Canadian Journal on Chemical Engineering & Technology Vol. 2 No.

9, December 2011

DYNAMIC SIMULATION OF SWEETENING PROCESS OF NATURAL GAS

T. Abbas, M. Ghauri, Z. Rashid, M. Shahid
Abstract Natural gas is incomparable to other energy sources in economics amenity and in environmental interests. Carbon dioxide (CO2), hydrogen sulphide (H2S) and other impurities are found in natural gas stream that concern the quality and performance of gas. In order to reduce their concentration less than 2 % to meet the contractual specification, amine sweetening process is used. In this paper, simulation study and modeling of equipment for gas sweetening plant with di-ethanolamine (DEA) has been investigated on HYSYS in DYNAMIC STATE. The aim of this study is to design, optimize the sweetening process and study of absorber design in both steady and dynamic state. Simulation results show that in dynamic mode the absorption of CO2 is constant throughout the process. Key Words Natural Gas, Amine Process, Simulation, Modeling, CO2, H2S.

(carbon dioxide and hydrogen sulfide).A natural gas stream is approximately two mole percent (mol%) sour. It means for every 100 kgmoles of gas 2 kgmoles of hydrogen sulfide (H2S) are present in it [3]. As a matter of fact, H2S and CO2 are corrosive in aqueous solution. Furthermore, they are very toxic in nature and have very low heating value. Due to these facts, sales gas is required to be sweetened to contain no more than a quarter grain H2S 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 [4]. There are quite a few treating processes available for removal of acid gases from natural gas, including Chemical solvents, Physical solvents, Adsorption Processes Hybrid solvents and Physical separation [5]. In the past few years, amine solvents for the removal of acid gases have received increased attentions. In this process the acidic components react with an alkanol-amine absorption liquid via an exothermic, reversible reaction in a gas/liquid contactor. In a following process step the acidic components are removed from the solvent in a regenerator, usually at low pressure and/or high temperature [6]. Monoethanol amine (MEA), di-ethanol amine (DEA), diisopropanol amine (DIPA) and N-methyl di-ethanol amine (MDEA) are widely accepted alkanol amines for industrial operations [7]. In the present paper, the use of amine diethanolamine (DEA) has been investigated for a variety of cases using a process simulation program HYSYS in dynamic state. II. AMINE PROCESS The low operating cost and flexibility of tailoring solvent composition to suit gas compositions make this process one of the most widely used [8].

I. INTRODUCTION Discovery and utilization of coal has tremendous effects in industrial development on this planet earth. That is why the nineteenth century was known as a century of coal and with the help of this fossil fuel industrial revolution in Europe took place as this provided the electricity to the entire Europe. As a matter of fact, the twentieth century was called the century of oil, the major energy source to support the expansion of global economy. Natural gas took over the position of coal as the number two energy source behind oil in the late twentieth century. This boom of global expansion is because of numerous factors, including development of new markets, substitution of coal as fuel for providing space and industrial utilities requirement, use of natural gas in making petrochemicals and fertilizers, and strong demand for low-sulfur fuels [1,2]. Natural gas mainly consists of large quantity of methane along with heavier hydrocarbons such as higher alkanes and alkenes; moreover in the raw state it often contains a considerable amount of non hydrocarbons, such as nitrogen and the acid gases

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Sour gas is firstly fed into a unit, scrubber, for the removal of entrained liquid phase, water and liquid hydrocarbons. The gas then enters the bottom of absorption tower most of the sweet gas exits at the top of tower.The regenerated amine usually called lean amine enters at the top of this tower and the two streams are contacted counter-currently. In this tower, CO2 and H2S are absorbed with the chemical reaction into the amine phase. The exit amine solution, loaded with CO2 and H2S is called rich amine. This stream is flashed, filtered and then fed to the top of a stripper to recover the amine and acid gases are stripped and exit at the top of the tower. The refluxed water helps in steam stripping the rich amine solution. The regenerated amine is recycled back to the top of the absorption tower as shown in figure 1.
Table.1 Comparison of Amine solvents [10]
Solvent Ch.Formula. Mol.wt Amine type Vap.Pressue 100oF(mm Hg) Freezing Point oF. Loading (mol Acidgas/mol amine) H2S/CO2 selectivity Solvent conc.(wt%) Acid gas (mol/m) Circulation (gal/mole acid gas) Steam rate(lb/gal) Reboiler temperature oF Heat of reaction(Btu/lb acid gas, H2S) MEA RNH2 61 Primary 1.05 15 0.35 1 15-20 0.3-0.4 100165 1-1.2 240 620 DEA R2NH 105 Secondary 0.058 20 0.5 1 20-35 0.5-0.6 60-125 0.9-1.1 245 630 DIPA R`NH 133 Secondary 0.01 16 0.7 2 30-40 0.3-0.4 ------------255 0

