Engineering Failure Analysis 34 (2013) 115–120

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Engineering Failure Analysis

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

Failure analysis and faults diagnosis of molecular sieve in

natural gas dehydration
Changjun Zou a,⇑, Pinwen Zhao a, Meng Wang a, Delei Liu a, Hongda Wang b, Zhang Wen c
a
School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, PR China
b
Sichuan Tianyi Science and Technology Co., Ltd., Chengdu 610500, PR China
c
PetroChina Tarim Oilfield Company, Kurla 841000, PR China

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

Article history: Natural gas dehydration by molecular sieves is one of the most promising processes. How-
Received 15 July 2012 ever, the sharply declined dehydration capability of the regenerative molecular sieve has
Received in revised form 23 July 2013 become a serious problem for molecular sieve recycling. A series of experiments is carried
Accepted 23 July 2013
out to investigate the failure factors, such as pH analysis, thermogravimetry, differential
Available online 31 July 2013
thermogravimetry, scanning electron microscope, X-ray diffraction, and Fourier transform
infrared spectrum characterizations. The results indicate that there are four main aspects
Keywords:
for the unavailability of the regenerative molecular sieve. First, the pH values and surface
Adsorption
Failure analysis
alkalinity decrease. Second, the secondary pore structure is diminished and blocked. Third,
Faults diagnosis the crystallite size increases, and the crystals are agglomerated. Finally, not only are the
Molecular sieve hydrocarbons adsorbed, but also alcohols, ethers and carbonyl sulfides are generated in
Natural gas dehydration pores.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Natural gas is the primary fuel of choice for distributed fuel cell-based power-generation systems due to its abundant
supply and well-developed infrastructure [1,2]. Global consumption of natural gas reached 2600 billion cubic meters in
2003 and there has been a continuous growth at an annual rate of 1.8% [3]. Though methane makes up more than 90% of
the natural gas composition [4], natural gas still contains many impurities, of which the most common undesirable contam-
inant is moisture [5]. In the process of producing and transporting natural gas, the presence of moisture can cause excessive
pressure drop, hydrate, the decrease of heating value, the reduction in gas transmission efficiency, and corrosion in trans-
mission pipelines, especially in the existence of acid gases [6–8]. In particular, the possibility of pipeline obstruction due
to the formation of hydrate is one of the most serious problems in the natural gas industry [9,10]. Therefore, moisture level
in natural gas must be maintained below a certain threshold to meet a requirement of water dew point before it entering
sales market or other downstream gas process such as gas liquid recovery [9]. There are several techniques employed for
dehydrating natural gas, and four major types of dehydration equipment are in current use: they are absorption by means
of liquid desiccants (i.e. glycol solutions), gas permeation via membrane, refrigeration and adsorption by solid desiccants
(molecular sieve, silica gel, alumina, etc.) [11–16]. From the viewpoint of economy and energy saving, molecular sieves used
for deep dehydration are more dominant and remain the most popular in industrial natural gas dehydration [6,17].
However, in many domestic and international natural gas purification plants, there exists a problem that the service life of
the molecular sieve cannot reach the expected design life in the running molecular sieve dehydration units. The aim of the

⇑ Corresponding author. Address: School of Chemistry and Chemical Engineering, Southwest Petroleum University, No. 8 Xindu Road, Chengdu 610500,
PR China. Tel.: +86 02883037327; fax: +86 02883037305.
E-mail address: changjunzou@126.com (C. Zou).

1350-6307/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.engfailanal.2013.07.031
116 C. Zou et al. / Engineering Failure Analysis 34 (2013) 115–120

present work is to conduct the failure analysis and faults diagnosis for the molecular sieve supplied by the natural gas dehy-
dration unit of a purification plant of China National Offshore Oil Corporation (CNOOC).

2. Material and methods

2.1. Materials

Natural gas, fresh and regenerative molecular sieves were used in the experiment, and they were supplied by Hengqin
Natural Gas Processing Terminal (CNOOC, Zhuhai). Table 1 shows the specification of the fresh molecular sieve. Table 2
describes the composition of natural gas when the pressure is 7.2 MPa and the temperature is 40 °C.

2.2. Measurement of pH value

pH Values of fresh and regenerative molecular sieves were measured by the following procedure. 50 g equivalent fresh
and regenerative molecular sieves were respectively soaked in 1 L ultra-pure water for 24 h, and then the pH values of aque-
ous solutions were measured by the use of PHSJ-4A type acidometer (Shengke Equipment Co., Ltd., Shanghai) at 20 °C.

2.3. Characterization

Fresh and regenerative molecular sieves were crushed and sieved to pass through a 200-mesh screen, and then they were
used without further treatment. Thermogravimetric analysis (TG) and differential thermogravimetric analysis (DTG) were
carried out to get the weight loss data under the nonisothermal operating condition by a thermal analyzer (STA 449 F3, NET-
ZSCH, Germany). The surface morphologies of fresh and regenerative molecular sieves were characterized with scanning
electron microscope (SEM; PHLIPS-XL30, Holland). The samples for SEM were mounted on sample stubs with double-sided
adhesive tape and vacuum coated with gold. X-ray diffraction pattern (XRD) was obtained from X-ray diffractometer (DX-
2000, Dadong) by using Cu Ka X-ray at 40 kV and 40 mA between 5° and 70° (2h) at a step size of 0.03°. The Fourier transform

Table 1
Physical properties of the fresh molecular sieve.

