Figure 1

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 increasing the production of liquid hydrocarbons synthesized by 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] As shown in Patent Document 2, a method and apparatus for producing liquid hydrocarbons has been proposed, which is premised on supplying oxygen to water in which carbon dioxide is dissolved, 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] However, in the prior art such as Patent Documents 1 and 2, the basic idea of efficiently producing liquid hydrocarbons by adjusting the concentration of carbon dioxide gas in the air that comes into contact with the upper interface where liquid hydrocarbons are present is not proposed at all. Furthermore, the idea of increasing the production of liquid hydrocarbons by focusing on the flow of water has not been disclosed or suggested at all. [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] An object of the present invention is to provide a method for producing liquid hydrocarbons extremely efficiently through the use of a photocatalyst in water containing dissolved oxygen and carbon dioxide, while focusing on the flow of water and increasing the production of liquid hydrocarbons. [Means for solving the problem]

[0013] In order to solve the above problems, the basic configuration of the present invention is as follows: (1) A method for synthesizing liquid hydrocarbons, which comprises 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 through 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 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 that has passed through the layer, a method for increasing the production of liquid hydrocarbons by providing a rotary shaft at the horizontal center of a reaction vessel and creating a fluidized state of water by rotating impellers that rotate near the bottom of the reaction vessel; (2) A method for synthesizing liquid hydrocarbons, which comprises 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 a 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, the method comprising providing one or more outward protruding regions on the wall of the reaction vessel and creating a fluidized state of water by means of screws or rotating blades provided near the inside of the protruding regions; (3) 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 a 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; Either bubbles of a mixture of carbon dioxide and air, or bubbles of carbon dioxide and air, are introduced onto the wall of the reaction vessel. surface Jets from one or more points along the a method for increasing the production of liquid hydrocarbons by forming a water flow state; (4) A method for synthesizing liquid hydrocarbons, which comprises 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 a 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, and wherein the bottom of the reaction vessel is made parallel to the horizontal direction or inclined relative to the horizontal direction, and a fluid state of water in the reaction vessel is formed by refluxing water from the lower outlet to the upper inlet of the reaction vessel using a pump. , It consists of: [Effects of the Invention]

[0014] Basic configuration (1)、(2)、(3)、(4) In the method, in the layer of liquid hydrocarbons produced in the region above water in the reaction tank, the layer is brought into contact with the passing gas mixture of carbon dioxide and air, and the upper interface of the layer is maintained in contact with the gas mixture of carbon dioxide and air, thereby making it possible to achieve extremely efficient reduction of carbon dioxide and synthesis of liquid hydrocarbons.

[0015] 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. Furthermore, the basic configuration (1)、(2)、(3)、(4) In the above, it is assumed that carbon dioxide is continuously supplied, but when the mixed gas of carbon dioxide and air is supplied to the bottom and / or side of the reaction tank, the above effect is naturally produced. Even if carbon dioxide and air, rather than the mixed gas, are supplied from the bottom and side of the reaction tank, respectively, or from the side and bottom of the reaction tank, respectively, the bubbles will produce a considerable proportion of a mixed gas of carbon dioxide and air by the time they pass through the layer, and the above-mentioned effect can be achieved.

[0016] Basic configuration (1)、(2)、(3)、(4) 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 through a photocatalytic reaction.

[0017] Basic configuration (1)、(2)、(3)、(4) In the case of (1), a mixed gas of carbon dioxide and air or air is 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.

[0018] In this way, the basic configuration (1)、(2)、(3)、(4) The present invention, which is based on the above, 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 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] ). (1)、(2)、(3)、(4) In the case where the concentration of carbon dioxide in the air in contact with the liquid hydrocarbons is adjusted to within the range of 430 ppm to 2000 ppm, the proportion of liquid hydrocarbons further synthesized can be set to 20 to 30%.

[0019] In addition to this efficient synthesis of liquid hydrocarbons, (1)、(2)、(3)、(4) In this method, the water in the reaction vessel is made to be in a fluidized state, thereby making it possible to increase the production of liquid hydrocarbons.

[0020] The reason for this increased production will be explained as follows: when the water is stationary and not flowing, the travel distance of the bubbles of the mixed gas of carbon dioxide and air or the bubbles of carbon dioxide and air in the reaction tank until they reach the layer of liquid hydrocarbons is merely the difference in height between the position at which each bubble flows in and the position at which the liquid hydrocarbons are present.

