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Acid salt corrosion in a hydrotreatment plant of a petroleum refinery

Article  in  Engineering Failure Analysis · December 2008

DOI: 10.1016/j.engfailanal.2007.11.014

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Engineering Failure Analysis 15 (2008) 1035–1041

www.elsevier.com/locate/engfailanal

Acid salt corrosion in a hydrotreatment plant

of a petroleum refinery
Paulo Pio Alvisi a,1, Vanessa de Freitas Cunha Lins b,*
a
Gabriel Passos Petroleum Refinery, PETROBRAS, Betim, Brazil
b
Corrosion and Surface Engineering Laboratory, Chemical Engineering Department, Engineering School, Federal University of
Minas Gerais, 35 Espı́rito Santo Street, 30160-030 Belo Horizonte, Minas Gerais, Brazil

Received 19 July 2007; accepted 26 November 2007

Available online 4 December 2007

Abstract

The operation of a diesel hydrotreatment plant was stopped after only 18 months of service due to the obstruction of a
set of heat exchangers, which are responsible for cooling of the stream that flows out from reactors. In particular, the
obstruction occurred mainly in one of them that operated with a low temperature. Chemical analysis of fouling of samples
obtained from obstructed tubes identified the presence of NH4Cl and the absence of NH4HS, whose presence is expected in
these units. The stream that flows out of the reactors has mainly H2S and NH3; however, the chloride contents lower than
the sulfide contents are sufficient to precipitate NH4Cl due to the differences between the stability of both salts. The steel
used in the equipment of this unit is austenitic stainless steel. Thus the presence of a hygroscopic salt must be eliminated
since its hydrolysis generates HCl, and severe restriction to the HCl content in the plant feedstocks must be observed con-
sidering that only a very small amount of this compound is expected from the organic chloride.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Petrochemical; Intergranular corrosion; Hydrogen-assisted cracking; Heat exchanger failures

1. Introduction

In a petroleum refinery, the saturation of the olefin in a specific fraction (diesel, naphtha) and the reduction
of impurities or heteroatoms such as sulfur and nitrogen are operations that must be done to increase the sta-
bility and reduce the corrosivity of fractions, and besides this, the oil industry is under increased pressure from
legislators to improve the quality of diesel fuel with a view of reducing exhaust emissions [1]. The olefin sat-
uration and the removal of impurities are performed in hydrotreatment plants by hydrogenation of hydrocar-
bons by H2 addition to the organic compounds, which are responsible for contamination and insaturation
[2,3].

*
Corresponding author. Tel.: +55 31 32381775; fax: +55 31 32381789.
E-mail addresses: [email protected] (P.P. Alvisi), [email protected] (V. de Freitas Cunha Lins).
1
Tel.: +55 31 35294584.

1350-6307/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2007.11.014
1036 P.P. Alvisi, V. de Freitas Cunha Lins / Engineering Failure Analysis 15 (2008) 1035–1041

The removal of impurities by hydrogenation produces inorganic compounds that can precipitate as acid
salt. The acid salts are hygroscopic and in this condition very aggressive to carbon steel, alloy steel, and stain-
less steel, which are typical construction materials of the hydrotreatment unit. The acid salt can also generate
the obstruction of tubes as well as corrosion.
The hydrotreatment unit of a petroleum refinery was projected to treat 3500 m3 of diesel oil per day. The
hydrogenation occurs in two reactors (R-01 and R-02) joined in series with nominal spatial velocities of
3  104 s1 and 5  104 s1 (R-01 and R-02, respectively), at 400 °C and pressure of 9.3 MPa.

