Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
  • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
  • F24S80/20—Working fluids specially adapted for solar heat collectors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/10—Liquid materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

• the present invention relates to a heat medium composition.
• the heat medium is widely used in applications such as heat removal for high-temperature exothermic reactions, heat storage bodies, and solar power generation, and is desired to be stable in a wide temperature range from room temperature to high temperature.
• a heat medium conventionally, an aromatic hydrocarbon heat medium composition, for example, a heat medium composition containing biphenyl and diphenyl oxide (diphenyl ether) has been disclosed (for example, see Patent Document 1).
• Patent Document 2 describes that the stabilizing action of diphenylene oxide used in the composition can be applied to a eutectic mixture obtained by adding diphenyl or naphthalene or the like to diphenyl ether.
• a heat medium composition in which diphenyl ether and benzophenone are mixed with at least one component selected from the group consisting of dibenzofuran (diphenylene oxide) and naphthalene at a predetermined ratio (see, for example, Patent Document 3).
• Patent Document 3 discloses that biphenyl can be further added to the heat medium composition.
• a heat medium comprising a mixture of aryl compounds having 2 to 5 phenyl groups, such as biphenyl, diphenyl oxide (diphenyl ether), o-terphenyl, and m-terphenyl, or biphenyl, naphthalene, o-terphenyl
• a quaternary mixture such as m-terphenyl has excellent pumpability at low temperatures due to freezing point depression (see, for example, Patent Document 4).
• Patent Document 4 describes that a small amount of dibenzofuran (diphenylene oxide) or the like may be incorporated into the heat medium.
• a heat medium composition composed of biphenyl, diphenyl ether and diphenylene oxide is excellent in heat resistance and easy to handle due to freezing point depression (see, for example, Patent Document 5).
• the present invention has been made in view of the above, and an object thereof is to provide a heat transfer medium composition that is liquid at a temperature of about 20 ° C., easy to handle, and excellent in heat resistance.
• the inventors of the present invention have a heat medium composition in which biphenyl, diphenyl ether, diphenylene oxide, and naphthalene are mixed at a predetermined ratio, which has excellent thermal stability even at 400 ° C. or higher, and is liquid at room temperature, for example, about 20 ° C. Therefore, it was found that the handleability was excellent, and the present invention was completed.
• the heat medium composition of the present invention contains 5 to 40% by mass of biphenyl, 10 to 70% by mass of diphenyl ether, 5 to 30% by mass of diphenylene oxide, and 5 to 30% by mass of naphthalene.
• the heat medium composition of the present invention in the above invention, is a ratio of 5 to 30% by mass of biphenyl, 10 to 70% by mass of diphenyl ether, 5 to 25% by mass of diphenylene oxide, and 5 to 25% by mass of naphthalene. It is characterized by including.
• the heat medium composition of the present invention in the above invention, is a ratio of 5 to 30% by weight of biphenyl, 10 to 60% by weight of diphenyl ether, 5 to 25% by weight of diphenylene oxide, and 5 to 25% by weight of naphthalene. It is characterized by including.
• the heat medium composition of the present invention is characterized in that, in the above-mentioned invention, it consists only of biphenyl, diphenyl ether, diphenylene oxide, and naphthalene.
• the heat medium composition of the present invention is characterized by being used for solar thermal power generation in the above invention.
• the heat medium composition of the present invention does not impair the thermal stability at a high temperature of 400 ° C. or higher, the heat medium composition can be used continuously for a long period of time. Easy.
• the organic heat medium exhibits the highest heat-resistant temperature, it can be suitably used for heat removal of a high-temperature exothermic reaction, a heat storage body, a solar power generation heat medium, and the like.
• the heat medium composition of the present invention comprises 5 to 40% by mass of biphenyl, 10 to 70% by mass of diphenyl ether, 5 to 30% by mass of diphenylene oxide, and 5 to 30% by mass of naphthalene. To do.
