Subscriber access provided by READING UNIV

Article
Design of an Intensified Reactive Distillation
Configuration for 2-Methoxy-2-Methylheptane
Arif Hussain, Le Quang Minh, Muhammad Abdul Qyyum, and Moonyong Lee
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b04624 • Publication Date (Web): 12 Dec 2017
Downloaded from http://pubs.acs.org on December 14, 2017

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Industrial & Engineering Chemistry Research is published by the American Chemical

Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 35 Industrial & Engineering Chemistry Research

1
2
3
4
Design of an Intensified Reactive Distillation Configuration for 2-Methoxy-2-
5
6 Methylheptane
7
8
9
Arif Hussaina, Le Quang Minha, Muhammad Abdul Qyyuma, Moonyong Leea*
10 a
11 School of Chemical Engineering, Yeungnam University, Gyeongsan 712-749, Rep. of Korea.
12
13
14
15
16
17 Submitted to: Journal of Industrial & Engineering Chemistry Research
18
19
20
21
22
23
24
25
26
27
28 *
29 Correspondence concerning this article should be addressed to:
30
31 Prof. Moonyong Lee
32
33 Email: [email protected]
34
35 Telephone: +82-53-810-2512
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 2 of 35

1
2
3 Abstract
4
5 The design of an intensified reactive distillation (RD) configuration for the production of 2-methoxy-2-
6
7 methylheptane (MMH) was proposed. Conventionally, high yield of MMH can be achieved by a large-
8
9
sized reactor or by recycling 2-methyl-1-heptene (MH). Both strategies are associated with high capital
10
11
12 and operating costs. This study proposed an innovative RD configuration that allows the production of
13
14 MMH with significantly lower energy costs, and total annual costs (TACs). The results demonstrate that
15
16 the proposed RD configuration can reduce energy demands, and total annual costs by up to 18.2, and
17
18 10.8 %, respectively, compared to those for a conventional reactor column sequence for the desired MMH
19
20 yield. In addition, different heat integration sequences were investigated to utilize the sensible heat to
21
22 save energy and the subsequent TAC. One heat integration sequence for the proposed configuration
23
24 further realized savings in energy, and TAC by up to 36.7, and 21.8 %, respectively.
25
26
27
28
Keywords: Reactive distillation; 2-methoxy-2-methylheptane; reactive holdup; capital and energy savings.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 3 of 35 Industrial & Engineering Chemistry Research

1
2
3 1. Introduction
4
5 The development of the lead-containing compounds added to gasoline to minimize knocking has gained
6
7 tremendous importance 1. Methyl tert-butyl ether (MTBE) has been considered an important “oxygenate”
8
9
to raise the oxygen content of gasoline. However, restrictive energy and environmental policies have
10
11
12 banned the use of MTBE as a fuel additive in gasoline due to its solubility in water and its widespread
13
14 detection in groundwater 2. This led to increased interests in higher-molecular-weight ethers that exhibit
15
16 significantly decreased solubility. One viable alternative is the chemical 2-methoxy-2-methylheptane
17
18 (MMH), produced through an etherification reaction between 2-methyl-1-heptene (MH) and methanol
19
20 (MeOH) 3. However, the main barrier to this approach is the high investment and operating costs
21
22 associated with the conventional process that uses a reactor followed by three distillation columns in
23
24 sequence. High yield of the desired product MMH could be achieved by using a large-sized reactor or an
25
26 excess of MH. Both strategies are associated with high capital and operating costs. For a specified yield
27
28
of MMH, Luyben 3 studied the optimum values of reactor vessel sizes and recycle flow rates to minimize
29
30 4
31
the total annual cost. Furthermore, Griffin et al. studied the effect of high and low values of an
32
33 equilibrium constant for the optimum operating conditions for the MMH plant. By designing innovative
34
35 equipment and implementing more energy-efficient production processes, practical solutions can be found
36
37 to overcome the constraints imposed on various raw materials and products. Process intensification is a
38
39 novel design strategy that aims to improve existing processes by reducing equipment size, energy
40
41 consumption, and overall plant footprint 5-6
. RD falls into the category of process intensification because
42
43 of its potential to integrate a conventional reactor column sequence into a single shell to improve the
44
45 performance of reactive processes. Currently, more than 150 RD columns with annual capacities of 100–
46
47
3000 kt are in operation worldwide 7. A huge scholarly database dealing with the modelling, simulation,
48
49 8-11
50
and industrial applications of RD can be found elsewhere . Industrial RD columns for etherification
51
52 reactions, especially for the MTBE process, have seen tremendous growth across the world over the last
53
54 few decades, with improved capital and operating savings. The MTBE process is, in fact, the largest
55
12
56 application of RD in terms of the number of columns and production capacity , but the future is
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 4 of 35

1
2
3 uncertain due to the legislation that prohibits its use. The growing interest in the chemical MMH to
4
5 replace MTBE necessitates an increase in the capacity in a cost-effective way to meet the increasingly
6
7 growing market demand.
8
9
Heat integration and intensification is another promising practical technique for minimizing the energy
10
11
12 consumption of distillation processes. The latent and sensible heat of the process stream is circulated into
13
14 the processes for exergy destruction. Several studies deal with the implementation of heat-integration in
15
16 reactive distillation systems for enhancing energy efficiency 6, 13-16.
17
18 This paper proposes an innovative RD configuration that allows the production of MMH with
19
20 significantly lower capital and operating costs. During the design, the temperature limitation of an acid
21
22 resin catalyst was overcome by selecting the appropriate reactive zone, reflux ratio, catalyst holdup, and
23
24 the suitable column pressure. This study further emphasized the potential benefits of heat integration for
25
26 the proposed RD column configuration to replace the conventional energy-intensive MMH production
27
28
process.
29
30
31
32
33 2. Process Studied
34
35 The proposed study is based on the conventional flowsheet for making MMH taken from the works of
36
3 4
37 Luyben and Griffin et al. to verify the feasibility of RD configuration. The reaction mechanism
38
39 involves the desired reversible reaction (Equation 1) between methanol (MeOH, CH3OH) and 2-methyl-
40
41 1-heptene (MH, C8H16) to form 2-methoxy-2-methylheptane (MMH, C9H20O). The same reactants
42
43 produce dimethyl ether (DME, C2H6O) and 2-methyl-2-heptanol (MHOH, C8H18O) as byproducts in an
44
45 undesirable irreversible reaction (Equation 2).
46
47
CH3OH + C8H16 ↔ C9H20O (1)
48
49
2CH3OH + C8H16 → C2H6O + C8H18O (2)
50
51
52 The corresponding rate equations in terms of the mole fraction for the desired and undesired reactions are
53
54 represented by Equations 3 and 4, respectively:
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 5 of 35 Industrial & Engineering Chemistry Research