Subject Descriptions
Nominal pore diameter 3 Angstroms
Type of crystal structure Cubic
Molecular formula 0.5K2O0.5Na2OAl2O32SiO2nH2O
Specific area 700–800 m2/g
Pore volume 0.27 cm3/g
Tapped bulk density 720 kg/m3
Design capacity 9–12 (kgH2O/100 kg molecular sieve)
Crushing strength 45 N
Heat capacity 200 J/(kg K)
Regeneration temperature 220–240 °C
Heat of desorption 4190 KJ/kg water
pH 10.5–11.5 for 50 g/L H2O as suspension at 20 °C

Table 2
Composition of the natural gas.

Components Mole fraction (%)

Nitrogen 0.369
Carbon dioxide 1.385
Hydrogen sulfide 0.0002
Methane 84.732
Ethane 7.354
Ethylene 0.053
Propane 3.666
i-Butane 0.567
n-Butane 0.721
i-Pentane 0.187
n-Pentane 0.158
neo-Pentane 0.001
Cþ6
0.311
 C. Zou et al. / Engineering Failure Analysis 34 (2013) 115–120 117

Table 3
pH values of sample solutions.

Sample Mass (g) Water (ml) pH value

Fresh molecular sieve 50.00 1000 11.24
Regenerative molecular sieve 50.00 1000 7.39
Ultra-pure water 0.00 1000 6.90

Fig. 1. TG and DTG curves of the fresh molecular sieve (a) and the regenerative molecular sieve (b).

infrared spectrum (FT-IR) was recorded with a Nicolet Nexus 470 spectrometer in the optical range of 400–4000 cm1 by
averaging 32 scans at a resolution of 4 cm1.

3. Results and discussion

3.1. pH Analysis

Equivalent aqueous solutions of molecular sieve samples and ultra-pure water were measured by the acidometer. The
results were listed in Table 3.
From Table 3, it can be seen that the pH value of the aqueous solution of the fresh molecular sieve was 11.24, and it was
3.85 points more than that of the regenerative molecular sieve. Namely, the alkalinity of the molecular sieve would decrease
after being used. The adsorption behavior of adsorbent started from the surface of the molecular sieve, and then gradually
penetrated into the internal crystal structure. Liquid or gas molecules adsorbed by molecular sieve would desorb owing to
the thermal motion, and the desorption rate increased with the increase of adsorbates. When it was equal to the adsorption
rate under a certain temperature and pressure, the adsorption behavior reached a dynamic equilibrium. The adsorption equi-
librium constant was affected by many factors, such as adsorption temperature, nature and composition of absorbent, as well
as surface acidity and alkalinity. Generally, the stronger alkalinity of the molecular sieve, the better the adsorption capacity
was. As shown in Table 3, the fresh molecular sieve had a higher alkalinity than the regenerative one, which indicated the
reason for the unavailability of the regenerative molecular sieve could be the loss of alkalinity.

3.2. Thermogravimetric analysis

After being used for the same time, the samples of fresh and regenerative molecular sieves were heated from 60 °C to
650 °C at heating rate of 20 °C in a dry stream of nitrogen. The TG and DTG curves are presented in Fig. 1.
As illustrated in Fig. 1, thermogravimetry showed the decomposition took place in three steps. The first mass loss step
was observed from 125 °C to 140 °C temperature range, which was attributed to dehydration of adsorption water. The sec-
ond mass loss at 230 °C was ascribed to dehydration of water hydrating metal cation such as Al3+. The third mass loss oc-
curred over 640 °C and was assigned to the loss of hydrocarbons. In addition, the mass losses at 230 °C for the fresh
molecular sieve and the regenerative molecular sieve were respectively 10.76% and 6.96%, which indicated that the adsorbed
water of the regenerative molecular sieve was less, and its water loss was less. The mass losses at 640 °C for the fresh
118 C. Zou et al. / Engineering Failure Analysis 34 (2013) 115–120

Fig. 2. SEM images of the fresh molecular sieve (a) and the regenerative molecular sieve (b).

molecular sieve and the regenerative molecular sieve were respectively 5.70% and 6.78%, which demonstrated that the
regenerative molecular sieve adsorbed more hydrocarbons.
When the water absorptivity and the hydrocarbon absorptivity of the fresh molecular sieve were considered as 100%, the
water absorptivity and the hydrocarbon absorptivity of the regenerative molecular sieve were respectively calculated by the
following equations:
AW ¼ ðDW =DW0 Þ  100% ð1Þ

AH ¼ ðDH =DH0 Þ  100% ð2Þ

where AW is the water absorptivity; DW is the water loss of the regenerative molecular sieve, g; DW0 is the water loss of the
fresh molecular sieve, g; AH is the hydrocarbon absorptivity; DH is the hydrocarbon loss of the regenerative molecular sieve,
g; DH0 is the hydrocarbon loss of the fresh molecular sieve, g.
Calculated by Eqs. (1) and (2), it was clear that the water absorptivity of the regenerative molecular sieve was 64.68%, and
it was 35.32% less than that of the fresh one, while the hydrocarbon absorptivity was 18.95% more than that of the fresh one.

