Engineering Failure Analysis 31 (2013) 387–393

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Failure analysis of a reactor effluent air cooler

Guofu Ou a,b,⇑, Kuanxin Wang a, Jianliang Zhan a, Meng Tang a, Huihui Liu a,b, Haozhe Jin a
a
The Lab of Multi-phase Deposition and Erosion, Zhejiang Sci-Tech University, Hangzhou 310018, China
b
Hangzhou Fluid Technology Co., Ltd., Zhejiang, Hangzhou 310018, China

a r t i c l e i n f o a b s t r a c t

Article history: In the present research, root causes of the tube explosion of a refinery hydrocracking reac-
Received 16 September 2012 tor effluent air cooler (REAC) were studied. For this purpose, anatomical analysis was firstly
Accepted 11 February 2013 used and ammonium salt crystals were found. Based on the actual operating conditions,
Available online 26 February 2013
ionic equilibrium model was established by Aspen software to calculate the crystal tem-
perature of the NH4Cl and NH4HS. The results indicate that NH4Cl crystal temperature ran-
Keywords: ged from 175 °C to 210 °C with different chlorine and nitrogen content of the feedstock,
Ammonium chloride
which is higher than the operating temperature of REAC. To analyze the impact of the
Air cooler
Tube explosion
air cooler structure on the ammonium salt deposition location, numerical simulation
Failure analysis including the air cooler header box and bundles was conducted by the Fluent software.
The results show that a bias flow regime exists because of the large vortex formed in both
sides of the header box inlet. The velocity and aqueous phase fraction of the multiphase
were low in the tubes of the header box inlet both sides, which result in the NH4Cl depo-
sition and under-deposit corrosion. In order to verify the failure analysis results, other in
service air coolers were inspected using the infrared camera, and the results show that
other air coolers had the plugging features at the same position. Finally, some recommen-
dations were given to mitigate the NH4Cl deposition.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Reactor effluent air cooler (REAC) failure has been recognized as a serious problem since the commercial development of
the hydroprocessing units [1,2]. Finding out the failure reasons and preventing the REAC system failure appearance again
have long been a hot issue in the oil refining field. In recent years, many research focused on the erosion–corrosion problem
of the multiphase flow and the results have played an important role in controlling the erosion–corrosion of the air cooler
[3,4]. However, the ammonium salt deposition and under-deposit corrosion of the air cooler have not attracted sufficient
attentions and accidents caused by the ammonium salt deposition still occurred frequently [5–7]. After a survey among more
than 20 Chinese refineries in 2011, it was found that the accident caused by ammonium salt deposition is more serious than
the erosion–corrosion. Recent years, some simplified thermodynamic models and multi-physical field coupling models were
established to analysis ammonium salt deposition. However, the impact of other substances (hydrocarbons, water, hydro-
gen, etc.) and the unbalanced air cooler structure were not taken into account in the most of these models [8,9]. More
researchers did not distinguish between the crystal and deposition of ammonium salt, which result in the inaccurate predic-
tion of deposited position [10]. Under practical conditions, the ammonium salt deposition related to the multiphase equilib-
rium, fluid flow, and liquid distribution. In this paper, ionic equilibrium model and the CFD simulation were used to analyze a

⇑ Corresponding author at: The Lab of Multi-phase Deposition and Erosion, Zhejiang Sci-Tech University, Hangzhou 310018, China. Tel.: +86 571
86843348; fax: +86 571 86843357.
E-mail address: [email protected] (G. Ou).

1350-6307/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.engfailanal.2013.02.025
388 G. Ou et al. / Engineering Failure Analysis 31 (2013) 387–393

REAC failure caused by the ammonium salt deposition. The analysis results were validated by inspecting other in service air
coolers. Finally, some recommendations were given to mitigate the ammonium salt deposition.

2. Process and air cooler failure

The reaction effluent cooling and separation process is shown in Fig. 1. The effluent stream is cooled through a series of
feed/effluent exchangers before enters a hot, high-pressure separator (HHPS). Wash water is injected into the HHPS vapor
stream before it enters the air coolers. The inlet and outlet header pipes of the air coolers (8 sets) are balanced designed
[11]. After cooled from 160 °C to 45 °C in the air cooler, the multiphase flow enters a cold, high-pressure separator (CHPS)
and separated into liquid, vapor and aqueous phase. The hydrocarbon liquid from the CHPS is routed into a cold, low-pres-
sure separator (CLPS) and vapor, mostly hydrogen, recycled back to the reactor. The HHPS liquid stream is also separated in a
cold, high-pressure separator (CHPS).
The explosion of the air cooler occurred in the 16th months of the run cycle, because of refining low-quality crude from
the Middle East. Inspection revealed that the explosion tube located in the first row near the entrance of the header box
(Fig. 2). The air cooler is made of 10# carbon steel and designed based upon the conventional design criteria [12]. Tube
stream velocity is ranging from 3.0 m/s to 6.1 m/s. More than 20 vol% of water remains the aqueous phase at the injection
point. NH4HS concentration of the sour water is below 8 wt%.

Recycle gase

Wash
Reactor Water Cold high- L
effluent pressure separator C

Hot high- Air Coolers

pressure
Feed/effluent L
separator C
exchangers
Sour water

Sour gas

Hot low- Cold low- L

C
pressure L pressure separator
C
separator

Sour water
Hot effluent liquid to
Cold effluent liquid to
fractionation section
fractionation section

Fig. 1. Reactor effluent cooling and separation process.

Fig. 2. The location of exploded air cooler tube.

 G. Ou et al. / Engineering Failure Analysis 31 (2013) 387–393 389

3. Analysis procedures and methods

3.1. Ammonium salt deposition analysis

3.1.1. Ammonium salt deposition mechanism

The hydroprocess units usually process streams containing heteroatom which will be converted to H2S, NH3, and HCl.
When the reaction effluent enters the cooling and separation system, as the temperature decreases, NH4Cl and NH4HS crystal
are formed in the vapor phase by the following reactions.

NH3 ðgÞ þ HClðgÞ NH4 ClðsÞ ð1Þ

NH3 ðgÞ þ H2 SðgÞ NH4 HSðsÞ ð2Þ

The equilibrium constants can be written as: K1 = PNH3  PHCl, K2 = PNH3  P H2 S , where PNH3, PHCl, and P H2 S represent partial
pressures of NH3, HCl, and H2S in the vapor phase. Once formed, the ammonium salts would not readily reverted back to
NH3, HC1 and/or H2S without much higher temperature or longer time. When vapor phase which contained ammonium salt
flows to the downstream, deposition will occur at where the velocity is low. If there is no adequate liquid to rapidly dissolve
and remove the ammonium salt, the amount of deposited salts will increase. As the ammonium salt accumulated, the veloc-
ity of the multiphase will be reduced and then the temperature will also be reduced due to the cooling of the outside air. In
return, the reduced temperature and velocity will cause further ammonium salt crystal and deposition. In summary, the
deposition of the ammonium salt is a self-accelerating process, once the ammonium salt deposition happened, under-depos-
it corrosion, plugging, explosion and other accidents would likely to occur.

3.1.2. Crystal temperature calculation method

In the effluent cooling process, each phase and component are dominated by the equilibrium. Ionic equilibrium model can
be established by Aspen software. By simulating the cooling and separation process (Fig. 1) of the reactor effluent using this
model, the Kp1 = PNH3  PHCl, Kp2 = PNH3  PH2 S of the vapor phase under different temperatures can be calculated. Drawing
this curve and the ammonium salt crystal equilibrium curve in the same graph, the intersection value is the ammonium salt
crystal temperature. For example, the calculation of NH4Cl crystal temperature was shown in Fig. 3.