1
2
3 RD = kDfXMeOHXMH - kDrXMMH (3)
4
5 RU = KU(XMeOH)2 (4)
6
7 where kDf and kDr are the forward and backward rate constants for the desired reaction. KU is the rate
8
9
constant for the undesired reaction. Table 1 list the values of reaction rate constants and the activation
10
11
12 energies for both reactions 4.
13
14 Table 1 Kinetic parameters. Adapted with permission from (Luyben, W. L. Design and Control of the
15
16 Methoxy-Methyl-Heptane Process. Ind. Eng. Chem. Res. 2010, 49, 6164-6175). Copyright (2010),
17
18 American Chemical Society.
19
20
21 kmol s-1kgcat-1 kJ kmol-1
22 kDf = 6.7 x 107 EDf = 90000
23 kDr = 2.1 x 10-6 EDr = 900
24 kU = 1.3 x 109 EU = 105900
25 2.1. Catalyst
26
27 The industrial grade Amberlyst 35Wet (Rohm & Haas) catalyst, which is macroreticular, strongly acidic,
28
29
cationic, polymeric catalyst was used to report the kinetic data for this etherification reaction 17. As per
30
31
32 Dow chemical product data sheet 18, the maximum operating temperature and the density were reported as
33
34 150°C and 800 g/L, respectively.
35
36 2.2. Conventional Process
37
38 The simplified flowsheet for the conventional process of producing MMH is illustrated in Figure 1. The
39
40 reaction between MeOH and MH is carried out in a fixed bed catalytic reactor. The reactor effluent
41
42 containing DME, MMH, MHOH, and unreacted MeOH and MH is fed to column C1. Column C1
43
44 separates the DME with mole purity of up to 99.9 %. The bottom stream originating from C1 column is
45
46 fed to column C2. The unreacted reactants are separated from MMH in column C2 and are recycled back
47
48
to the reactor from the distillate. Column C3 further purifies the desire product MMH and undesired
49
50
51 MHOH up to a mole fraction of 99.9 % as the distillate and bottom product, respectively.
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 6 of 35

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 Figure 1 Conventional flowsheet for producing MMH. Adapted with permission from (Luyben,
16
17
W. L. Design and Control of the Methoxy-Methyl-Heptane Process. Ind. Eng. Chem. Res. 2010,
18
19
20 49, 6164-6175). Copyright (2010), American Chemical Society.
21
22 2.3. Feasibility of RD for 2-methoxy-2-methylheptane (MMH)
23 4
24 An article by Griffin et al. suggested that the reaction mechanism for MMH production is a possible
25
26 candidate for a reactive distillation configuration, which can offer significant advantages. However, to
27
28 assure the feasibility of reactive distillation, the methodology adopted is based on an article by Shah. et.al
29
30 19
. For preliminary design, they provide guidelines and recommended values for (e.g. reaction/separation
31
32 temperature difference, chemical equilibrium constant Keq, rate constant for main reaction, side reaction
33
34 temperature, and the production capacity) to verify the economic feasibility of RD process. The step by
35
36
step procedure to perform feasibility analysis is shown in Figure 2. The process chemistry of MMH
37
38
39 involve reversible desired reaction that exhibit the problem of limiting chemical equilibrium conversion.
40
41 In addition, the main reaction is associated with an undesired irreversible reaction that produces
42
43 byproducts. Reactive distillation is a wise choice as it has ability to overcome the equilibrium limitations
44
45 and enhance selectivity when there are byproducts formation. Another criterion for economic feasibility
46
47 of reactive distillation is the temperature compatibility between the reaction [TR-main] and the distillation
48
49 [TD] operation. This temperature difference [TD-TR-main] should not exceed 50°C. In the conventional
50
51 process of MMH, the reaction occurs at 400 K due to catalyst activity, whereas the temperature of MMH
52
53 distillation column is 426 K. As the temperature difference between the separation and reaction is lower
54
55
than 50°C, conducting this reaction in a single unit can offer significant advantages. Chemical equilibrium
56
57
58
59
60 ACS Paragon Plus Environment
Page 7 of 35 Industrial & Engineering Chemistry Research

1
2
3 constant (Keq) has significant effects in the design of RD column. For conventional RD processes, the
4
5 recommended value of Keq should be greater than 1. The equilibrium constant for the desired reaction can
6
7 be determined by kf/kr. Based on Table 1, the equilibrium constant (Keq, at 423 K) gives a value of 316,
8
9
which confirms that the MMH system has the most favorable reaction kinetics to be implemented for RD
10
11
12 column design. The specific reaction rate for the main reaction should be higher than 10-5 kmol/kg.sec to
13
14 avoid large liquid holdups. For MMH reaction, the specific reaction rate for main reaction is significantly
15
16 higher which confirms the economic feasibility of reactive distillation. For RD processes, the selectivity
17
18 towards desired product could be reduced due to byproduct formation. Therefore, the operating
19
20 temperature of RD column [TRD] should be lower than that of side reactions [TS]. For MMH process, the
21
22 temperature of the side reaction is significantly higher than the RD operating temperature. Furthermore,
23
24 the RD is also attractive in terms of gross profit as the MMH production rate is 62 kt/year which is higher
25
26 than the range (0.5-1.0 kt/year) where RD is economical feasible.
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56 Figure 2 Feasibility flow diagram of MMH process for RD application.
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 8 of 35