2. Hydrotreatment process

The hydrodesulfurization and hydrodenitrogenation are performed by the development of the exothermic
reactions:
R–SH + H2 ! R–H + H2 S(g) ð1Þ
R–N + 2H2 ! R–H + NH3 (g) ð2Þ
While several kinds of residue upgrading processes are commercially proven, such as the fixed-bed, moving-
bed, and ebullated-bed processes, the fixed-bed processes are still the main process used [4]. In this study, the
reactions develop in a fixed-bed of catalyst (NiMo) [5], for thiol (R–SH), pyridine or pyrrol (R–N). The sulfur
and nitrogen removal is exothermic, and produces hydrogen sulfide and ammonia. Water vapor, CO2, and CO
can be produced by the reaction, which produces the naphthenic acid decomposition
2R0 –R00 –COOH + 2H2 ! 2R0 –H + 2R00 –H + H2 O(g) + CO2 (g) + CO(g) ð3Þ
This environment can produce HCl, but it is not the main product. However, chloride production can occur
by reactions such as
R–Cl + H2 ! R–H + HCl(g) ð4Þ
The HCl can also be introduced in the system by the plant feedstock; therefore, the stream that flows from the
reactors is chemically complex and contains diesel, hydrogen in excess, H2S, and NH3. Usually, the content of
H2S is higher than the concentration of NH3, and the stream can still have HCl, CO2, CO, and water vapor.
As the stream cools it heats the diesel oil and the cooling water.
After leaving the last heat exchanger (E-06-B), the mixture cools to 50 °C, and is submitted to a first sep-
aration in a vertical vase at high pressure (V-02), and to a second separation process at low pressure (V-03).
Three phases are produced: a gaseous phase rich in hydrogen, which must be recycled in the plant, a liquid
organic phase (diesel oil) containing mainly H2S as impurity, and an aqueous phase rich in ammonia and
H2S, which goes to treatment as residual water. This solution comes from the wash water, which is injected
at a point before the E-02 heat exchanger. Finally, the hydrocarbon goes into a stripper column (C-02), where
the H2S and the lighter impurities are separated and flow to the top of the tower, and the treated diesel is
stored.

3. Failure description

In March 2006, after 18 months of service the hydrotreatment unit stopped due to the obstruction of the
stream cooling system.
The set of four heat exchangers (E-04D-C-B-A) was considered the system most susceptible to suffering pre-
cipitation and the accumulation of salts due to the temperatures of the E-05 heat exchanger (350 °C) and to
the injection of wash water before the E-02 heat exchanger.
This hypothesis was confirmed after the liberation of the set of E-04 heat exchangers. Specifically, the E-
04A heat exchanger, in the exit area of lower temperatures (200 °C), showed the highest obstruction, Fig 1.
At the entrance of this equipment, and in the E-04B heat exchanger similar deposits were identified, in lower
concentration. X-ray diffraction analysis (XRD) of the deposits identified the presence of NH4Cl and the
absence of NH4HS.
 P.P. Alvisi, V. de Freitas Cunha Lins / Engineering Failure Analysis 15 (2008) 1035–1041 1037

Fig. 1. Exit of the E-04A heat exchanger with salt accumulation.

Fig. 2. Distribution of tubes that showed passage during hydrostatic test in the E-04A heat exchanger.

During the performance of the hydrostatic test, failures were identified in 83 tubes in the E-04A heat
exchanger (Fig. 2) and in 3 tubes of the E-04B heat exchanger, both with U-tubes in A-213Gr304L specifica-
tion, 3/400 BWG 14.

4. Failure mechanisms operating in equipment localized at a point after the reactors

In the hydrotreatment plant, the system that collects and cools the stream coming from reactors starts in the
E-05 heat exchanger and ends in the E-06B heat exchanger. This system consists of several heat exchangers (E-
05, E-04D-A, E-02, E-01, E-06AB), which reduce the stream temperature. Due to the presence of H2S and H2 at
high temperatures and high pressures, the tube between the E-05 and E-04A heat exchangers is made of AISI
347 stabilized stainless, the tube between the E-05 and E-04D/C heat exchangers is made of AISI 347, and the
tube between the E-04B and A heat exchangers is made of AISI 304L steel. This material specification is a result
of the probability of a sulfide attack or of a high temperature hydrogen attack (HTHA) [6,7].
1038 P.P. Alvisi, V. de Freitas Cunha Lins / Engineering Failure Analysis 15 (2008) 1035–1041

