CN107629763B - Novel environment-friendly water-based heat-conducting medium for solar water heater - Google Patents
Novel environment-friendly water-based heat-conducting medium for solar water heater Download PDFInfo
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- CN107629763B CN107629763B CN201710908505.1A CN201710908505A CN107629763B CN 107629763 B CN107629763 B CN 107629763B CN 201710908505 A CN201710908505 A CN 201710908505A CN 107629763 B CN107629763 B CN 107629763B
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a heat-conducting medium for a solar water heater, which comprises the following components in parts by weight: 30.0-50.0 parts of ethylene (propylene) glycol; 0.1-40.0 parts of ethylene (propylene) glycol dibenzoate; 0.01-2 parts of sodium polyphosphate; 0.01-1 part of benzotriazole; 0.01-0.1 part of sodium benzoate; 0.002-0.4 part of tributyl phosphate; 0.01-0.1 part of sodium hydroxide; 6.4-69.858 parts of deionized water. The heat-conducting medium for the solar water heater can automatically replenish lost ethylene glycol (propylene glycol), does not adopt compounds such as nitrite, chromate, borax and the like with high toxicity, is a novel and environment-friendly water-based heat-conducting medium, can work at a high temperature state for a long time, and greatly prolongs the service life of the heat-conducting medium.
Description
Technical Field
The invention relates to a heat-conducting medium, in particular to a novel environment-friendly water-based heat-conducting medium applied to a solar water heater.
Background
At present, China is in the period of urbanization high-speed development, and high-rise residences with the characteristics of high volume rate, high greenbelt rate and the like are main residential types in large and medium cities in the future. In residential buildings, the energy consumption in the process of producing domestic hot water is the second largest load except for heating and air conditioning, and the solar energy is used as a heat source to supply the domestic hot water, so that the energy-saving technology is effective.
The heat-conducting medium with long service life and high-efficiency heat-conducting performance is the key for improving the utilization rate of the solar water heater. At present, heat-conducting media used by various solar water heater production enterprises in China are basically formed by slightly modifying an automobile engine antifreeze solution. However, compared with the antifreeze used for automobile engines, the solar water heater has a very different use environment, and inevitably has different technical index requirements on the heat-conducting medium, such as stricter requirements on harmlessness to human bodies, longer service life, capability of meeting the requirement of working at a higher temperature for a long time, and the like.
An antifreezing liquid composition (CN 1037356A) for the cooling water tank of IC engine is prepared from benzoic acid, p-tert-butyl benzoic acid, n-hexanoic acid, lauric acid, sebacic acid, phthalic acid and tartaric acid, and inorganic salt as assistant metal corrosion inhibitor, such as borax, sodium nitrate and sodium dihydrogen phosphate.
An engine antifreeze (CN 101691484A) discloses a composition of an antifreeze for an engine, which is prepared by adopting a compound of organic acid and inorganic salt as a metal corrosion inhibitor of the antifreeze on the basis of inorganic and all-organic engine antifreeze, wherein the organic acid is sebacic acid and isooctanoic acid, and the inorganic salt is sodium molybdate.
The phosphorus-free multi-effect antifreeze (CN 101892035A) discloses a phosphorus-free antifreeze for automobile engines, which is used as a metal corrosion inhibitor in a manner of compounding organic acid and inorganic salt, wherein the inorganic salt is molybdate and sodium nitrate, and sebacic acid is used as an organic acid metal corrosion inhibitor to jointly protect metals.
An automobile antifreeze (CN 103160255A) with good stability discloses an antifreeze for an automobile engine, which takes molybdate, sodium nitrate and sebacic acid as metal corrosion inhibitors to provide durable metal corrosion inhibition protection for the automobile engine.
The heat-conducting media involved in the above patents all adopt ethylene glycol or propylene glycol and water as basic components, and adopt a compound system of organic acid and inorganic salt as a metal corrosion inhibitor of the heat-conducting media. However, ethylene glycol or propylene glycol is degraded in a high-temperature environment to generate acidic substances such as ethacrylic acid (propandiol), ethacrylic acid (propanaldehyde acid) and ethanedioic acid (malonic acid), which not only reduces the concentration of ethanediol and prevents the freezing point and the boiling point of the heat-conducting medium from meeting the initial requirements, but also causes metal corrosion and reduces the service life of the heat-conducting medium.