[0021] On the other hand, when the water is flowing, the bubbles move horizontally together with the water, increasing the distance they travel before reaching the liquid hydrocarbon layer.

[0022] Furthermore, when the bubbles move together with the water, the volume of the bubbles decreases due to the pressure generated by the water flow, and the time it takes for the bubbles to reach the liquid hydrocarbon layer also increases.

[0023] In this way, the increase in the travel distance and travel time of each bubble can be considered to be essentially the same as a state in which the volume of the reaction vessel has increased. The fact that an increase in the travel distance and travel time causes an increase in the chance of reactions leading to the synthesis of liquid hydrocarbons will be described later in accordance with specific mathematical formulas and further with the reaction formulas leading to the synthesis of liquid hydrocarbons.

[0024] Furthermore, the basic configuration (1)、(2)、(3)、(4) In the synthesis of a given liquid hydrocarbon in the above process, 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 function of plants. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a block diagram showing each operating state common to the methods of basic configurations (1), (2), (3), and (4). [Figure 2] 1A and 1B are schematic diagrams showing the supply of air, carbon dioxide, and a gas mixture, and the flow of water, which are common to basic configurations (1), (2), (3), and (4). (a) shows an embodiment in which a supply source that supplies a gas mixture of carbon dioxide and air from the bottom and / or side of the reaction tank is used, and the amount of air mixed in is adjusted. (b) shows an embodiment in which supply sources that supply carbon dioxide and air from the bottom and side of the reaction tank, respectively, and air is supplied above the reaction tank, and the supply amounts are adjusted. (c) shows an embodiment in which supply sources that supply carbon dioxide and air from the side and bottom of the reaction tank, respectively, and air is supplied above the reaction tank, and the supply amounts are adjusted. In (a), (b), and (c), the spots in the reaction tank indicate the layer of liquid hydrocarbons formed by synthesis, and the arrows indicate the direction of water flow. [Figure 3] This is a horizontal side view showing the basic configuration (1), where the arrow indicates the direction of water flow. [Figure 4] This is a horizontal cross-sectional view of the basic configuration (2). The arrow indicates the direction of water flow. [Figure 5] The figure shows the basic configuration (3), where (a) is a horizontal side view and (b) is a vertical cross-sectional view. The arrows indicate the direction of water flow. [Figure 6]10A and 10B are cross-sectional views showing the basic configuration (4), where (a) shows the case where the bottom surface of the reaction vessel is parallel to the horizontal direction, and (b) shows the case where the bottom surface of the reaction vessel is inclined to the horizontal direction. The arrows indicate the direction of water flow. DETAILED DESCRIPTION OF THE INVENTION

[0026] Basic configuration The common operating configurations for (1), (2), (3), and (4) are: As shown in the block diagram of Figure 1, this is a method for synthesizing liquid hydrocarbons (HC) by reducing carbon dioxide and water (W) to carbon monoxide and hydrogen via a photocatalyst in a reaction vessel (1) containing water (W) in which continuously supplied carbon dioxide is dissolved and which is mixed with liquid hydrocarbons (HC), and then synthesizing the liquid hydrocarbons (HC) through a chemical reaction between the carbon monoxide and the hydrogen via the photocatalyst. Bubbles of a mixed gas (M) of carbon dioxide and air (A) are supplied from the bottom and / or side of the reaction vessel (1), or bubbles of carbon dioxide and bubbles of air (A) are supplied from the bottom and side of the reaction vessel (1), respectively, 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) which has passed through the layer. In this method for synthesizing liquid hydrocarbons (HC), the water (W) in the reaction vessel (1) is fluidized.

[0027] Basic configuration The common device configurations for (1), (2), (3), and (4) are:As shown in the schematic diagrams of Figures 2(a), (b), and (c), this is an apparatus for synthesizing liquid hydrocarbons (HC) in a layered form in an upper region of the reaction tank 1, in which carbon dioxide, which is continuously supplied to the bottom and / or side of the reaction tank 1 and water W mixed with liquid hydrocarbons (HC), is reduced to carbon monoxide and hydrogen in the water W via a photocatalyst, and the carbon monoxide and hydrogen undergo a chemical reaction via the photocatalyst. The apparatus is provided with a photocatalytic means having the photocatalyst in the reaction tank 1, and is connected to a supply source 2 of a mixed gas M of carbon dioxide and air A at the bottom and / or side of the reaction tank 1, or to a carbon dioxide supply source 3 and an air supply source 4 at the bottom and side of the reaction tank 1, respectively, or is connected to a carbon dioxide supply source 3 and an air supply source 4 at the side and bottom of the reaction tank 1, respectively, and is equipped with a flow mechanism for the water W in the reaction tank 1.

