CN109777373B - Intermediate-temperature seasonal heat storage material - Google Patents
Intermediate-temperature seasonal heat storage material Download PDFInfo
- Publication number
- CN109777373B CN109777373B CN201910167308.8A CN201910167308A CN109777373B CN 109777373 B CN109777373 B CN 109777373B CN 201910167308 A CN201910167308 A CN 201910167308A CN 109777373 B CN109777373 B CN 109777373B
- Authority
- CN
- China
- Prior art keywords
- lithium
- potassium
- sodium
- zirconium
- hydrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a medium-temperature heat storage technology, which stores heat by utilizing a dehydration reaction of magnesium hydroxide or calcium hydroxide. The heat storage material comprises the following components: a compound containing one of magnesium or calcium selected from hydroxides and oxides; a compound containing at least one lithium; contains at least one of carbon and metal selected from graphite, graphene, carbon tubes, silicon carbide, stainless steel and nickel; a compound comprising at least one of zirconium or cerium. The heat storage material provided by the invention has the advantages of high stability, high heat storage density, no loss in long-term heat storage and short heat storage reaction time; the material preparation process is simple, the production is convenient, safe and reliable, the standardization of the material preparation can be realized, and the method is suitable for large-scale industrial production and has no three-waste discharge.
Description
Technical Field
Belongs to the technical field of new energy and energy storage, and particularly relates to a long-term efficient heat storage material.
Background
Heat storage is an effective means for solving the contradiction between time and place of energy supply and demand; the heat storage can improve the utilization rate of energy, reduce the energy waste and provide green energy for the society. Energy and environmental problems are two main problems which are generally concerned in the world at present, and the great development of green energy technology is particularly important in order to protect the environment and the sustainable development of economy and reduce pollutant emission. Among the green energy sources, wind energy and solar energy are clean energy sources which are distributed on the earth most widely and have the largest total resource amount. However, the heat utilization of solar energy is unstable in time and space, and great difficulty is brought to the heat utilization of solar energy. In order to effectively utilize solar energy, power grid peak shaving and industrial waste heat recycling, the heat storage technology is an effective means for solving the problems.
The heat storage technology is classified into two types, physical heat storage and chemical heat storage, which utilize sensible heat and latent heat of phase change. Sensible heat storage by using molten salt is industrialized, a 50MW photo-thermal power station is built by Andasol, Spain, molten salt is used as a heat storage carrier, and the photo-thermal power station comprises a thermal energy storage system consisting of 35000t of molten salt. However, since only sensible heat is used, the heat storage density is low, and the application range is limited. Aiming at the problems of the traditional phase change latent heat and sensible heat storage technology and the defects (short heat storage time, low energy storage density and large potential safety hazard) which are difficult to overcome and the urgency of the society for the requirement of green energy, the novel heat storage material is developed to break through the technical bottleneck of the existing heat storage material, and the problems of middle and high temperature green energy needed by winter heating and industrial production are practically solved by combining green energy such as solar energy, wind energy, geothermal energy and the like. The chemical heat storage time is long, the heat storage density is high, the heat storage density can be increased by multiple times, and the heat storage equipment can be miniaturized and applied to families. The medium-temperature heat storage not only has rich heat sources, such as electric energy, industrial waste heat, focused solar energy and the like, but also can meet the heat energy required by industrial and agricultural production, such as heating in winter, food baking, drying treatment of industrial products, drying treatment of sludge and the like. In order to solve the problems, the invention provides a medium-temperature chemical heat storage material.
The heat storage material is a key part of the heat storage technology, calcium hydroxide and magnesium hydroxide are decomposed at 380 ℃ to generate magnesium oxide, calcium oxide and water, 1380J/g of heat is absorbed, the hydration reaction of the calcium oxide and the magnesium oxide can release the heat, and the reversible thermochemical reaction can complete heat storage and release. However, since the dehydration process has a sintering phenomenon, calcium hydroxide and magnesium hydroxide generated during the water absorption process hinder the hydration reaction, a modified material is required to improve the reaction rate and the conversion rate.
