CN107739199A - A kind of high temperature resistant anti-thermal shock solar energy thermal-power-generating cordierite-mullite corundum composite ceramics heat supply pipeline and preparation method thereof - Google Patents
A kind of high temperature resistant anti-thermal shock solar energy thermal-power-generating cordierite-mullite corundum composite ceramics heat supply pipeline and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high temperature resistant anti-thermal shock solar energy thermal-power-generating cordierite-mullite corundum composite ceramics heat supply pipeline and preparation method thereof, powder material and mass percent are used in the composite ceramics heat supply pipeline：α‑Al2O340~60%, mullite 20~40%, Suzhou soil 4.18~14.4%, talcum 4.21~12.63%, commercial alumina 0.98~2.93%.Ceramic heat supply pipeline refractoriness under load >=1500 DEG C prepared by the present invention, water absorption rate ＜ 0.5%, 1100 DEG C~room temperature anti-thermal shock are circulated more than 30 times and not ftractureed, rupture strength >=70MPa, meet the requirement of solar energy thermal-power-generating heat supply pipeline.
Description
Technical field
The invention belongs to field of new energy technologies, and in particular to and a kind of high temperature resistant anti-thermal shock solar energy thermal-power-generating cordierite-
Mullite-corundum composite ceramics heat supply pipeline and preparation method thereof.
Background technology
Solar energy thermal-power-generating technology is first to convert the solar into heat by subsystems such as optically focused, heat absorption, heat exchange, defeated heat
Can, then convert heat energy into by generating set the new energy use technology of electric energy.Wherein, heat supply pipeline is carried on a shoulder pole in the entire system
The effect of heat transfer medium (water, conduction oil, fuse salt, liquid metal etc.) conveying is born, is whole heat generating system steady operation
Key.In order to improve generating efficiency, the 3rd generation solar energy thermal-power-generating technology will use air as heat transfer medium, its operating temperature
800~950 DEG C are up to, therefore heat supply pipeline must have excellent resistance to elevated temperatures, thermal shock resistance, high intensity and high cause
Density.
Heat supply pipeline material currently used for solar energy thermal-power-generating is similar with thermal power generation, mainly using heat-resisting alloy steel as
It is main, such as《Suggestions for Choice of Material for High Temperature Pipes of 1000 MW Class Ultra Supercritical Sets》One text compared for pearlitic steel, iron element
Body/martensite steel and New Heat-Resistant Steel are used in the feasibility in generating set high temperature steam pipeline, the results showed that Nickel-Based Steel
Performance it is more excellent, but its maximum operation (service) temperature is also only 690 DEG C.Therefore, in order to meet that solar heat power generation system is higher
(800~950 DEG C) of operating temperature needs, earthenware duct is optimal selection.
At present, common earthenware duct material has carborundum, aluminum oxide, mullite, cordierite etc., as Chinese invention is special
Profit《Thin wall silicon carbide heat exchanger》(CN2041392U) disclose a kind of for various industrial furnace smokes and the carbon of waste heat recovery
SiClx pipeline.Because the firing temperature of silicon carbide ceramics is generally more than 2200 DEG C, therefore the production cost of the pipeline is high, and gas
Close property is poor；Japanese invention patent《CERAMIC PIPE FOR ELECTRIC POWER》(JPS53121199 (A)) discloses one
Aluminium oxide ceramics pipeline of the kind for power system, although its resistance to elevated temperatures is preferable, due to aluminum oxide itself thermal expansion system
Number is big, causes that the thermal shock resistance of the pipeline is poor, and service life is short；Russian patent of invention《EXHAUST PIPE OF
GAS-TURBINE PLANT》(RU2208115 (C2)) discloses a kind of combustion gas turbine prepared using mullite as primary raw material
Blast pipe, mullite ceramic equally exist thermal shock resistance deficiency the shortcomings that similar with oxidation aluminium material.Chinese invention patent
《A kind of vehicle explosion-proof fuse porcelain tube and its manufacture method》(CN201310642074.0) one kind is disclosed as automobile to prevent
The cordierite ceramic pipe of quick-fried fuse, using the low thermal coefficient of expansion of cordierite, reach the effect of crack resistence, but cordierite
The mechanical strength of ceramics is relatively low.
