EP1129789A1 - Protection of the water-side surfaces of heat exchangers used in boilers and gas fired water heaters - Google Patents

Protection of the water-side surfaces of heat exchangers used in boilers and gas fired water heaters Download PDF

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Publication number
EP1129789A1
EP1129789A1 EP20000200746 EP00200746A EP1129789A1 EP 1129789 A1 EP1129789 A1 EP 1129789A1 EP 20000200746 EP20000200746 EP 20000200746 EP 00200746 A EP00200746 A EP 00200746A EP 1129789 A1 EP1129789 A1 EP 1129789A1
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EP
Grant status
Application
Patent type
Prior art keywords
water
limestone
exchangers
copper
sanitary
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.)
Granted
Application number
EP20000200746
Other languages
German (de)
French (fr)
Other versions
EP1129789B1 (en )
Inventor
Giorgio Ing. Pastorino
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.)
Riello SpA
Original Assignee
IABER SpA
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

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/04Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of rubber; of plastics material; of varnish

Abstract

In order to optimise the performance of boiler exchangers, avoiding the precipitation of calcium and magnesium carbonates, in addition to the fouling of the circuits caused by residual working products or by other foreign matters existing in the water network, while keeping drinkable the sanitary water produced according to the WRC standards, IABER S.p.A. has developed a treatment with particular fluorurated resins for the exchange surfaces.
Such resins adhere to metallic surfaces thus creating a few microns thick coating limiting the adhesion of limestone and of the deposits existing in heating circuits.

