Modeling and Optimization of Different Acid Gas Enrichment Structures via Coupling of Response Surface Method with Genetic Algorithm

Document Type : Research Article

Authors

Chemical Engineering Department, Faculty of Engineering Ferdowsi University of Mashhad, Mashhad, Iran

Abstract

Lean acid gases entering any sulfur recovery unit (SRU) can strongly damage the corresponding overall sulfur efficiency. The use of the acid gas enrichment (AGE) process is essential to increase recovery efficiency. Two novel scenarios are studied in the present work. The first low-pressure structure uses an enrichment tower with operating pressure above the atmosphere and lower than the regenerator pressure, while, the second high-pressure scenario limits the enrichment tower pressure between the amine flash drum and corresponding regenerator pressures. The combination of the Aspen-HYSYS process simulator and response surface method is successfully employed to generate training data and create reliable hyper-surfaces for mimicking the acid gas enrichment rate versus various operating parameters. An initial sensitivity analysis is recruited to pinpoint the most dominant input parameters. The optimization of fitted merit functions was carried out using our in-house genetic algorithm code. The corresponding enrichments for high and low-pressure scenarios were 83.63 and 70.53% respectively. These are more than 140% and 105% increases in H2S concentrations in comparison to the conventional design of the existing SRUs, which is based on around 34% H2S content in the acid gas feed. Economic and environmental evaluations of both scenarios revealed that the optimal low-pressure structure is much more favorable from the economic point of view, while the high-pressure design performs more environmentally friendly by reducing the SO2 emissions by at least 21.4%. To the best of our knowledge, the above complex and detailed study have never been performed previously for any AGE process.

Keywords


Nomenclatures

Parameter

Description

A

parameter based on heat exchanger material

 

Surface area

ANNs

artificial neural networks

AGE

Acid gas enrichment

AGSR

acid gas split ratio

ANDI

approximate number of decisive iterations

B

parameter based on heat exchanger material

BTEX

Benzene-Toluene-Ethyl Benzene-Xylene

CGAO

Constrained Genetic Algorithm Optimization

 

Installed cost

 

Base cost

 

Purchase cost

 

The added cost for platforms and ladders

 

Base cost for sieve trays

 

The cost for installed trays

 

Purchase cost of the empty vessel including nozzles, manholes and supports

 

Inside diameter in feet/in

DOE

Design of experiment

 

Fractional weld efficiency

ET

Enrichment tower

 

Driving factor

 

Tube length correction factor

 

Material factor

 

Number of tray factor

 

Type factor

 

Tray material factor

 

Type of tray factor

 

Pressure factor

GTU

Gas treating unit

 

Pump head in feet

HP

High pressure

 

Length of shell in feet/in

LAF

lean amine flow rate

LP

Low pressure

NN

neural network

 

Number of trays

 

Pump brake horsepower

 

Power consumption in horsepower

 

Internal design gage pressure in psig

 

Operating pressure in psig

PET

Pressure of enrichment tower

 

Flow rate through the pump in gallons per minute

R1

Response 1: H2S mole percent in acid gas

R2

Response 2: H2S mole percent in off gas from the top of the enrichment tower

RASR

rich amine split ratio

RSM

Response surface method

 

Maximum allowable stress of shell material at design temperature in lb/in2

SRU

Sulfur recovery unit

 

Wall thickness in inches

TLA

temperature of lean amine

TRA

temperature of rich amine

 

Weight in pounds

Greek Symbols

a

Multiplier for installed cost

 

Density of carbon steel

 

Fractional efficiency of electric motor

 

 

  1. Introduction

Most the natural gases produced from different reservoirs around the world are contaminated with various impurities, such as H2S, CO2, and water vapor. These impurities should be removed during various stages of gas processing, including sweetening and dehumidification processes. Acid gas components (CO2 and H2S) are traditionally removed from the sale gases using conventional amine treating processes. The acid gas produced in the gas treating unit (GTU) will have an unfavorably high CO2 to H2S ratio, when CO2 to H2S ratio is relatively high in a sour natural gas feed, leading to a poor quality feed of sulfur recovery unit (SRU). The acid gas feed stream typically requires at least 50 mole percent H2S, to achieve high temperature (T>926°C, 1700°F) combustion in the SRU Claus furnace. Otherwise, other Claus plant design options should be used instead of the straight thorough scheme such as split-flow design, and/or fire a supplemental fuel, recruit oxygen enrichment of the combustion air, or preheat the air and/or acid gas feed to the Claus furnace to maintain the highest attainable temperature (ZareNezhad & Hosseinpour, 2008) (Barvar, Safamirzaei, & Shariati, 2019). Acid Gas Enrichment (AGE) is widely used in the last three decades to process dilute acid gas streams. The process objective is to maximize CO2 slip and minimize the H2S leak into vent gas from the system, thereby producing a gas enriched in H2S to the greatest possible extent (Weiland, 2008).

AGE process is usually applied ahead of SRU to produce a richer acid gas stream. Its appropriate use can stabilize thermal section operation and achieve a higher temperature in the reaction furnace. Higher temperatures ensure partial or complete destruction of acid gas contaminants such as benzene, toluene, ethyl benzene, and xylene (BTEX components) (Garmroodi Asil, Shahsavand, & Mirzaei, 2017). 

Up to now, different aspects of the acid gas enrichment process are studied in the limited available research articles. Two main approaches are traditionally used. In the first scheme, the research was usually focused on the selection of the optimal or at least more suitable solvent to be used in the separate AGE process, positioned between GTU and SRU, for selective absorption of H2S and rejecting the problematic CO2 from the acid gas stream.

Chilukuri and Bowerbank proposed an integrated lined-ups structure that created a better quality acid gas feed to the SRU. They claimed that such an integrated structure created new cost-effective modes of operation, reduced plant complexity, managed a wide range of feed gas contaminant uncertainties, and reached stringent emission requirements (Chilukuri & Bowerbank, 2016).

 Dara et al studied the economic and environmental impact of a cooling system to cool down hot lean MDEA (40% by weight) solvent in an AGE unit located in the United Arab Emirates. It is found that reducing the lean solvent temperature increased the purity of both H2S and CO2 product streams (Dara et al., 2018).

