IL179261A - Tubular radiation absorbing device for a solar power plant with reduced heat losses - Google Patents

Tubular radiation absorbing device for a solar power plant with reduced heat losses

Info

Publication number
IL179261A
IL179261A IL179261A IL17926106A IL179261A IL 179261 A IL179261 A IL 179261A IL 179261 A IL179261 A IL 179261A IL 17926106 A IL17926106 A IL 17926106A IL 179261 A IL179261 A IL 179261A
Authority
IL
Israel
Prior art keywords
central tube
tube
chromium
absorber
hydrogen
Prior art date
Application number
IL179261A
Other languages
Hebrew (he)
Other versions
IL179261A0 (en
Original Assignee
Schott Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schott Ag filed Critical Schott Ag
Publication of IL179261A0 publication Critical patent/IL179261A0/en
Publication of IL179261A publication Critical patent/IL179261A/en

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S10/00—Solar heat collectors using working fluids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S10/00—Solar heat collectors using working fluids
    • F24S10/40—Solar heat collectors using working fluids in absorbing elements surrounded by transparent enclosures, e.g. evacuated solar collectors
    • F24S10/45—Solar heat collectors using working fluids in absorbing elements surrounded by transparent enclosures, e.g. evacuated solar collectors the enclosure being cylindrical
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S20/00—Solar heat collectors specially adapted for particular uses or environments
    • F24S20/20—Solar heat collectors for receiving concentrated solar energy, e.g. receivers for solar power plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S40/00—Safety or protection arrangements of solar heat collectors; Preventing malfunction of solar heat collectors
    • F24S40/40—Preventing corrosion; Protecting against dirt or contamination
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S40/00—Safety or protection arrangements of solar heat collectors; Preventing malfunction of solar heat collectors
    • F24S40/40—Preventing corrosion; Protecting against dirt or contamination
    • F24S40/46—Maintaining vacuum, e.g. by using getters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y02E10/44—Heat exchange systems

