EP0565371A2 - Boiler double buffers - Google Patents

Boiler double buffers Download PDF

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Publication number
EP0565371A2
EP0565371A2 EP93302761A EP93302761A EP0565371A2 EP 0565371 A2 EP0565371 A2 EP 0565371A2 EP 93302761 A EP93302761 A EP 93302761A EP 93302761 A EP93302761 A EP 93302761A EP 0565371 A2 EP0565371 A2 EP 0565371A2
Authority
EP
European Patent Office
Prior art keywords
steam
diamine
steam generating
generating system
liquid
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Withdrawn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
EP93302761A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0565371A3 (enrdf_load_stackoverflow
Inventor
Scott Martell Boyette
Anthony Michael Rossi
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.)
BetzDearborn Europe Inc
Original Assignee
Betz Europe 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 Betz Europe Inc filed Critical Betz Europe Inc
Publication of EP0565371A2 publication Critical patent/EP0565371A2/en
Publication of EP0565371A3 publication Critical patent/EP0565371A3/xx
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to methods for controlling metal loss in boiler/condensate steam systems. More particularly, the present invention relates to methods of controlling pH by feeding a single control agent to inhibit corrosion in both the liquid and steam phases of a boiler system.
  • Corrosion in steam generating systems results in damage to piping and equipment as well as the loss of high quality water and energy.
  • the corrosion products and process chemicals if returned to the boiler can contribute to the formation of damaging boiler deposits thereby reducing the overall system reliability and increasing operating and maintenance costs.
  • a second, more often utilized method of controlling carbonate caused corrosion is the addition of volatile amines to neutralize the carbonate and thereby increase the aqueous pH.
  • volatile amines are utilized, but some commonly used materials include cyclohexylamine, morpholine, and methoxypropylamine.
  • the most effective amines are those that possess high basicity and low molecular weight. The high basicity allows attainment of high pH after acid neutralization, and low molecular weight allows a greater molar concentration (and thus more neutralization).
  • the addition of volatile amines neutralizes the acid (H + ) generated by the solution of carbon dioxide in condensate. The amines hydrolyze in water to generate the hydroxide ions required for neutralization.
  • the condensate pH can be elevated to within a desired range (e.g. 8.5 to 9.5).
  • a desired range e.g. 8.5 to 9.5.
  • Numerous amines can be used for condensate pH neutralization and elevation.
  • the selection of the appropriate amine is currently controlled by the basicity, stability and distribution ratio characteristics of the particular amine.
  • Steam generating systems are operated under several different control programs, but the general purpose of all boiler control programs is to minimize corrosion of the metal surfaces. This is accomplished by maintaining the pH within a specific window of operation, a window determined experimentally to fit the particular metallurgy, chemistry, and pressure of the system. In high pressure systems, the feedwater is very pure with little hardness and iron, and little to no organic contaminants.
  • the boiler control methodology is designed to maintain a passive magnetite layer on the iron metallurgy and prevent adverse corrosion reactions at metal surfaces.
  • the solubility of magnetite is very pH dependent, with the minimum in a specific pH range.
  • Boiler corrosion control is designed to operate in this pH window of magnetite solubility and to prevent excessive deposition while maintaining a thin magnetite layer for passivity. This control scheme is designed to maximize the efficiency of heat transfer across the boiler and condensate surfaces. Maintaining a passive magnetite is critical on both the liquid and steam side of steam generating systems. Control agents, either a single component or a mixture of additives, must be able to maintain the pH of both aqueous phases near the magnetite pH minimum. High pressure (above about 14450 kpa, (1500 psig)) steam generating equipment control agents can be categorized into two groups; inorganic and organic. Inorganic agents are typically phosphate or borate-based, while the organic systems are usually amine-based with varying physical properties.
  • Inorganic control agents preserve the boilerwater chemistry in a non-corrosive state and are very effective at preventing problems on the water side of a steam generating system. However, they are of limited effectiveness on the steam side. Typical inorganic control agents must be used in combination with a volatile additive in order to provide pH control in the steam phase. Also, inorganic control agents often form insoluble salts with hardness and iron contaminants resulting in increased deposition. Thus, inorganic control agents are not typically employed on the steam side because of solubility and/or deposition problems.
  • Typical organic control agents can usually be classified as only either highly volatile or less volatile.
  • the highly volatile agents have very short residence times in steam generators and will tend to maintain the pH of the steam phase only.
  • the less volatile amines tend to maintain the pH of the liquid aqueous phase with limited activity in the steam phase.
  • organic additives tend to thermally decompose and form potentially corrosive species such as ammonia and or low molecular weight organic acids. Such decomposition can be caused by high temperatures and has been a matter of concern.
  • the present invention relates to methods of controlling the pH of a steam generating system in which a single amine pH control treatment agent is employed.
  • the amine control agents of the present invention are "double buffers" which help to maintain the pH of both the liquid and steam phases within the system in a preferred range, typically 8.5 to 9.5.
  • the control agents of the present invention also exhibit a strong buffering capacity and do not significantly break down into ammonia within a steam generating system.
  • the control agents of the present invention maintain the pH values of both liquid and vapor (steam) phases in a steam generating system by the addition of a single "double buffer" amine.
  • a method of inhibiting corrosion of metallic surfaces in both the liquid and vapour phases of a steam generating system which comprises providing a steam pH above 8.5, a blow down pH above 8.5, a difference between steam and blow down pH not greater than 1.5 and ammonia levels in the steam and blow down not greater than 0.4 ppm by adding to the aqueous phase of a steam generating system a non-oxygen containing alkylated diamine having at least two carbon atoms between the diamine nitrogen atoms.
  • a method of treating a steam generating system which comprises maintaining the pH of the liquid and vapour phases of a steam generating system within the range of 8.5 to 9.5 and providing ammonia levels in the liquid and vapor phases of not greater than 0.4 ppm by adding a non-oxygen containing alkylated diamine having at least two carbon atoms between the diamine nitrogen atoms.
  • the non-oxygen conforming alkylated diamines with at least two carbons between the diamine nitrogen atoms preferably have the general formula: wherein the R's which may be the same or different are H or alkyl, the R 1 's which may be the same or different are H or alkyl, R and R 1 are not both H and x equals 2 or more and is preferably 2 to 6.
  • Exemplary diamines include:
  • double buffer By means of the present invention there has been discovered a specific class of amines which act as “double buffers" in the treatment of a boiler system.
  • double buffer is meant that the control agents will effectively control pH in both the liquid and steam phases.
  • the control agents were found to provide effective pH buffering to maintain a desirable magnetite layer throughout a boiler system at relatively low treatment concentrations.
  • the control agents maintain a desirable magnetite layer by controlling pH to the range of about 8.5 to 9.5
  • the buffers used in the present invention show a resistance to degradation into ammonia.
  • the effectiveness of representative non-oxygen containing alkylated diamines used in the present invention was evaluated in testing performed in research scale boilers.
  • the research boilers employed in the following example are D-shaped electrically heated stainless steel assemblies with 4000 watt electrical immersion heaters that produce about 9kg/h (19.8 pounds per hour) of steam at a maximum operating pressure of about 14450 kpa (1,500 psig). Operation of the research boilers is described in US-A- 4 288 327.
  • the tests were run at about 10100 kpa (1,450 psig) at 50 cycles for 44 hours with no condensate return. Daily analyses were made of the steam and blowdown (liquid) products.
  • the feedwaterfor the boilers was supplied by a demineralizer train and treated with the control agent alkylated diamine. Hydroquinone at a treatment rate of 0.3 ppm was added to each feedwater tank as an oxygen scavenger. Hydroquinone was selected as the oxygen scavenger due to the need for quantitative testing for ammonia.
  • the control agent being tested was fed at a concentration of 10 ppm in the feedwater tank.
  • the boilers were run for 44 hours to establish equilibrium between the test chemistry and the research boiler. After 44 hours samples were analyzed for ammonia and pH.
  • Table 1 summarizes the results of such testing on a variety of amines and shows the unique effectiveness of the class of amines used in the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP93302761A 1992-04-08 1993-04-07 Boiler double buffers Withdrawn EP0565371A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86541992A 1992-04-08 1992-04-08
US865419 1992-04-08

Publications (2)

Publication Number Publication Date
EP0565371A2 true EP0565371A2 (en) 1993-10-13
EP0565371A3 EP0565371A3 (enrdf_load_stackoverflow) 1994-04-13

Family

ID=25345471

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93302761A Withdrawn EP0565371A2 (en) 1992-04-08 1993-04-07 Boiler double buffers

Country Status (2)

Country Link
EP (1) EP0565371A2 (enrdf_load_stackoverflow)
CA (1) CA2091097A1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1335041A1 (de) * 2002-01-29 2003-08-13 Bayer Aktiengesellschaft Korrosionsschutzmittel zum Schutz von metallischen Werkstoffen in stark alkalischem Medium
CN102910689A (zh) * 2012-11-09 2013-02-06 青海电力科学试验研究院 一种用于防止给水系统腐蚀的加药方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2659693A (en) * 1952-05-10 1953-11-17 Standard Oil Dev Co Process for preventing corrosion of ferrous metals
GB742342A (en) * 1952-10-23 1955-12-21 Rohm & Haas Improvements in or relating to isomerization of diaminobutynes
US3432527A (en) * 1964-11-05 1969-03-11 Armour Ind Chem Co Corrosion inhibitor composition and method
CA1339761C (en) * 1988-07-11 1998-03-24 Anthony M. Rossi Corrosion control composition and method for boiler/condensate stem system
US5091108A (en) * 1991-02-21 1992-02-25 Nalco Chemical Company Method of retarding corrosion of metal surfaces in contact with boiler water systems which corrosion is caused by dissolved oxygen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1335041A1 (de) * 2002-01-29 2003-08-13 Bayer Aktiengesellschaft Korrosionsschutzmittel zum Schutz von metallischen Werkstoffen in stark alkalischem Medium
CN102910689A (zh) * 2012-11-09 2013-02-06 青海电力科学试验研究院 一种用于防止给水系统腐蚀的加药方法

Also Published As

Publication number Publication date
EP0565371A3 (enrdf_load_stackoverflow) 1994-04-13
CA2091097A1 (en) 1993-10-09

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