ExxonMobil applied FLEXSORB™ SE solvent for AGE and tail gas clean-up. A novel compact and low-weight processing technology platform was used to perform selective H2S removal (Northrop, Seagraves, Ramkumar, & Cullinane, 2019). Al-Amri and Zahid proposed a new acid gas cleaning system that employed two GTUs instead of a conventional GTU+AGE system for treating high CO2 content natural gases while maintaining all process specifications such as sweet gas, acid gas, waste gas, and amine unit flashed gas with allowable concentrations. In contrast to conventional systems, acid gas was produced with the required purity in the first GTU, while sweet gas was produced in the second GTU, with the required spec. They claimed that the proposed design required 22% less energy demand compared to the conventional design because of the reduced amine circulation rate, leading to lower re-boiler duties (Al-Amri & Zahid, 2020).

In the Second strategy, necessary modifications are usually applied to an existing GTU configuration while using the conventional solvent (Garmroodi Asil & Shahsavand, 2014a). Palmer proposed four different structures to increase H2S concentration in the acid gas stream as well as to produce a valuable CO2 by-product (Patent No. 20040226441, 2004) (Patent No. 7147691, 2006). Mak et al suggested a few configurations in a patent in which a portion of an isolated hydrogen sulfide stream is introduced into an absorber operating as a carbon dioxide rejecter (Patent No. 7635408, 2009).

Mahdipoor and Dehghani investigated both technical and economic aspects of two AGE configurations. In the first scheme, AGE off-gas was sent to the incinerator, while in the second scenario, it was used as the feed for the tail gas treating unit (TGTU). They reported that routing AGE off-gas to TGTU increases the size and cost of TGTU equipment while reducing the environmental pollutants (Mahdipoor & Dehghani Ashkezari, 2016).

Dai et al investigated a novel two-stage flash process of acid gas removal from the natural gas stream. The first flash drum is used to remove most of the light hydrocarbons, while the second one is recruited to remove most of the CO2 and a small fraction of the H2S. Afterward, the liquid absorbent is sent to the regeneration column to remove the absorbed H2S. They concluded that, compared with the traditional acid gas removal and traditional AGE processes, the two-stage flash process of acid gas removal can successfully enrich acid gas while reducing the regenerator energy consumption (Dai, Peng, Qiu, & Liu, 2019).

Rameshni and Santo presented a patent for an integrated system that combined sour gas treating (for H2S Removal), separation of impurities (such as hydrocarbons, BTEX, and mercaptans), and partial acid gas enrichment. The new schemes comprised one or more absorbers coupled with the primary and secondary regenerators. The secondary regenerator function is to further enrich the H2S stream and to separate the hydrocarbons, mercaptans, and BTEX (Patent No. 20200039825, 2020).

As can be seen from the above literature review, research on acid gas enrichment was somehow limited. Furthermore, most of the research is focused on adding a separate enrichment unit placed between GTU and SRU unit, by using its solvent. Evidently, such an independent scheme provides more operational flexibility while leading to excessively high investment costs. When capital investments are limited, the second choice seems more realistic. In this scheme, the conventional GTU process is usually equipped with an enrichment tower to enhance acid gas enrichment. Evidently, such a design is less flexible from an operational view but severely reduces the required capital investments. Research on this approach is quite limited (Patent No. 20040226441, 2004) (Patent No. 7147691, 2006) (Patent No. 7635408, 2009). Due to shortcomings in capital investments in the Iranian natural gas refineries, the second approach will be investigated in the present work.

Garmroodi Asil and Shahsavand simulated three different enrichment schemes for Khangiran natural gas refinery acid gas enrichment. In the first scheme, a fraction of the acid gas from the top of the regenerator is recycled back to the main GTU contactor. In the other two, a fraction of the acid gas stream is recycled back to an added enrichment tower (ET), which was placed between the amine flash drum and the regenerator. In the second scheme, the ET pressure was lower than the regenerator pressure, while in the third scheme the ET pressure was kept between the flash drum and regenerator pressures. They concluded that the SRU feed stream can be enriched from its original value of nearly 34 mol% H2S to about 54 and 70 mol%, by resorting to the 2nd and 3rd schemes, respectively (Garmroodi Asil & Shahsavand, 2014b). Due to the importance of the acid gas enrichment process and the great impact of this process on economic and environmental issues of sulfur recovery units and also due to the relative lack of study in this field, the purpose of this article is to thoroughly investigate structures 2 and 3 and find the optimal structure and optimum values for operational variables.

 

  1. Novelty of the research

In the first step, the previous structures were slightly modified and the response surface method (RSM) along with artificial neural networks (ANNs) are used to model the entire process and provide the necessary cost function. Then genetic algorithm (GA) optimization technique is used to pinpoint the optimal operation conditions. Furthermore, the optimal selected scenario was studied from both economic and environmental viewpoints. To the best of our knowledge, such a complex approach has not been addressed, previously.

The present article compares two different schemes of AGE processes for the Khangiran natural gas refinery. An enrichment tower is used between the GTU amine flash drum and the corresponding regenerator column, in either of both designs. The pressure of the enrichment tower is kept below the regenerator pressure in the first scheme (low-pressure scenario), while in the second arrangement it is bounded between the amine flash drum and the regenerator pressures (high-pressure scenario).

To investigate the effect of more operational parameters, the enrichment structures of this study are slightly different from the previous ones (Patent No. 20040226441, 2004) (Patent No. 7147691, 2006) (Garmroodi Asil & Shahsavand, 2014b). For example, two heat exchangers are added to both rich and lean amine streams entering the ET, to investigate those streams' temperatures. Furthermore, a flow splitter has been installed on the rich amine stream to investigate the effect of the rich amine split ratio sent to ET.

In the present work, modeling and optimization of the acid gas enrichment process have been performed by resorting to RSM, ANN, and GA techniques, while in the previous studies, the effect of the operational parameters has been studied by simple trend analysis (i.e. plotting a few diagrams without applying any modeling or optimization method).

