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ISSN: 2319-5967

ISO 9001:2008 Certified


International Journal of Engineering Science and Innovative Technology (IJESIT)
Volume 3, Issue 3, May 2014
663

Determination and removal of acid gases from
natural gas produced from gas condensate
plant
Ashraf Yehia El-Naggar

Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt.
Chemistry department, Faculty of Science, Taif University, Kingdom of Saudi Arabia.
Abstract: The major role of gas-condensate plant is to process both associated and non associated gas to produce
high-quality natural gas and hydrocarbon liquids. Gas plants have field operations and a network of pipelines that feed
the raw natural gas and liquids into the plant. Field operations include dehydration, acid gas (CO
2
and H
2
S) removal and
compression. Unless the gas is completely free of any liquids, once it enters the plant, the gas and liquids go into inlet
receiving, where the initial gas-liquid separation is made. Our aim is monitoring of H
2
S and CO
2
to select and optimize
the conditions of sweetening regenerations in order to follow and prevent their gradient in gas plant.

Key Words: - Gas-condensate plant, Dehydration, Acid gas, Sweetening regenerations.
I. INTRODUCTION
After extracting the natural gas from the underground reservoirs, additional processing is conducted in the field
to prevent corrosion and other problems in downstream handling and processing equipment [1, 2], thus, the gas
as it leaves the reservoir, is normally saturated with water and, of course, it contains all the impurities normally
associated with the gas [3]. All plants have field operations and a network of pipelines that feed the raw natural
gas and liquids into the plant. Field operation may include dehydration, CO
2
and H
2
S removal, and compression
[4]. Gas and liquids that enters the gas plant pass emergency shutdown valves, which isolate the plant from
incoming streams and pig receivers, and then fed to an inlet separator that removes liquid water, heavy
hydrocarbons, brine, and particulate matter from the incoming natural gas [4]. The gas is separated from liquids
either in a two-phase process, in which gas is typically separated from water, or in a three-phase separation
operation, in which gas, water, and liquid hydrocarbons are separated [2, 5]. Three-phase separation is
necessary when appreciable liquid hydrocarbons are extracted with the gas and water [6]. Condensed water,
hydrocarbon liquids and solids are removed [4]. Water and solids are processed for disposal, and the
hydrocarbon liquids go on to liquid processing. Because of the corrosiveness of H
2
S and CO
2
in the presence of
water, the toxicity of H
2
S and the lack of heating value of CO
2
, sales gas is required to be sweetened to contain
no more than a quarter grain H
2
S per 100 standard cubic feet (4 parts per million) and to have a heating value of
no less than 920 to 980 Btu/scf, depending on the contract [7, 8].

II. EXPERIMENTAL
A. Sampling

1. For gas samples
(a) Sample Container Stainless steel sample containers were used. These containers are of a type that ensures
maximum safety and are resistant to corrosion by the product being sampled [9]. The sample container is fitted
with an internal outage tube to permit release of 20% of the container capacity. The end of the container is fitted
with outage tube.
(b) Sample Transfer Line - made of flexible metal hose, impervious to the product being sampled, was used.
The most satisfactory line is one equipped with two valves on the sample container end.
2. For Liquid samples "condensate samples"
A liquid sample was transferred under pressure from a sample point to a floating piston cylinder [10]. The
floating piston cylinder (FPC) is designed to collect liquid samples with no vaporization by displacing a piston
against a pressurizing fluid (usually an inert gas). The piston serves as a physical barrier between the sample and
the pressurizing fluid, at the sampling pressure. The position of the piston at the end of sampling indicates the
percent fill of the sample cylinder.





ISSN: 2319-5967
ISO 9001:2008 Certified
International Journal of Engineering Science and Innovative Technology (IJESIT)
Volume 3, Issue 3, May 2014
664

B Procedure
1. For gases
First, we prepared the connection for the sample cylinder and then opened the main valve of the process line.
We opened the second sampling valve and allowed gently flushing (no hydrocarbon condensation should be
visible) for 2 minutes (no icing of the valves or sampling lines should occur). The sample cylinder was
connected, and both needle valves were opened and flushing was allowed again for 1 minute. We closed the
outlet valve of the cylinder and waited 1 minute and closed the inlet valve. We opened the outlet valve and
release the sample. Repeat the flushing step and disconnect the cylinder and store in the box for transportation.
2. For condensates
First, we prepared the connection for the sample cylinder and then opened the main valve of the process line.
We opened the second sampling valve and flushed one liter of sample in an empty mineral water bottle. The
sample cylinder was connected, and both needle valves were opened and again one liter of sample was flushed
in an empty mineral water bottle. We closed the outlet valve of the cylinder and waited 1 minute and closed the
inlet valve. We opened the outlet valve and release the sample. Repeat the flushing step and disconnect the
cylinder and store in the box for transportation.

