EP0010390B1 - Procédé et composition pour la réduction de la corrosion aux parties froides - Google Patents
Procédé et composition pour la réduction de la corrosion aux parties froides Download PDFInfo
- Publication number
- EP0010390B1 EP0010390B1 EP19790302132 EP79302132A EP0010390B1 EP 0010390 B1 EP0010390 B1 EP 0010390B1 EP 19790302132 EP19790302132 EP 19790302132 EP 79302132 A EP79302132 A EP 79302132A EP 0010390 B1 EP0010390 B1 EP 0010390B1
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- EP
- European Patent Office
- Prior art keywords
- additive
- combustion
- amount
- combustion gases
- cold
- 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.)
- Expired
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Classifications
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- 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
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
Definitions
- the sulfur in the fuel is converted to sulfur dioxide and sulfur trioxide.
- sulfur trioxide and water vapor are in equilibrium with sulfuric acid. Below about 232°C. essentially all of the S0 3 is converted to H Z S0 4 for typical flue gas compositions of oil fired boilers.
- the resulting sulfuric acid condenses upon metal surfaces which are at temperatures below the acid dewpoint. Corrosion results from the attack of the condensed sulfuric acid on the metals.
- United States Patent Specification No. 2,053,024 there is disclosed a method of conditioning steam systems to prevent corrosion of the metal parts, which comprises introducing into the system an alkaline, water-soluble, volatile, non-aromatic amine.
- United Kingdom Patent Specification No. 1,338,908 discloses a method of preventing the corrosion'of a distillation apparatus producing an acid substance, which comprises controlling the pH of the finally condensed liquid to be in the range of 7-8 by adding at least one alkaline component selected from ethylene diamine, trimethylenediamine. propylene diamine and piperazine to the acid substance within the apparatus.
- the basic area to which the present invention is directed is often referred to in the industry as the "cold-end" of a boiler. This area is generally the path in the boiler system that the combustion gases follow after the gases have, in fact, performed their primary service of producing and/or super-heating steam.
- the last stages through which the hot combustion gases flow include the economizer, the air heater, the collection equipment or electrostatic precipitator, and then the stack through which the gases are discharged.
- the present invention is drawn to the present inventor's discovery of ethylene polyamines optionally in combination with aliphatic, water-soluble alkanolamines, as cold-end additives. It was determined that if this additive is fed, preferably in droplet form, and preferably as an aqueous solution, to the moving combustion gases upstream of the cold-end surfaces to be treated and preferably at a point where the gases are undergoing turbulence, it will travel along with the gases as vapor and/or liquid droplets and deposit on the downstream cold-end surfaces. It is understood that any reference to ethylene polyamine is intended to include mixtures of such compounds and any reference to alkanolamine is intended to include mixtures thereof.
- a point of turbulence of the combustion gases is a preferred feed point for the additive
- a point of laminar gas flow could also be used, provided that suitable mechanical means are utilized to create a zone of relative turbulence for proper treatment distribution.
- suitable mechanical means are utilized to create a zone of relative turbulence for proper treatment distribution.
- an increased number of spray nozzles may be suitably arranged within a gas flow conduit to provide adequate treatment distribution.
- the invention in addition to providing a method of reducing the amount of sulfuric acid corrosion of metal parts at the cold-end of a combustion system also provides a composition for such use which comprises (i) aliphatic, water-soluble alkanolamine, and (ii) ethylene polyamine.
- ethylene polyamines is intended to include hydrocarbon chains consisting of at least two amino groups connected by ethylene group(s). For example, the lowest homolog in the series would be ethylene diamine having the following structure:
- ethylene polyamines according to the present invention could best be described by the following:
- n is 0. It is the present inventor opinion that there is no upper limit for n in Formula I other than that based on the commercial availability of the material.
- the highest homolog tested was poly(ethylenimine) having the formula: which material had an average molecular weight of about 50,000 to 100,000; and, therefore, n was about 1000 to 2500. While all of the compounds tested had ethylene groups connecting the amino groups, it is believed that other lower alkyl interconnecting groups could be used. For example, it is the present inventor's belief that trimethylene or tetramethylene groups are suitable equivalents for the ethylene group. However, preliminary testing has indicated the hexamethylene interconnecting groups are unsuitable for the purpose.
- the additive can be fed neat; however, an aqueous solution of additive is preferred. Due to its high solubility in water, the concentration of actives in the aqueous solution could, of course, vary over a wide range, depending only on economics of handling and shipment and the characteristics of the feed system. For example, the additive could be shipped neat and diluted at the point of application. If dilution at the point of application is undesirable or not possible, then the additive would be sent pre-diluted. Due to costs of shipment and handling, it would be undesirable to ship very dilute aqueous solutions. The preferred lower concentration limit would be about 5% actives on a weight basis, with the most preferred lower limit being about 15%. The upper concentration limit could approach 100%, however, about 60% represents the preferred upper limit.
- the additive is preferably added to the combustion gases upstream, in the direction of flow of the combustion gases through the combustion system, of the metal parts, and may be added to the combustion gases at a point of turbulence or at a point of laminar flow.