[0028] Basic configuration (1)、(2)、(3)、(4) In the above, both a case where bubbles of a mixed gas M of carbon dioxide and air A are supplied from the bottom and / or side of the reaction vessel 1, and a case where bubbles of carbon dioxide and bubbles of air A are supplied from the bottom and side of the reaction vessel 1, respectively, or from the side and bottom of the reaction vessel 1, respectively, are included, but usually, in consideration of efficient synthesis of liquid hydrocarbons HC, the former is often adopted.

[0029] Basic configuration (1)、(2)、(3)、(4) In the above, the continuous supply of carbon dioxide is a technical premise for the production of liquid hydrocarbons (HC), but as already pointed out in the section on effects, the following technical basis can be presumed to be 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.

[0030] 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.

[0031] 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 the 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 has not yet been fully elucidated.

[0032] 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.

[0033] Basic configuration (1)、(2)、(3)、(4) The reason why increased production of liquid hydrocarbons HC can be realized by fluidizing the water in the reaction vessel 1 is as follows.

[0034] When the distance traveled by the bubbles of the mixed gas M of carbon dioxide and air A or the bubbles of the mixed gas of carbon dioxide and water in the horizontal direction due to the flow of water is L, and the distance from the bottom of the reaction vessel 1 to the lowest layer of liquid hydrocarbons HC in the reaction vessel 1 is H, the distance traveled by each of the bubbles to reach the lowest layer of liquid hydrocarbons HC is: The file is TIFF2025115797000010.tif1430.

[0035] That is, each of the moving distances is, relative to the distance H when there is no flow, TIFF2025115797000011.tif2234x increase. Moreover, since the bubbles move horizontally in accordance with the flow of water, viscous resistance occurs between the bubbles and the water, and the time it takes for the bubbles to reach the lowest layer of liquid hydrocarbons HC from the bottom of the reaction vessel 1 also increases by the amount of this increased viscous resistance.

[0036] To be more specific, When the water W in the reaction tank 1 is not moving, the volume of each bubble is V, the speed at which the bubbles rise is u, the gravitational constant is g, and the viscosity coefficient of the water W and the bubbles is μ. Since the flow speed at which the water W rises is constant, the buoyancy and viscous resistance on the bubbles are approximately equal. F=ρVg-kμu≒0 holds true. where ρ is the density of water, V is the volume of the bubble, g is the gravitational constant, μ is the viscosity coefficient between the bubble and water, u is the speed at which the bubble rises, and k is a proportionality constant. Therefore, u≈ρVg / (kμ) holds.

[0037] When each bubble flows together with the water W due to viscous resistance with the water W, it is assumed that there is a difference in speed between the water W and the bubble. Therefore, the flow velocity of each bubble is not the same as the flow velocity of the water W, but is smaller than that velocity, and therefore each bubble is subjected to pressure in the flow direction by the water W, resulting in a decrease in volume V. That is, the rising speed of the bubbles decreases due to the decrease in volume V. In the reduction of the volume V, the bubbles are deformed from their original spherical shape to a substantially elliptical shape.

[0038] In this way, since the rising speed of the bubbles becomes smaller due to the flow of water, the time it takes for the bubbles to reach the lowest layer of liquid hydrocarbons HC from the bottom of the reaction vessel 1 also increases compared to when the bubbles are not flowing together with the water W.

[0039] In this way, since the movement distance and rising time of each bubble increases due to the flow of each bubble and water W, the reaction formulas (1) and (2) above are more likely to occur than when the bubbles are not flowing together with the water W.

[0040] In order to smoothly advance the reaction formulas (1) and (2), the flow of water W is basically a laminar flow. However, in the case of turbulent flow, which has a flow velocity greater than that of laminar flow, the bubbles travel a longer distance and take longer to reach the bottom layer of liquid hydrocarbons HC from the reaction vessel 1. However, in the case of turbulent flow, it is unclear whether or not the establishment of the reaction equations (1) and (2) above will be hindered. However, if the degree of turbulence is low, it cannot be denied that there may be no hinderance.

[0041] Considering this situation, the basic configuration (1)、(2)、(3)、(4) In the case of turbulent flow, it will be necessary to consider in the future what flow velocity of turbulent flow can be adopted, based on the Reynolds number (Re).

[0042] 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.

[0043] 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.