More importantly, although the phenomenon that the automobile antifreeze is used as the solar heat-conducting medium exists in the market, the method that the automobile antifreeze is used as the solar heat-conducting medium has many defects or hidden troubles due to different applicable systems and performance requirements of the automobile antifreeze and the solar heat-conducting medium. For example: the parts of automobile engine and cooling system are made of die-cast aluminum alloy, cast iron, steel, brass, red copper, soldering tin and the like, wherein cast aluminum is the material of most parts in the system, and cast aluminum is the link which is most easily corroded and damaged, so the corrosion inhibition and pH value design of the automobile antifreeze mainly aims at the cast aluminum and comprehensively prevents corrosion of other metals. At present, metal materials in a split type solar system are carbon steel, brass, red copper and stainless steel, so that corrosion inhibition and pH value design of a special solar heat-conducting medium are specially prevented aiming at the metal materials used by the system, but the metal materials of an automobile engine and a cooling system can not be used as standards and bases, the use environments of an automobile antifreeze and a solar heat-conducting medium are completely different, and a plurality of problems are certainly caused when the automobile antifreeze is simply used as the solar heat-conducting medium.
Disclosure of Invention
In order to overcome the defects, the invention provides a heat-conducting medium for a solar water heater, which takes ethylene (propylene) glycol and water as basic components and provides a corrosion inhibition protection effect for metals such as carbon steel, red copper, brass, aluminum and the like by adding an inorganic/organic compound with a corrosion inhibition function. The added compounds of ethylene (propylene) glycol dibenzoate have potential decomposition capability, when the concentration of the heat-conducting medium is reduced due to thermal decomposition of ethylene (propylene) glycol, the ester compounds can be timely decomposed into ethylene (propylene) glycol, the effect of effectively supplementing the ethylene (propylene) glycol is achieved, the low freezing point and the high boiling point of the heat-conducting medium of the solar water heater are kept, and meanwhile, acid compounds (such as benzoic acid, stearic acid and the like) generated by the decomposition of the ester compounds are also efficient metal corrosion inhibitors. The heat-conducting medium for the solar water heater can automatically replenish lost ethylene glycol to generate an acid compound with a metal corrosion inhibition function, does not adopt compounds such as nitrite, chromate, borax and the like with high toxicity, is a novel and environment-friendly water-based heat-conducting medium, can work at a high temperature state for a long time, and greatly prolongs the service life of the heat-conducting medium.
In order to achieve the purpose, the invention adopts the following technical scheme:
a heat-conducting medium for a solar water heater comprises the following raw materials in parts by weight: 30.0-50.0 parts of ethylene (propylene) glycol; 0.1-40.0 parts of ethylene (propylene) glycol dibenzoate; 0.01-2 parts of sodium polyphosphate; 0.01-1 part of benzotriazole; 0.01-0.1 part of sodium benzoate; 0.002-0.4 part of tributyl phosphate; 0.01-0.1 part of sodium hydroxide; 6.4-69.858 parts of deionized water.
Preferably, 30.0-40.0 parts of ethylene (propylene) glycol; 0.1-20.0 parts of ethylene (propylene) glycol dibenzoate; 0.01-1 part of sodium polyphosphate; 0.01-0.5 parts of benzotriazole; 0.01-0.05 part of sodium benzoate; 0.002-0.2 parts of tributyl phosphate; 0.01-0.05 part of sodium hydroxide; 6.4-29.858 parts of deionized water.
Preferably, 40.0-50.0 parts of ethylene (propylene) glycol; 20.0-40.0 parts of ethylene (propylene) glycol dibenzoate; 1-2 parts of sodium polyphosphate; 0.5-1 part of benzotriazole; 0.05-0.1 part of sodium benzoate; 0.2-0.4 part of tributyl phosphate; 0.05-0.1 part of sodium hydroxide; 29.858-69.858 parts of deionized water.