1
2
3 3. Phase Equilibrium
4
5 The base case by Luyben 3 and Griffin et al. 4
provided the sketchy information about the conventional
6
7 flowsheet of 2-methoxy-2-methylheptane. In addition, their flowsheet provides the reaction kinetics and
8
9
the desired production rate. The intent of this paper is to present a preliminary results of a reasonable
10
11
12 conceptual design based on reactive distillation configuration. However, the feasibility of RD requires
13
14 valid vapor-liquid equilibrium data. This data is essential in order to obtain the Residual curve maps
15
16 (RCM). Since, there is no VLE data reported in the literature, therefore, all the unit operations were
17
3
18 simulated using Aspen Plus® built-in “UNIQUAC” physical property method, as suggested by Luyben
19
20 in the conventional process. The built-in UNIQUAC thermodynamic model only provide binary
21
22 interaction parameters between MeOH and DME. For all other separation, this study assumes ideal vapor-
23
24 liquid equilibrium behavior to propose the feasibility of RD configuration. The components MMH and
25
26 MHOH were generated using the molecular structures (Figure 3) because they were not available in the
27
28
Aspen databank. The result for the base case was retrieved to confirm the phase equilibrium diagrams for
29
30
31 separation. Figures 4a and 4b show the T-xy diagrams for separating DME/MeOH and MMH/MHOH
32
33 used in this simulation, respectively.
34
35
36
37
38
39
40
41
42
43 Figure 3 Molecular structures for MMH and MHOH. Adapted with permission from (Luyben, W. L.
44
45 Design and Control of the Methoxy-Methyl-Heptane Process. Ind. Eng. Chem. Res. 2010, 49, 6164-6175).
46
47
Copyright (2010), American Chemical Society.
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 9 of 35 Industrial & Engineering Chemistry Research

1
2
3
4
5 550 410
6 A B
7 500
400
Temperature (K)

Temperature (K)
8 390
9 450
10 380
11
400 370
12
13 360
14 350
T-x 10 atm 350 T-x 0.1 atm
15 T-y 10 atm T-y 0.1 atm
16 300 340
17 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
18
Mole Fraction DME Mole Fraction MMH
19
20
21 Figure 4 VLE diagram (A) DME/MeOH at 10 atm and (B) MMH/MHOH at 0.1 atm.
22
23
24 4. Proposed Configuration
25
26 4.1. RD Column
27
28 The newly proposed configuration based on the RD column is shown in Figure 5. The RD column has 35
29
30 total stages. There is no rectifying section; the reactive zone is between stages 2 and 12, followed by the
31
32
stripping section at the bottom. The stages are numbered according to the Aspen Plus stage notation with
33
34
35 stage 1 and 35 being the condenser and reboiler, respectively. The fresh MeOH stream as a low-boiling-
36
37 point reactant is fed at stage 13, while the fresh MH stream as a heavier reactant combined with a recycle
38
39 stream of a total of 128.98 kmol/h is introduced at stage 1. The column is operated at 1.77 atm. The high
40
41 MH/MeOH ratio makes this process a suitable candidate for RD implementation. A total estimated load
42
43 of 660 kg of acid resin catalyst per stage was used within the reactive zone. The column diameter from
44
45 liquid holdup calculation was estimated as 3.90 m.
46
47 4.2. Column C2
48
49 The distillate from the RD column is fed to stage 5 of a 12-stage C2 column. Column C2 serves the
50
51
purpose of delivering high-purity DME as the distillate product as a green energy source, while the
52
53
54
unreacted MeOH and MH are recycled at the bottom. The normal boiling point of DME is 248.2 K. The
55
56 operating pressure of column C2 was set at 10 atm, a value that permits the use of cooling water in the
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 10 of 35

1
2
3 condenser. The small distillate stream of 0.518 kmol/h with 99.9 mol % DME gave a condenser duty of
4
5 0.0045 MW. The bottom stream contained the unreacted MeOH and MH, which were recycled to the RD
6
7 column. The reboiler duty was 0.72 MW with a base temperature of 501.9 K, which used high-pressure
8
9
steam. The column diameter from Aspen tray sizing was 0.83 m.
10
11
12 4.3. Column C3
13
14 Column C3 received a feed stream from the bottom of the RD column. This column had a total of 15
15
16 stages with stage 8 being the feed location. The distillate product was 49.02 kmol/h with 99.9 mol %
17
18 MMH. The bottom was 0.49 kmol/h with 99.9 % of undesired MHOH. This column operated under 0.1
19
20 atm pressure, giving 0.64 and 0.18 MW condenser and reboiler duties, respectively. The reflux drum
21
22 temperature was 352 K and the temperature at the bottom was 401 K, accompanied by low-pressure
23
24 steam. The column diameter was estimated as 1.42 m.
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Figure 5 Proposed RD configuration for the MMH process.
54
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 11 of 35 Industrial & Engineering Chemistry Research