Disclosure of Invention
In order to solve the above-mentioned problem of hydroxide heat storage, an object of the present invention is to provide a heat storage material which has high stability, high heat storage density, high thermal conductivity, and almost no loss of energy stored for a long period of time.
It is another object of the present invention to improve the kinetics and reversible cycling of hydroxide decomposition reactions by using additives. The heat storage time is shortened.
The heat storage material provided by the invention has high stability and high heat storage density, and is suitable for medium-high temperature heat storage.
The heat storage material provided by the invention has good thermal stability, wide application temperature range, room temperature-500 ℃ and high cost performance.
The heat storage material provided by the invention can meet wider application requirements.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, and cerium phosphate and hydrate thereof. The metal hydroxide and the metal oxide are main materials, the compound of zirconium and cerium is an additive, and the addition amount is as follows: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; contains at least one of carbon, silicon dioxide and metal, and is selected from silicon dioxide, graphite, graphene oxide, carbon tube, silicon carbide, molecular sieve, stainless steel and nickel. The metal hydroxide and the metal oxide are main materials, the compound of zirconium and cerium is an additive, and the addition amount is as follows: 0.1-50%; in addition, at least one of carbon, silica and metal selected from the group consisting of silica, graphite, graphene oxide, carbon tubes, silicon carbide, molecular sieves, stainless steel and nickel is added in an amount of: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; zirconium and cerium compounds are used as additives, and the addition amount is as follows: 0.1-50%; further, a compound containing at least one kind of lithium selected from the group consisting of lithium oxide, lithium hydroxide hydrate, lithium chloride, lithium bromide, lithium sulfate, lithium sulfite, lithium carbonate, lithium nitrate, lithium acetate, lithium formate, lithium nitrite, lithium sulfonate, lithium silicate, lithium phosphate, lithium phosphite, lithium polyphosphate, lithium dihydrogen phosphate, lithium monohydrogen phosphate and lithium metaaluminate is added in an amount of: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; zirconium and cerium compounds are used as additives, and the addition amount is as follows: 0.1-50%; a compound containing at least one potassium selected from the group consisting of potassium oxide, potassium hydroxide, potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium nitrate, potassium acetate, potassium formate, potassium hydroxide hydrate, potassium nitrite, potassium sulfonate, potassium silicate, potassium phosphate, potassium phosphite, potassium polyphosphate, potassium dihydrogen phosphate, potassium monohydrogen phosphate, and potassium metaaluminate, in an amount of: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; zirconium and cerium compounds are used as additives, and the addition amount is as follows: 0.1-50%; a compound containing at least one sodium selected from the group consisting of sodium oxide, sodium hydroxide, sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium nitrate, sodium acetate, sodium formate, sodium hydroxide hydrate, sodium nitrite, sodium sulfonate, sodium silicate, sodium phosphate, sodium phosphite, sodium polyphosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, and sodium metaaluminate, in an amount of: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; zirconium and cerium compounds are used as additives, and the addition amount is as follows: 0.1-50%; contains at least one of carbon, silicon dioxide and metal, and is selected from silicon dioxide, graphite, graphene oxide, carbon tubes, silicon carbide, molecular sieve, stainless steel and nickel, and the addition amount is as follows: 0.1-50%; a compound containing at least one sodium selected from the group consisting of sodium oxide, sodium hydroxide, sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium nitrate, sodium acetate, sodium formate, sodium hydroxide hydrate, sodium nitrite, sodium sulfonate, sodium silicate, sodium phosphate, sodium phosphite, sodium polyphosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, and sodium metaaluminate, in an amount of: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; zirconium and cerium compounds are used as additives, and the addition amount is as follows: 0.1-50%; contains at least one of carbon, silica and metal selected from the group consisting of silica, graphite, graphene oxide, carbon tubes, silicon carbide, molecular sieves, stainless steel and nickel in an amount of: 0.1-50%; a compound containing at least one potassium selected from the group consisting of potassium oxide, potassium hydroxide, potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium nitrate, potassium acetate, potassium formate, potassium hydroxide hydrate, potassium nitrite, potassium sulfonate, potassium silicate, potassium phosphate, potassium phosphite, potassium polyphosphate, potassium dihydrogen phosphate, potassium monohydrogen phosphate, and potassium metaaluminate in an amount: 0.1 to 50 percent.
The invention provides a heat storage material, which comprises the following components: contains at least one metal hydroxide and metal oxide selected from calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide; a compound containing at least one of zirconium and cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconium nitrate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconia, yttrium zirconium composite, lanthanum zirconium composite, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium cerium sulfate and hydrate thereof, ammonium cerium nitrate and hydrate thereof, cerium phosphate and hydrate thereof; zirconium and cerium compounds are used as additives, and the addition amount is as follows: 0.1-50%; contains at least one of carbon, silica and metal selected from the group consisting of silica, graphite, graphene oxide, carbon tubes, silicon carbide, molecular sieves, stainless steel and nickel in an amount of: 0.1-50%; a compound containing at least one lithium selected from the group consisting of lithium oxide, lithium hydroxide hydrate, lithium chloride, lithium bromide, lithium sulfate, lithium sulfite, lithium carbonate, lithium nitrate, lithium acetate, lithium formate, lithium nitrite, lithium sulfonate, lithium silicate, lithium phosphate, lithium phosphite, lithium polyphosphate, lithium dihydrogen phosphate, lithium monohydrogen phosphate, and lithium metaaluminate, in an amount of: 0.1 to 50 percent.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 60-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium hydroxide, 0.1-20% of zirconium oxide and 0-20% of graphite.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 50-99% of magnesium hydroxide or calcium hydroxide, 1.0-50% of lithium hydroxide hydrate and 0.1-20% of zirconium oxide.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 50-99% of magnesium hydroxide or calcium hydroxide, 1.0-50% of lithium oxide and 0.1-20% of zirconium oxide.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 60-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium bromide and 0-20% of graphite.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 60-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium hydroxide and 0-20% of graphene.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 60-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium hydroxide hydrate, 1.0-20% of cerium nitrate and 0-30% of carbon tube.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 70-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium oxide and 0-10% of nickel.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 60-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium oxide and 0-20% of silicon carbide.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 50-99% of magnesium hydroxide or calcium hydroxide, 1.0-40% of lithium hydroxide hydrate and 0-20% of steel wire.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 70-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium hydroxide hydrate and 0-10% of nickel.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 60-99% of magnesium hydroxide or calcium hydroxide, 1.0-20% of lithium hydroxide and 0-20% of nickel.
The preparation method provided by the invention comprises the following steps: grinding the hydroxide and the additive into powder according to a certain mass ratio, and uniformly mixing.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 50-99% of magnesium hydroxide or calcium hydroxide, 1.0-40% of lithium oxide hydrate, 0-20% of steel wire and 1.0-20% of cerium nitrate.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 50-99% of magnesium hydroxide or calcium hydroxide, 1.0-40% of lithium oxide hydrate, 0-20% of graphite and 1.0-20% of zirconium nitrate.
The heat storage material provided by the invention preferably comprises the following components in percentage by mass: 50-99% of magnesium hydroxide or calcium hydroxide, 1.0-40% of lithium nitrate, 0-20% of graphite and 1.0-20% of zirconium nitrate.
The preparation method provided by the invention comprises the following steps: according to a certain mass ratio, soluble magnesium salt or calcium salt, soluble additive salt, graphite or metal and the like are coprecipitated, and the precipitate is washed, ground into powder and uniformly mixed.
The performance of the heat storage material is tested, the enthalpy change and decomposition temperature of dehydration reaction (see table 1), a weight loss experiment, an isothermal dehydration kinetic curve, cycle performance and the like are tested by a differential scanning calorimetry, and the heat storage effect of the invention is illustrated.
TABLE 1 dehydration temperature and enthalpy change for magnesium hydroxide composites
The storage and heat cycle test proves that the performance of the molten salt is stable, and the change of phase change enthalpy is small, which shows that the performance of the phase change material is reduced very little in the range of the test temperature, and the requirement of heat storage is met.
The invention has the beneficial effects that:
1. the material provided by the invention has the advantages of high stability, high latent heat and wide use temperature range.
2. The material provided by the invention has small attenuation of phase change heat storage capacity after multiple cycle tests.
3. The material provided by the invention has excellent high-temperature thermal stability and higher thermal conductivity.
4. The preparation method of the material provided by the invention is used for preparing the heat storage material, has the advantages of simple and easy operation process, convenient production, safety and reliability, can realize the standardization of material preparation, is suitable for large-scale industrial production, and does not discharge three wastes.
Detailed Description
Example 1
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (70%), lithium hydroxide (10%), graphite (20%); the conversion temperature is 280 ℃, and the heat of conversion reaction is 1010J/g.
Example 2
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (85%), lithium hydroxide hydrate (10%), graphite (5%); the conversion temperature is 280 ℃, and the heat of conversion reaction is 1050J/g.
Example 3
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (75%), lithium hydroxide hydrate (20%), graphite (5%); the conversion temperature is 280 ℃, and the heat of conversion reaction is 880J/g. After 10 heat storage and release cycles, the latent heat of phase change was 850J/g.
Example 4
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (80%), lithium oxide (10%), graphite (10%); the conversion temperature is 260 ℃, and the heat of the conversion reaction is 1180J/g.
Example 5
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (85%), lithium oxide (10%), nickel powder (5%); the conversion temperature was 255 ℃ and the heat of conversion reaction was 1170J/g.
Example 6
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (80%), lithium oxide (10%), zirconium nitrate (10%); the conversion temperature is 265 ℃ and the heat of conversion reaction is 1120J/g. The thermal conductivity reaches 26w/(m k).
Example 7
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (80%), lithium oxide (10%), cerium nitrate (10%); the conversion temperature is 276 ℃ and the heat of conversion reaction is 1160J/g.
Example 8
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (80%), lithium oxide (10%), cerium nitrate (10%), molecular sieve 4%; the conversion temperature is 271 ℃, and the heat of conversion reaction is 980J/g.
Example 9
The invention provides a heat storage material which comprises the following components in percentage by mass: calcium hydroxide (80%), cerium nitrate (10%), molecular sieve 4% and graphite 14%; the conversion temperature is 338 ℃, and the heat of conversion reaction is 1010J/g.
Example 10
The invention provides a heat storage material which comprises the following components in percentage by mass: calcium hydroxide (80%), potassium nitrate (10%), nickel 4%, graphite 14%; the conversion temperature was 326 ℃ and the heat of conversion reaction was 1100J/g.
Example 11
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium oxide (75%), lithium oxide (15%), silicon carbide (10%); the conversion temperature was 275 ℃ and the heat of conversion reaction was 1140J/g. The thermal conductivity reaches 21w/(m k).
Example 12
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium oxide (75%), potassium nitrate (15%), carbon powder (10%); the conversion temperature was 275 ℃ and the heat of conversion reaction was 1150J/g. The thermal conductivity reaches 27w/(m k).
Example 13
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium oxide (75%), lithium hydroxide (15%), stainless steel wire (10%); the conversion temperature was 255 ℃ and the heat of conversion reaction was 1050J/g. The thermal conductivity reaches 26w/(m k).
Example 14
The invention provides a heat storage material which comprises the following components in percentage by mass: calcium oxide (75%), lithium hydroxide (15%), cerium nitrate (10%); the conversion temperature was 355 ℃ and the heat of conversion reaction was 1150J/g.
The invention provides a heat storage material which comprises the following components in percentage by mass: calcium oxide (75%), cerium nitrate (10%), graphite 15%; the conversion temperature was 335 ℃ and the heat of conversion reaction was 950J/g.
Example 15
The invention provides a preparation method of the heat storage material in the embodiment 1 to the embodiment 8, which comprises the following steps: mixing and sieving magnesium hydroxide (80%), lithium oxide (10%) and silicon carbide (10%) according to a certain mass ratio to obtain the heat storage material.
Example 16
The invention provides a heat storage material which comprises the following components in percentage by mass: magnesium hydroxide (80%), lithium oxide (10%), graphene (10%); the conversion temperature is 260 ℃, and the heat of the conversion reaction is 980J/g.
Example 17
The invention provides a preparation method of the heat storage material in the embodiment 1 to the embodiment 8, which comprises the following steps: mixing and sieving magnesium hydroxide (70%), lithium oxide (10%) and silicon carbide (20%) according to a certain mass ratio to obtain the heat storage material.
Example 18
The invention provides a preparation method of the heat storage material in the embodiment 1 to the embodiment 8, which comprises the following steps: mixing and sieving magnesium hydroxide (70%), lithium oxide (10%), silicon carbide (20%) and zirconium nitrate (10%) according to a certain mass ratio to obtain the heat storage material.
Example 19
The invention provides a preparation method of the heat storage material in the embodiment 1 to the embodiment 8, which comprises the following steps: mixing and sieving magnesium hydroxide (70%), lithium hydroxide (10%), silicon carbide (20%) and cerium nitrate (10%) according to a certain mass ratio to obtain the heat storage material.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are applicable to all kinds of fields suitable for the invention, and further modifications may be readily made by those skilled in the art, so that the invention is not limited to the specific details and examples shown and described herein, without departing from the general concept defined by the claims and their equivalents.
Claims (8)
1. The medium-temperature heat storage material is characterized by comprising the following components: the first component is calcium hydroxide or magnesium hydroxide; the second component is an additive which comprises a compound of zirconium or cerium selected from the group consisting of zirconium oxide, zirconium oxychloride, zirconium hydroxide, zirconium chloride, zirconium oxychloride hydrate, zirconium nitrate, zirconium acetate, zirconium silicate, zirconium sulfate, zirconyl sulfate, zirconium chlorate, zirconium oxalate, zirconium carbonate, zirconyl nitrate, zirconium hydroxide hydrate, sodium zirconate, potassium zirconate, lithium zirconate, zirconium phosphate, zirconium phosphite, zirconium polyphosphate, zirconium dihydrogen phosphate, zirconium monohydrogen phosphate, composite zirconium oxide, yttrium zirconium complex, lanthanum zirconium complex, cerium hydroxide, cerium chloride and hydrate thereof, cerium nitrate and hydrate thereof, cerium acetate and hydrate thereof, cerium silicate, cerium sulfate and hydrate thereof, cerium oxide and hydrate thereof, cerium oxalate and hydrate thereof, cerium carbonate and hydrate thereof, ammonium sulfate and hydrate thereof, ammonium ceric nitrate and hydrate thereof, cerium phosphate and hydrate thereof, the addition amount of the calcium hydroxide or the magnesium hydroxide is 50-99%, and the addition amount of the additive is 0.1-50%.
2. An intermediate-temperature heat storage material according to claim 1, characterized in that the additives further comprise at least one of carbon, silica and metals selected from the group consisting of silica, graphite, graphene oxide, carbon tubes, silicon carbide, molecular sieves, stainless steel, nickel.
3. An intermediate-temperature heat storage material according to claim 1, characterized in that the additive also comprises at least one lithium compound selected from the group consisting of lithium oxide, lithium hydroxide hydrate, lithium chloride, lithium bromide, lithium sulfate, lithium sulfite, lithium carbonate, lithium nitrate, lithium acetate, lithium formate, lithium nitrite, lithium sulfonate, lithium silicate, lithium phosphate, lithium phosphite, lithium polyphosphate, lithium dihydrogen phosphate, lithium monohydrogen phosphate, lithium metaaluminate.
4. An intermediate-temperature heat storage material according to claim 1, characterized in that the additive also comprises at least one potassium compound selected from the group consisting of potassium oxide, potassium hydroxide, potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium nitrate, potassium acetate, potassium formate, potassium hydroxide hydrate, potassium nitrite, potassium sulfonate, potassium silicate, potassium phosphate, potassium phosphite, potassium polyphosphate, potassium dihydrogen phosphate, potassium monohydrogen phosphate, potassium metaaluminate.
5. An intermediate-temperature heat storage material according to claim 1, characterized in that the additive also comprises at least one sodium compound selected from the group consisting of sodium oxide, sodium hydroxide, sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium nitrate, sodium acetate, sodium formate, sodium hydroxide hydrate, sodium nitrite, sodium sulfonate, sodium silicate, sodium phosphate, sodium phosphite, sodium polyphosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, sodium metaaluminate.
6. An intermediate-temperature heat storage material according to claim 2, characterized in that the additive also comprises at least one sodium compound selected from the group consisting of sodium oxide, sodium hydroxide, sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium nitrate, sodium acetate, sodium formate, sodium hydroxide hydrate, sodium nitrite, sodium sulfonate, sodium silicate, sodium phosphate, sodium phosphite, sodium polyphosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, sodium metaaluminate.
7. An intermediate temperature heat storage material according to claim 2, characterized in that the additive also comprises at least one potassium compound selected from the group consisting of potassium oxide, potassium hydroxide, potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium nitrate, potassium acetate, potassium formate, potassium hydroxide hydrate, potassium nitrite, potassium sulfonate, potassium silicate, potassium phosphate, potassium phosphite, potassium polyphosphate, potassium dihydrogen phosphate, potassium monohydrogen phosphate, potassium metaaluminate.
8. An intermediate-temperature heat storage material according to claim 2, characterized in that the additive also comprises at least one lithium compound selected from the group consisting of lithium oxide, lithium hydroxide hydrate, lithium chloride, lithium bromide, lithium sulfate, lithium sulfite, lithium carbonate, lithium nitrate, lithium acetate, lithium formate, lithium nitrite, lithium sulfonate, lithium silicate, lithium phosphate, lithium phosphite, lithium polyphosphate, lithium dihydrogen phosphate, lithium monohydrogen phosphate, lithium metaaluminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910167308.8A CN109777373B (en) | 2019-03-06 | 2019-03-06 | Intermediate-temperature seasonal heat storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910167308.8A CN109777373B (en) | 2019-03-06 | 2019-03-06 | Intermediate-temperature seasonal heat storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109777373A CN109777373A (en) | 2019-05-21 |
| CN109777373B true CN109777373B (en) | 2021-01-26 |
Family
ID=66486191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910167308.8A Active CN109777373B (en) | 2019-03-06 | 2019-03-06 | Intermediate-temperature seasonal heat storage material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109777373B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143464A (en) * | 2020-09-24 | 2020-12-29 | 中盐金坛盐化有限责任公司 | Nitrate system molten salt heat transfer and storage medium and preparation method thereof |
| CN112920781B (en) * | 2021-01-25 | 2021-08-20 | 山东大学 | Heat-storage composite calcium-based heat storage spherical particle and preparation method and application thereof |
| CN115558470A (en) * | 2022-10-27 | 2023-01-03 | 中国科学院工程热物理研究所 | Nitrate modified calcium-based thermochemical energy storage material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003903B1 (en) * | 1978-02-24 | 1982-12-22 | Teijin Limited | Oxygen scavenger composition, heat-generating composition and structure, and their use as an oxygen scavenger or generator of heat |
| CN1357591A (en) * | 2001-12-28 | 2002-07-10 | 昆明理工大学 | Prepn process of composite heat accumualting material and composite filled heat accumulating chamber |
| CN102166532A (en) * | 2010-05-04 | 2011-08-31 | 昆明理工大学 | Heat-storing catalytic composite functional material and preparation method thereof |
| CN102888209A (en) * | 2012-09-21 | 2013-01-23 | 中国科学院过程工程研究所 | Medium-high temperature composite structural heat storage material, preparation method and application thereof |
| CN105838338A (en) * | 2016-04-25 | 2016-08-10 | 碧城（上海）新能源科技有限公司 | Nano mixed molten salt heat transfer and storage medium and preparation method thereof |
| CN106281256A (en) * | 2016-07-29 | 2017-01-04 | 刘勇 | Energy storage material modifying agent, its preparation method and application thereof |
| CN106518125A (en) * | 2016-12-08 | 2017-03-22 | 赵岩 | Composite phase-change heat storage brick coated by refractory material |
| CN107266047A (en) * | 2017-06-28 | 2017-10-20 | 郑善 | A kind of rare-earth ceramic high-temperature phase-change stores exoergic material and preparation method thereof |
| CN108624294A (en) * | 2018-06-08 | 2018-10-09 | 华北电力大学 | A kind of high temperature phase-change heat-storage material and preparation method based on gangue |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU83844A1 (en) * | 1981-12-18 | 1983-09-02 | Ramon Apellaniz | DEVICE FOR HEATING A FOOD CONTAINED IN A CAN |
| JPH0680394B2 (en) * | 1986-03-14 | 1994-10-12 | 三井研削砥石株式会社 | Chemical heat storage capsule |
| JPH02122169A (en) * | 1988-11-01 | 1990-05-09 | Hitachi Ltd | Chemical heat pump |
| FR2837830B1 (en) * | 2002-04-02 | 2004-05-21 | Rhodia Cons Spec Ltd | SELF-HEATING COMPOSITION BASED ON ORTHOPHOSPHORIC ACID IMPREGNATED ON A LARGE POROSITY MINERAL OXIDE, PREPARATION METHOD AND USE THEREOF |
| CN101644548A (en) * | 2009-08-13 | 2010-02-10 | 哈尔滨工程大学 | High-temperature chemical heat storage element and heat storage device based on high-temperature chemical heat storage element |
| JP5749050B2 (en) * | 2011-03-18 | 2015-07-15 | 株式会社豊田中央研究所 | Chemical regenerator and manufacturing method thereof |
| CN104650821A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Solid particle blocks for chemical heat storage |
| CN104650820A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Formula of chemical heat storage material for heat transfer |
| JP6566860B2 (en) * | 2014-12-22 | 2019-08-28 | 日本碍子株式会社 | Chemical heat pump |
| CN105423791A (en) * | 2015-11-11 | 2016-03-23 | 上海交通大学 | Adjustable chemical heat storage system |
| WO2017099197A1 (en) * | 2015-12-10 | 2017-06-15 | 国立大学法人京都大学 | Hydrate of rare earth metal sulfate, method for producing same, and chemical thermal storage material |
| JP6743685B2 (en) * | 2016-12-26 | 2020-08-19 | 株式会社豊田中央研究所 | Chemical heat storage material and manufacturing method thereof |
| CN108165238A (en) * | 2017-12-11 | 2018-06-15 | 高伟红 | A kind of proportioning of chemical heat-accumulating material for heat transfer |
| CN109097003B (en) * | 2018-08-27 | 2020-06-09 | 上海交通大学 | Thermochemical heat storage molded particle with optimized permeability and preparation method thereof |
-
2019
- 2019-03-06 CN CN201910167308.8A patent/CN109777373B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003903B1 (en) * | 1978-02-24 | 1982-12-22 | Teijin Limited | Oxygen scavenger composition, heat-generating composition and structure, and their use as an oxygen scavenger or generator of heat |
| CN1357591A (en) * | 2001-12-28 | 2002-07-10 | 昆明理工大学 | Prepn process of composite heat accumualting material and composite filled heat accumulating chamber |