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Description

on Tia ίΐ η£)»η 2» ) >*i iX7 na ρου π. ρ o ipn >Ί132 nn Tubular radiation absorbing device for a solar power plant with reduced heat losses Schott AG C.171010 TUBULAR RADIATION ABSORBING DEVICE FOR A SOLAR POWER PLANT WITH REDUCED HEAT LOSSES he following is a complete specification thereof: 179261/2 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tubular radiation absorbing device for solar thermal applications, especially for a parabolic trough collector in a solar power plant, which comprises a central tube made from a chromium steel, especially stainless steel, and a glass tubular jacket surrounding the central tube so as to form a ring-shaped space between the tubular jacket and the central tube. 2. Related Art Tubular radiation absorbing devices or absorber pipes are used in parabolic trough collectors to utilize solar radiation. The solar radiation is concentrated by a tracking mirror on a tubular radiation absorbing device and converted into heat.
The heat is conducted away by a heat-carrying medium passing through the tubular radiation absorbing device and is used directly as process heat or converted into electrical energy.
This sort of tubular radiation absorbing device typically comprises a coated central tube and a glass tubular jacket around it. The ring-shaped space between the tubes is evacuated. In operation a heat carrier fluid, especially an oil, is pumped through the central tube.
This sort of absorber tube is described, e.g., in DE 102 31 467 B4. A glass-metal transitional element is arranged at the free end of a glass tubular jacket. The central tube and the glass-metal transitional element are connected with each other so that they are slidable relative to each other in a longitudinal direction by means of at least one expansion compensating device.
Free hydrogen, which is dissolved in the heat carrier medium, is generated during aging of the heat carrier fluid. This hydrogen arrives in the evacuated ring-shaped space between the central tube and the glass tubular jacket by permeation through the central tube. The permeation rate increases with increasing operating temperature, which is between 300°C and 400°C, so that the pressure in the ring-shaped space rises. This pressure increase leads to increased heat losses and to a reduced efficiency of the tubular radiation absorbing device.
Suitable measures must then be taken to maintain a vacuum in the ring-shaped space. One measure that is taken to remove hydrogen is to combine it with a suitable material.
Getter material, which combines with the hydrogen gas that penetrates through the central tube into the ring-shaped space, is arranged in the ring-shaped space to maintain the vacuum. When the capacity of the getter material is exhausted, the pressure rises in the ring-shaped space until the partial pressure of the free hydrogen in the ring-shaped space reaches equilibrium with the hydrogen dissolved in the heat carrier medium. The equilibration pressure of the hydrogen in the ring-shaped space amounts to between 0.3 mbar and 3 mbar in the known absorber tubes. There is an increase in heat conduction in the ring-shaped space because of the presence of hydrogen in it. The heat losses due to heat conduction are about five times higher compared to air, i.e. clearly higher than with an absorber tube that has not been evacuated.
A getter arrangement is described in WO 2004/063640 A1 , in which a getter strip is arranged between the central tube and the tubular jacket in the ring-shaped space. This arrangement has the disadvantage that the strip is in a region, which can be exposed to direct radiation. The getter strip can be heated especially by radiation coming from the mirror that misses the central tube or strikes it but is largely reflected from it. Since the getter strip is nearly thermally isolated from the central tube and the tubular jacket in a vacuum, the temperature of the getter strip can vary greatly with the varying radiating conditions. Because the getter material with a predetermined loading degree has a temperature dependent equilibrium pressure (equilibrium between gas desorption and adsorption), temperature fluctuations of the getter material lead to undesirable pressure fluctuations. The temperature of the tubular jacket greatly increases after consumption of the getter material and the absorber tube becomes unusable.
A chromium oxide coating or layer has been provided on chromium-containing steel according to "Initial oxidation and chromium diffusion. I. Effects of surface working on 9-20 %-Cr Steels" by Ostwald and Grabke, Corrosion Science 46, pp. 1 1 13 - 1 127 (2004) in order to protect the steel from a reactive environment. The chromium-containing steel is provided with a coating by means of an H2-H2O atmosphere, which comprises an inner layer of Cr2O3 and an outer layer of (Mn,Fe)Cr2O4 spinel. 179261/2 SUMMARY OF THE INVENTION In a first aspect of the invention, the invention provides an absorber tube (1 ) for solar thermal applications, in particular for parabolic trough collectors in solar thermal power stations, comprising a central tube (3) made of chromium-containing steel, in particular special steel, and comprising an envelope tube (2) which is made of glass and surrounds the central tube (3) to form an annular space (6) between the central tube (3) and the envelope tube (2), characterized in that at least the inner side of the central tube (3) is provided with a chromium-oxide-containing barrier layer (4) that is largely impervious to hydrogen.
In a second aspect the Invention provides Process for producing a central tube (3) of an absorber tube (1) for solar thermal applications, comprising the following steps: - a central tube (3) is prefabricated from chromium-containing steel, in particular from special steel, - the central tube (3) is treated with a free-hydrogen-comprising water vapour at temperatures of 500°C to 700°C, in order to produce a chromium-oxide-containing barrier layer (4) that is largely impervious to hydrogen at least on the inner side of the central tube (3).
Passages of the description which are out of ambit of the claims do not constitute part of the invention. 179261/2 BRIEF DESCRIPTION OF THE DRAWINGS The objects, features and advantages of the invention will now be illustrated in more detail with the aid of the following description of the preferred embodiments, with reference to the accompanying figures in which: The sole figure is a cutaway longitudinal cross-sectional view through a preferred embodiment of the tubular radiation absorbing device according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT It is an object of the present invention to provide a tubular radiation absorbing device that has lower heat losses than conventional tubular radiation absorbing devices of the prior art.
This objection is attained by a tubular radiation absorbing device, in which the central tube has a barrier coating that is largely impermeable to hydrogen, at least one its interior side. This barrier coating contains chromium oxide, Cr203.
It has been surprisingly found that coatings containing chromium oxide largely prevent passage of hydrogen.
The hydrogen diffusion from the interior of the central tube to the ring-spaced space could be reduced by a factor of up to 50 by this barrier coating.
The coating having chromium oxide is obtained by treating the central tube comprising steel, especially stainless steel, in a process in which a surface layer of the central tube is converted into a coating containing chromium oxide.
The barrier coating has a preferred coating thickness of 0.5 m to 10 μιη. The barrier action of the barrier coating decreases when the coating thickness is smaller than the foregoing preferred coating thickness. Crack formation increases in coatings that are thicker than this preferred coating thickness due to temperature 179261/2 changes, so that the barrier action similarly decreases when the coating thickness is thicker than the foregoing preferred coating thickness.
The chromium oxide content of the barrier coating is preferably from 20 wt. % to 60 wt. %, especially 30 wt. % to 50 wt. %. The chromium oxide fraction is determined by the chromium content of the steel and the type and duration of the treatment of the central tube, as explained in connection with the claimed process. The barrier action for hydrogen is initiated at a chromium oxide content of 20 wt. %.
Preferably the central tube has an outer coating on its outside which contains chromium oxide.
However it is preferred that the thickness of the outer coating is less than the thickness of the barrier coating. This coating merely serves as an adherent layer for a subsequently applied selective thin layer. The thickness of the outer layer amounts to preferably less than 0.1 pm. It has been shown that a spinel layer, which has a rough surface and is porous, is formed on the upper surface of the chromium oxide coating with a layer thickness of greater than 0.1 pm. This spinel layer is not suitable to support a subsequently applied smooth selective thin layer. The spinel layer does not interfere with the interior barrier coating, so that greater thickness is possible.
The process for making a central tube from steel containing chromium, especially from chromium-nickel steel, comprises first prefabricating a central tube from the steel, especially stainless steel, and then subjecting this central tube to a steam oxidation, in which the central tube is treated with steam containing free hydrogen at temperatures of from 500°C to 700°C in order to provide a barrier coating that is largely impermeable to hydrogen, at least on the interior side of the central tube. 179261/2 Preferably the ratio VA = H2/H20 of the steam for treating the outer side of the central tube is greater than the ratio V-i = H2/H20 of the steam for treating the inner side of the central tube. The formation of the spinel layer on the outer side is avoided by these process steps.
A preferred ratio VA is from 10 to 1000, while a preferred ratio Vi is from 1 to 100. However in this case VA≥ \ .
According to another embodiment the coating thickness on the outer side can be reduced so that the central tube is worked or process on its outside prior to the steam treatment, so that it has a roughness Ra less than 0.3. Preferably the roughness Ra is less than 0.25.
A polishing procedure can be performed on the outer side of the central tube in order to perform this treatment.
In this second embodiment however the use of different values for the ratios VA and V-i is not required, but of course could be considered as an aid.
A tubular radiation absorbing device 1 for solar thermal applications is shown in the cross-sectional view of the sole figure. The tubular radiation absorbing device 1 comprises a central tube 3 made of metal and a glass tubular jacket 2 surrounding the central tube so that a ring-shaped space 6 is formed between the tubular jacket and the central tube.
A heat carrier medium, which contains free hydrogen, flows through the central tube 3, which is made of metal. The hydrogen can permeate metal and thus pass through the central tube 3 into the ring-shaped space 6. In order to prevent the free hydrogen from passing through the central tube 3, which e.g. is made from Chromium-Nickel-Molybdenum 17-12-2 Steel No. 1.4404, it is provided with a barrier coating 4 on its interior side, which contains Cr203. 179261/1 The inner coating 4 has a thickness of e.g. 10 pm. The coating 4 comprises a first layer and a further or second layer applied to the first layer. The first layer contains 30 % Cr203, from 15 to 18 % NiO, and from 50 to 54 % Fe203. The further or second layer is predominantly composed of Fe203, i.e. 98 % Fe203. The chromium oxide content of the second layer is only about 1 to 2 %. This second layer, which forms the spinel layer, still contains a small amount of nickel oxide.
The central tube 3 has an outer coating 5 on its outer side, which has a thickness of 0.05 pm. This coating 5 has no spinel layer. - 8a - 179261/2 The preparation of the oxide coatings 4, 5 takes place by means of a steam oxidation process according to the following parameters: H2/H20 ratio for both coatings 4,5, Outer surface of the central tube: polished, Ra < 0.2 μηι, Temperature T = 500°C, and Treatment time: 5 hours.
PARTS LIST 1 tubular radiation absorbing device 2 tubular jacket 3 central tube 4 barrier coating outer coating 6 ring-shaped space 9

Claims (12)

79261/2 We Claim:
1. Absorber tube (1) for solar thermal applications, in particular for parabolic trough collectors in solar thermal power stations, comprising a central tube (3) made of chromium-containing steel, in particular special steel, and comprising an envelope tube (2) which is made of glass and surrounds the central tube (3) to form an annular space (6) between the central tube (3) and the envelope tube (2), characterized in that at least the inner side of the central tube (3) is provided with a chromium-oxide-containing barrier layer (4) that is largely impervious to hydrogen.
2. Absorber tube according to Claim 1 , characterized in that the thickness of the barrier layer (4) is 0.5 pm to 10 pm.
3. Absorber tube according to either of Claims 1 and 2, characterized in that the chromium oxide content of the barrier layer (4) is 20% by weight to 60% by weight.
4. Absorber tube according to one of Claims 1 to 3, characterized in that the outer side of the central tube (3) is provided with a chromium-oxide- containing outer layer (5).
5. Absorber tube according to Claim 4, characterized in that the thickness of the outer layer (5) is less than the thickness of the barrier layer (4).
6. Absorber tube according to Claim 4 or 5, characterized in that the thickness of the outer layer (5) is≤ 0.1 pm.
7. Process for producing a central tube (3) of an absorber tube (1) for solar thermal applications, comprising the following steps: 10 179261/2 a central tube (3) is prefabricated from chromium-containing steel, in particular from special steel, the central tube (3) is treated with a free-hydrogen-comprising water vapour at temperatures of 500°C to 700°C, in order to produce a chromium-oxide-containing barrier layer (4) that is largely impervious to hydrogen at least on the inner side of the central tube (3).
8. Process according to Claim 7, wherein the ratio VA = H2/H20 in the steam for the treatment of the outer side of the central tube (3) is chosen to be greater than the ratio V| = H2/H2O of the steam for the treatment of the inner side of the central tube (3).
9. Process according to Claim 8, wherein the ratio VA is between 10 and 1000 and the ratio Vi is between 1 and 100, where VA≥ 10 · V|.
10. Process according to Claim 7, wherein the central tube is machined on the outer side prior to the steam treatment, such that the roughness RA < 0.3.
11. Process according to Claim 7 or 10, wherein the central tube is machined on the outer side prior to the steam treatment, such that the roughness < 0.25.
12. Process according to Claim 10 or 11 , characterized in that the central tube is polished on the outer side. For the Applicants, REINHOLD COHN AND PARTNERS By: 11
IL179261A 2005-11-25 2006-11-14 Tubular radiation absorbing device for a solar power plant with reduced heat losses IL179261A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102005057277A DE102005057277B4 (en) 2005-11-25 2005-11-25 absorber tube

Publications (2)

Publication Number Publication Date
IL179261A0 IL179261A0 (en) 2007-03-08
IL179261A true IL179261A (en) 2011-09-27

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Family Applications (1)

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IL179261A IL179261A (en) 2005-11-25 2006-11-14 Tubular radiation absorbing device for a solar power plant with reduced heat losses

Country Status (7)

Country Link
US (1) US20070235023A1 (en)
CN (1) CN1971168A (en)
DE (1) DE102005057277B4 (en)
ES (1) ES2328313B1 (en)
IL (1) IL179261A (en)
IT (1) ITTO20060837A1 (en)
MX (1) MXPA06013659A (en)

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DE102008010199A1 (en) * 2008-02-20 2009-08-27 Schott Ag Radiation-selective absorber coating, absorber tube and method for its production
US8683994B2 (en) * 2008-02-20 2014-04-01 Corning Incorporated Solar heat collection element with glass-ceramic central tube
KR101244027B1 (en) * 2008-07-08 2013-03-14 시너스 테크놀리지, 인코포레이티드 Flexible solar cell and fabricating method for the same
DE102009022059A1 (en) 2009-05-20 2010-11-25 Schott Solar Ag Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating
DE102009049471B3 (en) 2009-10-15 2011-04-07 Schott Solar Ag Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating
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CN102721209A (en) * 2012-06-29 2012-10-10 苏州嘉言能源设备有限公司 Non-vacuum groove type barrier coating for solar power generation
JP2015072076A (en) * 2013-10-02 2015-04-16 株式会社豊田自動織機 Solar heat collection pipe and manufacturing method thereof
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Also Published As

Publication number Publication date
IL179261A0 (en) 2007-03-08
ES2328313B1 (en) 2010-07-15
MXPA06013659A (en) 2008-10-09
DE102005057277B4 (en) 2010-08-12
ITTO20060837A1 (en) 2007-05-26
DE102005057277A1 (en) 2007-06-06
CN1971168A (en) 2007-05-30
US20070235023A1 (en) 2007-10-11
ES2328313A1 (en) 2009-11-11

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