But these earthenware ducts can not meet the requirement of solar heat power generation system.The present invention gives full play to not
Carry out stone and the advantages of corundum heat-resisting quantity is excellent and intensity is high, cordierite is made in mullite and corundum by the method for fabricated in situ
Intercrystalline is uniformly distributed, so as to significantly improve the thermal shock resistance of complex phase ceramic.In addition, by being glued with cordierite glass-ceramic matter
The method for connecing agent connection earthenware duct realizes the firm connection of overlength earthenware duct, meets the defeated heat of solar energy thermal-power-generating so as to prepare
It is required that earthenware duct.
The content of the invention
The technical problems to be solved by the invention are for above shortcomings in the prior art, there is provided one kind has resistance to
High temperature, anti-thermal shock, solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline of high intensity and high-compactness
And preparation method thereof.
In order to solve the above technical problems, technical scheme provided by the invention is：
A kind of high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline, institute are provided
Stating powder material and mass percent used in composite ceramics heat supply pipeline is：α-Al2O340~60%, mullite 20~40%,
Suzhou soil 4.18~14.4%, talcum 4.21~12.63%, commercial alumina 0.98~2.93%.
It is defeated that the present invention also provides above-mentioned high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics
The preparation method of hot channel, its step are as follows：
1) raw material proportioning：By α-Al2O3, mullite, Suzhou soil, talcum, commercial alumina respectively with ball mill ball milling 2~
4h, 250~325 mesh sieves are crossed, obtain α-Al2O3Powder, mullite powder, Suzhou soil powder, talcum powder, industrial alumina powder, then by institute
Powder body material is obtained to weigh in proportion, it is standby；
2) raw material mixing is old：Powder body material obtained by step 1) is placed in 2~4h of mixing in kneader, obtains mixed powder
Material, adds binding agent, lubricant and water mix 30~40min, then with vacuum deairing machine pugging, then old 24~
36h, obtain old good pug；
3) earthenware duct base substrate is prepared：Extrusion in pug input extruder obtained by step 2) is obtained into earthenware duct base substrate；
4) high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline is prepared：Will step
Rapid 3) gained earthenware duct base substrate, which is put into micro-wave oven, shapes, and is then placed in infrared drying oven and dries, finally will be dried
Earthenware base substrate is put into sintering in high temperature furnace, and to obtain high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum compound
Ceramic heat supply pipeline.
By such scheme, the step 2) binding agent is carboxymethyl cellulose, one or both of polyvinyl alcohol by appointing
The mixture of meaning ratio, addition are the 3~5% of mixed powder quality.
By such scheme, the step 2) lubricant is the mixing of one or both of tung oil, soya-bean oil in any proportion
Thing, addition are the 4~6% of mixed powder quality.
Preferably, the addition of the step 2) water is the 20~25% of mixed powder weight.
Preferably, step 3) the earthenware duct base substrate length is 1000~3000mm, and internal diameter is 100~300mm, outside
Footpath is 120~360mm, and extruder extrusion pressure is 3~6MPa.
By such scheme, the step 4) microwave power is 5kW, and frequency is 2450 ± 50MHz, when being shaped in micro-wave oven
Between be 20~40min.
By such scheme, the described infra-red drying the temperature inside the box of step 4) is 90~110 DEG C, and drying time is 1~2h.
By such scheme, the step 4) sintering process conditions are：1400 are warming up to 3~5 DEG C/min speed~
1500 DEG C, it is incubated 2~3h.
The present invention devises the ternary complex phase ceramic pipeline of the low middle high thermal expansion coefficient matching of dichroite-mullite-corundum,
Using natural clay as primary raw material the fabricated in situ cordierite between mullite and corundum, giving full play to mullite and corundum is high
While intensity, resistance to elevated temperatures, the defects of the two thermal shock resistance deficiency compensate for equally distributed cordierite.Again with violet
Green stone devitrified glass matter pipe bonding agent is medium, the firm connection of overlength earthenware duct is realized, so as to meet solar energy thermal-power-generating
The requirement of defeated hot systems.
