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Artigo Tcnico PEER-REVIEWED ARTICLE

Corroso em tubos de superaquecedor de


caldeiras de recuperao: um desafio
Corrosion of superheater tubes in recovery
boilers: a challenge
Autores/Authors*: Marcelo Hamaguchi
Esa Vakkilainen

Palavras-chave: Caldeiras de recuperao, corroso, Keywords: Corrosion, recovery boiler, review,


reviso, superaquecedores superheaters

RESUMO
A corroso uma das causas principais que reduzem a Abstract
confiabilidade em plantas de gerao de vapor. estimado Corrosion is one of the main causes of reduced
que problemas decorrentes de corroso em sistemas de caldei- reliability in steam generating systems. It is estimated
ras custem anualmente indstria bilhes de dlares. Muitos that problems due to boiler system corrosion cost
problemas de corroso ocorrem nas reas mais quentes da cal- industry billions of dollars every year. Many corro-
deira: tubos do fundo da fornalha, paredes de gua, screens e sion problems occur in the hottest areas of the boiler:
tubos de superaquecedores. So ainda reas problemticas os floor tubes, water wall, screen, and superheater tubes.
desaeradores, aquecedores de gua de alimentao e econo- Other problematic areas include deaerators, feed wa-
mizadores. Esta anlise expe o mecanismo mais provvel de ter heaters, and economizers. This review shows the
corroso em superaquecedores das caldeiras de recuperao most probable mechanism of corrosion in superheaters
do processo kraft. Devemos, todavia, estar cientes de que a of the kraft recovery boilers. We all have to be aware

O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010


corroso no pode ser evitada por completo, mas pode ser that corrosion can not be totally avoided, but can be
controlada. Para tanto, importante conhecer bem alguns controlled. For such achievement, it is important to
mecanismos de corroso em tubos de superaquecedor, o que understand some mechanisms of corrosion in super-
vem a ser o objetivo principal deste trabalho. heater tubes, which is the main purpose of this paper.

INTRODUO INTRODUCTION
Parece que controlar parmetros operacionais para mini- It seems that controlling operational parameters
mizar corroso em caldeiras um desafio sem fim para enge- to minimize corrosion in boilers is an endless chal-
nheiros, pesquisadores e operadores. A seleo de materiais lenge for engineers, researchers and operators. Se-
para superfcies de transferncia de calor uma das questes lection of materials for heat transfer surfaces is one
de resposta mais difcil (Vakkilainen, 2005). As escolhas of the most difficult questions to be answered (Vak-
so frequentemente baseadas em anos de experincia. No kilainen, 2005). Choices are often based on years
comeo, a temperatura do vapor era mantida ao redor dos of experience. In the beginning, steam temperature
350C. Isso significa que corroso do superaquecedor era was kept at around 350C. It means that superheater
incomum nessa poca e problemas de entupimentos devido corrosion at that time was uncommon and plugging
a depsitos nos superaquecedores eram tambm menos problems caused by deposits in the superheaters
O PAPEL - Junho 2010

frequentes (Bruno, 1997). Com a crescente importncia da were also less frequent (Bruno, 1997). As energy ef-
eficincia em energia, os objetivos tm sido progressivamente ficiency has become important, targets have been
modificados. O conhecimento dos detalhes do processo de progressively changing. Understanding the details

*Referncias dos Autores / Authors' references:


Universidade de Tecnologia de Lappeenranta, P.O. Box 20, FI-53581 Lappeenranta, Finland
Lappeenranta University of Technology, P.O. Box 20, FI-53581 Lappeenranta, Finland
Autor correspondente/ Corresponding author: 57
E-mail: marcelo.hamaguchi@lut.fi 57
corroso tarefa difcil dada a complexidade do ambiente a of the corrosion process is a difficult task because
que submetido um tubo de superaquecedor. Os diferentes of the complexity of the environment experienced by
fabricantes de caldeiras so competentes ao recomendar a superheater tube. Different boiler manufacturers
suas prprias ligas metlicas para superaquecedores, isso are able to recommend their own alloy materials for
baseados em seus parmetros, caractersticas do combustvel superheaters, based on the steam parameters, fuel
e, tambm, em sua experincia. properties, and also on their experience.
Devido a sempre maior preocupao ambiental nas Due to a rising environmental concern in pulp
fbricas de celulose, esto sendo considerados o fecha- mills, the closing up of the chemical cycles and the
mento dos circuitos qumicos e opes para a queima de option to burn effluents in the boilers are being
ef luentes nas caldeiras. Isso pode, por sua vez, aumentar considered. On the other hand, it can increase the
o contedo de elementos no-processo tais como potssio content of non process elements such as potassium
e cloreto no ciclo de recuperao, o que poderia induzir and chloride in the recovery cycle, which may induce
a inesperadas altas taxas de corroso. Contudo, Bruno unexpectedly high corrosion rates. However, Bruno
(2004) afirma ser ainda questionvel como cloreto e (2004) states that it is still questionable how chlo-
potssio participam nas reaes qumicas que corroem ride and potassium participate in the chemical reac-
a camada passiva de xido. tions which corrode the passive oxide layer.
Sabe-se muito bem serem necessrias temperaturas It is well known that higher steam temperatures
e presses de vapor mais altas para que haja aumento da and pressures are needed for increasing energy ef-
eficincia em energia, embora plantas de celulose modernas ficiency, even though considerable excess power are
j estejam produzindo considervel excesso de energia. O already being produced by modern pulp mills. The
conceito relevante, aqui, gerar mais eletricidade a partir important concept, here, is to generate more elec-
de fontes verdes e fazer o melhor uso do biocombustvel, tricity from green resources and make the best use of
como o caso do licor negro. A corroso do superaquecedor biofuel such as black liquor. Superheater corrosion
um srio obstculo a superar para fazer com que biomassa is an important obstacle that has to be overcome
e resduos sejam mais competitivos como fonte de energia in order to make biomass and waste more competi-
verde (Johansson et al., 2007). Condies de operao de tive as sources for green power (Johansson et al.,
caldeiras, caractersticas do combustvel, temperatura do 2007). Operational conditions of boilers, fuel prop-
vapor e custos do material do superaquecedor so alguns erties, steam temperature, and costs of superheater
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dos parmetros a considerar quando da seleo dos materiais material are some of the parameters to be taken into
apropriados. Isso significa que caldeiras dotadas de material account when selecting appropriate materials. It
com a mesma liga e queimando o mesmo combustvel podem means that boilers containing the same alloy mate-
se defrontar com diferentes mecanismos de corroso. rial, and burning the same fuel, may have to deal
Em comparao combusto de fssil e biomassa with different mechanism of corrosion.
usuais, as caldeiras de recuperao apresentam ambiente Compared to ordinary fossil and biomass com-
mais difcil para procedimentos de pesquisa da corroso bustion, recovery boilers constitute a more difficult
(Eriksson, 1998). Caldeiras que queimam biomassa, environment for corrosion probe investigations (Er-
por exemplo, vm assumindo posio proeminente em iksson, 1998). Biomass-fired boilers, for example,
questes de energia e meio ambiente em muitas partes are assuming prominent positions in energy and
do mundo e o mecanismo descrito neste trabalho pode environmental issues in many parts of the world.
ter aplicao tambm em caldeiras que operam com bio- The mechanism described in this paper may also be
massa. Contudo, os problemas mais severos de corroso, applied to biomass-fired boilers. However, the most
no caso, so esperados acontecer devido a depsitos ricos severe corrosion problems for them are expected to
em Cl formados nos tubos de superaquecedor (Nielsen occur due to Cl-rich deposits formed on superheater
et al., 2000). A deposio de cloreto alcalino causa tubes (Nielsen et al, 2000). The alkali chloride de-
O PAPEL - Junho 2010

