CN100427563C - Preparation method of high temperature heat storage material - Google Patents

Preparation method of high temperature heat storage material Download PDF

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CN100427563C
CN100427563C CNB2006100194799A CN200610019479A CN100427563C CN 100427563 C CN100427563 C CN 100427563C CN B2006100194799 A CNB2006100194799 A CN B2006100194799A CN 200610019479 A CN200610019479 A CN 200610019479A CN 100427563 C CN100427563 C CN 100427563C
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preparation
aggregate
temperature
powder
water
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CN1869146A (en
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朱教群
周卫兵
吴少鹏
李波
王金山
张炳
汤凯
周明杰
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a preparation method of high temperature heat storage materials. The present invention has the steps of material selection, proportioning and preparation. Basalt is used as coarse aggregate, bauxite chmotte is used as fine aggregate, and aluminate cement is used as cementing agent. Silicon micro powder, active alumina powder, natural graphite powder and kyanite micro powder are added in the mixture to prepare the heat storage materials. After the raw materials are dried and uniformly mixed, 4 to 6% of water is added in the raw materials, and then, the mixture is uniformly mixed and arranged in a steel mold. Demolding is carried out after 24 hours, and the mixture is cared by being arranged in water for 72 hours; then, the mixture is baked for 24 hours under the temperature of 100 to 120 DEG C, and the heat storage materials which can be used as solar energy for high-temperature steam power generation is obtained. The present invention has the advantages of reasonable material selection and advanced preparation process, so a kind of novel heat storage materials which can be used for solar energy high-temperature steam power generation are produced with low cost, the combination properties including heat storage, heat discharge efficiency, etc. are greatly improved, and simultaneously, the environmental pollution of industrial waste is avoided.