 

  1. Case study description

Figure (1-a) depicts the original acid gas sweetening unit of the Khangiran natural gas refinery in the absence of any acid gas enrichment. Figures (1-b) and (1-c) show our in-house version of the Palmer design for low and high-pressure AGE schemes, respectively (Patent No. 20040226441, 2004) (Patent No. 7147691, 2006) (Garmroodi Asil & Shahsavand, 2014b). Additional but different unit operations are required for each AGE design. For example, a pump is required to boost the pressure of the liquid stream departing the enrichment tower and receiving by the regeneration column, in the first scheme, while the use of a suitable compressor is essential in the second design to compress the acid gas stream leaving the acid gas splitter and entering the enrichment tower.

Compared to our previous work (Garmroodi Asil & Shahsavand, 2014b)  several modifications are used in the present study to enhance the overall enrichment efficiencies in both schemes. For example, heat exchangers are added to adjust the temperatures of lean amine and rich amine feed streams entering the enrichment tower of each scheme. Furthermore, the rich amine splitter is used in both designs to investigate the effect of the rich amine flow rate entering the enrichment tower. Table 1 provides the sour feed gas specifications entering each absorber of the four GTUs. Each GTU includes two parallel absorbers and two strippers.

 

Lean Amine to contactor

Pump

Compressor

Off Gas

Lean Amine from regenerator

Acid Gas

Rich Amine

Lean Amine

(b)

Off Gas

Lean Amine

Rich Amine

Lean Amine from regenerator

Acid Gas

(c)

Rich Amine

Sweet Gas

Sour Gas

Lean Amine

Acid Gas

(a)

Lean Amine

 to contactor


Figure 1: (a) Original gas sweetening unit,

(b) Low-pressure AGE scheme, (c) High-pressure AGE scheme

 

Table 1: Khangiran natural gas sweetening sour gas feed specifications entering each absorber of the four parallel gas treating units (GTUs) (Garmroodi Asil & Shahsavand, 2014b)

Parameter

Unit

Value

Flow rate

kmol/hr

7319

MMSCMD

4.15

Temperature

ºC

52

Pressure

kPa

7239.5

Analysis (mole%)

C1

C2

C3

iC4

nC1

iC5

nC5

C6+

88.64

0.53

0.06

0.01

0.03

0.01

0.01

0.03

H2O

H2S

N2

CO2

C6H6

C7H8

C8H10

 

0.38

3.4

0.37

6.5

0.018

0.01

0.002

 

 

3.1. Main operational input and output parameters

For a successful investigation of the entire process, the most important operational parameters must be recognized. Our primary investigations revealed that the following six parameters are anticipated to have relatively strong effects on the overall performance of the AGE schemes. 

  1. a) Enrichment tower pressure (PET), b) Acid gas split ratio (AGSR), which controls the recycled acid gas flow rate, c) Rich amine split ratio (RASR) that regulates the rich amine flow rate entering the middle tray of the enrichment tower, d) Lean amine flow rate (LAF) entering at the top tray of the enrichment tower, e) Lean amine temperature (TLA) and f) Rich amine temperature (TRA). Lean amine loading is not considered an independent input variable, since it strongly depends on the structure and specifications of the regenerator. Table 2 provides the corresponding bounds for the above operating parameters based on the allowable operational criteria.

Two obvious output parameters can be recognized as a) H2S mole percent in acid gas leaving the entire enrichment process and entering the sulfur recovery unit (designated as the first response: R1) and b) H2S mole percent in off gas leaving the top of the enrichment tower (response 2: R2). Evidently, R1 indicates the enrichment rate and R2 provides the environmental constraint, which will be used in the optimization algorithm.

 

Table 2: Operational inputs variables and the corresponding bounds

Parameter abbreviation

Unit

Min

Average

Max

PET

High pressure

psia

15

20

25

Low pressure

30

60

90

AGSR

fraction

0.5

0.7

0.9

RASR

fraction

0.5

0.75

1

LAF

kmol/s

0.544

1.362

2.18

TLA

ºC

40

60

80

TRA

ºC

40

60

80

 

3.2. Sensitivity analysis

The entire processes depicted in Figures (1b) and (1c) are simulated using Aspen-HYSYS (V11) process simulator. The acid gas - chemical solvents property package has been recruited for this purpose. Five equi-spaced points were considered for each of the six input variables and the corresponding responses R1 and R2 were computed via simulation for that input variable at the corresponding value, while other input variables are kept fixed at their average values, as depicted in Table 2.  

Figure 2 shows sensitivity analysis of two AGE process (denoted as HP and LP) responses R1 and R2 versus the scaled input variables across their entire corresponding input domains. All inputs are scaled between (-1) and (+1) for ease of illustration. Table 3 provides the conclusions obtained from Figure 2 about the degree of importance of various input parameters for both AGE scenarios. 

 

 

 

 

 

Figure 2: Sensitivity analysis of responses R1 and R2 versus various input variables.

Top) High pressure (HP) and Bottom) Low pressure (LP)

 

Table 3: Importance of various input parameters based on sensitivity analysis of Fig. 2.

Response

High-pressure ET

Response

Low-pressure ET

Strong

Intermediate

Weak

Strong

Intermediate

Weak

R1

SRAG

PET, RAT

LAT

R1

SRAG

SRRA,PET,LAF

LAT

R2

SRAG

LAF, LAT

RAT

R2

SRAG

LAF, SRRA

LAT

 

 

  1. Modeling of data

Due to the complexity of the AGE process, two different empirical modelings via response surface method (RSM) and MATLAB software neural network toolbox  arebeing used to model the entire process shown in Figures (1b) and (1c). Initially, RSM which is a subdivision of Design-Expert software (11.0.3.0) is used to specify the desired operating points in the input domain of Table 2, for both low and high pressure enrichment tower scenarios. Tables A1 and A2 of the appendix section provide the entire 78 operating points and the corresponding values of responses R1 and R2 for both low and high-pressure AGE designs, as predicted via the Aspen-HYSYS simulator for the processes depicted in Figures (1b) and (1c).

