CN1971168A - Absorption tube - Google Patents

Absorption tube Download PDF

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Publication number
CN1971168A
CN1971168A CNA2006101637402A CN200610163740A CN1971168A CN 1971168 A CN1971168 A CN 1971168A CN A2006101637402 A CNA2006101637402 A CN A2006101637402A CN 200610163740 A CN200610163740 A CN 200610163740A CN 1971168 A CN1971168 A CN 1971168A
Authority
CN
China
Prior art keywords
mesotube
trapping layer
absorption tube
hydrogen
chromium oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2006101637402A
Other languages
Chinese (zh)
Inventor
T·库克尔科恩
N·本茨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
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 CN1971168A publication Critical patent/CN1971168A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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

Abstract

An absorption tube, the invention relates to an absorption tube (1) for using solar energy, which includes a center tube (3) made of chromium steel and a sleeve (2) surrounding the center tube (3), which is made of glass, forming a annular space (6) between the center tube (3) and the sleeve (2). The center tube (3) at least has a blocking layer (4) without penetrating with regard to hydrogen to a great extent in the inner surface, which includes chromium oxide. The invention also relates to a method of manufacturing for a center tube (3), in which, the center tube (3) is processed by vapour including dissociative hydrogen with temperature of 500 DEG C to 700 DEG C, thereby forming the blocking layer (4) without penetrating with regard to hydrogen to a great extent.

Description

Absorption tube
Technical field
The present invention relates to a kind of absorption tube that is used for solar use.In addition, the present invention relates to a kind of method of making the mesotube of this type of absorption tube.
Background technology
The absorption tube that is used for the paraboloid trough type solar receiving system is used to utilize solar radiant energy.Solar radiant energy by focusing mirror to absorption tube and be converted into heat.Heat is shed by heat-carrying agent and directly is used as process heat or is converted into electric energy.
This absorption tube comprises a mesotube and a glass bushing with coating.Annular space between two pipes is pumped into vacuum.When work, pump into heat transport fluid by mesotube, especially oil.
A kind of such absorption tube is for example open in DE 102 31 467 B4.A glass metal transition element is set respectively on the free terminal of sleeve pipe.Mesotube and this glass metal transition element vertically can be connected to each other by at least one expansion compensation device with relatively moving.
Because heat transport fluid is aging, can produce free hydrogen, these hydrogen are dissolved in the heat transport fluid.Hydrogen passes mesotube by osmosis and arrives vacuum annular space between mesotube and the sleeve pipe.Permeability increases along with the rising of operating temperature, and operating temperature is between 300 ℃ to 400 ℃.Thus, the pressure in the annular space also raises.This pressure raises and causes the heat loss increase and make that the efficient of absorption tube is lower.
In order to keep the vacuum in the annular space, must take appropriate measures.A kind of measure of eliminating the hydrogen in the annular space is by suitable material hydrogenation to be closed.
For keeping vacuum, use gettering material at this in annular space, this degasification material can be with the hydrogen chemical combination that is penetrated into annular space by mesotube.If the capacity of degasifier exhausts, the pressure in the annular space continues to raise so, and the partial pressure of the free hydrogen that dissolves in annular space coexists heat-carrying agent reaches till the balance.The equalizing pressure of hydrogen in annular space is 0.3mbar to 3mbar in disclosed absorption tube.Existence heat conduction owing to hydrogen in annular space increases.Because this comparing with air is about 5 times higher heat conduction, heat loss is significantly higher than the absorption tube of non-vacuumizing.
WO 2004/063640 A1 discloses a kind of degasifier arrangement, and wherein the degasifier plate is set in the annular space between mesotube and the sleeve pipe.The shortcoming of this layout is that the degasifier plate is in the zone of direct raying.Especially by the mishit mesotube of mirror reflects or just skim over and radiation meeting that major part is reflected causes bake out agent plate.Because the degasifier plate almost is heat insulation with mesotube and sleeve pipe in a vacuum, so the temperature of plate and degasifier can the fluctuation tempestuously owing to radiation.And because the degasifier material has the equalizing pressure (balance between gas desorption and the absorption) that depends on temperature when the loading degree of regulation, the fluctuation of degasifier temperature can cause undesirable pressure oscillation.Behind degasifier material consumption light, the temperature of sleeve pipe rises strongly and makes absorption tube to use.
By Ostwald and Grabke at magazine Corrosion Science 46 (2004), as can be known, chromium steel has chromium oxide layer to the article of delivering on the 1113-1127 " Initial Oxidation and chromium diffusion.I.Effects of surface working on 9-20%-Cr steels ".For this steel of protection in corrosive environment, by H 2-H 2O-atmosphere is made coating, and this coating comprises inner Cr 2O 3Layer and outside (Mn, Fe) Cr 2O 4Spinel layer.
Summary of the invention
Task of the present invention provides a kind of absorption tube, and this absorption tube has still less heat loss than traditional absorption tube.
This task solves by a kind of like this absorption tube, and wherein mesotube has the trapping layer that hydrogen can't see through to a great extent in the surface at least within it, and this trapping layer contains chromium oxide.
Be confirmed astoundingly, the layer that contains chromium oxide can stop the infiltration of hydrogen largely.
Pass the hydrogen infiltration that trapping layer enters annular space by mesotube inside and can dwindle 50 times.
The layer that contains chromium oxide is by handling acquisition to the mesotube of being made by steel, particularly high-quality steel, and wherein the superficial layer of mesotube changes the layer that contains chromium oxide into.
The thickness of trapping layer is preferably 0.5 μ m to 10 μ m.If layer is thin excessively, the interception of trapping layer significantly descends so.If trapping layer is blocked up, crackle forms and can increase under temperature variations so, and this equally also can cause interception to descend.
The mass percent of the chromium oxide of trapping layer is preferably 20% to 60%, especially 30% to 50%.Method and time decision that the content of chromium oxide is handled by the content of chromium in the steel and mesotube, the processing method of mesotube described here and time are as described in the claim to a method.Be confirmed at this, produced greater than 20% o'clock for the interception of hydrogen mass percent at chromium oxide.
This mesotube also preferably has the skin that one deck contains chromium oxide at its outer surface.
At this, described outer field thickness is preferably less than the thickness of trapping layer.This layer exactly is used as the adhesion layer of the selection thin layer that carries out subsequently.Outer field thickness is preferred＜0.1 μ m.Show, thicker at outer field thickness, during promptly greater than 0.1 μ m, on the surface of chromium oxide layer, can form spinel layer, this spinel layer has coarse surface and itself is permeable.This spinel layer is not suitable for carrying the thin layer of the selection of respective smoothed.And for the trapping layer of inside, spinel layer then can not produce obstruction, thereby can use bigger thickness.
In by chromium steel, particularly method by chrome-nickel steel manufacturing mesotube, at first by steel, particularly by the prefabricated mesotube of high-quality steel, and subsequently mesotube is carried out steam oxidation, wherein use contain free hydrogen, temperature handles mesotube on the inner surface in mesotube at least at 500 ℃ to 700 ℃ steam, to form the trapping layer that can't see through to a great extent for hydrogen, this trapping layer contains chromium oxide.
Wherein, be the ratio V in the selected steam of outer surface of handling mesotube A=H 2/ H 2O preferably is higher than the ratio V in the selected steam of inner surface that be to handle mesotube I=H 2/ H 2O.Avoid forming on the outer surface spinel layer by this measure.
Described ratio V APreferably between 10 to 1000, and ratio V IPreferably between 1 to 100, wherein observe formula V A〉=10V I
According to another kind of embodiment, the layer thickness that forms on the outer surface can reduce like this, and promptly the outer surface to mesotube is processed before carrying out steam treatment, thereby makes roughness R a＜0.3.Preferably make roughness R a＜0.25.
Can be chosen in as processing mode on the outer surface of mesotube and polish.
In second kind of embodiment, no longer require different ratio V AAnd V I, but can with reference to property take in.
The specific embodiment
By accompanying drawing a kind of exemplary embodiment is described below.
The part of an absorption tube 1 shown in the drawings, it has a sleeve pipe 2 and the mesotube 3 made by glass.Between mesotube 3 and sleeve pipe 2, form annular space 6.
A kind of heat-carrying agent that contains free hydrogen of circulation in the mesotube 3, this free hydrogen can permeate by metal tube 3 and enter annular space 6.In order to stop the infiltration of free hydrogen, mesotube 3 surface within it is provided with and contains Cr 2O 3Trapping layer 4, wherein this mesotube 3 for example can be made by steel X2 chromium nickel molybdenum 17-12-2/ material number 1.4404.
Internal layer 4 for example has that thickness is 10 μ m, and is divided into the ground floor that is located immediately on the metal tube, Cr in this ground floor 2O 3Content is 30%, NiO content is 15% to 18% and Fe 2O 3Content is 50% to 54%.Also have the another one layer on this ground floor, this layer is mainly by Fe 2O 3Constitute, that is to say Fe 2O 3Content reaches 98%.Chromium oxide only accounts for about 1% to 2%.This second layer forms spinel layer and contains a spot of nickel oxide.
Also having thickness on the outer surface of mesotube 3 is the skin 5 of 0.05 μ m.Outer 5 do not have spinel layer.
The manufacturing of oxide layer 4,5 is carried out by means of the steam oxidation method according to following parameter:
H 2/ H 2O ratio=1 is for two layers 4,5;
The outer surface of mesotube: polishing, Ra＜0.2 μ m;
Temperature T=500 ℃;
Processing time: 5 hours.
Reference numerals list
1 absorption tube
2 sleeve pipes
3 mesotube
4 trapping layers
5 skins
6 annular spaces

Claims (12)

1. be used for solar use, in particular for the absorption tube of the paraboloid trough type solar receiving system of solar power plant, it comprises by chromium steel, the mesotube of especially being made by the high-quality steel (3) with around sleeve pipe (2) this mesotube (3), that made by glass, and between mesotube (3) and sleeve pipe (2), form annular space (6), it is characterized in that, described mesotube (3) surface at least within it has the trapping layer (4) that can't see through to a great extent for hydrogen, and this trapping layer (4) contains chromium oxide.
2. according to the described absorption tube of claim 1, it is characterized in that the thickness of described trapping layer (4) is 0.5 μ m to 10 μ m.
3. according to claim 1 or 2 described absorption tubes, it is characterized in that the mass percent of the chromium oxide of described trapping layer (4) is 20% to 60%.
4. according to each described absorption tube in the claim 1 to 3, it is characterized in that described mesotube (3) has the skin (5) that closes chromium oxide at its outer surface.
5. according to the described absorption tube of claim 4, it is characterized in that the thickness of described skin (5) is less than the thickness of described trapping layer (4).
6. according to claim 4 or 5 described absorption tubes, it is characterized in that the thickness of described skin (5)≤0.1 μ m.
7. make the method for the mesotube (3) of the absorption tube (1) that is used for solar use, it comprises the following steps:
-by chromium steel, especially by the prefabricated mesotube of high-quality steel (3),
-use contain free hydrogen, temperature handles mesotube (3) at least at 500 ℃ to 700 ℃ steam on the inner surface of mesotube (3), to form the trapping layer (4) that can't see through to a great extent for hydrogen, this trapping layer (4) contains chromium oxide.
8. in accordance with the method for claim 7, wherein be the ratio V in the selected steam of outer surface of handling mesotube (3) A=H 2/ H 2O will be higher than the ratio V in the selected steam of inner surface that be to handle mesotube (3) I=H 2/ H 2O.
9. wherein said ratio V in accordance with the method for claim 8, ABetween 10 to 1000, and described ratio V IBetween 1 to 100, wherein observe formula V A〉=10V I
10. in accordance with the method for claim 7, wherein said mesotube was processed outer surface before steam treatment, made its roughness R A＜0.3.
11. according to claim 7 or 10 described methods, wherein said mesotube was processed outer surface before steam treatment, made its roughness＜0.25.
12. according to claim 10 or 11 described methods, described mesotube is polished at its outer surface.
CNA2006101637402A 2005-11-25 2006-11-24 Absorption tube Pending CN1971168A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005057277A DE102005057277B4 (en) 2005-11-25 2005-11-25 absorber tube
DE102005057277.4 2005-11-25

Publications (1)

Publication Number Publication Date
CN1971168A true CN1971168A (en) 2007-05-30

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ID=38047552

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006101637402A Pending CN1971168A (en) 2005-11-25 2006-11-24 Absorption tube

Country Status (7)

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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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Also Published As

Publication number Publication date
MXPA06013659A (en) 2008-10-09
DE102005057277A1 (en) 2007-06-06
ES2328313A1 (en) 2009-11-11
IL179261A0 (en) 2007-03-08
ES2328313B1 (en) 2010-07-15
DE102005057277B4 (en) 2010-08-12
US20070235023A1 (en) 2007-10-11
ITTO20060837A1 (en) 2007-05-26
IL179261A (en) 2011-09-27

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