JP6992772B2 - Fluorocarbon decomposition method and its equipment, hydrogen production method, calcium fluoride production method and fuel cell - Google Patents

Description

Article 30, Paragraph 2 of the Patent Law Applicable Website Publication Date June 11, 2018 Website Address http: // www. isiem2018. org / systems / default / files / ORAL_PRESTATIONS. pdf Publishers Masanori Maeda, Naoki Mae, Masazumi Kanazawa, Reiji Hosokawa, Kazumichi Yanagisawa, Toshio Kono, Yuya Yano Contents of the published invention Sadanori Maeda, Naoki Maeda, Masazumi Kanazawa, Reiji Hosokawa, Kazumichi Yanagisawa, Toshio Kono , Yuya Yano in the proceedings of the International Symposium on International and Environmental Materials 2018 (ISIEM 2018) (International Symposium on Inorganic and Environmental Materials 2018) published on the website at the above address, Maeda Noriyuki, Maeda Naoki, Kanazawa. We have published a study invented by Masazumi, Reiji Hosokawa, Kazumichi Yanagisawa, Toshio Kono, and Yuya Yano to decompose hydrofluorocarbons (HFCs) by reaction with quicklime to produce calcium fluoride as the main reaction product. [Publications, etc.] Date June 18, 2018 Meeting name, venue International Symposium on International and Environmentals 2018 (ISIEM 2018) [International Symposium on Inorganic and Environmental Materials 2018] Ghent University 9000 Ghent Belgium] [Ghent University (Sint-Petersniu Street 25 B-9000 Ghent Belgium)] Publisher Kazumichi Yanagisawa Contents of the published invention Kazumichi Yanagisawa is an International Symposium on Inorganic and Incorporate20 Decomposes hydrofluorocarbons (HFCs) by reaction with raw lime invented by Sadanori Maeda, Naoki Mae, Masaki Kanazawa, Reiji Hosokawa, Kazumichi Yanagisawa, Toshio Kono, and Yuya Yano at (International Symposium on Inorganic and Environmental Materials 2018). Then, the research on producing calcium fluoride as the main reaction product was published.

The present invention decomposes and detoxifies a freon gas containing both hydrogen and fluorine, and at the same time, produces hydrogen, which is a useful resource as a decomposition gas, with a high yield and uses it as a fuel for a fuel cell, and further as a reaction residue. The present invention relates to a method for decomposing fluorogas and its equipment, a method for producing hydrogen, a method for producing calcium fluoride, and a fuel cell using hydrogen produced from freon gas as a fuel for obtaining calcium fluoride, which is a useful resource, as a high-purity solid substance. ..

CFC (chlorofluorocarbon), HCFC (hydrochlorofluorocarbon), HFC (hydrofluorocarbon), PFC (par) of fluorocarbons, which have been widely used for cleaning electronic parts, refrigerants for air conditioning equipment, freezers and refrigerators, spray agents, etc. Fluorocarbon), etc. cause environmental pollution such as ozone layer depletion and global warming, so it is a social requirement to properly recover and destroy them. Has passed. In 2015, the CFC Recovery and Destruction Law was amended to the CFC Emission Control Law, which further tightens regulations on CFC emissions and introduces a new perspective of recycling CFCs. In other words, with the depletion of resources, it is expected that Freon gas will not only be recovered and destroyed, but also recycled, and some of the already recovered Freon gas will be treated as recycled raw materials. It's coming.

From the time of enactment of the Freon Recovery / Destruction Law, which was an urgent social requirement for the recovery / destruction of freon gas, to the present, the present inventor heated a mixture of freon gas and water as a solvent shown in Patent Document 1. As superheated steam, iron is used as a reaction aid by passing the superheated steam through a reaction device under normal pressure heated to a predetermined temperature while holding it for a predetermined reaction time, or as shown in Patent Document 2. , Carbon, Various decomposition means of environmental pollutant gas using superheated steam such as means for decomposing freon gas by arranging one or more substances selected from carbon steel (hereinafter, "superheated steam invention") ) Is provided.

In addition, the present inventor changes the research viewpoint in the process of research and development to improve and develop the invention of superheated steam, and decomposes freon gas by calcium oxide (CaO) in the presence of superheated steam shown in Patent Document 3. Various inventions related to superheated steam such as decomposition means (hereinafter referred to as “Reference 3 invention”) are also provided.

Japanese Patent No. 32196889 Japanese Patent No. 321706 Japanese Patent No. 3730794

The superheated steam invention is an epoch-making invention capable of decomposing 100% of fluorocarbon gas, which was difficult to decompose at the time of provision, at normal pressure, and a fluorocarbon decomposition device for carrying out the superheated steam invention is widely used nationwide. However, it has established itself as a means of decomposing CFCs and has made a great contribution to the decomposition of CFCs.

However, now that the environmental load is required to be reduced, the technical field of chlorofluorocarbon decomposition has matured, and the standards for chlorofluorocarbon treatment have evolved as described above, the chlorofluorocarbon decomposition technology is also added to the decomposition of chlorofluorocarbons, and a different perspective from the conventional one. Has raised new issues to be resolved. Specifically, "to contribute to reducing the environmental load", "to be a technology that is more environmentally friendly", "to recover useful resources that can be reused", "to approach zero emissions", and "reaction residue". "Easy processing", "Efficient disassembly", "Longer life of disassembly equipment", "Lower cost (reduction of initial investment, running cost, etc.)", etc. It is an urgent task for Freon decomposition equipment to make progress to meet these social and historical demands.

The invention of superheated steam naturally requires equipment and energy to obtain superheated steam. In the invention of superheated steam shown in Patent Documents 1 and 2, it is shown that the reaction temperature is set to 650 ° C. or higher. However, in order to stably continue the chain reaction regardless of the type of chlorofluorocarbon, that is, to ensure the effectiveness of chlorofluorocarbon decomposition as an industrial device, the reaction temperature is maintained at 800 ° C to 1000 ° C. There is.

Therefore, as the technical field of fluorocarbon decomposition has matured, it is unavoidable to pursue economic efficiency as industrial equipment, reduce costs, and consider the global environment. Nowadays, various means of fluorocarbon decomposition by the invention of superheated steam are as follows. Have a problem. The problems of the invention of superheated steam shown below are also causes of imposing a load on the global environment.

[High energy cost to obtain superheated steam]
Since the invention of superheated steam always needs to keep the inside of the reactor in an atmosphere of superheated steam of 800 ° C. or higher, it requires equipment for producing superheated steam and energy cost for obtaining superheated steam, and the cost is high. Due to its high price, it is an obstacle to cost reduction and economical pursuit as a Freon decomposition device.

[The cost burden for maintaining the reaction temperature is large]
In the invention of superheated steam, the reaction temperature for decomposing freon gas is set to 800 ° C. to 1000 ° C., so that although the decomposition reaction is an exothermic reaction, the inside of the reactor is maintained at the above temperature. Since the power consumption of the reactor is large and it is necessary to bear the cost, it is difficult to meet the social demands of contributing to the reduction of cost and economy as a freon decomposition device and the reduction of environmental load. ing.

[Durability of the decomposition device is low, the life is short, and a strong acid decomposition gas is generated by the decomposition reaction]
In the invention of superheated steam, the decomposition of chlorofluorocarbons by the superheated steam produces a decomposition gas of a strong acid such as hydrofluoric acid or hydrochloric acid in the reactor. Since these strong acids cause severe corrosion of the reactor and the pipeline for transferring the strong acid to the neutralization tank, it is necessary to replace these parts as consumables at regular intervals in order to maintain the decomposition reaction normally. It has been forced. In particular, although the reactor uses expensive superalloys such as Inconel and Hastelloy, it has been corroded every few months and has to be replaced.

In addition, if the decomposition gas of the strong acid generated by the decomposition reaction leaks from the reaction pipeline to the outside of the system, it will lead to an accident. It is necessary to operate with a negative pressure inside, which complicates operation management. Further, as shown in Patent Document 2, when iron is used as a reaction aid, iron chloride and iron fluoride are precipitated as a solid, which may cause clogging of the pipeline. Further, when carbon or carbon steel is used as the reaction aid, the pipeline is not clogged, but there is a problem that the iron contained in the reaction vessel or the like gradually corrodes and the durability is lowered. Furthermore, carbon itself is expensive and requires a large amount of consumption. Therefore, in these respects as well, it is difficult to meet the social demands of extending the life of the CFC decomposing device, reducing the cost, pursuing economic efficiency, and contributing to the reduction of the environmental load.

[Difficulty in processing reaction residue]
In the superheated steam invention, in order to detoxify the decomposition gas of the strong acid of the by-product, mixed water of calcium hydroxide and water is sprayed on the decomposition gas in a shower shape as a neutralization treatment. Therefore, the reaction residue after the neutralization treatment contains a large amount of water and cannot be treated as industrial waste as it is. Therefore, it is possible to add a flocculant to the reaction residue to coagulate it, dehydrate it with a filter press, and then treat it as industrial waste. Therefore, it is difficult to meet the social demands of cost reduction and economic efficiency as a fluorocarbon decomposition apparatus because it is necessary to bear the cost for the treatment of the reaction residue.

On the other hand, the invention of Document 3 that decomposes freon gas or the like by the interaction between superheated steam and calcium oxide mainly aims to reduce the reaction temperature in the superheated steam invention, and has a reaction temperature of 400 ° C., which is much lower than that of the superheated steam invention. It is shown that the freon gas could be decomposed.

However, the invention of Document 3 still uses superheated steam, and the problem of the above-mentioned superheated steam invention is solely due to the existence of superheated steam, so that superheated steam exists and is involved in the decomposition of freon gas. As described above, the invention of Document 3 also has the above-mentioned [high energy cost for obtaining superheated steam], [high cost burden for maintaining the reaction temperature], [low durability of the decomposition device, short life, and so on. In addition, the problems of the above-mentioned superheated steam invention of [generating a decomposition gas of a strong acid by a decomposition reaction] and [difficulty in treating the reaction residue] remain as they are. Further, also in the invention of Document 3, although it is neutralized by calcium oxide after its formation, a strong acid is produced due to the intervention of superheated steam in the decomposition process of chlorofluorocarbons. Further, by cooling the decomposition gas of the invention of Document 3, the superheated steam is liquefied into water, and a trace amount of residual acidic substance is dissolved in water, and it is necessary to neutralize this. In addition, it is necessary to burn combustible gases such as methane (CH ₄ ), hydrogen (H ₂ ), and carbon monoxide (CO) among the decomposed gases before discharging them.

The invention of Document 3 also has problems due to the existence of these superheated steam, and has recently been "a technology that is more environmentally friendly", "recovering useful resources that can be reused", and "zero emission". It is the same as the invention of superheated steam that it is not possible to satisfy the newly raised social demands and historical demands such as "to get closer to the technology".