3.2. CFD simulation of the air cooler

To analyze the impact of the air cooler structure on the ammonium salt deposition location, Fluent software was used.
The REAC pipes are divided into three passes. Each pass is composed of 93 tubes with wings slice and divided into two rows.
Each tube is 25 mm in diameter, 3 mm in wall thickness, 9,000 mm in length, and is made of carbon steel. The typical inlet
temperature of the stream is 160 °C, while the outlet temperature is about 45 °C. The operation pressure is 14 MPa. The com-
puting model includes the REAC header box and the first pass is shown in Fig. 4. The mesh used in all structured hexahedron,
the total number of mesh is 1.96 million. Table 1 shows the physical parameters of the inlet stream, which was calculated by
Aspen Plus. The mixture and standard k–e turbulence model were used, mass-flow inlet was set at the entrance and pressure
outflow was set at the exit. The logarithm wall function was used at the fluid–solid interface. After iterative calculation, the
residuals of each equation are less than 106 and the quality difference of import and export is less than 1 e3.

0.30
Kp 1
0.25 K1

0.20
K (KPa2)

0.15

0.10

0.05 NH4Cl(S) NH3(g)+HCl(g)

0.00
120 140 160 180 200 220
Temperature ( )

Fig. 3. The NH4Cl crystal temperature calculation.

390 G. Ou et al. / Engineering Failure Analysis 31 (2013) 387–393

Fig. 4. (a) Modeling of the REAC first tubesheet. (b) Cross-section meshing of the REAC bundle.

Table 1
Physical property parameters of the inlet stream.

Vapor phase Liquid phase Aqueous phase

Flux (m3 h1) 1631 8.21 5.85
Density (kg m3) 18.23 610.30 896.42
Phase fraction (%) 99.15 0.50 0.36
Viscosity (Pa s) 1.16E  5 1.42E  4 3.2E  4

4. Results and discussion

4.1. Anatomical analysis

Visual inspections were conducted firstly after the accident happened. The exploded position is at the bottom of the tube
and bias to the side away from the header box inlet, 0.35 m away from the tube entrance. Fig. 5 shows the failure morphol-
ogy of the anatomical tube, where still some white crystal particles can be seen inside the tube. Therefore, the failure is
mainly caused by the deposition of ammonium salt which can absorb water and form saturated solution easily. Because
the corrosion rates of wet ammonium salt is very high, the carbon steel tube will be corroded quickly if ammonium salt
deposits on the wall.

4.2. Ammonium salt crystal analysis

History data of feedstock analysis shows that the chlorine content ranges from 1 ppm to 5 ppm, nitrogen from 0.05% to
0.3%, and sulfur from 0.7% to 1.5%. According to the crystal temperature calculation method, the crystal temperature of NH4Cl
and NH4HS can be calculated. Fig. 6 shows NH4Cl crystal temperature with different nitrogen and chlorine content of the
feedstock. As the nitrogen and chlorine content increase, the crystal temperature of NH4Cl increases, but the trend is grad-
ually slow. With the different nitrogen, chlorine content, the NH4Cl crystal temperature of the vapor phase ranged from
175 °C to 210 °C.

Fig. 5. Morphology of the exploded tube.

 G. Ou et al. / Engineering Failure Analysis 31 (2013) 387–393 391

210

NH4Cl Crystallization Temperature ( )

205

200

195

190

185

180

175

170
6
5 3000
4 2500
2000
3 1500
Cl ( 2 1000 )
ppm 1 500 ppm
) N(

Fig. 6. NH4Cl crystal temperature with different Feedstock N, Cl content.

Fig. 7. Pathline inside the air cooler header box and tubes.

The temperature of the inlet REAC stream is 160 °C, therefore the NH4Cl crystal has occurred in the effluent vapor phase
before entering the air coolers. After entering the air cooler, deposition will happen at where the velocity and liquid fraction
are low. The calculated NH4HS crystal temperature is between 60 °C and 40 °C with the same calculation method. Therefore,
the tube explosion is mainly caused by the NH4Cl deposition. Although NH4HS deposition may occur when the fluid temper-
ature decreased to 60–40 °C, the large amount of aqueous has formed which can quickly dissolve deposited crystals. There-
fore, the NH4HS deposition and under-deposit corrosion are impossible.