1
2
3 5. Sensitivity Analysis
4
5 5.1. Optimization of MeOH/Overall MH ratio
6
7 The reaction chemistry for MMH process also involve an undesirable irreversible reaction that produces
8
9
DME and MHOH. To achieve a higher selectivity towards the desired product MMH, the methanol
10
11
12 concentration must be kept low in the RD column, which requires a large recycle of MH from the
13
14 downstream separation section. The MeOH/overall MH feed ratio is optimized for different MH recycle
15
16 by using flowsheet design specification tool in Aspen plus. The fresh methanol feed was fixed at 50
17
18 kmol/h. The results demonstrate that small total MH recycle requires more catalyst weight per tray to
19
20 achieve design specification of 99 % MMH yield and vice versa. The corresponding energy costs also
21
22 reduces as the recycle flow rate decreases. The catalyst cost and the corresponding column diameter
23
24 however dominates the capital investment with small recycle flowrates. Table 2 summarizes the
25
26 alternative design to obtained 99 % MMH yield for different combination of required catalyst weight and
27
28
total MH recycle. The design that gives minimum TAC is associated with 7260 kg total catalyst with a
29
30
31
total MH flow rate of 129.5 kmol/h.
32
33 Table 2 Alternative designs to obtain 99 % MMH yield.
34
35 Alternative design to obtained 99% yield
36 Total MH Recycle (kmol/h) 135 129.9 125.5
37 6
38 Catalyst Cost (10 $) @ 10$/kg 0.0572 0.0726 0.132
39 C1/RD Column
40 H(m) 24.16 24.16 24.16
41
42 ID (m) 3.48 3.90 5.28
43 QR(kW) 1521 1340 1209
44 QC(kW) 3144 2917 2752
45
46 Column Vessel Cost (106$) 0.857 0.968 1.337
47 6
Exchanger Capital Costs (10 $) 0.200 0.187 0.177
48 6
49 Energy Costs (10 $/year) 0.429 0.379 0.343
50 C2 Column
51
H(m) 7.32 7.32 7.32
52
53 ID (m) 0.85 0.83 0.81
54 QR(kW) 770 725 691
55 QC(kW) 4.29 4.51 4.51
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 12 of 35

1
2
3
4 Column Vessel Cost (106$) 0.073 0.071 0.070
5 6
Exchanger Capital Costs (10 $) 0.084 0.081 0.079
6 6
7 Energy Costs (10 $/year) 0.240 0.225 0.215
8 C3 Column
9 H(m) 9.52 9.52 9.52
10
11
ID (m) 1.40 1.42 1.41
12 QR(kW) 166 186 178
13 QC(kW) 628 647 640
14
15 Column Vessel Cost (106$) 0.154 0.156 0.155
16 6
Exchanger Capital Costs (10 $) 0.076 0.079 0.078
17 6
18 Energy Costs (10 $/year) 0.050 0.055 0.053
19 6
Total Capital Cost (10 $) 1.501 1.615 2.027
20 6
21 Total Energy Cost (10 $/year) 0.718 0.660 0.611
22 6
TAC (10 $/year) 1.218 1.198 1.287
23
24
25 5.2. Effect of Catalyst Holdup
26
27 Stage holdup has a pronounced effect in the design of a reactive distillation column. The extent of
28
29
reaction at the reactive stages was examined by the Damkohler number (Da), which is the ratio of the
30
31
32
characteristic residence time to the characteristic reaction time. The methanol feed temperature (393 K)
33
34 was chosen as the reference temperature for calculating the value of the forward reaction rate constant (kf,
35
36 ref), leading to a value of 0.264 kmol h-1 kgcat-1. The catalyst weight was varied inside the reactive stages
37
38

M k ,
39

D =
40
41 F (5)
42 to obtain different values of the Da using Equation 5.
43
44
where Mcat is the mass of catalyst and F is the total feed flow rate to the RD column. The total feed flow
45
46
47 rate to the RD column was fixed at 178.98 kmol/h. A quick estimation of the Damkohler number could
48
49 determine whether the reaction rate was slow or fast in the RD column. For low values of Da (Da ≤ 0.1),
50
51 the system is dominated by phase equilibrium, whereas high values of Da (Da ≥ 10) correspond to a fast
52
53 reaction rate where chemical equilibrium is approached at the reactive stages. If the Da does not lie
54
55 between these values, then the process is in fact kinetically controlled 20.
56
57
58
59
60 ACS Paragon Plus Environment
Page 13 of 35 Industrial & Engineering Chemistry Research

1
2
3 The methanol conversion and MMH yield as a function of the Damkohler number are illustrated in Figure
4
5 6a. The large value of Damkohler number corresponding to the large catalyst holdup showed better
6
7 improvement in the reaction conversion and yield profile. Up to 660 kg of the catalyst, the temperature of
8
9
the last reactive stage was within the permissible catalyst deactivation temperature (423 K). Addition of
10
11
12 more catalyst, however, led to the catalyst deactivation temperature being exceeded, as shown in Figure
13
14 6b. Therefore, the optimum value of the Damkohler number was considered to be 0.97, associated with
15
16 7260 kg of total catalyst, for achieving 99 % MMH yield. The impact of the catalyst holdup on process
17
18 intensification in the RD column is illustrated in Figure 6c, where the reboiler and condenser heat duties
19
20 first decrease and then begin to increase with an increase in the Damkohler number.
21
22
23
24 0.994 Yield A 1.000
25 0.992 Conversion
0.999
26 0.990

Conversion (MeOH)
27 0.998
Yield (MMH)

28 0.988
0.997
29 0.986
30 0.984
0.996

31 0.995
0.982
32
0.994
33 0.980

34 0.978 0.993
0.4 0.6 0.8 1.0 1.2 1.4
35
36 Damkohler number
37
38
39
425
40 B
41
424
42
Stage 12 temperature (K)

43
423
44
45
422
46
47
421
48
49
420
50
51 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3
52 Damkohler number
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 14 of 35

1
2
3
4 2.965
1.375
5 Reboiler duty C 2.960
6 1.370 Condenser duty
2.955
7 1.365

Condenser duty (MW)

2.950
8

Reboiler duty (MW)

2.945
9 1.360
10 1.355
2.940

11 2.935
1.350
12 2.930
13 1.345 2.925
14 1.340 2.920
15 2.915
1.335
16 0.4 0.6 0.8 1.0 1.2 1.4
17
Damkohler number
18
19
20 Figure 6 (A) Conversion and yield profile, (B) last stage temperature, and (C) reboiler and condenser
21 duties as a function of the Damkohler number.
22
23 The philosophy behind understanding the impact of catalyst holdup in the design of the RD column was
24
25 further analyzed through the net reaction rate profile, which has been plotted as a function of the
26
27 Damkohler number in Figure 7. The high peaks showing a shift toward the bottom on increasing the
28
29 Damkohler number illustrate that the reaction mainly took place at the bottom of the reactive zone, which
30
31 is favorable in terms of internal heat integration due to heat of reaction between the reaction and
32
33
separation processes 21. The fact is further clarified on considering the corresponding heat duty profiles
34
35
36
for the reboiler and condenser of the RD column (Figure 6c).
37
38
39 22
40 20 Da = 0.53
Da = 0.71
41 18
Da = 0.89
Net reaction rate (kmol/h)