[0044] However, in reality, the reactions of the above formulas (1) and (2) are not promoted as the concentration of carbon dioxide increases. It has been found that when the concentration of carbon dioxide above the interface exceeds a certain level, the generation of liquid hydrocarbons (HC) may actually decrease.

[0045] 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.

[0046] 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.

[0047] It assumes a continuous supply of carbon dioxide The reaction formula In (1) and (2), 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 supplying air A.

[0048] 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 contrast, The reaction formula In the cases of (1) and (2), 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).

[0049] 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 generates molecular vibrations in the water W at frequencies orders of magnitude greater than thermal vibrations, and that the thermal vibrations that affect the water temperature have almost no effect on the molecular motions.

[0050] Basic configuration (1)、(2)、(3)、(4) In the synthesis method of Supplied mixed with carbon dioxide or alone An embodiment for adjusting the amount of supplied air A can be adopted, and in this case, a corresponding device is provided at the bottom and / or side as shown in FIG. 2(a). Supplied mixed with carbon dioxide or alone It is provided with a supply amount adjusting device 5 for the supplied air A. However, Figure 2(a) Carbon dioxide and This shows the case where a supply amount adjusting device 5 is used for the air A before it is mixed.

[0051] 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.

[0052] Basic configuration (1)、(2)、(3)、(4) In the synthesis method of (1), 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 is provided with an air supply source 4 and a supply amount adjusting device 5 above the reaction vessel 1, as shown in Figures 2(b) and (c).

[0053] 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.

[0054] In the above embodiment, a configuration is adopted in which the carbon dioxide concentration is measured above the upper interface, and in an apparatus corresponding to this embodiment, if a configuration is adopted in which a carbon dioxide concentration measuring device 6 is provided above the reaction tank 1 as shown in Figures 2(a), (b), and (c), an accurate carbon dioxide concentration can be set.

[0055] Basic configuration (1)、(2)、(3)、(4) In the case of the liquid hydrocarbon HC, 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 hydrocarbon HC, and the corresponding device in this case is one in which one or more filters are installed in the layer of liquid hydrocarbon HC.

[0056] In the case of the above embodiment, at the stage when the bubbles pass through the layer of liquid hydrocarbons HC, the bubbles generate a mixed gas M of carbon dioxide and air A at a considerable ratio, and as a result of the slowing down of the movement speed of the bubbles as described above, the contact time between the liquid hydrocarbons HC and the bubbles in the mixed state increases, thereby promoting the synthesis efficiency of the liquid hydrocarbons HC. Furthermore, when the resistance element and the filter are placed in the water W below the layer of liquid hydrocarbons HC, it is possible to promote the mixing of the supplied air A bubbles with the carbon dioxide bubbles without generating the mixed gas M.

[0057] Basic configuration (1)、(2)、(3)、(4) In the above, an embodiment can be adopted in which oxygen-containing water W in which nanobubbles are 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 are formed is connected to the bottom and / or side of the reaction tank 1.

[0058] 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.

[0059] Basic configuration (1)、(2)、(3)、(4) In the above, an embodiment can be adopted in which 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 in this case is provided in water W equipped with an ultrasonic vibration device, and 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 the reaction tank 1.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] Basic configuration (1)、(2)、(3)、(4) In the above, an embodiment can be adopted in which the concentration of carbon dioxide in the mixed gas M to be supplied is 430 ppm to 2000 ppm by previously adjusting the concentration of carbon dioxide in the mixed gas M to be supplied or by previously adjusting the ratio of the carbon dioxide and air A to be supplied, and in the above device, the above concentration can be achieved by providing a shielding plate on the upper side of the reaction tank 1 to block the rise of the mixed gas M of carbon dioxide and air A.

[0064] In the case of the above embodiment, the carbon dioxide concentration is set to a concentration considerably higher than 430 ppm, which is approximately equal to that at atmospheric pressure, in the entire region of the reaction vessel, and thus the reactions (1) and (2) can be promoted individually. In particular, when a configuration is adopted in which a predetermined gap is provided in the shielding plate and the size of the gap can be adjusted, the concentration can be appropriately selected by adjusting the gap.

[0065] Basic configuration (1)、(2)、(3)、(4) In this case, an embodiment characterized by irradiating the dissolved oxygen with ultraviolet light can be adopted, and the corresponding device is equipped with an ultraviolet light irradiating device for irradiating the oxygen dissolved in the reaction tank 1.

[0066] 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.

[0067] 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)

[0068] Below is the basic configuration (1)、(2)、(3)、(4) About individually explain.