Description

    1. State of Art
  • [0001]
    All heat exchangers producing hot water, are subject to limestone precipitation of calcium and magnesium carbonates and to fouling of the circuits due to residual working products or other foreign matters present in the water network.
  • [0002]
    Besides, in case water contains some particular additives (for instance glycoles), the migration of metallic ions (Copper, Aluminium, Stainless Steel) may occur. The corrosion of metallic surfaces is always potentially possible.
  • [0003]
    The precipitation of limestone is more significant, the higher is the water limestone contents (hardness of water), the higher is the water heating and the longer is the time water remains at high temperature.
  • [0004]
    The fouling due to limestone and solid foreign matters present in the network occurs in different types of exchangers, such as:
    • Bi-thermic exchangers for the combined production of hot water both for ambient heating and for sanitary (Fig. 1).
    • Primary exchangers for the production of hot water for ambient heating only (Fig. 2).
      • Plate-type exchangers for the production of sanitary hot water (Fig. 3).
      • Storage vessels for the production and the storage of sanitary hot water (Fig. 4).
      • Additional storage systems for sanitary hot water.
      • Exchangers for water heaters.
  • [0005]
    The exchangers intended for the production of sanitary hot water (plate-type, primary exchangers, vessels, sanitary water tanks and bi-thermic exchangers) shall keep drinkable the sanitary water produced according to WRC standards.
  • [0006]
    The metals used for exchangers are, according to the type:
    • Copper (Cu DHP, CU OF, SE CU)
    • Stainless Steel (AISI 316L, AISI 304)
    • Aluminium
  • [0007]
    The water-diluted product has a viscosity comparable to water viscosity and is such as to fill all the interstices of the exchangers.
  • [0008]
    The exchangers nowadays on sale need to be frequently cleaned with specific acids to remove limestone crusts and dirt deposits causing in the run of time the obstruction of the passages and the thermal unbalance of the exchangers.
  • 2. Description of the invention
  • [0009]
    In order to limit the above undesired effects, a procedure has been developed to treat the exchange surfaces with particular fluorurated resins. Such resins are provided with functional groups that adhere to the metallic surfaces to create a few microns thick coating limiting the adhesion of limestone and of the deposits present in heating circuits.
  • [0010]
    The peculiar features of the treatment, i.e. the anti-adhesion of limestone on the coated surfaces, have been checked both at IABER S.p.A. test laboratory (Ann. 1) and at the laboratory of the resin Manufacturer (Ann. 2), and through tests "on the field".
  • [0011]
    The performance of the thermal exchange and the hydraulic characteristics of the exchangers are not at all modified by the treatment.
  • [0012]
    The resin coating treatment is performed as follows. (diagram)
  • [0013]
    The water-diluted product has a viscosity comparable to water viscosity and such as to fill all the interstices of the exchangers.
  • 3. Innovations introduced by the invention
  • [0014]
    The treatment of exchangers and vessels with fluorurated resins allows to overcome one of the weakest points of exchangers i.e. a reduced performance in the run of time due to the deposit of limestone and dirt present in the network. Specifically, thanks to this treatment, the circuits obstructions due to the effects of limestone and of a variety of residual working products are reduced and, therefore, the useful life of the same exchangers in compliance with specifications is extended.
  • [0015]
    Particularly, limestone keeps on precipitating during the water heating but, when precipitated, it does not adhere firmly to walls. On the contrary, it is eliminated by the same water stream. Similarly, thanks to the anti-adhering characteristics of the treatment, foreign matters in water (dirt and residual working products) do not fix to the exchangers walls but they slide away together with the water stream.
  • [0016]
    Moreover, the surface protection from such resins reduces the migration of metallic ions in water, the corrosion of the same metals and assures a higher water sanitation coming into contact with the water-side surfaces.
  • 4. Patent Right Claims
  • [0017]
    The protection we claim with patent shall cover the application procedure of fluorurated products with low viscosity on the metallic surfaces made of Copper (CU DHP, CU OF, SE CU), Aluminium and Stainless Steel (AISI 316L, AISI 304) of the heat exchangers and vessels used for the production of sanitary hot water and ambient heating in storage or instantaneous gas-fired wall boilers and in water heaters.
  • [0018]
    The effect of the treatment is:
    • 1. to limit the limestone deposit;
    • 2. to limit the deposit of residual working products;
    • 3. to keep unaltered the sanitation characteristics of the produced sanitary water
    • 4. to keep unaltered the thermal exchange characteristics. 5.
  • 5. Laboratory tests carried out by IABER S.p.A.
  • [0019]
    Limestone tests have been carried out on treated vessels boiling the same quantity of water on a camp stove:
    • 1. VESSEL No. 1 : Heat-treated Copper without special treatments
    • 2. VESSEL No. 2 : Green Teflon SR43F coated Copper
    • 3. VESSEL No. 3 : Ausimont Silane coated Copper
  • REMARKS:
  • [0020]
    Limestone deposits occur in Vessels No. 1 and No. 2, which do not detach from the walls.
  • [0021]
    In Vessel No. 3 the limestone patina does not deposit on the walls and with the addition of fresh water the limestone solution dissolves.
  • 6. Laboratory tests carried out on account of IABER S.p.A.
  • [0022]
    The coating with functional perfluorpolyetheric products has been laid on some copper plates, in compliance with ordinary procedures.
  • [0023]
    The product has been applied by dip-coating with the following treatment formulas:
    • 1. 1-Phosphate
    • 2. 5-Phosphate
    • 3. 1-Silane
    • 4. 5-Silane
  • [0024]
    Copper test specimen has been plunged into the compounds for 10 minutes before heat-treatment:
    • Heating at T = 80°C for 7 minutes
    • Heating at T = 65°C for 40 minutes
    • Heating at T = 160°C for 12 minutes
  • [0025]
    Subsequent to the preparation of the specimen, some measurements of static and dynamic contact angle versus water, hexadecane, dodecane, decane and octane were carried out. Only the results relevant to the measurement of the static contact angle versus water carried out before limestone deposition, after deposition and after washing under cold tap water are herein reported.
  • Contact angle measurements for treated/untreated copper specimen, before limestone deposition (table 1) Contact angle measurements for treated/untreated copper specimen, after limestone deposition:
  • [0026]
    A calcium bicarbonate solution has been prepared. This is more soluble in water than the calcium carbonate (limestone) that tends to form and deposit at temperatures higher than 50°C. The treated/untreated specimen have been plunged into these boiling solutions for 3 hours. At the end of this time, the limestone deposit on all specimen was recorded; on specimen treated with Silane, however, the amount of the deposit was the lowest (also on phosphate a certain effect was noted). Here below the measurements of static contact angle versus water after limestone deposition under the described conditions are recorded.(table 2)
  • Contact angle measurements for treated/untreated copper specimen, after washing under tap flowing water:
  • [0027]
    Test specimen have been washed under a stream of cold tap-water for few seconds; after this time specimen have been stove-dried for 15 minutes and then the static contact angle versus water was measured again ( table 3)
  • [0028]
    The best treatment proved to be that with silanes (5-Silane specimen) showing:
    • lower limestone deposit
    • greater easiness in removing limestone
    • lower copper oxidation

Claims (8)

  1. Low viscosity resins are used.
  2. It is suitable both for metallic surfaces made from Copper (CU DHP, CU OF, SE CU) and for Aluminium and Stainless Steel (AISI
       316L, AISI 304).
  3. It can be applied to heat exchangers, to vessels, to storage tanks used for heating in wall or base gas-fired boilers and to water heaters.
  4. It limits the limestone deposit.
  5. It limits the deposit of residual working products.
  6. It keeps the characteristics of the sanitary water produced unaltered.
  7. It keeps the characteristics of the thermal exchange unaltered
  8. It prevents the migration of metallic ions.
EP20000200746 2000-03-03 2000-03-03 Protection of the water-side surfaces of heat exchangers used in boilers and gas fired water heaters Active EP1129789B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20000200746 EP1129789B1 (en) 2000-03-03 2000-03-03 Protection of the water-side surfaces of heat exchangers used in boilers and gas fired water heaters