• the inventors of the present invention provide a heat transfer medium composition containing biphenyl, diphenyl ether, diphenylene oxide, and naphthalene in a predetermined blending amount even at a temperature of about 20 ° C. (room temperature) and a high temperature, for example, about 400 ° C. Also found excellent thermal stability.
• the heat medium composition of the present invention contains 5 to 40% by mass of biphenyl, preferably 5 to 30% by mass, more preferably 10 to 30% by mass.
• the content of biphenyl is less than 5% by mass, the blending ratio of other components increases, and as a result, the composition easily solidifies and does not form a liquid at a temperature of about 20 ° C.
• the content of biphenyl is more than 40% by mass, the blending ratio of biphenyl is increased and it is easy to coagulate in the same manner, and does not form liquid at normal temperature (about 20 ° C.).
• the heat medium composition of the present invention contains 10 to 70% by mass of diphenyl ether, preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
• diphenyl ether When the content of diphenyl ether is less than 10% by mass, the blending ratio of other components increases, and as a result, it easily solidifies and does not form liquid at normal temperature (about 20 ° C.).
• the content of diphenyl ether is more than 70% by mass, the blending ratio of diphenyl ether increases and the composition easily becomes solidified and does not form liquid at normal temperature (about 20 ° C.).
• the heat medium composition of the present invention contains 5 to 30% by mass of diphenylene oxide, preferably 5 to 25% by mass, more preferably 5 to 20% by mass.
• diphenylene oxide When the content of diphenylene oxide is less than 5% by mass, the blending ratio of other components increases, and as a result, the composition easily solidifies and does not form liquid at normal temperature (about 20 ° C.).
• it is more than 30% by mass the blending ratio of diphenylene oxide is increased and it is easily solidified in the same manner and does not form liquid at ordinary temperature (about 20 ° C.).
• the heat medium composition of the present invention contains 5-30% by mass of naphthalene, preferably 5-25% by mass, more preferably 5-20% by mass.
• naphthalene preferably 5-25% by mass
• the blending ratio of other components increases, and as a result, the composition easily solidifies and does not form liquid at normal temperature (about 20 ° C.).
• the content of naphthalene is more than 30% by mass, the blending ratio of naphthalene increases and the solidification easily occurs, and the liquid does not form at normal temperature (about 20 ° C.).
• the heat medium composition of the present invention preferably comprises only biphenyl, diphenyl ether, diphenylene oxide, and naphthalene.
• the heat transfer medium composition is liquid at room temperature (about 20 ° C.) and is excellent in thermal stability at 400 ° C. or higher. Because.
• “consisting only of biphenyl, diphenyl ether, diphenylene oxide, and naphthalene” does not exclude impurities derived from biphenyl, diphenyl ether, diphenylene oxide, and naphthalene.
• the production method is not particularly limited, but biphenyl is generally produced using benzene as a raw material with a palladium catalyst.
• biphenyl is produced using benzene
• a small amount of triphenyl, quarterphenyl, polyphenyl and the like by-produced in biphenyl may be contained.
• Diphenyl ether is generally produced by a phenol bimolecular reaction with zeolite.
• a small amount of dibenzofuranphenylphenol, diphenylphenol and the like, which are by-produced in diphenyl ether, may be contained.
• Diphenylene oxide and naphthalene are contained in coal tar and can be obtained by distillation.
• Diphenylene oxide and naphthalene may contain trace amounts of methylnaphthalene, dimethylnaphthalene, fluorene, dibenzothiophene, acenaphthene, carbazole, phenyldibenzofuran, and the like.
• the heat medium composition of the present invention can be used continuously at a high temperature of 400 ° C. or more without impairing the thermal stability.
• the heat resistance of the heat medium composition can be evaluated by, for example, a heat stability test at 430 ° C. In the heat stability test of the heat medium composition, the heat medium composition was put into a sealable container, the container was sealed with nitrogen, and the pressure in the container was adjusted to 2 MPa (room temperature). The container charged with is kept at 430 ° C. for 96 hours. The heat resistance of the heat medium composition was evaluated by the decomposition rate of the heat medium composition.
• the decomposition rate by the heat stability test is preferably 2% or less, more preferably 1.3% or less.