42 16
Da = 0.97
43 14
44 12
45 10
46 8
47 6
48 4
49 2
50 0
51 0 2 4 6 8 10 12 14 16
52 RD column stages
53
54
55 Figure 7 Net reaction rate profile at different Damkohler numbers.
56
57
58
59
60 ACS Paragon Plus Environment
Page 15 of 35 Industrial & Engineering Chemistry Research

1
2
3 5.3. RD Column Sizing
4
5 Due to the hydraulic limitations, the reactive holdup cannot be more than the system liquid holdup,
6
7 otherwise, the catalyst will fill full in the stage. The following assumptions were made to size the column
8
9
diameter: (1) A reasonable liquid depth of 0.152 meters (6 inches) was assumed, (2) the catalyst
10
11
12 Amberlyst 35 occupies half of a reactive tray, (3) the downcomer occupies 10 % of the tray area 16. With
13
14 these assumptions, the diameter of the column was then determined using equation 6 to accommodate this
15
16 catalyst per tray. The column diameter is estimated as 3.90 meter using a bulk density of 800 kg/m3.
17
4
18
= 
0.152
19
20 (6)
21
22
23 6. Effect of Number of Reactive Trays
24
25 The effect of the number of reactive trays on the various design parameters was analyzed keeping in view
26
27 the upper limit of the temperature of the catalyst. As seen in Figure 8a, a yield of 99 % towards the
28
29 desired product (MMH) could be achieved at 11 reactive trays. These reactive trays also correspond to the
30
31 lower reboiler and condenser duties, as illustrated in Figures 8b and 8c. Furthermore, for the 11 reactive
32
33 stages, the temperature of the last stage was within the permissible limit where catalyst deactivation
34
35 would be avoided, as shown in Figure 8d. Adding more trays will result in either decrease in the required
36
37 yield or increase in the heat duties and the upper limit of the catalyst temperature.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 16 of 35

1
2
3
4
5 1.347
6 MMH produced (kmol/h)
48.98 99% MMH yield A B
7 48.96 1.346

Reboiler duty (MW)

8 48.94 1.345
9
48.92
10 1.344
11 48.90

12 48.88 1.343
13 48.86
1.342
14
48.84
15
16 2.926
17 2.925 C 428 D

Stage 12 temperature (K)

18
Condenser duty (MW)

2.924 426
19
2.923
20 424
21 2.922
422
22 2.921
23 2.920
420
24
2.919 418
25
26 8 9 10 11 12 13 14 8 9 10 11 12 13 14
27 Number of reactive trays Number of reactive trays
28
29
30
31 Figure 8 (A) Net MMH produced, (B) RD reboiler duty, (C) RD condenser duty, and (D) last reactive
32 stage temperature as a function of the number of reactive trays.
33
34
35 7. Optimization of Column Trays
36
37 The total number of trays for the RD column, column C2, and column C3 were optimized for the
38
39 minimum TAC. Adding more trays would reduce the column diameter and heat exchanger area; however,
40
41 it would also increase the height of the column, which would ultimately increase the column capital
42
43 investment. Table 3 lists the effects of the column trays on these competing variables. Moreover, for these
44
45 columns, the optimum feed locations were chosen to give the minimum reboiler duties. The optimum
46
47
numbers of trays for the RD column, column C2, and column C3 were found to be 35, 12, and 15,
48
49
50
respectively.
51
52 Table 3 Optimization of column trays.
53
54 RD-Column C2-column C3-column
55 NT 30 35 40 10 12 15 10 15 22
56 NFMHopt 1 1 1 - - - - - -
57
58
59
60 ACS Paragon Plus Environment
Page 17 of 35 Industrial & Engineering Chemistry Research

1
2
3 NFMeOHopt 13 13 13 - - - - - -
4
NFopt 4 5 6 4 8 13
5
ID(m) 3.61 3.60 3.58 0.93 0.83 0.8 1.6 1.42 1.39
6
7 QR (MW) 1.478 1.340 1.313 0.791 0.724 0.718 0.352 0.185 0.173
8 QC (MW) 3.055 2.917 3.235 0.005 0.004 0.001 0.814 0.647 0.634
9 Shell 0.317 0.350 0.389 0.067 0.071 0.085 0.120 0.156 0.216
10 Heat Exchanger 0.196 0.187 0.205 0.086 0.081 0.080 0.103 0.079 0.077
11 Tot. Capital Cost (106$) 0.513 0.537 0.593 0.153 0.153 0.165 0.223 0.235 0.293
12 Tot. Energy Cost (106 $/y) 0.383 0.347 0.340 0.246 0.225 0.223 0.091 0.048 0.045
13
TAC (106 $/y) 0.554 0.526 0.538 0.297 0.276 0.278 0.166 0.126 0.142
14
15
16
17 8. Impact of Operating Pressure
18
19 8.1. Pressure RD column
20
21 According to the calculated values of the Damkohler number, the system was kinetically controlled.
22
23 When a RD column involves kinetically controlled reactions, the operating pressure thus has a significant
24
25 influence on the RD column performance parameters such as the conversion, yield, and net reaction rate
26
27 profiles 21. A higher operating pressure results in better process intensification in terms of internal heat
28
29
integration due to reaction heat involved. However, the operating pressure should be selected carefully to
30
31
32
achieve the maximum benefits from process intensification and to avoid elevated temperatures in the
33
34 reaction zone that could lead to catalyst deactivation. The net reaction rate profile with different operating
35
36 pressures is shown in Figure 9a. The high peaks move further to the bottom on increasing the column
37
38 operating pressure. This is because reaction mainly occurs at the bottom of the reactive zone, which
39
40 favors process intensification between the reaction and separation involved due to exothermic heat of
41
42 reaction. The corresponding heat duties for the reboiler and condenser decreased, as shown in Figure 9b.
43
44 Figure 9c illustrates the effect of the column pressure on the conversion and yield of MMH. The high
45
46 operating pressure resulted in a high temperature in the reactive zone, which favored high conversion
47
48
because of the activation energy of forward reaction being larger than that of the backward reaction. The
49
50
51
desired yield of MMH was obtained at the operating pressure of 1.77 atm. Moreover, the temperature
52
53 profile was within the permissible limit (423 K) within which catalyst deactivation could be avoided.
54
55 Further increase in the operating pressure results in a higher temperature not suitable for the MMH
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 18 of 35