Therefore, the present invention solves the problems of the superheated steam invention and the invention of Document 3 caused by the existence of superheated steam, and detoxifies chlorofluorocarbons and the like in order to solve the new problems required for modern chlorofluorocarbon decomposition. The purpose is to provide a new decomposition technology for the purpose of generating useful resources from chlorofluorocarbons and the like based on the decomposition technology and to utilize them.

Although the above-mentioned invention of Document 3 has not been implemented as an industrial device, it shows the existence of calcium oxide in the presence of superheated steam as a reactant for decomposing chlorofluorocarbons. Therefore, in order to solve the above-mentioned problems, the present inventor made a fundamental change in the idea, and conducted diligent research on the decomposition of chlorofluorocarbons only by calcium oxide, away from the superheated steam which was an essential configuration.

First, at a reaction temperature of 400 ° C. disclosed in Document 3, the flon gas is brought into direct contact with calcium oxide without interposing superheated steam, that is, without supplying water or steam as a solvent to the reactor. The extent to which freon gas can be decomposed was attempted using the reactor used in the present invention shown in FIG.

In FIG. 5, reference numeral 30 denotes a reactor having a diameter of 125 mm and a height of 200 mm, in which crushed stone of silicon carbide 35 (SiC) as a refractory material is laid, and calcium oxide 25 (CaO) as a reactant is 0.85 kg. Was charged from the calcium oxide input port 32 provided above the reactor 30 and filled. Then, the reactor 30 is heated by the heating heater 34 to keep the inside at 400 ° C., and the Freon R32 (CH ₂ F ₂ ) of HFC, which is the Freon gas 1 to be decomposed filled in the gas cylinder 2, is charged with the pressure adjusting valve 37 and the gas. It was supplied at 0.3 kg / h from the gas supply port 31 via the flow meter 38. Then, the decomposed gas 5 decomposed by direct contact with the calcium oxide 25 in the reactor 30 and discharged from the gas discharge port 33 was sampled at the sampling point 3 and analyzed by a gas chromatograph. As a result, the decomposition rate was maintained at about 85% until 20 minutes after the start of charging Freon R32, but the decomposition rate did not reach 99.9%, and the decomposition rate decreased with the passage of time. .. After that, the supply of Freon R32 was stopped when the decomposition rate became almost zero with the passage of time. The supply amount of Freon R32 was 0.33 kg, which is 0.41 equivalent to 0.85 kg of calcium oxide 25. Table 1 shows the experimental results of the decomposition rate of Freon R32 and the components of the decomposition gas 5 in the time zone showing a high decomposition rate as Comparative Example 1.

As shown in Table 1, in the direct contact reaction between calcium oxide and chlorofluorocarbon R32 in which superheated steam does not intervene in Comparative Example 1, the decomposition rate of chlorofluorocarbon R32 is 84. The decomposition rate was only 9%, which was far below the decomposition rate of 99.9% specified in the Freon Emission Control Law. Further, since a considerable amount of hydrocarbon gas such as ethylene remains as the decomposition gas 5 at 5.8%, it cannot be adopted as a decomposition technology for chlorofluorocarbons.

Therefore, the present inventor conducted research on the technical causal relationship between calcium oxide and superheated steam in the decomposition of freon gas based on the experimental results of the invention of Document 3 and Comparative Example 1, and as a result, the following inference was obtained. ..
Reasoning 1: Calcium oxide as a reactant has good heat conduction, but because it is porous, the heat conduction path is long, and it seems that a certain amount of time is required for the temperature to reach the center.
Inference 2: From the invention of Document 3, assuming that the temperature at which the decomposition reaction of chlorofluorocarbons begins to occur in a chain reaction due to calcium oxide is 400 ° C., the decomposition reaction starts in the portion (outer surface) close to the heating source of calcium oxide, but the heating source. It is considered that the decomposition reaction does not easily proceed to the inside of the porous material far from the surface, and therefore, in Comparative Example 1, the decomposition rate remained at the maximum of 84.9%.
Inference 3: In the invention of Document 3, the reason why the decomposition rate of 99.9% or more could be achieved is that even if the reaction temperature is 400 ° C., the inside of the porous calcium oxide is overheated by the intervention of superheated steam. It is considered that the internal temperature of calcium oxide can be heated to 400 ° C. by the infiltration of steam and acting as a heat medium, and the temperature required for the continuation of the chain decomposition reaction is maintained.
Inference 4: Although the superheated steam at 400 ° C. shown in the invention of Document 3 can decompose freon gas, its decomposition rate is extremely low and the decomposition efficiency is poor, but the direct contact reaction between calcium oxide and freon gas is an exothermic reaction. Therefore, as the decomposition reaction progresses, the temperature of calcium oxide rises locally, and the temperature of the superheated steam in contact with this portion also rises above 400 ° C. Is considered to be producing.

Document 3 discloses that the generated acid gas is immediately neutralized by contact with calcium oxide in the reactor, and the acid gas released from the reactor without being neutralized is disclosed. It is also disclosed that a means for neutralization is needed. The gas released from the reactor without being neutralized was inferred as follows.
Inference 5: If acid gas is generated near the outlet of the reactor, it may no longer have a chance to come into contact with calcium oxide, in which case the acid gas will be released from the reactor to the outside without being neutralized. To be considered.

Based on these inferences 1 to 5, the present inventor substitutes the action of superheated steam as a heat medium in the invention of Document 3 by other means, and can use calcium oxide to chlorofluorocarbon without using superheated steam. It was hypothesized that the decomposition rate of 99.9% or more specified in the Emission Control Law could be decomposed. Based on this hypothesis, apart from the purpose of the invention of Document 3 to reduce the reaction temperature in the superheated steam invention, the reactor of the Freon decomposition apparatus shown in FIG. 5 was used as in Comparative Example 1 as a solvent as in Comparative Example 1. The reaction temperature was raised to 450 ° C., 500 ° C., and 550 ° C. without supplying the water or steam of We attempted decomposition by direct contact with and analyzed the composition of the decomposed gas during the time period when the decomposition rate was high. The results are shown in Table 2 as Comparative Examples 2 to 4.

Comparative Example 2 had a reaction temperature of 450 ° C., and Comparative Example 3 had a reaction temperature of 500 ° C.. As the reaction temperature of Comparative Example 1 was increased from 400 ° C., the decomposition rate was 94.5%, 99.5. Although it improved to%, the decomposition rate stipulated in the Freon Emission Control Law did not reach 99.9% or more. When the reaction temperature reaches 550 ° C., the decomposition rate reaches 99.9% or more, but a hydrocarbon-based gas is also produced, although it is a very small amount. Based on these test results, the following findings were obtained as a result of research on the decomposition of chlorofluorocarbon R32 and calcium oxide by direct contact reaction.
Findings 1: If the reaction temperature is maintained at 550 ° C or higher, the decomposition rate can be decomposed to 99.9% or higher without the intervention of superheated steam.
Finding 2: It is possible to decompose to a decomposition rate of 99.9% or more at a temperature much lower than the reaction temperature of 800 ° C. carried out in the invention of superheated steam.
Finding 3: It may be possible to control the decomposition gas to hydrogen, carbon monoxide, and carbon dioxide only, that is, to prevent other gases from being detected, and the amount of hydrogen and carbon monoxide produced in the decomposition gas accounts for a large amount. matter.
Finding 4: Along with the improvement of the decomposition rate, the hydrocarbon gas such as ethylene contained in the decomposition gas is approaching zero.
Finding 5: It is worth considering the recovery of hydrogen, which is abundant in the decomposition gas.
Finding 6: Since it is not necessary to intervene superheated steam, the above-mentioned various problems caused solely by the presence of superheated steam do not occur. For example, since the reaction residue can be obtained as a solid substance, the treatment is easy.
Finding 7: Analysis of the reaction residue consisting of solid matter revealed that calcium fluoride, which is a useful resource, was contained in a recoverable state.

In order to further study based on these findings and solve the problems of the present invention, according to claim 1, chlorofluorocarbons containing both hydrogen and fluorine are in direct contact with calcium oxide in a reactor kept at a predetermined temperature. Provided is a method for decomposing chlorofluorocarbons, which is decomposed into a decomposition gas consisting only of hydrogen, carbon monoxide and carbon dioxide by reacting.

Then, according to claim 2, hydrogen and monoxide are generated by storing calcium oxide inside and supplying a freon gas containing both hydrogen and fluorine to a reactor heated to a predetermined temperature to cause a direct contact reaction with calcium oxide. Provided is a method for decomposing flon gas to obtain a target gas composed of hydrogen containing a trace amount of carbon dioxide by decomposing into a decomposing gas consisting only of carbon and carbon dioxide and removing carbon monoxide from the decomposing gas.

Further, according to claim 3, hydrogen and monoxide are generated by storing calcium oxide inside and supplying a freon gas containing both hydrogen and fluorine to a reactor heated to a predetermined temperature to cause a direct contact reaction with calcium oxide. It decomposes into a decomposition gas consisting only of carbon and carbon dioxide, and the decomposition gas is held at a predetermined temperature and supplied to the aqueous shift reaction tube together with water vapor to cause an aqueous shift reaction, from carbon monoxide in the decomposition gas. Hydrogen is generated to form a second decomposition gas, and the second decomposition gas is supplied to a steam condensing tank to condense and remove the steam in the second decomposition gas to obtain a third decomposition gas, which remains from the third decomposition gas. Provided is a method for decomposing a freon gas by removing carbon monoxide to obtain a target gas consisting of hydrogen containing a trace amount of carbon dioxide.

Then, according to claim 4, the method of keeping the decomposition gas at 200 ° C. or higher, and according to claim 5, the temperature inside the reactor, the decomposition rate of freon gas containing both hydrogen and fluorine is 99.9% or more. According to claim 6, a method for keeping the temperature in the reactor at 600 ° C. or higher is provided.

According to claim 7, a reactor containing calcium oxide inside, a heating means for heating the reactor to a predetermined temperature, and a freon gas containing both hydrogen and fluorine are directly contact-reacted with calcium oxide in the reactor. It consists of a carbon monoxide removal device that supplies a decomposition gas consisting only of hydrogen, carbon monoxide and carbon dioxide, and removes carbon monoxide from the decomposition gas to obtain a target gas consisting of hydrogen containing a trace amount of carbon dioxide. A device for decomposing the obtained freon gas is provided.