3.3. Scanning electron microscopy analysis

The surface color of the fresh molecular sieve was slightly yellow, while that of the regenerative molecular sieve was gray.
This suggested that the coking and the carbonization of adsorbed hydrocarbons occurred in the sieve pores during the regen-
eration of the molecular sieve. The pore structures were observed by scanning electron microscopy at 10,000-times magni-
fication. The SEM images of fresh and regenerative molecular sieves are shown in Fig. 2.
The pore structure of the molecular sieve consisted of crystal internal pore structure and external pore structure. Gener-
ally, the crystal internal pore structure was called the primary pore structure, and the crystal external pore (bore diame-
ter P 10,000 nm) was referred to as the secondary pore structure. As shown in Fig. 2, the primary pore structure cannot
be seen, but it was clear that the secondary pore structure of the regenerative molecular sieve was crushed and was smaller
than that of the fresh molecular sieve. It was probably caused by the destruction of the rigid skeleton and the decrease of
structural strength. The negative change of the secondary pore structure in the regenerative molecular sieve could lead to
a decline in the adsorption capacity, and it also resulted in an increase of flow resistance in the dehydration process.

3.4. X-ray diffraction analysis

XRD is a widely used technique in the study of assessing the structure, and to check whether a new compound has been
produced from the parent molecules. The peak position (angle of diffraction) is an indication of a crystal structure, and peak
 C. Zou et al. / Engineering Failure Analysis 34 (2013) 115–120 119

Fig. 3. Powder X-ray diffraction patterns of the fresh molecular sieve (a) and regenerative molecular sieve (b).

Fig. 4. FT-IR spectrum of organic compounds obtained from the regenerative molecular sieve.

heights are the measures of samples crystallinity in a diffractogram. Fig. 3 presents the powder X-ray diffraction patterns of
fresh and regenerative molecular sieves.
It can be seen that the initial and strong broad peaks in the XRD pattern of the regenerative molecular sieve were very
similar to that of the fresh molecular sieve, which indicated that the regenerative molecular sieve did not change signifi-
cantly in chemical composition and crystalline phase. When there were no stress and crystal defects, the crystallite size
of the molecular sieve could be determined by the Scherrer’s formula. Being calculated, the crystallite size of the fresh molec-
ular sieve was found to be 69.278 nm, while that of the regenerative molecular sieve was 85.663 nm. Combined with the
previous analysis, it was obtained that the regenerative molecular sieve showed narrower pore and larger crystallite size,
which indicated the occurrence of an agglomeration.

3.5. Fourier transform infrared spectroscopy analysis

Fourier transform infrared spectroscopy was utilized to indentify vibration modes of different functional groups in the
organic compound obtained from the regenerative molecular sieve. The results are shown in Fig. 4.
As can be observed, the absorption peaks appeared at 1652.24 cm1 and 1455.53 cm1, which were related to the stretch-
ing vibrations of C@C in olefins and benzene ring, respectively. Also, a sharp absorption peak at 3361.88 cm1 was due to the
stretching vibration of water. Besides, the bands at 1122.87 cm1 and 1066.90 cm1 belonged to the stretching vibration
120 C. Zou et al. / Engineering Failure Analysis 34 (2013) 115–120

peak of CAOAC and the OAH bending vibration of ACH2OH group, respectively. In addition, the stretching vibration at
1236.48 cm1 was attributed to the AC@SA group. It could be inferred that the organic compound did not only contain
hydrocarbons, and it might also include alcohols, ethers and carbonyl sulfides. Molecular sieve has a high affinity to polar
molecules and unsaturated molecules, and it has a higher selective adsorption for the molecule of large polarizability. Thus,
ethylene and ethane were more likely to be adsorbed by the molecular sieve. Additionally, due to the presence of ethylene,
alcohols and ethers were probably generated by the hydroxylation reaction on the inner surface of the molecular sieve.

4. Conclusions

In the paper, a series of experiments was carried out to investigate the failure factors for regenerative molecular sieve,
such as pH analysis, TG, DTG, SEM, XRD and FT-IR characterizations. The results indicated that there were four main aspects
for the unavailability of the regenerative molecular sieve.

(1) The pH values decreased due to the surface alkalinity being neutralized by the acidic components of natural gas.
(2) The secondary pore structure was diminished and blocked, which was probably caused by the destruction of the rigid
skeleton and the decrease of structural strength.
(3) The crystallite size increased, and the crystals agglomerated.
(4) Not only were the hydrocarbons adsorbed, but also alcohols, ethers and carbonyl sulfides were generated in pores.

Acknowledgment

This work was financial supported by Graduate Innovation Foundation of Southwest Petroleum University (GIFSS0717).

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