persistente para problemas intermitentes de obstrues position is a persistent cause for intermittent fouling
e corroso, especialmente em plantas que queimam bio- and corrosion problems, especially in biofuel-fired
combustveis (Pyyknen e Jokiniemi, 2003). O potssio plants (Pyyknen and Jokiniemi, 2003). Potassium
elemento alcalino que tambm preocupa (Baxter et al., is also one alkali element of concern (Baxter et
1998), mas a magnitude de determinado mecanismo de al., 1998), but the magnitude of certain corrosion
corroso tambm depende da biomassa em uso. Se o con- mechanism also depends on the biomass in use. If
tedo de potssio for alto, como em palhas, a sulfatao potassium content is high, like in straw, the sulfation
58
do cloreto de potssio no gs e nas fases condensadas of potassium chloride in the gas and condensed
pode induzir inesperadamente a altas taxas de corroso phases may induce unexpectedly high corrosion
(Lisa et al., 2009). Experincias envolvendo corroso a rates (Lisa et al., 2009). Experiments involving high
alta temperatura em superaquecedores de caldeiras de temperature corrosion of superheaters in biomass-
biomassa foram realizadas e relatadas em detalhes por fired boiler are performed and reported in details by
Montgomery et al. (1996). Montgomery et al. (1996).

CORROSO DE SUPERAQUECEDOR EM CALDEIRAS DE SUPERHEATER CORROSION IN RECOVERY BOILERS


RECUPERAO Black liquor is a residue that contains lignin,
O licor negro um resduo que contm lignina, celulose, cellulose, impurities and consumed chemicals from
impurezas e qumicos provenientes do digestor. A recupera- digesters. In order to recover the chemicals for pulp-
o dos qumicos para reuso na polpao acontece mediante ing, its combustion is carried out in the kraft recov-
a combusto do licor, feita na caldeira de recuperao kraft. ery boiler. According to Salmenoja (2004), four prin-
Conforme Salmenoja (2004), tm sido identificados quatro cipal corrosion mechanisms have been identified:
mecanismos principais de corroso: (1) oxidao a alta tempe- (1) high temperature oxidation, (2) sulfidation, (3)
ratura, (2) sulfidao, (3) oxidao ativa e (4) corroso a quente. active oxidation, and (4) hot corrosion. These can be
Esses mecanismos podem estar presentes individualmente ou present individually or as a mixture of two or more
como uma associao de dois ou mais mecanismos diferentes. different mechanisms.

Oxidao a alta temperatura High temperature oxidation


o mecanismo de corroso mais frequente, onde os It is the most abundant corrosion mechanism,
xidos so os produtos predominantes da corroso. A where the oxides are the most dominant corrosion
oxidao est presente em praticamente todos os casos products. Oxidation is present almost in every case
de corroso e, tipicamente, acontece quando metais so of corrosion and typically occurs when metals are
expostos a altas temperaturas em gases contendo acima exposed to high temperatures in gases containing
de 1% em vol. de oxignio. Oxidao a alta temperatura more that 1% vol. oxygen. High temperature oxida-
no normalmente considerada um problema em caldeiras tion is normally not considered a problem in modern
de recuperao modernas, isso devido aos parmetros recovery boilers because of the moderate steam
moderados aplicados ao vapor. Contudo, o aumento de parameters applied. However, the increase in steam

O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010


temperatura e presso do vapor, que alternativa para temperature and pressure, which is an alternative for
maximizar a relao energia-calor, pode converter a oxida- maximizing power-to-heat ratio, the oxidation of su-
o dos tubos do superaquecedor em questo importante. perheater tubes may become an important issue.
Baker et al. (2003) tm testado as novas ligas Ni-Cr-Mo-Si Baker et al. (2003) have tested new Ni-Cr-Mo-Si
como meio de minimizar o impacto da oxidao a alta tem- alloys in order to minimize the impact of high tem-
peratura. Eles demonstraram que todas as ligas testadas perature oxidation. They showed that all alloys tested
em oxignio com frequncia de ciclos para temperatura in oxygen with more frequent cycling to ambient tem-
ambiente tiveram aumentos significativos de taxas de perature experienced significant increases in oxida-
oxidao, com exceo da liga TD (Apndice 1). Contudo, tion rate, except for alloy TD (Appendix 1). However,
a liga TD composta por 75% de Ni e metais-terrosos the alloy TD is composed by 75% Ni and rare earth
raros, o que a faria invivel do ponto de vista econmico. metals, which seems unfeasible for the economic
E mais, desconhecido se tal liga poderia resistir a outros standpoint. Besides, it is unknown if such alloy can
mecanismos de corroso. resist against other mechanisms of corrosion.

Sulfidao Sulfidation
Sulfidao um dos mecanismos de corroso mais recor- Sulfidation is one of the most common corrosion
O PAPEL - Junho 2010

rentes que levam a perda de metal em caldeira de recuperao mechanisms leading to metal loss in kraft recov-
kraft (Salmenoja, 2004). Ela pode atacar a fornalha inferior, ery boilers (Salmenoja, 2004). It can attack lower
aberturas e superaquecedores. A sulfidao requer condies furnace, openings and superheaters. Sulfidation
redutoras, mas pode ser efetivamente evitada mediante o requires reducing condition, but it can be effectively
controle apropriado da combusto e a limitao da quantidade avoided by proper combustion control and by limit-
de arraste. O ferro reage com enxofre na fase gs formando ing the amount of carryover. The iron reacts with
sulfeto de ferro MeS, elemento que pode reduzir a camada sulfur in the gas phase, forming iron sulfide MeS,
59
59
oxidada protetora dos tubos metlicos (Vakkilainen, 2005). which can reduce the protective oxidized layer of
A reao descrita em (1), onde Me ferro (Fe), cromo (Cr) metal tubes (Vakkilainen, 2005). The reaction is
ou nquel (Ni): described by (1), where Me is iron (Fe), chromium
(Cr), or nickel (Ni):
H2S(g) + Me > MeS + H2(g) (1)
H2S(g) + Me > MeS + H2(g) (1)
Corroso devido a sulfidao baixa at os 250C, mas,
quando utilizado ao carbono, aumenta rapidamente acima Corrosion due to sulfidation is low up to 250C, but
dos 310C. Esse tipo de corroso diminui quando aplicada when carbon steel is used it increases rapidly above
liga que contenha cromo. Ao inoxidvel 304L o mais 310C. This type of corrosion decreases when alloy
tipicamente aplicado para o controle da corroso por sulfi- containing chrome is selected. Stainless steel 304L is
dao (Figura 1). Por sua vez, o nquel muito suscetvel a the most typical to control sulfidation corrosion (Fig-
sulfidao e ligas compostas com altos teores de Ni podem ure 1). On the other hand, nickel is very susceptible
sofrer sulfidao muito rapidamente a temperaturas acima to sulfidation and alloys composed of high Ni con-
dos 630C (Salmenoja, 2004). Um dos produtos da corroso, tents can sulfidize very rapidly at temperature higher
uma mistura de nquel e sulfeto de nquel (NiS), funde nessa than 630C (Salmenoja, 2004). One of the corrosion
temperatura. Portanto, ligas com alto teor de nquel no products, a mixture of nickel and nickel sulfide (NiS),
devem ser usadas acima dos 630C. melts at this temperature. Therefore, high nickel alloys
Um caso curioso envolvendo corroso do superaquecedor, should not be used at temperatures above 630C.
provavelmente por mecanismo de sulfidao, foi testemu- One curious case involving corrosion of superheater,
nhado por certa fbrica de celulose (Suik, 2000). A presso probably by sulfidation mechanism, was witnessed
de trabalho da caldeira era de 3,3-3,5 MPa e a temperatura by one pulp mill (Suik, 2000). The boiler operating
cerca de 430C-450C. Durante o tempo em que aconteceu pressure was 3.3-3.5 MPa and temperature around
corroso rpida era utilizada uma mistura de tiossulfato 430C-450C. During the time when rapid corrosion
(Na2S2O35H2O) e sulfato (Na2SO4) como sal de reposio occurred, a mix of thiosulphate (Na2S2O35H2O) and
(make up) e havia quantidades significativas de enxofre nas sulphate (Na2SO4) were used as make-up salt, and there
superfcies metlicas, sob a camada de depsitos. Foi afir- was significant amounts of sulfur on the metal sur-

