US20130180475A1 - Waste heat boiler - Google Patents

Waste heat boiler Download PDF

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Publication number
US20130180475A1
US20130180475A1 US13/822,144 US201013822144A US2013180475A1 US 20130180475 A1 US20130180475 A1 US 20130180475A1 US 201013822144 A US201013822144 A US 201013822144A US 2013180475 A1 US2013180475 A1 US 2013180475A1
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US
United States
Prior art keywords
process gas
heat exchange
tube
outlet
waste heat
Prior art date
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Abandoned
Application number
US13/822,144
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English (en)
Inventor
Hans Georg Christiansen
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Topsoe AS
Original Assignee
Individual
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Filing date
Publication date
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Assigned to HALDOR TOPSOE A/S reassignment HALDOR TOPSOE A/S ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHRISTIANSEN, HANS GEORG
Publication of US20130180475A1 publication Critical patent/US20130180475A1/en
Abandoned legal-status Critical Current

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B35/00Control systems for steam boilers
    • F22B35/007Control systems for waste heat boilers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00Methods of steam generation characterised by form of heating method
    • F22B1/02Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00Methods of steam generation characterised by form of heating method
    • F22B1/02Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • F22B1/1838Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines the hot gas being under a high pressure, e.g. in chemical installations
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B35/00Control systems for steam boilers
    • F22B35/001Controlling by flue gas dampers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B9/00Steam boilers of fire-tube type, i.e. the flue gas from a combustion chamber outside the boiler body flowing through tubes built-in in the boiler body
    • F22B9/10Steam boilers of fire-tube type, i.e. the flue gas from a combustion chamber outside the boiler body flowing through tubes built-in in the boiler body the boiler body being disposed substantially horizontally, e.g. at the side of the combustion chamber
    • F22B9/12Steam boilers of fire-tube type, i.e. the flue gas from a combustion chamber outside the boiler body flowing through tubes built-in in the boiler body the boiler body being disposed substantially horizontally, e.g. at the side of the combustion chamber the fire tubes being in substantially horizontal arrangement
    • 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
    • F28D21/00Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D21/0001Recuperative heat exchangers
    • F28D21/0003Recuperative heat exchangers the heat being recuperated from exhaust gases
    • F28D21/001Recuperative heat exchangers the heat being recuperated from exhaust gases for thermal power plants or industrial processes
    • 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
    • F28D7/00Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/10Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
    • F28D7/103Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically consisting of more than two coaxial conduits or modules of more than two coaxial conduits
    • 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
    • F28D7/00Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/16Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
    • F28D7/163Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation with conduit assemblies having a particular shape, e.g. square or annular; with assemblies of conduits having different geometrical features; with multiple groups of conduits connected in series or parallel and arranged inside common casing
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F27/00Control arrangements or safety devices specially adapted for heat-exchange or heat-transfer apparatus
    • F28F27/02Control arrangements or safety devices specially adapted for heat-exchange or heat-transfer apparatus for controlling the distribution of heat-exchange media between different channels
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2250/00Arrangements for modifying the flow of the heat exchange media, e.g. flow guiding means; Particular flow patterns
    • F28F2250/06Derivation channels, e.g. bypass
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2265/00Safety or protection arrangements; Arrangements for preventing malfunction

Definitions

  • the present invention is directed to the recovery of waste heat from chemical reactions. More particularly, the invention relates to a waste heat boiler with improved control of cooling effect.
  • Waste heat boilers are most generally used for the generation of steam by waste heat recovered from hot process streams.
  • those boilers are designed as shell-and-tube exchangers with a plurality of heat exchanging tubes arranged within a cylindrical shell.
  • the characteristic components of the boiler are the tubes mounted in tubesheets at a front-end head and a rear-end head within the shell.
  • steam production is accomplished on the shell side of the tubes by indirect heat exchange of a hot process stream flowing through the boiler tubes.
  • the shell side is through a number of risers and down-comers connected to a steam drum, which may be arranged above or as an integral part of the boiler shell.
  • Boilers handling fouling and/or corrosive process streams must be designed to a higher duty than required when clean in order to allow for satisfying lifetime under serious fouling and/or corroding conditions.
  • the heat transferring surface of the boiler tubes has further to be adapted to expected corrosion and fouling factors in the stream. To provide for a desired and substantially constant cooling effect during long term operation of the boilers, appropriate heat transfer and temperature control is required.
  • a major drawback of the known boilers of the above type is vigorous corrosion on the metallic surface of the by-pass, particularly the by-pass outlet and flow control valve, which are in contact with the un-cooled process stream at temperatures as high as 1000° C. or even higher.
  • Known art has sought to solve this problem in various manners such as cooling the control valve with a cooling fluid or to avoid a hot by-pass stream and in stead divide the heat exchanger in different sections with different heat-exchange level and therefore different process gas outlet temperatures. Examples of known art are disclosed in U.S. Pat. No. 5,452,686A, US2007125317A, U.S. Pat. No. 4,993,367A, GB1303092A, U.S. Pat. No. 1,918,966A and EP0357907A.
  • An object of this invention is to avoid the drawbacks of the known waste heat boilers by providing a boiler of the shell-and-tube heat exchanger type with an improved heat transfer and temperature control.
  • a further object of this invention is to provide a waste heat boiler with a simpler and less expensive design than known art waste heat boilers.
  • a further object of this invention is to provide a waste heat boiler with a process gas by-pass tube and a control valve for simple control of the by-pass process gas stream and accordingly the process gas outlet temperature, without exposing the control valve to excessive temperatures leading to corrosion.
  • a waste heat boiler for heat exchanging a relatively hot process gas with a cooling media
  • the waste heat boiler comprises at least one shell part (a heat exchange section second shell part), and at least two tube sheets placed in an inlet end and an outlet end of the heat exchange section second shell part, whereby this second shell part and the two tube sheets enclose the heat exchange section of the waste heat boiler.
  • a plurality of heat exchange tubes and at least one process gas by-bass tube are placed in the heat exchange section and are fixed in the first tube sheet near the first end of each tube and fixed in the second tube sheet near the second end of each tube.
  • At least one cooling media inlet and at least one cooling media outlet are located on the waste heat boiler to enable a cooling media to flow into and out of the heat exchange section on the shell side of the tubes.
  • the cooling media is thus enclosed by the second shell part and the first and the second tube sheet.
  • a process gas inlet section is located near the first tube sheet, on the opposite side than the cooling media.
  • the inlet section may further be enclosed by a first shell part at the process gas inlet end.
  • a process gas outlet section is located near the second tube sheet also on the opposite side of the cooling media.
  • the outlet section may further be enclosed by a third shell part.
  • an outlet process gas collector is located such that it collects at least a part of the process gas exiting the at least one by-pass tube and also collects the cooled process gas exiting a part of the heat exchange tubes.
  • Process gas flows from the first shell part, process gas inlet end, to the heat exchange tube inlets and the by-pass tube inlet, through the heat exchange tubes and the at least one by-pass tube, out of the heat exchange tube outlets and the at least one by-pass process gas outlet to the third shell part, process gas outlet end.
  • a cooling media flows into the heat exchange section via the cooling media inlet and is in contact with the shell side of the heat exchange tubes and can be in contact with the shell side of at least one by-pass tube before the cooling media exits the heat exchange section through the cooling media outlet.
  • the process gas enters the process gas inlet section at a first temperature and exits the heat exchange tubes at a second relatively low temperature.
  • the process gas exiting the by-pass tube has a third temperature which is lower or equal to the first temperature, but higher than the second temperature.
  • the outlet process gas collector mixes at least a part of the by-pass process gas and a part of the heat exchanged process gas.
  • the mixed process gas temperature has a fourth temperature which is higher than the second temperature, but lower than the third temperature.
  • the amount of heat exchanged process gas and the amount of by-pass gas in this mix is composed such that this fourth temperature is low enough to prevent excessive corrosion of the control valve which is located downstream of the collected by-pass and heat-exchanged process gas.
  • the control valve controls the amount of mixed process gas in the total process gas stream exiting the waste heat boiler.
  • the total process gas stream exiting the waste heat boiler should be of a certain fifth temperature, which is higher than or equal to the second temperature, but lower than the fourth temperature.
  • the control valve can control the volume flow of mixed process gas as compared to the total exiting process gas volume flow and thus control the fifth temperature even with varying second and fourth temperatures and volume flows. Accordingly, with a constant high first temperature and the aim of a constant low fifth temperature, but a rising second temperature due to fouling/corrosion of the heat-exchange pipes; the fifth temperature can be kept constant by use of the control valve to decrease the volume flow of the by-pass process gas having a fourth temperature.
  • the mixing of the heat exchanged process gas and the by-passed process gas in the outlet process gas collector can be enhanced by mixing means located in the collector up-stream of the control valve.
  • the mixing means can be of any known function and materials.