The above mentioned steels are necessary because of a possibility of an intergranular attack (IGA) or inter-
granular stress corrosion cracking (IGSCC) caused by acids such as H2SxO6. Such attack can occur when the
steel was sensitized during plant operational stops, when humid air is present in the system and the acid is
produced by sulfides/humid air interaction. Corrosion and erosion–corrosion still occur, promoted by H2S
or ammonium bisulfide, NH4HS. The specification of tubes of austenitic stainless steel remains necessary
although the carbon steel or the alloy steel can also be used. As AISI 304L steel is more resistant to a salt
attack than carbon steel or alloy steel, it is used to make heat exchangers that operate at low temperatures,
E-01 and E-06AB. However, this metallurgy shows significant limitations relative to the contact with ammo-
nium chloride, NH4Cl.
The decrease in temperature at values lower than 200 °C makes it possible to use carbon steel where the
equipment thickness is oversized. The carbon steel is utilized in pipes that connect the E-04A/E-02/E-01/E-
06AB/V-02/V-03/C-02 equipment. The heat exchanger E-02 has a tubular bundle in 1.25%Cr–0.50%Mo- alloy
steel, but carbon steel can also be used.
The use of alloy steel as a substitute for stainless steel, which is the metallurgy adopted in the bundle of the
E-01 and E-06AB equipment, is due to the injection of wash water that comes from the water treatment unit
rendering a low risk of using steel which comes into contact with NH4HS since the solution has a bisulfide
concentration less than 2% (w/w) [6]. In Fig. 3, metallurgy is shown, and the temperature is also shown at
two points. The water is injected with a flow of 21 m3/h in order to prevent precipitation and to solubilize
the salt.
Low temperatures, presence of H2S/NH4HS and water are factors which generate corrosion and embrittle-
ment of carbon and alloyed steels. Embrittlement is a process generated by hydrogenation of steel, which
occurs in parallel with an FeS formation.
The FeS, which originates in steel that comes into contact with H2S/NH4HS in an alkaline environment due

to the presence of NHþ 4 OH , can precipitate. Then, steel corrosion, steel embrittlement (hydrogen induced
cracking, HIC, and stress oriented hydrogen induced cracking, SOHIC), and the obstruction of tubes and
the E-02 heat exchanger can occur.

5. Precipitation of ammonium salts

Gaseous streams containing H2S, NH3 and HCl can precipitate acid salts such as NH4Cl and NH4HS.
Considering the following reversible reaction:
NH3 (g) + HCl(g) = NH4 Cl(s) ð5Þ

Fig. 3. Heat exchangers and pipes system at a point after the R-02 reactor.
 P.P. Alvisi, V. de Freitas Cunha Lins / Engineering Failure Analysis 15 (2008) 1035–1041 1039

and the salt stability constant, k1:

k 1 ¼ pNH3  pHCl ð6Þ
for a given temperature, the precipitation can occur if
10k1 < pNH3  pHCl ð7Þ
where pNH3 and pHCl are partial pressures of ammonia and hydrogen chloride [8].
With a decrease in temperature, the amount of ammonia and hydrogen chloride necessary for precipitation
decreases [9]. Therefore, precipitation can occur if the concentration of ammonia is sufficient [9].
One important question that can be considered is that the hydrotreatment unit produces a higher concen-
tration of H2S than that of HCl, and the mechanism of NH4Cl production must be explained. The answer
seems to be the higher trend of precipitation of ammonium chloride than that of bisulfide. This can be con-
firmed by examining the curve of variation of stability constant (k2) of NH4HS relative to the following
reaction:
NH3 (g) + H2 S(g) = NH4 HS(s) ð8Þ
The salt stability constant is
k 2 ¼ pNH3  pH2 S ð9Þ
where pH2 S is the partial pressure of hydrogen sulfide. For a given temperature, the precipitation can occur if
10k2 < pNH3  pH2 S [9]. For precipitation of NH4HS at 200 °C (390 °F) to occur it is necessary that
pH2 S > 10þ6 =pNH3 ð10Þ
The temperature observed at the point of salt accumulation of the heat exchanger (E-04A) is about 200 °C.
In the same conditions for the precipitation of NH4Cl, we should have
pHCl > 103 =pNH3 ð11Þ
Moreover, a humid salt is necessary in both cases to produce under deposit corrosion. In the case of steel in
contact with NH4HS, the following reaction can occur:
Fe + 2NH4 HS ! FeS+(NH4 )2 S + 2H ð12Þ
Fig. 4 shows the C–0.5%Mo alloyed steel tube corrosion caused by ammonium bisulfide. The tube is from a
bundle of heat exchangers.

