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damage in Waste Heat ; Major root causes and remediation

The crucial factor determining damages of high-pressure waste heat boilers in plants are of the tube surface with (Fe3O4) in combination with exceptionally high local heat fluxes.

The main reasons for the magnetite fouling are (i) Flow Accelerated Corrosion (FAC) in the preboiler / feed system (ii) First Condensate Corrosion (FCC) in steam and condensate equipment (iii) Ineffective chemical cleaning and conditioning programs for the boilers

The main goal of treatment programs should be to keep the boiler heat transfer surface free from deposits. Conventional chemical treatment programs are not always successful. Polyamine treatment can offer an alternative approach.

Harrie Duisters, Jo Savelkoul DSM Agro, 6160 MG Geleen, The Netherlands

Introduction. tant to understand and prevent corrosion damage of these boilers. ocated at Geleen in The Netherlands, DSM Agro operates two ammonia plants, each This paper describes: with a nameplate capacity of 1360 mtpd of L - mechanism of magnetite (Fe3O4) formation in the ammonia. One plant (AFA-2) was designed and con- plants boiler water system via various corrosion proc- structed by Bechtel; the plant was commissioned in esses like flow-accelerated corrosion and first conden- 1971. The other plant (AFA-3) was designed and con- sate corrosion structed by M.W. Kellogg based on Kellogg's reduced - fouling of boiler tubes by precipitation of this mag- energy ammonia ; the plant was commis- netite preferentially at places with high heat fluxes sioned in July 1984. Current capacity of both plants is - remediation methods to prevent fouling and prevent 1500 mtpd. boiler tube failures

In DSM’s ammonia plants, like in all other ammonia plants, the waste heat boilers are an important part of the process that can have a big on energy effi- ciency and reliability of the plant. Therefore it is impor- Description of the Waste Heat Boilers bundle a cylindrically shaped cone is installed to mix the hot gas passing through the by-pass tube with the DSM’s AFA-2 ammonia plant has a conventional colder gas leaving the tubes before the gas is sent to the design. The hot reformed gas leaving the secondary re- . The tube material is 13CrMo44 (1Cr- former passes through a boiler whereby the gas is 0.5Mo Steel, ASME Specification SA-387, Grade 11, cooled to the required inlet of the high tem- Class 2). The inlet and outlet section and the hot tube perature shift converter. The boiler consists of two tube sheet are refractory lined. The tubes have ferrules at the bundles in series, placed in a common shell, see Figure inlet made of Alloy 800H. To protect the refractory of 1. The second tube bundle has an external gas by-pass the hot tube sheet, the refractory is covered with an Al- to control the inlet temperature of the high temperature loy 800H liner. The cone at the outlet and the internal shift converter. The boiler produces 68 bar (970 psi) bypass valve are constructed in Alloy 800H material. steam.

The first section of the boiler has 500 tubes, the second section 829 tubes. The tube material is 15Mo3 (l/4Mo-steel, ASME Specification SA-204). The boiler shell is constructed of 19Mn5 (C-Mn steel, ASME SA- 299). The inlet section, the inlet tube-sheet, the section between both tube bundles and the outlet dome are all refractory lined. There is only a small shroud installed at the point where the by-pass line branches off from the section between both tube bundles. The shroud ma- terial is SS 316Ti. Tubes in the hot section are equipped with Alloy 800H ferrules at the tube inlet.

Figure 2: AFA-3 WHB lay-out

Although Kellogg has designed the plant, the boil- ers are not the conventional Kellogg design used in other units. DSM selected boilers with thin tubesheets and a reinforcing structure behind the tubesheets. Tubes have been welded to the tubesheet by internal bore welding. HP-steam (125 bar, 1785 psi) is generated in three boilers, downstream of: - the secondary reformer - the high temperature shift converter - the ammonia converter. Figure 1: AFA-2 WHB lay-out All three boilers have natural circulation of water and are connected to one common .