[0069] As shown in Figure 3, the basic configuration (1) In the reactor 1, a rotating shaft is provided at the horizontal center position of the reactor 1, and a flow state of the water W is formed by a rotating blade 7 that rotates near the bottom of the reactor 1. is doing .

[0070] Basic configuration (1) In the above, there is a technical advantage in that the flow of water W is achieved by a simple configuration of a single rotating blade 7, but the reason for providing the rotating blade 7 near the bottom of the reaction tank 1 is to avoid disturbing the reaction formulas (1) and (2) within the reaction tank 1 as much as possible.

[0071] Basic configuration (1) In particular, when a configuration is selected in which the rotation range of the rotating blades 7 extends to the vicinity of the inside of the wall of the reaction vessel 1, a fluidized state can be ensured in the entire area of the reaction vessel 1, which can contribute to efficiently increasing the production of liquid hydrocarbons HC.

[0072] As shown in Figure 4, the basic configuration (2) In this case, the wall of the reaction vessel 1 to Outward protruding area Set one or more 10s and Near the inside of the protruding region 10 The water W is made to flow by the screw or rotating blades 7 provided in the is doing . FIG. 4 shows a case where a screw is used to achieve a fluidized state.

[0073] Basic configuration (2) In the Near the inside of the protruding region 10 By providing for the above, the influence on the reaction formulas (1) and (2) can be reduced by: Basic configuration (1) There is a technical advantage in that it can be reduced to a smaller state than in the case of the protruding region The vertical range of the area in 10 is not specified. That is, it is possible to extend the reactor from the bottom of the reactor 1 to near the lowest layer of the liquid hydrocarbon HC layer. However, in a wide area in the vertical direction The protruding region 10 When a screw or a rotary blade 7 is provided, the protruding region It is advisable to provide a plurality of such devices in the vertical direction within 10.

[0074] As shown in Figure 4, Basic configuration (2) In the screw or the rotor blade 7, The inner wall of the reactor is curved toward the outward protruding region 10 of the reactor wall. When a configuration characterized by the provision of the screw or rotary blade 7 is selected, it is also possible to minimize the influence of the screw or rotary blade 7 on the reaction formulas (1) and (2).

[0075] Figure 5 (a) The basic configuration, as shown in (3) In this case, bubbles of a mixed gas M of carbon dioxide and air A, or bubbles of carbon dioxide and air A are introduced onto the wall of the reaction vessel 1. surface From one or more points along Forming a fluid state of water W .

[0076] Basic configuration (3) In the above, there is a technical advantage in that it is possible to supply a mixed gas M of carbon dioxide and air A or carbon dioxide and air A to the reaction tank 1 and to flow water W at the same time, but in order to achieve a uniform flow state, it is preferable to provide multiple jet locations and jet devices. In order to set the jet direction to the wall position or its vicinity, 5As shown in (a), it is advisable to use a pipe that communicates from the outside to the inside and runs along the above direction. In the basic configuration (3), as shown in Figure 5(b), an embodiment can be adopted in which the jet direction of each bubble is inclined downward from the horizontal, resulting in each bubble colliding with the bottom and wall surfaces.

[0077] As shown in Figure 6(a) and (b), the basic configuration (4) In this case, the bottom of the reaction tank 1 is made parallel to the horizontal direction or inclined to the horizontal direction, and a flow state of the water W is formed, and a flow state of the water in the reaction tank is formed by circulating the water W from the lower outlet to the upper inlet of the reaction tank 1 using a pump P. is doing .

[0078] Basic configuration (4) Also, the flow of water W can be realized by a simple configuration using a pump P for circulation. However, if the bottom of the reaction tank 1 is horizontal, the pump reflux is the cause of the flow, but if the bottom of the reaction tank 1 is inclined, the flow within the reaction tank is achieved by the inclination, so the pump reflux does not necessarily have to be the cause of the flow, and it is also possible to design it so that it simply serves to return water from the outlet to the inlet of the reaction tank.

[0079] The following will explain the present invention based on examples. [Example]

[0080] Example 1 is a basic configuration (1)、(2)、(3)、(4) In this method, the liquid hydrocarbons HC and the water W in a mixed state flow into the reaction vessel 1.