1
2
3 process. Figure 9d shows the temperature of the last stage of the reactive zone as a function of the RD
4
5 column operating pressure. The best option was to fix the operating pressure at 1.77 atm to ensure a
6
7 suitable upper limit temperature for the reactive zone. However, the operating pressure of 2 atm was
8
9
optimum in terms of internal heat integration.
10
11
12
13 1.55-atm A
24
14 1.77-atm
15 21 2.0-atm
Net reaction rate (kmol/h)

16 18
17 15
18 12
19
9
20
21 6
22 3
23 0
24 2 4 6 8 10 12 14 16 18
25 RD column stages
26
27
28
29 6.0
Condenser Duty B
30 5.5
Reboiler Duty
31 5.0
32 4.5
Heat Duties (MW)

33 4.0
34 3.5
35 3.0
36 2.5
37 2.0
38
1.5
39
1.0
40 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
41 RD column pressure (atm)
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 19 of 35 Industrial & Engineering Chemistry Research

1
2
3
4
5 1.0 Yield C
6 0.9 Conversion
7

Converision and Yield

0.8
8
0.7
9
0.6
10
11 0.5
12 0.4
13 0.3
14
0.2
15
16 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

17 RD column pressure (atm)

18
19
20
440
21 Stage 12 Temp D
22 430
23 420
24
Temperature (K)

410
25
26 400
27 390
28
29 380
30 370
31
360
32 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
33 RD column pressure (atm)
34
35
36 Figure 9 RD column pressure as a function of (A) net reaction rate, (B) heat duties, (C) conversion and
37 yield, and (D) stage 12 temperature.
38
39 8.2. Pressure C2 and C3 column.
40
41 To assess the economic impact of pressure, different operating pressures for C2 and C3 column are
42
43 chosen for minimum TAC. Table 4 gives detailed results for both columns over a range of pressures. For
44
45 both columns energy costs increases as pressure is increased. In addition, columns diameter decreases as
46
47 pressure increases. The operating pressure of column C2 is set at 10-atm, which gives a reflux-drum
48
49 temperature of 318 K and permits the use of cooling water. The base temperature of C2 column is high
50
51
(501 K), which uses high pressure steam. There is a possibility to operate C2 column at lower pressure
52
53
that might be economical since the condenser duty is very small compared to the reboiler duty. This
54
55
56 alternative design was briefly explored for lower pressures. For operating pressure of 6-atm, the reflux
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 20 of 35

1
2
3 drum temperature was 299 K which require 267 K refrigerant at $7.89/GJ. The cost of 5.616 kW of
4
5 refrigeration is only 1396 $/year. The bottom temperature decreases from 501 to 472 K, which still
6
7 require high-pressure steam. The savings in energy cost is about 79415 $/year as reboiler duty decreases
8
9
from 0.724 to 0.469 MW. These alternative designs were not considered since this paper is comparative
10
11
12 study with the base case configuration where DME column operates at 10-atm as well. Furthermore, by
13
14 operating the C2 column at 10-atm, the bottom stream at 501 K can be effectively utilized for possible
15
16 heat integration sequences. The resulting savings from this stream in a heat integration sequence
17
18 (developed in later section) gives savings of about 143009 $/year in terms of energy cost. For pressure in
19
22
20 C3 column, the selection criteria is based on an article by Luyben , where the minimum practical
21
22 operating pressure is assumed to be 0.1-atm. Since, the normal boiling points of MMH and MHOH are
23
24 higher than the water-cooled condenser (318 K), this means that column could be operated under vacuum
25
26 if it is economical attractive. Therefore, the operating pressure selected for C3 column is 0.1-atm which
27
28
gives minimum TAC.
29
30
31
Table 4 Pressure selection for C2 and C3 column.
32
Column C2 Column C3
33
34
Pressure (atm) 4 6 10 0.1 0.3 0.6
35 QR (kW) 306.1 469.4 724.8 185.4 349.7 576.8
36 QC(kW) 7.534 5.616 4.507 647.2 673.9 792.9
37 TR (K) 450.9 472 501.9 401.6 432.1 453.8
38 TC (K) 285.6 299.5 318.1 352.1 383.3 406
39 Steam HP HP HP MP MP HP
40 Diameter (m) 1.21 1.12 0.83 1.42 1.07 1
41 Capital cost (106$) 0.152 0.120 0.153 0.235 0.197 0.205
42 Energy cost (106 $/y) 0.097 0.147 0.225 0.055 0.098 0.188
43 TAC (106 $/y) 0.147 0.187 0.276 0.134 0.164 0.257
44
45
46 9. Selection of Reflux Ratio
47
48 The influence of the reflux ratio on the performance of the RD column was investigated further. The
49
50
relationship between the conversion of MeOH and MH with the reflux ratio is illustrated in Figure 10a. A
51
52
53
slight decrease was observed for MeOH conversion, while the MH conversion increased, when the reflux
54
55 ratio increased. The desired MMH yield of 99 % was achieved at a reflux ratio of 3.60, where the
56
57
58
59
60 ACS Paragon Plus Environment
Page 21 of 35 Industrial & Engineering Chemistry Research