After necessary preprocessing and internal optimization, two parallel multiple input single output (MISO) data sets of Tables A1 and A2 are used by the RSM technique to ultimately provide equations (a) to (d) for the functionality of R1 and R2 at high and low-pressure scenarios, respectively. As can be seen, the lean amine temperature (LAT) is omitted from equation (a), which is in accordance with the sensitivity analysis of Table 3.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Figure 3 illustrates the relatively successful recall performances of the RSM fitted hyper-surfaces for R1 and R2 at both high and low pressures using equations (a) to (d). Since the values of response R2 drastically vary in the entire domain of inputs as depicted in Tables A2 and A3, therefore the logarithmic plot is used to emphasize the lower values of R2<0.2. Due to environmental considerations, the amount of H2S in the off-gas leaving the top of the enrichment tower should be less than 2000 ppm (Al-Amri & Zahid, 2020).

 

 

Figure 3: Recall performances of response surface method (RSM) for R1 and ln (R2) corresponding to high and low pressure (HP and LP) scenarios

 

 

In the second attempt, data sets of Tables A1 and A2 are used to train four separate artificial neural networks (NN) via the neural network fitting toolbox of MATLAB software. After several trials, the best architecture was selected as a single hidden layer feed-forward network with 10 Sigmoid neurons. The back propagation method coupled with the Levenberg-Marquardt optimization technique is used for the training process. Figure 4 depicts similar recall performances of the above 4 mentioned neural networks for responses R1 and R2 at both high and low pressures.

 

 

 

Figure 4: Recall performances of Neural network (NN) model for R1 and ln(R2) corresponding to high and low pressure (HP and LP) scenarios.

 

 

In practice, the recall performances can be mischievous. To ensure that the above-fitted hyper-surfaces perform adequately in the generalization phase, the corresponding performance should be evaluated over the entire domain of the inputs. Figures 5 and 6 compare various three-dimensional generalizations performances of RSM and MATLAB-NN fitted surfaces for both responses R1 and R2 at high and low-pressure scenarios. Table 3 is used to select the most important input parameters as the abscissa of all 3D plots. The other input parameters are kept fixed at the corresponding average values.

As can be seen in Figures 3 and 4, both RSM and MATLAB-NN models perform quite similarly in their recall performances. However, they perform differently in their generalization performances, especially when mimicking the response R2, as depicted in Figures 5 and 6. For both R1 and R2 responses, the RSM predictions are smoother compared to the relatively oscillatory behavior of MATLAB-NN.

Since, the differences in the generalization performances of the above models, as depicted in Figure 6, are not very extensive, therefore, both models will be used in the optimization process to pinpoint the best optimal operating conditions to achieve maximum enrichment while satisfying the constraint R2<0.2.

 

 

 

Figure 5: Comparison of 3D generalization performances of MATLAB-NN and RSM models for responses R1 and R2 at low pressure ET, over the entire domain of the corresponding inputs.

 

Figure 6: Comparison of 3D generalization performances of MATLAB-NN and RSM models for responses R1 and R2 at high-pressure ET, over the entire domain of the corresponding inputs.

 

 

  1. Searching for the optimal operating conditions

The fitted hyper-surfaces of the above section are used as the merit functions of the optimization process to find the optimal operating conditions. The genetic algorithm (GA) optimization method, which is based on the survival of the fitness, is used. It uses three main operations of selection, crossover, and mutation to produce new stronger generations from the old population.  An in-house computer code was developed based on our previously published article (Lotfikatooli & Shahsavand, 2017a). Although GA is a powerful goal-oriented optimization method, however, it usually suffers from lack of a reliable termination criteria. Traditionally, some pre-specified maximum number of generations is usually used as the termination criterion. In many practical applications, the stopping criteria can significantly influence both the final optimal solution and the overall execution time of the entire optimization process. A modified version of GA is presented and successfully applied in our previous works  (Lotfikatooli & Shahsavand, 2017a) (Lotfikatooli & Shahsavand, 2017b), which uses a novel termination criterion parameter named ANDI (approximate number of decisive iterations). The Constrained Genetic Algorithm Optimization (CGAO) coupled with the previously devised ANDI termination criterion which is used in the present work is slightly different from the main algorithm used in our earlier article (Lotfikatooli & Shahsavand, 2017b).  It is modified to accommodate for the constraint(s) and solve the constrained optimization problems. Figure A1, in the appendix depicts the complete flowchart for the above-constrained optimization process, which recruits ANDI for its termination criteria.

Table 4 presents the reported optimization results employing our in-house GA when RSM and MATLAB-NN fitted hyper-surfaces are used as the objective function for R1 and constraint for R2 at both high and low-pressure scenarios. To ensure the optimal performances of the acid gas enrichment at the above optimal points, all R1 and R2 values are re-computed and checked via the Aspen-HYSYS simulations.

 

 

Table 4: Comparison of GA optimization results obtained for both low and high-pressure scenarios via RSM and NN models with Aspen-HYSYS simulations, using the conventional constraint on R2.

Model/ET

Pressure scenario

PET

[psia]

AGSR

RASR

LAF

[kmol/s]

TLA

[ºC]

TRA

[ºC]

Model Predictions

Aspen-HYSYS Predictions

R1

R2

R1

R2

RSM/LP

25

0.6623

1

2.18

56.81

80

65.35

0.2

63.32

0.0086

NN/LP

25

0.7561

1

1.027

47.51

40.27

68.78

0.2

63.98

0.0132

RSM/HP

90

0.8234

1

2.18

40.51

80

74.83

0.19

69.75

0.0041

NN/HP

90

0.8187

0.7498

2.18

79.92

80

80.93

0.17

77.31

0.0677

 

 

Table 4 clearly illustrates that for all cases, the model predictions at the optimal points for R1 are relatively close to the values obtained from Aspen-HYSYS simulations. On the other hand, both RSM and MATLAB-NN considerably over-predict the values of R2, when compared to the more reliable values generated via Aspen-HYSYS simulations at the prevailing optimal operating conditions.

