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Article pubs.acs.org/IECR Design and Assessment of a Membrane and Absorption Based Carbon Dioxide Removal Process
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Article

Design and Assessment of a Membrane and Absorption Based Carbon Dioxide Removal Process for Oxidative Coupling of Methane

Alberto Penteado, * Erik Esche, Daniel Salerno, Hamid Reza Godini, and Günter Wozny

Process Dynamics and Operations Group, Technische Universtita ẗ Berlin, Sekretariat KWT-9, Straße des 17, Juni 135, D-10623 Berlin, Germany

ABSTRACT: The oxidative coupling of methane (OCM) is a direct path for converting methane into
ABSTRACT: The oxidative coupling of methane (OCM) is a direct path for converting methane into ethene (ethylene), which
is one of the most important building blocks for the chemical industry. Carbon dioxide is generated as a byproduct in the reactor
and must be separated in order to produce the pure ole fin. This step is commonly achieved by amine scrubbing, in which a
signi fi cant amount of energy is consumed for regenerating the amine. In this contribution, a hybrid system employing gas
separation membranes and absorption is modeled and simulated in order to carry out preliminary engineering design and
economic evaluations to assess the feasibility of applying this process on industrial scale. It is demonstrated that the hybrid
process offers economic advantage when compared to the standalone absorption process when carbon dioxide is used as diluent
in the OCM reactor.

INTRODUCTION

The oxidative coupling of methane (OCM) is the catalytic conversion of methane into ethene (ethylene), which is one of the most valuable building blocks for the chemical industry with a global production of over 141 million tones in 2011. 1 Thus, OCM allows for a direct path from feedstock such as natural gas, shale gas, or biogas into value-added chemicals, avoiding the intermediate production of syngas. 2 As a result of ethylene being normally produced through naphtha or ethane cracking, which are very energy demanding and generate a signi cant amount of carbon dioxide emissions, OCM also presents an opportunity for emission reduction in the chemical industry. 3 In 1982 Keller and Bhasin published the rst determination of active catalysts for OCM. 4 To date, several catalysts have been tested for OCM such as La 2 O 3 /CaO, 5 Li/MgO, 6 and Mn Na 2 WO 4 /SiO 2 . 7 Also, di erent reactor concepts, such as membrane reactors 8 and udized bed reactors, 9 as well as dierent feeding policies have been studied experimentally and through simulations 10 and optimizations. 11 The high temper- ature required for the OCM reaction, which is typically above 973 K, also leads to the oxidation of the educt methane (CH 4 )

also leads to the oxidation of the educt methane (CH 4 ) © 2016 American Chemical

© 2016 American Chemical Society

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and the products ethane (C 2 H 6 ) and ethylene (C 2 H 4 ) into carbon monoxide (CO) and carbon dioxide (CO 2 ). Besides that, the reaction network is highly exothermic and higher temperatures tend to favor the combustion reactions, reducing selectivity toward products. This highlights the importance of novel active and selective catalyst development combined with e cient reactor design. Su et al. suggests an upper bound of 28% for the C 2 yield (combined C 2 H 4 and C 2 H 6 yield), considering a continuous single-pass process with CH 4 and O 2 cofeed. 12 This means that even with enhanced reaction performance the downstream separation task is far from trivial. Hence, an integrated approach considering both the reactor and the separation steps is needed in order to synthesize an e cient OCM process. The OCM process structure commonly consists of a reaction section, a compression section, in which the reactor outlet is cooled, compressed, and the condensed

Received: January 11, 2016 Revised: May 31, 2016 Accepted: June 14, 2016 Published: June 14, 2016

DOI: 10.1021/acs.iecr.5b04910 Ind. Eng. Chem. Res. 2016, 55, 7473 7483

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Industrial & Engineering Chemistry Research Article Figure 1. Block diagram of the OCM process. Figure 2.

Figure 1. Block diagram of the OCM process.

Article Figure 1. Block diagram of the OCM process. Figure 2. Process fl ow diagram for

Figure 2. Process ow diagram for an exemplary hybrid CO 2 removal process employing a single membrane and absorption (process con guration b).

water is removed, a carbon dioxide removal section, and nally

a distillation section, consisting of two cryogenic distillation columns to remove the light components and to separate the ethylene from the ethane. The classical OCM process structure

is reproduced in the block diagram in Figure 1 . Besides the

presented structure, other congurations are currently under investigation. Notably, the use of CO 2 as diluent gas instead of

N 2 tends to avoid the formation of more CO 2 in the reactor,

thus enhancing the C 2 yield. Furthermore, CO 2 helps to handle the reactions exothermicity, avoiding the formation of hotspots. This is of special interest when combining OCM with the dry reforming of methane, 13 given that the latter could use both the heat and the carbon dioxide produced in the OCM reactor. The carbon dioxide removal is one of the most critical steps. Specially, if CO 2 dilution is used, then this step accounts for a reasonable share of the ethylene production cost. The CO 2 removal is commonly achieved by reactive absorption with amines (process conguration a) as shown in the right side (absorption section) of Figure 2 . In the absorption process, a signi cant amount of heat is required in order to regenerate the

amine solution in a stripping column. Experiments carried out on mini-plant scale at Technische Universtita ẗ Berlin showed that by employing the benchmark absorber monoethanolamine (MEA) 30 wt % aqueous solution, as much as 5 MJ per kilogram of removed CO 2 is required. 14 This can be reduced by the use of other amines, such as N -methyl-diethanolamine

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(MDEA) and piperazine (PZ). Using a mixture of 37 wt % MDEA and 3 wt % PZ, the energy consumption is reduced to 3.7 MJ/kg CO 2 . 14 The synthesis of new energy-e cient uids for CO 2 absorption is currently an active research eld; however, industrial applicability is still limited due to the fact that these uids are not yet produced in large scale and at commercial prices. Gas separation membranes can alternatively be employed for CO 2 separation. Glassy polymeric membranes, such as cellulose acetate and polyimides, can be applied for natural gas sweetening, especially for small to medium capacities (6000 50 000 N m 3 /h) or even for larger capacities in remote or o shore applications 15 and for biogas upgrading. 16 , 17 Applic- ability for ue gas treatment is limited because separation in membranes is driven by the pressure di erential. This is not a drawback for the OCM process because compression is already required to carry out the cryogenic distillation step. Gas separation membranes o er many advantages such as straightforward installation, small spatial footprint, quick start- up, simple operation, and reduced environmental impact. 15 Scale-up is also relatively easy because it happens mainly in terms of adding more modules operating in parallel. This is however an economic disadvantage if compared to traditional separation techniques, such as distillation and absorption, which tend to scale up very well. A further concern for the OCM process is the ethylene loss because it is a high-value product. Current membrane technology does not o er a

DOI: 10.1021/acs.iecr.5b04910 Ind. Eng. Chem. Res. 2016, 55, 7473 7483

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signi cant CO 2 selectivity toward C 2 H 4 , so a standalone membrane-based separation would hardly make any sense. The combination of membrane and absorption in a hybrid process could, however, exploit the advantages of both techniques and provide a cost-e cient solution for OCM. An exemplary process ow diagram for a hybrid CO 2 separation system using a one-stage membrane separation and absorption/desorption (process conguration b) is presented in Figure 2. A hybrid process concept employing a single at sheet envelope polyimide membrane module and absorption (such as in process con guration b) has been investigated on mini-plant scale at Technische Universita ẗ Berlin, showing a further reduction in the energy requirement down to 2.8 MJ/kg CO 2 . 14 However, for capturing 90% of the inlet CO 2 amount, around 13% of the inlet C 2 H 4 is lost. This is hardly acceptable for industrial purposes. A two-stage stripping membrane cascade, in which the retentate outow is fed to a second membrane module as shown in Figure 3 (process conguration d) has been proposed to reduce this loss. 18 The system is optimized in order to minimize the energy applied for the CO 2 removal, which led to an energy requirement of 2.4 MJ/kg CO 2 , but ethylene loss is still above 8%. When imposing an upper bound to the ethylene loss, the required energy is again increased.

the ethylene loss, the required energy is again increased. Figure 3. Process fl ow diagrams for

Figure 3. Process ow diagrams for the membrane sections of the di erent process con gurations: (c) single membrane with permeate recycle, (d) two-stage stripping cascade, and (e) two-stage recti cation cascade.

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Hence, a proper balance between the energy savings and the product loss is missing to e ectively assess whether the hybrid membrane-absorption process is of advantage. In this contribution, the feasibility of applying the hybrid process industrially is investigated through rigorous simulations and preliminary economic evaluation taking into consideration the

e ect of product loss. Di erent feed scenarios are considered so

as

to re ect alternative OCM reactor concepts to produce 100

kt

per year of ethylene. Dierent process congurations for the

CO 2 removal step are thoroughly analyzed aiming for the removal of 97% of the inlet CO 2 .

MODELING

The overall model is divided into a membrane section and a absorption section. The model for the membrane module is initially implemented in the free modeling environment

MOSAIC.

modeling, simulation, and optimization environment, providing

a LATEX-based equation input for creating a model. The

model is thus written together with its description at a documentation level, and a problem speci cation can be created by selecting the input variables. Equation systems can be solved internally using the available BzzMath numerical library. 20 MOSAIC s code generation tool can also automati- cally generate code for the solution in di erent programming languages and environments, such as Matlab, Scilab, gPROMs, Modelica, C++, Python, AMPL, GAMS, or even a user-de ned language. A code for the solution of the membrane model in Aspen Custom Modeler (ACM) is generated, and the ACM model is subsequently exported as a unit operation into Aspen Plus for owsheet simulations. The absorption section is modeled in Aspen Plus using the thermodynamic and unit operation models contained therein and using an example le provided in the software s library as a starting point. The full absorption/desorption model is detailed and validated against experimental data elsewhere. 21 Absorption Section. Thermodynamics. A nonsymmetric electrolyte model already implemented in Aspen Plus, namely, ENRTL-RK, is applied for the liquid phase. The set of electrolyte equilibrium reac tions is introduced, and the equilibrium constants are calculated by minimizing the system s Gibbs free energy. A PC-SAFT equation of state is used for the vapor phase because it is the default in the example le used. Parameters for MEA and water are regressed or retrieved by Aspen Technology 21 from various sources, and the other parameters are taken from the software s databank. The Redlich Kwong equation of state is tested as a numerically cheaper alternative providing similar results. The binary parameters for Henry constants implemented in the example le are kept. Additionally, parameters for the Henry constant of ethylene in MEA are estimated on the basis of data from Carroll and Mather 22 in order not to underestimate ethylene loss in the absorption process. Reactions. The full set of liquid-phase reactions can be seen below. Minimization of the Gibbs free energy is used for the equilibrium reactions ( eqs 13 ) and kinetic parameters from Pinsent et al. 23 and Hikita et al. 24 are used for the kinetically controlled reactions ( eqs 4 7 ).

19

MOSAIC is a convenient equation oriented

MEAH

+

H O

+⇌

2

MEA

+

+

H O

3

(1)

2H O

2

+

H O

3

+

OH

(2)

DOI: 10.1021/acs.iecr.5b04910 Ind. Eng. Chem. Res. 2016, 55, 7473 7483

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HCO

CO

HCO

2

32

+⇌

+

OH

3

CO

2

H O

CO

3

OH

HCO

+

2

3

MEA

++→

22

CO

H O

+

+

H O

3

MEACOO

+

+

H O

3

(3)

(4)

(5)

(6)

MEACOO

+

+

H O

3

MEA

++

CO

22

H O

(7)

Mass and Heat Transfer. The absorption and stripping columns are designed through rate-based simulations using the built-in correlations in Aspen Plus. Sulzer structured packings Mellapak 350X and 350Y are selected as the internals of the absorption and stripping columns, respectively, as they are recommended by the vendor and commonly employed for CO 2 capture. The study of the performance of di erent packing types is outside of the scope of this contribution. Plug ow is assumed for the vapor, whereas the liquid is assumed to be well- mixed. Liquid and vapor lms are nonideal with reactions taking place in the liquid phase. Correlations by Bravo et al. (1985) 25 and Hanley and Chen (2012) 26 are applied for the mass transfer coe cients and interfacial area. The Chilton and Colburn method is used for the heat transfer coecient. 27 Packing hold-ups are calculated as proposed by Bravo et al.

(1992)

Pressure drop is calculated according to vendors

correlation. These correlations have been previously assessed in literature showing good agreement with experimental data for

the given application.

Both authors highlight the

importance of tting parameters such as the interfacial area factor, the heat transfer factor, and the liquid and vapor mass transfer coe cient factors to precisely mimic plant performance and behavior. The diameters of the absorber (4 cm) and the stripper (10 cm) available for experiments are rather small, which greatly increases wall eects that are negligible in industrial-sized equipment. The purpose of this work is to provide basic engineering design to allow for a preliminary cost

estimation on industrial scale, so no attempt to match experimental data from the mini-plant is made, and these factors are left to unity. Membrane Section. A at sheet envelope type membrane module is considered for this application. It consists of a cylindrical metal casting containing round membrane envelopes placed in series around an inner tube for the permeate outlet. The retentate ows through the shell side, being directed by the ow diverters. The module is schematically represented in Figure 4 . The membrane envelopes are produced in two dierent versions. The rst one has a polyimide active layer (PI/Matrimid), oering high CO 2 selectivity toward hydro-

28

29 , 30

ering high CO 2 selectivity toward hydro- 28 29 , 30 Figure 4. Schematic representation of

Figure 4. Schematic representation of the at sheet envelope type membrane module.

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carbons, and the second one is a poly(ethylene oxide)

poly(butylene terephtalate) thin lm composite membrane (PEO/PolyActive), which o ers lower CO 2 selectivity but

higher permeances. The membrane materials and modules are designed and produced by co-workers at the Helmholtz- Zentrum Geesthacht Center for Materials and Coastal Research, Germany. 17 A 1D solution-di usion model is applied on the basis of

balance and ux equations. 31

state 32 is applied on the retentate side, whereas ideal gas is assumed for the low pressure permeate side. The ow is assumed to be isothermal on both sides with a 5 K cooling on the permeate side to account for the Joule Thomson e ect. Negligible concentration polarization and pressure drop are observed experimentally, so these e ects are not considered in

the model. An Arrhenius-type equation is used to calculate the permances in the PI membrane, whereas the free-volume-

theory equation is used to calculate the permeances in the PEO membrane. The parameters for these equations are obtained by

Brinkmann et al.

system is discretized using orthogonal collocation on nite elements with third-order Lagrangian polynomials on Radau roots. The number of nite elements for the simulation and optimization runs is xed to 10, which provides reasonable computation time and results identical to simulations carried out with 20 nite elements. Basic model equations such as the component mole balance in the permeate side ( eq 8 ) and retentate side (eq 9 ) and the permeance calculations for the PI

The resulting di erential algebraic equation

The PengRobinson equation of

17

membrane ( eq 10 ) and PEO membrane ( eq 11) are presented. Further details on the implementation, such as numerical reformulations on the PengRobinson equation of state for improved numerical stability, are given by Esche et al. 18

P

 

R

P

)

h

 
 

i

f

i

 

(

 

R

f

i

P

)

h

 

i

i

 

PI

 

exp

E

RT

a, i

R

E

 

exp

 

a, i

RT

i

d z

d n

R

i

d z

= Lf (

i

=− Lf

L

PI

i

=

L

0,PI

i

L

PEO

i

=

L

0,PEO

i

PEO

d n

−+ σ

R

i

2

NC

i = 1

1

0

f

i

R

+

P

f

i

m

σ

i

2

i

2

exp(

T

m T

i

R

)

⎟ ⎟

(8)

(9)

(10)

(11)

The model has been validated using data from mini-plant experiments showing a good agreement in pressures up to 20 bar, but the accuracy decreases for higher pressures. 33 The model is later applied for the optimal design of the two-stage stripping cascades. 18 The model is herein further extended in MOSAIC to allow for integration into Aspen Plus simulations. For the model to be able to simulate industrial ow rates, a scale-up by numbering-up approach is applied. This consists of dividing the inlet ow by the design ow rate for the membrane module to obtain the necessary number of parallel modules. A single module is then calculated, and the resulting ows for the permeate and retentate streams are multiplied to the number of modules to obtain the total outlet ows. An overall energy

DOI: 10.1021/acs.iecr.5b04910 Ind. Eng. Chem. Res. 2016, 55, 7473 7483

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balance is formulated by introducing ACM enthalpy function calls in MOSAIC. Ports are introduced to allow for the model to be connected to streams in Aspen. MOSAIC s code generation is used to automatically generate a code in ACM modeling language, which is compiled in Aspen Custom Modeler and exported as a custom unit operation into Aspen Plus. The compressors are modeled as isentropic with an eciency of 0.72 and two stages with interstage and outlet coolers down to 308 K. The intermediate pressure is the geometric average between the suction and discharge pressures.

SIMULATION AND OPTIMIZATION

The models are solved using the available numerical methods inside Aspen Plus v8.6. The Sparse solver is applied for the membrane modules. The Broyden method is applied for converging tear streams, providing signi cantly better con- vergence than the default Wegstein method. The SQP method is applied for sequential optimization in the membrane section. No proper variable translation could be achieved when switching from sequential mode into equation-oriented mode, so simultaneous optimization could not be performed. Optimal design of the absorption section is thus carried out only in the form of extensive simulation studies and sensitivity analyses. The simulation and design of the CO 2 capture processes are performed for an OCM plant producing 100 kt of ethylene per year in the reactor. The overall CO 2 capture target of 97% is adopted for both the standalone absorption and the hybrid process congurations. To reect the di erent reactor design and operating policies currently under investigation, four feed scenarios with di erent compositions are considered in this study. It is assumed that the reactor outlet passes through a compression and cooling section, where all the water is removed and the gas enters the CO 2 capture section compressed up to 10 bar and cooled down to 308 K. The dierent compositions are presented in Table 1. Composition I

Table 1. Feed Gas Composition Scenarios

 

composition (mol %)

 

feed scenario

CO 2

C 2 H 4

N 2

CH 4

I

11.0

6.0

33.0

50.0

II

9.0

9.0

16.7

65.3

III

24.5

4.5

8.0

63.0

IV

38.0

5.0

10.0

47.0

emulates the outlet of an OCM reactor using N 2 dilution. Composition II mimics a reactor using a really high CH 4 to O 2 ratio instead. Finally, compositions III and IV consider the use of CO 2 dilution in the reactor. Utilities are introduced to the simulation in order to determine their consumption and cost rates. The default utility costs from Aspen Plus are used because they reect typical chemical plant values. Additionally, a value is attributed to the ethylene loss based on current ethylene market prices. 34 These values are displayed in Table 2 . Adopting the ethylene market price for the ethylene loss is a conservative approach. At this stage of the process, the ethylene price is certainly lower because it still needs to be further processed to achieve chemical or polymer grade. The membranes are less selective to ethylene than the absorption, so this assumption tends to favor the process con guration with standalone absorption. It ensures, however, that the feasible scenarios are industrially

Table 2. Utility and Ethylene Loss Costs

description

cost

unit

steam

2.2 × 10 9 2.12 × 10 10 2.15 × 10 8

USD/J USD/J USD/J USD/kg C 2 H 4

cooling water

electricity

ethylene loss

1.00

applicable for a wide range of ethylene prices without the need for estimating the costs for the other process steps that are outside of the scope of this contribution. Absorption Section. An initial analysis is performed in order to determine the best operating pressure for the absorption column. The upstream water removal/compression section is typically operated at 10 bar, and the downstream distillation section is operated at 32 bar. 35 These pressures are, therefore taken as the lower and upper bounds to be considered for the absorption section. The question is whether to perform the compression from 10 to 32 bar upstream or downstream of the absorber column. A higher pressure is bene cial, for it facilitates the CO 2 absorption. This reduces both the necessary liquid to gas ratio ( L / G), which is the ratio between the total mass ow rate of amine solution and the total mass ow rate of gas, and the reboiler duty. Therefore, the pressure of 32 bar has been previously adopted for the operation of the absorption

section.

however, more ethylene is lost. This behavior is demonstrated in Figure 5 for feed scenario II.

14

By operating the absorber at a higher pressure,

II. 14 By operating the absorber at a higher pressure, Figure 5. Reboiler duty (black diamonds)

Figure 5. Reboiler duty (black diamonds) and ethylene loss (white squares) for di erent absorption operating pressures.

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To properly assess the merit of operating the absorber at a higher pressure, the total operating cost, comprising the utility cost rate and ethylene loss cost rate, for di erent pressures within this range is calculated. It is assumed that the gas is received at 10 bar, and a rst compressor can raise the pressure up to an intermediate value for the operation of the absorber. The outlet of the absorber is then further compressed up to 32 bar by a second compressor. Figure 6 exhibits the result of this analysis for feed scenario II with the total operating cost and its most relevant components: steam for the reboiler, electricity for the compressors, and the ethylene loss. Electricity for the pumps and the cooling water are accounted for but are left out of the plot for sake of clarity. Despite the fact that the reboiler duty is lower at higher operating pressures, the ethylene loss and the total compression duty are higher, resulting in a higher

DOI: 10.1021/acs.iecr.5b04910 Ind. Eng. Chem. Res. 2016, 55, 7473 7483

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Industrial & Engineering Chemistry Research Article Figure 6. Operating cost for di ff erent absorber

Figure 6. Operating cost for di erent absorber operating pressures. Total operating cost rate (crosses), electricity for compression cost rate (squares), steam cost rate (diamonds), and ethylene loss cost rate (triangles).

operating cost. The ethylene loss cost rate is the variable most aected by the operating pressure. The main cost driver is the compression, and performing the compression in the down- stream of the absorber is preferred for the total gas ow rate to be compressed is smaller given that the CO 2 is removed. This is even more critical for the CO 2 diluted scenarios, as the

reduction in the total gas ow rate is more signi cant. Thus, the pressure of 10 bar is selected for the absorption column. By analyzing Figure 6 , it also possible to picture that there may be

a minimum total cost which lies below the lower bound of 10

bar imposed by the upstream water removal section. This shall be further investigated when synthesizing the full OCM process. The work ow developed to simulate the absorption section

is very similar to the one previously described by Agbonghae et

al.;

capture for natural-gas- red or coal- red power plants as well as natural gas combined cycle power plants. In this contribution, further details are given on the speci c tools inside Aspen Plus to provide a guideline on the simulation and optimal design of such systems using the software. This task is described by

a combination of science and art

based on experience . The owsheet starts with an equilibrium calculation of the absorption column. A proper starting value for the amine solution ow rate is specied based on previously reported L/ G ratios to achieve convergence. The inlet lean amine solution is

preloaded with approximately 0.1 mol CO 2 /mol MEA because this will be a recycle stream from the stripping column once the owsheet is complete. This strategy helps to close the recycle later. The absorber is operated at 10 bar, and pressure drop is neglected at this point. With the column initialized in equilibrium mode, a packing type is selected to run a packing sizing, which calculates the column diameter for a given fractional capacity. The default fractional capacity of 0.62 is used, and a foaming factor of 0.85 is applied. The calculation mode is then set to rate-based, and a packing rating is performed by applying the previously mentioned correlations and specifying the packing type and height and the calculated diameter. Once the column has converged in rate-based mode,

a rst estimation of the packing hold-ups is obtained. Then, the

reaction kinetics can be introduced in the specication sheet.

Agbonghae et al. as being

36

however, the applications described therein comprise CO 2

36

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The next step is to achieve the desired CO 2 capture target of 97%. This can be done with the use of a design speci cation, which varies the amine solution ow rate in order to achieve a speci ed CO 2 capture. A sensitivity analysis is then performed by changing the packed height and calculating the necessary amine solution ow rate in each case. Increasing the absorber packed height decreases the required amount of amine for a given CO 2 capture target, thus reducing the L / G ratio. The sensitivity analysis results for feed scenario II can be seen in Figure 7 a. After arriving at 18 m of packed height, the reduction in the L/ G ratio is below 0.1%; therefore, this packed height is selected for the absorber.

therefore, this packed height is selected for the absorber. Figure 7. Sensitivity analysis for the packed

Figure 7. Sensitivity analysis for the packed height of the (a) absorber and (b) stripper. Mass transfer correlations by Bravo et al. (1985) 25 (white squares) and by Hanley and Chen (2012) 26 (black diamonds).

Once the absorber design is nished, the ash, the rich-amine pump, and the lean rich exchanger are simulated. The pressure in the ash is nearly atmospheric to allow for a reasonable amount of CO 2 to be removed from the rich-amine stream. The rich pump increases the pressure to 2.5 bar. The lean rich exchanger is initially simulated as a heater, given that no recycle stream is yet available. The procedure to design the stripping column is similar to that of the absorber; however, speci cations for the partial condenser and for the reboiler are necessary. The stripper is operated at 2.5 bar. The previously reported required duty of around 4 MJ/kg CO 2 14 is employed to provide reasonable starting values for the reboiler duty, whereas the distillate ow is set to be large enough compared to the inlet CO 2 and H 2 O ows. Once the stripper is

DOI: 10.1021/acs.iecr.5b04910 Ind. Eng. Chem. Res. 2016, 55, 7473 7483

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converged in rate-based mode including the reaction kinetics, design speci cations are introduced to x a lean-amine loading (α LEAN ) of 0.1 mol CO 2 /mol MEA at the bottom by varying the reboiler duty and the CO 2 mass fraction at the top at 0.9 by

varying the distillate ow rate. A sensitivity analysis is again performed by changing the stripper packed height and calculating the necessary reboiler duty on each case. The result

of this sensitivity analysis for feed scenario II is presented in

Figure 7 b. The reduction in the reboiler duty by adding 1 m of packing drops below 0.1% for a packed height of 12 m; therefore, this packed height is selected for the stripping column. Figure 7 also presents a comparison between the two employed mass transfer correlations in both the absorption and stripping columns. While they di er in the lower range of packed heights, the results are identical in the actual operating range of both columns. In this case, both correlations provide identical results, and the one by Hanley and Chen 26 is preferred because convergence is achieved more quickly and easily when changing the packed height during the sensitivity analyses. The calculated pressure drop per unit height in the 2.7 m diameter absorber and 2.9 m diameter stripper are lower than

the value of 2 mbar/m informed by the vendor and that typically recommended in literature 37 as the maximum allowed pressure drop per unit height. The pressure drop are 1.2 mbar/

m in the absorber and 0.4 mbar/m in the stripper. This

indicates that the default fractional capacity of 0.62 adopted by

the software is rather low for this type of packing, and a higher

fractional capacity, between 0.7 and 0.8, could be applied resulting in smaller column diameters. The stripper s bottom stream is pumped up to 10 bar in the lean pump and is now available for closing the energy recycle in

the lean rich exchanger. The heater block is replaced by a heat

exchanger block, which preheats the rich-amine stream by cooling the lean-amine stream. The di erence between the hot stream outlet temperature and the cold stream inlet temper- ature is set to 10 K. The cooled amine solution enters a mixer/ tank, in which a makeup stream is added to replace the water and amine losses in the gaseous streams. The makeup is

calculated by a balance block. The outlet of the mixer is cooled down to 308 K and is recycled back to the absorber by the use of a transfer block, which copies this stream into the inlet lean amine stream, virtually closing the recycle. The design specication xes the α LEAN in the bottom of the stripper to

the same value as the lean amine entering the absorber, so these

streams are nearly identical. Therefore, only few iterations are necessary to converge the owsheet once the transfer block is activated and the recycle closed. Attempts to close the recycle

by actually connecting the streams are useless and would hardly

permit any change in the operating point in order to perform any further analysis of the system. Thus, the presented strategy greatly improves the stability and usability of the model. A change in operating point can be easily achieved by the following steps. The transfer block is deactivated, leading the amine recycle stream to be purged. The design variables are changed. The simulation is run once and then once again after

reactivating the transfer block. This procedure is used to conduct a sensitivity analysis for the lean-amine loading. The rich-amine loading at the bottom of the absorber ( α RICH ) is bound by the amine absorption capacity to around 0.5 mol CO 2 /

mol MEA . It is possible to achieve the same CO 2 capture duty by

recirculating a higher amount of a more loaded amine (higher

α LEAN ) or a lesser amount of a leaner amine (lower α LEAN ). Using a leaner amine solution is desired in the absorber, for its increased CO 2 absorption capacity reduces the L / G ratio. However, more heat must be introduced in the stripping to regenerate it. Thus, using a higher α LEAN can decrease the reboiler duty up to a certain point. However, if α LEAN is too high, then more amine is recirculated through the system, which causes additional heating, cooling, and pumping costs and increases equipment size. To nd the optimal operating point, the speci cation for the lean-amine solution is varied from 0.1 to 0.2 mol CO 2 /mol MEA , and the utility costs for each case are reported. The sensitivity analysis results for feed scenario II are presented in Figure 8 . The minimum utility

II are presented in Figure 8 . The minimum utility Figure 8. Sensitivity analysis for the

Figure 8. Sensitivity analysis for the operating point (lean loading and L / G ratio). Utility cost rate (black diamonds) and L / G ratio (white squares).

consumption can be achieved at around 0.14 mol CO 2 /mol MEA , and the respective L/ G ratio in the absorber is 2.12 kg/kg. The speci c reboiler duty in this case is 3.85 MJ/kg CO 2 . This methodology is repeated to all four feed scenarios because the standalone absorption is to be used as reference to be compared with the hybrid processes. The total utility cost divided by the amount of captured CO 2 is calculated as the speci c absorption cost and assumed to be constant for each scenario during the optimization of the upstream membrane section. Membrane Section. The design of the membrane section is achieved through sequential optimization. This section is simulated in a separate owsheet and di erent process con gurations are considered. The standalone absorption (process con guration a) is taken as the base case for the comparison. For the hybrid processes, the following cong- urations are considered: (b) single membrane unit and absorption as in Figure 2, (c) single membrane unit with permeate recycle and absorption, (d) two-stage stripping cascade and absorption, and (e) two-stage recti cation cascade and absorption. The owsheets for the membrane sections of process con gurations ce are shown in Figure 3 . The optimization problem can be stated as the minimization of an objective function, consisting of a simplied operational cost, subject to the model equations described in the Modeling section. The simpli ed operational cost consists of the utility cost and the cost applied to the ethylene lost in the outlet streams, as given in Table 2 , as well as the cost to remove the

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remaining CO 2 on the retentate stream through absorption (to reach the total of 97%) at the xed cost per kg of CO 2 calculated in the base case (process con guration a). The optimization variables in the membrane module are the membrane areas and the permeate pressure. In this version of the software, one single optimization variable can be selected inside a custom unit operation for optimization. Therefore, the membrane area is selected as the optimization variable, and the optimization is run repeatedly for dierent manually introduced values of the permeate pressure. Splitters are added to allow for the membrane modules to be bypassed and for streams to be purged. These are not shown in the process ow diagrams for sake of clarity. The split ratios are also selected as optimization variables. By increasing the membrane areas, more CO 2 can be captured, thus reducing the necessary amine ow rate and the reboiler duty in the absorption section. However, by increasing the membrane areas, more ethylene is lost and utility costs, such as electricity for compression, are also added in process congurations c e. This optimization intends to size the membrane section for each process con guration by providing a simple balance (simpli ed operational cost) between the costs on each section. For the owsheets presenting a simpli ed operational cost lower than the operational cost of the base case (process conguration a), a rigorous simulation and design of the downstream absorption section is carried out as previously described in order to obtain a detailed operational cost and to design the equipment to allow for the equipment cost estimation. Economic Analysis. The operational cost (OPEX) is calculated as the sum of the cost rates for the utilities and for the ethylene loss. This is enough to allow for a comparison between the di erent process congurations studied and to analyze the CO 2 capture step of the OCM process individually. An yearly operational factor of 0.95 is assumed, resulting in 8322 operating hours per year. The capital investment cost (CAPEX) is calculated as the sum of all the installed equipment cost. The cost of equipment is estimated using Aspen Economic Analyzer, which allows for the on-the- y sizing and cost estimation of equipment based on an up-to-date data bank. The absorber and stripper are structured packed columns as previously described. The centrifugal pumps are installed with a reserve in parallel. The lean rich exchanger, the amine solution cooler, the condenser, and the gas coolers are classic TEMA BEM type shell and tubes exchangers, whereas the reboiler is a kettle-type TEMA BKU exchanger. The mixer/tank and the condenser accumulator are horizontal pressure vessels. The compressor is a multistage centrifugal compressor. Costing for the membrane modules is carried out separately based on the pressure vessel, given that this is the major cost driver for the module. To keep calculations conservative, no degression factor for the serial production of the modules is applied, and an installation cost factor of 1.2 is used. The base material for the equipment in the absorption section is stainless steel AISI 304, whereas carbon steel is adopted in the membrane section. The total cost of each process conguration is calculated as the sum of the operational cost (OPEX) with the annualized capital investment cost (CAPEX) as given in eq 12. The IR is the interest rate of 15%, and N is the operational life of the plant, which is assumed to be 20 years.

Total Cost OPEX

=

+

IR(IR

+

N

1) )

1)

CAPEX

(1

+

IR)

N

(12)

RESULTS AND DISCUSSION

All simulated owsheets are able to achieve the CO 2 removal target of 97%. None of the hybrid process con gurations

present an advantage over the standalone absorption for feed scenarios I and II. For these scenarios, the optimizer bypasses the membranes, brings the membrane areas to the lower bound,

or runs into local solutions worse than the base case. In these

cases, the ethylene loss is costlier than the energy savings achieved by introducing an upstream membrane process. The low CO 2 concentration in the gas streams does not allow for su cient driving force for an eective separation through gas permeation. When considering gas ows diluted with N 2 or CH 4 in the OCM reaction step, standalone absorption oers a better performance for the downstream CO 2 capture step. Most membranes for carbon dioxide separation, including the ones considered in this publication, have been developed and applied for natural gas sweetening and/or biogas upgrading, 17 to which product loss is not as critical given the lower value of the produced pipeline quality natural gas. The PEO membrane has

a CO 2 selectivity toward C 2 H 4 of around 3 at room temperature, which is found to be insu cient for the given industrial application. No economically feasible conguration applying the PEO membrane is found. For the hybrid process to become interesting with these feed scenarios, higher performance membranes, in terms of permeances and CO 2 selectivity toward C 2 H 4 , are required. For the CO 2 diluted gas streams (feed scenarios III and IV), the higher inlet CO 2 concentration leads to a more e cient separation in the membranes. Furthermore, the higher CO 2 amount to be removed requires a higher amine ow rate in the standalone absorption, which increases the ethylene loss in this section. By applying the PI membrane in both single and recti cation cascade con gurations (b and e, respectively), the operational cost for the CO 2 separation can be reduced. For con gurations c and d, the optimizer led the membrane

modules to be bypassed, brought the membrane areas to their lower bounds, or the simpli ed operational cost is still higher than that of the base case a, so these congurations are left out of the detailed economic analysis. The single membrane con guration b o ers the simplest alternative for the hybrid process because only the installation of the membrane modules

is necessary. For the recti cation cascade e, the permeate gas

compressor and the coolers are also required. However, the recti cation cascade allows for the recovery of plenty of the ethylene permeating through the rst membrane module. Hence, it allows for increased membrane areas, drastically reducing the removal duty of the absorption section. For the case with the highest inlet CO 2 concentration (feed scenario IV) the recti cation cascade removes more than 60% of the inlet CO 2 while losing only 2% of the inlet C 2 H 4 . Besides that, the permeate of the second membrane module is a nearly pure carbon dioxide stream that can be recycled directly as diluent to the reactor or employed in another process without any further processing. The main simulation results are presented in Table 3 . The presented values are the membrane areas per module and the CO 2 capture and C 2 H 4 loss in each section for the feasible combinations of feed scenario and process cong-

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Table 3. Main Simulation Results for the Feasible Process Congurations

 

membrane section absorption section

feed scenario and con guration

 

CO 2

C

2 H 4

CO 2

C

2 H 4

membrane areas (m 2 )

capture

(%)

loss

(%)

capture

(%)

loss

(%)

IIIa

97.0

1.5

IIIb

1.0

17.9

1.3

79.1

1.3

IIIe

3.6 and 6.2

38.9

0.8

58.1

1.0

IVa

97.0

2.3

IVb

2.5

39.5

3.7

57.5

1.6

IVe

5.5 and 7.2

63.5

2.0

33.5

1.1

uration. The optimal permeate pressures are 1.1 bar for these cases. From the capital investment point of view, the owsheet for the hybrid process tends to be costlier because it has more equipment. However, the membrane section takes up part of the CO 2 removal duty, so the equipment in the absorption section is smaller for the hybrid process. Notably, by adding the membrane section, the diameters of the columns can be reduced because the total gas ow rate is lower. The membrane modules are relatively cheap compared to the absorption and stripping columns. The construction materials that can be applied in the membrane section are also cheaper than those in the absorption section. Consequently, a trade-o between adding more equipment and reducing the size of current expensive equipment is observed. For feed scenario III, the equipment cost of both hybrid processes are slightly higher than that of the standalone absorption. For feed scenario IV, however, the equipment cost for both hybrid processes are lower. As expected, the CAPEX for the recti cation cascade is higher than the single membrane module, given that the compressor and the coolers are necessary, but because this conguration reduces even further the removal duty of the absorption section, the actual increase in CAPEX is not that high. The calculated operational cost, the capital investment cost, and the total cost are presented in Table 4 . The process

Table 4. Economic Analysis Results

scenario and

OPEX

CAPEX

total cost

con guration

(kUSD/year)

(kUSD)

(kUSD/year)

IIIa

8142

15653

10643

IIIb

7696

17024

10416

IIIe

7518

18706

10507

IVa

12122

23922

15944

IVb

11262

18542

14224

IVe

9726

19764

12884

conguration b (with a single PI membrane) oers the lowest total cost when considering the feed scenario III. However, the dierence in the total cost is relatively low and most likely much lower than the margin of error contained in the cost estimates. For feed scenario IV, the cheapest process conguration is the recti cation cascade e. The dierence in this case is more signi cant, showing that the gas permeation is certainly a cost-e ective alternative when considering highly CO 2 diluted gas streams for the OCM process. The annualized total cost for these CO 2 removal steps are 104 USD/t C 2 H 4 and 128 USD/t C 2 H 4 . These costs are relatively low considering the

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current ethylene market price and that the CO 2 capture step represents a large share in the nal ethylene production cost in these scenarios.

CONCLUSIONS

A model has been successfully developed in order to simulate

an absorption and membrane based hybrid process for removing carbon dioxide from an outlet gas stream of the

oxidative coupling of methane reactor. The work ow allows for the documentation-based modeling in MOSAIC with the subsequent integration of models into Aspen owsheets. This is

of particular interest for the implementation of customized unit

operation models for novel process equipment. While MOSAIC is a convenient modeling platform, the custom unit operation model, in this case a gas separation membrane module, can be later integrated into a process owsheet in combination with well-established unit operations for the process synthesis and cost estimation steps. The hybrid CO 2 removal process for OCM is thoroughly analyzed, and its economical feasibility is assessed taking into consideration the product (ethylene) loss. Dierent cong- urations of the hybrid process are compared with the state-of- the-art technology, which is the stand-alone absorption process

with a 30 wt % monoethanolamine (MEA) aqueous solution. It

is demonstrated that ethylene loss plays a major role in the

economic feasibility of the CO 2 capture step of the OCM process, because ethylene is a high-value product. For OCM reaction concepts employing N 2 or CH 4 dilution, the hybrid CO 2 removal process is hardly of any economic advantage compared to the standalone absorption. While energy savings could be achieved, the product loss does not compensate for it. The use of the PEO membrane for the given application is also found to be infeasible, given its low CO 2 selectivity toward C 2 H 4 . However, when considering carbon dioxide diluted ows in the OCM reactor, the hybrid process is economically attractive. The concept of combining OCM with other CO 2 intensive and specially endothermic processes, such as the dry reforming of methane, has a lot of potential and shall be further investigated. Gas permeation can bring a signicant advantage for the CO 2 removal step in this case. For feed scenario III, the best con guration is a single PI membrane, whereas for feed

scenario IV, a two-stage PI membrane recti cation cascade is the most economical one. Outlook. It is important to model and simulate in detail each step of the OCM process individually. This helps to enhance the understanding and provide input for the design of the integrated owsheet. However, for an optimal process synthesis, the whole process superstructure has to be

considered simultaneously. To achieve that, surrogate models that are more suitable for optimization have to be applied. It is necessary to include economic terms, notably, the operational cost, to the objective function to ensure that the solutions are economically feasible. Furthermore, the environmental impact

of the OCM process must also be assessed within the process

synthesis stage. Alternative separation techniques, such as pressure and temperature swing adsorption, are still to be investigated. Finally, the OCM is also to be combined with other chemical processes, such as ethane cracking, considering that many shale gas compositions are also rich in ethane, dry

reforming of methane because it could use the heat and the carbon dioxide produced in the OCM reactor, and methanol

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production given that it could make use of the H 2 from the reformer and the available CO 2 .

AUTHOR INFORMATION

Corresponding Author

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS

A.P. gratefully acknowledges the support from CAPES, Coordination for the Improvement of Higher Education Personnel Brazil (grant number: BEX 11946/13-0). Financial support from the Cluster of Excellence Unifying Concepts in Catalysis by the German Research Foundation (DFG EXC 314) is also gratefully acknowledged.

NOMENCLATURE

Base Names

σ Lennard-Jones molecular diameter [Å]

CAPEX Capital cost/expenditure [U.S. dollars (USD)]

E a

Activation energy [kJ/kmol]

f Fugacity [Pa]

h

IR

L Permeance [kmol/(m 2 s Pa)]

m 0

m T

N Number of operating years [years]

n Molar ow [kmol/s]

OPEX Operational cost/expenditure [USD/year]

Memnbrane height [m] Yearly interest rate [%]

Parameter in free-volume theory [Pa 1 ]

Parameter in free-volume theory [K 1 ]

R

Universal gas constant [kJ/(kmol K)]

z

Membrane length [m]

Subscripts

i Chemical component i

Superscripts

0

P

PEO

PI

R

Reference condition

Permeate side

Poly(ethylene oxide) membrane

Polyimide membrane

Retentate side

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