1
2
3 conversion of MeOH was 99.9 %, as illustrated in Figure 10b. The corresponding reboiler duty as a
4
5 function of the molar reflux ratio is illustrated in Figure 10c. Therefore, a reflux ratio of 3.60 was selected
6
7 for the RD column for obtaining 99 % MMH yield.
8
9
10
0.385
11 0.9996 A
12 0.9995 0.380
13
0.9994
14
MeOH conversion
0.375

MH conversion
15 0.9993

16 0.9992 0.370
17 0.9991
18 0.365
0.9990
19 X(MeOH) 0.360
20 0.9989 X(MH)

21 1.8 2.1 2.4 2.7 3.0 3.3 3.6 3.9 4.2

22 Molar reflux ratio
23
24
25
26 1.00 Yield specification 99% B
27
0.98
28
29 0.96
MMH Yield

30 0.94
31
0.92
32
33 0.90
34 0.88
35
0.86
36 1.8 2.1 2.4 2.7 3.0 3.3 3.6 3.9 4.2
37 Molar reflux ratio
38
39
40
41 1.8
C
42 1.6
Reboiler duty RD column (MW)

43 Yield specification 99%

1.4
44
45 1.2

46 1.0
47 0.8
48
49 0.6

50 0.4
51 0.2
52 1.8 2.1 2.4 2.7 3.0 3.3 3.6 3.9 4.2
53 Molar reflux ratio
54
55
Figure 10 (A) Conversion, (B) yield, and (C) RD reboiler duty, as a function of the reflux ratio.
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 22 of 35

1
2
3
4
5 10. Heat Integration Sequences
6
7 Column C2, which operated at 10 atm, had a base temperature of 501.9 K. Different heat integration
8
9
sequences were investigated by circulating the hot stream to various sections of the proposed RD
10
11
12 configuration to further reduce the energy consumption. First, this hot temperature stream was circulated
13
14 to provide boil-up energy to the bottom section of the RD column and the C3 column for potential energy
15
16 reduction. Furthermore, it can be used to boil up the bottom section of column C3 while the feed
17
18 preheating of C2 and C3 columns can be exploited further. Because this process stream contains
19
20 unreacted MeOH and MH that should be recycled after possible heat integration sequences to achieve the
21
22 desired conversion and yield inside the RD column.
23
24 10.1. Heat Integration Sequence 1
25
26 In the first heat integration sequence, the bottom of the RD and C3 column were subjected to boiling
27
28
using the sensible heat from the bottom of C2 column. In the simulation, a refluxed absorber was selected
29
30
31
for the RD and C3 column. The bottom streams originating from C2 was firstly introduced to the hot side
32
33 while the vapor boilup stream from RD column was introduced to the cold side of the shell and tube heat
34
35 exchanger HEX-1. Note that the minimum approach was set at 10 K and the overall heat-transfer
36
37 coefficient U was assumed by 0.0203 cal/sec-m2-K from Luyben 3 for all heat exchangers considered in
38
39 this study. The heat exchanger area was required to be maintained at 16.63 m2 so 0.36 MW of heat can be
40
41 transferred into the cold liquid stream. The reboiler duty could be reduced from 1.34 MW to 0.98 MW
42
43 using an auxiliary trim reboiler to fully vaporize the cold vapor boilup stream. In sequence, the outlet of
44
45 the hot stream originating from HEX-1 was passed through the hot side of another heat exchanger HEX-2
46
47
to provide boilup to the bottom of the C3 column. The heat exchanger area for HEX-2 was required at
48
49
50
5.12 m2 for providing 0.18 MW of heat to fully vaporized the cold vapor boilup stream through sensible
51
52 heat. The diameter of column C3 was reduced to 1.4 m because the internal vapor flow decreased as a
53
54 result of heat integration. The hot outlet stream at 433 K from HEX-2, which contained unreacted MeOH
55
56 and MH, was recycled back to the RD column. The resulting heat integration sequence 1 gives savings of
57
58
59
60 ACS Paragon Plus Environment
Page 23 of 35 Industrial & Engineering Chemistry Research

1
2
3 149050 $/year in terms of operating cost. Figure 11 illustrates the schematic of the proposed heat
4
5 integration sequence 1.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 11 Heat integration sequence (1) for the proposed configuration.
31
32 10.2. Heat Integration Sequence 2
33
34 In this heat integration, the bottom of the RD column was subjected to boiling using the sensible heat of
35
36 the bottom stream from column C2. In the simulation, a refluxed absorber was selected for the RD
37
38 column. The bottom stream originating from the RD column was split into the column C3 feed and vapor
39
40 boilup streams. Meanwhile, the bottom stream originating from column C2 was introduced to the hot side
41
42 while the vapor boilup stream originating from the RD column was introduced to the cold side of the shell
43
44 and tube zones of heat exchanger HEX-1. The heat exchanger area was required to be maintained at 16.54
45
46
m2. The reboiler duty could be reduced from 1.34 MW to 0.98 MW. Because the heat duty of column C2
47
48
49 cannot replace that of the RD column, an auxiliary trim reboiler was needed to fully vaporize the cold
50
51 vapor boilup stream. The boilup stream was then introduced to the bottom of the RD column. In sequence,
52
53 the outlet of the hot stream originating from HEX-1 was passed through another heat exchanger HEX-2 to
54
55 preheat the feed stream of column C2. There is a maximum temperature constraint of 413 K for
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 24 of 35

