EP0393115A1 - Heat pipe employing hydrogen oxidation means - Google Patents

Heat pipe employing hydrogen oxidation means

Info

Publication number
EP0393115A1
EP0393115A1 EP89900416A EP89900416A EP0393115A1 EP 0393115 A1 EP0393115 A1 EP 0393115A1 EP 89900416 A EP89900416 A EP 89900416A EP 89900416 A EP89900416 A EP 89900416A EP 0393115 A1 EP0393115 A1 EP 0393115A1
Authority
EP
European Patent Office
Prior art keywords
heat pipe
recited
hydrogen
copper
oxidizer means
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.)
Withdrawn
Application number
EP89900416A
Other languages
German (de)
English (en)
French (fr)
Inventor
En-Jian Guangzhou Inst.Energy Conversion Chen
Zao-Rong Guangzhou Inst.Energy Conversion Lin
Li-Ying Guangzhou Inst. Energy Conversion Chen
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.)
Alstom Power Inc
Original Assignee
ABB Air Preheater Inc
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 ABB Air Preheater Inc filed Critical ABB Air Preheater Inc
Publication of EP0393115A1 publication Critical patent/EP0393115A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28DHEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F28D15/02Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28DHEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F28D15/02Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes
    • F28D15/0258Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes with means to remove contaminants, e.g. getters
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B5/00Water
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates generally to heat pipes, in particular to heat pipes using water or other hydrogen containing liquid as the working fluid and formed of a material which reacts with the working fluid to produce non-condensible hydrogen gas. More specifically, the present invention relates to improving the performance characteristics of such heat pipes by providing within the condenser portion of the heat pipe means for oxidizing any hydrogen gas formed during operation of the heat pipe.
  • Steel-water heat pipes that in heat pipes having a steel enclosure and employing water as a working fluid, have been widely used in heat exchange applications throughout industry.
  • Such heat pipes include, for example, closed thermosiphons, heat pipes having porous wicks, and rotating heat pipes.
  • Steel heat pipes are those wherein the heat pipe enclosure defining the working cavity of the heat pipe is made of an iron alloy, such as carbon steel or stainless steel, or iron or any iron alloy containing a metal lying above hydrogen gas in the electromotive series, such as nickel, chrominum, manganese, and others. It is well known that when such steel heat pipes are placed in operation, a series of chemical reactions will typically occur between the water working fluid and the steel wall of the heat pipe cavity at the temperatures at which the heat pipes are generally utilized.
  • the hydrogen gas may even accumulate in the wick in the condenser portion of the working cavity to the extent that an annular layer of hydrogen gas is formed about the wall of the condenser portion of the working cavity thereby effectively preventing condensation of the vapor phase of the working fluid.
  • One method is to improve the chemical compatibility of the heat pipe enclosure with the working fluid.
  • water As the working fluid, it is known to provide a protective layer on the inner surface of the steel heat pipe enclosure to effectively line the heat pipe cavity to prevent contact between the water and the steel enclosure.
  • the protective layer must be made of a material which will not react with the water.
  • copper is selected as the protective lining since it is known not to react with water at the working temperature typically encountered in industrial uses.
  • One such heat pipe known as a duplex-tube heat pipe, is formed of an inner copper tube force fit within an outer stainless steel pipe.
  • duplex-tube heat pipes have been commonly employed in industrial heat exchangers such as gas-to-air heat exchangers used to preheat combustion on fossil-fuel steam generators.
  • Such duplex-tube heat pipes are difficult and expensive to manufacture.
  • complete integrity of the copper lining can not be ensured over long periods of operation and eventual contact between steel and water can not be completely precluded. Therefore, even in such copper-lined heat pipes, hydrogen gas is likely to be formed and accumulate slowly over time when water is used as the working fluid, thereby limiting the effective service life of the heat pipe.
  • hydrogen gas may also be released either directly from breakdown of the hydrocarbon fluid or reaction of the breakdown products with the steel enclosure. Additionally, water may also be present in small amounts as a contaminant in hydrocarbon based working fluids.
  • An alternative approach to addressing the accumulation of hydrogen gas in steel-water heat pipes is to provide a means of alleviating the accumulation of the hydrogen gas within the heat pipe cavity, rather than attempting to prevent its formation.
  • One such approach is to release the accumulated hydrogen gas from the heat pipe cavity by some form of vent means.
  • a valve assembled on the end of condensation section of the heat pipe can be used to release accumulated hydrogen gas periodically when heat pipe is in operation. But this way has obviously disadvantages, e.g., the operation of the valves is troublesome and inconvenient, secondly, unavoidable leakage of the valves may shorten the service life of the heat pipe.
  • 3,503,438 is a palladium vent tube sealed to the wall of heat pipe and having a closed inner end and an open outer end to allow the hydrogen gas to continually permeate through the palladium out of the heat pipe.
  • palladium is a rare and precious metal, and for both reasons of cost and availability can not be widely used in industrial applications.
