US20070235171A1 - Apparatus for Processing Highly Corrosive Agents - Google Patents

Apparatus for Processing Highly Corrosive Agents Download PDF

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Publication number
US20070235171A1
US20070235171A1 US10/596,156 US59615605A US2007235171A1 US 20070235171 A1 US20070235171 A1 US 20070235171A1 US 59615605 A US59615605 A US 59615605A US 2007235171 A1 US2007235171 A1 US 2007235171A1
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US
United States
Prior art keywords
titanium
zirconium
tube
alloy
layer
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.)
Abandoned
Application number
US10/596,156
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English (en)
Inventor
Domenico Romiti
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.)
Casale SA
Original Assignee
Urea Casale SA
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 Urea Casale SA filed Critical Urea Casale SA
Assigned to UREA CASALE S.A. reassignment UREA CASALE S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROMITI, DOMENICO
Publication of US20070235171A1 publication Critical patent/US20070235171A1/en
Assigned to CASALE SA reassignment CASALE SA MERGER (SEE DOCUMENT FOR DETAILS). Assignors: AMMONIA CASALE SA, CASALE CHEMICALS SA, METHANOL CASALE SA, UREA CASALE SA
Priority to US15/132,927 priority Critical patent/US20160231070A1/en
Abandoned legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/02—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor for obtaining at least one reaction product which, at normal temperature, is in the solid state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/16—Heat-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
    • F28D7/1615—Heat-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 the conduits being inside a casing and extending at an angle to the longitudinal axis of the casing; the conduits crossing the conduit for the other heat exchange medium
    • F28D7/1623—Heat-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 the conduits being inside a casing and extending at an angle to the longitudinal axis of the casing; the conduits crossing the conduit for the other heat exchange medium with particular pattern of flow of the heat exchange media, e.g. change of flow direction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/086—Heat exchange elements made from metals or metal alloys from titanium or titanium alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2275/00—Fastening; Joining
    • F28F2275/06—Fastening; Joining by welding