• the decomposition rate of the heat medium composition can be measured by gas chromatography mass spectrometry.
• the ratio of the liquid component produced after the thermal stability test can be evaluated by the decomposition rate measured by the following method.
• An example of analysis conditions is shown below.
• Carrier gas Helium injection amount: 0.2 ⁇ L
• the melting point of the heat medium composition of the present invention is preferably 20 ° C. or less. When the melting point is 20 ° C., handling becomes easy. Although it is preferable that it is 12 degrees C or less, even if it is a case where it exceeds 12 degrees C, it can be used without a problem, if an auxiliary heat retention system like a heat storage tank is used together, for example.
• the heat medium composition of the present invention exhibits the highest heat-resistant temperature as an organic heat medium, it can be used for heat removal of a high temperature exothermic reaction, a heat storage body, solar power generation, for example, a heat medium for concentrating solar power generation, etc. Useful.
• the heat medium composition of the present invention is heated by, for example, using a semi-cylindrical condensing mirror to concentrate sunlight on a pipe installed in front of the mirror and heating the heat medium flowing in the pipe. It can be used as a heating medium for solar power generation of a parabolic trough system that generates steam by generating steam using a heating medium.
• the boiling point of the heat medium composition of the present invention is about 220 to 300 ° C., it may be used under pressure when used at a high temperature above the boiling point.
• Example 1 Biphenyl, diphenyl ether, diphenylene oxide, and naphthalene were blended so as to have the ratio (mass%) shown in Table 1 below to prepare a heating medium composition 1.
• 20 g of heat medium composition is packed in a U-shaped pipe having an inner diameter of 14 mm, a width of 65 mm, and a height of 158 mm, nitrogen is filled in the U-shaped pipe and the pressure is adjusted to 2 MPa, and then a thermal stability test is performed at 430 ° C. for 96 hours. went. The appearance of the heat medium composition before the test at 12 ° C. and 20 ° C.
• the heating medium composition 1 was liquid even at 12 ° C., and the decomposition rate after the thermal stability test was 1.2%.
• Example 2 to 5 Biphenyl, diphenyl ether, diphenylene oxide, and naphthalene were blended in the proportions (mass%) shown in Table 1 below to prepare heating medium compositions 2 to 5.
• the test was performed in the same manner as in Example 1 except that the prepared heat medium compositions 2 to 5 were used. The results are also shown in Table 1.
• the heat medium composition 2 showed a solid content at 12 ° C., but the heat medium compositions 3 to 5 were liquid even at 12 ° C.
• the heat medium compositions 2 to 5 had a decomposition rate of 1.0 to 1.3% after the heat stability test, and it was found that the heat medium compositions were excellent in heat stability.
• a heat medium composition 15 was prepared by blending the formulation disclosed in JP-A No. 05-009465, that is, biphenyl, diphenyl ether, and diphenylene oxide in the proportions (mass%) shown in Table 1 below. The same operation as in Example 1 was carried out except that the adjusted heat medium composition 15 was used. The results are also shown in Table 1. It was found that the heat transfer medium composition 14 disclosed in Japanese Patent Application Laid-Open No. 05-009465 is not liquid at 20 ° C.
• the heat medium composition of the present invention can be used continuously at higher temperatures, it is suitable for heat removal of a high temperature exothermic reaction, a heat storage body, solar power generation and the like.
• the heat medium composition of the present invention in the above-mentioned field, it becomes possible to extend the life and improve the power generation efficiency, and to reduce the running cost.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
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• Combustion & Propulsion (AREA)
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• General Engineering & Computer Science (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• 2013
  • 2013-08-01 JP JP2013160506A patent/JP2015030778A/ja active Pending
• 2014
  • 2014-07-16 US US14/900,197 patent/US20160146510A1/en not_active Abandoned
  • 2014-07-16 WO PCT/JP2014/068949 patent/WO2015016073A1/ja not_active Ceased
  • 2014-07-16 CN CN201480037011.5A patent/CN105339458A/zh active Pending

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