Conceptual Design and Operational of Acid Gas Removal Unit in Liquefied Natural Gas Plant

L. F. Y. Irene Universiti Teknologi PETRONAS Bandar Seri Iskandar 31750 Tronoh Perak Darul Ridzuan
Abstract A design model on Acid Gas Removal Unit (AGRU) for Liquefied Natural Gas (LNG) plant have been developed, which describe the selection and evaluation of technology followed by selection of amine solvent and also the detailed design of AGRU with regenerative methyl-di-ethanolamine (MDEA) absorption process, including heat and material balance, equipment selection and design as well as process control. The design is proved to be feasible through ICON simulation in which the product output with the acid gas compositions in treated gas meets the typical LNG specification for CO2 and H2S concentration which are < 50 ppm mole CO2 and < 3.3ppm mole of H2S. Keywords Liquefied Natural Gas (LNG), Acid Gas Removal Unit (AGRU), methyl-di-ethanolamine (MDEA) I. INTRODUCTION III. LNG is natural gas that is cooled down to -161C into its liquid state in order to facilitate transportation and export as LNG is 600 times smaller in volume compared to natural gas. Before natural gas is liquefied, impurities such as carbon dioxide, hydrogen sulfide, water, mercury, nitrogen and heavy hydrocarbon are required to be removed. The overall LNG plant is shown in figure 1. LITERATURE REVIEW/ THEORY Table 1: Compositions of Each Component in Feed Gas Components Methane (CH4) Ethane (C2H6) Propane (C3H8) Butane (C4H10) Pentane (C5H12) Carbon dioxide (CO2) Hydrogen sulfide (H2S) Nitrogen (N2) Mercury (Hg) Water (H2O) Feed compositions (mol %) 87.03 0.785 0.294 0.098 0.049 9.809 0.025 1.471 0.001 0.438

Theories applied into the design include, but not limited to mass and energy balance, vapor liquid equilibrium, unit operations and process control which are discussed as below. i. Mass and Energy Balance

Mass balance is an application of conservation of mass in physical process. Law of conservation of mass states that mass of an isolated system cannot be created or destroyed [1]. The rate of mass holdup in the system or accumulation can be represented by: ( ( ) ( ) ) ( )

Figure 1: Overall Process of LNG Plant Removal of acid gas mainly carbon dioxide (CO2) and hydrogen sulfide (H2S) is studied in this paper. AGRU is essential in LNG plant to prevent acid gas components to freeze out and cause blockage in the liquefaction plant as well as to meet the relevant H2S and sulfur specifications for the re-gasified pipeline gas. II. OBJECTIVE

If the system does not change with time or in steady state, net accumulation will be zero. And if chemical reaction does not present, production and consumption terms are typically zero where the total balance of the equation will be reduced to: Mass Input = Mass Output According to law of conservation of energy, energy can neither be created nor destroyed. At steady state, energy balance equation will be: Total energy input = total energy output

The objective of this project is to design AGRU for a new LNG plant with a feed gas supply of 700 MMSCFD (186.7 kg/s) from gas field K9, which is located 131km offshore from Bintulu. The design with the following feed compositions are required to produce product or treated gas that meets the typical LNG specification with maximum 50 ppm mole of CO2 and maximum 3.3 ppm mole of H2S.

ii.

Vapor-Liquid Equilibrium

Vapor-liquid equilibrium is a boiling liquid that is at its bubble point and a condensing vapour that is at its dew point. Bubble point is the temperature and pressure at which the first bubble appears in a boiling

liquid whereas dew point is the first dew that appears at that particular temperature and pressure [2, 3]. The bubble point equation is

Disturbance variables : input variables that cause controlled variables to deviate from their respective set points.

Where yi = concentration of the first component in vapour state xi = concentration of the first component in the liquid state Ki = equilibrium constant By assuming ideal gas law applies, the equilibrium constant of individual component can be calculated by deriving from Raoults law into

Basic of control strategies There are a few types of control strategies that are considered to be implemented in AGRU, which are: Feedback Control Feedback control compares measured value of the output to the desired set point and takes appropriate corrective action. Feedback control is efficient in achieving the targeted set point of the product but it responds more slowly since it does not take any corrective action until after disturbance has upset the process. So, there will be time delay in feedback control. Feedforward control Feedforward control is based on measuring disturbance by anticipating effect of that disturbance will have on the process and automatically taking corrective action on another input variable to counteract the disturbance. Hence, feedforward control requires disturbances to be measured explicitly. Feedforward control is usually used for frequent disturbances occurring or when disturbances are too large that controlled variable cannot be kept within tolerable limits. Cascade control Cascade control combines two feedback controllers with the primary controllers output serving as the secondary controllers set point. The two feedback control loops in cascade control are nested with the secondary loop located inside the primary control loop (master control). Each control strategies have its advantages and suitability to be used in different control loops, which is decided in process control scheme. IV. METHODOLOGY

Where Pvap,i PT iii.

