JP2021096064A - Method for recycling organic solvent waste fluid as fuel and organic solvent waste fluid recycling process system used for method for recycling organic solvent waste fluid as fuel - Google Patents

Abstract

To provide a method for recycling organic solvent waste fluid as fuel, which can efficiently recover energy.SOLUTION: A method for recycling organic solvent waste fluid as fuel includes: an oxidation process of oxidizing metallic particles in an oxidation tower to obtain oxidized metallic particles; a reduction process of generating carbon dioxide from organic solvent waste fluid by causing the oxidized metallic particles to react with the organic solvent waste fluid in a reduction tower and obtaining metallic particles by reducing the oxidized metallic particles; and a circulation process of circulating the metallic particles and the oxidized metallic particles between the oxidation tower and the reduction tower.SELECTED DRAWING: Figure 1

Description

The present invention relates to an organic solvent waste liquid recycling treatment system used in a method of recycling organic solvent waste liquid as fuel and a method of recycling organic solvent waste liquid as fuel.

A part of the organic solvent waste liquid is recovered and reused, but most of it is incinerated. Incineration is costly _{and releases the CO 2} produced by incineration into the atmosphere, which has an adverse effect on the environment.

Patent Document 1 proposes a system that recovers energy from the retained heat while directly treating an organic solvent waste liquid that is a source of odorous gas by using a gas turbine.

Japanese Unexamined Patent Publication No. 2004-184003

In the deodorizing / disposal apparatus described in Patent Document 1, _{no consideration is given to CO 2} generated by the combustion of the organic solvent waste liquid gas, and there is still room for improvement from the viewpoint of energy efficiency.

The present invention has been made in view of the above circumstances, and provides an organic solvent waste liquid recycling treatment system used in a method of recycling an organic solvent waste liquid that can efficiently recover energy as a fuel and a method of recycling an organic solvent waste liquid as a fuel. The challenge is to provide it.

An oxidation step of oxidizing metal particles in an oxidation tower to obtain metal oxide particles, and a reaction of the metal oxide particles with an organic solvent waste liquid in a reduction tower to generate carbon dioxide from the organic solvent waste liquid and the oxidation. An organic solvent waste liquid characterized by having a reduction step of reducing metal particles to obtain metal particles and a circulation step of circulating the metal particles and metal oxide particles between the oxidation tower and the reduction tower. It is a method of recycling as fuel.

A second aspect of the present invention is an oxide tower in which metal particles react with an oxidizing agent to generate metal oxide particles, and the metal oxide particles generated in the oxide tower react with an organic solvent waste liquid to form the organic substance. Carbon dioxide is generated from the solvent waste liquid, and the metal oxide particles circulate between the oxidation tower and the reduction tower while being oxidized and reduced. It is an organic solvent waste liquid recycling treatment system used in a method of recycling an organic solvent waste liquid as a fuel, which comprises a circulation flow path and a chemical loop combustion unit provided with the chemical loop combustion unit.

According to the present invention, it is possible to provide an organic solvent waste liquid recycling treatment system used in a method of recycling an organic solvent waste liquid as a fuel that can efficiently recover energy and a method of recycling an organic solvent waste liquid as a fuel.

It is the schematic which shows an example of the organic solvent treatment system of this embodiment. It is the schematic which shows an example of the organic solvent treatment system of this embodiment. It is the schematic which shows an example of the culture unit in this embodiment.

<Organic solvent treatment system>
Hereinafter, the organic solvent treatment system of the present embodiment will be described with reference to the drawings. The present embodiment is not limited to the following.

(First Embodiment)
In the organic solvent treatment system A1 of the present embodiment, as shown in FIG. 1, the oxide tower 1 in which the metal particles react with the oxidizing agent to generate the metal oxide particles and the metal oxide particles generated in the oxide tower 1 are formed. It is provided with a reduction tower 3 in which carbon dioxide is generated from the organic solvent by reacting with the organic solvent and the metal oxide particles are reduced to the metal particles, and the metal particles are oxidized while undergoing oxidation and reduction. The chemical loop combustion unit A10 is provided so as to circulate between the tower 1 and the reduction tower 3.

The chemical loop combustion unit A10 in the present embodiment is provided with one reduction tower 3 inside the oxidation tower 1. The oxidation tower 1 is a cylindrical outer tower made of a heat-resistant material such as a steel plate. The upper end surface of the oxidation tower 1 is also closed by a top plate 2 made of a heat-resistant material such as a steel plate. In the oxidation tower 1, a reduction tower 3 having the same central axis and a diameter smaller than that of the oxidation tower 1 is installed. The reduction tower 3 is a circular tower body. The upper end of the reduction tower 3 penetrates the top plate 2 and extends to the outside of the oxidation tower 1, and the lower end reaches the vicinity of the lower end of the oxidation tower 1.