The basic reactions with CO2 and H2S are [8,9] 2 + 1

H2S reacts with MEA, DEA, or MDEA to form hydrogen sulfide and protonated amine. + 2 + 2 2 3

Based on above reactions, 1.7 lbs of DEA can be used to react with the same amount of acid gas as 1.0 lb of MEA. Because of its lower corrosive nature, higher strength upto 35% (wt) of DEA can be used. Loading up to 0.65 mol of acid gas per mole of DEA can cause fewer operational problems than MEA because the elimination of the degradation products and the absence of a reclaimer. DEA is weaker than MEA so that Corrosion is less in a process where DEA is used instead of MEA. Foaming is reduced due to absence of degradation and corrosion products [8]. III. Simulation and Modeling The simulation model is developed on Aspentech HYSYS 7.1.The type of fluid package selected is Amine Package.DEA used as an aqueous absorbent to absorb H2S and CO2 from sour gas streams. Before entering the contractor, the sour gas is passed through an inlet separator where entrained droplets of liquid are removed from the gas stream. Specification of sour gas is shown in table 2.
Table 2. Inlet sour gas and amine specifications Parameters Values 1245 kgmole/hr 1886 kgmole/hr 86 oF 99 oF 28% 998 psia 995 psia 2.5 mole% 4.13 mole %

Among the amines shown in the above table 1, the most common, less expensive, easy to install and operate absorbent is Di-ethanolamine (DEA). It is a comprehensive substitute of MEA and becoming the most widely used gas sweetening solvent. It is a secondary amine with lower reactivity and less corrosive than MEA. Moreover, it reacts with COS and CS2 and the product can be regenerated. It is less volatile hydrocarbon and possesses low heat of reaction than MEA. It means DEA is easy in processing and easy to regenerate [8].

Inlet gas flow rate Inlet liquid flow rate Inlet gas temperature Inlet liquid Temperature Amine concentration Gas in pressure L. Amine in pressure H2S in sour gas CO2 in sour gas

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Figure 1. Process Flow Sheet.

The whole process is modeled and simulated in dynamic state as shown in figure (1) in order to get the best absorption results, to avoid foaming, to meet the sweet gas specification which may be result of poor contact of sour gas and solvent. In order to avoid all these problems controller loops are used that after regular interval of time check the composition of streams and take the action to get exact required sweet gas specification all the times. IV. Results and Discussion The aim of the study is to investigate the effect of using diethanolamine (DEA)) on the natural gas treatment process using the process simulation program HYSYS in dynamic state. Temperature profile It can be observed that in figure (2, steady state) and figure (3, dynamic state) the temperature continues to increase. This may be explained as follows. As the liquid flows down the tower, it continues to absorb acid gas. This absorption is accompanied by a heat of

reaction, which causes the temperature of the liquid to continue to rise. The temperature drop at the bottom of the tower results from the cold gas entering the bottom and contacting the hot liquid flowing downwards. The cold gas absorbs heat from the hot liquid causing its temperature to decrease. This results in a temperature profile at bottom of the tower.
70 65 60

o Temperature [ C ]

55 50 45 40 35 30 0 5 10 15 20 25

No. of Stages

Figure 2. Temperature Profile Vs No. of Stages (steady state).

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80

70

o Tem perature [ C]

60

50

40

30 0 5 10 15 20 25

No. of Stages

Figure 3. Temperature Profile Vs No. of Stages (dynamic state)

Absorption of CO2 and H2S The absorption of CO2 and H2S on different stages of absorber with 20 trays can be observed in figure (4). The sweet gas has composition of CO2 and H2S in mole fraction are 0.0000004 and 0.0000001 respectively with net molar flow in MMSCFD for both liquid and vapor phases in absorber as shown in figure(5). The whole process is simulated in dynamic mode, sweet gas with constant composition of CO2 and H2S is obtained, the strip chart covering the complete simulation results of CO2 and H2S is shown in figure (6)
0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000

M ole Fraction A bsorbed

10 No.of Stages

15

20

25

No.of Stages vs CO2 Absorbed No.of Stages vs H S Aborbed

2

Figure 4. Mole Fraction of CO2 and H2S absorbed

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42 40

Strip Chart of Simulation Results Strip chart of simulation model shows the constant result of sweetening process. The integrator runs from 0 to 20 minutes, CO2 concentration in sweet gas is regularly observed. In figure (6) it can be seen that CO2 concentration is 0.000000 (mole fraction) with same flow rate of DEA to absorber throughout the process.
0 5 10 15 20 25

Net Molar Flow [MMSCFD]

38 36 34 32 30 28 26 24 22

No. of Stages
No.of Stages vs Vapor Molar Flow No.of Stages vs Liquid Molar Flow

Figure 5. Molar Flow in absorber

Figure 6: Strip chart of Simulation Results

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Conclusion The principle investigation was directed to study the effect of using diethanolamine (DEA), as solvent on the gas treatment process using the software HYSYS HYSYS. In all cases, DEA was the best result in the absorption processes of CO2 and H2Sfrom the natural g in gas dynamic state The simulation result show that, by using of the 1886(kg mole /h) DEA with T=99 oF and P=995 (psia) were the best result in the absorption processes of CO2 (0.0000004, mole fraction) and H2S (0.0000001, mole fraction) without any fluctu fluctuation throughout the dynamic process.