5.0
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10,00%
1,00%
4.5
Ao carbono / Carbon steel 10,00%
Taxa de corroso (mm/ano) / Corrosion rate (mm/year)

4.0

3.5
Taxas de corroso para dife-
3.0 rentes concentraes de H2S
Corrosion rates for different
concentration of H2S
2.5

10,00%
2.0

1.5
1,00%

1.0
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0,10%
0.5

0.0
250 300 350 400 450 500 550 600
Temperatura (C) / Temperature (C)
Figura 1. Efeito da temperatura e do H2S na taxa de corroso (Salmenoja e Tuiremo, 2001)
60
Figure 1. Effect of temperature and H2S on corrosion rate (Salmenoja and Tuiremo, 2001)
mado que o uso de Na2S2O35H2O poderia originar sulfeto face under the deposit layer. They state that the use of
extra e assim reduzir o ponto de fuso dos depsitos, com Na2S2O35H2O might form extra sulfide and so reduce
crescimento da taxa de corroso. Segundo Bruno (2004), melting point of deposits and increase the corrosion
em uma caldeira de recuperao a qumica do enxofre ainda rate. According to Bruno (2004), in a kraft recovery
predomina sobre quaisquer influncias do cloreto. Isso prope boiler the sulfur chemistry is still dominating over any
que a qumica do enxofre poderia ser esquema de reao do chloride influences. It means that the sulfur chemistry
mais alto interesse para estudo. may be most interesting reaction scheme to study.
Yli-Olli et al. (2007) testaram, sob condies de reduo, Yli-Olli et al. (2007) tested, under reducing condi-
materiais como 304L, Sanicro 38, Sanicro 36Mo, Sanicro 65, tions, materials such as 304L, Sanicro 38, Sanicro
4C54 e HR11N em diferentes misturas de gases de sulfeto 36Mo, Sanicro 65, 4C54 and HR11N in different hydro-
de hidrognio (H2S) e monxido de carbono (CO), com e gen sulphide (H2S) and carbon monoxide (CO) gas mix-
sem adio de vapor dgua. Os resultados mostraram que a tures, with and without addition of water vapour. The
adio de 15% de vapor dgua protegia o material de teste results showed that an addition of 15% of water vapour
da sulfidao. Sem o vapor dgua, a sulfidao comeou protected the test materials from sulfidation. Without
a baixas concentraes de H2S e foi se acelerando com o water vapour, sulfidation started at low H2S concentra-
aumento da concentrao. Nesses testes, o ao inoxidvel tions and was accelerated by increasing the concentra-
austentico 304L e o Sanicro 36Mo demonstraram a melhor tion. In these tests the austenitic stainless steel 304L
resistncia sulfidao. and Sanicro 36Mo had the best sulfidation resistance.

Oxidao ativa Active oxidation


A oxidao ativa reporta-se a um processo onde a forma- Active oxidation refers to a process where volatile
o de cloreto metlico voltil incrementa a oxidao da liga. metal chloride formation enhances the oxidation of the
Nas ligas Fe-Cr, cloreto de ferro (FeCl2) principalmente alloy. In Fe-Cr alloys, iron chloride (FeCl2) is mainly
responsvel por oxidao ativa. Foram examinados alguns responsible for active oxidation. Some mechanisms for su-
mecanismos de corroso por cloro do superaquecedor (Gra- perheater chlorine corrosion have been discussed (Grabke
bke et al.,1995), e podem ser sugeridas algumas reaes. et al., 1995), and some reactions can be suggested. Alkali
Cloretos alcalinos do fluxo de gs condensam nos tubos do chlorides from the flue gas condense on the superheater
superaquecedor e reagem com os xidos de ferro ou cromo: tubes and react with iron or chromium oxides:

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2NaCl(s) + Fe2O3(s) + 0,5O2 > 2NaFeO2 + Cl2 hematita (2) 2NaCl(s) + Fe2O3(s) + 0.5O2 > 2NaFeO2 + Cl2 hematite (2)
3NaCl(s) + 2Fe3O4(s) + 2O2 > 3NaFe2O4 + 1,5Cl2magnetita 3NaCl(s) + 2Fe3O4(s) + 2O2 > 3NaFe2O4 + 1.5Cl2 magnetite
(3) (3)
Os cloretos alcalinos no depsito podem tambm reagir The alkali chlorides in the deposit can also react
com dixido de enxofre da fase gs: with sulfur dioxide from the gas phase

2NaCl(s) + SO2 (g) + O2 > Na2SO4 + Cl2 (4) 2NaCl(s) + SO2 (g) + O2 > Na2SO4 + Cl2 (4)

O cloro formado propaga-se atravs de trincas ou poros no The chlorine formed diffuses through cracks or
depsito para a interface metlica e na ausncia de oxignio, pores in the deposit to the metal interface and in ab-
condies redutoras, reage com ferro: sence of oxygen, reducing conditions, reacts with iron:
Fe(s) + Cl2 (g) > FeCl2 (s) (5) Fe(s) + Cl2 (g) > FeCl2 (s) (5)

A altas temperaturas, o cloreto de ferro volatilizado: At high temperatures, the iron chloride is volatilized:
FeCl2 (s) > FeCl2 (g) (6) FeCl2 (s) > FeCl2 (g) (6)
O PAPEL - Junho 2010

Os cloretos de ferro gasosos formados reagem com oxig- The formed gaseous iron chlorides react with oxygen
nio dando origem a um xido de ferro poroso e regenerando forming a porous iron oxide and regenerating chlorine.
cloro. A sequncia das reaes pode ser observada na Figura 2. The sequence of reactions can be observed in Figure 2.