Preferably, the ethylene (propylene) glycol dibenzoate is one or a mixture of ethylene glycol dimethyl ester, ethylene glycol diethyl ester, ethylene glycol dipropyl ester, ethylene glycol dibutyl ester, ethylene glycol dipentyl ester, ethylene glycol dihexyl ester, ethylene glycol diheptyl ester, ethylene glycol dinonyl ester, ethylene glycol didecyl ester, ethylene glycol distearate, ethylene glycol dibenzoate, propylene glycol dimethyl ester, propylene glycol diethyl ester, propylene glycol dipropyl ester, propylene glycol dibutyl ester, propylene glycol dipentyl ester, propylene glycol dihexyl ester, propylene glycol diheptyl ester, propylene glycol dioctyl ester, propylene glycol dinonyl ester, propylene glycol didecyl ester, propylene glycol distearate and propylene glycol dibenzoate.
Preferably, the sodium polyphosphate is sodium tripolyphosphate.
The invention also provides a preparation method of the heat-conducting medium for the solar water heater, which comprises the following steps:
1) adding ethylene (propylene) glycol, ethylene (propylene) glycol dibenzoate and tributyl phosphate into the reaction container I in sequence, and uniformly mixing for later use;
2) sequentially adding deionized water, sodium polyphosphate, benzotriazole and sodium benzoate into the reaction vessel II, and uniformly mixing for later use;
3) and adding the mixture of the reaction container I and the reaction container II into a reaction container III, adding sodium hydroxide to adjust the pH value, uniformly mixing to form a transparent solution, and filtering to obtain the catalyst.
Preferably, the weight parts of the raw materials are as follows: 30.0-50.0 parts of ethylene (propylene) glycol; 0.1-40.0 parts of ethylene (propylene) glycol dibenzoate; 0.01-2 parts of sodium polyphosphate; 0.01-1 part of benzotriazole; 0.01-0.1 part of sodium benzoate; 0.002-0.4 part of tributyl phosphate; 0.01-0.1 part of sodium hydroxide; 6.4-69.858 parts of deionized water.
Preferably, in step 3), the pH is adjusted to 9.0. Corrosion and scale inhibition components added in the automobile antifreeze or the heat-conducting medium based on the automobile antifreeze formula are not suitable for a solar system and have the risk of rusting. The special heat-conducting medium for solar energy needs to have long-acting performance, and the heat-conducting medium cannot be replaced within a few years, so that the special heat-conducting medium for solar energy is added with the efficient buffer aid, can ensure that the solution is at an appropriate pH value and reserve alkalinity for a long time, prevents the heat-conducting medium from being acidified, and has better long-acting performance.
Preferably, in the step 3), a filter with the diameter of 0.5-1 μm is adopted for filtration.
The invention also provides a heat-conducting medium prepared by any one of the methods.
The invention also provides application of any one of the heat-conducting media in manufacturing a solar water heater.
The invention has the advantages of
(1) The ester compound with the potential capability of decomposing into the ethylene (propylene) glycol is added into the basic components of the ethylene (propylene) glycol and the water, when the concentration of the ethylene (propylene) glycol is reduced due to thermal decomposition of a heat-conducting medium in the using process, the ester compound can be decomposed into the ethylene (propylene) glycol in time, the effect of effectively supplementing the ethylene (propylene) glycol is achieved, the low freezing point and the high boiling point of the heat-conducting medium of the solar water heater are ensured, meanwhile, the acid compound (such as benzoic acid, stearic acid and the like) generated by the decomposition of the ester compound is also a high-efficiency metal corrosion inhibitor, and the ester compound and the inorganic salt metal corrosion inhibitor in the system cooperate to jointly provide the protection effect on metals such as carbon steel, red copper, brass, aluminum and the like.
(2) The invention overcomes the defects of the heat-conducting medium of the solar water heater that the freezing point of the heat-conducting medium is increased and the boiling point is reduced due to the thermal degradation loss of the ethylene (propylene) glycol in the heat-conducting medium, and can generate the organic acid compound with metal corrosion inhibition capability by adding the ester compound with potential decomposition capability to timely supplement the lost ethylene (propylene) glycol. The novel environment-friendly water-based heat-conducting medium can work at a high temperature state for a long time, and the service life of the heat-conducting medium is greatly prolonged.
(3) The preparation method is simple, high in heat conduction efficiency, strong in practicability and easy to popularize.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The first embodiment is as follows:
1000kg of heat-conducting medium used at the temperature of minus 25 ℃ is prepared.
Pumping 430kg of ethylene glycol into a reaction kettle 1, starting the reaction kettle to stir simultaneously, adding 0.02kg of tributyl phosphate, and stirring for 30 minutes; 565.7kg of deionized water is pumped into a reaction kettle 2, the reaction kettle is started to stir at the same time, and then 3kg of sodium tripolyphosphate, 0.5kg of benzotriazole and 0.5kg of sodium benzoate are added and stirred for 30 minutes; pumping the solution in the reaction kettles 1 and 2 into a reaction kettle 3, adding 0.28kg of sodium hydroxide, adjusting the pH value of the solution to 9.0, continuously stirring for 30 minutes to finally form a transparent solution, and filtering the transparent solution through a filter of 0.5-1 mu m after the transparent solution is inspected to be qualified, and then subpackaging. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the results of corrosion tests on carbon steel, red copper, brass and aluminum are shown in table 1:
TABLE 1
Example two:
1000kg of heat-conducting medium used at the temperature of minus 25 ℃ is prepared.
Pumping 440kg of propylene glycol into a reaction kettle 1, starting the reaction kettle to stir simultaneously, adding 0.02kg of tributyl phosphate, and stirring for 30 minutes; 555.7kg of deionized water is pumped into a reaction kettle 2, the reaction kettle is started to stir at the same time, then 3kg of sodium tripolyphosphate, 0.5kg of benzotriazole and 0.5kg of sodium benzoate are added, and the stirring is carried out for 30 minutes; pumping the solution in the reaction kettles 1 and 2 into a reaction kettle 3, adding 0.28kg of sodium hydroxide, adjusting the pH value of the solution to 9.0, continuously stirring for 30 minutes to finally form a transparent solution, and filtering the transparent solution through a filter of 0.5-1 mu m after the transparent solution is inspected to be qualified, and then subpackaging. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the results of corrosion tests on carbon steel, red copper, brass and aluminum are shown in table 2:
TABLE 2
Example three:
1000kg of heat-conducting medium used at the temperature of minus 25 ℃ is prepared.
Pumping 400kg of ethylene glycol into a reaction kettle 1, starting the reaction kettle to stir simultaneously, then adding 30kg of ethylene glycol didecyl ester and 0.02kg of tributyl phosphate, and stirring for 30 minutes; 565.7kg of deionized water is pumped into a reaction kettle 2, the reaction kettle is started to stir at the same time, and then 3kg of sodium tripolyphosphate, 0.5kg of benzotriazole and 0.5kg of sodium benzoate are added and stirred for 30 minutes; pumping the solution in the reaction kettles 1 and 2 into a reaction kettle 3, adding 0.28kg of sodium hydroxide, adjusting the pH value of the solution to 9.0, continuously stirring for 30 minutes to finally form a transparent solution, and filtering the transparent solution through a filter of 0.5-1 mu m after the transparent solution is inspected to be qualified, and then subpackaging. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the corrosion test results of the heat-conducting medium to carbon steel, red copper, brass and aluminum are shown in the table 3:
TABLE 3
Example four:
the heat-conducting medium for the solar water heater is the same as the heat-conducting medium in the embodiment, and is not repeated, except that 30kg of ethylene glycol distearate is added into a reaction kettle 1. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the results of corrosion tests on carbon steel, red copper, brass and aluminum are shown in table 4:
TABLE 4
Example five:
the heat-conducting medium for the solar water heater is the same as the heat-conducting medium in the embodiment, and is not repeated, except that 30kg of ethylene glycol dibenzoate is added into a reaction kettle 1. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the corrosion test results of the heat-conducting medium to carbon steel, red copper, brass and aluminum are shown in the table 5:
TABLE 5
It can be seen from the first embodiment and the third to fifth embodiments that the ethylene glycol diester compound is not added, the freezing point of the heat-conducting medium rises and the boiling point of the heat-conducting medium drops after 1 year of operation, and the heat-conducting medium has obvious corrosivity to various metals, and the embodiment that the ethylene glycol didecyl ester, the ethylene glycol distearate and the ethylene glycol dibenzoate are added has the advantages that the freezing point and the boiling point of the heat-conducting medium are hardly changed after 1 year of operation, the corrosivity of the metals is also remarkably reduced, and the embodiment that the ethylene glycol dibenzoate has the best effect.
Example six:
1000kg of heat-conducting medium used at the temperature of minus 25 ℃ is prepared.
Pumping 410kg of propylene glycol into a reaction kettle 1, starting the reaction kettle to stir simultaneously, then adding 30kg of propylene glycol didecyl ester and 0.02kg of tributyl phosphate, and stirring for 30 minutes; 555.7kg of deionized water is pumped into a reaction kettle 2, the reaction kettle is started to stir at the same time, and then 3kg of sodium tripolyphosphate, 0.5kg of benzotriazole and 0.5kg of sodium benzoate are added and stirred for 30 minutes; pumping the solution in the reaction kettles 1 and 2 into a reaction kettle 3, adding 0.28kg of sodium hydroxide, adjusting the pH value of the solution to 9.0, continuously stirring for 30 minutes to finally form a transparent solution, and filtering the transparent solution through a filter of 0.5-1 mu m after the transparent solution is inspected to be qualified, and then subpackaging. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the corrosion test results of the heat-conducting medium to carbon steel, red copper, brass and aluminum are shown in table 6:
TABLE 6
Example seven:
the same parts of the heat-conducting medium for the solar water heater as those in example six are not described again, except that 30kg of propylene glycol distearate is added into the reaction kettle 1. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the corrosion test results of the heat-conducting medium to carbon steel, red copper, brass and aluminum are shown in table 7:
TABLE 7
Example eight:
the same parts of the heat-conducting medium for the solar water heater as those in example six are not described again, except that 30kg of propylene glycol dibenzoate is added into the reaction kettle 1. The freezing point and boiling point of the prepared heat-conducting medium of the solar water heater and the corrosion test results of the heat-conducting medium to carbon steel, red copper, brass and aluminum are shown in the table 8:
TABLE 8
From the second embodiment and the sixth to eighth embodiments, it can be seen that in the first embodiment without the propylene glycol diester compound, after the heat-conducting medium operates for 1 year, the freezing point is raised, the boiling point is lowered, and the heat-conducting medium has obvious corrosivity to various metals, and in the embodiment with the propylene glycol didecyl ester, the propylene glycol distearate and the propylene glycol dibenzoate, the freezing point and the boiling point of the heat-conducting medium are hardly changed after the heat-conducting medium operates for 1 year, the corrosivity of the metals is also remarkably lowered, and the embodiment with the propylene glycol dibenzoate has the best effect.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1. A heat-conducting medium for a solar water heater is characterized by comprising the following raw materials in parts by weight: 30.0-50.0 parts of ethylene glycol or propylene glycol; 0.1-40.0 parts of ethylene glycol dibenzoate or propylene glycol dibenzoate; 0.01-2 parts of sodium polyphosphate; 0.01-1 part of benzotriazole; 0.01-0.1 part of sodium benzoate; 0.002-0.4 part of tributyl phosphate; 0.01-0.1 part of sodium hydroxide; 6.4-69.858 parts of deionized water.
2. The heat transfer medium of claim 1, wherein 30.0 to 40.0 parts of ethylene glycol or propylene glycol; 0.1-20.0 parts of ethylene glycol dibenzoate or propylene glycol dibenzoate; 0.01-1 part of sodium polyphosphate; 0.01-0.5 parts of benzotriazole; 0.01-0.05 part of sodium benzoate; 0.002-0.2 part of tributyl phosphate; 0.01-0.05 part of sodium hydroxide; 6.4-29.858 parts of deionized water.