Based on the optimal results presented in Table 4, it is evident that the MATLAB-NN provides better enrichment in both low and high-pressure scenarios. RSM fails because it has less flexibility while searching in the R2 range.

Since both models largely over-predict the values of R2, therefore it was decided to increase the constraint value (R2) from the actual value of 0.2 mole% (2000 ppm) to a proper value for each case. Table 5 illustrates the new optimal results when the appropriate constraint value was selected via a trial and error procedure. In each case, the Aspen-HYSYS simulation result was computed and checked to ensure that the environmental constraint (R2<0.2) is satisfied. As can be seen, the RSM model provides higher acid gas enrichment values at the corresponding optimal points for both low and high pressures. Both values are considerably better than the optimal enrichment rates obtained from Table 4.

 

 

Table 5: Similar comparisons as to Table 4 but employing a much higher constraint on R2, due to over-predictions of both RSM and NN models for R2 values.

Model/ET

Pressure scenario

PET

[psia]

AGSR

RASR

LAF

[kmol/s]

TLA

[ºC]

TRA

[ºC]

Model Predictions

 Aspen-HYSYS Predictions

R1

R2

R1

R2

RSM/LP

25

0.7108

1

2.18

56.23

80

68.48

0.4

70.53

0.0481

NN/LP

25

0.7499   

1

1.0414  

44.97  

43.09

68.75

0.37

64.27

0.0105

RSM/HP

90

0.8593

1

2.18

55.98

80

79.08

1.16

83.63

0.1414

NN/HP

90

0.8312   

0.8284   

2.18  

80

80

82.18

0.29

79.81

0.1259

 

 

Table 6, summarizes the improvement achieved in the present work via different approaches compared to our previous study (Garmroodi Asil & Shahsavand, 2014b) and the actual design enrichment data collected from the existing AGE unit, based on the H2S mole percent (@ 34 mol%) in the acid gas entering the sulfur recovery unit in the absence of AGE unit. The above improvements are due to both structural modification (such as more flexible lean and rich amine temperatures) and using more advanced modeling and optimization techniques (RSM, Matlab-NN, and GA).

 

 

Table 6: Improvements achieved in the present study compared to our previous work (Garmroodi Asil & Shahsavand, 2014b) and actual design data based on original acid gas H2S mole%, in the absence of AGE unit.

Case

Percent enrichment (R1)

Percent improvement (No AGE:0)

LP

HP

LP

HP

Present study, best results via GA + MATLAB-NN and R2 constraint = 0.2 mole%

63.98

77.31

82.80

120.89

Present study, best results via GA + RSM and flexible R2 constraint

70.53

83.63

101.51

138.94

Our previous study

54

70

54.29

100.00

Actual field data

50

-

42.86

-

 

 

  1. Economic evaluation

Figure 1 illustrates that the backbone of both high and low-pressure structures are essentially the same. However, some different equipment is used in each scenario. For example, the expensive compressor in high-pressure scenario is substituted with a more affordable pump in a low-pressure scenario. The cost estimates for different equipment are performed separately to compare them from an economic standpoint, using the cost estimation correlations of Table 7, as presented in reference to the year 2000 (Seider, Seader, & Lewin, 2018). The required specifications of the corresponding equipment involved in economic evaluations (such as height and diameter of ET, powers of the pump, and compressor) have been obtained by resorting to the Aspen-HYSYS process simulator and reported in Table 8. Table 9 presents the overall cost estimation of different equipment used in high and low-pressure enrichment structures, corrected for June 2021. The Chemical Engineering Plant Cost Index (CEPCI) in June 2021 was around 717.6, which was 21.4% greater than the corresponding value in June 2020 (591.1). As can be seen, the equipment cost for those parts which are different in the two scenarios is around 7 times more for the high-pressure structure, compared to the low-pressure design, most of which is due to the cost of acid gas compressor.

 

 

Table 7- Cost estimation formulas used in the economic evaluation of various scenarios (Seider et al., 2018)

Enrichment Tower

Amine Pump

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Acid Gas Heat exchanger

 

 

 

 

 

Acid gas Compressor

 

 

 

 

 

Table 8- Parameters used in economic calculations (Seider et al., 2018) (Walas, 1998)

 

Enrichment Tower (carbon steel column and stainless steel valve tray)

 

 

 

 

 

 

 

 

 

 

 

a

HP

118

650

0.284

15000

0.85

75.3

1

24

1

1.18

3

LP

126

708

0.284

15000

0.85

10.3

1

24

1

1.18

3

Amine Pump (centrifugal stainless steel)

Acid gas Compressor (motor driven, stainless steel)

 

 

 

 

 

 

a

 

 

 

a

3748

145

2

2

1

181.7

2

2.5

1

3267.17

1.3

Acid Gas Heat exchanger (shell and tube carbon steel /stainless steel)

 

 

 

 

 

a

 

 

 

 

 

 

 

1.75

0.13

1.05

1

2.1

 

 

 

 

 

 

                                                         

 

 

Table 9: Equipment costs (unit:1000$)

 

HP

LP

Enrichment Tower

539

417

Amine Pump

-

72

Acid gas Compressor

2883

-

Acid Gas Heat exchanger

110

-

Total Cost (CEPCI=394.1 (2000))

3532

489

Total Cost (CEPCI =717.6 (2021))

6431

890

 

Since the low-pressure scenario pump requires much less electrical power consumption than the compressor of the high-pressure structure, therefore the low-pressure design would be more realistic from a merely economic standpoint, regarding both capital investment and operating costs.

 

  1. Environmental improvements due to acid gas enrichment

To investigate the effect of acid gas enrichment scenarios on the overall performances of four existing Khangiran sulfur recovery units, the entire combination of a typical gas treating unit (GTU) and corresponding sulfur recovery unit (SRU) is simulated using the SULSIM package of the Aspen-HYSYS process simulator for both enrichment scenarios. Figure 7 shows the corresponding simulated flow diagrams. 

