EP0010390B1

EP0010390B1 - Method and composition for reducing cold-end corrosion

Info

Publication number: EP0010390B1
Application number: EP19790302132
Authority: EP
Inventors: Richard J. Sujdak
Original assignee: Betz Europe Inc
Current assignee: BetzDearborn Europe Inc
Priority date: 1978-10-13
Filing date: 1979-10-08
Publication date: 1982-09-29
Also published as: EP0010390A1; CA1113236A; DE2963783D1

Description

As is well known to boiler operators, sulfur-containing fuels present problems not only from a pollutional point of view, but also with respect to the life and operability of metallic equipment and parts which are in contact with the flue gases containing the sulfur by-products of combustion. While the problem will be discussed herein with respect to boilers, it should be understood that both the problem and its solution could apply to other systems, such as process furnaces.
Upon combustion, the sulfur in the fuel is converted to sulfur dioxide and sulfur trioxide. In the flue gas, sulfur trioxide and water vapor are in equilibrium with sulfuric acid. Below about 232°C. essentially all of the S0₃ is converted to H_ZS0₄ 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.
As can be appreciated, the greater the sulfur content of the fuel, the more sulfuric acid will likely be produced. This is particularly the case in industrial and utility operations where low grade oils are used for combustion purposes.
In United States Patent Specification No. 2,972,861 there is disclosed a method of reducing combustion gas acid corrosion of metals in a combustion system, which comprises introducing at least one liquid tertiary amine into the combustion gases prior to contact of the combustion gases with the metais.
In 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. Further, 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.
In larger boiler systems, 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. While 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. For example, 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.
The term "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:
Also for example, a higher homolog in the series would be tetraethylenepentamine having the structure:
In terms of a general formula, ethylene polyamines according to the present invention could best be described by the following:
Since ethylene diamine is the lowest homolog in the series, the lower limit for 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. In any event, 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.
Except for high molecular weight species which are highly viscous, 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.
There are numerous well known methods available to the artisan for feeding the additive to the combustion gases. For example, the additive may be added in droplet form, it may be added in aqueous form, it may be sprayed into the combustion gases. In one embodiment 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). However, 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. Thus, 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. With respect to the ethylene polyamine, whether used above or together with an alkanolamine the particular species is also seen to be an important consideration with respect to feedrate. For example, for a fuel oil containing 1 % sulfur, 3.2x10^-4 mole of triethylenetetramine per liter (mol/I) of fuel oil consumed has proven to be efficacious; while only 2.5x 10-e mole of high molecular weight poly(ethylenimine) per liter of fuel oil consumed (mol/I) was required to do the job. It is the inventors' opinion that the upper limit would depend only on economic considerations. Accordingly, for fuel oil containing 1% sulfur (weight basis), 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. Based on economic considerations, 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. Accordingly, 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.
The drawings (Figs. 1 to 6) accompanying the present application, which illustrate the invention are all graphs drawing the degree of corrosion using various materials at various conditions.

Examples

Example 1

In order to assess the efficacy of the materials of the invention, various tests were conducted using a D-type boiler manufactured by Keeler. The boiler is rated at 11,800 kg of steam per hour and is normally operated at 1330 kPa pressure.
Since the primary function of a cold-end additive is to eliminate or reduce corrosion caused by the condensation of sulfuric acid, techniques that measure corrosion were expected to yield the most direct information about product performance. Accordingly, the well known method of quantifying the reduction in corrosion of a stainless steel air-cooled probe was used for determining efficacy as cold-end additives. The probe used was similar to a standard British Central Electricity Research Laboratories (CERL) acid deposition probe. The construction and operation of this probe are well known in the art as evidenced by an article entitled "An Air-Cooled Probe for Measuring Acid Deposition in Boiler Flue Gases" by P. A. Alexander, R. S. Fielder, P. J. Jackson and E. Raask, page 31, Volume 38, Journal of the Institute of Fuel; which article is hereby incorporated by reference to indicate the state of the art. Flue gas constituents were allowed to condense on the probe for 45 minutes. The probe was then immediately washed with doubly distilled water and analyzed for iron and sufate. Corrosion was measured by analyzing the probe washings for water soluble iron, which is also a well known technique.
Since 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.
Immediately before base loading, 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 S0₃ 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 10³ liters of fuel oil consumed (mol/10³l, 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.
As can be seen from Table 1, the ethylene polyamines tested were quite effective in reducing the corrosion of the test probe. On the other hand, ethylamine tested, which is known as a neutralizing agent for SO_x gases in wet scrubbers, was ineffective. It was, accordingly, the present inventor's conclusion that the ethylene polyamines are effective cold-end additives while ethylamine is not.
The accompanying drawings are graphic representations of test results comparing various ethylene polyamines, as indicated below, to base conditions.
In 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. During the test period, 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).
As can be seen from Figure 1, the ethylene polyamines did indeed significantly reduce corrosion as compared to base conditions.
In 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. 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 °C. The results for base conditions are represented by solid circles, the results for ethylene diamine are represented by solid squares, and the results for poly(ethylenimine) are represented by solid triangles. During the test period 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.
As can be seen from Figure 2, the ethylene polyamines did indeed significantly reduce corrosion as compared to base conditions.

Example 2 (Comparative)

In order to assess the efficacy of the alkanolamines, tests were conducted using the D-type boiler described in Example 1 above.
The well known method of quantifying the reduction in corrosion of the above-described air-cooled probe was again used for determining efficacy as cold-end additives. Flue gas constituents were allowed to condense on the probe for 45 minutes. The probe was then immediately washed with double distilled water and analyzed for iron and sulfate. Corrosion was measured by analyzing the probe washings for water soluble iron.
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.
Immediately before base loading, the boiler was taken through a soot blowing cycle, and the burner tip was manually cfeaned. The boiler was then base loaded for one hour. Fuel oil of precisely the same composition must be 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 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. Using a Research Appliance Corporation sampling device, the concentration of S0₃ 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 results of a first series of tests are reported below in Table 2, wherein a different test number indicates that tests were conducted on a different day.
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).
As can be seen from the results reported in Table 2, a variety of alkanolamines demonstrated cold-end additive efficacy.
The results of a second series of tests are reported below in Table 3, wherein a different test number indicates that tests were conducted on a different day. The additive feedrates are reported as mole per 1000 litres of oil consumed (mol/l O³l), and the corrosion results are reported as % reduction in iron content of the probe washings for the indicated temperatures. These test results are seen to demonstrate the ability of the alkanolamines tested to reduce cold-end corrosion.
Having thus established the efficacy, individually, of ethylene polyamine and aliphatic, water-soluble alkanolamine as cold-end additives, the efficacy of combined treatments were evaluated in a further series of tests. Indeed, it is considered highly desirable to be able to combine the individual additives on an optimized uost basis. Furthermore, depending on the particular problem to be treated, it may be desirable to combine the additives to take advantage of the respective strengths of each and/or to possibly supplement the relative weaknesses of each.
The results of this further series of tests are reported in the accompanying drawings which contain graphic representations comparing various combinations of the ethylene polyamine and alkanolamine to base conditions. The materials tested were monoethanolamine (MEA), obtained from Fisher, and triethylenetetramine (TETA), obtained from both Fisher and Aldrich.

Example 3

Using the same testing procedures as described in Example 2 above, the efficacy of the combined treatment was evaluated. The results of these tests are reported in Figures 3 and 4 as plots of concentration of iron in the probe washings, in ppm against sampling temperature, °C. These tests results are to be interpreted according to the following legend presented in Table 4 below.

Example 4

The efficacy of various combined treatments was evaluated in tests using a boiler at a well-known oil refinery. The test procedures were generally the same as described in Example 2 above. The boiler was manufactured by Riley. During the tests, the boiler produced between 57,600 and 70,300 kilograms of steam per hour, and it was baseloaded during each experiment. The generated steam was near 371 °C at 4100 kPa pressure. Flue gas temperatures at the location of the corrosion probe ranged from 363°C to 382°C. The materials tested were MEA, and TETA, both obtained from Union Carbide. The results of these tests are reported in Figures 5 and 6 as plots of concentration of iron in the probe washings, in ppm, against sampling temperature (°C). For Figure 5, the sulfur content of the fuel oil was 0.69%, and for Figure 6, it was 0.43%. These tests results are to be interpreted according to the following legend presented in Table 5 below:

Based on the results reported above in Tables 1-3 and Figures 1 and 2, which results are seen to demonstrate the efficacy, individually, of aliphatic, water-soluble alkanolamine and ethylene polyamine, and the results reported in Figures 3-6, a treatment composition comprising these materials in combination is seen to have efficacy as a cold-end additive. From Figure 3 it can be seen that the product represented by the open triangle was more effective than either constituent alone. The mole ratio of the alkanolamine to ethylene polyamine for that product was about 2.3 to 1.

In addition to the efficacy as a cold-end additive, preliminary evidence has indicated that reduction for fouling on cold-end surfaces may be an added benefit of using the described materials.

Claims

1. A method of reducing the amount of sulfuric acid corrosion of metal parts at the cold-end of a combustion system and In contact with combustion gases derived from the combustion of sulfur containing fuel by adding to the combustion gases an effective amount for the purpose of an additive comprising ethylene polyamine of the general formula

wherein n is 0 or an integer.

2. A method as claimed in claim 1, wherein the combustion system is a steam generating system and the fuel is sulfur-containing oil.

3. A method as claimed in claim 1 or 2, wherein said additive is an aqueous solution of ethylene polyamine which is added to said combustion gases at the rate of from 6.3 x 10-⁴ to 6.3 mole per 10' I of fuel consumed.

4. A method as claimed in claim 1 or 2, wherein said combustion gases flow along a path at the cold-end of the combustion system from a first zone of relative turbulence to a second zone at which said metal parts are located, wherein said additive comprises in combination:

(i) aliphatic, water-soluble alkanolamine, and

(ii) at least one member of the group consisting of ethylene polyamines of the formula given in claim 1

and wherein said additive travels along with said combustion gases as vapor and/or liquid droplets from said zone of relative turbulence to said second zone and deposit on said metal parts.

5. A method as claimed in claim 4, wherein said ethylene polyamine is added in an amount of from 2.5 x 10^-3 to 6.0 moles per 10³ I of Fuel consumed, and wherein said alkanolamine is added in an amount of from 0.32 to 6.3 mole per 10³ I of fuel consumed.

6. A method as claimed in claim 5, wherein the total amount of additive does not exceed 6.9 mole per 10³ I of fuel consumed.

7. A method as claimed in any of claims 4 to 6, wherein said ethylene polyamine is triethylenetetramine in the amount of 0.41 mole per 10³ I of fuel consumed, and wherein said alkanolamine monoethanolamine in the amount of 0.96 mole per 10³ I of fuel consumed.

8. A cold-end additive composition for reducing the amount of sulfuric acid corrosion of metal parts at the cold-end of a combustion system in contact with combustion gases derived from the combustion of sulfur-containing fuel, said composition comprising in combination:

(i) aliphatic, water-soluble alkanolamine, and

(ii) ethylene polyamine of the formula defined in claim 1.

9. A composition as claimed in claim 8, wherein the alkanolamine is monoethanolamine.

10. A composition as claimed in claim 8 or 9, wherein the ethylene polyamine is triethylenetetramine.

11. A composition as claimed in. claim 10, wherein the mole ratio of monoethanolamine to triethylenetetramine is about 2.3 to 1.