Definitions

  • the present invention in its most general aspect, refers to apparatuses intended for treating highly corrosive chemical agents, with respect to which a specialized, effective and long-lasting protection is required.
  • this invention concerns an apparatus of the aforementioned type, in which the treating of corrosive agents is substantially a heat-treating.
  • the present invention refers to an apparatus of the type considered, comprising or essentially consisting of a tube bundle heat exchanger, structured to carry out a heat exchange between two fluids one of which is highly corrosive.
  • Heat exchange apparatuses falling within the scope of protection of the present invention are, for example, synthesis, decomposition, condensation or evaporation reactors, stripping apparatuses, boilers, concentrators and similar devices that require the heat exchange between a process fluid and an operating fluid.
  • the present invention concerns apparatuses that can be used in urea production plants, for the decomposition of ammonium carbamate into ammonia and carbon dioxide, also known as strippers, and, respectively, apparatuses for the condensation of ammnonia and carbon dioxide into ammonium carbamate, also known as condensers.
  • heat exchange apparatuses of the type specified above operate, in an urea production plant, in critical operative conditions, normally of high pressure and high temperature of the process fluid and are therefore continuously subjected to high mechanical and thermal stresses.
  • the process fluid often also exerts a corrosive and/or erosive action on the surfaces with which it comes into contact due, in particular, to the presence of highly corrosive agents.
  • the corrosive and/or erosive action reveals itself in particular at the tube bundle, and generally inside the tubes of which it is composed, of the stripping and condensation apparatuses present in the high pressure section of an urea production plant.
  • the tubes of the tube bundle of such heat exchange apparatuses are, indeed, generally crossed on their inside by a process fluid that, in the case of urea, has, as main compounds, highly corrosive agents like ammonium carbamate and carbon dioxide. These substances exert an aggressive consumption and erosion action of the inner surfaces of such tubes with which they come into contact.
  • the technical problem underlying the present invention is therefore that of providing a tube bundle heat exchange apparatus of the type specified above, that allows the quoted drawbacks with reference to the prior art to be overcome; in other words that allows an effective and long-lasting resistance against corrosive chemical agents treated in it to be ensured, that is easy to realize, reliable and that does not require frequent and onerous maintenance interventions.
  • a tube bundle heat exchange apparatus of the type considered above, characterized in that said tube bundle comprises at least one titanium or titanium alloy tube, coated with a layer of zirconium or zirconium alloy.
  • the titanium tube is internally coated with the layer of zirconium or zirconium alloy.
  • the titanium or titaniuam alloy tube has a thickness between 1.0 and 10 mm, whereas the coating layer of zirconium or zirconium alloy has a thickness between 0.3 and 2.0 mm.
  • said at least one titanium or titanium alloy tube is only partially coated with the layer of zirconium or zirconium alloy, which, preferably, extends in such a tube starting from an end thereof, or close to an end thereof, for the entry of a process fluid, towards an opposite end thereof, for a portion between 5 and 30%.
  • the titanium or titanium alloy tube and the coating layer of zirconium or zirconium alloy are bonded together metallurgically, for example by hot-drawing, or through welding.
  • the heat exchange tube according to the present invention obtained by the titanium/zirconium combination, is extremely resistant both to the mechanical and thermal stresses and to the corrosive/erosive attack of the process fluids with which it comes into contact.
  • FIG. 1 schematically illustrates a section view of a tube bundle heat exchange apparatus according to the present invention
  • FIG. 2 schematically illustrates a section view of a detail of the apparatus of FIG. 1 .
  • the heat exchange apparatus shall be described, purely for indicating and not limiting purposes, with specific reference to a descending film tube bundle heat exchanger 10 , with vertical tubes, that has advantageous and specific use as a stripper of a urea production plant, but it is clear that it can be used as a condenser, evaporator, boiler, reactor or similar apparatuses based upon the heat exchange between two fluids.
  • the heat exchanger 10 has advantageous and specific use as a stripper or condenser in a high pressure synthesis section of an urea plant, and more precisely of a urea plant of so-called CO2 or ammonia stripping, not represented because it is conventional.
  • a section generally comprises at least one synthesis reactor, a stripper for the decomposition of the ammonium carbamate and of the-free ammonia present in the reaction mixture coming from the reactor, and a condenser for the condensation of vapors comprising carbon dioxide and ammonia coming from the stripper.
  • These apparatuses are in fluid communication with each other so as to form a so-called substantially isobaric synthesis loop, i.e. operating at the same pressure usually between 140-170 bar.
  • the heat exchanger 10 comprises a shell 11 , with a vertical axis A-A, closed at the opposite ends by respective walls or bottoms 12 , 13 , a tube bundle 14 (of which just one tube 14 a is illustrated in the figures for the sake of simplicity), supported longitudinally in said shell 11 , through tube plates 15 , 16 , upper and lower respectively, perimetrically fixed (for example welded) gas-tight to said shell 11 .