Description

A kind of preparation method of high-temperature heat-storage material
Technical field
The present invention relates to the heat accumulating field, particularly a kind of solar energy high temperature steam-electric power preparation method of heat accumulating.
Background technology
The heat accumulation conceptual design is the important technology in the solar steam generating, and the performance of heat accumulating and cost are one of the construction cost of decision large-sized solar power plant and principal element of running cost.The heat accumulating that is used for solar electrical energy generation should satisfy following requirement: heat accumulating should have high energy density; Heat accumulating and heat exchanger fluid should have good thermal conduction; Heat accumulating should have good chemistry and mechanical stability; Good chemical compatibility is arranged between heat accumulating and heat exchanger and the heat exchanger fluid; In heat accumulation and heat release working cycle, answer completely reversibility; Low-cost.The height of working temperature has directly determined the thermo-efficiency of system, and the working temperature that improves heat accumulating has great importance.
Mainly contain fused salt (KNO as the heat accumulating in the solar steam generating at present 3, NaNO 3Or both mixtures), iron ore.But fused salt exist one very obvious defects be its stronger corrodibility, heat exchanging pipe and other affiliated facility are had very strong corrosion behavior, increased the running cost of power plant thus, also reduced the security of system stability.Iron ore then owing to be loose stacking states, is unfavorable for heat accumulation and exothermic process, influences the efficient of system.The concrete heat accumulating is one of ideal candidates heat accumulating that is used for the solar steam generating owing to have plurality of advantages such as stable performance, cost is low, heat storage capacity is strong.Document (1) has been reported Japanese scholar's United States Patent (USP), and wherein with sodium sulfate, ammonium chloride, Sodium Bromide and ammonium sulfate are the heat accumulating that main raw material is formed.The patent of document (2) has reported then and has been used for the solar energy heat-storage material that major ingredients is a sodium-chlor.Document (3-5) has been reported under the low temperature, at the fatty acid phase-change heat-storage material of building use.Document (6-7) has then been reported the phase-change heat-storage material of forming with paraffin and expanded graphite.But the heat accumulating of reporting in the above document, or be that cost is too high, or can only use under low temperature, and the heat accumulating of using as sun power must be considered the performance of its use under prerequisite cheaply.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of high-temperature heat-storage material is provided, this method is practical, its new type high temperature of producing hangs down the cement concrete heat accumulating, have low-cost and excellent comprehensive performance, thereby can satisfy requirement as the heat accumulating of solar energy high temperature steam-electric power energy usefulness.
The technical solution adopted for the present invention to solve the technical problems is: comprise selection, batching and preparation process, it is an aggregate with basalt, bauxitic clay, adding silicon powder, aluminate cement and nanoscale kyanite, natural graphite micro mist is raw material, and preparation is as the heat accumulating of solar energy high temperature steam-electric power.
(1) raw material is formed and composition range:
Weight ratio and granularity that raw material is formed are: basalt aggregate 25~50%, granularity 10~30m m; Bauxitic clay aggregate 25~38%, granularity 1~10mm; 500 order aluminate cements 3~10%; 500 order kyanites 5~20%; 500 order silicon powders 1~5%; 800 order natural graphites 1~5%; Efficient composite water-reducing agent 0.2~1%.
(2) preparation: with above-mentioned raw materials through dried be mixed even after, add 4~6% water, remix evenly places the punching block mould, the demoulding after 24 hours placed the water maintenance 72 hours under 20~25 ℃ of temperature, baking got final product in 24 hours under 100~120 ℃ of temperature then.