A circular tower-shaped air header 4 forming a concentric circle with the oxide tower 1 is attached to the lower end of the oxide tower 1, and the upper end of the air header 4 is an air nozzle 5. The air header 4 is connected to the blower 6, and the air pressure regulated through the flow meter 7 and the pressure regulating valve 8 is sent to the air header 4 and ejected from the air nozzle 5 into the oxide tower 1. As will be explained later, this air functions as an oxidant.

A tower-shaped fuel nozzle 9 is arranged at a position in the center of the air header 4 facing the lower end of the reduction tower 3 so as to maintain a predetermined gap in the vertical direction. The inner diameter of the fuel nozzle 9 is slightly smaller than the inner diameter of the lower end of the reduction tower 3. An organic solvent is supplied to the fuel nozzle 9 through a shutoff valve 10, a pressure regulating valve 11, and a check valve 12, and is ejected toward the lower end opening of the reduction tower 3. As will be described later, this organic solvent functions as a reducing agent.

In this example, a gap is provided between the fuel nozzle 9 and the air header 4 surrounding the outside thereof, and a tower-shaped separate gas nozzle 13 is arranged in the gap. The separate gas nozzle 13 is supplied with an oxygen-free inert gas _{such as N 2} gas and CO _{2 gas through the pipe 14.}

A circular tower-shaped lower header 15 is attached to the bottom of the oxidation tower 1 so as to surround the outside of the air header 4 described above. The bottom surface of the lower header 15 is a horizontal plane, but the upper surface is a conical surface 16, and the lower end of the conical surface is substantially the same surface as the air nozzle 5. The outer peripheral surface of the lower header 15 is in contact with the inner peripheral surface of the oxide tower 1, and the first fluid pipe 18 through which the fluid to be heated flows through the hole 17 formed in the wall surface of the oxide tower 1 is the outer peripheral surface of the lower header 15. Is connected to.

A circular tower-shaped upper header 19 is attached above the oxidation tower 1 so as to be in contact with the top plate 2. The inner diameter and outer diameter of the upper header 19 are substantially the same as the inner diameter and outer diameter of the lower header 15. A second fluid pipe 21 of the fluid to be heated is connected to the upper header 19 through a hole 17 formed in the top plate 2 of the oxide tower 1. In this example, the second fluid pipe 21 communicates with the heat load unit 100 of an on-site steam utilization facility, an industrial furnace, or the like.

A heat-resistant wall 22 made of a heat-resistant material such as a heat-resistant roof tile or a heat-resistant ceramic fiber is formed along the inner wall of the oxide tower 1 from the upper conical surface 16 of the lower header 15 to an appropriately upper position. The upper end surface of the heat-resistant wall 22 is a conical wall 23. An intermediate header 24 having a slanted plate shape as a whole is attached so that the lower end surface of the heat-resistant wall 22 is aligned with the upper end conical wall 23, and the inner and outer diameters of the intermediate header 24 are the lower header 15 and the inner diameter. Is almost equal to the outer diameter. Then, at a position slightly above the position where the intermediate header 24 is attached, the solid air separating device 25 is attached to the reduction tower 3.

A plurality of heat transfer tubes 26 are attached in parallel with the central axis of the oxide tower 1 so that the internal spaces of the lower header 15, the intermediate header 24, and the upper header 19 communicate with each other. In the figure, the plurality of heat transfer tubes 26 are arranged in a plurality of rows in the radial direction so that each example is composed of a plurality of heat transfer tubes, but the heat transfer tubes 26 are arranged in the oxide tower 1. Is optional, and as will be described later, it may be appropriately arranged on the condition that it does not interfere with the flow of the metal particles contained in the oxidation tower 1.

The lower header 15, the intermediate header 24, and the upper header 19 are made of a material having excellent heat resistance, and the heat transfer tube 26 is made of a material / shape having excellent heat resistance and thermal conductivity. Further, as will be described later, in the heat transfer tube 26, a portion located between the lower header 15 and the intermediate header 24 and a portion located between the intermediate header 24 and the upper header 19 are made of different materials. Is desirable.

An exhaust port 27 is provided in the upper part of the oxidation tower 1, and the exhaust gas from the exhaust port 27 (as described later, N ₂ is the main component and a _{small amount of O 2} is contained) is passed through the solid air separator 28 to the outside air. Is exhausted to.

The above configuration is necessary for the chemical loop combustion unit A10 in the present embodiment to operate, but the chemical loop combustion unit A10 further includes the following piping system in order to perform more efficient operation.

The exhaust gas from the exhaust port 27 passes through the solid air separator 28 and then through the heat exchanger 29. _{Then, the N 2} gas that has passed through the heat exchanger 29 is stored in a storage tank (not shown). When necessary, _{a part of the mixed gas of N 2} and O ₂ is boosted by the blower 30 and sent from the pipe 14 to the separator gas nozzle 13 through the shutoff valve 31 and the pressure regulating valve 32.