[0081] 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]

[0082] Basic configuration (1)、(2)、(3)、(4)The present invention, based on the above, efficiently synthesizes liquid hydrocarbons by contacting the entire surface of the bubbles with a gas mixture of carbon dioxide and air in the layer in which liquid hydrocarbons are produced, and further by contacting the gas mixture of carbon dioxide and air with the upper interface of the layer, and then, by facilitating the occurrence of the reactions (1) and (2) by the state of water flow, thereby achieving a significant advantage in that it is possible to increase the production of liquid hydrocarbons, and is of great industrial value. [Explanation of symbols]

[0083] W water A. Air HC Liquid hydrocarbons (abbreviation for hydrocarbon) M: A mixture of carbon dioxide and air P pump 1 Reaction vessel 10 Protruding areas on the reactor wall 11 Circulation pipe 2. Source of carbon dioxide and air mixture 3. Sources of carbon dioxide 4. Air supply source 5 Supply amount adjustment device 6. Carbon dioxide concentration measuring equipment 7 Rotating blades or screws

Claims

1. 1. 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 through 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 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 that has passed through the layer; and a method for increasing the production of liquid hydrocarbons by fluidizing the water in the reaction vessel.

2. 2. The method for increasing the production of liquid hydrocarbons according to claim 1, wherein a rotating shaft is provided at the horizontal center of the reaction vessel, and a fluidized state of the water is created by rotating blades near the bottom of the reaction vessel.

3. 3. The method for increasing the production of liquid hydrocarbons according to claim 2, wherein the rotation range of the rotor blades extends to the vicinity of the inside of the wall of the reaction vessel.

4. 2. The method for increasing the production of liquid hydrocarbons according to claim 1, wherein one or more bypasses are provided by protruding outward from the wall of the reaction vessel, and a fluidized state of the water is created by a screw or a rotating blade provided in the bypass.

5. 3. The method for increasing the production of liquid hydrocarbons according to claim 2, wherein an inner wall is provided inside the screw or rotary blades, and an inlet and an outlet of the bypass are formed between the inner wall and the outer wall.

6. 2. The method for increasing production of liquid hydrocarbons according to claim 1, wherein the water is made to flow in a fluidized state by jetting either bubbles of a mixed gas of carbon dioxide and air, or bubbles of carbon dioxide and air, from one or more locations along the inside of the wall of the reaction vessel or in the vicinity thereof.

7. 5. The method for increasing production of liquid hydrocarbons according to claim 4, wherein the direction of the jet of bubbles is inclined downward from the horizontal direction.

8. 2. The method for increasing production of liquid hydrocarbons according to claim 1, wherein the bottom of the reaction tank is parallel to the horizontal direction or inclined relative to the horizontal direction, and a flow state of water in the reaction tank is created by circulating water from the lower outlet to the upper inlet of the reaction tank using a pump.

9. 7. The method for increasing production of liquid hydrocarbons according to claim 6, wherein, when the bottom of the reaction vessel is inclined, the inclination direction of the flowing water surface and the inclination direction of the bottom of the reaction vessel are the same.

10. 9. The method for increasing the production of liquid hydrocarbons according to any one of claims 1, 2, 4, 6 and 8, characterized in that the amount of air mixed or supplied at the bottom and / or side is adjusted.

11. 9. The method for increasing production of liquid hydrocarbons according to claim 1, wherein air is fed to the upper side of the upper interface and the amount of air fed is adjusted.

12. 9. The method for increasing production of liquid hydrocarbons according to claim 1, wherein a resistance element for reducing the movement speed of the bubbles is provided in the layer of liquid hydrocarbons.

13. 9. The method for increasing production of liquid hydrocarbons according to any one of claims 1, 2, 4, 6, and 8, characterized in that oxygen-containing water in which nanobubbles have been formed by ultrasonic vibrations is supplied to the bottom and / or side of the reaction tank.

14. 9. The method for increasing production of liquid hydrocarbons according to any one of claims 1, 2, 4, 6, and 8, characterized in that 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 the reaction tank.

15. 9. The method for increasing liquid hydrocarbon production according to any one of claims 1, 2, 4, 6 and 8, wherein the concentration of carbon dioxide in the mixed gas to be supplied is adjusted to 430 ppm to 2000 ppm by adjusting the concentration of carbon dioxide in the mixed gas to be supplied or by adjusting the ratio of carbon dioxide and air to be supplied.

16. 9. The method for increasing the production of liquid hydrocarbons according to any one of claims 1, 2, 4, 6 and 8, characterized in that the dissolved oxygen is irradiated with ultraviolet light.

17. 9. The method for increasing production of liquid hydrocarbons according to claim 1, wherein the liquid hydrocarbons and the water are in a mixed state and flow into a reaction vessel.

Images