- the additive may be added in droplet form, it may be added in aqueous form, it may be sprayed into the combustion gases.
- the additive could be sprayed at a point of turbulence of the combustion gases upstream of the problem area using any well known atomizing spray nozzle(s).
- precautions should be taken to ensure that the problem areas will encounter treated flue gas. For instance, if the problem area is located centrally within a flow conduit for the combustion gases, the spray should be directed into the conduit in such a manner as to ensure that a sufficient amount of additive is present in the centre of the conduit upon reaching the location of the problem area.
- an axially located spray nozzle which sprays the additive in the same direction that the combustion gases flow would be recommended for such a centrally located problem area. While the additive could be fed neat an aqueous solution is preferred.
- the amount of additive used could vary over a wide range depending on the nature and severity of the problem to be solved and would be a function of the sulfur content of the oil.
- the particular species is also seen to be an important consideration with respect to feedrate.
- mol/I triethylenetetramine per liter
- the upper limit would be considered to be 6.3x10 -3 mol/I based on economic considerations, with 3.2 10 -3 mol/I representing a preferred upper limit.
- the active alkanolamine could be fed in an amount as low as 3.2x10 -4 mol/I.
- the preferred lower limit is 6.3x10 -4 mol/I.
- the amount of active alkanolamine could be as high as 6.3x10- 3 mol/I, with 4.7x10 -3 mol/I representing the preferred upper limit.
- the inventive additive is considered to comprise from 2.5 x10 -6 to 6.0x10 -3 mol/I of ethylene polyamine and from 3.2x10 -4 to 6.3 ⁇ 10 -3 mol/I of alkanolamine.
- the preferred relative proportions are from 6.3 to 10 -4 to 3.2x10 -3 mol/I ethylene polyamine and from 6.3x10 -4 to 4.7x10 -3 mol/I alkanolamine. Based on economic considerations, the total amount of active additive should not exceed 6.9x 10 -3 mol/I.
- the temperature of the combustion gases at the point of feed is typically 204°C to 399°C, but this range could widen depending on the gas temperature at the furnace exit.
- a cold-end additive should be capable of travelling along with the combustion gases and depositing on the downstream cold-end surfaces to be treated, the various additives tested were sprayed, using a standard atomizing spray nozzle arrangement, into the combustion gases at a point of turbulence located upstream of the air-cooled probe.
- the boiler was taken through a soot blowing cycle, and the burner tip was manually cleaned. The boiler was then base loaded for one hour prior to initiating testing. Fuel oil of precisely the same composition was fired over a given period of time to ensure reproducibility of baseline data throughout the period. However, for critical testing, daily determination of baseline data is recommended.
- the boiler was fired with number 6 grade fuel oil containing 1% sulfur (by weight). The oil was preheated to 76.7°C and atomized with steam. Combustion air was at ambient temperature. Flue gas temperatures at the sampling point ranged from 227°C to 249°C.
- the sulfuric acid dewpoint using either a Land Dewpoint Meter or a corrosion probe was typically 128°C. Using a Research Appliance Corporation sampling device, the concentration of S0 3 was determined to be above 7 parts per million parts of combustion gas (ppm, on volume basis).
- the materials tested were ethylene diamine, available from Union Carbide; diethylenetriamine, obtained from Fisher; triethylenetetramine, obtained from Aldrich; tetraethylenepentamine, obtained from Aldrich; poly (ethylenimine), also obtained from Aldrich, and ethylamine, obtained from Pennwalt.
- the results of a series of tests are reported below in Table 1, wherein a different test number indicates that tests were conducted on a different day.
- the % O2 reported is the oxygen content of the combustion gas on a volume basis.
- the additive feedrates are reported as mole(s) of feed per 10 3 liters of fuel oil consumed (mol/10 3 l, and the probe corrosion results are reported as % reduction in iron content of the probe washings for the indicated temperatures as compared to base condition corrosion.
- Figure 1 are reported the results of tests comparing diethylenetriamine and triethylenetetramine to base conditions. As can be seen from the figure, the results are graphically reported as a plot of concentration of iron in the probe washings, in ppm, against the sampling temperature in °C. The results for base conditions are represented by circles, the results for diethylenetriamine are represented by squares, and the results for triethylenetetramine are represented by triangles.
- the boiler was operated at approximately 6,350 kg of steam per hour with oxygen being 6% of the flue gas.
- the additives were both fed at a rate of 2.1x10 -3 mole per liter of oil consumed (2.1 x 10 -3 mol/I).
- Figure 2 are reported the results of tests comparing ethylene diamine and poly(ethylenimine) to base conditions.
- the poly(ethylenimine) has a molecular weight average of about 50,000 to 100,000 such that n in Formula I above would be about 1000 to 2500.
- the results are graphically reported as a plot of concentration of iron in the probe washings, in ppm, against the sampling temperature °C.
- the results for base conditions are represented by solid circles
- the results for ethylene diamine are represented by solid squares
- the results for poly(ethylenimine) are represented by solid triangles.
- the boiler was operated at approximately 5,450-5,900 kg of steam per hour with oxygen being about 6% of the flue gas.
- the ethylene diamine was fed at a rate of 2.4x 10- 3 mol/I of fuel oil consumed, and the poly(ethylenimine) was fed at a rate of 0.23 milliliters per liter of oil consumed. Due to the uncertainty of the exact molecular weight of the poly-(ethylenimine), no exact molar feedrate was calculable. However, based on the noted molecular weight range for the material and a density of approximately 1 gram per milliliter, the feedrate was about 2.5 10 -6 to 4.4 x 10 -e mol/I.
- the various additives tested were sprayed, using a standard atomizing spray nozzle arrangement, into the combustion gases at a point of turbulence located upstream of the air-cooled probe.
- the boiler was fired with number 6 grade fuel oil containing 1% sulfur (by weight).
- the oil was preheated to 77°C and atomized with steam. Combustion air was at ambient temperature. Flue gas temperatures at the sampling point ranged from 227°C to 249°C.
- the sulfuric acid dew point using either a Land Dew Point meter or a corrosion probe was typically 128°C.
- concentration of S0 3 was determined to be about 7 parts per million parts of combustion gas (ppm, on volume basis).
- the oxygen content of the flue gas was kept at about 6%.
- the materials tested were monoethanolamine, obtained from Fisher; 2-(ethylamino)ethanol, obtained from Fisher; 3-amino-1-propanol, obtained form Eastman; 2-amino-2-methyl-1-1 propanol, obtained from iMC; 2-dibutyl-amino-ethanol, obtained from Eastman; 2-amino-2-ethyl-1,3-propanediol, obtained from Aldrich; 1-amino-2-propanol, obtained from Eastman; triethanolamine. obtained from Eastman; and diisopropanolamine, obtained from Dow.
- the additive feedrates are reported as mole(s) of additive per liter of oil consumed (mol/l,) and the probe corrosion results are reported as 96 reduction in iron content of the probe washings for the indicated temperatures as compared to base condition corrosion. Negative results indicate a condition of increased corrosion of the probe as compared to base conditions.
- the steam loads are reported as kilograms per hour (kg/h).
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- 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)
- Solid Fuels And Fuel-Associated Substances (AREA)
Claims (12)
et cet additif circule à l'état de vapeur et/ou de gouttelettes liquides avec les gaz de combustion, de la zone d'une turbulence relative à la seconde zone où il se dépose sur les parties métalliques.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US950960 | 1978-10-13 | ||
US05/950,960 US4185071A (en) | 1978-10-13 | 1978-10-13 | Ethylene polyamines as cold-end additives |
US1968679A | 1979-03-12 | 1979-03-12 | |
US06/019,687 US4206172A (en) | 1978-10-13 | 1979-03-12 | Alkanolamines and ethylene polyamines as cold-end additives |
US19687 | 1979-03-12 | ||
US19686 | 1979-03-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0010390A1 EP0010390A1 (fr) | 1980-04-30 |
EP0010390B1 true EP0010390B1 (fr) | 1982-09-29 |
Family
ID=27361268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19790302132 Expired EP0010390B1 (fr) | 1978-10-13 | 1979-10-08 | Procédé et composition pour la réduction de la corrosion aux parties froides |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0010390B1 (fr) |
CA (1) | CA1113236A (fr) |
DE (1) | DE2963783D1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103614727B (zh) * | 2013-11-28 | 2015-12-09 | 阜阳安固锅炉压力容器制造有限公司 | 一种水基金属表面防锈液及其制备方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2053024A (en) * | 1934-02-16 | 1936-09-01 | Western Chemical Company | Compound and method for conditioning boiler, steam and condensate systems |
US2750339A (en) * | 1953-04-03 | 1956-06-12 | Exxon Research Engineering Co | Method for inhibiting corrosion |
US2972681A (en) * | 1956-08-10 | 1961-02-21 | Westinghouse Electric Corp | Cinefluorographic apparatus |
NL262711A (fr) * | 1960-03-23 | |||
US3406042A (en) * | 1965-12-14 | 1968-10-15 | Cons Edison Co New York Inc | Process for corrosion control |
GB1338908A (en) * | 1969-12-08 | 1973-11-28 | Kurita Water Ind Ltd | Method of preventing corrosion in distillation apparatus substituent |
US4134727A (en) * | 1976-08-12 | 1979-01-16 | Betz Laboratories, Inc. | Aqueous solution of sodium metasilicate and N-aminoethyl ethanolamine as a cold-end additive |
-
1979
- 1979-09-13 CA CA335,548A patent/CA1113236A/fr not_active Expired
- 1979-10-08 DE DE7979302132T patent/DE2963783D1/de not_active Expired
- 1979-10-08 EP EP19790302132 patent/EP0010390B1/fr not_active Expired
Also Published As
Publication number | Publication date |
---|---|
EP0010390A1 (fr) | 1980-04-30 |
CA1113236A (fr) | 1981-12-01 |
DE2963783D1 (en) | 1982-11-11 |
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