Innovation part of the present invention is to adopt and makes full use of micropowder technology, adopt high efficiency water reducing agent and low-dosage aluminate cement as jointing compound simultaneously, not only significantly reduce the consumption (just having reduced the production energy consumption of raw material) and the mixing water amount of cement in the heat accumulating, can also significantly improve heat accumulating stability and work-ing life of (700~1300 ℃) under working temperature; What is more important, select 500 order fineness for use, purity is greater than 95% silicon powder fine powder, in aquation is synthetic, generate mullite with the active oxidation aluminium powder, make heat accumulating have the hot operation temperature, the aquamaine stone flour of Tian Jiaing is when high temperature simultaneously, can be transformed into mullite, make the certain expansion of the inner generation of sample offset the contraction of sample, further improve the intensity of material.In addition, the graphite of interpolation has performances such as excellent heat absorption, heat accumulation, further improves heat accumulation, the exothermal efficiency of heat accumulating.
Embodiment
The present invention be a kind of be that coarse aggregate, bauxitic clay grog are fine aggregate with basalt; With the aluminate cement is jointing compound; Add micro mists such as silicon powder, active oxidation aluminium powder, natural graphite powder, kyanite, add efficient composite water-reducing agent 0.2~1%, prepare the method for high-temperature heat-storage material.Silicon powder is selected 500 order fineness for use, and purity is greater than 95% fine powder; In aquation is synthetic, generate mullite with the active oxidation aluminium powder, make heat accumulating have the hot operation temperature.Efficient composite water-reducing agent adopts novel modified naphthalene series water-reducing agent and dispersant with high efficiency, not only plays the effect of diminishing enhanced, makes the flowability of synthetic material obtain tangible improvement simultaneously.The working temperature of the heat accumulating of the present invention's preparation can be up to 1300 ℃.Specific as follows;
1. the weight ratio and the granularity of raw material composition are: basalt aggregate 25~50%, granularity 10~30m m; Bauxitic clay aggregate 25~38%, granularity 1~10mm; 500 order aluminate cements 3~10%; 500 order kyanites 5~20%; Active oxidation aluminium powder 1~8%; 500 order silicon powders 1~5%; 800 order natural graphites 1~5%; Efficient composite water-reducing agent 0.2~1%.
2. preparation: with above-mentioned raw materials through dried be mixed even after, add 4~6% water, remix evenly places the punching block mould, the demoulding after 24 hours placed the water maintenance 72 hours under 20~25 ℃ of temperature, baking got final product in 24 hours under 100~120 ℃ of temperature then.
The invention will be further described to enumerate several examples below, rather than limit the present invention.
Embodiment 1
Weight ratio and granularity that raw material is formed are: basalt aggregate 37%, granularity 10~30mm; Bauxitic clay aggregate 33%, granularity 1~10mm; 500 order aluminate cements 8%; 500 order active oxidation aluminium powders 5%; 500 order kyanites 7%; 500 order silicon powders 5%; 800 order natural graphites 5%; Add efficient composite water-reducing agent 0.3%.
Above-mentioned raw materials through dried be mixed even after, add 5% water, mix and be placed in the punching block mould, the demoulding after 24 hours, maintenance is after 72 hours in the water under 20~25 ℃ of temperature, baking is 24 hours under 100~120 ℃ of temperature.The density of heat accumulating is 2.88g/cm 3, on the omnipotent test machine for mechanism of INSTRON-1195, record, the ultimate compression strength 〉=60MPa of material, folding strength 〉=10MPa records volumetric heat capacity 125kWh/m on the comprehensive thermal analyzer 3, conductometer records thermal conductivity 1.88W/mK, refractoriness: 1590 ℃.This routine resulting heat accumulating can be as the heat accumulating of solar energy high temperature steam-electric power.
Embodiment 2
Weight ratio and granularity that raw material is formed are: basalt aggregate 35%, granularity 10~30mm; Bauxitic clay aggregate 35%, granularity 1~10mm; 500 order aluminate cements 6%; 500 order active oxidation aluminium powders 4%; 500 order kyanites 11%; 500 order silicon powders 5%; 800 order natural graphites 4%; Add efficient composite water-reducing agent 0.5%.
Raw material through prepare burden dried be mixed even after, add 5.5% water, mix and be placed in the punching block mould, the demoulding after 24 hours, maintenance is after 72 hours in the water under 20~25 ℃ of temperature, baking is 24 hours under 100~120 ℃ of temperature.The density of heat accumulating is 2.86g/cm 3, on the omnipotent test machine for mechanism of INSTRON-1195, record the ultimate compression strength 〉=70MPa of material, folding strength σ b〉=11MPa, volumetric heat capacity 128kWh/m 3, thermal conductivity 1.82W/mK, refractoriness: 1590 ℃.This routine resulting heat accumulating can be as the heat accumulating of solar energy high temperature steam-electric power.
Embodiment 3
Weight ratio and granularity that raw material is formed are: basalt aggregate 30%, granularity 10~30m m; Bauxitic clay aggregate 40%, granularity 1~10mm; 500 order aluminate cements 5%; 500 order active oxidation aluminium powders 8%; 500 order kyanites 9%; 500 order silicon powders 3%; 800 order natural graphites 5%; Add efficient composite water-reducing agent 0.4%.
Above-mentioned raw materials through dried be mixed even after, add 5% water, mix and be placed in the punching block mould, the demoulding after 24 hours, maintenance is after 72 hours in the water under 20~25 ℃ of temperature, baking is 24 hours under 100~120 ℃ of temperature.The density of heat accumulating is 2.94g/cm 3, on the omnipotent test machine for mechanism of INSTRON-1195, record, the ultimate compression strength 〉=55MPa of material, folding strength 〉=10MPa records volumetric heat capacity 130kWh/m on the comprehensive thermal analyzer 3, conductometer records thermal conductivity 1.98W/mK, refractoriness: 1590 ℃.This routine resulting heat accumulating can be as the heat accumulating of solar energy high temperature steam-electric power.
Embodiment 4
Weight ratio and granularity that raw material is formed are: basalt aggregate 40%, granularity 10~30m m; Bauxitic clay aggregate 30%, granularity 1~10mm; 500 order aluminate cements 4%; 500 order active oxidation aluminium powders 6%; 500 order kyanites 11%; 500 order silicon powders 4%; 800 order natural graphites 5%; Add efficient composite water-reducing agent 0.6%.
Above-mentioned raw materials through dried be mixed even after, add 5.3% water, mix and be placed in the punching block mould, the demoulding after 24 hours, maintenance is after 72 hours in the water under 20~25 ℃ of temperature, baking is 24 hours under 100~120 ℃ of temperature.The density of heat accumulating is 2.92g/cm 3, on the omnipotent test machine for mechanism of INSTRON-1195, record, the ultimate compression strength 〉=60MPa of material, folding strength 〉=10MPa records volumetric heat capacity 132kWh/m on the comprehensive thermal analyzer 3, conductometer records thermal conductivity 2.05W/mK, refractoriness: 1590 ℃.This routine resulting heat accumulating can be as the heat accumulating of solar energy high temperature steam-electric power.
Embodiment 5
Weight ratio and granularity that raw material is formed are: basalt aggregate 45%, granularity 10~30mm; Bauxitic clay aggregate 30%, granularity 1~10mm; 500 order aluminate cements 3.5%; 500 order active oxidation aluminium powders 6%; 500 order kyanites 6%; 500 order silicon powders 4.5%; 800 order natural graphites 5%; Add efficient composite water-reducing agent 0.8%.
Above-mentioned raw materials through dried be mixed even after, add 5.3% water, mix and be placed in the punching block mould, the demoulding after 24 hours,
Maintenance is after 72 hours in the water under 20~25 ℃ of temperature, and baking is 24 hours under 100~120 ℃ of temperature.The density of heat accumulating is 2.96g/cm 3, on the omnipotent test machine for mechanism of INSTRON-1195, record, the ultimate compression strength 〉=60MPa of material, folding strength 〉=10MPa records volumetric heat capacity 135kWh/m on the comprehensive thermal analyzer 3, conductometer records thermal conductivity 2.20W/mK, refractoriness: 1590 ℃.This routine resulting heat accumulating can be as the heat accumulating of solar energy high temperature steam-electric power.
Bibliography
[1]Kakiuchi;Hiroyuki;Oka;Masahiro,US?patent(No.5567346)
[2]Ross;Randy,US?patent(No.5685151)
[3]Kadir?Tuncbilek,Ahmet?Sari,Sefa?Tarhan?et?al.Lauric?and?palmitic?acidseutectic?mixture?as?latent?heat?storage?material?for?low?temperature?heatingapplications?Energy,2005,30(5):677-692
[4]Ahmet?Sari.Eutectic?mixtures?of?some?fatty?acids?for?latent?heat?storage:Thermal?properties?and?thermal?reliabillity?with?respect?to?thermal?cycling,EnergyConversion?and?Management,2006,47(9-10):1207-1221
[5]Atul?Sharma,Lee?Dong?Won,D?Buddhi?and?Jun?Un?Park.Numerical?heat?transferstudies?of?the?fatty?acids?for?different?heat?exchanger?materials?on?the?performanceof?a?latent?heat?storage?system?Renewable?Energy,2005,30(14):2179-2187
[6]Zhengguo?Zhang?and?Xiaoming?Fang.Study?on?paraffin/expanded?graphitecomposite?phase?change?thermal?energy?storage?material Energy?Conversion?andManagement,2006,47(3):303-310
[7]V.Shatikian,G.Ziskind?and?R.Letan.Numerical?investigation?of?a?PCM-basedheat?sink?with?internal?fins.International?Journal?of?Heat?and?Mass?Transfer,2005,48(17):3689-3706

Claims (6)

1. the preparation method of a high-temperature heat-storage material comprises selection, batching and preparation process, it is characterized in that: be that coarse aggregate, bauxitic clay grog are fine aggregate with basalt; With the aluminate cement is jointing compound; Interpolation silicon powder, active oxidation aluminium powder, natural graphite powder, kyanite micro mist prepare heat accumulating,
(1) raw material is formed and composition range:
Weight ratio and granularity that raw material is formed are: basalt aggregate 25~50%, granularity 10~30mm; Bauxitic clay aggregate 25~38%, granularity 1~10mm; 500 order aluminate cements 3~10%; 500 order kyanites 5~20%; Active oxidation aluminium powder 1~8%; 500 order silicon powders 1~5%; 800 order natural graphites 1~5%; Add efficient composite water-reducing agent 0.2~1%.
(2) preparation:
With above-mentioned raw materials through dried be mixed even after, add 4~6% water, remix evenly places the punching block mould, the demoulding after 24 hours placed the water maintenance 72 hours under 20~25 ℃ of temperature, baking got final product in 24 hours under 100~120 ℃ of temperature then.
2. the preparation method of high-temperature heat-storage material according to claim 1 is characterized in that the weight ratio that raw material is formed is: basalt aggregate 37%, bauxitic clay aggregate 33%, aluminate cement 8%, active oxidation aluminium powder 5%, silicon powder 5%; Kyanite 7%; Natural graphite 5%; Efficient composite water-reducing agent 0.3%.
3. the preparation method of high-temperature heat-storage material according to claim 1 is characterized in that the weight ratio that raw material is formed is: basalt aggregate 35%, bauxitic clay aggregate 35%, aluminate cement 6%, active oxidation aluminium powder 4%, silicon powder 5%; Kyanite 11%; Natural graphite 4%; Efficient composite water-reducing agent 0.5%.
4. according to the preparation method of claim 1 or 2 or 3 described high-temperature heat-storage materials, it is characterized in that: silicon powder is selected 500 order fineness for use, and purity is greater than 95% fine powder; In aquation is synthetic, generate resistant to elevated temperatures mullite with the active oxidation aluminium powder.
5. the preparation method of high-temperature heat-storage material according to claim 1 is characterized in that: novel modified naphthalene series water-reducing agent and the dispersant with high efficiency of efficient composite water-reducing agent employing.
6. according to the described high-temperature heat-storage material of arbitrary claim in the claim 1 to 3, it is characterized in that heat accumulating as the solar energy high temperature steam-electric power.
CNB2006100194799A 2006-06-27 2006-06-27 Preparation method of high temperature heat storage material Expired - Fee Related CN100427563C (en)

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* Cited by examiner, † Cited by third party
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CN101876488B (en) * 2009-11-10 2012-07-04 武汉理工大学 Method for arranging structure of heat exchange pipes of concrete heat storage system for solar thermal power generation
CN107986721A (en) * 2017-12-14 2018-05-04 深圳市昌龙盛机电技术有限公司 A kind of composite concrete heat accumulating and preparation method thereof

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CN101148577B (en) * 2007-10-18 2010-05-19 昆明理工大学 Aluminum/aluminum oxide base composite phase transition thermal storage material
CN101876487B (en) * 2009-11-10 2012-07-18 武汉理工大学 Method for manufacturing prefabricated concrete heat storage module for solar heat power generation
CN102277139B (en) * 2011-06-22 2014-07-02 武汉理工大学 Sensible heat and latent heat composite medium-temperature heat storage material and preparation method thereof
CN102322759A (en) * 2011-06-22 2012-01-18 武汉理工大学 Concrete heat storage device with low cost for solar energy air conditioner
CN104650819A (en) * 2013-11-17 2015-05-27 成都奥能普科技有限公司 Formula of solid particle blocks for high-temperature heat transfer
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CN104673192A (en) * 2013-11-29 2015-06-03 中广核太阳能开发有限公司 Heat storage material for solar high-temperature steam power generation and preparation method thereof
CN103833302B (en) * 2014-03-18 2016-08-17 武汉理工大学 A kind of accumulation of heat concrete of coating phase-change materials and preparation method thereof
CN105347770B (en) * 2014-08-18 2017-10-24 武汉理工大学 A kind of industrial high-temperature heat accumulation concrete material and preparation method thereof
CN110078460A (en) * 2019-05-20 2019-08-02 河北秦暖新能源科技有限公司 A kind of solid heat storage material applied to pouring molding
CN117585967A (en) * 2019-06-18 2024-02-23 河北省农林科学院经济作物研究所 Sensible heat storage bearing wall material and preparation method and application thereof

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CN107986721A (en) * 2017-12-14 2018-05-04 深圳市昌龙盛机电技术有限公司 A kind of composite concrete heat accumulating and preparation method thereof

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