Further, according to claim 8, a reactor containing calcium oxide inside, a heating means for heating the reactor to a predetermined temperature, and a freon gas containing both hydrogen and fluorine are directly contacted with calcium oxide in the reactor. An aqueous shift reaction tube that supplies water vapor and a decomposition gas consisting only of hydrogen, carbon monoxide and carbon dioxide obtained in the above process, and an aqueous shift reaction in the aqueous shift reaction tube produced hydrogen from carbon monoxide in the decomposition gas. It consists of a steam condensing tank that supplies 2 decomposition gas and a carbon monoxide remover that supplies a 3rd decomposition gas that condenses the water vapor in the 2nd decomposition gas in the steam condensing tank. Provided is a freon gas decomposition device for obtaining a target gas composed of hydrogen containing a trace amount of carbon dioxide, and according to claim 9, as a carbon monoxide removing device, a selective carbon monoxide oxidizing device or a carbon monoxide adsorption device is provided. Provides a configuration that uses the device.

Further, according to claim 10, a method for producing hydrogen which produces hydrogen containing a trace amount of carbon dioxide from chlorofluorocarbon by decomposing chlorofluorocarbon containing both hydrogen and fluorine by the above-mentioned chlorofluorocarbon decomposition method is provided.

Further, according to claim 11, by decomposing chlorofluorocarbons containing both hydrogen and fluorine by the above-mentioned chlorofluorocarbon decomposition method, calcium fluoride in a state of being contained as a solid in the reaction residue after decomposition of chlorofluorocarbons is produced. A method for producing calcium fluoride is provided, and according to claim 12, a method in which the purity of calcium fluoride is 97% or more is provided.

Further, according to claim 13, the freon gas decomposition device having the above-described configuration is connected to a fuel cell in which the negative electrode and the positive electrode are separated via an electrolyte membrane and hydrogen as a fuel is supplied to the negative electrode, and both hydrogen and fluorine are supplied. Provided is a fuel cell for generating power by supplying a target gas composed of hydrogen containing a trace amount of carbon dioxide obtained by supplying the contained freon gas to the freon gas decomposition apparatus and decomposing it to the negative electrode as fuel. Then, according to claim 14, a configuration is provided in which the electric power generated by the fuel cell is used as the electric power source of the heating means of the freon gas decomposition device.

According to the present invention described above, since the superheated steam is not used, the energy and equipment for obtaining the superheated steam required in the conventional superheated steam invention and the document 3 invention are not required, and the superheated steam is decomposed. There is no generation of acidic gas due to involvement and there is no need to shower mixed water with calcium hydroxide and water to neutralize the acidic gas. Therefore, since the reaction residue becomes a solid substance, the treatment becomes easy, and the durability of the decomposition apparatus can be maintained high. Moreover, the reaction temperature may be about 600 ° C., and the reaction temperature can be significantly reduced as compared with the superheated steam invention. Therefore, the power consumption for maintaining the temperature inside the reactor is reduced and the running cost is suppressed. This makes it possible to extend the life of the disassembly device.

In addition, the decomposition gas can be controlled to specific gases such as hydrogen, carbon monoxide, and carbon dioxide, and no other hydrocarbon-based gas is generated, so that the treatment is easy. Since the proportion of hydrogen contained in the decomposition gas is large, it can be recovered and reused as a useful resource. Specifically, electric power can be generated by supplying the target gas containing a large amount of hydrogen obtained by decomposing the freon gas containing both hydrogen and fluorine to the negative electrode of the fuel cell as fuel, and the electric power can be generated by the decomposition apparatus. It can be used as it is as various power sources such as a heater. Alternatively, by storing electricity in the battery, it can be used for other than the disassembling device. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a new device in which a decomposing device for chlorofluorocarbons containing both hydrogen and fluorine and a different kind of device such as a fuel cell are organically bonded. Moreover, by using the electric power obtained from the fuel cell as the power source for the decomposition device, it is more environmentally friendly, can be reused from the freon gas containing both hydrogen and fluorine, and hydrogen as a useful resource can be recovered infinitely. , Can approach zero emissions.

The decomposition gas contains almost the same amount of carbon monoxide as hydrogen, and when hydrogen is supplied as fuel for a fuel cell, carbon monoxide becomes a catalyst poison and the life of the catalyst is extremely shortened. Remove and burn. Alternatively, in order to make effective use of carbon monoxide, water vapor is supplied to the decomposition gas and the decomposition gas is kept at a predetermined temperature to cause an aqueous shift reaction, and hydrogen is generated from the carbon monoxide. Together with the hydrogen produced by the decomposition, the amount of hydrogen contained in the target gas supplied to the fuel cell can be doubled, and the amount of power generated by the fuel cell can be increased. Moreover, since carbon monoxide combustion treatment is not required, it is possible to approach zero emissions. Since carbon dioxide contained in the target gas is a trace amount that does not affect the electrolyte membrane of the fuel cell, it may be supplied to the negative electrode of the fuel cell together with hydrogen.

Since the decomposing chlorofluorocarbon contains fluorine as well as hydrogen, calcium fluoride, which has a high resource value as a reaction residue, can be obtained as a recoverable solid substance with a high purity of 97% or more, and can be reused as a useful resource. It will be possible to use it. Therefore, according to the present invention, it is possible to realize a technology that is more friendly to the global environment, and it is possible to contribute to the reduction of the environmental load, which is the social demand and the era demand for the fluorocarbon decomposition device.

The basic block diagram which shows 1st Embodiment of the decomposition method of chlorofluorocarbon which concerns on this invention. The basic block diagram which shows 1st Embodiment of the chlorofluorocarbon decomposition apparatus which concerns on this invention. The basic block diagram which shows the 2nd Embodiment of the decomposition method of chlorofluorocarbon which concerns on this invention. The basic block diagram which shows the 2nd Embodiment of the chlorofluorocarbon decomposition apparatus which concerns on this invention. Partial block diagram of the disassembly device. A partial block diagram showing another example of the disassembly device. The schematic diagram which shows the decomposition reaction of chlorofluorocarbon by calcium oxide.

Hereinafter, a method for decomposing chlorofluorocarbons and an apparatus thereof, a method for producing hydrogen, a method for producing calcium fluoride, and an embodiment of a fuel cell according to the present invention will be described with reference to the drawings. Among chlorofluorocarbons, the present invention targets chlorofluorocarbons containing both hydrogen and fluorine in the composition of HFC (hydrofluorocarbon), HCFC (hydrochlorofluorocarbon) and the like. Therefore, CFCs (chlorofluorocarbons), PFCs (perfluorocarbons), etc., which contain fluorine but do not contain hydrogen in their composition, and chlorofluorocarbons, which contain hydrogen but do not contain fluorine, are not targeted for decomposition.

In the invention of Document 3, a large amount of methane (CH ₄ ) was contained as the decomposition gas, but by eliminating the intervention of superheated steam, the composition of the decomposition gas was changed to a specific gas component as shown in Findings 3, 4 and 5. It can be controlled and the ratio of hydrogen in the decomposition gas can be increased. Hydrogen is attracting attention as a representative of clean energy, and is a useful resource with future potential. Therefore, the present invention does not merely decompose the freon gas to make it harmless, but also recovers hydrogen as a useful resource from the decomposed gas in a reusable manner, and further, the fuel of the fuel cell in order to obtain the electric power required for the decomposition apparatus. One of the issues is to use it as a fuel cell. Although hydrogen was contained in the decomposed gas in the invention of Document 3, the technical problem with the decomposed gas was exclusively to detoxify it for the final treatment, such as resource recovery from the decomposed gas other than detoxification. The issue was not recognized.

In addition, fluorine is used as a raw material for various functional chemicals such as refrigerant fluorocarbons, resins, lithium-ion secondary batteries, and optical glass, and is also used as a cleaning agent and etching agent in processes such as semiconductor manufacturing and metal surface processing. In some fields, there are no alternatives, and it is an important resource. The starting material for fluorine products is fluorite (calcium fluoride, CaF ₂ ), and about 6 million tons of fluorite are mined every year around the world, but the remaining reserves are about 240 million tons. It is estimated that it may be exhausted in about 40 years, and it is expected that demand will increase further in the future as developing countries grow. In addition, there are few resource-rich countries for fluorite, and in recent years, China, which is the largest resource-rich country, has implemented export restrictions and price increases, and there are concerns about stable supply to Japan. Therefore, it is an important issue to find a new minable place and at the same time to be able to recycle the fluorine contained in the waste as a raw material from the viewpoint of protecting natural resources.

Although calcium fluoride is contained in the reaction residue obtained by decomposing fluorine-containing chlorofluorocarbons such as HFC, in the invention of superheated steam and the invention of Document 3, the water content of the reaction residue is high due to the superheated steam, and as a reaction residue. Not only is it difficult to recover calcium fluoride, but it is also difficult to increase its treatment method and treatment cost. In the present invention, as shown in Findings 5 and 6, the reaction residue can be obtained as a solid substance. Therefore, if the fluorocarbon containing fluorine is decomposed, calcium fluoride can be easily reused as the reaction residue in the solid state. It is possible to recover. Therefore, one of the problems of the present invention is to recover calcium fluoride in a reusable manner. Therefore, the decomposition target of the present invention is a chlorofluorocarbon gas containing both hydrogen and fluorine.

As described above, HFC and HCFC are typical examples of chlorofluorocarbons containing both hydrogen and fluorine, which are the targets of the present invention. Demand for these gases is expected to continue to increase as alternative chlorofluorocarbon gases, and the amount of decomposition treatment is expected to increase in proportion to this. Above all, HFC is considered to become the mainstream of alternative CFCs in the future, and by applying the present invention, the efficiency of decomposition, the life of decomposition equipment will be extended, the initial investment and running costs will be reduced, and the earth will be further improved. It is environmentally friendly, can contribute to the reduction of environmental load, and can recover hydrogen and calcium fluoride as useful resources that can be reused, and can approach zero emissions as a whole.

[First Embodiment]
A method for decomposing chlorofluorocarbons according to the present invention and a first embodiment of the apparatus thereof will be described with reference to FIGS. 1, 2, and 5. As shown in FIG. 1, the method for decomposing chlorofluorocarbons according to the present invention is chlorofluorocarbon 1 containing both hydrogen and fluorine collected from an air conditioner, a refrigerator, or the like and stored in a gas cylinder 2 (hereinafter, simply referred to as "chlorofluorocarbon 1"). Is decomposed into a decomposition gas 5 consisting of only hydrogen 10, carbon monoxide 20, and carbon dioxide 15 by directly contacting and reacting with calcium oxide 25 in a reactor 30 maintained at a predetermined temperature 36 of, for example, 600 ° C. It is basic.

FIG. 2 is a basic configuration diagram showing a first embodiment of the fluorocarbon decomposition apparatus according to the present invention, and FIG. 5 is a partial configuration diagram thereof. Inside the reactor 30, crushed stone of silicon carbide (SiC) 35 as a refractory material is laid, and a predetermined amount of granular or lumpy calcium oxide 25 is placed on the crushed stone, and a calcium oxide inlet is provided above the reactor 30. It is charged from 32 and stored, and the inside is heated by a heating means such as a heating heater 34 and maintained at a predetermined temperature 36, for example, 600 ° C. In the reactor 30, the fluorocarbon 1 to be decomposed is supplied from the gas cylinder 2 to the reactor 30 from the gas supply port 31 via the pressure regulating valve 37 and the gas flow meter 38. The reason why the silicon carbide 35 is laid in the reactor 30 is that the calcium oxide 25 filled in the reactor 30 and the gas supply port 31 of the freon gas 1 are separated, and the freon gas supplied to the reactor 30 with respect to the calcium oxide 25. This is to spread 1.

The chlorofluorocarbon 1 supplied to the reactor 30 is decomposed by only hydrogen 10, carbon monoxide 20, and carbon dioxide 15 by directly contacting calcium oxide 25 held at a predetermined temperature 36, for example, 600 ° C. by a heating heater 34. It is decomposed into gas 5. The meaning of "only" means that no gas other than the above-mentioned three specific types of gas is detected from the decomposed gas 5. As described above, one of the features of the present invention is that the decomposition gas 5 is controlled to the above-mentioned three specific gases of hydrogen 10, carbon monoxide 20, and carbon dioxide 15. Hereinafter, Examples 1 to 5 in which various chlorofluorocarbons 1 including HFC chlorofluorocarbon R32 are decomposed using the chlorofluorocarbon decomposition apparatus shown in FIGS. 2 and 5 are shown.

A crushed stone of silicon carbide 35 (SiC) as a refractory material was laid in a vertical reactor 30 having a diameter of 125 mm and a height of 200 mm shown in FIG. As an agent, 0.85 kg of calcium oxide 25 (CaO) having a particle size of about 4 mm was charged from the calcium oxide inlet 32 provided above the reactor 30 and filled. The reactor 30 had a superficial velocity (volume flow rate / cross-sectional area) of 0.1 to 0.3 cm / s and a space velocity (SV) of 100 to 200 h ^-1 . Then, the reactor 30 is heated by the heating heater 34 to keep the inside at 600 ° C., and the HFC Freon R32 (CH ₂ F ₂ ) filled in the gas cylinder 2 is 0 via the pressure control valve 37 and the gas flow meter 38. The decomposition gas 5 supplied to the reactor 30 at 3 kg / h and discharged from the gas discharge port 33 was sampled at the sampling point 3 and analyzed by a gas chromatograph. The conditions are the same as those of Comparative Example 1 to Comparative Example 4, including the filling amount of calcium oxide 25, the type of Freon gas 1, and the flow rate of Freon gas 1, except that the internal temperature of the reactor 30 is set to 600 ° C. A sluice valve 4a is provided between the gas cylinder 2 and the pressure control valve 37, a sluice valve 4b is provided between the pressure control valve 37 and the gas flow meter 38, and a sluice valve is provided between the gas flow meter 38 and the gas supply port 31. 4c are installed respectively, and it is possible to supply / shut off the front gas 1.

Freon R32 is supplied with the same configuration as in Example 1 except that the internal temperature of the reactor 30 is maintained at 700 ° C., and the decomposed gas 5 discharged from the gas discharge port 33 is sampled at the sampling point 3 to form a gas chromatograph. Analyzed in.

The decomposed gas 5 was analyzed with the same configuration as that of Example 1 except that the chlorofluorocarbon 1 to be decomposed was HFC chlorofluorocarbon R134a (C ₂ H ₂ F ₄ ).

The decomposition gas 5 was analyzed with the same configuration as that of Example 1 except that the Freon gas 1 was HFC Freon R410A. Freon R410A is a mixed Freon in which Freon R32 (CH ₂ F ₂ ) and Freon R 125 (C ₂ HF ₅ ) are mixed at a ratio of 50:50.

The decomposed gas 5 was analyzed with the same configuration as that of Example 1 except that the chlorofluorocarbon 1 to be decomposed was HFC chlorofluorocarbon R404A. Freon R404A is a mixed Freon in which Freon R143a (C ₂ H ₃ F ₃ ), Freon R134a (C ₂ H ₂ F ₄ ) and Freon R 125 (C ₂ HF ₅ ) are mixed at a ratio of 52: 4: 44. be. Table 3 shows the analysis results of the decomposition gas 5 shown in Examples 1 to 5.

As shown in Table 3, the decomposition gas 5 of Example 1 having a reaction temperature of 600 ° C. does not contain chlorofluorocarbon R32, and the residual rate of chlorofluorocarbon R32 contained in the reaction residue 40 is less than 0.1%. Yes, Freon R32 is decomposed and detoxified at a decomposition rate of 99.9% or more. Further, the decomposition gas 5 of Example 1 is controlled only by three specific gases of 45.8% hydrogen 10, 44.3% carbon monoxide 20, and 9.9% carbon dioxide 15. , No other gas has been detected. Further, the decomposition gas 5 of Example 2 in which the reaction temperature of Example 1 was raised from 600 ° C. to 700 ° C. did not contain Freon R32, and the residual rate of Freon R32 contained in the reaction residue 40 was 0. It is less than .1%, and Freon R32 is decomposed and detoxified at a decomposition rate of 99.9% or more. Further, the decomposition gas 5 is controlled only by three specific gases of 46.2% hydrogen 10, 44.3% carbon monoxide 20, and 9.5% carbon dioxide 15. No gas was detected, and the composition of the decomposed gas 5 is the same as that of the first embodiment.

Also in Examples 3 to 5 in which the chlorofluorocarbon gas to be decomposed was changed from chlorofluorocarbon R32 (Examples 1 and 2) to chlorofluorocarbon R134a, chlorofluorocarbon R410A, and chlorofluorocarbon R404A, the chlorofluorocarbon was decomposed at a reaction temperature of 600 ° C. with a decomposition rate of 99.9% or more. It is detoxified, and the decomposition gas 5 is also controlled only by three specific gases of hydrogen 10, carbon monoxide 20, and carbon dioxide 15, and no other gas is detected.

Therefore, compared to Comparative Example 4 at a reaction temperature of 550 ° C., which can decompose freon gas at a decomposition rate of 99.9%, but produces hydrocarbon-based gases other than hydrogen, carbon monoxide, and carbon dioxide as decomposition gas. In Examples 1 and 3 to 5 in which the reaction temperature is 600 ° C., the composition of the decomposition gas 5 is controlled to only three specific gases of hydrogen 10, carbon monoxide 20, and carbon dioxide 15 together with the decomposition of the freon gas 1. be able to. The decomposition results of Example 2 and Example 1 at a reaction temperature of 700 ° C. are similar, and it can be seen that a reaction temperature of 600 ° C. is sufficient. The reaction temperature is selected at a temperature at which the decomposition gas 5 can be controlled only by three specific gases of hydrogen 10, carbon monoxide 20, and carbon dioxide 15, that is, a temperature at which components other than those described above are not detected from the decomposition gas 5. If it is a condition, it may be less than 600 ° C., and the present invention does not specify the temperature condition above 600 ° C.

The decomposition mechanism of HFC Freon R32 (CH ₂ F ₂ ) in direct contact with calcium oxide 25 as Freon gas 1 shown in Examples 1 and 2 will be verified with reference to FIG. 7. FIG. 7 is a schematic diagram showing the decomposition reaction of freon gas by calcium oxide 25, and as shown in step A, freon R32 in direct contact with calcium oxide 25 invades calcium oxide 25 and is as shown in step B. The fluorine (F) of Freon R32 (CH ₂ F ₂ ) and the oxygen (O) of calcium oxide 25 (CaO) are first substituted, and calcium fluoride (CaF ₂ ) is produced. After that, it is considered that each reaction shown in steps C, D, and E occurs from the state shown in step B.

In step C, as shown in the reaction formula below, two types of decomposition gases, hydrogen 10 and carbon monoxide 20, are released as decomposition gases.
2CaO + 2CH ₂ F ₂ → 2CaF ₂ + 2CH ₂ + O ₂ → 2CaF ₂ + 2CO + H ₂

In step D, as shown in the reaction formula below, two types of decomposition gases, hydrogen 10 and carbon dioxide 15, are released as decomposition gases, and carbon (C) remains inside the calcium oxide 25. ..
2CaO + 2CH ₂ F ₂ → 2CaF ₂ + 2CH ₂ + O ₂ → 2CaF ₂ + CO ₂ + C + 2H ₂

In step E, as shown in the reaction formula below, methane (CH ₄ ), which is a hydrocarbon gas, is released as a decomposition gas together with carbon dioxide.
CaO + CH ₂ F ₂ → CaF ₂ + CH ₂ + 0.5O ₂ → CaF ₂ + WCO ₂ + XC _Y H _Z
(When W = 1, X = 1, Y = 1, Z = 4)

In both Example 1 and Comparative Example 4, HFC Freon R32 (CH ₂ F ₂ ) was decomposed by directly contacting it with calcium oxide 25, and in Example 1, a decomposition rate of 99.9% or more was achieved. The decomposition gas 5 produced by the decomposition is only three types of hydrogen 10, carbon monoxide 20, and carbon dioxide 15, and no other gas is detected. On the other hand, although the decomposition rate of Comparative Example 4 is 99.9% or more, a hydrocarbon gas other than hydrogen 10, carbon monoxide 20, and carbon dioxide 15 is detected as the decomposition gas 5. This hydrocarbon gas is considered to be methane (CH ₄ ) as shown in the reaction of step E in FIG. The difference between the two is the reaction temperature.

Similarly, in Example 2 in which the reaction temperature was maintained at 700 ° C., and in Examples 3 to 5 in which the reaction temperature was maintained at 600 ° C. and the types of Freon gas to be decomposed were different, the decomposition gas 5 was hydrogen 10, monoxide. It is controlled only by three specific gases, carbon 20 and carbon dioxide 15, and no other gas is detected. On the other hand, in Comparative Examples 3 to 1 in which the reaction temperature was set to 500 ° C., 450 ° C., and 400 ° C., which are lower than 550 ° C. in Comparative Example 4, not only the decomposition rate of 99.9% could not be achieved, but also the decomposition gas 5 was used. Hydrocarbon-based gas is produced, and the lower the temperature, the larger the amount produced.

From these facts, the reaction shown in steps C, D, and E in FIG. 7 is caused by the reaction temperature, and if the reaction temperature is kept above a predetermined temperature, the freon gas is decomposed at a decomposition rate of 99.9% or more. It can be detoxified, and the decomposition gas 5 is controlled to only three specific gases, hydrogen 10, carbon monoxide 20, and carbon dioxide 15, without generating a hydrocarbon gas such as methane shown in step E of FIG. It is possible to make effective use of hydrogen 10 which is contained in a large amount in the decomposition gas 5. If the reaction temperature is maintained at 600 ° C. as shown in Examples 1 and 3 to 5, the decomposition reaction shown in step E of FIG. 7 is not generated and the decomposition reaction of steps C and D of FIG. 7 is controlled. It is possible. The reaction temperature is selected at a temperature at which the decomposition gas 5 can be controlled only by three specific gases of hydrogen 10, carbon monoxide 20, and carbon dioxide 15, that is, a temperature at which components other than those described above are not detected from the decomposition gas 5. If it is a condition, it may be lower than 600 ° C. or may be higher than 600 ° C., and the present invention does not specify the temperature condition above 600 ° C.

The decomposition reactions of calcium oxide 25 heated and held at 600 ° C. and five types of chlorofluorocarbons 1 of HFC, chlorofluorocarbon R32, chlorofluorocarbon R22, chlorofluorocarbon R134a, chlorofluorocarbon R125, and chlorofluorocarbon R143a, shown in each example are as follows.
<< Freon R32: CH ₂ F ₂ >>
[Main reaction]
2CaO + 2CH ₂ F ₂ → 2CaF ₂ + 2CH ₂ + O ₂ → 2CaF ₂ + 2CO + H ₂
[Adverse reaction]
2CaO + 2CH ₂ F ₂ → 2CaF ₂ + 2CH ₂ + O ₂ → 2CaF ₂ + CO ₂ + C + 2H ₂
<< Freon R22: 2CHClF ₂ >>
[Main reaction]
3CaO + 2CHClF ₂ → CaCl ₂ + 2CaF ₂ + CO + CO ₂ + H ₂
[Adverse reaction]
3CaO + 2CHClF ₂ → CaCl ₂ + 2CaF ₂ + 0.5C + 1.5CO ₂ + H ₂
<< Freon R134a: C ₂ H ₂ F ₄ >>
[Main reaction]
2CaO + C ₂ H ₂ F ₄ → 2CaF ₂ + 2CO + H ₂
[Adverse reaction]
2CaO + C ₂ H ₂ F ₄ → 2CaF ₂ + C + CO ₂ + H ₂
<< Freon R125: C ₂ HF ₅ >>
[Main reaction]
5CaO + 2C ₂ HF ₅ → 5CaF ₂ + 3CO + CO ₂ + H ₂
[Adverse reaction]
5CaO + 2C ₂ HF ₅ → 5CaF ₂ + 1.5C + 2.5CO ₂ + H ₂
<< Freon R143a: 2C ₂ H ₃ F ₃ >>
[Main reaction]
3CaO + 2C ₂ H ₃ F ₃ → 3CaF ₂ + CO + C + 3H ₂
[Adverse reaction]
3CaO + 2C ₂ H ₃ F ₃ → 3CaF ₂ + 2C + 0.5CO ₂ + 3H ₂

The relationship between the supply amount of Freon gas 1 to be decomposed and the amount of calcium oxide 25 may be appropriately selected within a range in which a decomposition rate of 99.9% or more can be achieved. As shown in Examples 1 to 5, the supply amount of Freon gas 1 is set to 0.3 kg / h (volume flow rate 2.15 L / min) with respect to the amount of calcium oxide 25 stored in the reactor 30 of 0.85 kg. As a result, a decomposition rate of 99.9% or more could be achieved. If the amount of calcium oxide 25 is the same, the purity of calcium fluoride produced as will be described later is increased by reducing the flow rate of the supplied chlorofluorocarbon 1.

Next, as shown in FIG. 2, the decomposition gas 5 is supplied to appropriate carbon monoxide removing devices 50a and 50b, and the carbon monoxide removing 51 is performed as shown in FIG. As the carbon monoxide removing devices 50a and 50b, for example, a selective carbon monoxide oxidizing device or a carbon monoxide adsorbing device can be used. As the carbon monoxide adsorber, an adsorbent having a pore diameter that adsorbs carbon monoxide and does not adsorb carbon dioxide and hydrogen can be used. The Leonard Jones constant (molecular diameter) of carbon monoxide and carbon dioxide is 0.359 nm for carbon monoxide and 0.399 nm for carbon dioxide, so the pore diameter between them is 0.36 nm × 0.36 nm. It is possible to separate with a zeolite having a structure code RHO having a structure code of RHO or a zeolite having a structure code CHA having a pore diameter of 0.38 nm × 0.38 nm. The pore diameter of the adsorbent is larger than the molecular diameter of hydrogen 10, but since zeolite does not adsorb hydrogen 10, hydrogen 10 simply passes through the pores. In the illustrated example, two carbon monoxide removing devices 50a and 50b were used, but the number is not specified. Further, in FIG. 2, 4e, 4f, 4g, 4h, and 4i are sluice valves, respectively, and are supplied to the carbon monoxide removing devices 50a and 50b of the decomposition gas 5 or from the carbon monoxide removing devices 50a and 50b.・ It is possible to shut off.

The carbon monoxide 20 removed from the decomposition gas 5 is detoxified by being desorbed from the adsorbent and subjected to combustion treatment 53 by the combustion device 52, and then released into the atmosphere 52a. As a result, the carbon monoxide removal 51 can be performed from the decomposition gas 5 to obtain the target gas 55 composed of the hydrogen 10 containing a trace amount of carbon dioxide 15, and the hydrogen 10 can be recovered as a useful resource. Although the target gas 55 containing hydrogen 10 as a main component contains a small amount of carbon dioxide 15, it does not hinder the effective use of hydrogen 10. Therefore, one of the features of the present invention is that hydrogen 10 containing a trace amount of carbon dioxide 15 is generated from chlorofluorocarbon 1 by decomposing chlorofluorocarbon 1, so that it can be reused as a useful resource. The carbon dioxide 15 may be removed from the decomposition gas 5 together with the carbon monoxide 20, or the carbon dioxide 15 may be removed from the target gas 55.

The freon gas decomposition device is connected to a fuel cell 70 that separates the negative electrode 70a and the positive electrode 70b via an electrolyte membrane and supplies hydrogen as a fuel to the negative electrode 70a, and hydrogen containing a trace amount of carbon dioxide 15 generated from the freon gas 1. The target gas 55 composed of 10 is supplied as fuel to the negative electrode 70a of the fuel cell 70 to generate power. The generated electric power is stored in the battery 71 and can be used as electric power for various power sources 73 from the inverter 72 via an appropriate control box. Specifically, it can be used as a power source for the heating heater 34 that heats the reactor 30 or as a power source for other control systems. The power supply to the heater 34 of the Freon gas decomposition device and the power supply of other control systems may be directly performed from the inverter 72 via the wiring 74 without going through the control box. As a result, the decomposition of Freon gas 1 can be realized by a method close to zero emission without imposing a load on the environment. Reference numeral 75 is an oxygen supply port for supplying oxygen to the positive electrode 70b, 76 is a discharge port for water, nitrogen, carbon dioxide, etc. generated by power generation, and 77 is a discharge tank for storing water.

On the other hand, the reaction residue 40 after decomposing the chlorofluorocarbon 1 with the calcium oxide 25 can be easily treated as a solid substance because superheated steam does not intervene in the decomposition of the chlorofluorocarbon 1. As will be described later, this solid contains a solid of calcium fluoride 45 and can be reused as a useful resource.

[Second Embodiment]
Next, a method for decomposing chlorofluorocarbons according to the present invention and a second embodiment of the apparatus thereof will be described with reference to FIGS. 3, 4, and 5. The same steps and the same members as those in the first embodiment are designated by the same reference numerals, and the description thereof will be omitted. In the second embodiment, hydrogen 10 is generated from the carbon monoxide 20 contained in the decomposition gas 5 by an aqueous shift reaction 60, the total amount of hydrogen 10 generated from the decomposition gas 5 is increased, and the amount of power generated by the fuel cell 70 is increased. It is characterized by increasing.

The composition of the decomposition gas 5, for example, the decomposition gas 5 of Freon R32 (HFC) shown in Example 1 is 10: 45.8% for hydrogen, 20: 44.3% for carbon monoxide, and 15: 9.9% for carbon dioxide. Yes, it contains as much as 44.3% carbon monoxide 20. Since hydrogen 10 can be generated from the carbon monoxide 20 by the aqueous shift reaction 60 as shown in the following equation 1, the carbon monoxide 20 in the decomposition gas 5 is burned as shown in the first embodiment. Instead of 53 (see FIG. 1), it will be effectively used as a raw material for increasing the amount of hydrogen 10.
CO + H ₂ O ⇔ CO ₂ + H ₂ (1 set)

Therefore, the decomposition gas 5 composed of hydrogen 10, carbon monoxide 20, and carbon dioxide 15 discharged from the reactor 30 is supplied to the aqueous shift reaction tube 65 (see FIG. 4), and steam is supplied into the aqueous shift reaction tube 65. By supplying a predetermined amount of steam 61 from the tube 66 and keeping the temperature of the decomposition gas 5 at a predetermined temperature 62 (for example, 200 ° C.), hydrogen monoxide 20 in the decomposition gas 5 is hydrogenated by the aqueous shift reaction 60. 10 is generated and used as the second decomposition gas 6. In addition, in FIG. 4 and in the pipeline after the gas sampling point 3, sluice valves (not shown) are installed at appropriate positions, and gas such as the second decomposition gas 6 can be supplied / shut off. ..

In the aqueous shift reaction 60, the reaction from either the right side or the left side of the set proceeds depending on the temperature, and the lower the temperature, the more the reaction proceeds from the left side to the right side to generate hydrogen. The equilibrium constant increases as the temperature decreases, but the reaction rate slows down. Therefore, in this embodiment, 200 ° C. was selected as the predetermined temperature 62 in the feasible temperature range from the equilibrium constant and the generally controllable temperature range. In addition, the decomposition gas 5 is produced by directly contacting the fluorocarbon gas 1 and the calcium oxide 25 at 600 ° C., which increases the cost for cooling the temperature of the decomposition gas 5 to a temperature lower than 200 ° C. It is also to avoid it. The predetermined temperature 62 of the decomposition gas 5 is not limited to 200 ° C., and a temperature suitable for the aqueous shift reaction 60 may be appropriately selected.

（２式）


この２式をｘについてとけば
ｘ＝０．９４（ｍｏｌ／ｖ）
が得られる。したがって１モルの一酸化炭素２０から０．９４モルの水素１０が生成されることになり、この状態で平衡状態となる。実施例１の分解ガス５についての水性シフト反応６０の結果を表４に示す。 Since the equilibrium constant K = 2.359 × 102 at ²⁰⁰ ° C., if the molar concentration of each gas before the reaction is [carbon monoxide: 1 mol / V] [water: 1 mol / V], the equilibrium is achieved. The molar concentration of carbon dioxide and water on the right side of time is the same, and if this is x, the following two equations are obtained from the definition of the equilibrium constant.

(2 formulas)


If these two equations are solved for x
x = 0.94 (mol / v)
Is obtained. Therefore, 0.94 mol of hydrogen 10 is produced from 1 mol of carbon monoxide 20, and an equilibrium state is reached in this state. Table 4 shows the results of the aqueous shift reaction 60 for the decomposition gas 5 of Example 1.

The aqueous shift reaction 60 is allowed to proceed while measuring the hydrogen concentration in the decomposed gas 5 (see FIG. 3) from the gas sampling port 67 installed in the aqueous shift reaction tube 65, and the decomposed gas is taken from the steam supply pipe 66 as needed. The steam supply 61 is repeated in step 5. When the production of hydrogen 10 from the carbon monoxide 20 in the decomposition gas 5 is completed, the second decomposition gas 6 that has undergone the aqueous shift reaction 60 is supplied to the steam condensing device 68 to perform steam condensation 64 to remove steam. The third decomposition gas 7 is obtained. After that, the third decomposition gas 7 is supplied to an appropriate carbon monoxide removing device 50, and the carbon monoxide removing 51 is performed to obtain the target gas 55. The carbon monoxide 20 removed from the third decomposition gas 7 is detoxified by a combustion treatment 53 by a combustion device 52 such as by desorbing from an adsorbent, and then released into the atmosphere 52a. This is because the aqueous shift reaction 60 is an equilibrium reaction and cannot convert all the carbon monoxide 20 into hydrogen 10, so that the remaining carbon monoxide 20 needs to be detoxified.

Since the hydrogen 10 obtained by the aqueous shift reaction 60 described above has carbon monoxide 20 in the decomposition gas 5 converted to hydrogen 10 in addition to the hydrogen 10 contained in the decomposition gas 5, the first embodiment is used. About twice the amount of hydrogen 10 can be obtained.

The obtained target gas 55 is supplied as fuel to the negative electrode 70a of the fuel cell 70 to generate electricity in the same manner as in the first embodiment, and is reused as a power source for the heating heater 34 or the like in the same manner as in the first embodiment. conduct.

Since the chlorofluorocarbon 1 to be decomposed in the present invention contains fluorine as well as hydrogen, calcium fluoride (CaF ₂ , fluorite) as a useful resource for the reaction residue 40 in both the first embodiment and the second embodiment ) 45 is contained as a solid substance. Therefore, according to the present invention, calcium fluoride 45 can be recovered in the form of a reusable solid substance. Even if the reaction residue 40 is discarded, it is a solid substance, so that the treatment is easy. Therefore, the present invention is characterized in that by decomposing chlorofluorocarbon 1, calcium fluoride 45 in a state of being contained as a solid in the reaction residue 40 after decomposition of chlorofluorocarbon 1 is generated and can be reused as a useful resource. It is one of. Further, if the purity of the recovered calcium fluoride 45 can be controlled to be high, the possibility of reuse will be further expanded.

Calcium fluoride 45 with a purity of 60% to 80% is equivalent to the purity of ordinary natural fluorite, and is a slag-promoting flux for calcium oxide mainly for removing impurities in the steelmaking process of cast steel products. It is used as. Further, when the purity is 97% or more, it can be used mainly as a raw material for hydrofluoric acid, and its value is dramatically increased. Further, when the purity is 99.95% or more, it is mainly used as an optical crystal material for high-grade lenses and the like.

When the purity of calcium fluoride 45 contained in the reaction residue 40 of Example 1 was confirmed, it was 49.4%. The amount of Freon R32 added was 0.32 kg, which corresponds to 0.4 equivalent, with respect to 25: 0.85 kg of calcium oxide. In order to increase the purity of the calcium fluoride 45 contained in the reaction residue 40, the amount of freon gas 1 supplied to the calcium oxide 25 stored in the reactor 30 is increased, and the amount of fluorine that reacts with the calcium oxide 25 is increased. However, if the supply amount of flon gas 1 is simply increased with respect to the amount of calcium oxide 25, the decomposition capacity of calcium oxide 25 stored in the reactor 30 will be exceeded and the decomposition rate will deteriorate. Therefore, it becomes impossible to achieve a decomposition rate of 99.9% or more.

Therefore, in the present invention, in order to maintain the decomposition rate of Freon gas 1 of 99.9% or more and increase the purity of calcium fluoride 45 contained in the reaction residue 40, the reaction is carried out as another example of the decomposition apparatus of Freon gas 1. The role of the vessel 30 is to be assigned to the first reactor 30a for increasing the purity of calcium fluoride 45 contained in the reaction residue 40 and the second reactor 30b for maintaining the decomposition rate of chlorofluorocarbons of 99.9% or more. We decided to divide the roles. By this division of roles, chlorofluorocarbon 1 can be decomposed to a decomposition rate of 99.9% or more, and the purity of calcium fluoride 45 contained as a solid substance in the reaction residue 40 can be controlled to be high, for example, a purity of 97% or more. It will be possible to collect it at. The configuration was described with reference to FIG. 6, and various chlorofluorocarbons 1 including HFC chlorofluorocarbon R32 were decomposed. The first reactor 30a and the second reactor 30b can be used in place of the reactor 30 in any of the first and second embodiments described above.

As shown in FIG. 6, a second reactor 30b having the same configuration as the first reactor 30a having a diameter of 125 mm and a length of 200 mm is connected in series, and crushed stone of silicon carbide (SiC) 35 as a refractory material is placed inside each of them. It was laid, and calcium oxide 25: 0.85 kg as a reactant was charged into each of the calcium oxide inlets 32a and 32b provided above the first reactor 30a and the second reactor 30b and filled therein. .. Then, the first reactor 30a and the second reactor 30b are heated by the heating heaters 34a and 34b, the inside of each is kept at 600 ° C., and the HFC front R32 (CH ₂ F ₂ ) filled in the gas bomb 2 is charged. The decomposed gas 5 supplied from the gas supply port 31a into the first reactor 30a, directly contacted with the calcium oxide 25 to decompose, and discharged from the gas discharge port 33a of the first reactor 30a is discharged from the gas supply port 31b. It was supplied into the second reactor 30b, directly contacted with calcium oxide 25 to decompose, and discharged from the gas discharge port 33b of the second reactor 30b. By sampling the decomposition gas 5 discharged from the gas discharge port 33b at the sampling point 3 and analyzing it with a gas chromatograph, the decomposition rate of the decomposition gas 5 discharged from the gas discharge port 33b is 99.9% or more. 0 through the pressure control valve 37 and the gas flow meter 38 so as to be 0.7 equivalent (0.54 kg) with respect to 0.85 kg of calcium oxide 25 filled in the first reactor 30a within the range that can be held. It was supplied at 3 kg / h. The purity of calcium fluoride 45 in the reaction residue 40 in the first reactor 30a and the second reactor 30b was measured. In FIG. 6, 4a, 4b, 4c, 4m, 4n, and 4o are sluice valves, and Freon gas 1 and decomposition gas 5 can be supplied / shut off in their respective pipelines.

Calcium fluoride 45 in the reaction residue 40 in the first reactor 30a and the second reactor 30b has the same configuration as in Example 6 except that the supply amount of Freon R32 is 1.0 equivalent (0.78 kg). The purity was measured.

Calcium fluoride 45 in the reaction residue 40 in the first reactor 30a and the second reactor 30b has the same configuration as in Example 6 except that the supply amount of Freon R32 is 1.1 equivalent (0.86 kg). The purity was measured.

Calcium fluoride 45 in the reaction residue 40 in the first reactor 30a and the second reactor 30b has the same configuration as in Example 6 except that the supply amount of Freon R32 is 1.2 equivalent (0.94 kg). The purity was measured. Table 5 shows the analysis results of the purity and the like of calcium fluoride 45 contained in the decomposition gas 5 and the reaction residue 40 shown in Examples 6 to 9.

As shown in Table 5, by setting the supply amount of Freon R32 to 1.1 (0.86 kg) or more, the reaction residue 40 of the first reactor 30a can be used as a raw material for hydrofluoric acid by a fluorine chemical manufacturer. High-purity calcium fluoride 45 having a purity of more than 97% can be recovered. Therefore, it is possible to control the purity of calcium fluoride 45 recovered from the reaction residue 40 by adjusting the supply amount of Freon gas.

In Examples 6 to 9, since the decomposition rate of Freon R32 is maintained at 99.9% or more, the purity of calcium fluoride 45 as the reaction residue 40 in the second reactor 30b is remarkably low. The purity of calcium fluoride 45 can be increased by storing the reaction residue 40 in the second reactor 30b together with the calcium oxide 25 in the first reactor 30a to be newly decomposed and decomposing the chlorofluorocarbon 1. .. An example is shown as Example 10 using the reaction residue 40 in the second reactor 30b in Example 8.

The same as in Example 8 except that the reaction residue 40: 0.90 kg in the second reactor 30b in Example 8 was stored in the first reactor 30a in addition to the calcium oxide 25 stored in the first reactor 30a. In the configuration, Freon R32 was supplied at 0.3 kg / h until the purity of calcium fluoride 45 in the reaction residue 40 of the first reactor 30a reached 97%, and the first reactor 30a and the second reaction were supplied. The purity of calcium fluoride 45 in the reaction residue 40 in the reactor 30b was measured. The results are shown in Table 6. The amount of Freon R32 added was 0.65 kg, which is 0.82 equivalent to 0.85 kg of calcium oxide 25.

As shown in Example 10, the reaction residue 40 in the second reactor 30b of Example 8 in which the purity of calcium fluoride 45 remains at 18.5% is first combined with calcium oxide 25 in the decomposition of the new freon gas 1. By storing it in the reactor 30a and decomposing the freon gas 1, the purity of calcium fluoride 45 contained in the reaction residue 40 could be dramatically increased to 97.2%. After that, by repeating this operation, the purity of calcium fluoride 45 contained in the obtained reaction residue 40 can be controlled to be high, and for example, it can be recovered with a purity of 97% or more. The first implementation is to control the decomposition gas 5 to only three specific gases, hydrogen 10, carbon monoxide 20, and carbon dioxide 15, to make effective use of hydrogen 10, and to generate hydrogen from carbon monoxide 20. It is the same as the embodiment and the second embodiment.

In recent years, fuel cells have been attracting attention as a new power source. The most typical hydrogen-oxygen fuel cell obtains electricity directly from the electrochemical reaction between hydrogen and oxygen (air), and since only water is discharged from the fuel cell itself, it is clean and extremely quiet. Are better. A fuel cell is configured to supply fuel such as hydrogen from one side separated by an electrolyte membrane and oxygen (air) from the other side. Fuel, which is a negative electrode active material, has the property of wanting to pass electrons to oxygen, which is a positive electrode active material, and when both positive and negative electrodes are connected through an external circuit, current is generated by the movement of electrons from the negative electrode active material to the positive electrode active material. It flows. Here, when the positive and negative active materials come into direct contact with each other, a so-called short-circuit state in which electrons are directly exchanged occurs, and a current cannot be taken out to the outside. Therefore, both the positive and negative electrodes are separated by an electrolyte membrane. However, if electrons move between the positive and negative electrodes through an external circuit, the same kind of charge will continue to accumulate in both the positive and negative electrodes, and the current will not flow immediately. Therefore, the electrolyte membrane conducts ions between the positive and negative electrodes to release the accumulated charge, and a steady current can be obtained. The most typical hydrogen-oxygen fuel cell reactions are shown below.
H ₂ → 2H ⁺ + 2e ^－ ………………………… (3 formulas)
1/2O ₂ + 2H ⁺ + ^2e- → H ₂ O ……………… (4 formulas)

Hydrogen is generated in the decomposed gas by decomposing the chlorofluorocarbon gas containing hydrogen, but there has been no knowledge that links the hydrogen contained in the decomposed gas with the fuel cell. In addition, due to the following obstacles, hydrogen generated by the decomposition of freon gas containing hydrogen can be used as fuel for the fuel cell simply by connecting the decomposing device for the freon gas containing hydrogen to the fuel cell. There wasn't. In addition, in order to enable the use of hydrogen as an actual industrial device, the following issues regarding the amount of hydrogen generated by the hydrogen-containing freon gas decomposition device and the power generation generated by the fuel cell must be solved. , It is not possible to achieve a synergistic effect by combining a fuel cell with a decomposing device for freon gas containing hydrogen. In contrast to this conventional technique, the present invention supplies hydrogen 10 generated by decomposing freon gas 1 to a fuel cell 70 as fuel to generate electric power, and the obtained electric power is used as a heater 34 of a decomposing device for freon gas 1 and the like. One of the features is that it is used as a power source for. Therefore, the problems, the amount of power generation, the power application, and the like of the fuel cell 70 using the target gas 55 composed of hydrogen 10 containing a trace amount of carbon dioxide 15 obtained by the present invention as fuel will be verified below.

First, the problems of the fuel cell and carbon monoxide, which are obstacles when the hydrogen 10 produced by the present invention is used as the fuel of the fuel cell 70, will be examined. Since the platinum catalyst, which is often used as an electrode of a fuel cell, is corroded by carbon monoxide, if the decomposition gas contains carbon monoxide together with hydrogen, hydrogen cannot be used as a fuel for the fuel cell. In order to make the fuel cell usable for a long period of time, it is necessary to reduce the concentration of carbon monoxide to the order of several ppm or less. In addition to hydrogen, carbon monoxide is present in the decomposition gas according to the present invention at a high concentration, and cannot be used as it is as a fuel for a fuel cell.

On the other hand, since carbon dioxide does not corrode the electrodes, even if a certain amount is supplied to the fuel cell together with hydrogen, the power generation of the fuel cell is not adversely affected.

Next, the problems of the amount of hydrogen 10 produced by the present invention, the amount of power generation, and the use of the generated power will be verified. In order to combine the hydrogen contained in the decomposition gas with the fuel cell, it is necessary to secure the necessary amount of hydrogen that enables the fuel cell to generate electricity. Further, by using the electric power generated by the fuel cell as the electric power of the decomposition device of the front gas 1 according to the present invention, the synergistic effect of the two can be achieved for the first time.

In the present invention, in order to solve the above-mentioned inhibition reasons and problems, the carbon monoxide 20 contained in the decomposition gas 5 is removed by the carbon monoxide removing device 50, so that the decomposition gas 5 is the hydrogen 10 and the fuel cell 70. It becomes a trace amount of carbon dioxide 15 that is acceptable as a fuel. Further, paying attention to the carbon monoxide 20 contained in the decomposition gas 5 in substantially the same amount as the hydrogen 10, hydrogen 10 is generated from the carbon monoxide 20 by the above-mentioned aqueous shift reaction 60 instead of simply removing the hydrogen monoxide 20, and the amount of hydrogen 10 is slightly increased. By removing the remaining carbon monoxide 20 with the carbon monoxide removing device 50, the target gas 55 contains approximately twice the amount of hydrogen 10 contained in the decomposition gas 5 and a trace amount allowed as fuel for the fuel cell 70. It becomes 15 carbon monoxide. That is, the target gas 55 is composed of hydrogen 10 containing a trace amount of carbon dioxide 15. Further, when the amount of hydrogen 10 is insufficient, the generated hydrogen 10 can be stored in a gas cylinder or the like and used as fuel for a fuel cell.

The negative electrode 70a and the positive electrode 70b are separated from each other by separating the negative electrode 70a and the positive electrode 70b with the negative electrode 70a and the negative electrode 70a. It is supplied as fuel to the negative electrode 70a of the fuel cell 70 that supplies hydrogen 10 as fuel to generate power. Therefore, according to the present invention, the above-mentioned reasons for inhibition and problems can be solved, and the hydrogen 10 produced by decomposing the chlorofluorocarbon 1 can be effectively used as the fuel for the fuel cell 70.

Next, taking Freon R32 (molecular weight 52 g / mol) as an example, the amount of hydrogen 10 and carbon monoxide 20 produced by decomposing Freon gas 1 and the obtained carbon monoxide 20 as raw materials are subjected to hydrogen by an aqueous shift reaction 60. 10 is generated, and the maximum amount of hydrogen when added to the hydrogen 10 obtained by the decomposition reaction is verified. In the decomposition reaction of CFCs R32 by calcium oxide 25, 1 mol of hydrogen is obtained from 1 mol of CFCs from the following 5 equations, so that 22.4 liters of hydrogen, which is the volume of 1 mol of hydrogen, is produced. .. When the supply amount of Freon R32 is 5 kg (5000 g) / h, hydrogen of 2153.7 l / h can be obtained by the decomposition treatment for 1 hour as shown in the formula 7.
CaO + CH ₂ F ₂ = CaF ₂ + CO + H ₂ (5 formulas)
Number of treated moles of Freon 5000/52 = 96.15 mol / h (6 formulas)
22.4 l / mol × 96.15 mol / h = 2153.7 l / h (7 formulas)

Similarly, from the formula 5, 1 mol of carbon monoxide can be obtained from 1 mol of freon, so that 22.4 liters of carbon monoxide, which is the volume of 1 mol of carbon monoxide, is produced. When the supply amount of Freon R32 is 5 kg / h, carbon monoxide of 2153.7 l / h can be obtained as shown in the following formula 8.
22.4 l / mol × 96.15 mol / h = 2153.7 l / h (8 formulas)

Similarly, for each freon gas 1 to be decomposed in the present invention, hydrogen 10 and carbon monoxide 20 and carbon monoxide 20 are produced by an aqueous shift reaction 60 as raw materials when the supply amount per hour is 5 kg / h. Table 7 shows the results of calculation for the maximum amount of hydrogen to which the hydrogen 10 was added.

Next, the amount of power generated by the fuel cell using the above-mentioned amount of hydrogen as fuel, in other words, the amount of hydrogen as fuel required for power generation by the fuel cell will be verified. The reaction formulas for electrolysis are summarized below.
2H ₂ O = 2H ₂ + O ₂ + 2 × 236.965 (kJ)
Since the amount of movement of electrons is one from each hydrogen atom of water, a total of four electrons move. Therefore, considering Faraday's law and the fact that the valence of hydrogen is 1, a charge of 1F (Faraday) = 96500 (C / mol) is required to extract 1 g equivalent of hydrogen. This value is the number of e ^- charge 1.60206 × ^10-19 (C) and 1 mol of electrons (in the case of monovalent, the number of electrons emitted from 1 mol of atom is the same as the number of 1 mol of atom). It is a value multiplied by 6.02486 × 10 ²³ (1 / mol). According to the electrolysis reaction formula, one electron is flowing from each of 4 mol hydrogen atoms, so that a total charge of 96500 × 4 = 386000 (C) is flowing.

Examining the free energy of Gibbs in the electrolytic reaction formula, the free energy of water itself is ΔG = -236.965KJ, but since it shifts to +, it is an endothermic reaction in which the reaction to the right does not normally proceed. By adding electrical energy, the reaction proceeds to the right, and the required energy is 2 x 236.965 = 473.93KJ.
Will be.
To add this energy
From W (J / S) = V (v) x A (C / S)
473.93 (KJ) /386 (KC) = 1.228 (V)
Voltage is required. This voltage is a constant value that is not affected by the amount of charge that flows. This is because the relationship between the amount of electric charge flowing and the free energy (ΔG) is proportional. In reality, an overvoltage is generated due to the influence of polarization that occurs around the electrode, and it is said that decomposition does not proceed at this voltage and at least 2 (v) or more is required.

The amount of hydrogen 10 required for power generation by the fuel cell 70 will be verified. The reaction of the fuel cell 70, which separates the negative electrode 70a and the positive electrode 70b via an electrolyte membrane and supplies hydrogen 10 as a fuel to the negative electrode 70a, is the reverse of the above-mentioned electrolysis and is as follows.
2H ₂ + O ₂ = 2H ₂ O-2 x 236.965 (KJ)
The hydrogen 10 flowing to the negative electrode 70a, which is the fuel electrode, takes electrons by a platinum catalyst and becomes H ₊ + e ⁻ . Since the electrons cannot pass through the electrolytic solution, they travel through the conducting wire, and the hydrogen ions are attracted to + (the potential of the opposite station increases when the electrons are emitted) and move through the electrolyte. On the other hand, the positive electrode 70b, which is an oxygen electrode, receives the flowing electrons by the platinum catalytic effect ^and becomes O−. These oxygen ions react with two hydrogen ions that have passed through the electrolyte to form _H2O . A common electrolyte is a polymer electrolyte electrolyte (PEFC), which allows only hydrogen ions to pass through (small passage holes and only hydrogen ions can pass through). When the generated voltage is calculated, the free energy (ΔG) and the number of passing electrons are 4 (because it is 4 hydrogen atoms), and the numbers at the time of water splitting can be used as they are.
Since 473930 (J) = 4 × 96500 (C) × V (v), V = 1.2277 (v). However, this is also actually 0.9 to 0.7 (v) due to polarization around the electrodes. The reaction enthalpy change is ΔH _f = 285.56 KJ / mol, and ΔH _f −ΔG _f = 285.56- (-236.965) = −48.595 KJ is from the surroundings even if it is not from the electric power (KW). It can be taken from the heat.