3. The heat transfer medium of claim 1, wherein 40.0 to 50.0 parts of ethylene glycol or propylene glycol; 20.0-40.0 parts of ethylene glycol dibenzoate or propylene glycol dibenzoate; 1-2 parts of sodium polyphosphate; 0.5-1 part of benzotriazole; 0.05-0.1 part of sodium benzoate; 0.2-0.4 part of tributyl phosphate; 0.05-0.1 part of sodium hydroxide; 29.858-69.858 parts of deionized water.
4. A preparation method of a heat-conducting medium for a solar water heater is characterized by comprising the following steps:
1) adding ethylene glycol or propylene glycol, ethylene glycol dibenzoate or propylene glycol dibenzoate and tributyl phosphate into the reaction container I in sequence, and uniformly mixing for later use;
2) sequentially adding deionized water, sodium polyphosphate, benzotriazole and sodium benzoate into the reaction vessel II, and uniformly mixing for later use;
3) adding the mixture of the reaction container I and the reaction container II into a reaction container III, adding sodium hydroxide to adjust the pH value, uniformly mixing to form a transparent solution, and filtering to obtain the compound;
the weight parts of the raw materials are as follows: 30.0-50.0 parts of ethylene glycol or propylene glycol; 0.1-40.0 parts of ethylene glycol dibenzoate or propylene glycol dibenzoate; 0.01-2 parts of sodium polyphosphate; 0.01-1 part of benzotriazole; 0.01-0.1 part of sodium benzoate; 0.002-0.4 part of tributyl phosphate; 0.01-0.1 part of sodium hydroxide; 6.4-69.858 parts of deionized water.
5. The method of claim 4, wherein in step 3), the pH is adjusted to 9.0.
6. The method according to claim 4, wherein in step 3), the filtration is performed by using a filter of 0.5 to 1 μm.
7. A heat transfer medium prepared by the method of any one of claims 4 to 6.
8. Use of a heat transfer medium for a solar water heater according to any one of claims 1-3 or a heat transfer medium according to claim 7 for manufacturing a solar water heater.
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| CN109439290B (en) * | 2018-12-05 | 2021-03-16 | 山东恒利热载体工程技术有限公司 | Environment-friendly organic heat carrier and preparation method thereof |
| CN109652023B (en) * | 2018-12-29 | 2020-11-06 | 中国船舶重工集团公司第七一八研究所 | Solar heat-conducting medium and preparation method thereof |
| JP7198101B2 (en) * | 2019-02-01 | 2022-12-28 | 谷川油化興業株式会社 | heat exchange medium |
| CN111995992A (en) * | 2020-08-03 | 2020-11-27 | 河北颛俪新能源科技有限公司 | Anti-freezing superconducting liquid for heating and preparation method thereof |
| CN115305068B (en) * | 2022-09-15 | 2024-04-09 | 纯牌科技股份有限公司 | Preparation method of long-acting heat dissipation liquid for automobile |
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| CN1147006A (en) * | 1996-08-06 | 1997-04-09 | 北京北方大康科贸有限责任公司 | Multifunctional antifreezing fluid and preparing process thereof |
| CN101376802B (en) * | 2007-08-27 | 2011-01-05 | 比亚迪股份有限公司 | Anti-freezing cooling liquid and preparation thereof |
| CN101769641A (en) * | 2010-02-10 | 2010-07-07 | 山东省科学院能源研究所 | solar water heater |
| CN103773323A (en) * | 2014-01-06 | 2014-05-07 | 沈阳化工大学 | Antifreezing fluid for automobile engine |
| CN103806004B (en) * | 2014-02-25 | 2015-09-30 | 山东省科学院能源研究所 | Solar water heater heat-exchange working medium |
| CN104531087A (en) * | 2014-12-01 | 2015-04-22 | 张山 | Superpolymer composite antifreezing solution |
| CN104610933B (en) * | 2014-12-24 | 2018-05-08 | 中国人民解放军空军油料研究所 | A kind of aviation coolant |
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