4.3. Flow field analysis of the REAC

Fig. 7 shows the pathline inside the half of REAC header box and the first pass. Because of the unbalanced air cooler struc-
ture, a large vortex formed in the both sides of header box inlet, which can cause non-uniform distribution of the multiphase
effluent stream. The stream enters the REAC tubes in a helix form, resulting in the formation of a bias flow regime.
392 G. Ou et al. / Engineering Failure Analysis 31 (2013) 387–393

4.4 Velocity
-3
Aqueous phase fracion 4.0x10
4.2

-3
4.0 3.8x10

Aqueous volume fraction

3.8
velocity (m/s) -3
3.6x10
3.6
-3
3.4 3.4x10

3.2 -3
3.2x10
Effluent Inlet
3.0
-3
3.0x10
2.8

0 5 10 15 20 25 30 35 40 45
Tubes number

Fig. 8. The velocity and aqueous fraction of the first row tubes.

The stream velocity and aqueous fraction of each tube in the first row are shown in Fig. 8. From the inlet of the header box,
the stream velocity of each tube shows a suddenly fall and then gradually raise trend. The maximum velocity just appeared
at the tubes below the header box inlet, while the minimum velocity appeared at the both sides close to the inlet. The aque-
ous phase fraction of the tubes below the header box inlet is low and gradually rising to the both sides. The velocity and
aqueous fraction distribution trend of the second row are similar to the first row, while the aqueous phase fraction is higher
than it.
Therefore, the ammonium chloride in the vapor phase will first deposit at the tubes on both sides close to the header box
inlet where the velocity is lower than other tubes. Because the aqueous fraction is also low, deposited ammonium chloride
will rapidly absorb the small amount of water and corrosion the carbon steel tubes. With the continuous reduction of the
temperature after the stream entered the tubes, the increased condensing liquid could diluted and removed the NH4Cl crys-
tals. In conclusion, the forepart of the tubes which located in the sides close to the header box inlet is the most dangerous
ammonium chloride deposition failure area. This is the reasons that the REAC tube located at the side of the header box inlet
exploded.

4.4. Verification and prevention

To confirm the analysis results, infrared camera was used to inspect the in service REAC. The surface temperature of the
unexploded REAC is shown in Fig. 9a. There are obvious two tubes in both sides of header box which the temperature is low-
er than the others. This means that the tubes have been plugged by the deposited ammonium chloride and the under-deposit
corrosion products. The plugged tube position is the same with the have exploded REAC tube. Tube explosion may occur if
not promptly treated. The new REAC surface temperature which replaced the exploded one is shown in Fig. 9b. It can be seen
that the new REAC surface temperature is uniform, temporarily no plugging phenomenon.To prevent this type of failure, the
following are recommended:
1. Control chlorine and nitrogen content of the feedstock to avoid NH4Cl crystal at a higher temperature.
2. Increase the wash water and add mixer after the injection point to dissolve more NH4Cl crystals.
3. Change the REAC structure or add perforated baffle in the header box to distribute the multiphase effluent stream to each
tubes uniformly.

5. Conclusions

Process simulation combined with CFD numerical calculation is an effective method to analyze the ammonium salt depo-
sition. The tube explosion of REAC was mainly caused by NH4Cl deposition and under-deposit corrosion. The unbalanced
REAC structure makes the non-uniform distribution of the velocity and phase fraction, which can cause the ammonium salt
deposition more easily in some tubes. The deposition analysis results are in good agreement with the infrared camera
inspection results. Reducing chlorine and nitrogen content of the crude oil, changing the REAC structure, and adding mixer
or perforated baffle in the REAC system can be used to eliminate the ammonium chloride deposition and under-deposit.
 G. Ou et al. / Engineering Failure Analysis 31 (2013) 387–393 393

120.0 ℃

20.0 ℃

Fig. 9a. The old REAC surface temperature.

120.0 ℃

20.0 ℃

Fig. 9b. The new REAC surface temperature.

Acknowledgements

The project is supported by the Natural Science Foundation of China (Nos. 50976106, U1261124) and National Key Tech-
nology R&D Program (No. 2012BAK13B03-02).

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