SPE 131908

Formation of Carbonyl Sulfide During Molecular Sieve Dehydration Process

from High Sour Natural Gas in China
Tu Yan, Chang Honggang, He Jinlong, RINGT PetroChina Southwest Oil & Gasfield Company

Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the CPS/SPE International Oil & Gas Conference and Exhibition in China held in Beijing, China, 8–10 June 2010.

This paper was selected for presentation by a CPS/SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract
Molecular sieves with high silica content are usually selected for dehydration of sour natural gas because of their tolerance to
H2S. Some special acid-resistant molecular sieves can maintain their dehydration capabilities over long period.But carbonyl sulfide
(COS) is formed by the reaction of H2S and CO2,which is catalyzed by molecular sieves during natural gas dehydration.
The overall development program at Luojiazhai Gas Field(high sour gas contents) of petrochina southwest oil and gas field
company chose the molecular sieve adsorption process to dehydrate sour natural gas, but the gas field has not been developed up
to now.A set of of the molecular sieve adsorption equipments has been applied at Liangfeng gathering station of Wanzhou city.
This is the first plant for high sour gas dehydration using molecular sieve in China. The wet natural gas contains 9% H2S, 11%
CO2 and 200ppmv COS. The dry gas flows to a natural gas treating plant to remove H2S and CO2 to meet pipeline specifications.
We found that the water dew points of the treated gas were always lowered to less than -10 .But this molecular sieve displayed
a certain extent of catalytic activity for the reaction converting H2S and CO2 to COS and H2O. The generated amount of changed
greatly during operating cycle. The concentration of COS will rise while hot stripping gas moves through the bed.
So for sour gas dehydration and desulfurization, these data may prevent serious design errors. Molecular sieve manufactures
were able to gain valuable assistance.

Introduction
Natural gas dehydration using solid adsorbents (molecular sieves, alumina and silica gel) is one of the convenient water
removal options. Other choices include cooling (refrigeration or cryogenic separation) or hygroscopic liquids (di or triethylene
glycol) to dry gas. Compared with other adsorbents, such as slilca gel and alumina, molecular sieves offer higher adsorption design
loadings, greater resistance to fouling and coking, and the ability to remove moisture in single-step operation, So these make
molecular sieve uniquely suitable for drying sour natural gas. Molecular sieves with high silica content are usually selected for
dehydration of sour natural gas because of their tolerance to H2S(A.M.Aitanl,1993；Arthur L. et.al,1985). Some molecular sieve
dehydration processes for sour, hydrocarbon wet, wellhead natural gas (e.g., 20%H2S, 5%CO2) have been proved
successful(J.J.Collins,1963). The catalytic activity and structure of molecular sieves have a significant influence on the COS
formation in high sour natural gas (H2S ＋CO2)（W.Lutz,et.al,1999）.COS is formed in a variety of thermal and catalytic
conversion processes in natural gas dehydration according to the following reaction:
H2S＋CO2↔COS＋H2O ............................................. (1)
However, up to now the fomation of COS involving in dehydration of high sour gas with molecular sieves has not been paid
enough attention. Just very few literatures reported about COS formation at low tempreture, such as at
50℃,93℃.( A.M.Aitanl,1993) or at lower H2S and CO2 contents ( M.R.Cines,et.al,1976) .Some article just suggested to use a small-
pore molecular sieves in order to avoid the reactions which forms COS within the pores. Less alkalinity is in favor of suppressing
the COS formation. ( P.S.Northrop, et.al, 2008)
COS has been found to be highly detrimental in the sweetening process since it forms, such as with MEA, a stable
nonregenrable complex, thus increases operation cost. At the same time, high COS concentration may result that an amine-based
gas sweetening process can’t meet pipeline specification of producted gas. Moreover, COS is a source of corrosion too. Some
2 SPE 131908

special acid-resistant molecular sieves can maintain their dehydration capabilities over long periods, but we don’t know if it can
suppress undesirable side effects.

Facilities and Process Flow diagram

The molecular sieve adsorption process at Luojiazhai Gas Field of petrochina southwest oil and gas field company was chosen
to dehydrate sour natural gas(Luo Xiaojun, et.al, 2007), but the gas field has not been developed up to now.One of the molecular
sieve dehydration unit has been installed. There is a two-tower dehydration unit using 5 Å acid-resistant sieves at Liangfeng station
of Wanzhou city. This is the first unit which uses molecular sieve to dehydrate the high sour natural gas in China. The wet natural
gas ,which comes from Feng003-X3 Well ,contains about 9% H2S, 11% CO2 and 200ppm COS.The output of natural gas varies
from 0.15 to 0.3 millions m3/d, the pressure is 8Mpa. the capacity of this dehydrator is 0.5 millions m3/d. To prevent hydrate
formation and corrosion damage in the gathering and transmission lines, it is necessary to reduce water content of the treated gas to
below a water dew point of -10℃.The dry gas will flow to a natural gas processing plant to be purified to meet pipeline
specifications.
A flow diagram of the unit is shown in Figure 1. The two beds consist of 1/8-inch striped molecular sieves. Each tower is 1 m
in diameter, 4 m high and contains 1477 kg of molecular sieves. The beds are supported by structural grid. The molecular sieve is
placed on top of 1/4-inch alumina balls (approximately 50kg). A layer of support balls on top of the adsorbent bed servers an a fluid
buffer and prevents movement of adsorbent on the surface caused by high local velocities. Top buffer was 50 Kg 5/8-inch alumina
balls. The normal cycle time for the adsorption process (for one bed) is 8hr. The feed gas enters at the top of the bed during the
adsorption cycle.During regeneration cycle, the water saturated tower is heated for a period of 4hr. The amount of regeneration gas
in the same direction as the feed gas is about 6 percent to 10 percent of wet raw material sour gas. After the heating period, the bed
was cooled by same amount wet sour gas in the same direction as the feed gas. The bed was cooled down to surrounding
temperature. The operating parameters can be adjusted to extend or shorten the regeneration process.
This adsorbent is a clay-bound, acid-resistant molecular sieves product. It will adsorb molecules with critical diameters up to
approximately 5 angstroms.It has been specially formulated for the natural gas processing industry to dry and purify sour natrual
gas and liquids.Molecular sieves can be regenerated for re-use by heating.The molecular sieves manufacturer recommended
regeneration temperature is 285 , but to suppression COS formation, regeneration temprature is reduced to 250 at inlet of
regenerator.During heating period, the temperature of heating bed is keeped at exceed 220 at least more than half hours.
To analyse COS concentration, Samples were taken by sampling ports within the operating plant.Two types gas
chromatographs were used to measure concentration of H2S, CO2 ,and COS respectively in the feed gas, regeneration gas or
treated gas. Measurement range was expanded by diluting the sample with nitrogen.A dew point analyzer measured water content
of the product streams.