Fig. 4. Corrosion generated by deposits of NH4HS in a C–0.5%Mo (p/p) tube of heat exchanger.
1040 P.P. Alvisi, V. de Freitas Cunha Lins / Engineering Failure Analysis 15 (2008) 1035–1041

Fig. 5. Pitting corrosion in tube made of AISI 304L steel in the E-04A heat exchanger that presents deposits of NH4Cl.

Hydrolysis of NH4Cl can be represented by the following reaction:

NH Cl(s) + H O(l) ! NH OH(s) + Hþ Cl
4 2 4 ð13Þ
A strong acid is produced generating chlorides in an environment with low pH, at a salt–steel interface. The
contact between stainless steel and salt can create an active–passive cell, and can generate pitting, crevice cor-
rosion, or stress corrosion cracking (SCC). Fig. 5 shows the result of a contact of NH4Cl with AISI 304L steel,
a sample of constructive material of tubes of the E-04A heat exchanger. Visual examination of this sample
showed that pitting was responsible for wall perforation (2.1 mm in thickness) of 83 tubes after 18 months
of service.

6. Prevention

The corrosion process caused by NH4HS must be taken into consideration due to the cooling of the stream
coming from the reactors, and the formation of H2S and ammonia in the system.
However, the presence of NH3 and HCl is also possible, and the corrosion of equipment caused by NH4Cl
must also be considered. Bisulfide tends to precipitate at points of lower temperatures than the areas in which
ammonium chloride precipitates. It is more likely that the bisulfide precipitates in areas of temperatures lower
than the dew point of vapor. Both salts are hygroscopic; therefore, the presence of free water is not a require-
ment for corrosion to occur.
To remove or to solubilize the salt precipitated is necessary to prevent precipitation.
Considering the solubility of both salts in aqueous solutions, wash water is usually injected. The function of
wash water is to clean the vapor, removing HCl, H2S, and ammonia. The partial pressure of these contami-
nants is then decreased, precipitation is avoided, and the salts are dissolved in water. A fraction of 25% (w/w)
of injected water must be liquefied at the injection point. This water must have the following characteristics:
pH between 7 and 9, absence of cyanide, a chloride content limited to 100 ppm (optimum content of 5 ppm),
and 50 ppm of oxygen (optimum content of 15 ppm) [6]. The water must be injected at a point before the salt
precipitation. Therefore, it is necessary to install an additional point for the injection of water. The use of
austenitic stainless steel is not recommended due to the presence of chlorides as solid salt or as aqueous solu-
tion in the environment.
The concentration corrosion cell is caused by the deposition of humid salt, and aqueous solutions contain-
ing salt solubilized are aggressive to the equipment. An opposite effect can occur if the amount of water
injected is not sufficient. The limit of 2% (w/w) for salt content is recommended, for bisulfide aqueous solution
in contact with carbon steel. However, this same solution can generate erosion–corrosion. A flow rate of 3 m/s
 P.P. Alvisi, V. de Freitas Cunha Lins / Engineering Failure Analysis 15 (2008) 1035–1041 1041

is recommended to minimize erosion and salt deposition [6]. Carbon steel can also suffer hydrogen embrittle-
ment due to its contact with solutions containing NH4HS/H2S. Similar restrictions are applied to the Cr–Mo
alloyed steel. AISI 347 and 304L stainless steels have been widely used in the hydrotreatment plant. The steels
used are adequate for contact with NH4HS solution or with salt deposits in the absence of chlorides. In the
presence of chlorides, nickel alloys such as 825 alloy, the austenitic–ferritic stainless steels, or the superausten-
itics must be used [6].
The efficient removal of salt is necessary to hydrotreatment plants that operate with equipment made of
austenitic stainless steels. The contamination of the plant feedstock with HCl must be avoided.

7. Conclusions

A premature failure of 20% of a tubular bundle in AISI 304L of a heat exchanger was caused by NH4Cl
salt. The damaged equipment in service came into contact with streams coming from reactors of a diesel
hydrotreatment plant. The failure was localized at a point before the injection point of wash water. The stream
that flows out of the reactors has H2S and NH3, and HCl contents lower than the sulfide contents, which are
sufficient to precipitate NH4Cl due to the differences between the stability of both salts. The steel used in part
of equipment was austenitic stainless steel. The presence of hygroscopic salt must be eliminated since its
hydrolysis generates HCl. The introduction of an additional point for the injection of wash water and an ade-
quate selection of material for contact with chlorides are necessary.

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