  • Hydrogen getters proposed for use in heat pipes include tantalum, titanium, and niobium as disclosed in U.S. Patent No. 4,043,387; lanthanum, yttrium or scandium, combined with barium, calcium or lithium as disclosed in U.S. Patent No. 4,159,737; or a zirconium intermetallic alloy, such as ZrMn 2 alloy, as disclosed in U.S. Patent No. 4,586,561.
  • such hydrogen getters typically are capable of adsorbing less hydrogen gas as temperature increases.
  • such hydrogen getters are effective in heat pipes only under conditions of relatively low working temperature such as experienced when used for permafrost stabilization as discussed in the aforementioned U.S. Patent No. 4,586,561, but would be much less effective in heat pipes used in industrial applications such as gas-to-gas heat exchange, wherein the condenser portion of the heat pipe would commonly be exposed to gas temperatures of at least 500 ⁇ F.
  • the heat pipe of the present invention includes an enclosure defining a closed working cavity and water disposed within the working cavity as the working fluid, the enclosure being formed of a material which reacts with water to generate hydrogen gas.
  • Oxidizer means is disposed within the working cavity in the condenser portion of the heat pipe, the oxidizer means comprising a substance which will react with the hydrogen gas generated during operation of the heat pipe to oxidize said hydrogen gas into water.
  • the requirements for such a substance are that, it can not be decomposed under the working temperature of the heat pipe, can not be dissolved in the water, and can not react with water or steam, but it should react with hydrogen to form the water and another product whose physicoche ical properties are stable and its saturated steam pressure almost equal to zero under.the working temperature of the heat pipe.
  • Such oxidizer substances comprise those metal oxides having an electrode potential (or reduction potential) which is higher than that of hydrogen, i.e., the electrode potential (or reduction potential) of such a suitable metal oxide should be a positive potential relative to the zero electrode potential of hydrogen.
  • Such metal oxides are able to cause a redox reaction with hydrogen and are suitable for use as the oxidizer means in the heat pipe of the present invention.
  • suitable metal oxides include, inter alia, CuO, Pb0 2 , Mn0 2 , and HgO. Mixtures of such metal oxides and compounds containing such metal oxides or chemicals which can produce such metal oxides by heating also may be used as the oxidizer means in the heat pipe of the present invention. From view point of effect and cost, the preferred oxidizer is CuO or mixture containing CuO, most preferably, a sintered mixture containing Cu and CuO with a small amount r 2 0 3 .
  • the oxidizer means of the present invention may be disposed in the heat pipe in block, granular, thread, powder or specially shaped form easily put in place.
  • the oxidizer means has a porous structure for increasing the available contact area with hydrogen.
  • the oxidizer means may be disposed in a gas permeable container with good structural strength, e.g., a pocket made of iron or copper wire meshes with fine mesh, or made in form of special shape block designed to be inserted in the end of condenser portion of the heat pipe.
  • Figure 1 the sole figure of drawing, is a sectional side elevation view of the heat pipe of the present invention with the hydrogen gas oxidizer means disposed in the working cavity at the condenser end of the heat pipe.
  • the heat pipe 10 comprises a tubular enclosure 20 which defines a closed working cavity 50 wherein a working fluid 70 is enclosed. End caps 80 and 90 are inserted in the ends of the tubular enclosure 20 in sealing relationship to seal the open ends of the tubular enclosure 20 and close the working cavity 50 to prevent either the liquid or vapor phase of the working fluid 70 from escaping out of the working cavity.
  • the outer surface of the heat pipe 10 is provided with fins 40, shown as spiral wound outwardly extending surface, which serves to increase the gas to metal contact surface of the heat pipe thereby increasing the heat transfer effectiveness between the heating gas and the gas to be heated and the heat pipe 10.
  • the inner surface of the enclosure 20 is provided with a wick in the conventional, well known manner to enhance heat transfer through the enclosure 20 to the working fluid 70 within the working cavity 50.
  • the heat pipe 10 is mounted in the division wall 60 of the heat exchanger which separates the heat exchanger into a first flowpath for the heating gas 5 on one side of the division wall and a second flowpath for the gas 7 to be heated on the opposite of the division wall.
  • a portion of the working fluid 70 is evaporated as it absorbs heat transferred from the heating gas 5 through the wall of the evaporator portion 15 of the enclosure 40.
  • the vapor phase of the working fluid 70 passes into the condenser portion 25 of the heat pipe 10.
  • the vapor phase of the working fluid 70 is condensed as it releases heat through the wall of the condenser portion 25 of the enclosure 40 to the cooler temperature gas 7.
  • the condensed liquid phase of the working fluid then flows back into the evaporator portion 15 of the heat pipe 10 and the cycle is repeated.
  • the working fluid 70 is a hydrogen containing fluid and the enclosure 40 of the heat pipe is made of a material which reacts with the working fluid, the reaction of the enclosure with the working fluid results in the formation of non-condensible hydrogen gas in the working cavity 50.
  • Generation of hydrogen gas within the working cavity 50 is particularly prevalent when water is the working fluid 70 and the enclosure 40 is made of a ferrous metal or alloy such as carbon steel, stainless steel or iron-nickel alloys.
  • hydrogen oxidizer means 30 is disposed within the working cavity 50 in the condenser portion 25 of the heat pipe 10.
  • the oxidizer means 30 is in the form of a plug-like block which is inserted through and its base threaded into a central hole in the upper end cap 90 so that oxidizer means 30 extends into and is disposed within the working cavity 40 in the condenser portion 25 of the heat pipe 10.
  • a protective cap 100 is then threaded over the base of the oxidizer means 30 to protect the base end of the oxidizer means 30 from the gas flowing over the heat pipe 10 when it is pl ced in service.
  • the oxidizer means 30 of the present invention comprises a substance which is insoluble in the working fluid and which is capable of reacting with hydrogen gas to give up elemental oxygen to oxidize the hydrogen to water.
  • Particularly suitable as substances for forming the oxidizer means 30 of the present invention are metal oxides which have an electrode potential (or reduction potential) higher than that of hydrogen, that is a positive electrode potential with respect to hydrogen. Examples of suitable metal oxides include CuO, Pb0 2 , Mn0 2 and HgO, among other.
  • the oxidizer means 30 may also comprise a mixture or compound containing such a metal oxide or a material which when heated to the working temperature of the heat pipe will produce such a metal oxide.
  • cupric oxide i.e., CuO
  • Cupric oxide and mixtures containing cupric oxide has been found to be most effective as a hydrogen oxidizer at working temperatures around 160 ⁇ C (320 ⁇ F).
  • the effectiveness of the cupric oxide as a hydrogen oxidizer may be increased and the elimination of the hydrogen gas sped up by heating the portion of the working cavity wherein the oxidizer means 30 is disposed so as to raise the temperature of the oxidizer means 30.
  • an effective low temperature hydrogen oxidizer comprises a mixture of about one part by weight copper and four parts by weight cupric oxide, which mixture is pressed into a porous shape, generally a plug shaped block although any desired shape may be used, and then sintered in air at a temperature of about 800°C for a period of about one to two hours.
  • An alternative low temperature hydrogen oxidizer suitable for use as the oxidizer means of the present invention comprises a mass of sintered copper wire.
  • a plurality of copper wires are sintered in air at a temperature of about 820°C for a period of about 2 to 4 hours to produce a layer of cupric oxide on the copper wire.
  • the oxidizer means 30 may be used as the sole mechanism for combating hydrogen accumulation in steel-water heat pipes or it may be used in conjunction with other methods of improving the chemical enclosure such as the coating of the inner surface of the working cavity 40 with a passivation layer or the inclusion of a corrosion retarding chemical dissolved in the working fluid, both of which provisions would reduce with rate of hydrogen gas generation by retarding the reaction of the water 70 with the steel enclosure 40.
  • the heat pipe of the present invention includes oxidizer means 30 for oxidizing the hydrogen gas generated in the heat pipe working cavity to water which unlike prior art devices, serves to produce water.
  • steel-water heat pipes incorporating the oxidizer means 30 may be referred to as "recovery type" heat pipes in that the working fluid, i.e., water, destroyed by reaction with the steel enclosure is regenerated by the oxidizer means 30.
  • the hydrogen gas accumulating in the working cavity oft the heat pipe is vented to the exterior of the heat pipe rather than recovered as working fluid.
  • the hydrogen gas accumulating in the working cavity oft the heat pipe is vented to the exterior of the heat pipe rather than recovered as working fluid.
  • the hydrogen gas accumulating in the working cavity oft the heat pipe is vented to the exterior of the heat pipe rather than recovered as working fluid.
  • the hydrogen gas accumulating in the working cavity oft the heat pipe is vented to the exterior of the heat pipe rather than recovered as working fluid.
  • C747810 is collected or adsorbed on the getter rather than recovered as working fluid.
  • the heat pipe of the prevent invention is simple and cost effective to manufacture, only differing from prior art steel-water pipes customarily used in the industry in the inclusion of a small amount of oxidizer substance within the working cavity.
  • the presence of the oxidizer extends the effective service life of the steel-water heat pipe by several times, and as the heat pipe of the present invention will retain excellent heat transfer performance until eventual failure of its enclosure by wearing and corroding, the advantage is obvious.
  • Heat pipe heat exchangers incorporating the heat pipes of the present invention have particular application in the field of industrial waste heat recovery for gas-to-gas heat exchange, such as combustion air preheating or flue gas reheating.
  • the heat pipe of the present invention has been described with reference to the particular embodiment thereof shown in the drawing, it should be realized that various changes and modifications may be made therein without departing from the spirit and scope of the invention.
  • the oxidizer means 30 need not be in the form of a plug inserted in the very end of the working cavity at the condenser end of the heat pipe. Rather, the oxidizer means 30 may be in any form or desired shape and placed at any location within the working cavity 50 within the condenser portion 25 of the heat pipe 10.
  • the oxidizer means 30 may comprise metal oxide in a particulate, powder or thread form disposed at more than one location within the working cavity 50 in the condenser portion 25 of the heat pipe 10 or housed within a gas permeable container means, such as a stainless steel or copper wire mesh vessel, preferably disposed in the working cavity 50 of the heat pipe 10 at the end of the condenser portion 25 thereof adjacent the end cap 90.
  • a gas permeable container means such as a stainless steel or copper wire mesh vessel, preferably disposed in the working cavity 50 of the heat pipe 10 at the end of the condenser portion 25 thereof adjacent the end cap 90.
  • the heat pipe 10 of the present invention need not be disposed in the vertical orientation shown in the drawing, but rather may be disposed at an acute angle to the horizontal so long as the end of the condenser portion 25 lies upwardly of the evaporator portion 15 of the heat pipe.

Landscapes

  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Sorption Type Refrigeration Machines (AREA)
EP89900416A 1988-10-19 1988-10-19 Heat pipe employing hydrogen oxidation means Withdrawn EP0393115A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1988/003636 WO1990004748A1 (en) 1988-10-19 1988-10-19 Heat pipe employing hydrogen oxidation means

Publications (1)

Publication Number Publication Date
EP0393115A1 true EP0393115A1 (en) 1990-10-24

Family

ID=22208953

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89900416A Withdrawn EP0393115A1 (en) 1988-10-19 1988-10-19 Heat pipe employing hydrogen oxidation means

Country Status (4)

Country Link
EP (1) EP0393115A1 (ko)
JP (1) JPH03501998A (ko)
KR (1) KR900702315A (ko)
WO (1) WO1990004748A1 (ko)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991007209A1 (de) * 1989-11-15 1991-05-30 Klaus Rennebeck Verfahren zum reinigen, entgasen, keimfreimachen und/oder dekontaminieren sowie für dieses verfahren geeigneter gasbrenner und verfahren zu dessen herstellung
JP2006162243A (ja) * 2004-11-10 2006-06-22 Osaka Gas Co Ltd 水素ガス除去装置
JP5231143B2 (ja) * 2008-09-04 2013-07-10 株式会社フジクラ アルミニウム製ヒートパイプ
GB201100504D0 (en) * 2011-01-12 2011-02-23 Mallinckrodt Inc Process
US10816276B2 (en) 2016-02-29 2020-10-27 Furukawa Electric Co., Ltd. Heat pipe
RU2715924C1 (ru) * 2016-05-02 2020-03-04 Тата Стил Лимитед Способ и устройство для плавки

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242738B2 (en) * 1986-04-23 1995-01-11 Showa Aluminum Corporation Heat pipe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9004748A1 *

Also Published As

Publication number Publication date
KR900702315A (ko) 1990-12-06
JPH03501998A (ja) 1991-05-09
WO1990004748A1 (en) 1990-05-03
JPH0579915B2 (ko) 1993-11-05

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