| CN102166532A (en) * | 2010-05-04 | 2011-08-31 | 昆明理工大学 | Heat-storing catalytic composite functional material and preparation method thereof |
| CN102888209A (en) * | 2012-09-21 | 2013-01-23 | 中国科学院过程工程研究所 | Medium-high temperature composite structural heat storage material, preparation method and application thereof |
| CN105838338A (en) * | 2016-04-25 | 2016-08-10 | 碧城（上海）新能源科技有限公司 | Nano mixed molten salt heat transfer and storage medium and preparation method thereof |
| CN106281256A (en) * | 2016-07-29 | 2017-01-04 | 刘勇 | Energy storage material modifying agent, its preparation method and application thereof |
| CN106518125A (en) * | 2016-12-08 | 2017-03-22 | 赵岩 | Composite phase-change heat storage brick coated by refractory material |
| CN107266047A (en) * | 2017-06-28 | 2017-10-20 | 郑善 | A kind of rare-earth ceramic high-temperature phase-change stores exoergic material and preparation method thereof |
| CN108624294A (en) * | 2018-06-08 | 2018-10-09 | 华北电力大学 | A kind of high temperature phase-change heat-storage material and preparation method based on gangue |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109777373A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Progress in thermochemical energy storage for concentrated solar power: A review | |
| Wu et al. | Research progress of solar thermochemical energy storage | |
| CN109777373B (en) | Intermediate-temperature seasonal heat storage material | |
| CN110628392A (en) | Hydroxide heat storage material | |
| Shkatulov et al. | Modification of magnesium and calcium hydroxides with salts: An efficient way to advanced materials for storage of middle-temperature heat | |
| CN102974360B (en) | Methane steam reforming catalyst and preparation method thereof and method for utilizing smoke of gas-powered generator | |
| Takasu et al. | Application of lithium orthosilicate for high-temperature thermochemical energy storage | |
| CN104087254A (en) | High-heat-conductivity inorganic phase-change energy storage material | |
| CN101219783B (en) | Method for producing electrode material with ferrophosphorus | |
| Wang et al. | Thermal energy storage for solar energy utilization: Fundamentals and applications | |
| Zhao et al. | Progress in thermal energy storage technologies for achieving carbon neutrality | |
| CN103756647A (en) | Particle-molten salt compound heat-transferring and heat-accumulating medium material and preparation method thereof | |
| CN113606974A (en) | Composite metal oxide thermochemical heat storage material, thermochemical heat storage module and preparation method | |
| CN110159499B (en) | Solar photo-thermal power generation system and method based on calcium-based thermochemical energy storage system | |
| CN104194735A (en) | Carbon-based chemical heat storage nano-composite material and preparation method thereof | |
| Zhang et al. | Resource utilization of solid waste in the field of phase change thermal energy storage | |
| CN113403040B (en) | MgO-based thermochemical energy storage material and preparation method thereof | |
| WO2014044652A1 (en) | Use of a calcium potassium nitrate salt for the manufacture of a heat transfer fluid | |
| Milone et al. | Thermal energy storage with chemical reactions | |
| CN109735310B (en) | Full-spectrum photo-thermal conversion heat storage material and preparation method thereof | |
| CN111909664A (en) | Inorganic fiber composite chlorine system molten salt heat storage material and preparation method and application thereof | |
| CN102344778A (en) | Preparation method of high-temperature phase-change composite material | |
| Lei et al. | Redox cycle of calcium manganite for high temperature solar thermochemical storage systems | |
| CN103694963A (en) | Composite phase change material and preparation method thereof | |
| Sun et al. | Doping magnesium hydroxide with Ce (NO3) 3: a promising candidate thermochemical energy storage materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |