Anlise de corroso e estudos de inibio no processo de dessulfurizao mida de gs

natural
O gs natural uma espcie de combustvel limpo, conveniente, eficiente, de alta
qualidade e tambm uma matria-prima importante para a indstria qumica.
Geralmente, existem nele algumas impurezas como o sulfeto de hidrognio (H2S) que
podem causar muitos problemas, incluindo a poluio do ar e corroso. Portanto, a
purificao do gs natural torna-se muito importante. O processo de dessulfurizao
pode ser dividido em tecnologia seca ou mida. A dessulfurizao mida, na qual a
soluo lquida normalmente contm algumas substncias alcalinas para reforar a
qualidade de purificao do gs, um dos processos mais promissores na
dessulfurizao de gs natural. O mtodo da amina do lcool, um tipo de tecnologia
molhada, o processo o mais extensamente usado por causa da capacidade grande, da
estabilidade e da confiabilidade da operao [2]. No entanto, deve notar-se que alguns
srios problemas de corroso foram encontrados nesse processo. No processo de
purificao de gs natural, a corroso pode causar perdas significativas nas propriedades
e apresenta riscos para os humanos. Alm disso, a poluio da soluo de amina e a
perda devido corroso aumentaro o custo de produo.
A Fig 1 mostra o fluxograma do processo da dessulfurizao molhada do gs natural na
planta em Sichuan que apresenta dois tipos de morfologias de corroso, que
demonstram que tanto a corroso uniforme como a por pites se formam na superfcie do
metal dentro da torre de absoro.
FIG 1

composio

qumica do
gs natural est na Tabela 1
A corroso, que ocorreu no processo de dessulfurizao mida do gs natural, pode
ser afetada por muitos fatores, tais como a concentrao de amina, a temperatura, a
presso e a velocidade do fluido. No entanto, a concentrao de amina lcool e a
temperatura podem ser consideradas como os principais fatores. O objetivo do presente
trabalho investigar a corroso e a inibio da corroso de ligas de ao de Fe-Al que
so usadas nas usinas de purificao de gs natural. A Tabela 2 apresenta a composio
qumica deste liga de ao de Fe-Al
Tabela 1
Component

H2

N2

CO2

H2S

COS

H2 O

CH4

C2H6

Others

wt%

0.02

0.55

9.99

17.98

0.02

0.09

71.20

0.12

0.03

Tabela
Chemical composition (wt%) of FeAl alloy steel.
Element

Al

Si

Ca

Cr

Fe

Nb

wt%

28.06

12.45

1.73

0.08

2.34

6.43

43.72

5.21

Mecanismo de corroso do H2S

A soluo aquosa de H2S pode ser dissociada em H+, HS e S2. um processo de
despolarizao quando corri o metal

Primeiramente, o H2S absorvido na superfcie de ferro na soluo. Ento, uma srie

de reaes de adsoro de nions e dessoro de ferro acontecem. Finalmente, Fe2+ ou
FeS produzido atravs de oxidao andica e hidrlise. Os processos podem ser
resumidos em quatro sub-reaes descritas nas equaes (3)(6), onde ad significa
estado de adsoro.

Em solues de cido fraco, depois da dessoro de H +, o FeHSad muda diretamente

para FeS, que produzido por uma reao andica eletroqumica. Esse FeS desacelera a
corroso e se for compactado, tem uma boa adeso ao substrato. Entretanto, quando o
FeS gerado no denso, ele formar uma galvanizao forte com a diferena de
potencial de 0.2 V a 0.4 V, de modo que possa promover a corroso do metal de base.
Alm disso, quando o enxofre se apresenta na soluo ou no substrato de metal, ele
impede que os tomos de hidrognio se transformem em uma molcula de hidrognio
numa certa extenso.
Efeitos da concentrao de lcool e amina na corroso
O H2S fornecido pela reao de Na2S e H3PO4 usado em fluxo de contracorrente
atravs de solues de MDEA de diferentes concentraes (30%, 40% e 50%). A
concentrao do A concentrao do gs cido carregado pelas trs solues de amina foi
mantida a 0,5 mol de gs cido / 1 mol de amina. Em seguida, os espectros de
impedncia e as curvas de polarizao foram medidos a 25 C. Os resultados foram
ilustrados nas Figs. 4 e 5.

Da fig. 4, pode ver-se que os espectros de impedncia eletroqumica medidos foram

aproximadamente semicirculares e o dimetro do semicrculo mudou com a
concentrao de amina. Isto sugeriu que o comportamento de corroso da liga de ao de
Fe-Al foi influenciado pela concentrao de amina de lcool no processo de utilizao
de soluo de amina de lcool para remoo de gs cido. Conforme ilustrado na Fig. 4,
o dimetro do arco capacitivo diminuiu inicialmente e depois aumentou com a
concentrao crescente de amina do lcool, o que indicou que a corroso da liga de ao
de Fe-Al primeiro aumentou e depois diminuiu no processo de remoo de gs cido.
Quanto maior a concentrao de amina, maior a quantidade de H 2S absorvido pela
unidade de volume de amina sob a mesma carga de gs cido, o que levou ao aumento
da taxa de corroso. No entanto, uma maior concentrao de MDEA (tal como a
concentrao era de 50%), resultaria num valor de pH mais elevado, o que era menos
condutor para a reao andica.
Conforme ilustrado na Fig. 5, o processo de corroso foi controlado pelo nodo nestas
experincias pelo fato de o valor de ba ser geralmente maior do que o de bc. Na curva
de polarizao, o potencial de corroso da soluo MDEA concentration was 40%
moved to the positive polarization potential direction. This indicated that the MDEA
solution was more effective on the anode electrode, namely it was more corrosive.

Fig. 5. Polarization curves of alcohol amine acidic

solutions at different concentrations at 25 C.

4.3. Effect of temperature on corrosion

H2S supplied by the reaction of Na 2S and H3PO4 was used to countercurrent flow
through MDEA solutions of 40% concen-tration. The concentration of the acid gas
loaded was maintained at 0.5 mol acid gas/1 mol amine. Then, impedance spectra and
polarization curves were measured at 30 LC, 40 LC, 50 LC and 55 LC. The results were
illustrated in Figs. 6 and 7.
From Fig. 6, the measured electrochemical impedance spectra were approximately
semi-circular and the diameter chan-ged with the temperature. The specific performs as
the diameter first decreased and then increased with the increase of the temperature.
Various electro-chemical corrosion parameters obtained from the Tafel curve were
presented in Table 5. In addition, the change trend of Icorr was as the same as that of the
diameter in EIS when the temperature ranged from 30 LC to 55 LC. It showed that the
corrosion of FeAl alloy steel in alcohol amine solution of acid gas first increased and
then decreased with the increasing temperature. The maximum value appeared at 50 LC,
which meant the solution was the most corrosive at this temperature.
During the transfer process, the kinetics of electrode reaction was sped up with the
increasing temperature, thus the response speed was improved and the corrosion rate of
steel was enhanced. However, when the temperature was higher than 50 LC, a dense
and strong adhesion film was produced on the surface of steel, so that the film can
prevent the corrosion of steel. On the other hand, the results may be explained by that
increasing temperature can exacerbate corrosion in the dynamics while increasing
temperature also contributed corrosive acid gas to be desorbed, which can effectively
slow down the corrosion at the same time.
As presented in Fig. 7, the corrosion process of 40% alcoholic solution was
controlled by the anode. The amine solution has the strongest corrosive at the
temperature of 50 LC.

4.4. Effect of corrosion inhibitor on corrosion

H2S supplied by the reaction of Na 2S and H3PO4 was used to countercurrent flow
through 40% alcoholic solution, and then the 1 wt% ethylene glycol, diethanol amine
and triethanolamine were added respectively. Impedance spectrum and polari-zation
curve were measured under 50 LC. The results were showed in Figs. 8 and 9.
As illustrated in Fig. 8, the corrosion behavior of FeAl alloy steel in the acid gas
removal process was affected by the cor-rosion inhibitor. Among them, the radius of
capacitive arc with ethylene glycol solution was smaller than the blank solution. This
indicated that the corrosion of ethylene glycol solution was larger than the blank
solution. That is to say, ethylene glycol has a promotive effect on corrosion.

Fig. 9. Polarization curves of 40% alcohol amine acidic solution with corrosion inhibitor at 50 LC.

The capacitive arc radius of both the diethanol amine solution and triethanolamine
were larger than that of the blank solution, moreover, the radius of the triethanolamine
solution was the largest. In addition, the polarization curves of amine solution adding
TEA and DEA were on the left side of blank solution curve while the curve of amine
solution adding glycol was on the right. Thus, it can be concluded that the corrosion of
the triethanolamine solution was the minimum. Because the glycol was active and
acidic in oxygen, it was propitious to the anode reaction and increased the corrosive of
solution. How-ever, diethanol amine and triethanolamine were two of corrosion
inhibitors in the industry. After adding corrosion inhibitor to the amine solution, the
metal electrode surface absorbed inhibitors molecules to form a protective film. Thus,
the protec-tive film prevented the corrosive ion absorbed on the metal surface and also

prevented the oxygen atom spreading in the solution, which protected the metal
electrode. Therefore, they can suppress anodic reaction to inhibit the corrosion.
Conclusion
(1) The morphology and chemical composition of the formed corrosion scales were
characterized indicating that the corrosion scale of FeAl alloy steel was mainly
FeS.
(2) The concentration of 40% amine solution was the most corrosive for FeAl alloy
steel.
(3) Corrosion on FeAl alloy steel in the process of wet desulfurization was first
increased and then decreased with the increasing of temperature, and the solution
was the most corrosive at 50 LC.
(4) Corrosion inhibitors such as diethanol amine and triethanolamine can reduce the
corrosion rate.