The beneficial effects of the present invention are：
1st, the present invention is prepared for dichroite-mullite-corundum composite ceramics by in-situ synthesis, has given full play to violet green grass or young crops
The characteristics of high temperature resistant, high intensity of the excellent thermal shock resistance of stone, mullite and corundum, therefore its refractoriness under load exceedes
1500 DEG C, water absorption rate ＜ 0.5%, 1100 DEG C~room temperature anti-thermal shock is circulated more than 30 times and not ftractureed, and thermal shock resistance is good, anti-folding
Intensity >=70MPa, meet the requirement of solar energy thermal-power-generating heat supply pipeline.2nd, the present invention utilizes part natural clay and synthesis
The cost of dichroite-mullite-corundum composite ceramics pipeline prepared by raw material is about 5000 yuan/ton, and traditional heat-resisting alloy steel
The average price of pipeline is up to 14000 yuan/ton, greatlys save cost.3rd, preparation technology of the present invention is simple, it is easy to accomplish industrialization,
With good market application foreground.
Brief description of the drawings
Fig. 1 is two of dichroite-mullite-corundum composite ceramics heat supply pipeline section prepared by the embodiment of the present invention 1
Secondary charge pattern；
Fig. 2 is the EDS energy spectrum analysis figures of specified point in Fig. 1.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
Prepare high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline, specific step
It is rapid as follows：
1. raw material ball milling：By α-Al2O3, mullite, Suzhou soil, talcum, commercial alumina use ball mill ball milling 2h respectively,
250 mesh sieves are crossed, it is standby；
2. raw material proportioning：Mass percent shared by each raw material is：α-Al2O340%th, mullite 40%, Suzhou soil 10%,
Talcum 8%, commercial alumina 2%；
3. raw material mixes：By α-Al2O3, mullite, Suzhou soil, talcum, industrial alumina powder 2h is mixed in kneader,
Mixed powder is obtained, adds binding agent, lubricant and water mix 30min, then with vacuum deairing machine pugging, old 24h,
Obtain old good pug；
The binding agent is carboxymethyl cellulose, and addition is the 3% of mixed powder weight；Lubricant is tung oil, is added
Measure as the 4% of mixed powder weight；The addition of water is the 20% of mixed powder weight；
4. earthenware duct base substrate is extruded：It will be extruded in old good pug input extruder, it is 1000mm to cut into length,
Internal diameter is 100mm, and external diameter is 120mm earthenware duct base substrate；Extruder extrusion pressure is 3MPa；
5. base substrate is shaped and dried：Extruded ceramic pipeline base substrate is put into micro-wave oven the 20min that shapes, is then placed in infrared
Through 90 DEG C of dry 1h in drying box, dried base substrate is obtained；Microwave power is 5kW, frequency 2450MHz；
6. earthenware duct is burnt till：Dried earthenware base substrate is put into electrical kiln, heated up with 3 DEG C/min heating rate
To 1400 DEG C, 2h is incubated, obtains earthenware duct.
After tested, the refractoriness under load of earthenware duct of the invention be 1500 DEG C, water absorption rate 0.45%, 1100 DEG C~
Room temperature anti-thermal shock is circulated more than 30 times and not ftractureed, and rupture strength 73.5MPa, meets the use of solar energy thermal-power-generating heat supply pipeline
It is required that.Tested through XRD, cordierite, mullite, corundum, magnalium point in composite ceramics heat supply pipeline finished product manufactured in the present embodiment
The mass percent of spar is respectively：4.2%th, 47.7%, 41.2%, 6.9%.Dichroite-mullite manufactured in the present embodiment-
The cost of corundum composite ceramics pipeline is about 5000 yuan/ton, and the average price of traditional heat-resisting alloy steel conduit is up to 14000 yuan/ton,
Greatly save cost.
It is the secondary electron image of the section of ceramic heat supply pipeline manufactured in the present embodiment as shown in Figure 1, it can be seen that material
Consistency is high, there's almost no connection stomata, is circular or semi-moon shaped hole of holding one's breath, is favorably improved the thermal shock resistance of sample
Energy.Fig. 2 is the EDS energy spectrum analysis of specified point in Fig. 1, it is known that heat supply pipeline material is that expected dichroite-mullite-corundum is multiple
Condensation material, crystal combination is close, is interweaved, and assigns sample high intensity.
Embodiment 2
Prepare high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline, specific step
It is rapid as follows：
1. raw material ball milling：By α-Al2O3, mullite, Suzhou soil, talcum, commercial alumina use ball mill ball milling 4h respectively,
325 mesh sieves are crossed, it is standby；
2. raw material proportioning：Mass percent shared by each raw material is：α-Al2O360%th, mullite 20%, Suzhou soil 12%,
Talcum 6%, commercial alumina 2%；
3. raw material mixes：By α-Al2O3, mullite, Suzhou soil, talcum, industrial alumina powder 4h is mixed in kneader,
Mixed powder is obtained, adds binding agent, lubricant and water mix 40min, then with vacuum deairing machine pugging, old 36h,
Obtain old good pug；
The binding agent is carboxymethyl cellulose and polyvinyl alcohol 1:1 mixture, addition are mixed powder weight
5%；Lubricant is tung oil and soya-bean oil 1:1 mixture, addition are the 5% of mixed powder weight；The addition of water is mixing
The 25% of powder weight；
4. earthenware duct base substrate is extruded：It will be extruded in old good pug input extruder, it is 2500mm to cut into length,
Internal diameter is 300mm, and external diameter is 360mm earthenware duct base substrate；Extruder extrusion pressure is 6MPa；
5. base substrate is shaped and dried：Extruded ceramic pipeline base substrate is put into micro-wave oven the 40min that shapes, is then placed in infrared
Through 110 DEG C of dry 2h in drying box, dried base substrate is obtained；Microwave power is 5kW, frequency 2500MHz；
6. earthenware duct is burnt till：Dried earthenware base substrate is put into electrical kiln, heated up with 5 DEG C/min heating rate
To 1500 DEG C, 3h is incubated, obtains earthenware duct.
After tested, the refractoriness under load of earthenware duct of the invention be 1600 DEG C, water absorption rate 0.1%, 1100 DEG C~
Room temperature anti-thermal shock is circulated more than 30 times and not ftractureed, and rupture strength 114MPa, meets the use of solar energy thermal-power-generating heat supply pipeline
It is required that.
Embodiment 3
Prepare high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline, specific step
It is rapid as follows：
1. raw material ball milling：By α-Al2O3, mullite, Suzhou soil, talcum, commercial alumina use ball mill ball milling 3h respectively,
250 mesh sieves are crossed, it is standby；
2. raw material proportioning：Mass percent shared by each raw material is：α-Al2O350%th, mullite 30%, Suzhou soil 10%,
Talcum 8.5%, commercial alumina 1.5%；
3. raw material mixes：By α-Al2O3, mullite, Suzhou soil, talcum, industrial alumina powder 3h is mixed in kneader,
Mixed powder is obtained, adds binding agent, lubricant and water mix 30min, then with vacuum deairing machine pugging, old 30h,
Obtain old good pug；
The binding agent is polyvinyl alcohol, and addition is the 4% of mixed powder weight；Lubricant is soya-bean oil, and addition is
The 5% of mixed powder weight；The addition of water is the 22% of mixed powder weight；
4. earthenware duct base substrate is extruded：It will be extruded in old good pug input extruder, it is 2000mm to cut into length,
Internal diameter is 250mm, and external diameter is 300mm earthenware duct base substrate；Extruder extrusion pressure is 5MPa；
5. base substrate is shaped and dried：Extruded ceramic pipeline base substrate is put into micro-wave oven the 30min that shapes, is then placed in infrared
Through 100 DEG C of dry 2h in drying box, dried base substrate is obtained；Microwave power is 5kW, frequency 2450MHz；
6. earthenware duct is burnt till：Dried earthenware base substrate is put into electrical kiln, heated up with 3 DEG C/min heating rate
To 1460 DEG C, 2h is incubated, obtains earthenware duct.
After tested, the refractoriness under load of earthenware duct of the invention be 1550 DEG C, water absorption rate 0.31%, 1100 DEG C~
Room temperature anti-thermal shock is circulated more than 30 times and not ftractureed, rupture strength 93MPa, meets that the use of solar energy thermal-power-generating heat supply pipeline will
Ask.
Claims (7)
1. a kind of high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline, its feature exist
In powder material and mass percent are used in the composite ceramics heat supply pipeline：α-Al2O340~60%, mullite 20~
40%, Suzhou soil 4.18~14.4%, talcum 4.21~12.63%, commercial alumina 0.98~2.93%.
2. high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics described in a kind of claim 1 is defeated
The preparation method of hot channel, it is characterised in that step is as follows：
1) raw material proportioning：By α-Al2O3, mullite, Suzhou soil, talcum, commercial alumina use ball mill 2~4h of ball milling, mistake respectively
250~325 mesh sieves, obtain α-Al2O3Powder, mullite powder, Suzhou soil powder, talcum powder, industrial alumina powder, then by gained powder
Body material weighs in proportion, standby；
2) raw material mixing is old：Powder body material obtained by step 1) is placed in 2~4h of mixing in kneader, obtains mixed powder, then
Add binding agent, lubricant and water and mix 30~40min, then with vacuum deairing machine pugging, then old 24~36h, obtain
To old good pug；
3) earthenware duct base substrate is prepared：Extrusion in pug input extruder obtained by step 2) is obtained into earthenware duct base substrate；
4) high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics heat supply pipeline is prepared：By step 3)
Gained earthenware duct base substrate, which is put into micro-wave oven, shapes, and is then placed in infrared drying oven and dries, finally by dried ceramics
Pipe body is put into sintering in high temperature furnace and obtains high temperature resistant anti-thermal shock solar energy thermal-power-generating dichroite-mullite-corundum composite ceramics
Heat supply pipeline.
3. preparation method according to claim 2, it is characterised in that the step 2) binding agent is carboxymethyl cellulose, gathered
The mixture of one or both of vinyl alcohol in any proportion, addition are the 3~5% of mixed powder quality.
4. preparation method according to claim 2, it is characterised in that the step 2) lubricant is one in tung oil, soya-bean oil
Kind or two kinds of mixtures in any proportion, addition are the 4~6% of mixed powder quality.
5. preparation method according to claim 2, it is characterised in that the step 4) microwave power is 5kW, and frequency is
2450 ± 50MHz, shaping time is 20~40min in micro-wave oven.
6. preparation method according to claim 2, it is characterised in that the described infra-red drying the temperature inside the box of step 4) be 90~
110 DEG C, drying time is 1~2h.
7. preparation method according to claim 2, it is characterised in that the step 4) sintering process conditions are：With 3~5
DEG C/min speed is warming up to 1400~1500 DEG C, it is incubated 2~3h.
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| CN201711066293.3A CN107739199B (en) | 2017-11-02 | 2017-11-02 | High-temperature-resistant thermal-shock-resistant solar thermal power generation cordierite-mullite-corundum composite ceramic heat transmission pipeline and preparation method thereof |
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| CN201711066293.3A CN107739199B (en) | 2017-11-02 | 2017-11-02 | High-temperature-resistant thermal-shock-resistant solar thermal power generation cordierite-mullite-corundum composite ceramic heat transmission pipeline and preparation method thereof |
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| CN107739199A true CN107739199A (en) | 2018-02-27 |
| CN107739199B CN107739199B (en) | 2020-09-01 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113321494A (en) * | 2021-06-11 | 2021-08-31 | 武汉理工大学 | Oxidation-resistant long-life heat absorption and storage integrated corundum-mullite ceramic and preparation method thereof |
| CN114231056A (en) * | 2021-10-29 | 2022-03-25 | 攀钢集团攀枝花钢铁研究院有限公司 | High-emissivity infrared radiation coating and preparation method thereof |
| CN114230322A (en) * | 2021-12-27 | 2022-03-25 | 景德镇晶达新材料有限公司 | Preparation method of aluminum oxide composite ceramic powder |
| CN115572179A (en) * | 2022-09-20 | 2023-01-06 | 佛山市金刚材料科技有限公司 | Alumina foamed ceramic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110483027A (en) * | 2019-08-26 | 2019-11-22 | 湖南辰州矿业有限责任公司 | A kind of production antimony oxide fire resistant air-duct and preparation method thereof |
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| CN113321494B (en) * | 2021-06-11 | 2022-10-14 | 武汉理工大学 | Oxidation-resistant long-life heat absorption and storage integrated corundum-mullite ceramic and preparation method thereof |
| CN114231056A (en) * | 2021-10-29 | 2022-03-25 | 攀钢集团攀枝花钢铁研究院有限公司 | High-emissivity infrared radiation coating and preparation method thereof |
| CN114230322A (en) * | 2021-12-27 | 2022-03-25 | 景德镇晶达新材料有限公司 | Preparation method of aluminum oxide composite ceramic powder |
| CN115572179A (en) * | 2022-09-20 | 2023-01-06 | 佛山市金刚材料科技有限公司 | Alumina foamed ceramic and preparation method thereof |
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