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE2000628922 DE60028922T2 (en) 2000-03-03 2000-03-03 Surface protection of water surface heat exchangers of boilers and gas water heaters
DE2000628922 DE60028922D1 (en) 2000-03-03 2000-03-03 Surface protection of water surface heat exchangers of boilers and gas water heaters
ES00200746T ES2265862T3 (en) 2000-03-03 2000-03-03 Protection of inner surfaces of the water circuit of heat exchangers used in boilers and gas water heaters.
EP20000200746 EP1129789B1 (en) 2000-03-03 2000-03-03 Protection of the water-side surfaces of heat exchangers used in boilers and gas fired water heaters
CN 01111245 CN1200778C (en) 2000-03-03 2001-03-05 Heat exchanger and method for preventing heating circuit from being scald

Publications (2)

Publication Number Publication Date
EP1129789A1 true true EP1129789A1 (en) 2001-09-05
EP1129789B1 EP1129789B1 (en) 2006-06-21

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Family Applications (1)

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EP20000200746 Active EP1129789B1 (en) 2000-03-03 2000-03-03 Protection of the water-side surfaces of heat exchangers used in boilers and gas fired water heaters

Country Status (4)

Country Link
EP (1) EP1129789B1 (en)
CN (1) CN1200778C (en)
DE (2) DE60028922T2 (en)
ES (1) ES2265862T3 (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082140A (en) * 1972-11-14 1978-04-04 Austral-Erwin Engineering Company Heat exchange method
US4125152A (en) * 1977-09-19 1978-11-14 Borg-Warner Corporation Scale resistant heat transfer surfaces and a method for their preparation
FR2476145A1 (en) * 1980-02-15 1981-08-21 Crans Forges Internally coating roll-bonded heat exchange panel - with thin varnish film to improve-corrosion resistance
GB2084486A (en) * 1980-09-29 1982-04-15 Borg Warner Heat transfer surfaces having scale resistant fluorocarbon polymer coatings thereon
US4344993A (en) * 1980-09-02 1982-08-17 The Dow Chemical Company Perfluorocarbon-polymeric coatings having low critical surface tensions
US4503099A (en) * 1983-06-15 1985-03-05 Borg-Warner Corporation Heat transfer surfaces having scale resistant polymer coatings thereon
US4588643A (en) * 1983-03-18 1986-05-13 The Dow Chemical Company Perfluorocarbon polymeric coatings having low critical surface tensions
JPS61149794A (en) * 1984-12-24 1986-07-08 Nissan Motor Co Ltd Heat exchanger with treatment of inner surface
WO1992016310A1 (en) * 1991-03-25 1992-10-01 Alfa-Laval Thermal Ab Method of providing heat transfer plates with a layer of a surface protecting material
WO1996021836A1 (en) * 1995-01-12 1996-07-18 The Dow Chemical Company Heat exchanger having enhanced heat transfer capability
US5562156A (en) * 1994-02-10 1996-10-08 Ohmiya Corporation Immersion type heat exchanger

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082140A (en) * 1972-11-14 1978-04-04 Austral-Erwin Engineering Company Heat exchange method
US4125152A (en) * 1977-09-19 1978-11-14 Borg-Warner Corporation Scale resistant heat transfer surfaces and a method for their preparation
FR2476145A1 (en) * 1980-02-15 1981-08-21 Crans Forges Internally coating roll-bonded heat exchange panel - with thin varnish film to improve-corrosion resistance
US4344993A (en) * 1980-09-02 1982-08-17 The Dow Chemical Company Perfluorocarbon-polymeric coatings having low critical surface tensions
GB2084486A (en) * 1980-09-29 1982-04-15 Borg Warner Heat transfer surfaces having scale resistant fluorocarbon polymer coatings thereon
US4588643A (en) * 1983-03-18 1986-05-13 The Dow Chemical Company Perfluorocarbon polymeric coatings having low critical surface tensions
US4503099A (en) * 1983-06-15 1985-03-05 Borg-Warner Corporation Heat transfer surfaces having scale resistant polymer coatings thereon
JPS61149794A (en) * 1984-12-24 1986-07-08 Nissan Motor Co Ltd Heat exchanger with treatment of inner surface
WO1992016310A1 (en) * 1991-03-25 1992-10-01 Alfa-Laval Thermal Ab Method of providing heat transfer plates with a layer of a surface protecting material
US5562156A (en) * 1994-02-10 1996-10-08 Ohmiya Corporation Immersion type heat exchanger
WO1996021836A1 (en) * 1995-01-12 1996-07-18 The Dow Chemical Company Heat exchanger having enhanced heat transfer capability

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 010, no. 353 (M - 539) 28 November 1986 (1986-11-28) *

Also Published As

Publication number Publication date Type
CN1348089A (en) 2002-05-08 application
DE60028922D1 (en) 2006-08-03 grant
CN1200778C (en) 2005-05-11 grant
ES2265862T3 (en) 2007-03-01 grant
DE60028922T2 (en) 2007-03-01 grant
EP1129789B1 (en) 2006-06-21 grant

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