  • the process gas inlet section is lined with a ceramic liner for protecting the first shell part from the relative hot process gas.
  • the mixing means and the process gas collector can be lined with a ceramic liner.
  • the cooling media can be water or it can be steam.
  • the cooling media can be water when entering the heat exchange section and a part of the water or all of the water can be heated by the indirect heat-exchange with the relative hot process gas such that all or a part of the cooling media exiting the heat exchange section via the cooling media outlet is steam.
  • the second shell part or both the first, the second and the third shell part can be substantially cylindrical.
  • the cylindrical shape can be advantageous as it is a pressure robust and material saving shape.
  • substantial is meant any shape which is oblong in one cross sectional view and any shape which is not far from circular in another cross sectional view, such as circular, elliptic, square, pentagonal, hexagonal etc.
  • a plurality of heat exchange tubes are placed in a substantially circular array in the tube sheets and the by-pass tube or the at least one by-pass tube is placed substantially in the center of the array.
  • substantially meant, that the location does not have to be mathematically accurate, the shapes can vary to a large extent as long as consideration to heat-exchange effectiveness and material costs are respected.
  • the waste heat boiler is used in a process plant producing wet sulphuric acid.
  • Waste heat boiler for heat exchanging a relatively hot process gas with a cooling media comprising
  • FIG. 1 is a cross sectional view of the waste heat boiler 100 according to an embodiment of the invention.
  • the waste heat boiler comprises a first shell part, process gas inlet end 110 ; a second shell part, heat exchange section 120 and a third shell part, process gas outlet end 130 ; all having a substantially cylindrical shape and substantially the same diameter, but as can be seen on the figure, not necessarily the same material thickness.
  • the material thickness as well as the choice of material can be varied depending on the process conditions.
  • a first tube sheet, process gas inlet end 115 separates the first shell part from the second shell part.
  • a second tube sheet, process gas outlet end 125 separates the second shell part from the third shell part.
  • the internal surface of the process gas inlet section can have a liner 111 , for instance a ceramic liner to protect the internal surfaces from the high temperatures of the inlet process gas.
  • the first and the second tube sheets have corresponding bores to accommodate heat exchange tubes 123 .
  • the heat exchange tubes stretch at least from the first tube sheet through the heat exchange section and at least to the second tube sheet.
  • the connection between each heat exchange tube and each of the tube sheets are made gas and liquid tight.
  • Each heat exchange tube has a heat exchange tube inlet 114 located in the process gas inlet section and a heat exchange tube outlet 134 located in the process gas outlet section.
  • the first and the second tube sheets also have at least one corresponding bore for at least one process gas by-pass tube 124 .
  • the connection between the process gas by-pass tube and the first and the second tube sheet is made gas and liquid tight.
  • the process gas by-pass tube has a by-pass process gas inlet 113 located in the process gas inlet section and a by-pass process gas outlet 133 located in the process gas outlet.
  • the process gas by-pass tube can be provided with a lining (not shown) which can protect the tube from the relative high process gas temperatures and which may also reduce the indirect heat exchange between the cooling media and the by-passed process gas.
  • a cooling media inlet 121 provides fluid connection of a cooling media to the heat exchange section.
  • the at least one cooling media inlet can be located in any position on the second shell part or even on the first or the second tube sheet, as long as fluid connection to the heat exchange section is provided.
  • a location on the shell part of the heat exchange section is shown on FIG. 1 .
  • a cooling media outlet 122 located in fluid connection to the heat exchange section provides outlet of the cooling media from the heat exchange section.
  • Each of the heat exchange tubes and the process gas by-pass tube thus provides fluid connection from the process gas inlet section through the heat exchange section and to the process gas outlet section, thereby enabling the process gas to flow through the heat exchange section without direct contact to the cooling media.
  • the process gas flowing in the heat exchange tubes is in indirect heat-exchange with the cooling media, whereas the part of the process gas which is by-passed, i.e.
  • the process gas by-pass tube is in less or relative low or substantially no indirect heat-exchange with the cooling media: If the by-pass tube is not lined, the by-passed process gas will have some heat-exchange with the cooling media, but the heat-exchange in the by-pass tube will be relative lower than the heat-exchange in the heat exchange tubes due to the by-pass tube's higher volume to surface ratio. If the by-pass tube is lined, for instance with a ceramic liner, the indirect heat-exchange between the by-passed process gas flowing in the by-pass tube and the cooling media will be relative low or close to zero. In any case, the temperature of the heat-exchanged process gas exiting the heat exchange tube outlets is considerably lower than the temperature of the by-passed process gas exiting the by-pass process gas outlet.
  • an outlet process gas collector 136 is located in the process gas outlet section. It collects the by-passed process gas and a part of the heat-exchanged process gas.
  • the process gas collector collects the by-passed process gas and the heat-exchanged process gas exiting the heat-exchange tubes located nearest to the by-pass tube in a circular array around the by-pass tube.
  • Outlet process gas mixing means are located inside the process gas collector ensuring mixing of the by-passed and the part of the heat-exchanged process gas to an extent so the control valve, by-pass tube outlet 135 is not exposed to a critical amount of process gas with a temperature so high it will lead to substantial corrosion of the control valve.
  • Said control valve controls the amount of mixed process gas which is exited from the outlet process gas collector to the process gas outlet section.
  • the control valve can vary the temperature of the process gas exiting the process gas outlet section within an interval between the temperature of the heat-exchanged gas and the mixed by-pass gas. Or more important, the control valve can keep the temperature of the process gas exiting the process gas outlet section on a certain level, even though the temperature of the heat-exchanged process gas vary due to for instance reduced indirect heat-exchange because of for instance fouling in the heat-exchange tubes.
  • FIG. 2 shows the waste heat boiler of FIG. 1 with the temperatures noted.
  • the temperatures have the following relations:

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Geometry (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Control Of Steam Boilers And Waste-Gas Boilers (AREA)
  • Feeding And Controlling Fuel (AREA)
  • Chimneys And Flues (AREA)
  • Details Of Heat-Exchange And Heat-Transfer (AREA)
US13/822,144 2010-09-30 2010-09-30 Waste heat boiler Abandoned US20130180475A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/005968 WO2012041344A1 (en) 2010-09-30 2010-09-30 Waste heat boiler

Publications (1)

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US20130180475A1 true US20130180475A1 (en) 2013-07-18

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US13/822,144 Abandoned US20130180475A1 (en) 2010-09-30 2010-09-30 Waste heat boiler

Country Status (16)

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US (1) US20130180475A1 (uk)
EP (1) EP2622297B1 (uk)
JP (1) JP5746353B2 (uk)
KR (1) KR20140005865A (uk)
CN (1) CN103270383B (uk)
AU (1) AU2010361358B2 (uk)
BR (1) BR112013006139A2 (uk)
CA (1) CA2811676A1 (uk)
DK (1) DK2622297T3 (uk)
EA (1) EA201390473A1 (uk)
ES (1) ES2541838T3 (uk)
MX (1) MX2013003048A (uk)
PL (1) PL2622297T3 (uk)
UA (1) UA108669C2 (uk)
WO (1) WO2012041344A1 (uk)
ZA (1) ZA201301534B (uk)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016135299A1 (en) * 2015-02-27 2016-09-01 Technip France Waste heat boiler system, mixing chamber, and method for cooling a process gas
CN110081722A (zh) * 2019-04-25 2019-08-02 四川陆亨能源科技有限公司 一种高效余热锅炉
US11073347B2 (en) 2017-05-26 2021-07-27 Alfa Laval Olmi S.P.A. Shell-and-tube equipment with bypass
JP7453405B2 (ja) 2020-03-10 2024-03-19 アルファ-ラヴァル・コーポレート・アーベー ボイラおよびボイラを動作させる方法

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JP6472267B2 (ja) * 2015-02-20 2019-02-20 三菱重工業株式会社 エコノマイザ、コンポジットボイラ、及び使用方法
DE102015013517A1 (de) * 2015-10-20 2017-04-20 Borsig Gmbh Wärmeübertrager
RU2679580C1 (ru) * 2018-05-14 2019-02-11 Владислав Юрьевич Климов Теплообменник
RU2770973C1 (ru) * 2020-11-20 2022-04-25 Акционерное общество "НПО Энергомаш имени академика В.П. Глушко" Теплообменник
WO2022172354A1 (ja) * 2021-02-10 2022-08-18 日本管機工業株式会社 希硫酸製造装置及び希硫酸製造方法

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DE2927161B1 (de) * 1979-07-05 1981-04-23 Joachim 5000 Köln Pohl Verfahren und Vorrichtung zur Wassererhitzung durch Waermerueckgewinnung aus den Abgasen eines Heizungskessels
US4406396A (en) * 1980-03-24 1983-09-27 Habegger Millard A Method and apparatus for regulating flue draft
US4993367A (en) * 1988-08-18 1991-02-19 Borsig Gmbh Heat exchanger
US5452686A (en) * 1993-03-26 1995-09-26 Haldor Topsoe A/S Waste heat boiler
US7412945B2 (en) * 2005-12-01 2008-08-19 Alstom Technology Ltd. Waste heat boiler
US20090038302A1 (en) * 2006-03-16 2009-02-12 Takeshi Yamada Exhaust gas heat recovery device
US20110131961A1 (en) * 2009-12-04 2011-06-09 Hyundai Motor Company Exhaust heat recovery device

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016135299A1 (en) * 2015-02-27 2016-09-01 Technip France Waste heat boiler system, mixing chamber, and method for cooling a process gas
US20180045468A1 (en) * 2015-02-27 2018-02-15 Technip France Waste heat boiler system, mixing chamber, and method for cooling a process gas
EP3262363B1 (en) 2015-02-27 2020-04-29 Technip France Waste heat boiler system and method for cooling a process gas
US10782073B2 (en) * 2015-02-27 2020-09-22 Technip France Waste heat boiler system, mixing chamber, and method for cooling a process gas
US11073347B2 (en) 2017-05-26 2021-07-27 Alfa Laval Olmi S.P.A. Shell-and-tube equipment with bypass
CN110081722A (zh) * 2019-04-25 2019-08-02 四川陆亨能源科技有限公司 一种高效余热锅炉
JP7453405B2 (ja) 2020-03-10 2024-03-19 アルファ-ラヴァル・コーポレート・アーベー ボイラおよびボイラを動作させる方法

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ZA201301534B (en) 2014-04-30
JP2013539006A (ja) 2013-10-17
JP5746353B2 (ja) 2015-07-08
BR112013006139A2 (pt) 2016-06-14
CN103270383B (zh) 2015-09-30
KR20140005865A (ko) 2014-01-15
MX2013003048A (es) 2013-05-30
UA108669C2 (uk) 2015-05-25
EP2622297A1 (en) 2013-08-07
WO2012041344A1 (en) 2012-04-05
EA201390473A1 (ru) 2013-09-30
CN103270383A (zh) 2013-08-28
EP2622297B1 (en) 2015-04-29
AU2010361358A1 (en) 2013-04-04
DK2622297T3 (en) 2015-07-27
ES2541838T3 (es) 2015-07-27

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