[4] Mackenzie. D. H., Prambil .F.C., Daniels. C.A., and Bullin J.A, Design and operation of selective sweetening Plant using MDEA, Energy Progress., pp 31-36. 1987. 36. [5] Sohbi.B., Meakaff.M., Emtir.M., and Elgarni M, The using of mixing amines in an industrial gas sweetening plant, World Academy of Science, Engineering and Technology.,vol. 31,pp 1-2. Technology ,2007. [6] Huttenhuis.P.J.G., Agrawal.N.J., Hogendoorn.J.A., and ] Versteeg. G.F, Gas solubility of H2S and CO2 in aqueous solutions of N-methyl diethanol amine, Journal of Petroleum Science and Engineering., vol.55, pp.122-134. 2007. DOI:10.1016/j.petrol.2006.04.01. [7] Zare Aliabad.H, Mirazei S,Removal of CO2 and H2S using ] Aqueous Alkanolamine solusions, World Academy of Science, Engineering and Technology.,vol.49, pp.1-2. 2009. .,vol.49, pp.1 [8] Abdel-Al.H.K., Aggour.M., and Fahim.M.A., Petroleum and gas Field Processing Marcel Dekker, Inc., 2003.pp. 281-282. 281 ISBN: 0-8247-0962-4. [9]Danckwerts.P.V, The reaction of CO2 with ethanolamines, Chem.Eng.Sci.vol.,34,pp.443-446. 446. 1979. DOI:10.1016/00092509(79)85087-3. [10] Abdel-Al. H.K., Aggour. M., and Fahim M.A., Petroleum and Al. gas Field Processing , Marcel Dekker, Inc., 2003. pp 280-281. Inc. ISBN: 0-8247-0962-4.

REFERENCES
[1] Vadud.A.S. Natural gas desulfurization.Slovenska Technicka Slovenska Univerzita V Bratislave, 2009. [2] Ikoku,C.U, Natural Gas Production Engineering. Engineering.,New York: John Weley & Sons, Krieger Publishing Company., 1984. pp 1213. ISBN: 0-89464-639-7. [3] Abdel-Al. H.K., Aggour. M., and Fahim M.A, Petroleum and Al. gas Field Processing , Marcel Dekker, Inc., 2003, pp 269 , 269-271. ISBN: 0-8247-0962-4.

BIOGRAPHIES

Engr. Tauqeer Abbas is Research Associate in the department of Environmental and Energy Engineering at COMSATS Institute of Information Technology Vehari Vehari-Pakistan. Born in 1988-Pakistan. He holds is B.Sc degree in the field of Chemical Engineering from COMSATS Institute of Information Technology, Lahore, Pakistan. His area of interest is Energy Conservation, Modeling and Simulation of Separation Processes. He is an active member of Proces System Process Engineering Group of Biomass Conversion Research Center, CIIT, Lahore, Pakistan. He is quite energetic and young researcher, always ready to accept challenges. His email id is tauqeerabbas@ciitvehari.edu.pk

Engr. Zeeshan Rashid is Lecturer in Chemical Engineering Department at COMSATS Institute of Information Technology LahoreLahore Campus, Pakistan. Born in 1985- Pakistan. He 1985 did his M.S from University of Teesside, U.K in Process Manufacturing Engineering. His Manufacturi INSERT area of research is Modeling and Simulation and process design. He worked as Process Technologist in Aker Solution Pvt Limited, UK. Dr. Muhammad Shahid is Assistant Professor in the department of Environmental and Energy Engineering at COMSATS Institute of Information Technology Vehari-Pakistan. Vehari He is Ph.D. from INP-ENSAT, ToulouseINP France in the field of Soil & Environmental Sciences. His area of interest includes Environmental Toxicology, Soil Science and Green Energy. His doctoral thesis has been awarded Loplod een Escande award by INP-ENSAT. He has several publications in ENSAT. the field of Soil & Environmental Sciences in high impact factor journals.

Dr. Moinuddin Ghauri is Associate Professor in Chemical Engineering Department at COMSATS Institute of Information Technology Lahore-Campus Pakistan. Born Campus, in 1963-Pakistan. He holds Ph.D. in the field of Chemical Engineering, Energy and Environment Conservation from the INSERT University of Sheffield, UK. Energy and Environment is his focus area. He has exposure of working with leading National, Multinational and European instituti institutions. He is author of twenty technical teaching-learning resources for learning Environmental Control Technology and modules for Chemical Technology at technical education Pakistan. He is creative by . nature and loves creative and challenging assignments.

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