  • a first chamber 17 between the upper bottom 12 , and the outer wall 15 a of the upper tube plate 15 ; a second chamber 18 , between the tube plates 15 and 16 and a third chamber 19 , between the outer wall 16 a of the lower tube plate 16 and the lower bottom 13 of the shell 11 .
  • outer wall of the tube plate we mean to identify the wall of said tube plate facing towards the outside of the tube bundle.
  • the first chamber 18 is in fluid communication with the outside of the apparatus 10 , through an entry duct 20 of, for example, a process fluid, formed in the upper bottom 12 , whereas the third chamber 19 , or lower chamber, is in fluid communication with the outside through an exit duct 21 of the fluid, formed in the lower bottom 13 .
  • the second chamber 18 is in communication with the outside of the shell 11 through an upper duct 23 , for the introduction into it of an operating heat exchange fluid, for example steam at a predetermined pressure and temperature, able to be used to carry out the desired heat exchange with the process fluid to be stripped; a lower duct 22 takes care of discharging the operating heat exchange fluid from said second chamber 18 .
  • an operating heat exchange fluid for example steam at a predetermined pressure and temperature
  • the tubes 14 a of the tube bundle 14 have respective upper and lower end portions 14 b , 14 c , fixed for example through welding 24 as indicated in FIG. 2 , in the corresponding tube plates 15 and 16 , and are open in the first chamber 17 and in the third chamber 19 , respectively, which are thus in mutual fluid communication.
  • the tubes 14 a of the tube bundle 14 are made of titanium or titanium alloy and are coated with a layer 25 of zirconium or zirconium alloy.
  • a coating layer 25 is inside the titanium or titanium alloy tubes 14 , i.e. applied to the inner surface of such tubes.
  • the titanium used is titanium ASTM GR. 1-2-3-4-5-6-7- or equivalent, whereas the zirconium is of the ASTM GR. 60702/60704/60705 type, or equivalent.
  • the titanium tube 14 a also has a thickness between 2.0 and 5.0 mm, whereas the zirconium inner coating layer 25 has a thickness between 0.5 and 1.2 mm.
  • the zirconium coating 25 only partially covers the titanium heat exchange tube 14 a .
  • a coverage of the zirconium layer 25 is present solely at the upper end portion 14 b of the heat exchange tube 14 a , and in particular in the portion of the tube 14 a immediately below the upper tube plate 15 .
  • the zirconium layer 25 extends in the tube 14 a starting from an upper end 26 thereof for the entry of a process fluid, towards an opposite end 27 thereof, for a portion between 10 and 20%.
  • an anticorrosion protective coating is realized in the heat exchanger 10 according to the invention solely in the critical points and zones of the tube bundle 14 , where, from the studies carried out by the Applicant, the corrosive/erosive action of the process fluid is higher, in any case managing to ensure an effective and long-lasting resistance to corrosion also in the other parts of the tube bundle thanks to the arrangement of titanium or titanium alloy tubes.
  • the zirconium layer 25 can completely coat the inner surface of the tubes 14 a of the tube bundle 14 .
  • the titanium tube 14 a and the zirconium coating layer 25 are preferably bonded together metallurgically, for example by hot-drawing, or through welding.
  • a strong, stable and long-lasting link is obtained between the two metals, which makes it practically impossible for them to detach even when subjected to the most extreme operative conditions, thus ensuring continuous resistance to corrosion.
  • the hot-drawing or the welding of the tube according to the invention is realized by using per se known techniques.
  • a further advantage of the present invention with respect to the apparatuses according to the prior art is given by the fact that the arrangement of titanium or titanium alloy tubes 14 a ensures a long-lasting and effective resistance to corrosion thereof also at their lower and upper ends. Indeed, such ends, going into the chambers 17 and 19 , are particularly subjected to the corrosive attack of the process fluid (liquid and gaseous) present in such chambers.
  • the parts outside of the tube bundle 14 are preferably made of titanium or titanium alloy or are coated (cladded) with a layer of titanium or titanium alloy, so as to ease the fixing of the tubes 14 a with such tube plates.
  • the upper and lower tube plates 15 , 16 are made of carbon or stainless steel, coated on the outside with a layer of about 3-15 mm of titanium or titanium alloy.
  • a process fluid is fed into the first chamber 17 of the exchanger 10 according to the present invention through the entry duct 20 , from here descends along the inner wall of the tubes 14 a of the tube bundle 14 , without filling up, forming a thin film on it that leaves a consistent empty space at the center of the tubes themselves (see vertical axis B-B of FIG. 2 ).
  • an operating heat exchange fluid is fed into the second chamber 18 of the heat exchanger 10 through the upper entry duct 23 , and circulates inside of it coming into contact with the outer wall of each single tube 14 a of said tube bundle 14 .
  • the product coming out from the tubes 14 a is collected in the third chamber 19 from where it is discharged to the outside of the heat exchanger 10 through the exit duct 21 .
  • the operating heat exchange fluid comes out from the second chamber 18 through the lower exit duct 22 .
  • the process fluid comprises an aqueous urea solution, ammonium carbamate, amonia and carbon dioxide, where carbamate and carbon dioxide are highly aggressive agents that notoriously exert a considerable corrosive action on the metallic surfaces with which they come into contact.
  • such a corrosive action which is particularly virulent inside the tubes of the tube bundle of such apparatus, is effectively neutralized by the arrangement of titanium or titanium alloy tubes, at least partially coated on the inside by a layer of zirconium or zirconium alloy.