C Analysis
1. Gas chromatographic analysis of hydrocarbon gases
Hydrocarbons from C
1
to C
9
, carbon dioxide CO
2
, and nitrogen N
2
were analyzed using Agilent model 6890
plus HP gas chromatograph equipped with thermal conductivity detector "TCD" and flame ionization detector
"FID". The packed columns Porapack-Q, 40 ft in length and 1/8 inch in internal diameter or and DB-1 capillary
column, 60m in length and 0.320mm in internal diameter were also used in attachment with TCD and FID
respectively. Helium gas was used as carrier gas flowing at a rate of 4ml min
-1
. The elution of the studied gas
mixture was achieved with temperature programming form 50C to 200C at a rate of 10C min
-1
. The
quantitative analysis of the gas mixture was achieved using a standard natural gas sample of known composition
and according to the standard
(159)
. The injector and detector temperatures were 200C and 250C, respectively.
The data was estimated by integration of the area under the resolved chromatographic profiles, using the HP
computer of software chemstation.

2. Analysis of Sulfur Compounds (H
2
S & R-SH)
Hydrogen sulfide and mercaptans present in natural gas samples were analyzed using Perkin-Elmer Clarus 500
gas chromatograph equipped with the new and recent Amperometric Sulfur Detector ASD. Tuned DiPMS
(Dipoly methyle siloxane) capillary column 60m in length, 0.32 in internal diameter and 4 m film thickness
was used in attachment with Amperometric sulfur detector ASD. Helium gas was used as carrier gas flowing at
a rate of 35 psi. The elution of the studied gas mixture was achieved with temperature programming starts form
35C and hold for 5 min and then increasing to 150C at a rate of 10C min
-1
and hold for 1min. The reactor
temperature is 825C.

III. RESULTS AND DISCUSSIONS
As the gas streams exit the outlet separators, the saturated feed gas, passes from the filter and enters the bottom
of the absorber and passes through a Benfield solution, which is used in more than 600 plants worldwide. The
Benfield process is a chemical absorption of the H
2
S, CO
2
and to some extent COS. The Benfield process is
based on an aqueous solution of potassium carbonate and bicarbonate, with potassium vanadate as an anodic
inhibitor and with an amine as an accelerant [11]. The potassium carbonate solution enters the absorber at the
top. As the solution flows down the column contacting the up-flowing acid gases (CO
2
& H
2
S), the absorption
reactions proceed, and the liberated heat of absorption increases the temperature of the solution. When the
upward flowing raw natural gas containing CO
2
and H
2
S contacts the down flowing potassium carbonate
solution in a counter current flow. The potassium carbonate absorbs CO
2
and H
2
S and these reactions can be
represented as follow [12]:
K
2
CO
3
+ H
2
O + CO
2
2KHCO
3

K
2
CO
3
+ H
2
S KSH + KHCO
3







ISSN: 2319-5967
ISO 9001:2008 Certified
International Journal of Engineering Science and Innovative Technology (IJESIT)
Volume 3, Issue 3, May 2014
665

1. Gas streams from outlet Benfield absorption process
A. Compositional analysis
Table (1) gives the compositional analysis of the gas samples from outlet absorber Tr-1 and Tr-2. The
compositions of the gas samples from outlet absorbers Tr-1 and Tr-2 are nearly the same. These gas samples
contain up to 3 mol % of carbon dioxide which agree with the pipeline specification limits. Compared to the
percent of carbon dioxide in the gas from outlet separators, it is clear that the Benfield solution removes up to 60
% of the original CO
2
. The molecular weight of the gas samples from outlet absorbers are lower than that of
inlet absorber indicating that beside the absorption of the acid gas components (H
2
S and CO
2
) the Benfield
solution absorbs to some extent high molecular weight hydrocarbons from the feed gas. Accordingly, both the
molecular weights and specific gravities decreased. On the other hand, the lower molecular weight
hydrocarbons concentrations increased. Also, an advantage of the Benfield solution is that there is minimum
co-absorption of hydrocarbons resulting in slight change in the paraffinic composition [13]. Other reason of the
slight paraffinic change comes from the distribution of the absorbed amount of CO
2
on all paraffinic
compositions in order to keep the total weight percent of the gas sample.

B. Sulfur analysis and physical properties
The results of sulfur analysis of gas samples from outlet absorbers in the two trains Tr-1 and Tr-2 are given in
Table (2). From these results, it was found that the Benfield solution successfully pick up almost all the
hydrogen sulfide from the feed gas in all three trips. In addition, the Benfield absorption process removed up to
73% and 66 % of methyl mercaptan from the inlet gases of Tr-1 and Tr-2 respectively for the first trip samples.
Also it removed up to 75 % in the second trip samples and 70 % and 72 % for Tr-1 and Tr-2 respectively for the
third trip samples.