Exhaust gas discharged from the upper part of the reduction tower 3 (CO ₂ and H ₂ O steam as described later) flows into the air-water separation device 33 in which cooling water from the outside circulates, and the steam is liquefied. After separation, the exhaust gas containing 90% or more of CO ₂ is discharged to the outside and stored in a storage tank (not shown). When necessary, a part of the exhaust gas containing 90% or more of CO ₂ is boosted by the blower 34 and sent from the pipe 14 to the separator gas nozzle 13 through the shutoff valve 35 and the pressure regulating valve 32.

The water generated by the steam separator 33 reaches the heat exchanger 29 via the shutoff valve 36 and the pump 37, exchanges heat there, and then passes through the pressure regulating valve 38 and the check valve 39 as necessary. , It is supplied as water vapor in the fuel supply pipeline to the fuel nozzle 9.

The operation of the chemical loop combustion unit A10 described above will be described. In advance, the internal space of the oxidation tower 1 is filled with the metal particles M. The filling amount is such that the metal particles M do not reach the solid air separation device 25 attached to the reduction tower 3. The metal particles M may contain not only metal but also metal oxide particles. Preferred metal particles M include iron (Fe) or iron oxide (FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ). After filling, the metal particles M are preheated to about 600 ° C. by a preheating means such as a preheating burner arranged in the oxide tower or an electric heater attached to the peripheral wall of the oxide tower 1 (not shown). Further, the lower header 15, the intermediate header 24, the upper header 19, all the heat transfer tubes 26, and the first fluid pipe 18 and the second fluid pipe 18 are filled with a solution to be heated, for example, water.

After preheating or during preheating, a predetermined amount of air (which may be air at an ambient temperature) that functions as an oxidant is supplied to the air header 4 and ejected from the air nozzle 5 into the oxidation tower 1. Further, a predetermined amount of an organic solvent that functions as a reducing agent is ejected from the fuel nozzle 9 toward the reducing tower 3. _{Further, an inert gas such as N 2} and CO ₂ is ejected from the separator gas nozzle 13 toward the inside of the oxidation tower 1. At the beginning of the operation, the inert gas is supplied from an external inert gas source or from the inert gas source stored in the storage tank in the system during the previous operation.

The air ejected from the air nozzle 5 flows into the oxidation tower 1, and the organic solvent from the fuel nozzle 9 flows into the reduction tower 3. At that time, in the chemical loop combustion unit A10, the separate gas nozzle 13 is located between the air nozzle 5 and the fuel nozzle 9, and the inert gas is ejected from the separate gas nozzle 13, so that the air and the fuel gas after the ejection are mixed. You can avoid doing it.

In the oxidation tower 1, the metal particles M preheated to the reaction temperature react with oxygen in the supplied air to generate the metal oxide particles MO. At that time, heat is generated by the oxidation reaction of the metal, and the temperature of the metal particles M, the metal oxide particles MO, and the air flowing in the oxide tower 1 rises. However, heat is generated by the oxidation reaction of the metal, and a high temperature portion of 1500 ° C. or higher is not formed, and thermal NO _x is not generated as described above. When the metal particles M include the metal oxide particles MO, the metal oxide particles MO correspond to the metal oxide particles in a form in which the metal oxide particles are further oxidized. For example, when the metal particles M are Fe ₃ O ₄ , the metal oxide particles MO are Fe ₂ O _{3 and the} like.

The metal oxide particles MO and the remaining metal particles M flow down in the oxidation tower 1 and flow into the reduction tower 3, and then rise in the reduction tower 3. In the process of ascending in the reduction tower 3, the metal oxide particles MO are reduced by the organic solvent and return to the metal particles M. In the above chemical loop combustion unit A10, the upper surface 16 of the lower header 15 has a conical surface that becomes lower toward the center, so that the movement of the metal oxide particles MO from the bottom of the oxidation tower 1 to the reduction tower 3 is Proceed smoothly. Further, the solid component and the gas component rising in the reduction tower 3 are separated into a solid and a gas by the action of the solid air separation device 25 in the process of rising, and the gas further rises from the upper part of the reduction tower 3. It is exhausted. The solid, that is, the metal particles M and the remaining metal oxide particles MO are returned to the inside of the oxidation tower 1.

In the oxidation tower 1, the metal particles M are brought into a fluidized state by the action of the air ejected from the air nozzle 5, so that the metal particles M or a part of the oxide MO thereof is more than when it was initially stored. It can happen that it soars upwards. In the chemical loop combustion unit A10, the heat-resistant wall 22 is formed on the inner wall surface below the oxidation tower 1, so that the heat-resistant wall 22 is above the horizontal cross-sectional area of the region where the heat-resistant wall 22 is formed. The horizontal cross-sectional area of the area where is not formed is large. Therefore, the metal particles M or the oxide MO thereof that have soared into the space higher than the vicinity of the solid air separation device 25 have a small superficial velocity and are likely to fall downward. Further, the metal particles M or the oxide MO thereof that has fallen on the upper surface of the intermediate header 24 surely falls downward along the surface of the intermediate header 24 because the upper surface of the intermediate header 24 has a conical surface. Therefore, it is possible to facilitate the oxidizing action of the metal particles M and suppress the discharge of the metal particles from the exhaust port 27 at the upper part of the oxidation tower 1. Although not shown, the metal particles discharged from the exhaust port 27 at the upper part of the oxide tower 1 are separated by the solid air separation device 28 and returned to the inside of the oxide tower 1 when necessary.

On the other hand, the heat generated by the oxidation of the metal particles M in the oxidation tower 1 is transmitted to the heated fluid flowing in the heat transfer tube 26 through the wall surface of the heat transfer tube 26, and heats the heated fluid. That is, in the chemical loop combustion unit A10, the heat of the metal particles M generated by the oxidation reaction is transferred to the gas (input air) and at the same time directly exchanged with the heat transfer tube 26 located in the metal particles M. , The exhaust gas temperature does not rise significantly. Therefore, _{the generation of NO x} can be further suppressed. In addition, the average temperature of the gas (input air) in the oxide tower 1 is also lowered, whereby the superficial velocity is suppressed, so that the cross-sectional area of the oxide tower 1 can be reduced. As a result, the device can be miniaturized, the surface area per combustion amount can be suppressed, and the heat dissipation loss can be reduced.

In the chemical loop combustion unit A10, the region below the intermediate header 24 is a region in which metal particles are stored, and in that region, the heat transfer tube 26 receives a lot of frictional wear due to contact with the metal particles. On the other hand, the region above the intermediate header 24 is a region where gas is mainly present, and the frictional wear of the heat transfer tube 26 is small. Therefore, the material of the heat transfer tube 26 is a material having excellent wear resistance in the portion located between the lower header 15 and the intermediate header 24, and is compared in the portion located between the intermediate header 24 and the upper header 19. It can be a material with low wear resistance. Cost reduction is possible by using such different materials.

The fluid to be heated, which is heated by heat exchange in the oxidation tower 1, circulates from the upper header 19, the second fluid pipe 18, the heat load unit 100, and the first fluid pipe 18, and returns to the lower header 15. come. The circulation of the heated fluid to be heated may be reversed.

By contributing to the oxidation reaction in the oxidation tower 1, the input air becomes high-temperature exhaust gas and is discharged from the exhaust port 27. Exhaust gas, depending on the supply amount of air, a high concentration of N ₂ Gasuka containing no O _2, a gas containing residual O ₂ and N _2. As described above, the exhaust gas passes through the solid air separator 28 and the heat exchanger 29, and then _{is sent to an N 2} storage tank tower (not shown) for storage, but some N ₂ is boosted by the blower 30 and shut off. It is sent from the pipe 14 to the separator gas nozzle 13 through 31 and the pressure regulating valve 32.

On the other hand, the exhaust gas from the reduction tower 3 is composed of CO ₂ and H ₂ O generated by the reduction reaction, and since it is a high temperature gas, H ₂ O is water vapor. The exhaust gas from the reduction tower 3 is condensed by the brackish water separation device 33 in which the cooling water is circulated and separated into water and a gas containing a _{high concentration (90% or more) of CO 2.} The obtained CO ₂ gas is further concentrated by appropriate means if necessary, and then stored as it is _{or as liquefied CO 2.} When _{necessary, a part of the CO 2} gas is boosted by the blower 34 and sent from the pipe 14 to the separator gas nozzle 13 through the shutoff valve 35 and the pressure regulating valve 32. Therefore, in the chemical loop combustion unit A10 shown in FIG. 1, the air supplied from the air nozzle 5 and the fuel gas supplied from the fuel nozzle are separated for the purpose of separating them, except during the initial operation. It becomes possible to self-sufficient the _{inert gas (N 2} or CO ₂ ) to be supplied from the gas nozzle 13.

The water generated by the air-water separation device 33 exchanges heat with the high-temperature exhaust gas from the oxide tower 1 in the heat exchanger 29 to become steam, and when necessary, the steam passes through the pressure regulating valve 38 and the check valve 39 and is a fuel gas. Is mixed in. By requiring the supply of water vapor, it is possible to efficiently proceed the reduction reaction even when a relatively inexpensive metal particle material such as Fe is used. Further, it is possible to efficiently proceed the reduction reaction of the metal oxide even with an organic solvent.

In the above example, the first fluid line 18 and the second fluid line 21 have been described as being discontinuous, but depending on the type and form of the heat load unit 100, the first fluid line 18 A continuous circulation path may be formed between the heat load section 100 and the second fluid line 21. In any case, it is explained that the same effect can be obtained even if the entire pipeline system is configured with the second fluid pipeline 21 as the inflow side and the first fluid pipeline 18 as the outflow side. I don't need it.

In addition, a plurality of reduction towers may be provided inside the oxidation tower. An air header, an air nozzle, a fuel nozzle, a separate gas nozzle, and the like may be arranged at the lower end of the oxidation tower so as to correspond to each reduction tower.
Further, instead of the reduction tower being provided inside the oxidation tower, the reduction tower and one oxidation tower may be provided inside. Further, a plurality of oxidation towers may be provided inside the reduction tower, and an air header, an air nozzle, a fuel nozzle, a separate gas nozzle, etc. are provided at the lower end of the reduction tower so as to correspond to each oxidation tower. May be arranged.

Further, the oxidation tower and the reduction tower may be separated, and both may be connected by a flow path in which the oxidized metal particles MO move and a flow path in which the reduced metal particles M move.

Further, air (oxidizing agent), organic solvent (reducing agent), and separate gas (inert gas) may be supplied from the oxidation tower and the upper part of the reduction tower. Further, the oxidation tower and the reduction tower may be separated, and both may be connected by a flow path in which the oxidized metal particles MO move and a flow path in which the reduced metal particles M move.

(Second Embodiment)
In the organic solvent treatment system A2 of the present embodiment, as shown in FIG. 2, the oxide tower 1 in which the metal particles react with the oxidizing agent to generate the metal oxide particles and the metal oxide particles generated in the oxide tower 1 are formed. It is provided with a reduction tower 3 in which carbon dioxide is generated from the organic solvent by reacting with the organic solvent and the metal oxide particles are reduced to the metal particles, and the metal particles are oxidized while undergoing oxidation and reduction. A chemical loop combustion unit A10 that circulates between the tower 1 and the reduction tower 3 and a culture unit B1 that cultivates algae using carbon dioxide produced from the chemical loop combustion unit A10. Be prepared.
The same components as those of the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.

The exhaust gas from the reduction tower 3 is composed of CO ₂ and H ₂ O generated by the reduction reaction, and since it is a high-temperature gas, H ₂ O is water vapor. The exhaust gas from the reduction tower 3 is condensed by the brackish water separation device 33 in which the cooling water is circulated and separated into water and a gas containing a _{high concentration (90% or more) of CO 2.} The obtained CO ₂ gas is sent to the culture unit B1 via a pipe. In the present embodiment, CO ₂ can be selectively recovered by using the chemical loop combustion unit. In addition, the recovered CO ₂ concentration is extremely high and can be used efficiently.

As shown in FIG. 3, the culture unit B1 includes a mounting table 40, a culture tank 41, a gas blower 42, a bubbling filter 43, a stirring motor 44, a stirring blade 45, a temperature sensor 46, and a control panel 47. It is a device having and. In the culture unit B1, carbon dioxide from the reduction tower 3 is supplied into the culture solution 48 containing algae in the culture tank 41. The shape of the culture unit is not particularly limited, and in addition to the tank type having a stirring function shown in FIG. 3, a shelf type with natural flow, a cloth type, and the like can also be used.

The mounting table 40 supports the culture tank 41 so that the culture tank 41 is located higher than the ground. The material and shape of the mounting table 40 are not particularly limited, but need to have sufficient strength to sufficiently support the culture tank 41 filled with the culture solution 48 and its peripheral devices. The mounting table 40 is provided with a pipe 49 on the bottom surface of the _{culture tank 41 for supplying CO 2 gas into the culture tank 41.}

The culture tank 41 is a tank for photosynthesizing algae. In the culture unit B1, carbon dioxide in the exhaust gas can be consumed by causing the algae to photosynthesize in the culture tank 41, and the algae can be cultured by causing the algae to photosynthesize. The shape of the culture tank 41 is not particularly limited, but a culture tank 41 preferably made of a material having translucency so that light hits the entire culture solution 48.

The capacity of the culture tank 41 is not particularly limited, but it is preferable that the culture tank 41 can accommodate, for example, about several hundred liters of the culture solution 48.

The culture tank 41 contains the culture solution 48. The culture tank 41 is installed higher than the ground by placing it on the mounting table 40, for example. The shape and capacity of the culture tank 41 are not particularly limited, but for example, the culture tank 41 is made of stainless steel and can accommodate about 500 liters of the culture solution 48. The culture solution 48 is supplied to the culture tank 41 by opening the lid 50.

The culture unit B1 is preferably installed in a sunny place. Culturing of algae depends on the culturing environment such as sunshine hours and temperature, and is preferably performed in a warm area, but culturing in a distant place requires transportation cost. In the present embodiment, the temperature of B1 is adjusted by using the heat load unit 100 through which the second fluid pipe 21 communicates, and the artificial light irradiation means by using the electric power obtained by the chemical loop power generation. It is also possible to perform photosynthesis at any time and place by using. The artificial light irradiation means preferably includes an artificial light source and a light guide path that supplies the artificial light from the artificial light source to a predetermined part of the incubator. Examples of the artificial light source include light emitting diodes, cold cathode tubes, organic EL lighting, fluorescent lamps, halogen lamps, metal halide lamps, xenon lamps and the like.

The gas blower 42 is provided below the culture tank 41 and is connected to the pipe 49. _{The gas blower 42 sends CO 2} gas into the culture tank 41 via the pipe 49.

The bubbling filter 43 is installed at the bottom of the culture tank 41 and is connected to the gas blower 42 via a pipe 49. The bubbling filter 43 has innumerable minute pores that emit _{CO 2 gas.} The size of the pores is not particularly limited, but the finer the bubbles of the _{CO 2 gas released into the culture solution 48, the better the CO 2} gas dissolves in the culture solution 48. The shape of the bubbling filter 43 is not particularly limited, but for example, a long filter having minute pores formed throughout the culture solution 48 is preferable.

The stirring motor 44 drives a stirring blade 45 that stirs the culture solution 48. Drive motor 3
Reference numeral 5 is installed in the center of the lid portion 50 of the culture tank 41, for example.

The stirring blade 45 is installed in the culture solution 48 in the culture tank 41. The material and the number of feathers of the stirring blade 45 are not limited as long as the culture solution 48 in the culture tank 41 can be stirred as a whole.

The temperature sensor 46 measures the temperature of the culture solution 48 in the culture tank 41. The temperature sensor 46 is installed, for example, on the lid portion 50 of the culture unit B1 or the like. The measured liquid temperature information is sent to the control panel 47.

The control panel 47 is installed close to the outside of the culture tank 41. The control panel 47 controls information such as the liquid temperature sent from the temperature sensor 46. By monitoring the liquid temperature of the culture solution 48 with the control panel 47 and keeping it in an appropriate state, it is possible to prepare a culture environment capable of efficient culture. Culture management by control panel Control can be performed by electricity obtained from the chemical loop combustion unit.

In the culture unit B1 having the above configuration, the carbon dioxide gas supplied from the reduction tower 3 is sent into the culture tank 41 by the gas blower 42 via the bubbling filter 43. In the culture unit B1, the carbon dioxide gas sent from the bubbling filter 43 is dissolved in the entire culture solution 48 by stirring with the stirring blade 45. In the culture unit B1, carbon dioxide is easily dissolved in the culture solution 48 by forming innumerable fine bubbles by the bubbling filter 43.

In the culture unit B1, the temperature sensor 46 measures the temperature in the culture solution 48. Although not shown, the culture unit B1 is maintained at an optimum temperature by attaching a heating device or a cooling device to the culture tank 41 and heating and cooling according to the temperature of the culture solution 48 in the culture tank 41.
As a cooling device, for example, a hose is installed along the inner surface of the bottom of the culture tank 41 so as not to come into contact with the stirring blade 45, and cooling can be performed by heat exchange by passing cooling water through the hose. The hose can enter the inside of the culture tank 41 from the lower part of the culture tank 41, go around the inside of the culture tank 41, and go out from the lower part of the culture tank 41. Further, as the heating device, for example, a heater, which is a device for heating by providing a heater in the culture tank 41, can be mentioned. The carbon dioxide concentration can be adjusted by controlling the flow rate of the exhaust gas with the gas blower 42 leading to the culture tank 41.

In the culture unit B1, by stirring the culture solution 48 in the culture tank 41 with the stirring blade 45, the algae, the culture solution 48, and the carbon dioxide in the exhaust gas are appropriately mixed, and the algae locally gather and precipitate. Can be prevented.

<Method of treating organic solvent>
Hereinafter, the method for treating the organic solvent of the present embodiment will be described with reference to the above-mentioned organic solvent treatment system of the present embodiment as an example. The present embodiment is not limited to the following.

(First Embodiment)
The organic solvent treatment method of the present embodiment includes an oxidation step of oxidizing metal particles in an oxidation tower to obtain metal oxide particles, and reacting the metal oxide particles with an organic solvent in a reduction tower to obtain metal oxide particles from the organic solvent waste liquid. It has a reduction step of generating carbon dioxide and reducing the metal oxide particles to obtain metal particles, and a circulation step of circulating the metal particles and the metal oxide particles between the oxidation tower and the reduction tower. ..

The organic solvent used in the present embodiment is not particularly limited, and for example, organic agents used for organic synthesis of paints, plastics, etc., and chemicals in general can be used, among which, for example, photolithography, DSA lithography, and in. Examples thereof include various chemicals used when manufacturing semiconductor elements and liquid crystal display elements by print lithography technology.
Examples of the chemical solution include those containing a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an ether solvent, and an amide solvent; and a hydrocarbon solvent. Further, as a chemical solution for lithography containing a resin, a resin solution in which a resin component for resist is dissolved in an organic solvent component, a resist composition described later, an insulating film composition, an antireflection film composition, and directed self-assembling (Directed Self Assembly). : DSA) Examples include block copolymer compositions applied to technology, resin compositions for imprinting, and the like. In addition, examples of the lithographic chemical solution used for pattern formation and the like include a pre-wet solvent, a resist solvent, a developing solution and the like.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl. Examples thereof include ketones, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl acetate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, and n-heptyl alcohol. Alcohols such as n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether and diethylene glycol monomethyl Examples thereof include glycol ether solvents such as ether, triethylene glycol monoethyl ether and methoxymethylbutanol.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the above glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be mentioned.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

As the organic solvent used in the present embodiment, a used or unnecessary organic solvent waste liquid is preferable from the viewpoint of recycling waste as fuel, and an organic solvent generated when manufacturing a semiconductor element or a liquid crystal display element is preferable. Waste liquid is more preferable. Examples of the organic solvent waste liquid include the above-mentioned various chemical solutions and mixed solutions thereof.

_{In the present embodiment, CO 2} obtained in the reduction step may be reacted with a chemical product to produce a new chemical product. _{By reacting all the CO 2} obtained in the reduction step, the _{amount of CO 2} gas discharged to the outside world can be reduced to zero by using the treatment method of the present embodiment. Examples of the _{chemicals used for the reaction with CO 2} include sodium hydroxide, potassium hydroxide, and calcium hydroxide, and examples of the chemicals produced from each include sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium carbonate. ..

(Second Embodiment)
The organic solvent treatment method of the present embodiment includes an oxidation step of oxidizing metal particles in an oxidation tower to obtain metal oxide particles, and reacting the metal oxide particles with an organic solvent in a reduction tower to obtain metal oxide particles from the organic solvent waste liquid. A reduction step of generating carbon dioxide and reducing the metal oxide particles to obtain metal particles, a circulation step of circulating the metal particles and the metal oxide particles between the oxidation tower and the reduction tower, and the reduction. It has a culture step of supplying the carbon dioxide obtained in the step to an algae culture tank to cultivate the algae.

In the culture step, CO _{2 is supplied so that the CO 2} concentration in the gas supplied to the culture solution is 10% to 50% and the CO ₂ concentration in the culture solution is 0.01% to 30%. Is preferable.
By _{introducing a large amount of CO 2} , the pests that prey on the algae can be killed, and the algae can _{take in a large amount of CO 2} into the body and produce sugar.
Further, in the culturing step, the light source used for causing the algae to photosynthesize may be natural light, artificial light, or a combination thereof. The wavelength of the artificial light to be irradiated is preferably 380 to 780 nm, preferably white light or red light. Intensity of the irradiated artificial light is preferably ^{1~400μmol / m 2 / sec, 20~150μmol} / m 2 / sec is more preferable.

Examples of the medium for culturing algae in the culturing step include known media for freshwater microalgae containing various nutrient salts, trace metal salts, vitamins and the like, and media for marine microalgae. In addition, an agar plate medium prepared based on a known medium for freshwater microalgae can also be used.
Examples of nutrient salts include _{nitrogen sources such as NaNO 3} , KNO ₃ , NH ₄ Cl, (NH ₄ ) ₂ SO ₄ , and urea; _{phosphorus sources such as K 2} HPO ₄ , KH ₂ PO ₄ , and sodium glycerophosphate.
Examples of trace metals include iron, magnesium, manganese, calcium, zinc and the like, and examples of vitamins include vitamin B1 and vitamin B12.

Examples of algae include cyanobacteria, green algae, treboxia, euglena, prassinophyceae, and primitive red algae.
Examples of cyanobacteria include Chroococcae, Stigonematacae, Mastigocladacae, Oscillatroriacae and the like. Examples of the genus Synechococcus include Synechococcus libidus, Synechococcus elongatus and the like. Examples of the genus Synechocystis include Synechocystis minervae and the like. Examples of the genus Mastigocladus include Mastigocladus laminosus and the like. Examples of the genus Phormidium include Phormidium laminosus and the like. Examples of the genus Symploca include Symploca thermolis and the like. Examples of the genus Aphanocapsa include Aphanocapsa thermolis and the like.

Examples of green algae include Chlamydomonas, Dunaliella, Senedesmus, Botryococcus, Stickococcus, Nannochloris, Desmodesmus and the like.
Examples of chlorella include Chlorella vulgaris and Chlorella saccharophila. Examples of the genus Dunaliella include Dunaliella salina and Dunaliella tertiolecta. The genus Chlamydomonas includes Chlamydomonas reinhardtii, Chlamydomonas moewushii, Chlamydomonas semas menas, Chlamydomonas, Chlamydomonas, Chlamydomonas, Chlamydomonas, Chlamydomonas, Chlamydomonas, Chlamydomonas, Chlamydomonas. Examples of the genus Scenedesmus include Scenedesmus obliques and the like. The genus Shichococcus includes the genus Shichococcus ampliformis. Examples of the genus Nannochloris include Nannochloris beavertailis. Scenedesmus
s) Examples of the genus include Desmodesmus subspictus and the like.
The euglenoids, Euglena acus, Euglena caudata, Euglena chadefaudii, Euglena deses, Euglena gracilis, Euglena granulata, Euglenaintermedia, Euglena mutabilis, Euglena oxyuris, Euglena proxima, Euglena spirogyra, Euglena viridis, Euglena vermiformis and the like.
Examples of Prasinophyceae include Tetracermis.
Primitive red algae include Cyanidioschyzon, Cyanidium, Gardieria, Porphyridium and the like.

The algae to be cultivated can be selected according to the target production substance. Euglena is preferred for applications such as health foods and cosmetics. In recent years, algae capable of producing biodiesel have been attracting attention. Algae produce biodiesel by absorbing carbon dioxide in the atmosphere by photosynthesis. In the case of such applications, algae of the genus Pseudocorycystis, algae of the genus Cyanidioschyzon, algae of the genus Chlamydomonas, and algae of the genus Pseudocolysistis are preferable.
The produced biodiesel can be collected from cultured algae. Cells can be crushed by a general method such as French press or homogenizer and then extracted with an organic solvent such as n-hexane, or cells can be collected on a filter such as glass fiber, dried, and then an organic solvent or the like. There is a method of extracting by. Another example is a method in which cells are collected by centrifugation, freeze-dried to powder, and extracted from the powder with an organic solvent. The desired biodiesel can be obtained by volatilizing the solvent after extraction under reduced pressure or normal pressure, and by heating or at room temperature.

According to this embodiment, the treatment of the organic solvent waste liquid can be performed at no cost, the CO ₂ immobilization treatment which is avoided as a greenhouse gas can be performed, and the bio is produced by _{the CO 2} used for the immobilization. You can get fuel.
When the organic solvent treatment system of the present embodiment is installed near the airport, biofuel produced from the organic solvent can be used as jet fuel at low cost.

A1, A2 ... Organic solvent treatment system,
A10 ... Chemical loop combustion unit,
1 ... Oxidation tower,
2 ... Top plate,
3 ... Reduction tower,
4 ... Air header,
5 ... Air nozzle,
6 ... Blower,
9 ... Fuel nozzle,
10 ... Shutoff valve,
11 ... Pressure regulating valve,
12 ... Check valve,
13 ... Separate gas nozzle,
14 ... plumbing,
15 ... Bottom header,
16 ... Conical noodles,
17 ... hole,
18 ... First fluid piping,
19 ... Top header,
21 ... Second fluid piping,
22 ... Heat-resistant wall,
23 ... Conical wall,
24 ... Intermediate header,
25 ... Solid air separator,
26 ... Heat transfer tube,
27 ... Exhaust port at the top of the oxidation tower,
28 ... Solid air separator,
29 ... heat exchanger,
30 ... Blower,
31 ... Shutoff valve,
32 ... Pressure regulating valve,
33 ... Brackish water separator,
34 ... Blower,
35 ... Shutoff valve,
B1 ... Culture unit,
40 ... Stand,
41 ... Culture tank,
42 ... Gas blower,
43 ... Bubbling filter,
44 ... Stirring motor,
45 ... Stirring blade,
46 ... Temperature sensor,
47 ... Control panel,
48 ... Culture solution,
49 ... plumbing,
50 ... lid

Claims (5)

Oxidation process to obtain metal oxide particles by oxidizing metal particles in the oxidation tower,
A reduction step in which the metal oxide particles are reacted with an organic solvent waste liquid in a reduction tower to generate carbon dioxide from the organic solvent waste liquid, and the metal oxide particles are reduced to obtain metal particles.
A circulation step of circulating the metal particles and the metal oxide particles between the oxidation tower and the reduction tower, and
A method of recycling organic solvent waste liquid as fuel. The method for recycling the organic solvent waste liquid according to claim 1, further comprising a culture step of supplying the carbon dioxide obtained in the reduction step to an algae culture tank and culturing the algae. The method for recycling the organic solvent waste liquid according to claim 2, wherein the algae produce biodiesel in the culture step. An oxide tower in which metal particles react with an oxidizing agent to generate metal oxide particles and metal oxide particles generated in the oxide tower react with an organic solvent waste liquid to generate carbon dioxide from the organic solvent waste liquid. A chemical comprising a reduction tower in which the metal oxide particles are reduced to the metal particles, and a circulation flow path in which the metal particles circulate between the oxidation tower and the reduction tower while undergoing oxidation and reduction. With the loop combustion unit,
An organic solvent waste liquid recycling treatment system used in a method of recycling organic solvent waste liquid as fuel. The organic solvent waste liquid recycling treatment system according to claim 4, further comprising a culture unit for culturing algae using carbon dioxide produced from the chemical loop combustion unit.

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