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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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
US10/596,156 2004-03-16 2005-02-24 Apparatus for Processing Highly Corrosive Agents Abandoned US20070235171A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/132,927 US20160231070A1 (en) 2004-03-16 2016-04-19 Apparatus for processing highly corrosive agents

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04006215A EP1577632A1 (en) 2004-03-16 2004-03-16 Apparatus for treating highly corrosive agents
EP0400621.50 2004-03-16
PCT/EP2005/001934 WO2005095883A2 (en) 2004-03-16 2005-02-24 Apparatus for processing highly corrosive agents

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/001934 A-371-Of-International WO2005095883A2 (en) 2004-03-16 2005-02-24 Apparatus for processing highly corrosive agents

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/132,927 Continuation US20160231070A1 (en) 2004-03-16 2016-04-19 Apparatus for processing highly corrosive agents

Publications (1)

Publication Number Publication Date
US20070235171A1 true US20070235171A1 (en) 2007-10-11

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ID=34833610

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US10/596,156 Abandoned US20070235171A1 (en) 2004-03-16 2005-02-24 Apparatus for Processing Highly Corrosive Agents
US15/132,927 Abandoned US20160231070A1 (en) 2004-03-16 2016-04-19 Apparatus for processing highly corrosive agents

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/132,927 Abandoned US20160231070A1 (en) 2004-03-16 2016-04-19 Apparatus for processing highly corrosive agents

Country Status (9)

Country Link
US (2) US20070235171A1 (ru)
EP (2) EP1577632A1 (ru)
CN (1) CN100547340C (ru)
AT (1) ATE377743T1 (ru)
CA (1) CA2557035C (ru)
DE (1) DE602005003216T2 (ru)
EG (1) EG24807A (ru)
RU (1) RU2350876C2 (ru)
WO (1) WO2005095883A2 (ru)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120097378A1 (en) * 2009-05-06 2012-04-26 Saipem S.P.A. Tube bundle equipment with liquid flow regulator elements
US20130123536A1 (en) * 2008-07-17 2013-05-16 Saipem S.P.A. Tube-bundle equipment for processing corrosive fluids
WO2015191302A1 (en) * 2014-06-09 2015-12-17 Wahlco, Inc. Urea to ammonia process
US20190277490A1 (en) * 2018-03-07 2019-09-12 Zhejiang Liju Boiler Co., Ltd. Flameless Steam Boiler

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7922065B2 (en) 2004-08-02 2011-04-12 Ati Properties, Inc. Corrosion resistant fluid conducting parts, methods of making corrosion resistant fluid conducting parts and equipment and parts replacement methods utilizing corrosion resistant fluid conducting parts
ITMI20061223A1 (it) 2006-06-26 2007-12-27 Snam Progetti Tubo bimetallico resistente alla corrosione e suo utilizzo in apparecchiature a fascio tubiwero
EP2286909A1 (en) * 2009-08-17 2011-02-23 Stamicarbon B.V. An apparatus for the decomposition of non-converted ammonium carbamate in urea solutions in a urea synthesis process
CN102226661A (zh) * 2011-04-01 2011-10-26 大连海水淡化工程研究中心有限公司 薄壁钛换热管及生产方法
US10118259B1 (en) 2012-12-11 2018-11-06 Ati Properties Llc Corrosion resistant bimetallic tube manufactured by a two-step process
EP2801396A1 (en) 2013-05-10 2014-11-12 Casale Sa Use of duplex stainless steel in an ammonia-stripping of urea plants
CN113476880B (zh) * 2017-10-27 2023-01-24 斯塔米卡邦有限公司 高压氨基甲酸盐冷凝器

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US4156500A (en) * 1976-06-02 1979-05-29 Sumitomo Electric Industries, Ltd. Method and apparatus for producing copper clad steel wire
US4252182A (en) * 1979-03-20 1981-02-24 Ecolaire Incorporated Tube sheet shield
US4253516A (en) * 1978-06-22 1981-03-03 Westinghouse Electric Corp. Modular heat exchanger
US4288109A (en) * 1979-01-19 1981-09-08 Sterling Drug, Inc. Corrosion resistant assembly and method of making it
US4562887A (en) * 1983-04-28 1986-01-07 Bbc Brown, Boveri & Company, Limited Water-cooled condenser tube-plate attachment
US4893744A (en) * 1981-12-25 1990-01-16 Akira Takayasu Lining method using clad pieces and a clad piece for the method
US5181559A (en) * 1990-12-05 1993-01-26 Asea Brown Boveri Ltd. Water-cooled condenser
US5579988A (en) * 1995-06-09 1996-12-03 Rmi Titanium Company Clad reactive metal plate product and process for producing the same