2FeCl2 (g) + 1,5 O2 > Fe2O3 + 2Cl2 (7) 2FeCl2 (g)


+ 1.5 O2 > Fe2O3 + 2Cl2 (7)
3FeCl2 (g) + 2O2 > Fe3O4 + 3Cl2 (8) 3FeCl2 (g)
+ 2O2 > Fe3O4 + 3Cl2 (8)
61
61
Depsito
Deposit

Tubo metlico
Metal tube
Produtos de
corroso
Corrosion products

Figura 2. Oxidao ativa: sequencia de reaes ocorrendo em depsitos (Nielsen, 2000)


Figure 2. Active oxidation: sequence of reactions occurring in deposits (Nielsen, 2000)

O cloro liberado pode penetrar novamente a camada, The liberated chlorine may penetrate again the
desse modo renovando o ciclo de oxidao ativa (reaes 5 scale, thus refurbishing the cycle of active oxidation
a 8) e levando a taxas de corroso extremamente altas aos (reactions 5 to 8) leading to extremely high corrosion
de baixa liga e de ligas base-Fe. Ainda, tem sido observada rates of low alloyed steels and Fe-base alloys. Also,
oxidao ativa em aos com liga-Cr e ligas Fe-Cr. Ligas fer- active oxidation has been observed for Cr-alloyed
rticas Fe-Cr parecem mais propensas a esse tipo de ataque, steels and Fe-Cr alloys. Ferritic Fe-Cr alloys seem
embora ligas formadoras de alumina possam, algumas vezes, to be most prone to this kind of attack while alumina
O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010

tambm serem suscetveis a isso. Aparentemente, somente forming alloys may sometimes also be susceptible to it.
aos com alto contedo de Ni e ligas base-Ni resistem razo- Seemingly, only high Ni-containing steels and Ni-base
avelmente bem a esses ataques, o que pode ser uma de suas alloys withstand such attack reasonably well, which
razes as menores presses de vapor dos cloretos de nquel may have one of its reasons in the lower vapour pres-
(Malkow et al., 2004). sures of nickel chlorides (Malkow et al., 2004).
Segundo a reao 4, oxidao ativa pode ser tambm According to reaction 4, active oxidation may
originada pela sulfatao de cloretos alcalinos nos depsi- also be ignited by the sulfation of alkali chlorides in
tos. Isso acontece quando estiver disponvel SO2 suficiente the deposits. It occurs when enough SO2 is available
nos gases de sada. Em condies midas, pode acontecer a in the flue gases. In wet conditions, the following re-
seguinte reao (Warnqvist, 1976): action may occur (Warnqvist, 1976):

2NaCl(s) + SO2 (g) + 0,5O2 + H2O (g) > Na2SO4 + 2HCl (g) (9) 2NaCl(s) + SO2 (g) + 0.5O2 + H2O(g) > Na2SO4 + 2HCl (g) (9)

Como resultado dessa reao se d a formao de cloreto As a result of this reaction, gaseous hydrogen chlo-
de hidrognio gasoso; que percorre os dispositivos de remo- ride is formed. It passes the dust removal devices and
O PAPEL - Junho 2010

o de p e deixa o processo como emisso via duto de gs. exits the process as flue gas emission. Then, in prin-
Ento ser possvel, em tese, facilitar a remoo do cloro do ciple, it is possible to facilitate removal of the chlorine
ciclo de recuperao. Obviamente que a produo de HCl from the recovery cycle. Obviously the yield of HCl
por via dessa reao limitada pelo equilbrio qumico e by this reaction is limited by the chemical equilibrium
cinticas, e tambm pelas quantidades molares relativas de and kinetics, and also by the relative molar amounts
cloreto e SO2 no gs de sada. Oxignio e vapor dgua esto of chloride and SO2 in the flue gas. Oxygen and water
62 normalmente presentes em quantidades suficientes. Reaes vapor are usually present in sufficient amounts. Reac-
2, 3, 4 e 9 podem tambm acontecer na presena de potssio, tions 2, 3, 4 and 9 may also occur in presence of po-
KCl. O cloro liberado pode causar reao de corroso se a tassium, KCl. Released chlorine may cause corrosion
sulfatao ocorrer prximo da superfcie do tubo, o que reaction if the sulfation occurs near the tube surface,
pode levar a oxidao ativa e aumentar a corroso dos tubos which may lead to active oxidation and increased cor-
(Salmenoja, 2004). rosion of the tubes (Salmenoja, 2004).
Conforme Salmenoja et al., (1999), corroso significa- According to Salmenoja et al., (1999), significant
tiva de ligas base-Fe-Cr na presena de HCl em condies corrosion of high Cr-Fe-based alloys in the presence
oxidantes ocorre somente quando a temperatura do metal of HCl in oxidative conditions occurs only when the
for superior a 600C. Nesse caso, aumentar o teor de Cr na metal temperature is above 600C. Then, increas-
liga parece benfico contra corroso na presena de HCl. ing Cr content in the alloys appears to be beneficial
Contudo, nas condies da caldeira de recuperao a pre- against oxidation in the presence of HCl. However, in
sena de vapor dgua deve ser levada em considerao. Se recovery boiler conditions, the presence of water va-
houver presena de cloretos alcalinos fundidos, a mistura por must be taken into consideration. If molten alkali
de suas fases fundidas dissipa o vapor dgua, aumentan- chlorides are present, their molten mixture phases
do grandemente a capacidade de oxidao do fundido. dissolve water vapor, enhancing greatly the oxidation
sabido que o vapor dgua aumenta a severidade do ata- power of the melt. Water vapor is known to enhance
que bsico em fundidos de cloretos alcalinos dissolvidos the severity of the basic attack in molten alkali chlo-
(Mkip, 2004). Outra reao possvel de acontecer na ride melts (Mkip, 2004). Another reaction that
sulfatao de carbonatos alcalinos pelo dixido de enxofre may occur is the sulfation of alkali carbonates by the
livre no fluxo de gases de sada. Depsitos de superaque- free sulfur dioxide in the flue gases. Modern recovery
cedor de caldeira de recuperao moderna tipicamente boiler superheater deposits typically contain 5-25
contm 5%-25% em peso de carbonatos alcalinos: wt% of alkali carbonates:

NaCO3(s) + SO2 (g) + 0,5O2 > Na2SO4 + CO2 (g) (10) NaCO3(s) + SO2 (g) + 0.5O2 > Na2SO4 + CO2 (g) (10)

Dixido de carbono no gs corrosivo. Carbonatos Carbon dioxide is not a corrosive gas. Alkali
alcalinos so sulfatados antes dos cloretos alcalinos (Tran carbonates are sulfated prior to alkali chlorides

O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010


e Villarroel, 1999), significando serem necessrios altos (Tran and Villarroel, 1999), which means that high
nveis de SO2 para sulfatar os cloretos caso carbonatos levels of SO 2 are needed to sulfate the chlorides if
estejam presentes nos depsitos. Ento, carbonatos al- carbonates are present in the deposits. Therefore,
calinos podem retardar o incio da oxidao ativa em alkali carbonate may retard the ignition of active
superaquecedores de caldeira de recuperao. Salmenoja oxidation in recovery boiler superheaters. Salmeno-
e Mkel (2000) participaram de caso interessante em ja and Mkel (2000) experienced one interesting
que a corroso do superaquecedor no aconteceu. Eles case where the superheater corrosion did not occur.
concluram que a FMT (First melting temperature Pri- They concluded that the FMT (First melting tem-
meira temperatura de fuso) era alta. Alm disso, havia perature) was high. In addition, there was relatively
um relativamente grande teor de carbonato dos depsitos high carbonate content of superheater deposits,
do superaquecedor, que atuou como tampo e protegeu o which acted as a buffer and protected the superheat-
superaquecedor da corroso. ers from corrosion.
Embora tenha sido ocasionalmente proposto que Although it has been occasionally suggested that
corroso poderia ser tambm causada por cloro (Cl 2) do corrosion may also be caused by chlorine (Cl2) from
HCl, a possibilidade de tal corroso pequena. Segundo HCl, the possibility of such corrosion is small. Ac-
O PAPEL - Junho 2010

Adams et al. (1997), isso devido ao fato de a concen- cording to Adams et al. (1997), this is because the
trao de HCl ser pequena e as condies nas caldeiras concentration of HCl is small, and the conditions in
de recuperao no serem favorveis formao de Cl 2 . recovery boilers are not in favor of Cl2 formation.
O equilbrio 2HCl(g) + 0,5O2(g) > H 2O (g) + Cl 2(g) indica The equilibrium 2HCl(g) + 0.5O2(g) > H2O(g) + Cl2(g)
que a formao de Cl 2 termodinamicamente possvel indicates that the formation of Cl2 is thermodynami-
somente em temperaturas superiores a 550C e em at- cally possible only at temperatures above 550C and
mosferas oxidantes. in oxidizing atmospheres. 63
63
Formao de depsitos e corroso a quente causada por Deposit formation and hot corrosion caused by
lcalis alkalis

Formao de depsitos Deposit formation


A dimenso da deposio de sal em uma caldeira de recupera- The salt deposit extent in a recovery boiler depends
o depende grandemente da capacidade da caldeira, da compo- greatly on the capacity of the boiler, the composition
sio e desempenho da combusto do licor negro, das condies and combustion behavior of black liquor, the boiler
de operao da caldeira na fornalha inferior e das estratgias de operating conditions in the lower furnace and the
operao dos sopradores de fuligem (Tran, 2004). A obstruo operating strategies of the sootblowers (Tran, 2004).
por sujidade aumenta quando h mais partculas nos gases de Fouling increases when more particles are present in
exausto, quando as partculas so pegajosas e quando a eficincia the flue gases, when particles are sticky and when the
do sopramento baixa. Ainda que as superfcies do trocador de sootblowing efficiency is low. Even though the heat ex-
calor no duto do gs sejam sopradas continuamente, a acumulao changer surfaces in the flue gas channel are continu-
intensa de depsitos pode exigir uma parada no-programada da ously soot blown, massive deposit accumulation may
caldeira e, com isso, uma significativa perda financeira. require an unplanned shutdown of the recovery boiler,
Depsitos nas superfcies do superaquecedor so principal- thus causing significant financial losses.
mente causados por impacto inercial de partculas arrastadas, Deposits on superheater surfaces are caused, main-
que so partculas de fundido parcialmente oxidadas e/ou part- ly, by inertial impaction of carryover particles, which
culas de gotas de licor negro parcialmente queimadas e levadas are partially oxidized smelt particles and/or particles
pelo fluxo de gs. Segundo Backman et al., (1987), partculas da of partially-burned black liquor droplets entrained in
fumaa tambm tm influncia na dimenso do depsito. Ele the flue gas. According to Backman et al., (1987), fume
causado por termoforese, que acontece quando fluxo de gs particles also have influence on the deposition extent.
quente passa por superfcies de transferncia mais frias e forma It is caused by thermophoresis, which happens when
gradiente de temperatura (Figura 3). A taxa de deposio por hot flue gases pass colder transfer surfaces, and tem-
termoforese proporcional a esse gradiente de temperatura, perature gradient forms (Figure 3). Thermophoretic
alm do dimetro das partculas e da concentrao de partcu- deposition rate is proportional to this temperature
las (Mikkanen, 2001 e Laursen, 1998). Partculas no fumo so gradient, besides particles diameter and particle con-
formadas por condensao de vapores de compostos de sdio e centration (Mikkanen, 2001 and Laursen, 1998). Fume
O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010

de potssio no fluxo de gs. Fumos geralmente ocorrem na parte particles are formed by condensation of vapors of so-

TUBO TUBO Legenda:


Depsito em tubo / Tube deposit
TUBE TUBE Legend:
Fluxo gs de sada
Flue gas flow
Tipos de cinzas areas
(vapores e partculas pequenas)
Fly ash species
(vapors and small particles)
Tipos de cinzas areas
O PAPEL - Junho 2010

(partculas grandes)
Fly ash species
(large particles)

a Difuso e termoforese b Impacto inercial


Diffusion and thermophoresis Inertial impaction

Figura 3. Mecanismos que controlam deposio e maturao de depsitos de cinza (Zbogard, 2009)
64
Figure 3. Mechanisms that control deposition and maturation of ash deposits (Zbogard, 2009)
alta do superaquecedor, no banco gerador e no economizador dium and potassium compounds in the flue gas. Fume
preferencialmente parte baixa do superaquecedor, pois que usually forms in the upper superheater, generator bank
as temperaturas da parte baixa so demasiado altas para que and economizer rather than the lower superheater be-
acontea condensao. Na parte inferior do superaquecedor o cause the lower superheater temperatures are too high
arraste dominante, formando depsitos duros, amalgamados for condensation to occur. In the lower superheater
e semelhantes a fundido (Minday et al., 1997). Pyyknen e carryover is dominant, forming hard, fused and smelt-
Jokiniemi (2003) tm demonstrado que a taxa de deposio like deposits (Minday et al., 1997). Pyyknen and Joki-
determinada pelo impacto inercial no superaquecedor. niemi (2003) have demonstrated that deposition rate is
A taxa de formao de depsitos em tubos de caldeira governed by inertial impaction in superheaters.
de recuperao funo da quantidade de fase lquida exis- The rate of formation of deposits on recovery boiler
tente no depsito. Os depsitos no mantm lquido abaixo tubes is a function of the amount of liquid phase pres-
do primeiro ponto de fuso e agem como partculas slidas. ent in the deposit. The deposits have no liquid below
Quando os depsitos contm entre 15% e 70% de fase lquida, the first melting temperature and act as solid particles.
eles sero pegajosos e causadores de entupimentos rpidos When the deposits contain between 15% and 70%
caso no sejam removidos. Reduo de transferncia de liquid phase, they will be sticky and cause rapid plug-
calor do fluxo de gases um dos principais inconvenientes ging if not removed. Reduced heat transfer from flue
dos depsitos em caldeiras de recuperao. A transferncia gases is one of the major disadvantages of deposits in
afetada pelas propriedades da camada de cinzas, como seriam recovery boilers. It is affected by the ash layer proper-
a condutividade trmica, a emissividade e a espessura. O ties like thermal conductivity, emissivity and thickness.
ambiente da caldeira favorece o crescimento de incrustaes The boiler environment leads to multilayer growth of
multicamadas, que influenciado pelas caractersticas mor- scales, which is influenced by morphological charac-
folgicas da deposio. Portanto, parece que mecanismos de teristics of deposition. Therefore, it seems that corro-
corroso e suas taxas sejam imprevisveis. sion mechanisms and its rates are unpredictable.