During these simulations, the main semphasis was on maximizing the hydrogen sulfide concentration in the acid gas stream entering SRU, which leads to maximum elemental sulfur production rate, especially in the reaction furnace of the thermal section. Enriching the acid gas entering the sulfur recovery unit has several other benefits as well, such as reducing the Benzene-Toluene-Ethyl Benzene-Xylene (BTEX) content of the acid gas stream, due to flash vaporization of BTEX components in the enrichment tower, especially when dealing with the low-pressure scenario. Furthermore, the enriched acid gas creates higher combustion chamber temperatures leading to better destruction of BTEX components and providing much-improved catalyst performance due to less BTEX deposition on the catalysts of various SRU catalytic beds.

The current Aspen-HYSYS simulator performs very adequately in the simulation of both GTU and AGE processes, while it has some difficulties in simulating the SRU reaction furnace, due to complete combustion of BTEX components, even at relatively low temperatures of around 800°C. In light of the above discussion, it is anticipated that the actual improvement due to the use of the AGE process would be practically higher than the predictions provided via the Aspen-HYSYS simulator.

The sour gas feed data depicted in Table 1 was used to simulate the original GTU. The rich amine stream collected from the amine flash drum is then used as the feed for both high and low-pressure scenarios of Figures (7a) and (7b). Table 10 provides the acid gas stream specifications outgoing from the three scenarios.

 

 

Table 10: Acid gas specifications entering typical Khangiran SRU for various scenarios.  

Scenarios

Flow rate

H2S mole%

CO2 mole%

kgmole/hr

MMSCMD

Original design

743.2

0.422

34.22

56.52

LP-RSM optimal point

363.1

0.206

70.53

20.76

HP-RSM optimal point

304.6

0.173

83.63

7.33

 

 

 

 

Figure 7: Aspen-HYSYS simulation schemes for: a) Low pressure enrichment scenario, b) High pressure enrichment structure and c) Typical sulfur recovery unit

 

 

Table 11 compares the overall environmental benefits of various optimal enrichment scenarios with the original design conditions, due to less sulfur dioxide emission into the adjacent atmosphere. In the original design, the furnace temperature is usually lower than the threshold required for complete combustion of BTEX components, therefore both conditions are considered. When using AGE in either of the two optimal scenarios, the furnace temperature is sufficiently high to completely burn BTEX.  Furthermore, small differences in the moles of H2S entering the SRUs for various scenarios are due to differences in the lean loading amine streams, collected from the bottoms of the corresponding regenerators.

 

 

Table 11: Comparison of sulfur recovery and sulfur dioxide emissions of different scenarios for a typical SRU of Khangiran natural gas refinery.

Scenarios

Furnace Temperature (°C)

Sulfur recovery

efficiency %

Annually SO2 Emission***

(ton/year)

Percent improvement in SO2 Emission

Original design

849.4 (841) *

86.17

196.8 (197) **

-

LP-RSM optimal point

1109

88.73

161.8

17.8

HP-RSM optimal point

1224

89.11

155.5

21.0

     *Assuming no BTEX combustion (actual data)

     ** Simulation result (actual data (Dahiya & Myllyvirta, 2019))

     *** Based on the entire capacities of four SRUs.

 

 

As can be seen, the more expensive high-pressure scenario can at least reduce the sulfur dioxide discharge by about 21%, while the much less low-pressure scenario can successfully reduce the sulfur dioxide emission for the entire refinery by 17.8%. A more detailed study considering other benefits of the acid gas enrichment on the overall performance of the sulfur recovery unit will result in a much higher environmental protection efficiency, due to less discharge of BTEX components into the surrounding atmosphere, among many others (Ibrahim, Jagannath, & Raj, 2020).

 

  1. Conclusion

A relatively complex approach is used in the present work for the first time by coupling various powerful tools such as Aspen-HYSYS simulation software, response surface method, artificial neural network, and genetic algorithm optimization technique to select the optimal acid gas enrichment scenario for an Iranian natural gas refinery. Initial sensitivity analysis of the two proposed scenarios for the acid gas enrichment of the Khangiran sour gas treating units revealed that, while the acid gas split ratio is the most influential operating parameter, however, the enrichment tower pressure and the corresponding inlet streams temperatures and flow rates can also appreciably affect the overall H2S enrichment rate.

It was established that the recall performances of both RSM and NN methods are almost identical, while the RSM method provides a more realistic performance on generalization. This issue was validated by resorting to optimization of the corresponding hyper-surfaces using an in-house genetic algorithm (GA) code. The maximum enrichment rates of 83.63 and 70.53 were obtained from a sour feed gas containing 3.4% H2S, by optimizing the RSM model cost function for high and low pressure scenarios. The original design of the existing SRUs receives the acid gas from GTU with 34 mole percent H2S content. Therefore, the optimal enrichment processes show more than 140% and 105% increase compared to the present existing conditions for high and low-pressure scenarios, respectively. The low-pressure scenario, which requires much less capital investment and operating costs seems more realistic from a merely economic perspective. It was also shown that both scenarios at their optimum points can significantly reduce sulfur dioxide emissions.

Appendix

 

Table A1- Response values R1 and R2 computed via Aspen-HYSYS software at operating points for low pressure ET scenario as recommended via response surface method (RSM).

 

Factor 1

Factor 2

Factor 3

Factor 4

Factor 5

Factor 6

Response 1

Response 2

Run

A:PET

B:SRAG

C:SRRA

D:LAF

E:RAT

F:LAT

R1

R2

 

Psia

   

kmol/s

C

C

%mol

%mol

1

15

0.5

1

2.18

40

80

44.1228

0.0413358

2

20

0.7

0.75

1.362

60

80

59.9393

8.20114

3

25

0.5

0.5

2.18

80

80

50.5903

0.0412789

4

25

0.5

0.5

0.544

40

80

45.6514

0.375319

5

15

0.9

0.5

2.18

40

40

59.5756

27.7181

6

15

0.9

1

0.544

40

40

62.0208

27.1411

7

20

0.7

1

1.362

60

60

65.1932

2.30191

8

25

0.7

0.75

1.362

60

60

62.5534

4.09786

9

15

0.5

1

2.18

80

80

54.1344

4.79367

10

25

0.9

0.5

0.544

40

80

54.1604

25.5881

11

15

0.9

0.5

2.18

80

80

55.5614

16.2237

12

25

0.5

1

2.18

80

40

45.1921

0.00518298

13

25

0.5

0.5

0.544

80

40

49.9796

11.1621

14

20

0.7

0.75

1.362

60

60

60.4333

9.17839

15

15

0.9

1

2.18

80

40

65.4

27.4696

16

15

0.5

0.5

0.544

80

80

45.1473

13.6197

17

15

0.9

0.5

0.544

40

80

50.6618

24.8096

18

25

0.5

0.5

2.18

80

40

43.832

0.00620884

19

20

0.7

0.75

1.362

40

60

60.8498

0.022401

20

15

0.9

1

0.544

80

40

60.4704

23.3582

21

25

0.9

0.5

0.544

40

40

54.3474

30.4109

22

15

0.5

1

0.544

40

40

44.8251

0.0119849

23

15

0.5

1

0.544

80

80

46.4423

14.9287

24

15

0.5

0.5

2.18

80

40

48.6988

0.00686747

25

25

0.9

0.5

2.18

40

80

60.852

20.2511

26

20

0.7

0.75

2.18

60

60

63.3249

1.41772

27

25

0.5

0.5

0.544

40

40

44.2495

0.0109377

28

25

0.5

1

0.544

80

40

53.0146

7.25796

29

15

0.5

0.5

2.18

80

80

50.7408

3.43621

30

25

0.5

1

2.18

80

80

52.1495

0.0567168

31

25

0.9

0.5

2.18

80

40

60.5626

29.2311

32

20

0.5

0.75

1.362

60

60

46.9367

0.0204106

33

25

0.9

0.5

2.18

40

40

62.5191

27.2648

34

15

0.9

0.5

2.18

80

40

55.9798

28.9146

35

15

0.5

0.5

0.544

80

40

45.1703

18.705

36

25

0.9

0.5

0.544

80

80

53.7632

23.7326

37

25

0.5

1

0.544

40

80

41.8218

0.209929

38

15

0.5

0.5

0.544

40

80

48.7423

0.706643

39

20

0.7

0.75

1.362

60

40

60.9657

7.26474

40

15

0.9

0.5

0.544

80

80

48.985

20.5213

41

15

0.5

0.5

2.18

40

40

44.1551

0.00676205

42

25

0.5

1

2.18

40

40

40.0117

0.00510461

43

15

0.5

1

2.18

80

40

53.3585

0.00696705

44

15

0.9

0.5

0.544

40

40

50.9159

30.1713

45

15

0.9

1

0.544

80

80

60.4927

19.6503

46

15

0.9

1

0.544

40

80

61.9308

22.3809

47

20

0.7

0.75

0.544

60

60

56.8792

15.3107

48

25

0.9

1

0.544

80

40

70.3441

26.6673

49

15

0.5

1

0.544

40

80

44.9141

0.40198

50

20

0.7

0.75

1.362

80

60

59.8121

14.8743

51

15

0.5

0.5

2.18

40

80

45.7852

0.0413587

52

25

0.9

1

2.18

80

80

73.9589

18.3458

53

15

0.9

1

2.18

40

80

66.6166

15.6113

54

15

0.5

1

0.544

80

40

46.8383

19.4779

55

15

0.9

1

2.18

80

80

65.6654

15.8929

56

20

0.9

0.75

1.362

60

60

61.4378

24.7559

57

20

0.7

0.5

1.362

60

60

54.9387

15.019

58

25

0.9

1

0.544

40

40

66.7766

25.6801

59

15

0.5

1

2.18

40

40

43.2068

0.00647958

60

25

0.9

0.5

0.544

80

40

53.7743

29.063

61

15

0.5

0.5

0.544

40

40

47.939

0.0134247

62

25

0.9

1

2.18

80

40

72.8013

26.014

63

15

0.7

0.75

1.362

60

60

57.3435

13.2546

64

25

0.5

0.5

2.18

40

40

41.3825

0.00544899

65

25

0.5

0.5

0.544

80

80

49.5572

9.66309

66

15

0.9

0.5

2.18

40

80

57.787

17.7032

67

25

0.5

0.5

2.18

40

80

42.3952

0.0384868

68

20

0.7

0.75

1.362

60

60

60.3504

9.03678

69

25

0.9

1

2.18

40

40

71.2099

21.7056

70

25

0.9

0.5

2.18

80

80

60.3696

20.1676

71

25

0.5

1

0.544

40

40

41.6818

0.0100958

72

25

0.9

1

0.544

40

80

66.5476

21.6834

73

25

0.5

1

0.544

80

80

52.1237

9.14713

74

25

0.9

1

0.544

80

80

70.4479

21.7388

75

25

0.5

1

2.18

40

80

40.4737

0.032961

76

25

0.9

1

2.18

40

80

70.6139

16.7845

77

15

0.9

1

2.18

40

40

67.4887

24.1257

78

15

0.9

0.5

0.544

80

40

48.9938

24.6286

 

Table A2- Response values R1 and R2 computed via Aspen-HYSYS software at operating points for high pressure ET scenario as recommended via response surface method (RSM).

 

Factor 1

Factor 2

Factor 3

Factor 4

Factor 5

Factor 6

Response 1

Response 2

Run

A:PET

B:SRAG

C:SRRA

D:LAF

E:RAT

F:LAT

R1

R2

 

Psia

   

kmol/s

C

C

%mol

%mol

1

90

0.9

1

0.544

80

80

83.7012

17.9227

2

90

0.9

1

2.18

80

80

85.6779

14.3673

3

90

0.9

1

0.544

40

40

75.8552

17.6094

4

90

0.5

0.5

0.544

40

40

36.3959

0.00467031

5

60

0.5

0.75

1.362

60

60

36.4775

0.012417

6

30

0.7

0.75

1.362

60

60

63.5769

0.056371

7

90

0.5

0.5

2.18

40

80

34.5075

0.00278651

8

90

0.9

1

2.18

80

40

83.5846

13.7944

9

90

0.5

1

0.544

40

40

34.4322

0.000395484

10

90

0.9

1

0.544

80

40

83.1977

18.5042

11

30

0.9

1

0.544

40

40

68.1368

24.7971

12

90

0.5

1

0.544

80

40

39.1589

0.00508551

13

90

0.9

1

0.544

40

80

76.0453

16.4777

14

90

0.9

0.5

2.18

80

40

69.634

24.3033

15

30

0.9

1

2.18

80

40

74.791

25.0203

16

30

0.9

0.5

2.18

80

40

61.9894

28.9347

17

60

0.7

0.75

1.362

60

60

55.0449

0.016735

18

60

0.7

0.75

1.362

60

40

53.0647

0.00590996

19

30

0.9

0.5

0.544

40

80

55.1408

25.8551

20

90

0.9

0.5

2.18

40

40

68.3719

22.17

21

90

0.9

0.5

0.544

80

40

63.9895

29.8154

22

30

0.5

0.5

0.544

40

40

43.1216

0.00981525

23

30

0.5

0.5

0.544

80

40

51.3966

5.9979

24

30

0.5

0.5

2.18

80

40

42.2317

0.00601212

25

60

0.7

0.75

1.362

80

60

61.983

0.0158951

26

30

0.9

0.5

0.544

40

40

55.3267

30.5317

27

30

0.5

1

2.18

40

40

38.6186

0.00442404

28

90

0.7

0.75

1.362

60

60

50.6708

0.013148

29

30

0.9

1

0.544

40

80

68.0367

21.1452

30

60

0.7

0.75

1.362

60

60

55.0533

0.0167535

31

90

0.5

0.5

0.544

40

80

37.6317

0.064463

32

60

0.7

0.75

1.362

60

80

57.1298

0.059614

33

90

0.9

1

2.18

40

40

78.7093

8.47214

34

90

0.9

0.5

2.18

80

80

70.3689

23.5528

35

60

0.7

0.5

1.362

60

60

59.5152

0.0157278

36

90

0.5

0.5

2.18

40

40

34.4805

0.000291153

37

90

0.5

0.5

0.544

80

80

46.3661

0.816679

38

90

0.9

1

2.18

40

80

79.4581

10.1073

39

30

0.5

1

0.544

40

80

40.6151

0.126146

40

30

0.5

1

2.18

40

80

39.5422

0.0367127

41

30

0.9

0.5

2.18

40

80

61.9608

21.0223

42

90

0.5

1

2.18

40

40

34.6002

0.000387214

43

60

0.7

1

1.362

60

60

51.3594

0.0159103

44

30

0.5

1

2.18

80

80

48.4741

0.0328846

45

60

0.9

0.75

1.362

60

60

71.3155

23.6261

46

30

0.5

1

0.544

80

40

52.8843

2.57803

47

30

0.9

1

0.544

80

40

72.9669

26.9501

48

30

0.9

1

0.544

80

80

73.0355

22.0119

49

30

0.9

1

2.18

40

40

72.3916

20.4824

50

90

0.5

1

2.18

40

80

34.6146

0.00193967

51

30

0.5

0.5

0.544

80

80

50.5235

7.60777

52

30

0.9

0.5

0.544

80

40

55.3032

30.0472

53

90

0.5

1

0.544

80

80

40.7484

0.218617

54

30

0.9

0.5

2.18

80

80

61.9427

21.3697

55

30

0.9

0.5

2.18

40

40

63.4013

26.7168

56

90

0.9

0.5

0.544

40

80

61.6071

26.1676

57

30

0.9

1

2.18

40

80

72.0062

16.8438

58

30

0.9

0.5

0.544

80

80

55.2621

24.5956

59

90

0.5

1

2.18

80

40

34.6148

0.000396313

60

30

0.5

0.5

2.18

40

80

41.1934

0.0300863

61

90

0.5

1

0.544

40

80

34.4319

0.00195149

62

90

0.5

1

2.18

80

80

34.9148

0.0168304

63

90

0.5

0.5

0.544

80

40

44.7919

0.00687693

64

60

0.7

0.75

2.18

60

60

50.7093

0.0162127

65

30

0.5

0.5

2.18

80

80

48.9861

0.0451943

66

30

0.5

1

0.544

80

80

51.5185

6.94788

67

90

0.9

0.5

2.18

40

80

68.932

21.9293

68

90

0.5

0.5

2.18

80

40

34.7082

0.00146629

69

90

0.9

0.5

0.544

40

40

61.4464

28.7544

70

30

0.5

1

2.18

80

40

42.6805

0.00483675

71

90

0.9

0.5

0.544

80

80

64.1047

26.7955

72

60

0.7

0.75

1.362

40

60

49.2587

0.0142836

73

30

0.5

0.5

2.18

40

40

40.2656

0.00467988

74

90

0.5

0.5

2.18

80

80

39.0117

0.0385336

75

30

0.5

0.5

0.544

40

80

44.6115

0.312708

76

60

0.7

0.75

0.544

60

60

60.0773

0.218728

77

30

0.9

1

2.18

80

80

76.407

18.9269

78

30

0.5

1

0.544

40

40

40.5696

0.00895545

 

 

 

No

Yes

No

Yes

Yes

Yes

No

Yes

Start

Initialize chromosomes at random

Convert chromosome from binary to decimal

No

Enter: input domains, input accuracies, population size, cross over and mutation probabilities (Pc & Pm), proper number of iteration

 

Check Constraint

i=0

Iter=0

i=i+1

iter=iter+1

Convert all chromosomes from binary to decimal

Compute individual and total fitness

Make sure to pass best chromosome with largest fitness to new generation

Compute individual and cumulative probabilities

Select other chromosomes of the new generation based on their cumulative probabilities

Make sure that the best chromosome does not undergo crossover and mutation process

Apply cross over and mutation based on corresponding Pc, Pm

Return to the previous state

Convert chromosomes from binary to decimal

Check Constraint

Abs{best point (i)-best point (i-1)}<=ε

iter<max iter

Save best point

Report the optimal results

Stop

i<2

No

Figure A1: simplified flowchart of Constrained Genetic Algorithm Optimization with ANDI termination criteria

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