In the AFA-3 ammonia plant hot gas from the secon- Both AFA-2 and AFA-3 have horizontal boilers dary reformer passes through a boiler where 125 bar with the hot gas going through the tubes. In this way (1785 psi) steam is produced. Then the gas passes any fouling in the boiler will drop down to the bottom through two steam superheaters arranged in series be- of the shell side where it can be removed by a blow- fore the gas enters the high temperature shift converter. down operation. A lay-out of the boiler is shown in Figure 2. The boiler tube bundle with 300 tubes has an internal by-pass tube In the past 50 years, WHB corrosion damage fre- provided with a control valve at the outlet to control the quently has been discussed at the Ammonia Safety outlet gas temperature of the boiler and, with that, the Symposiums. Also DSM plants have had their share of amount of steam produced. At the exit side of the tube serious boiler problems and costly damages.

Iron are released from the steel lattice into the water. They hydrolyze to magnetite, which, because of Corrosion and fouling basics in WHBs its poor/low forms a porous, relatively loose outer layer on the steel surface. Typically, corrosion damage in WHBs is limited to

a restricted area with the vast majority of boiler metal Moreover, ions diffuse into the steel lattice surface still intact. Therefore, corrosion phenomena in and react with iron to magnetite that forms a tight, boilers can generally not be explained on the basis of strongly adherent inner layer. In fact, the latter is the bulk conditions like pressure, temperature and boiler truly protective layer that slows down corrosion reac- . tions to an acceptable level. Measuring the hydrogen

gas concentration in steam provides an indication for Most WHBs are constructed out of carbon steel. completion of the magnetite formation process: in a This low-cost material is applicable in steam systems new boiler with clean steel surfaces it takes about 50 by virtue of its capacity to form a protective magnetite, hours. Fe O , layer on its surface. In essence, magnetite forma- 3 4 tion is the corrosion reaction of steel with water liberat- In recirculating boiler water the upper porous mag- ing hydrogen gas: netite layer is sensitive to erosion. It is continuously

→ flushed away from the surface and transported from tur- Step 1: 3 Fe + 6 H2O 3 Fe (OH)2 + 3 H2 bulent zones to less turbulent areas. There, it settles as the inevitable grayish black boiler sediment. → Step 2: 3 Fe (OH)2 Fe3O4 + 2 H2O + H2

Overall: 3 Fe + 4 H2O → Fe3O4 + 4 H2

The above reaction stoichiometry does not reveal that the protective layer is comprised of two dis- tinct magnetite phases, see Figure 3 [ref. 1]. Iron transport and magnetite formation due to Flow Accelerated Corrosion (FAC) Porous Loose Fe3O4 layer in the feed water system

At the relatively low (<200 °C , <392 Tight Fe3O4 layer °F) in the pre-boiler system, the formation of a protec- Original steel tive magnetite layer (Step 2) is not instantaneous and it surface is therefore sensitive to Flow Accelerated Corrosion (FAC). In FAC, also referred to as Erosion-Corrosion, Current steel surface the intermediate Fe(OH)2 (Step 1) is flushed away from the surface before it is converted to magnetite. The iron contained in the feed water ultimately contributes to boiler sediment in the boiler. In fact, FAC is one of the important causes of iron transport towards the boilers. Solid Carbon Steel

As shown in Figure 4, FAC depends on flow veloc- ity, temperature (Figure 4a), pH and oxygen concentra- Figure 3: Microscopic picture of carbon steel tion (Figure 4b) [ref. 2]. covered with two distinct magnetite phases; a solid protective inner layer and a po- rous loose outer layer From the past it was recognized that oxygen in boiler feed water can cause oxygen corrosion in the boiler water. The use of oxygen scavengers to inhibit this oxygen corrosion leads to reducing conditions and leads as shown in Figure 4b, to an increase of FAC in 10 the boiler feed water system. In modern WHBs reduc- mm/a ing conditions in the boiler feed water should be

1 avoided. An effective thermal degassing down to ap- proximately 10 ppb oxygen is sufficient.

0.1 P = 40 bar P = 40 bar T = 180 °C V = 35 m/s pH = 7 pH = 7 ≤ µ ≤ µ O2 5 g/kg O2 5 g/kg t = 200h t = 200h 0.01 Mild steel coupon Mild steel coupon Iron transport and magnetite formation containing 0.3% Mo containing 0.3% Mo due to First Condensate Corrosion (FCC)

Wall reduction thickness 0.001 in steam condensate lines 0 10 20 30m/sec 50 050100150 °C 250 Flow Temperature Saturated steam together with volatile impurities and conditioning chemicals from the boiler are trans- Figure 4a: The effect of flow velocity and tem- ported through the steam superheaters. The exit steam perature on Flow Accelerated Corrosion (FAC) from the superheaters is dry.

10

mm/a

1

0.1 P = 40 bar P = 40 bar T = 180 °C T = 120 °C w = 39 m/s w = 35 m/s O ≤ 5 µg/kg pH = 7 0.01 2 t = 200 - 400h t = 200h Mild steel coupon Mild steel coupon containing 0.3% Mo containing 0.3% Mo

0.001 Wall thickness reduction thickness Wall 678910 110 100 200 300µg/kg 500 pH Oxygen concentration

Figure 4b: The effect of pH and oxygen concen- tration on Flow Accelerated Corrosion (FAC) Figure 5: Picture of First Condensate Corrosion in a

Water flow velocity, temperature and alloying ele- Upon cooling in turbines and condensers, acidic ments are design parameters. The pH and oxygen con- impurities such as carbonic and short-chain fatty tent depend on the boiler feed regime. will preferentially and successively dissolve into So-called high-All-Volatile-Treatment (AVT), with a the first condensate droplets prior to alkalis like ammo- boiler feed water pH of up to 9.8 may be employed to nia and . Carbon steel is susceptible to localized minimize FAC. An important disadvantage of high- acid attack by these first condensate droplets. This so AVT is the elevated of the steam condensate called First Condensate Corrosion (FCC) again is a resulting in high cation loads to the cation exchangers source of iron oxide fouling of boilers when condensate in the condensate polishing section of the plant. is reused without proper polishing.

The root cause: fouling of heat transfer that non-volatile corrosive impurities in the boiler water surfaces due to precipitation of may concentrate strongly under porous magnetite. The magnetite concentration factor depends on the thickness of the po- rous layer and the local heat flux. Figure 6 [ref. 5] “External” magnetite originating from FAC and shows the concentration factor as a function of the heat FCC or “internal” transported inside the boiler does no flux and the thickness of the magnetite layer. harm when deposited in areas with low heat fluxes, such as the bottom of a steam drum. However, the situation becomes dangerous when magnetite settles on heat transfer surfaces like the tubes of a WHB: the iron oxide particles form a porous layer and act as an insu- lating barrier that hinders heat transfer resulting in ris- ing metal temperatures.

Magnetite predominantly settles on heat transfer surfaces. Because of the intensive contact with the mag- netite covered metal surface, the recirculating boiler water is saturated with magnetite. At the onset of steam generation the remaining boiler water becomes super- saturated and magnetite is precipitated. The higher the heat flux, the more steam is generated and the more Figure 6: The concentration factor of the boiler magnetite is deposited. water as function of the heat flux and the thick- ness of the magnetite layer Design parameters of WHBs are largely determined by the process conditions, simply because steam gen- eration is not the primary goal of a chemical plant. For In high heat flux boilers with localized heat fluxes instance, a WHB may have to satisfy the requirement of of up to >800 kW/m2, relative thick magnetite layers rapid process fluid cooling in order to arrest unwanted are formed. As shown in Figure 6 concentration factors secondary reactions. In terms of WHB design, this re- in the order of one million can be reached under such quirement translates to a compact design with locally circumstances. This means that the concentration of very high heat fluxes. Also WHBs have a large impact non-volatile impurities in the porous iron oxide layer on the investment costs of a new plant and therefore may be one million times higher than their correspond- process licensors aim at reducing size and investment ing concentrations in the bulk of the boiler water. costs of the WHBs. Unfortunately, in many WHB de- Hence, in case of acidic boiler water contaminants such signs the highest heat flux area in the boiler coincides as hydrochloric acid, the difference in the pH-values of with a low-point where magnetite is easily accumu- water in or in close proximity to the magnetite layer and lated. the bulk of the boiler water can amount to six decades.

Especially for vertical WHBs where the hot process If the heat flux is (too) high, an ultra high purity gas is entering at the bottom of the tubes, this is an im- water quality would be needed to prevent corrosion portant issue. Here the hottest parts of the tubes coin- damage. In ammonia plants it is technically and eco- cide with the preferred place of settlement of magnetite nomically not possible to produce this high-purity water particles. as is done in power stations. Instead, in ammonia plants the focus is to make the WHB less sensitive to corro- In horizontal boilers a major part of the solid mag- sion damage by controlling local heat fluxes and at- netite particles will settle onto the bottom shell of the tempting to keep heat transfer surfaces free of deposits. boiler where contact with the tubes may not be present and removal is possible using a blow-down procedure.

Research at Central Electricity Research Laborato- ries England [ref. 4] mid seventies has demonstrated Boiler corrosion processes From Figure 7 it is apparent that magnetite has the lowest solubility in neutral to slightly alkaline water. Most corrosion reactions under boiler conditions Iron, the principal constituent of steel, exhibits ampho- are autocatalytic: once started they will progress at in- teric behavior: magnetite dissolves in both acidic and creasing rates and cannot be stopped anymore. strongly alkaline water. From this figure it s also evi- dent that at near neutral conditions, the influence of pH Typical forms of attack in boilers are on magnetite solubility is less pronounced at higher (i) acid corrosion, temperatures. (ii) caustic corrosion (iii) phosphate corrosion. Acid corrosion. Hydrochloric acid and caustic soda are widely used to regenerate exchange resins in demineralized wa- The dissolution of steel and magnetite, respectively, ter and condensate polishing plants. Following each re- in hydrochloric acid are given by the following chemi- generation stage, traces of these chemicals will enter the cal reactions: steam system, whereas ion exchanger operation upsets may result in breakthrough of HCl or NaOH at elevated 2 Fe + 2 HCl → 2 FeCl2 + H2 concentrations.

2 FeCl2 + 2 H2O → 2 Fe (OH)2 + 2 HCl Phosphate is employed as a boiler treatment chemi- cal. Acid, caustic and phosphate may be concentrated in porous magnetite layers and reach corrosive concentra- Fe3O4 + 8HCl → FeCl2 + 2 FeCl3 + 4 H2O tions. The corrosion damage resulting from each of these types of attack has in common that the area of Hydrochloric acid, the corrodent in these model re- magnetite dissolution and subsequent steel degradation actions, is continuously regenerated. It acts as a cata- is very small compared to the total boiler surface area. lyst. The net result is the formation of a thick porous Therefore, the corresponding corrosion reactions take magnetite layer and the evolution of readily detectable place under very specific “micro” conditions and are quantities of hydrogen gas. Acid attack typically occurs not just related to “macro” conditions like the boiler at pH values well below 5. water quality.

The solubility of magnetite as a function of pH is Caustic corrosion given in Figure 7 [ref. 6]. In the high alkalinity range, iron and magnetite are made soluble through the formation of ferrates according to the chemical reactions below. A local pH > 13 is needed for these reactions to take place.

Fe3O4 + 4 NaOH → 2 NaFeO2 + Na2FeO2 + H2O

Fe + NaOH → Na2FeO2 + H2

3 Na2FeO2 + H2O → Fe3O4 + 6 NaOH + H2

As with acid attack, copious amounts of magnetite and hydrogen gas are formed.

Figure 7: Solubility of magnetite in water

Phosphate corrosion

Sodium phosphate with molar Na to PO4 ratios between 2 and 3 can become highly corrosive liq- uids above 273 °C (523 °F). In high heat flux boilers where sodium phosphates are used as a watercondi- tioning chemical, phosphate enrichment may lead to corrosive conditions. The following reactions describe the suggested stoichiometry of phosphate attack:

2 Na2HPO4 + Fe3O4 → NaFePO4 + Na3PO4 + Fe2O3 + H2O

Na2HPO4 + Fe + H2O → NaFePO4 + Na3PO4 + H2

Fe2O3 + Fe + H2O → Fe3O4 + H2

Again the final result is corrosion damage and the

formation of large quantities of magnetite and hydrogen Figure 8: Microscopic picture of steel surface gas. covered by layered/stratified magnetite caused

by Hot Water Oxidation / Hydrogen Damage

It is believed that in Hot-Water-Oxidation, magnet- ite is formed via wuestite (FeO), an iron oxide incapa- Hot Water Oxidation/Hydrogen Damage ble of protecting the underlying steel. The stability ar- eas of magnetite and wuestite are depicted in the The formation of a protective magnetite layer is a Chaudron diagram of Figure 9. As mentioned before, well controllable process up to a certain temperature increased concentrations of alloying elements such as that is dependent on the alloying elements in the steel. Cr and Mo make steel less vulnerable to Hot-Water- Above this “critical” temperature, the reaction of steel Oxidation. with water becomes uncontrolled and the oxidation of the steel becomes uninhibited

The result of this corrosion process is a smooth but deeply damaged steel surface covered by lay- ered/stratified magnetite up to several mm in thickness (see Figure 8). The steel structure typically shows hy- drogen damage. In older European literature this type of corrosion damage is described as “Hot Water Oxida- tion” (HWO). In modern American literature it is called “Hydrogen Damage”, although this merely describes the secondary failure mode associated with excessive iron oxide formation at higher temperatures.

Figure 9: Stable phases of iron and iron in gas mixtures of hydrogen and water vapor; FeO is wuestite, Fe3O4 is magnetite Remediation: The classic approach of 10.0 TSP + 1 ppm NaOH 4.0 boiler water treatment 3.0 PT

9.5 Phosphate treatment 1.0 EPT CPT From experience in the past with low-pressure boil-

ers operating on softened water it was recognized that pH at 25°C 9.0 Na: PO4 = 3.0 = CPPT 0.4 high alkalinity water protects boilers against corrosion. Na: PO4 = 2.8 0.3 Fouling of boilers with was inhibited by means Na: PO4 = 2.6 of the addition of (poly) phosphate. This type of condi- 0.2

8.5 (ppm) concentration NaOH Equivalent tioning later on also became the basis for WHBs operat- 0 1 2 3 4 5 6 7 8 9 10 ing on demineralized water. Phosphate added to the PO4 concentration (ppm) boiler water in the form of the alkaline trisodiumphos- phate took over the buffering role of sodium bicar- Figure 10: Operating Ranges for Boiler Water bonate in softened water. Phosphate Treatment

From so-called “Hide Out” phenomena it was then understood that phosphate can concentrate in porous All Volatile Treatment (AVT) magnetite layers in WHBs and cause phosphate corro- sion (phosphate wastage) in high heat flux high- To overcome the corrosion problems with phos- pressure boilers. phate in high-pressure boilers the so-called AVT was introduced. In this approach only amines are dosed to The sole advantage of phosphate treatment is buff- increase the pH of the boiler water, the simplest and ering of the boiler water, more specifically of the water widely used being ammonia. in or near porous iron oxides containing the highest concentrations of non-volatile corrodents. In modern With this type of alkalization it is very important to WHBs such impurities may emanate as traces of regen- bear in mind that pH measurements carried out at room eration chemicals from water from mixed bed ion ex- temperature (pH 25 °C (77 °F)) are not at all represen- changers. Even so, phosphates are rarely used in WHBs tative of the pH at the operating temperature of the today. At the DSM ammonia plant AFA-3 an Equilib- boiler (pH T) because pH is temperature dependant. rium Phosphate Treatment (EPT) program is main- Furthermore, the pH in a porous magnetite layer cannot tained but at the lowest possible concentration because be buffered with volatile amines. This is why AVT pro- in 2002 phosphate corrosion has taken place in flow re- grams require high purity boiler water. At DSM AVT stricted areas in the boiler downstream the secondary programs are used in high pressure WHBs but not in the reformer. At AFA-2 ever since the commissioning in two ammonia plants. 1971, a Coordinated Phosphate Treatment (CPT) pro- gram is used in which the WHBs are treated with a mix- ture of caustic and phosphate because of the use of non- Dispersing chemicals & chemical cleaning treated process condensate as boiler feed water. Up till now no WHB corrosion damage has occurred in DSM In the classic approach, porous magnetite layers in AFA-2 plant. WHBs can only be dealt with by using iron that remove iron oxide particles from the boiler water For the various operating ranges of boiler water before they can settle phosphate treatment see Figure 10. By power plant standards, boilers should periodi- cally be chemically cleaned during shutdowns in order to prevent corrosion damage. Low heat flux boilers should be chemically cleaned once every eight years, medium heat flux boilers once every five years and high heat flux boilers once every three years. By con- trast, chemical cleaning of boilers is not common in ammonia plants since it is generally considered too ex- pensive and time consuming.

Polyamine as an alkaline filming and dispersing agent can offer an interesting option to keep ammonia plant WHB surfaces free from fouling and corrosion. From the studies and experiences referred to in this pa- per, it was recognized that only clean boiler surfaces can limit corrosion damage especially under upset con- ditions. The use of polyamines for integral boiler sys- tem treatment seems to offer this possibility.

The most important advantage of polyamine treat- ment meanwhile is its tolerance to boiler water impuri- ties, which in our opinion is mainly due to the cleanli- ness of the heat transfer surface, and the pH buffering capacity in the magnetite deposits. Recent papers de- scribe experience with polyamines for the conditioning Figure 11: The fouling behavior of a steam of high-pressure steam systems [ref. 7] turbine before and after the application of poly- amine Since 1996 polyamine treatment is successfully in use at DSM in a nitric acid plant with 80 bar Lamont Reuse of process condensate in boilers and a condensing steam turbine. Previously un- ammonia plants and the impact on WHB der phosphate treatment this plant suffered from steam turbine fouling. After the application of the polyamine damage treatment no more turbine fouling occurred, see Figure Following a polishing step, process condensate is 11. Furthermore in another chemicals plant of DSM re-used as boiler feed water in many ammonia plants. with 35 bar water wall boilers that suffered from boiler Depending on catalyst activity, process condensate in tube due to FAC and FCC, polyamine has been ammonia plants typically contains alcohols, in particu- used successfully. Both plants have a non-polished lar methanol. In the pre-boiler system these alcohols condensate return. may be thermally degraded or oxidized to organic ac- ids, predominantly short-chain fatty acids such as for- mic, acetic, butanoic and glycolic acid. In that case, the BFW pH after the last preheater/economizer may devi- ate quite significantly from the pH of BFW exiting the . This decreasing alkalinity of BFW increases susceptibility to FAC in the pre-boiler system and, thus, the transport of corrosion products towards the WHB. In addition to the pH difference of Boiler Feed Water between the deaerator and the WHB, there is of course the aforementioned discrepancy between the Boiler Water pH at T and at 25 °C (77 °F). At DSM plants this misunderstanding of boiler water cycle characteristics has led to incorrect boiler operation in the past.

Since the organic acids are volatile, they report to the steam. Their presence in condensate can be deduced from electric conductivity measurements following cation removal; the conductivities of acids are much greater than the conductivities of their respective am- monium or sodium salts. In the cation exchanger NH4+ References and Na+ ions are replaced by H+ the latter having a ten times higher specific conductivity. That is why the cation exchanger cartridge may be considered an “am- 1. S. Pollmann, Werkstoffe und Korrosion 22, 1/1971, plifier” for the conductivity measurements. 8-16.

In case of the re-use of process condensate as boiler 2. W. Kastner, P. Hofmann, H. Nopper, VGB feed water an acid conductivity between 0,5 and 1,5 Kraftwerkstechnik, 70 (1990), Heft 11, and alloying µS/cm in the steam condensate is common. In this re- elements. gard it should be kept in mind that steam turbine manu- facturers allow an acid conductivity of no more than 0,2 3. J. Savelkoul et all, Power Plant Chemistry 2001, µS/cm to avoid corrosion. Higher acid conductivity en- 3(6). hances FAC and FCC with the risk of corrosion prod- ucts entering the WHB. 4. G.M.W. Mann, Central Electricity Research Labo- ratories, England: September 1975. RD/L/N/124/75.

5. G. Mann, EPRI RP 1171-1, Jan. 1984. Conclusions 6. G. Bohnsack, ISBN 3-8027-2667-7. Due to extreme high local heat fluxes WHBs are very sensitive to corrosion damage. During operation 7. A. Bursik, Power Plant Chemistry, 2004, 6(9), 549- fouling of heat transfer surfaces with corrosion products 555 aggravates this situation. These corrosion products are mainly magnetite formed by Flow Accelerated Corro- sion (FAC) and First Condensate Corrosion (FCC). The classic approach to keep the boiler water as free as pos- sible from alkaline and acidic impurities (such as in power stations) generally is not feasible in ammonia plants.

The main goal of boiler water treatment programs should be to keep the WHB heat transfer surface free from deposits. Conventional chemical treatment pro- grams are not always successful. WHB polyamine treatment seems to offer an alternative approach to am- monia plants operators. Harrie Duisters

Jo Savelkoul