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JPS60238492A (ja) * 1984-05-09 1985-11-27 Sumitomo Metal Ind Ltd チタン又はチタン合金の腐食防止方法
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RU2009429C1 (ru) * 1992-04-20 1994-03-15 Виталий Григорьевич Барон Теплообменный аппарат
US6670050B2 (en) * 1997-05-30 2003-12-30 Honeywell International Inc. Titanium-based heat exchangers and methods of manufacture
GB9809528D0 (en) * 1998-05-06 1998-07-01 Warren Raymond MIG welding shroud
ITMI20021009A1 (it) * 2002-05-13 2003-11-13 Snam Progetti Apparecchiatura a fascio tubiero per processare fluidi corrosivi

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973624A (en) * 1973-04-06 1976-08-10 Stal-Laval Apparat Ab Condenser
US4156500A (en) * 1976-06-02 1979-05-29 Sumitomo Electric Industries, Ltd. Method and apparatus for producing copper clad steel wire
US4253516A (en) * 1978-06-22 1981-03-03 Westinghouse Electric Corp. Modular heat exchanger
US4288109A (en) * 1979-01-19 1981-09-08 Sterling Drug, Inc. Corrosion resistant assembly and method of making it
US4252182A (en) * 1979-03-20 1981-02-24 Ecolaire Incorporated Tube sheet shield
US4893744A (en) * 1981-12-25 1990-01-16 Akira Takayasu Lining method using clad pieces and a clad piece for the method
US4562887A (en) * 1983-04-28 1986-01-07 Bbc Brown, Boveri & Company, Limited Water-cooled condenser tube-plate attachment
US5181559A (en) * 1990-12-05 1993-01-26 Asea Brown Boveri Ltd. Water-cooled condenser
US5579988A (en) * 1995-06-09 1996-12-03 Rmi Titanium Company Clad reactive metal plate product and process for producing the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130123536A1 (en) * 2008-07-17 2013-05-16 Saipem S.P.A. Tube-bundle equipment for processing corrosive fluids
US8518337B2 (en) * 2008-07-17 2013-08-27 Saipem S.P.A. Tube-bundle equipment for processing corrosive fluids
US20120097378A1 (en) * 2009-05-06 2012-04-26 Saipem S.P.A. Tube bundle equipment with liquid flow regulator elements
US9068781B2 (en) * 2009-05-06 2015-06-30 Saipem S.P.A. Tube bundle equipment with liquid flow regulator elements
WO2015191302A1 (en) * 2014-06-09 2015-12-17 Wahlco, Inc. Urea to ammonia process
US9586831B2 (en) 2014-06-09 2017-03-07 Wahlco, Inc. Urea to ammonia process
US20190277490A1 (en) * 2018-03-07 2019-09-12 Zhejiang Liju Boiler Co., Ltd. Flameless Steam Boiler
US10767854B2 (en) * 2018-03-07 2020-09-08 Zhejiang Liju Boiler Co., Ltd. Flameless steam boiler

Also Published As

Publication number Publication date
CN100547340C (zh) 2009-10-07
EP1577632A1 (en) 2005-09-21
DE602005003216T2 (de) 2008-08-28
RU2006136086A (ru) 2008-04-27
EG24807A (en) 2010-09-19
CA2557035C (en) 2011-06-21
EP1735578A2 (en) 2006-12-27
EP1735578B1 (en) 2007-11-07
WO2005095883A3 (en) 2007-03-08
ATE377743T1 (de) 2007-11-15
CN101091099A (zh) 2007-12-19
US20160231070A1 (en) 2016-08-11
DE602005003216D1 (de) 2007-12-20
WO2005095883A2 (en) 2005-10-13
RU2350876C2 (ru) 2009-03-27
CA2557035A1 (en) 2005-10-13

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AS Assignment

Owner name: UREA CASALE S.A., SWITZERLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ROMITI, DOMENICO;REEL/FRAME:017844/0825

Effective date: 20060615

AS Assignment

Owner name: CASALE SA, SWITZERLAND

Free format text: MERGER;ASSIGNORS:AMMONIA CASALE SA;UREA CASALE SA;METHANOL CASALE SA;AND OTHERS;REEL/FRAME:034533/0456

Effective date: 20140527

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION