CN103075828A - Silicon dioxide (SiO2) aerogel trough-type solar heat-collecting tube and preparation method thereof - Google Patents
Silicon dioxide (SiO2) aerogel trough-type solar heat-collecting tube and preparation method thereof Download PDFInfo
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- CN103075828A CN103075828A CN2013100378364A CN201310037836A CN103075828A CN 103075828 A CN103075828 A CN 103075828A CN 2013100378364 A CN2013100378364 A CN 2013100378364A CN 201310037836 A CN201310037836 A CN 201310037836A CN 103075828 A CN103075828 A CN 103075828A
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Abstract
The invention discloses a silicon dioxide (SiO2) aerogel trough-type solar heat-collecting tube and a preparation method thereof. The SiO2 aerogel trough-type solar heat-collecting tube comprises a glass sleeve, a metal heat-absorbing tube and transparent SiO2 aerogel, wherein the metal heat-absorbing tube is arranged in the glass sleeve; the SiO2 aerogel is located between the glass sleeve and the metal heat-absorbing tube; the SiO2 aerogel is in a hollow cylinder shape; the outer surface of the SiO2 aerogel is tightly jointed with the inner surface of the glass sleeve; the inner surface of the SiO2 aerogel is tightly jointed with the outer surface of the metal heat-absorbing tube; and both ends of the SiO2 aerogel are respectively sealed by metal bellows, ceramic heat insulation rings and alloy covers to obtain the SiO2 aerogel trough-type solar heat-collecting tube. The transparent SiO2 aerogel of the SiO2 aerogel trough-type solar heat-collecting tube is high in solar energy transmittance and super in heat-insulating property, so that heat conduction and convection between the metal heat-absorbing tube and the glass sleeve and heat loss caused by heat radiation can be effectively stopped, and the work efficiency of the heat-collecting tube is greatly improved. Moreover, the SiO2 aerogel trough-type solar heat-collecting tube is stable in performance, high in degree of reliability, simple and convenient in manufacturing process and lower in cost.
Description
Technical field
The invention belongs to solar energy heat utilization technical field, relate to a kind of solar energy thermal-power-generating high-temperature heat-collection pipe, especially a kind of with transparent heat-insulated SiO
2Aerogel material is as groove type solar thermal-collecting tube of thermal insulation layer and preparation method thereof.
Background technology
The problems such as energy shortage, resource exhaustion, environmental pollution have had a strong impact on people's life and the development of restriction society.The research and development of clean energy resource and regenerative resource are competitively carried out in countries in the world.Solar energy is one of regenerative resource of current tool development prospect.
At present, comparatively ripe solar energy thermal-power-generating technology mainly contains photovoltaic generation and solar energy thermal-power-generating.In the solar energy thermal-power-generating technology, produce high temperature and then generating by optically focused, efficient is higher, has more application prospect.
Different according to the optically focused mode, optically focused class solar energy thermal-power-generating technology mainly contains: (1) tower type solar energy thermal power generation; (2) trough type solar power generation; (3) disc type solar energy heat generating; (4) Fresnel solar can the heat generating.Wherein, the groove type solar collecting system is commercialization one of potential mode of tool of generating electricity by way of merging two or more grid systems in the solar energy thermal-power-generating technology.For the trough type solar power generation system, high-temperature heat-collection pipe is one of system core parts, is used for absorbing solar energy, converts thereof into heat energy output.
What present used solar energy thermal-power-generating generally used with high-temperature heat-collection pipe is metal-glass vaccum heat-collecting tube.Its general structure is: the surface is coated with the metal tube inner tube of high-temperature selective coating and has the glass outer tube formation of high permeability.In order to reduce the heat loss in the thermal-arrest process, improve collecting efficiency, the space between the inner and outer pipes is evacuated.Temperature of Working in the solar energy heat collection pipe is generally at 400 ℃, and glass outer tube temperature is about 100 ℃, because the significant difference of thermal coefficient of expansion between metal inner pipe and the glass outer tube need to be carried out expansion compensation, common way is to compensate by metal bellows.Pass through the kovar alloy sealing-in between bellows and the glass tube, and because the glass outer tube is easy crushing material.Easily leak gas or the crack appears in glass bushing at seam crossing in transportation and use procedure, this meeting is so that the disappearance of whole heat-collecting pipe vacuum degree, thereby greatly reduces the operating efficiency of thermal-collecting tube.
Aeroge (aerogel) has that density is low, porosity is high, thermal conductivity is extremely low, can effectively see through sunshine, and centering far infrared barrier property is good, can effectively intercept heat of high temperature to the radiant heat transfer loss of low temperature, and heat preservation and insulation is better than again existing any material, is the desirable transparent insulate material of high-temperature heat-collection pipe.Yet, because SiO
2The intensity of aeroge is lower, and fragility is large, wears no resistance, and whole aerogel material cost is high, and existing industrialization product mostly is powder body material, and this gives SiO
2The engineering of aeroge is used and is brought limitation.At present, address this problem and generally adopt compound method to enlarge SiO
2The range of application of aeroge contains composite, its preparation method and the application of aeroge such as one kind of Chinese patent CN1171094A(), CN1546312A(contains composite, its preparation method and the application thereof of aeroge and adhesive), 1622852A(heat resistant aerogel insulation composite and preparation method thereof, aerogel binder composition and preparation method thereof), CN1546312A(aeroge composite and flexible insulation film and preparation method thereof) and one kind of CN101143981A(contain powdery paints of aerogel particle and preparation method thereof) etc.But need point out, the prepared aeroge of these complex techniques all can't obtain good solar energy transmitance, is not suitable for the transparent heat-insulated heat insulation effect of high-temperature heat-collection pipe.
Summary of the invention
For the defective of solar vacuum heat-collecting pipe technology, the present invention proposes and adopt transparent thermal insulation SiO
2The aerogel material technology substitute vacuum technique as the thermal insulation layer of thermal-collecting tube to realize the solution of printing opacity and heat-insulation and heat-preservation purpose, provide a kind of simple in structure easy with manufacturing process, the degree of reliability is high, and cost is lower, the high-temperature heat-collection pipe of stable performance and preparation method thereof.
The present invention realizes above-mentioned purpose by following technical solution:
A kind of SiO
2Aeroge groove type solar thermal-collecting tube, comprise glass bushing and metal heat absorption tube, described metal heat absorption tube is sleeved in the glass bushing and the two ends of metal heat absorption tube extend out to glass bushing outward to connect external heat solenoid road, is provided with transparent SiO between described glass bushing inner surface and the metal heat absorption tube outer surface
2Aeroge, and transparent SiO
2The aeroge two ends rely on the seal member sealing.
Described transparent SiO
2Aeroge is the open circles tubular, and its outer surface and glass bushing inner surface closely engage, and inner surface engages with the metal heat absorption tube intimate.
The transparent SiO of described open circles tubular
2The difference of aerogel material external diameter and internal diameter is 8 ~ 25mm.
Described transparent SiO
2Aeroge has following characteristic, and the aperture is 10 ~ 30nm, and porosity is not less than 90%, and thermal conductivity is not higher than 0.020W/m
2K, the total transmitance of solar energy is not less than 90%.
Described seal member comprises two metal bellows, two heat insulation loop and two alloy covers, described two metal bellows are welded on respectively the two ends of metal heat absorption tube, so that the intimate of the inner surface of metal bellows and metal heat absorption tube is joined, described two heat insulation loop are set in the outer and inner surface of heat insulation loop of metal bellows and the intimate of metal bellows is joined, the outer surface of two heat insulation loop and the inner surface of glass bushing are sealing adhesive, and two metal bellows at metal heat absorption tube two ends and two heat insulation loop are with SiO
2Aeroge sealing is fixing, and described two alloy covers are covered respectively in two glass bushings and the two heat insulation loop outside, and again with glass bushing joint seal welding.
The outer surface of described metal heat absorption tube is coated with solar spectral selective absorbing coating, and the thickness of coating is 20 ~ 70 μ m, and described solar spectral selective absorbing coating is TiAlON, NbAlON composite oxide of metal or black chrome coating.
Above-mentioned SiO
2The preparation method of aeroge groove type solar thermal-collecting tube may further comprise the steps:
Step 1: with alkoxy silane, distilled water, absolute ethyl alcohol, hydrochloric acid and surface modifier mix and blend and it is evenly mixed and disperse, then add ammoniacal liquor and make with the pH value of regulating mixed solution that it is hydrolyzed, the condensation chemical reaction, the stable vitreosol system of formation in solution;
Step 2: the vitreosol for preparing watered cast from the cylindrical die that inner surface is made of the glass bushing inner surface metal heat absorption tube outer surface, outer surface, treat its gel, form and heat absorption metal tube and the integrated wet gel of glass bushing;
Step 3: 25 ~ 45 ℃ of lower burin-in process 1 ~ 5 day;
Step 4: after aging the finishing, to be positioned over heat absorption metal tube and the integrated wet gel of glass bushing and carry out the drying processing in the supercritical fluid drying equipment, obtain the integrated aeroge thermal-collecting tube of combining closely with absorb heat outer surface of metal pipe and glass bushing inner surface;
Step 5: with the sealing of glass bushing two ends, namely obtain SiO
2Aeroge groove type solar thermal-collecting tube.
In the described step 1, the mol ratio of the alkoxy silane of vitreosol system, absolute ethyl alcohol, distilled water, hydrochloric acid, ammoniacal liquor and surface modifier is 1:3 ~ 12:2 ~ 9:0.8 ~ 5.4 * 10
-3: 0.8 ~ 5.4 * 10
-3: 0.1 ~ 1, making step is for mixing alkoxy silane, absolute ethyl alcohol, surface modifier, distilled water, hydrochloric acid in proportion first, and uniform stirring dropwise drips ammoniacal liquor again after 4 ~ 8 hours, stirs after dripping it to be mixed in 5 ~ 15 minutes again, left standstill at last 10 ~ 20 minutes, again casting.
Described alkoxy silane comprises ethyl orthosilicate or methyl silicate.
Described surface modifier comprises one or more in dimethyldiethoxysilane, dimethyldimethoxysil,ne, trimethyl methoxy diethyl diethoxy silane, diethoxy dibutoxy silane, the trim,ethylchlorosilane.
The present invention uses the SiO with high transmission rate and ultralow thermal conductivity
2Aeroge is about to transparent SiO as the thermal insulation layer of groove type solar thermal-collecting tube
2Aeroge is filled between metal heat absorption tube and the glass bushing, can be when not losing solar energy, the effectively heat conduction between blocking-up metal heat absorption tube and the glass bushing, convection heat transfer' heat-transfer by convection and the heat radiation that is produced by metal heat absorption tube, and also can avoid in transportation and use procedure, causing the damage of thermal-collecting tube, both improve operating efficiency and the convenient transportation of thermal-collecting tube, greatly prolonged the service life of thermal-collecting tube simultaneously.
The present invention compares with existing groove type solar vacuum heat collection pipe, has the following advantages:
(1) SiO
2The aeroge thermal-collecting tube is simple in structure, safe and reliable, the life-span is long.High-temperature heat-collection pipe provided by the present invention need not to adopt vacuum design, but adopts transparent SiO
2Aeroge realizes that the solar radiant energy of endothermic tube sees through and the heat-insulation and heat-preservation purpose, and thermal-collecting tube can not lose efficacy because of leakage problem.In addition, transparent SiO
2Aeroge also can play the effect of support member, improves the compression strength of whole thermal-collecting tube.
(2) adopt the interior endothermic tube of sol-gel technology and glass bushing and metal to prepare aerogel material as integrated casting, gel process and the supercritical fluid drying technique of part casting mold, simplified operation, reduced wet gel in the demoulding, enter the infringement that causes because intensity is low in stove and the handling process, production efficiency and finished product rate have been improved, cost is low, on the other hand, enlarged the engineering range of application of aeroge;
(3) high-temperature heat-collection pipe that adopts sol-gel technology and glass bushing and metal heat absorption tube to make as integrated casting, gel process and the supercritical fluid drying technique of part casting mold, has manufacturing process simple, and aeroge not only has preferably elasticity and intensity, and can also have preferably with the surface of glass bushing and metal heat absorption tube and be combined.
(4) prepare surface modifiers such as adding dimethyldiethoxysilane in the sol-process, make SiO in the aeroge
2The surface of the skeleton that nano particle forms forms alkyl, is being lower than under 550 ℃ the serviceability temperature, and product has good hydrophobicity, and technique is simple, and cost is low.
Description of drawings
Fig. 1 is the SiO in the embodiment of the invention 1
2The overall structure schematic diagram of aeroge groove type solar thermal-collecting tube;
Wherein 1 is glass bushing, and 2 is metal heat absorption tube, and 3 is solar spectral selective absorbing coating, and 4 is transparent SiO
2Aeroge, 5 is that metal bellows, 6 is that heat insulation loop, 7 is alloy covers.
The specific embodiment
The specific embodiment
In order to make technical problem to be solved by this invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is illustrated in further detail.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, but protection domain is not subjected to the restriction of these embodiment.
Please refer to Fig. 1, SiO of the present invention
2Aeroge groove type solar thermal-collecting tube comprises glass bushing 1 and is positioned at the metal heat absorption tube 2 of glass bushing 1, and it is outer to connect external heat solenoid road that the two ends of metal heat absorption tube 2 extend out to glass bushing 1, metal heat absorption tube 2 outer surfaces are coated with solar spectral selective absorbing coating 3, fill transparent SiO cylindraceous between described glass bushing 1 and the metal heat absorption tube in glass bushing 12
2Aeroge 4, transparent SiO cylindraceous
2The inner surface of aeroge 4 outer surfaces and glass bushing 1 is combined closely, transparent SiO cylindraceous
2Aeroge 4 inner surfaces are combined with the intimate of metal heat absorption tube 2, by metal bellows 5, heat insulation loop 6 and alloy covers 7 with transparent SiO
2The end face sealing-in of aeroge 4; Metal bellows 5 is welded on respectively the two ends of metal heat absorption tube 2, so that the intimate of the inner surface of metal bellows 5 and metal heat absorption tube 2 is joined, heat insulation loop 6 is sleeved on the outer and inner surface of heat insulation loop 6 of metal bellows 5 and the intimate of metal bellows 5 is joined, the inner surface of the outer surface of heat insulation loop 6 and glass bushing 1 is sealing adhesive, and the metal bellows 5 at metal heat absorption tube 2 two ends and heat insulation loop 6 are with SiO
2Aeroge sealing is fixing, and described alloy covers 7 is covered in glass bushing 1 and heat insulation loop 6 outsides, and again with glass bushing 1 joint seal welding.This device is as the part of solar energy absorption plant, and two ends all are connected in the heating power pipeline.
Compare with existing groove type solar vacuum heat-collecting Manifold technology, between glass bushing 1 and the metal heat absorption tube in glass bushing 12, adopt transparent SiO
2Aeroge 4 is as thermal insulation layer, barrier metal endothermic tube 2 is to the convection heat transfer' heat-transfer by convection between heat conduction, metal heat absorption tube 2 and the glass bushing 1 of glass bushing 1 outer surface and by the heat radiation of metal heat absorption tube 2 to glass bushing 1 outer surface effectively, so that high-temperature heat-collection pipe has better heat-insulating property, simultaneously because transparent SiO
2The introducing of aeroge also can provide the compressive property of high-temperature heat-collection pipe, significantly improves its service life.
Embodiment 1, prepares above-mentioned SiO
2Aeroge groove type solar thermal-collecting tube
With alkoxy silane, absolute ethyl alcohol, surface modifier, distilled water, hydrochloric acid 1:3 ~ 12:0.1 ~ 1:2 ~ 9:0.8 ~ 5.4 * 10 in proportion
-3Mix, uniform stirring dropwise drips ammoniacal liquor again after 4 ~ 8 hours, and the mol ratio of ammoniacal liquor and hydrochloric acid is 1:1.Stirring after dripping mixed it in about 5 ~ 15 minutes again, stop to stir and left standstill 10 ~ 20 minutes, water again and cast from the cylindrical die that inner surface is made of the glass bushing inner surface metal heat absorption tube outer surface, outer surface, wait for its gel, form and heat absorption metal tube and the integrated wet gel of glass bushing.
After colloidal sol lost flowability fully, 25-45 ℃ was worn out 1 ~ 5 day.
With being positioned in the supercritical fluid drying equipment with heat absorption metal tube and the integrated wet gel of glass bushing after the burin-in process, add the drying medium absolute ethyl alcohol in drying equipment, the nitrogen of preliminary filling 1 ~ 4MPa, programming rate with 30 ~ 120 ℃/h is heated to 250 ~ 270 ℃ again, behind insulation 1 ~ 5h, again with the speed release pressure of 0.1 ~ 1.0MPa/h to 0MPa, sweep 30 ~ 120min with the nitrogen punching at last.Obtain and heat absorption metal tube and the integrated SiO of glass bushing
2Aeroge.
Metal heat absorption tube is stainless steel tube, and outer surface is by SiO
2Aeroge closely coats, metal heat absorption tube and SiO
2It is the low radiation-selective heat absorbing coating (black chrome coating) that is coated in the endothermic tube outer surface between the aeroge.Two metal bellows are welded on respectively SiO
2On the metal heat absorption tube at aeroge two ends.One end and SiO
2Aeroge near, with SiO
2In the middle of aeroge is locked in.The inner surface of heat insulation loop and the intimate of metal bellows are joined, an end and the SiO of heat insulation loop
2Aeroge closely engages, and heat insulation loop outer surface and glass bushing inner surface are sealing adhesive, and both are fixedly linked.Alloy covers is blocked glass bushing and heat insulation loop, and with glass bushing joint seal welding.
To carry out supercritical drying with heat absorption metal tube and the integrated wet gel of glass bushing and process the SiO of acquisition
2Aeroge engages closely with metal heat absorption tube and glass bushing.
Heat insulation loop is ceramic material, is that with engaging of metal bellows welding, heat insulation loop can effectively stop glass bushing and metal heat absorption tube to carry out heat transmission by metal bellows.
Claims (10)
1. SiO
2Aeroge groove type solar thermal-collecting tube, it is characterized in that, comprise glass bushing and metal heat absorption tube, described metal heat absorption tube is sleeved in the glass bushing and the two ends of metal heat absorption tube extend out to glass bushing outward to connect external heat solenoid road, is provided with transparent SiO between described glass bushing inner surface and the metal heat absorption tube outer surface
2Aeroge, and transparent SiO
2The aeroge two ends rely on the seal member sealing.
2. a kind of SiO according to claim 1
2Aeroge groove type solar thermal-collecting tube is characterized in that, described transparent SiO
2Aeroge is the open circles tubular, and its outer surface and glass bushing inner surface closely engage, and inner surface engages with the metal heat absorption tube intimate.
3. a kind of SiO according to claim 2
2Aeroge groove type solar thermal-collecting tube is characterized in that, the transparent SiO of described open circles tubular
2The difference of aerogel material external diameter and internal diameter is 8 ~ 25mm.
4. a kind of SiO according to claim 2
2Aeroge groove type solar thermal-collecting tube is characterized in that, described transparent SiO
2Aeroge has following characteristic, and the aperture is 10 ~ 30nm, and porosity is not less than 90%, and thermal conductivity is not higher than 0.020W/m
2K, the total transmitance of solar energy is not less than 90%.
5. a kind of SiO according to claim 2
2Aeroge groove type solar thermal-collecting tube, it is characterized in that, described seal member comprises two metal bellows, two heat insulation loop and two alloy covers, described two metal bellows are welded on respectively the two ends of metal heat absorption tube, so that the intimate of the inner surface of metal bellows and metal heat absorption tube is joined, described two heat insulation loop are set in the outer and inner surface of heat insulation loop of metal bellows and the intimate of metal bellows is joined, the outer surface of two heat insulation loop and the inner surface of glass bushing are sealing adhesive, and two metal bellows at metal heat absorption tube two ends and two heat insulation loop are with SiO
2Aeroge sealing is fixing, and described two alloy covers are covered respectively in two glass bushings and the two heat insulation loop outside, and again with glass bushing joint seal welding.
6. a kind of SiO according to claim 1
2Aeroge groove type solar thermal-collecting tube, it is characterized in that, the outer surface of described metal heat absorption tube is coated with solar spectral selective absorbing coating, the thickness of coating is 20 ~ 70 μ m, described solar spectral selective absorbing coating is TiAlON, NbAlON composite oxide of metal or black chrome coating.
7. each described SiO of claim 1-6
2The preparation method of aeroge groove type solar thermal-collecting tube is characterized in that, may further comprise the steps:
Step 1: with alkoxy silane, distilled water, absolute ethyl alcohol, hydrochloric acid and surface modifier mix and blend and it is evenly mixed and disperse, then add ammoniacal liquor and make with the pH value of regulating mixed solution that it is hydrolyzed, the condensation chemical reaction, the stable vitreosol system of formation in solution;
Step 2: the vitreosol for preparing watered cast from the cylindrical die that inner surface is made of the glass bushing inner surface metal heat absorption tube outer surface, outer surface, treat its gel, form and heat absorption metal tube and the integrated wet gel of glass bushing;
Step 3: 25 ~ 45 ℃ of lower burin-in process 1 ~ 5 day;
Step 4: after aging the finishing, to be positioned over heat absorption metal tube and the integrated wet gel of glass bushing and carry out the drying processing in the supercritical fluid drying equipment, obtain the integrated aeroge thermal-collecting tube of combining closely with absorb heat outer surface of metal pipe and glass bushing inner surface;
Step 5: with the sealing of glass bushing two ends, namely obtain SiO
2Aeroge groove type solar thermal-collecting tube.
8. a kind of SiO according to claim 7
2The preparation method of aeroge groove type solar thermal-collecting tube, it is characterized in that, in the described step 1, the mol ratio of the alkoxy silane of vitreosol system, absolute ethyl alcohol, distilled water, hydrochloric acid, ammoniacal liquor and surface modifier is 1:3 ~ 12:2 ~ 9:0.8 ~ 5.4 * 10
-3: 0.8 ~ 5.4 * 10
-3: 0.1 ~ 1, making step is for mixing alkoxy silane, absolute ethyl alcohol, surface modifier, distilled water, hydrochloric acid in proportion first, and uniform stirring dropwise drips ammoniacal liquor again after 4 ~ 8 hours, stirs after dripping it to be mixed in 5 ~ 15 minutes again, left standstill at last 10 ~ 20 minutes, again casting.
9. a kind of SiO according to claim 8
2The preparation method of aeroge groove type solar thermal-collecting tube is characterized in that described alkoxy silane comprises ethyl orthosilicate or methyl silicate.
10. a kind of SiO according to claim 8
2The preparation method of aeroge groove type solar thermal-collecting tube, it is characterized in that, described surface modifier comprises one or more in dimethyldiethoxysilane, dimethyldimethoxysil,ne, trimethyl methoxy diethyl diethoxy silane, diethoxy dibutoxy silane, the trim,ethylchlorosilane.
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| CN104515313A (en) * | 2013-09-29 | 2015-04-15 | 宁夏银晨太阳能科技有限公司 | Vacuum glass heat collection pipe for solar water heater and production technology thereof |
| CN105197946A (en) * | 2015-09-06 | 2015-12-30 | 湖南上懿丰新材料科技有限公司 | Method of preparing silica aerogel particles with regular shapes |
| CN105197944A (en) * | 2015-09-06 | 2015-12-30 | 湖南上懿丰新材料科技有限公司 | Method of preparing silica aerogel particles with regular shapes |
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| CN109019611A (en) * | 2018-08-17 | 2018-12-18 | 中南大学 | A kind of block transparent silicon dioxide aerogel and its fast preparation method and application |
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| CN105197944A (en) * | 2015-09-06 | 2015-12-30 | 湖南上懿丰新材料科技有限公司 | Method of preparing silica aerogel particles with regular shapes |
| CN105236425A (en) * | 2015-09-06 | 2016-01-13 | 湖南上懿丰新材料科技有限公司 | Method of preparing regular-shape SiO2 aerogel granules |
| CN108613395A (en) * | 2016-12-26 | 2018-10-02 | 北京有色金属研究总院 | A kind of highly-efficient solar collecting pipe |
| CN109019611A (en) * | 2018-08-17 | 2018-12-18 | 中南大学 | A kind of block transparent silicon dioxide aerogel and its fast preparation method and application |
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Application publication date: 20130501 |