Presentation of Data and Results

We found that the water dew points of the treated gas were always lowered to less than -10℃.But this molecular sieve displayed
a wide range of catalytic activity for the reaction converting H2S and CO2 to COS and H2O. The concentration of COS changed
greatly during the period. Specially as hot gas moves through the bed .Table 1 shows effection of regeneration gas tempreture on
COS concentration. The maximum value of COS concentration in the regeneration gas was about 6000 ppmv and COS
concentration of the treated gas was about 1000 ppmv.Through diluting feed wet gas with other well gas stream,the raw material
H2S concentration could effect COS formation was detected. The effection of H2S concentration of the feed gas on COS
concentration in some cycle were given in Table 2. Higher COS concentration was normally associated with higher feed H2S
concentration, and COS concentration increased as temperature of regenerator elevated.The trend of lower COS concentration at
lower temperature was observed for all process.

Conclusions
This type acid-resistant molecular sieve displays very well dehydration ability in high sour natural gas dehydration.The water
dew point of the treated gas can meet the requirement of the contract. However, COS will be formed when molecular sieve
dehydration unit treats high sour natural gas (H2S+CO2), Because the molecular sieve acted as a ctalyst for COS formation. there is
a peak value of COS concentration during regeneration. The increased COS concentration in the raw sour gas may cause the
purified gas not to meet the pipeline specification, especially if all sour natural gas in some gas field were be dehydrated used this
molevular sieves and aqueous amine is applied to desulfurize. The design technicists should pay greatly attention to this
phenomenon in order to choice the correct treating processes.
So when designing for sour gas dehydration and desulfurization, above data may prevent serious design errors and molecular
sieve manufactures were able to be given valuable assistance.
SPE 131908 3

Acknowledgments
Special thanks for our colleague: Xia Junling, Pei Jinqun, Yang Zijie. They gave us helping during this research project.We also
thank Chongqing gas field of petrochina southwest oil & gas field company for providing the field test condition and for
permission to use the molecular sieve dehydration plant.

References:
1. A.M.Aitanl, “Sour natural gas drying”Hydrocarbon Processing,(1993),Appril, 67-73
2. Arthur L. KohI, Fred C. Riesenfeld, Gas Purification , fourth Edition，(1985)
3. J.J.Collins ,“A Report on Acid-Resistant Molecular Sieve Types AW-300 and AW-500“，Union Carbide Corporation,
Linde Molecular Sieve Bulletin.(1963)
4. W.Lutz,J,-Chr.Buhl and H.Thamm, “A New COS-Suppressing Zeolite for Gas-Sweetening,” Katalysatoren, 115, Heft 2,87-
89,February (1999)
5. M.R.Cines,D.M.Haskell,and C.G.Houser, “Molecular Sieves For Removing H2S From Natural Gas”,CEP August (1976),89-
93
6. P.S.Northrop,Narasimhan Sundram, “Strategies For Effective Natural Gas Treatment with Adsorbents”,Proceedings of the
Laurence Reid Gas Conditioning Conference,(2008)
7. Luo Xiaojun; Liu Xiaotian; Wan Shuhua , “Application of Molecular Sieve Adsorption Method for Dehydration of High Sour
Natural Gases,” Chemical Engineering of Oil & Gas,Vol.36,No.2, 118-123,(2007)

Temperature of the COS concentration of the

COS concentration of COS concentrtion of the
regeneration gas in gas in outlet of regenerator
treated gas ×10-6 feed gas ×10-6
the bottom of bed ×10-6
214.8 726.32 2964.85 234.8
223.9 935.27 3513.79 243.54
225 1086.68 6195 251.51
125.6 584.22 1768.38 223.1
50.6 364.71 882.98 200.2
35.7 207.36 363.8 205.04

Table 1 Effect of the regeneration gas temperature on COS concentration

Note:feed wet gas :H2S, 9vol.% ;CO2,11vol.%;0.26 millions m3/d

Table 2 Effect of H2S concentration in feed wet gas on COS concentration of regeneration gas and treated gas

H2S concentration
in the feed gas （ 7.34 7.39 7.92 7.80 9.2 9.52
%）
COS
concentration in 137.2 123.8 177.42 171.2 210.14 250.1
-6
the feed gas ×10
COS
concentration in 332.42 357.67 535.82 676.35 987 1077.93
the treated gas
×10-6
COS
concentration of
the gas in outlet 1600.79 2065.02 2449.84 3158.83 3241 4583.39
of regenerator
×10-6
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Figure 1 Process flow diagram of molecular sieve dehydration unit for sour natural gas