Corroso a quente Hot corrosion


No mecanismo de corroso a quente, a camada protetora In the mechanism of hot corrosion, the protective ox-
de xido de metais e ligas dissolvida pelos processos de ide scale of metals and alloys is dissolved by oxidation

O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010


oxidao, que so afetados por depsitos de sais fundidos. processes, which are affected by molten salt deposits. As
Como dito anteriormente, os gases portadores de Cl2, HCl, mentioned before, the gases containing Cl2, HCl, NaCl,
NaCl, e KCl causam corroso ativa das ligas metlicas, mas and KCl cause active oxidation of the metal alloys, but
esses gases podem tambm influenciar a corroso gerada por such gases may also influence the corrosion caused by
outros mecanismos, tais como corroso de ligas do supera- other mechanisms, such as molten alkali sulfate corro-
quecedor por sulfato alcalino fundido. O primeiro ponto de sion of superheater alloys. The first melting temperature
fuso desses sais (T0) um conceito importante e til, que of these salts (T0) is an important and useful concept that
auxilia na resposta a questes relativas a corroso severa em helps answering questions about severe corrosion in the
caldeiras (Hupa, 2004). T0 a temperatura em que ocorre a boilers (Hupa, 2004). T0 is the temperature at which the
primeira fase fundida quando o sal aquecido. So tambm first molten phase appears when the salt is heated. Dif-
dadas definies variadas para as fases de amolecimento con- ferent definitions are also given for sticky stages as the
forme o sal seja progressivamente derretido; a temperatura salt is progressively melted: the sticky temperature, T15,
viscosa, T15, quando a frao fundida de 15%, a temperatura at which the molten fraction is 15%; the flow tempera-
de circulao, T70, e a temperatura de fuso total, T100. Essas ture, T70; and the temperature for completing melting,
temperaturas so fortemente dependentes da composio T100. These temperatures are strongly dependent on the
O PAPEL - Junho 2010

do sal, que basicamente uma mistura de Na2SO4, K 2SO4, salt composition, which is basically a mixture of Na2SO4,
NaCl, KCl, Na2CO3 e K 2CO3. Haver carbonato na fornalha K2SO4, NaCl, KCl, Na2CO3 and K2CO3. There will be
superior da caldeira kraft, mas o sulfato ser predominante carbonate in the upper furnace of the kraft boiler, but the
na composio dos depsitos, tanto nos tubos do superaque- sulfate will dominate the composition of deposits both on
cedor resfriados a vapor como nos tubos da fornalha superior the superheater steam-cooled tubes and on the upper fur-
resfriados a gua (Bruno, 2001). nace water-cooled tubes (Bruno, 2001).
A temperatura do metal do tubo - em contato com o lado The temperature of the tube metal - which faces the 65
65
interno do depsito exterior -, normalmente estimada em internal side of the external deposit -, is usually esti-
cerca de 30-50C acima da temperatura local do vapor (ou mated to be around 30C-50C above the local steam
gua) para superaquecedores expostos a radiao direta e (or water) temperature for superheaters that see direct
cerca de 10C-20C acima da temperatura local do vapor (ou radiation and around 10C-20C above the local steam
gua) para superaquecedores protegidos da radiao direta (or water) temperature for superheaters that are shielded
(por exemplo: atrs do nariz). Isso devido ao gradiente from direct radiation (e.g. behind nose). This is due to
trmico atravs do tubo causado pela diferena de tempe- the thermal gradient through the tube caused by the tem-
ratura entre o vapor e o fluxo de gs. Consequentemente, a perature difference between the steam and the flue gases.
temperatura mdia da superfcie do metal do tubo na sada Consequently, the mean surface temperature of the tube
do superaquecedor pode ser to alta quanto 530C ou 550C metal at the superheater outlet can be as high as 530C
se a temperatura do vapor for 480C ou 500C. or 550C if the steam temperature is 480C or 500C.
Em um estudo de caso (Hiner et al., 2000), depois da ins- In a study case (Hiner et al., 2000), after instal-
talao de precipitadores de alta eficincia em duas fbricas, lation of high efficiency precipitators in two mills,
a maior captura de cloretos de sdio e potssio aumentou as the higher capture of sodium and potassium chloride
quantidades de cloretos reintroduzidos no licor mediante a increased the amounts of chlorides that are re-intro-
reciclagem da cinza. As duas unidades incorreram em maior duced into the liquor via ash recycling. Both units
frequncia de lavagens, menor disponibilidade e rpida experienced increased water wash frequency, reduced
deteriorao das temperaturas do vapor superaquecido. Em availability, and rapid degradation of superheated
consequncia, as temperaturas de sada do vapor precisaram steam temperatures. Subsequently, steam outlet tem-
ser reduzidas de 482C para 468C a fim de reduzir as taxas peratures had to be reduced from 482C to 468C
de corroso no superaquecedor secundrio. H tambm a to decrease corrosion rates in the secondary super-
possibilidade de a queima de licor com teor de slidos mais heater. There is also the possibility that higher solid
alto ter diminudo as emisses anteriores de cloreto como firing decreased the previous emissions of chloride as
HCl, o que levou a aumento de Cl no ciclo do licor. HCl, which led to increase of Cl in the liquor cycle.
Skrifvars et al. (2008), aps testes de laboratrio com Skrifvars et al. (2008), after laboratory tests with
material de superaquecedor, apresentaram dois novos termos superheater material, introduced two new terms to the
comunidade da corroso: corroso sub-T0, indicando a corrosion community: sub-T0 corrosion, indicating
O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010

corroso que ocorre abaixo de qualquer fuso do depsito e corrosion taking place below any melting of the depos-
corroso super-T0, indicando corroso que acontece quando o it and super-T0 corrosion, indicating corrosion taking
depsito contm fundido. Todos sabemos que a corroso au- place when the deposit contains melt. We all know that
menta com temperatura acima da faixa de fuso do depsito corrosion increases at temperature above the super-
do superaquecedor. Contudo, os pesquisadores concluram heater deposit melting range. However, they concluded
que corroso poderia tambm acontecer a temperaturas cla- that corrosion could take place also at temperatures
ramente abaixo de qualquer fuso do sal dos depsitos, no clearly below any melting of the salt deposits, when
caso de haver presena de cloro no sal. Isso significa que a chlorine was present in the salt. It implies that purging
purga de cloro e potssio do ciclo de recuperaes qumicas of chlorine and potassium from the chemicals recovery
em uma fbrica de celulose kraft deve ser muito eficiente cycle of a kraft pulp mill needs to be very efficient to
para que se abram possibilidades a aumento de temperaturas open the possibilities for increased steam tempera-
do vapor. Alguns pesquisadores, como Jaretun e Aly (2000) tures. Some researchers like Jaretun and Aly (2000)
e Minday et al. (1997), estudaram a remoo de cloreto e and Minday et al., (1997) studied the removal of chlo-
potssio do ciclo de recuperao kraft. ride and potassium from the kraft recovery cycle.
Keiser et al. (2007) realizaram algumas experincias Keiser et al. (2007) have performed some experiments
O PAPEL - Junho 2010

com a criao, em laboratrio, de um pior caso de depsito by creating, in laboratory, a worst case synthetic su-
sinttico em superaquecedor, com T0 ao redor dos 525C. O perheater deposit, with T0 around 525C. The target was
objetivo era avaliar a aptido de ligas metlicas. Foi constata- to evaluate alloy suitability. It was noticed that corrosiv-
do que a corrosividade do depsito sinttico era intensificada ity of the synthetic deposit was significantly enhanced
significativamente na presena de mistura de gs reativo. in the presence of the reactive gas mixture. There was a
Ocorreu efeito danoso de enxofre e oxignio em combinao detrimental influence of sulfur and oxygen, in combina-
66 com cloro. Os resultados no foram de todo consistentes tion with chlorine. The results were not totally consistent
Figura 4. Imagem por microscpio ptico de superfcie de tubo de superaquecedor de caldeira de recuperao que teve corroso acelerada por
mecanismo de oxidao ativa (Mkip et al., 2004) / Figure 4. Optical microscope image of recovery boiler superheater tube surface which
has experienced accelerated corrosion by the mechanism of active oxidation (Mkip et al., 2004)

com a esperada tendncia de menores taxas de corroso with the expected trend of lower corrosion rates for
para ligas com mais altos teores de cromo. Os pesquisadores higher chromium-containing alloys. They conclude that
concluram que ainda h escasso conhecimento da sinergia there is still a poorly understood synergy between the
entre os reagentes responsveis pela corroso constatada, reactants responsible for corrosion observed, both below
tanto abaixo como acima da T0 do depsito. Fujikawa et al. and above the T0 of the deposit. Fujikawa et al. (1999)
(1999) pesquisaram os efeitos da composio do depsito e investigated the effect of deposit composition and steam
da temperatura do vapor no comportamento da corroso em temperature on corrosion behavior for different steels.
aos diferentes. Concluram que Cr, Mn e Mo eram elementos They concluded that Cr, Mn and Mo were significantly
significativamente benficos. N e Ni eram tambm benficos beneficial elements. N and Ni were also beneficial above
acima de 600C, enquanto C era um elemento extremamente 600C, while C was an extremely harmful element. They
prejudicial. Eles tambm selecionaram o seguinte ao inoxi- also selected the following austenitic stainless steel as

O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010


dvel austentico como novo ao resistente a corroso: 0,03C new corrosion resistant steel: 0.03C - 1.0Si - 2.5/3.5Mn
1,0Si 2,5/3,5Mn -12,5/15,5Ni -21,0/23,0Cr 1,0/2,0Mo -12.5/15.5Ni -21.0/23.0Cr - 1.0/2.0Mo - 0.10/0.25N.
0,10/0,25N. Todavia, segundo Hupa (2004), pesquisa deve However, according to Hupa (2004), research has to be
ser feita continuamente para investigar a ao da fase fundida continuously done in order to explore the role of the mol-
na corroso do superaquecedor. ten phase for superheater corrosion.

Queimando combustvel auxiliar Burning oil as auxiliary fuel


Alguns casos de falhas demonstram que oxidao ativa Some failures cases show that active oxidation is,
, sem nenhuma dvida, um forte mecanismo de corroso without any doubt, an effective corrosion mechanism
em caldeiras de recuperao (Mkip et al., 2004). Foi en- in recovery boilers (Mkip et al., 2004). They
contrado vandio em depsitos (Figura 4), o que pode ter found vanadium in the deposits (Figure 4), which
contribudo para a falha ao ser catalisado xido de enxofre may have contributed to the failure by catalyzing
a trixido de enxofre e, com isso, ser causada rpida sul- sulfur oxide to sulfur trioxide conversion and then
fatao de cloreto alcalino. Caldeiras de recuperao kraft leading to rapid alkali chloride sulfation. Kraft
podem evidenciar altas taxas de corroso ao queimar leo recovery boilers may have high corrosion rates
O PAPEL - Junho 2010

como combustvel auxiliar. A presena de vandio pode when burning oil as auxiliary fuel. The presence of
explicar a influncia do leo na corroso do superaquece- vanadium may explain its influence on superheater
dor. Milanez (2007) analisou a concentrao de vandio em corrosion. Milanez (2007) analyzed the vanadium
cinza de caldeira de recuperao kraft e encontrou 30 ppm, concentration of kraft recovery boiler ash and found
o que pode resultar em ambiente altamente corrosivo para 30 ppm, which may create a highly corrosive envi-
superaquecedores. ronment to superheaters.
A maioria dos pesquisadores concorda que corroso Most investigators agree that accelerated corrosion 67
67
acelerada por cinza de leo ocorre devido ao fluente by oil ash occur due to fluxing action of molten sodium
de complexos de vandio fundido sobre a camada protetora vanadium complexes on the protective oxide scale
de xido nos tubos (Joseph, 1991). No leo combustvel on the tube (Joseph, 1991). In fuel oil, the important
as impurezas importantes so: Na (sdio at 300 ppm), V impurities are: Na (sodium up to 300 ppm), V (vana-
(vandio at 150 ppm) e S (enxofre entre 0,6% e 3,6%). Du- dium up to 150 ppm) and S (sulfur between 0.6% and
rante a combusto, essas impurezas fundem ou vaporizam 3.6%). During combustion, these impurities melt or
e ficam depositadas sobre o metal a temperatura inferior vaporize and get deposited on metal at temperatures
temperatura de condensao da espcie especfica. An- below the condensation temperature of the specific
dijani (2004) descreve falhas de alguns tubos de caldeira species. Andijani (2004) describes failure of some
principalmente causadas por corroso a quente induzida boiler tubes mainly caused by sulfur and vanadium in-
por enxofre e vandio. O vandio, como impureza em leo duced hot corrosion. Vanadium as an impurity in fuel
combustvel, causa srios problemas de corroso devido oil causes serious corrosion problems because of the
formao de V2O5, que tem ponto de fuso de 670C. O formation of V2O5, which has a melting point of 670C.
problema frequentemente composto caso haja presena The problem is often compounded if sodium is pres-
de sdio, pois certas misturas de xidos V-Na tm ponto ent because some V-Na mixed oxides have still lower
de fuso ainda mais baixo. Por exemplo, vanadil-vanadato melting point. For example, sodium vanadyl-vanadate
de sdio 5Na 2O.V2O4.11V2O5 funde a 535C. Outro produto 5Na2O.V2O4.11V2O5 melts at 535C. Another corrosion
corrosivo coirmo do pentxido de vandio o ortovanada- causing daughter product of vanadium pentoxide is
to (3NiO.V2O5). Depsitos lquidos assim formados fluem orthovanadate (3NiO.V2O5). Liquid deposits formed
sobre as camadas protetoras de xidos nas ligas estruturais, in this way flux the protective oxide layers on struc-
fazendo-as vulnerveis a rpida corroso. Tm sido muitas tural alloys, making them vulnerable to rapid corro-
as proposies sugeridas para prevenir a corroso leo- sion. Many approaches have been taken to prevent
cinza a alta temperatura: (1) tratamento do leo para dele high-temperature oil-ash corrosion: (1) oil treatment
retirar vandio, sdio e enxofre; (2) uso de ligas resistentes to remove vanadium, sodium, and sulfur from the oil;
a corroso e de revestimentos protetores; (3) baixo excesso (2) the use of corrosion-resistant alloys and protective
de ar de operao; (4) uso de magnsio metlico, xido de coatings; (3) low-excess air operation; (4) use of mag-
magnsio ou aditivos dolomticos. nesium metal, magnesium oxide, or dolomite additives.
O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010

CONCLUSO CONCLUSION
Os mecanismos exatos de ataque oxidante em tubos The exact mechanisms of oxidative attack of super-
do superaquecedor, seja por ambiente gasoso agressivo ou heater tubes by either an aggressive gaseous environ-
por variados compostos qumicos formados de cinzas, de ment or by several complex chemicals formed from
depsitos de subprodutos ou de produtos corrosivos, no ashes, deposit by-products or corrosion products,
esto claros devido s dificuldades inerentes a duplicao are unclear due to difficulties involved in duplicat-
e percepo das reaes que acontecem in situ. Ainda que ing and understanding the reactions going on in-situ.
estudos relacionados a fenmenos da corroso sejam publi- Even though studies concerning corrosion phenomena
cados continuamente, sinalizando que solues podem ser are continuously published, which means that solu-
recomendadas, resulta necessria pesquisa adicional para que tions can be recommended, it seems that additional
seja investigada com maiores detalhes a ao dos mecanismos research is needed to explore in more detail the role
envolvidos na corroso do superaquecedor. Considerado que of the mechanisms involved in superheater corrosion.
durante a operao da caldeira pode acontecer a associao Since a mixture of two or more different mechanisms
de dois ou mais mecanismos de corroso, torna-se difcil of corrosion may happen during the boiler operation,
O PAPEL - Junho 2010

determinar as causas precisas dos danos ao superaquecedor. it is difficult to precisely find the causes of superheater
Para que a vida til do superaquecedor possa ser prolongada, damages. In order to extent the lifetime of superheater
a soluo atual para as fbricas de celulose basicamente a de tubes, the solution for pulp mills today is basically
estabelecer um limite para os parmetros do vapor. Todavia, to set a limit for the steam parameters. However, this
essa soluo, bem como a remoo de parte do cloreto e do solution, as well as removing part of the chloride and
potssio do sistema de licor negro, no assegura a eliminao potassium from the black liquor system, does not guar-
68 da corroso no superaquecedor. antee the elimination of superheater corrosion.
Apndice 1. Exemplo de composies de vrios materiais de superaquecedor (Vakkilainen, 2005). A composio real pode variar dependendo
do fabricante do tubo e do lote de fabricao / Appendix 1. Example compositions of various superheater materials (Vakkilainen, 2005). The
actual composition can vary depending on the tube manufacturer and the production batch
Material Cr Ni Mo Si Cu Al Mn C Fe Outro / Other
15Mo3 0.30 0.30 0.30 0.26 0.30 - 0.65 0.16 97.60 -
SA213 - T12 1.00 - 0.50 0.45 - - 0.45 0.10 97.50 P,S
13CrMo44 1.00 0.30 0.30 0.26 0.30 - 0.55 0.14 97.10 -
SA213 - T11 1.25 - 0.50 0.75 - - 0.45 0.15 96.90 P
10CrMo910 2.30 - 1.00 - - - 0.50 - 96.10 -
SA213 - T22 2.25 - 1.00 0.75 - - 0.45 0.15 95.40 P
X10CrMoVNb91 9.00 0.30 1.00 0.40 - - 0.50 - 88.70 V, Nb
SA213 - T91 9.00 0.33 0.99 0.24 - 0.03 0.45 0.11 88.70 Cb,N
HCM 12 12.00 - 1.00 - - - - - 86.90 V, Nb
X20CrMoV121 12.00 0.50 1.00 0.50 - - 0.50 0.23 85.20 V
AISI 304 19.00 9.50 - - - - - - 71.40 -
SS 3338 18.00 12.00 - 0.72 - - 0.15 - 69.20 Nb, Ta
AISI 316 17.00 11.00 2.70 - - - - - 69.20 -
AISI 321 18.50 10.20 - 0.75 - - 2.00 0.06 68.50 -
AISI 347 17.50 10.30 - 1.30 - 0.70 1.60 0.08 68.40 Nb, Ta
245 MA 21.00 11.00 - 1.70 - - - - 66.20 -
2205 22.00 5.50 3.20 1.00 - - 2.00 - 66.20 -
Esshete 1250 16.00 11.00 1.25 1.00 - - 7.00 - 62.50 V, Nb
AISI 309 23.00 14.50 - 0.70 - - 1.50 0.10 60.20 P
HR2M 22.20 14.40 1.49 0.55 - - 3.14 0.03 58.10 N
YUS170 24.40 13.20 1.50 0.78 - - 0.58 0.02 59.50 N, P

O PAPEL vol. 71, num. 6, pp. 57 - 71 JUN 2010


800 modificado 20.00 30.00 1.50 0.20 - - 1.50 0.10 53.90 Ti,Nb,V
800 modified
AISI 310 25.00 20.50 - 0.50 - - - 0.08 53.80 -
SAVE 25 23.00 18.00 - 0.40 3.00 - 1.00 0.10 52.30 Nb,W,N
NF709 20.00 25.00 1.50 0.60 - - 1.0 0.07 50.80 Ti,Nb,N
Liga 800 HT 21.00 32.50 - 0.50 0.40 0.40 0.75 0.05 44.30 Ti
Alloy 800 HT
HR3C 25.00 29.50 - 0.42 1.28 - 1.10 0.06 42.60 N
AC66 27.00 32.00 - 0.25 - 0.02 0.80 0.06 39.20 Ce, Nb
Sanicro 28 27.00 31.00 3.50 - 1.00 - 0.05 0.01 37.30 -
Sanicro 38 21.00 38.00 2.50 0.30 1.70 - 0.80 - 35.60 Ti
Liga 825 22.00 39.00 3.50 0.36 - - 0.50 - 34.50 Ti
Alloy 825
HR11N 28.50 41.20 1.06 0.12 - - 0.50 0.01 28.60 N
HR120 25.00 37.00 2.50 0.60 0.18 0.10 0.70 0.05 27.50 Nb,Co,W
O PAPEL - Junho 2010

Nicrofer 45 TN 27.00 46.90 - 2.70 - 0.20 - 0.08 23.00 Re


Super 625 21.00 52.70 8.97 0.21 - 0.28 0.20 0.01 15.80 Nb
Liga 600 15.50 74.00 - 0.25 0.26 - 0.50 0.07 9.30 V, Nb
Sanicro 65 21.00 61.00 8.40 0.35 - - 0.38 - 8.80 -
Liga 625 21.00 58.00 9.00 0.50 - 0.40 0.50 0.10 5.00 Nb, Ti
Alloy 625
Liga TD 22.00 74.80 3.00 1.40 - - - 0.01 0.10 Ce, La 69
69
Alloy TD
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