2. Rich and lean Benfield Samples
The compositional analysis of the dissolved gases in both rich and lean carbonate solutions are given in Table
(3). The results show that there are some variations in the compositions of dissolved gases from the two
separators, which may be due to the absorption efficiency. The dissolved gases are characterized by the presence
of high concentrations of carbon dioxide 71.427 to 70.218 mol % for separators Tr-1 and Tr-2 respectively.
From the results of CO
2
concentrations, it may be shown that higher absorbing efficiency was observed in Tr-1.
With respect to the dissolved gases in the lean carbonate solutions, as observed in gases dissolved in rich
samples, there are some variations in the composition; high absorption efficiency observed in separator Tr-1. It
was found that the gases dissolved in lean samples from Tr-1 and Tr-2 contains high percentages of CO
2

compared with that of rich Benfield solutions.

Table 1: The compositional analysis of gas samples from outlet Benfield absorbers Tr-1 and Tr-2

Separators Tr-1 Tr-2
Percentages
Components
Mol %

Wt % Mol %

Wt %
Nitrogen
1.053 1.389 1.044 1.385
Methane
78.847 59.581 78.963 59.979
Carbon Dioxide
3.254 6.746 3.143 6.55
Ethane
8.862 12.554 8.972 12.776
Propane
4.63 9.618 4.745 9.91
i-Butane
0.916 2.508 0.907 2.496
n-Butane
1.507 4.126 1.413 3.889
i-Pentane
0.315 1.071 0.292 0.998
n-Pentane
0.274 0.931 0.244 0.834
Hexane +
0.342 1.260 0.277 1.183
Total
100.000
100.000 100.000 100.000






ISSN: 2319-5967
ISO 9001:2008 Certified
International Journal of Engineering Science and Innovative Technology (IJESIT)
Volume 3, Issue 3, May 2014
666

Table 2: Hydrogen sulphid, Mercaptan and physical properties of gas samples from outlet absorber Tr-1
and Tr-2
Analytical Parameters
Tr-1 Tr-2
Mol Wt
21.228
21.118
Specific gravity
0.7329
0.7291
H
2
S, ppm
Nil
Nil
Mercaptan, ppm
6.7
2.4

3. Vent gases from Benfield Regenerators
In the regenerator, CO
2
is driven out of the carbonate solution because of its lower partial pressure in the acid
gas relative to the corresponding equilibrium pressure of the carbonate solution

[11].

Table 3: CO
2
and compositional analysis of gases dissolved in rich and lean Benfield samples of Tr-1 and T-2

Separators Tr-1 Tr-2 Tr-1 Tr-2
Samples

Components
Rich Benfield Samples Lean Benfield Samples
Mol % Mol % Mol % Mol %
Nitrogen
0.662 0.673 0.68 0.613
Methane
11.082 12.161 4.866 5.077
Carbon Dioxide
71.427 70.218 78.681 78.123
Ethane
9.506 9.763 7.246 7.404
Propane
1.978 1.822 4.007 4.119
i-Butane
1.075 1.053 0.712 0.732
n-Butane
1.162 1.101 1.251 1.21
i-Pentane
0.642 0.718 0.548 0.51
n-Pentane
0.645 0.717 0.545 0.551
Hexane +
1.821 1.774 1.464 1.661
Totals 100.000 100.000
100.000 100.000

The regenerator column runs at near atmospheric pressure and is heated to 112C using hot oil. The sudden
reduction in pressure experienced in the regenerator flashes a large amount of the acid gases on the regenerator's
tray. The steam from the reboiler passes up the packed column and strips the CO
2
and H
2
S from the solution.
The steam provides heat to break the chemical bond between the carbonate and CO
2
and accordingly, KHCO
3
is
converted back to K
2
CO
3
. The compositional analysis of Vent gases from Benfield regenerators is given in
Table (4). It was found that the gas samples are composed mainly of carbon dioxide ranging from 96.42 mol %
and 94.98 mol % for separators Tr-1 and Tr-2 respectively, in addition to some middle hydrocarbon fractions.
The results of the molecular weights of the gas samples indicate that they are characterized by their high
molecular weights. These gases being vented to the atmosphere, some safety considerations should be taken into
considerations. The results of sulfur analysis are given in Table (4). Of course, the hydrogen sulfide and methyl
mercaptan exhibit high values due to the main aim of the Benfield solution which is the absorption of the sulfur
compounds. The concentration of the H
2
S and CH
3
SH in the vented gas sample from the Benfield regenerator
Tr-1 is higher than that of Tr-2 due to their higher values in the gas from outlet separator Tr-1 than that from
outlet separator Tr-2. The concentration of methyl marcaptan shows the same behavior.

Table 4: CO
2
and compositional analysis of vent gas samples from Benfield Regenerators Tr-1 and T-2

Separators Tr-1 Tr-2

Components
Mol % Wt % Mol % Wt %
Nitrogen
0.00 0.00 0.00 0.00
Methane
1.25 0.45 1.62 0.58





ISSN: 2319-5967
ISO 9001:2008 Certified
International Journal of Engineering Science and Innovative Technology (IJESIT)
Volume 3, Issue 3, May 2014
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Carbon Dioxide
96.42 95.22 94.98 93.01
Ethane
0.10 0.07 0.12 0.08
Propane
0.03 0.03 0.06 0.06
i-Butane
0.01 0.01 0.01 0.01
n-Butane
0.01 0.01 0.02 0.02
i-Pentane
0.01 0.01 0.01 0.01
n-Pentane
0.01 0.01 0.01 0.01
Hexane +
2.16 4.19 3.13 6.08
Totals 100.000 100.000
100.000 100.000
H2S, ppm 158.6 80.2
Mercaptan, ppm 4.20 1.05
Mol Wt 44.569 44.941
Specific gravity 1.5388 1.5517

IV. CONCLUSION
The performance of acid gas removals unite has been monitored by evaluating the amounts of
hydrogen sulfide, methyl mercaptan and carbon dioxide. The gas streams at the outlet Benfield
absorbers are free from hydrogen sulfide contents and contain much lower contents of methyl
mercaptans reflecting the high efficiency of the Benfield absorbers to remove acid gas.

The gas vented from Benfield regenerators are composed mainly of carbon dioxide that stripped from
the rich carbonate solution. The vented gases contain significant proportions of chloride ions.

The high values of hydrogen sulfide present in the gas vented from Benfield regenerators attract our
attention to sever health consideration and its recovery should be taken into account.

The sulfide contents in rich and lean Benfield samples make the regenerator's tower susceptible to
corrosion especially in the presence of water moisture. These high values of sulfides are due to the
accumulation of such sulfides in both lean and rich Benfield solutions containers.

REFERENCES
[1] J. E. Amoore, E. Hautala, Odor as an aid to chemical safety: odor thresholds compared with threshold limit values and
volatilities for 214 industrial chemicals in air and water dilution. Journal of Applied Toxicology, Vol. 3, P. 272290,
(1983).
[2] EIIP, Preferred and Alternative Methods For Estimating Air Emissions From Oil and Gas Field Production and
Processing Operations, Emission Inventory Improvement Program (EIIP), Eastern Research Group, Inc, chapter 10, vol.
II., (1999).
[3] A. H. Younger, Natural Gas Processing Principles and Technology, part II, university of Calgary, P. 13-1, (2004).
[4] A. J. Kidnay and W. R. Parrish, Fundamentals of natural gas processing, Taylor & Francis Group, P. 1:218 (2006).
[5] J. E. Rucker, and P. S. Robert, The Petroleum Industry Air Pollution Engineering Manual, AP-40, Air and Waste
Management Association. Pittsburgh, Pennsylvania, (1992).
[6] GRI, Preliminary Assessment of Air Toxic Emissions in the Natural Gas Industry, Phase I, Topical Report, Gas
Research Institute, GRI-94/0268. Chicago, IL, (1994).
[7] U. Daiminger, W.Lind, Adsorption Processes for Natural Gas Treatment, Engelhard Corp, U.S.A., P. 14 (2004).
[8] TNRCC, Technical Guidance Package for Annual Air Emissions Inventory Questionnaires, Oil and Gas Industry, Draft,
Texas Natural Resource Conservation Commission, Austin, Texas, (1996).
[9] Annual Book of ASTM Standards, "Standard Test Method for Analysis of Natural Gas by Gas Chromatography",
ASTM: D 1945-03, ASTM International, Vol. , P. 1-17, 2003.





ISSN: 2319-5967
ISO 9001:2008 Certified
International Journal of Engineering Science and Innovative Technology (IJESIT)
Volume 3, Issue 3, May 2014
668

[10] Annual Annual Book of ASTM Standards, "Standard Practice for Sampling Liquefied Petroleum (LP) Gases (Manual
Method)", ASTM: D 1256-97, ASTM International, Vol., P. 1-3, 1997.
[11] Obaiyed Training Manual, Vol. 2: Introduction to Obaiyed Processes, Badr Petroleum Company (BAPETCO), prepared
by, The Egyptian Maintenance Company.
[12] R. N. Maddox, J. H. Erbar, Gas Conditioning and Processing-Advanced Techniques an Applications, Campbell, J.M.,
Campbell Petroleum Series, Norman, Okla, (1982).
[13] J.M. klinkenbijl, M.L. Dillon, E.C Heyman, Gas Pre-Treatment and their Impact on liquefaction Processes, Shell
International Oil Products, Research & Technology Center Amsterdam, Presented at , GPA Nashville TE meeting, P. 3-
4, 2
nd
March 1999.