Here, the amount of hydrogen 10 that must be supplied to the fuel cell 70 is roughly calculated. Assuming that the electromotive force of one cell is 0.7V, 100000 (A) is passed and the output is 70 (KW). From 1F (Faraday) = 96500 (C)
Since 100,000 (C) / 96500 (C) = 1.036≈1, 1 g equivalent of hydrogen element (H) is 1 g, so approximately 1 F charge is required to flow 100,000 (A), and 1 g. Hydrogen is needed. Since the hydrogen molecule (H ₂ ) is 2 g / mol and 22.4 l, 1 g is 22.4 / 2 = 11.2 (l). Therefore, if 11.2 liters of hydrogen is flowed in 1 second, an output of 70 KW can be obtained in 1 cell. However, the voltage of a normal fuel cell is used by AC-converting a DC voltage of about 100 V with an inverter. That is, (100 / 0.7 =) 142 cells are connected in series and used. When connected in series, the voltage is additive, but the hydrogen flow rate per cell is 70,000 (w) and the voltage is 100 (v), so the current is 70,000 (w) / 100 (v) = 700 (A). Is required.
700 (C) / 96500 (C) = 7.25 × 10 ^-3
Therefore, the amount of hydrogen required per unit time (1s) flowing through each cell is
11.2 (l) × 7.25 × 10 ^-3 = 0.082 (l).

According to the present invention described above, since the superheated steam is not used, the energy and equipment for obtaining the superheated steam required in the conventional superheated steam invention and the document 3 invention are not required, and the superheated steam is decomposed. There is no generation of acidic gas due to involvement and there is no need to shower mixed water with calcium hydroxide and water to neutralize the acidic gas. Therefore, since the reaction residue becomes a solid substance, the treatment becomes easy, and the durability of the decomposition apparatus can be maintained high. Moreover, the reaction temperature may be about 600 ° C., the reaction temperature can be significantly reduced as compared with the superheated steam invention, and the power consumption for maintaining the temperature inside the reactor can be reduced, so that the running cost can be reduced. It is possible to suppress the problem and to extend the life of the disassembly device.

In addition, the decomposition gas can be controlled to specific gases such as hydrogen, carbon monoxide, and carbon dioxide, and no other hydrocarbon-based gas is generated, so that the treatment is easy. Since the proportion of hydrogen contained in the decomposition gas is large, it can be recovered and reused as a useful resource. Specifically, electric power can be generated by supplying the target gas containing a large amount of hydrogen obtained by decomposing the freon gas containing both hydrogen and fluorine to the negative electrode of the fuel cell as fuel, and the electric power can be generated by the decomposition apparatus. It can be used as it is as various power sources such as a heater. Alternatively, by storing electricity in the battery, it can be used for other than the disassembling device. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a new device in which a decomposing device for chlorofluorocarbons containing both hydrogen and fluorine and a different kind of device such as a fuel cell are organically bonded. Moreover, by using the electric power obtained from the fuel cell as the power source for the decomposition device, it is more environmentally friendly, can be reused from the freon gas containing both hydrogen and fluorine, and hydrogen as a useful resource can be recovered infinitely. , Can approach zero emissions.

The decomposition gas contains almost the same amount of carbon monoxide as hydrogen, and when hydrogen is supplied as fuel for a fuel cell, carbon monoxide becomes a catalyst poison and the life of the catalyst is extremely shortened. Remove and burn. Alternatively, in order to make effective use of carbon monoxide, water vapor is supplied to the decomposition gas and the decomposition gas is kept at a predetermined temperature to cause an aqueous shift reaction, and hydrogen is generated from the carbon monoxide. Together with the hydrogen produced by the decomposition, the amount of hydrogen contained in the target gas supplied to the fuel cell can be doubled, and the amount of power generated by the fuel cell can be increased. Moreover, since carbon monoxide combustion treatment is not required, it is possible to approach zero emissions. Since carbon dioxide contained in the target gas is a trace amount that does not affect the electrolyte membrane of the fuel cell, it may be supplied to the negative electrode of the fuel cell together with hydrogen.

Since the decomposing chlorofluorocarbon contains fluorine as well as hydrogen, calcium fluoride, which has a high resource value as a reaction residue, can be obtained as a recoverable solid substance with a high purity of 97% or more, and can be reused as a useful resource. It will be possible to use it. Therefore, according to the present invention, it is possible to realize a technology that is more friendly to the global environment, and it is possible to contribute to the reduction of the environmental load, which is the social demand and the era demand for the fluorocarbon decomposition device.

1 ... Freon gas containing both hydrogen and fluorine 2 ... Gas cylinder 3 ... Sampling point 5 ... Decomposition gas 6 ... Second decomposition gas 7 ... Third decomposition gas 10 ... Hydrogen 15 ... Carbon dioxide 20 ... Carbon monoxide 25 ... Calcium oxide 30 ... Reactor 31 ... Gas supply port 32 ... Calcium oxide inlet 33 ... Gas discharge port 34 ... Heating heater 35 ... Silicon carbide 36, 62 ... Predetermined temperature 37 ... Pressure control valve 38 ... Gas flow meter 40 ... Reaction residue 45 ... Huh Calcium chemicals 50, 50a, 50b ... Carbon monoxide remover 55 ... Target gas 60 ... Aqueous shift reaction 61 ... Steam supply 63 ... Hydrogen concentration measurement 64 ... Steam condensation 65 ... Aqueous shift reaction tube 66 ... Steam supply tube 67 ... Gas sampling Mouth 68 ... Steam condensing device 70 ... Fuel cell 70a ... Negative negative 70b ... Positive

Claims (14)

It is characterized in that chlorofluorocarbons containing both hydrogen and fluorine are decomposed into decomposition gas consisting only of hydrogen, carbon monoxide and carbon dioxide by directly contact-reacting with calcium oxide in a reactor kept at a predetermined temperature. How to decompose fluorocarbons. It consists of only hydrogen, carbon monoxide and carbon dioxide by supplying calcium oxide inside and supplying fluorocarbon gas containing both hydrogen and fluorine to a reactor heated to a predetermined temperature and causing a direct contact reaction with calcium oxide. Decomposes into decomposition gas,
A method for decomposing chlorofluorocarbons, which comprises removing carbon monoxide from the decomposition gas to obtain a target gas consisting of hydrogen containing a trace amount of carbon dioxide. It consists of only hydrogen, carbon monoxide and carbon dioxide by supplying calcium oxide inside and supplying fluorocarbon gas containing both hydrogen and fluorine to a reactor heated to a predetermined temperature and causing a direct contact reaction with calcium oxide. Decomposes into decomposition gas,
The decomposition gas is held at a predetermined temperature and supplied to the aqueous shift reaction tube together with steam to cause an aqueous shift reaction, and hydrogen is generated from carbon monoxide in the decomposition gas to obtain a second decomposition gas.
The second decomposition gas is supplied to the steam condensing tank to condense and remove the steam in the second decomposition gas to obtain the third decomposition gas.
A method for decomposing chlorofluorocarbons, which comprises removing residual carbon monoxide from a third decomposition gas to obtain a target gas composed of hydrogen containing a trace amount of carbon dioxide. The method for decomposing chlorofluorocarbons according to claim 3, wherein the decomposition gas is maintained at 200 ° C. or higher. The method for decomposing chlorofluorocarbons according to claim 1, 2, 3 or 4, wherein the temperature in the reactor is maintained at a temperature at which the decomposition rate of chlorofluorocarbons containing both hydrogen and fluorine is 99.9% or more. The method for decomposing chlorofluorocarbons according to claim 1, 2, 3 or 4, wherein the temperature in the reactor is maintained at 600 ° C. or higher. A reactor containing calcium oxide inside, a heating means for heating the reactor to a predetermined temperature, and hydrogen obtained by directly reacting freon gas containing both hydrogen and fluorine in the reactor with calcium oxide. It consists of a carbon monoxide remover that supplies a decomposition gas consisting only of carbon oxide and carbon dioxide.
A chlorofluorocarbon decomposition device characterized by removing carbon monoxide from the decomposition gas to obtain a target gas consisting of hydrogen containing a trace amount of carbon dioxide. A reactor containing calcium oxide inside, a heating means for heating the reactor to a predetermined temperature, and hydrogen obtained by directly contacting a freon gas containing both hydrogen and fluorine in the reactor with calcium oxide. An aqueous shift reaction tube that supplies a decomposition gas and water vapor consisting only of carbon oxide and carbon dioxide, and a water vapor that supplies a second decomposition gas that produces hydrogen from carbon monoxide in the decomposition gas by an aqueous shift reaction in the aqueous shift reaction tube. It consists of a condensing tank and a carbon monoxide removing device that supplies a third decomposition gas obtained by condensing the water vapor in the second decomposition gas in the steam condensing tank.
A fluorocarbon decomposition apparatus characterized in that carbon monoxide is removed from the third decomposition gas to obtain a target gas composed of hydrogen containing a trace amount of carbon dioxide. The fluorocarbon gas decomposition device according to claim 7 or 8, wherein a selective carbon monoxide oxidizing device or a carbon monoxide adsorbing device is used as the carbon monoxide removing device. Hydrogen characterized by producing hydrogen containing a trace amount of carbon dioxide from chlorofluorocarbon by decomposing chlorofluorocarbon containing both hydrogen and fluorine by the method for decomposing chlorofluorocarbon according to any one of claims 2 to 3. Production method. Calcium fluoride in a state of being contained as a solid in the reaction residue after decomposition of chlorofluorocarbons by decomposing chlorofluorocarbons containing both hydrogen and fluorine by the method for decomposing chlorofluorocarbons according to any one of claims 1 to 6. A method for producing calcium fluoride, which comprises producing. The method for producing calcium fluoride according to claim 11, wherein the purity of calcium fluoride is 97% or more. The freon gas decomposition device according to any one of claims 7 to 9 is connected to a fuel cell that separates the negative electrode and the positive electrode via an electrolyte membrane and supplies hydrogen as a fuel to the negative electrode, and transfers both hydrogen and fluorine. A fuel cell characterized in that power is generated by supplying a target gas composed of hydrogen containing a trace amount of carbon dioxide obtained by supplying the contained freon gas to the freon gas decomposition apparatus and decomposing it to the negative electrode as fuel. The fuel cell according to claim 13, wherein the electric power generated by the fuel cell is used as a power source for a heating means of a freon gas decomposition device.

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