= vapour pressure of component = system pressure Unit Operations

The unit operations in acid gas removal process are gas liquid separation and absorption of gases. Gas Liquid Separation

Gas and liquid separation is separation of liquid particle from gas particle which depends on the settling velocity. Higher volumetric flow rate will require larger diameter of vessel for settling down the liquid particle. The minimum allowable diameter can be determined by deriving from fluid flow equation Q = A V to get the following equation. Absorption of gases Absorption of gases is the removal of one or more selected components from a mixture of gases into a suitable liquid with principle of working is based on interphase mass transfer. There are two types of absorption, namely chemical and physical absorption. Chemical absorption occurs when chemical reaction between solute and absorbent occurs whereas physical absorption is solely physical and depends on rate of diffusion of solute into absorbent [4, 5]. The number of equilibrium stages for absorption process can be determined by using Souders and Brown equation which is shown below.

To achieve the objective, the project is divided into several parts and the sequence is shown in figure below. Background Study of Process of AGRU Initial Evaluation and Technology Selection Preliminary Flow Diagram Calculation on Heat and Material Balance Equipment Selection and Design

Regeneration of gases is just the opposite of absorption or also known as desorption iv. Process Control

Developing Process Control Scheme Process Flowsheeting Report Writing Figure 2: Methodology of Project V. 1. RESULT AND DISCUSSION

According to Towler [6], process control is essential in every plant in order to ensure safe plant operation, achieve production rate and quality with minimal cost. Control in plant can be incorporated in automatic control loops or used as manual monitoring of the process operation. Process control can be characterized by identifying three important types of variables which are: Controlled variables : variables which quantify the performance or quality of final product, also known as output variable Manipulated variables : input variables that are adjusted dynamically in order to maintain the controlled variables to be in its specified limits in the presence of disturbance variables

Technology Selection and Evaluation

Study was done for the available acid gas removal technologies. Among the technologies revised are: H2S scavenger process, chemical amine absorption, physical amine absorption, mixed amine absorption, membrane separation and cryogenic fractionation. Chemical amine absorption process is selected to be used in this project as it can cope up with the high feed flow rate of 186.7 kg/s and high pressure of 60 barA as well as able to remove acid gas components in product/treated

gas to meet typical LNG specification. Besides, chemical amine absorption process is economically justified as it requires lower energy consumption with the lowest hydrocarbon loss among the technologies. Therefore, chemical amine absorption is the most suitable technology to be use for this case. 2. Amine Solvent Selection and Evaluation

Reflux Drum, V-1103 where the condensed water will be separated and reflux back to Regenerator while acid gas flows to Incinerator unit. Makeup water is added to the Reflux Drum, V-1103 to ensure the solvent is in correct specification for absorption efficiency. 4. Heat and Material Balance

The solvent of 50 weight (wt) % MDEA with 50 wt % water was selected to be used. This is because MDEA is tertiary amine which will not degrade based on its structure. Besides, based on chemical reactions equations with acid gas components, MDEA has higher loadings of acid gas compared to other solvents which means less solvent will be required. Heat of reaction of MDEA with CO2 is 575 Btu/lb which is the lowest among the solvents [7]. This shows that regeneration of MDEA solvent will require the less heat in which will reduces the operating cost. Therefore, MDEA is the most suitable solvent to be used. 3. Process Flow of AGRU

Heat and material balances for AGRU have been developed. The summary of important process variables are summarised in table below. Table 2: Important Process Variables Calculated Stream Treated gas Flash gas Parameters H2O composition, mol % Temperature, C Flow, kg/s CO2 composition, mol % Flow, kg/s Lean solvent coolers duty, kW Temperature, C Temperature, C Condenser duty, kW Flow, kg/s Reboiler duty, kW Design Case 0.24 69.64 35.23 64.64 456.59 52732 69.64 118.0 16478 2.58 94566

Process flow of AGRU with MDEA is decided which is characterized as absorption process and regeneration process. Absorption process Feed gas at 20C and 60 barg will enters through Feed Gas Knockout Vessel, V-1107 to knockout carried over water and heavy hydrocarbon before entering bottom of tray 1 Absorber, C-1101. In the Absorber, feed gas will flow upwards and contact countercurrently with lean MDEA solvent which is sprayed from top of absorber. Passing through 63 valve trays in the column, acid gas components will be absorbed into the lean MDEA solvent and treated gas will leave from top of column to next gas treating unit while solvent concentrated with acid gas which is known as fat solvent or rich solvent will leave the absorber bottom to flash vessel. The lean solvent flow rate depends on the concentration of CO2 in the feed gas as more solvent will be needed to absorb more acid gas from the feed gas. Absorber bottom is equipped with a raschig ring packed bed to reduce hydrocarbon entrainment into the solvent. Regeneration process The fat solvent is regenerated in two steps. First is through Flash Vessel, V-1101 and then through Regenerator, C-1103 where all the acid gas absorbed will be removed from the solvent. The fat solvent from the Absorber will flow into Flash Vessel which is flashed off at low pressure of 5 barg. This vessel serves two purposes which are: Degassing and stabilization of the fat solvent by disposing of volatile, dissolved light hydrocarbons Flashing of partial of the acid gas in the solution The flash gas leaving the top of Flash Vessel will be sent to fuel gas system. And the fat solvent leaving the vessel will flow through Lean and Fat Heat Exchanger, E-1102 to be pre-heated before entering into the Regenerator, below the wash tray and above the stripping section. In the Regenerator, acid gas components are stripped off from the solvent at elevated temperature and low pressure using steam generated in the Reboiler. Reboiler heating is via low pressure (LP) steam where reboiler duty depends on the acid gas concentration in the feed gas. The higher the concentration, more heat will be needed to totally strip off the acid gas so higher will be the reboiler duty. The lean solvent accumulates at the bottom of Regenerator in which will be routed back to Absorber via the solvent circulation loop. Overhead vapour in the Regenerator is washed by reflux water sprayed on the top tray of Regenerator. Then, the wet acid gas stream is air cooled in the Regenerator Overhead Condenser, E-1105 prior to

Lean solvent to absorber Fat solvent exit absorber Lean solvent exit regenerator Regenerator overhead Makeup water Total heat required in reboiler

ICON simulation was conducted and composition of acid gas in product was obtained and shown in table below. Table 3: Comparison of ICON Simulation Result with Typical LNG Specification Acid gas components CO2 H2S iCON result 2.647 ppm 0.0242 ppm Typical LNG specification 50 ppm mol 3.3 ppm mol

Therefore, with ICON result of CO2 and H2S concentration meeting the product specification, it is proven that the design is feasible. 5. Equipment Selection and Design

The next step is selecting and designing equipment required for AGRU which are briefly described in table below. Table 4: Functions of Each Equipment in AGRU Tag no. C-1101 Equipment Absorber column Function To remove acid gas components by contacting counter current feed with lean solvent to meet the product specification To regenerate MDEA solvent To cool down lean solvent To recover heat from lean solvent to fat solvent To cool down wet acid gas stream in order to condensed water

C-1103 E-1101 E-1102 E-1105

Regenerator column Lean solvent cooler Lean and fat heat exchanger Regenerator overhead condenser

E-1106 P-1101 P-1102 P-1103 V-1101

Regenerator reboiler Charge pump Booster pump Reflux pump Flash vessel

V-1103 V-1107

Reflux drum Feed gas knockout vessel

To produce enough steam for stripping of acid gas from solvent To pump lean solvent into absorber To pump hot lean solvent to lean and fat heat exchanger To Pump water reflux back to regenerator column To flash off entrained light hydrocarbon and partial of the acid gas components To separate liquid water and acid gas stream To knockout carry over water and heavy hydrocarbon

Acid gas components in treated gas or output CO2 H2S

Composition, ppm Composition, ppm

2.647 0.0242

Designs were done for one of each type of equipment which are absorber, feed gas knockout vessel, lean and fat heat exchanger and reflux pump. Equipment Data Requisition Sheet (EDRS) for the equipment are synthesised. 6. Process Control Scheme

Therefore, with selection and evaluation of available acid gas removal technologies, selection of amine solvent, heat and material balance, process flow sheeting, equipment selection and design as well as process control scheme accomplished, the proposed design for Acid Gas Removal Unit of a new LNG plant is justified as well as proven by using ICON simulation in which the product output with the acid gas compositions in treated gas meets the typical LNG specification for CO2 and H2S concentration which are < 50 ppm mole CO2 and < 3.3ppm mole of H2S. Hence, the objective to design Acid Gas Removal Unit for a new LNG plant with 700 MMSCFD of natural gas feed is achieved. VII. ACKNOWLEDGEMENT

Control scheme was divided into five divisions to control level, flow, pressure and temperature for the five major equipments during any upset occurs in the system. This is implemented in order to have a simple and safe plant operation to achieve the output target of LNG with desired product purity of CO2 <50ppm and H2S <3.3ppm. Summary of the process control scheme developed is shown in table 5. After completing the process control scheme, a complete Process Flow Scheme (PFS) for AGRU was drawn and shown in figure 3 and 4. VI. CONCLUSION

The author appreciates the assistance and support of the following individuals throughout the project. Thanks to Mr Jinson Ho, Process Engineer of Malaysia LNG Sdn. Bhd. and other colleagues for their guidance as well as constructive feedbacks. VIII. 1. 2. 3. 4. REFERENCES

In a nutshell, a model Acid Gas Removal Unit was designed effectively to remove acid gas components (CO2 and H2S) from feed natural gas stream with: Table 6: Critical Design Spec Units Flow, kg/s Flow, kg/s Flow, kg/s Flow, kg/s Design Case 186.68 137.00 456.59 41.98

5. 6.

7.

Natural gas inlet Treated gas outlet MDEA solvent required Total amount of acid gas removed

Fedler, R. M. and Rousseau, R. W. (2005). Elementary Principles of Chemical process. John Wiley & Sons, Inc Geankoplis, c. J. (2003). Transport Processes and Separation Process Principles. Pearson Education International. Norman, P. L. and Elizabeth, T. L. (2008). A Working Guide to Process Equipment. Mac Craw Hill. Richardson, J. F., Harker, J. H. and Backhurst, j. R. (1991).Chemical engineering Volume 2: Particle Technology and Separation Processes. Butterworth-Heinemann. Coupler, J. R., Penney, W. R., Fair, J. R. and Walas, S. M. (2005). Chemical Process Equipment. 2nd edition. Elsevier Inc. Towler, G. and Sinnott, R. (2008). Chemical Engineering Design. Principles, practice and economics of plant and process design. Elsevier Inc. Aden, A. (2009). Survey and Down-Selection of Acid Gas Removal Systems for the Thermochemical Conversion of Biomass to Ethanol with a Detailed Analysis of an MDEA System. Nexant Inc.

Table 5: Summary of Process Control Scheme for AGRU Equipment Feed gas KO vessel Control Requirement To control liquid level in V-1107 To control liquid level in C-1101 To control treated gas purity To avoid flooding in V-1101 To control pressure of V-1101 To maintain purity of lean MDEA solvent To maintain liquid level in V-1103 Controlled Variable Liquid holdup in V1107 Liquid holdup in C1101 Composition of acid gas in treated gas Liquid holdup in V1101 Pressure in V-1101 Temperature at tray 7 of C-1103 Liquid holdup in V1103 Manipulated Variable Flow rate of stream 21 Flow rate of fat solvent exit absorber Flow rate of lean MDEA solvent Flow rate of fat solvent exit V-1101 Flow rate of flash gas exit V-1101 Flow rate of LP steam to reboiler Flow rate of reflux back to C-1103 Disturbance Variable Amount of heavy hydrocarbon or water in feed gas Flow rate of lean MDEA solvent Composition of acid gas in feed gas Flow rate of fat solvent enter V-1101 Pressure of fat solvent enter V-1101 Flow rate of reflux Temperature of reflux Control Strategy Feedback control Feedback control Feedforward control Feedback control Feedback control Cascade control Cascade control

Absorber

Flash vessel Regenerator and reboiler Reflux drum

Figure 3: Process Flow Scheme (PFS) of AGRU

Figure 4: Continuation of PFS for AGRU