1
2
3 preheating the feed stream of C2 column. Increasing the temperature further will result in lower DME
4
5 purity which needed a large reflux ratio to meet the design specification. Therefore, in all heat integration
6
7 sequences the maximum temperature was fixed at 413 K where feed preheating of C2 column was done.
8
9
As a result, this sensible heat required a heat transfer area of 0.82 m2 to increase the feed temperature
10
11
12 from 407 K to 413 K. The reboiler duty was reduced from 0.72 MW to 0.692 MW. The diameter of
13
14 column C2 and C3 was reduced to 0.78 m and 1.40 m respectively, because the internal vapor flow
15
16 decreased as a result of heat integration. The hot outlet stream at 453 K from HEX-2, which contained
17
18 unreacted MeOH and MH, was recycled back to the RD column. The resulting heat integration sequence
19
20 2 gives savings of 112182 $/year in terms of operating cost. Figure 12 illustrates the schematic of the
21
22 proposed heat integration sequence 2.
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Figure 12 Heat integration sequence (2) for proposed configuration.
47
48 10.3. Heat Integration Sequence 3
49
50 In this heat integration, the bottom stream of column C2 was circulated to provide the sensible heat for
51
52
vapor boil-up of column C3. The bottom stream originating from column C3 was first split into the
53
54
MHOH product and vapor boilup streams. As illustrated in Figure 13, the bottom stream originating from
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 25 of 35 Industrial & Engineering Chemistry Research

1
2
3 column C2 was introduced to the hot side while the vapor boilup stream from column C3 was introduced
4
5 to the cold side of the shell and tube heat zones of exchanger HEX-1. The hot stream from column C2
6
7 fully vaporized the cold vapor boilup stream through sensible heat giving a heat exchanger area of 2.42
8
9
m2. The hot outlet stream was circulated through another heat exchanger HEX-2 to provide sensible heat
10
11
12 to preheat the feed stream of column C2, which gave a heat transfer area of 0.49 m2. The diameter of
13
14 column C2 and C3 was reduced to 0.79 m and 1.39 m respectively, because the internal vapor flow
15
16 decreased as a result of heat integration. The hot outlet stream at 477 K from HEX-2, which contained
17
18 unreacted MeOH and MH, was recycled back to the RD Column. The resulting heat integration sequence
19
20 3 gives savings of 59324 $/year in terms of operating cost. Figure 12 shows the schematic of the proposed
21
22 heat integration sequence 3.
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Figure 13 Heat integration sequence (3) for proposed configuration.
47
48 10.4. Heat Integration Sequence 4
49
50 This heat integration sequence proposed feed preheating of the columns C2 and C3 using the process
51
52 stream originating from the bottom of column C2 as the heat source. The heat integration sequence 4 is
53
54 shown in Figure 14. First, the hot stream from column C2 was used as a heat source in the heat exchanger
55
56 HEX-1 to preheat the feed stream of column C3. As a result, the reboiler duty was reduced to 0.013 MW,
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 26 of 35

1
2
3 which gave a heat transfer area of 4.72 m2. The hot outlet stream from HEX-1 was further introduced to
4
5 another heat exchanger HEX-2 to provide sensible heat to preheat the column C2 feed stream. The
6
7 reboiler duty decreased to 0.69 MW, while the required heat exchanger area was 0.48 m2. The hot outlet
8
9
stream at 478 K from HEX-2, which contained unreacted MeOH and MH, was recycled back to the RD
10
11
12 Column. In the simulation, the minimum approach temperature was set at 10 K, while an overall heat-
13
14 transfer coefficient U = 0.0203 cal/sec-m2-K was used for heat exchanger HEX-1 and HEX-2 3. The
15
16 diameter of column C2 and C3 was reduced to 0.79 m and 1.40 m respectively, because the internal vapor
17
18 flow decreased as a result of heat integration. The resulting heat integration sequence 4 gives savings of
19
20 55912 $/year in terms of operating cost.
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44 Figure 14 Heat integration sequence (4) for proposed configuration.
45
46
47 11. Design Economics
48
49 For economic evaluation, the capital costs (pertaining to the column shell, heat exchangers, and catalyst)
50
51 and operating costs (steam in the reboilers, and condenser utilities) were taken into consideration. An
52
53 economic assessment of the proposed configuration for the desired yield of MMH was carried out in
54
55
terms of the total annual cost (TAC), with the aid of Equation 7 taken from Kaymak and Luyben 23:
56
57
58
59
60 ACS Paragon Plus Environment
Page 27 of 35 Industrial & Engineering Chemistry Research

1
2
Capital cost
TAC = + Operating Cost
3 (7)
4
Payback period
5
6
The basis for economics and equipment sizing are summarized in Table 5, taken from the report by
7
8
9 Douglas 24 and Turton et al. 25. The payback period of three years and energy costs for low pressure (LP),
10
11 medium pressure (MP), and the high pressure (HP) steams were taken to be similar as those in the base
12
13 case for fair comparison.
14
15 Table 5 Basis for economic and equipment sizing.

17640 ∗ D7.899 ∗ L8.;8<

16
17 Column Shell Cost
18 Column Diameter (m) Aspen Tray Sizing
19
20 Column Length (m) NT trays with 0.61m spacing plus 20% extra length.
21 Heat Exchanger Capital costs
22 Condenser
Q >?
23
7296 ∗ A>? 8.9@ , A>? =
Capital Cost ($)
U>? + ∆T>?
24
25

U>? = 0.852 kW/K. m< 

26
27 Heat Transfer Coefficient

∆T>? = Reflux Drum Temp − 318 K

28
Differential Temperature (K)
29
30 Reboiler
Q O
31
7296 ∗ A O
8.9@
,A =
Capital Cost ($)
O
U O + ∆T
32
33 O

U = 0.568 kW/K. m< 

34
35
Heat Transfer Coefficient O
36 Differential Temperature (K) ∆T O = 34.8 K
37
38 Energy Cost ($/year) LP steam = $7.78/GJ
39 MP steam = $8.22/GJ
40 HP steam = $9.88/GJ
41
42 Cooling Water ($/year) $0.354/GJ
43 Catalyst Cost ($) $10/kg
44
45
46
47
12. Results and Discussion (Proposed Configuration w/o HI)
48
49 12.1. RD Column
50
51 The bottom product at stage 35 contained the desired MMH and a small quantity of the undesired product
52
53 MHOH. The distillate product was a small quantity of DME, produced as a byproduct, together with
54
55 unreacted MeOH and excess MH, to be recycled. The conversions of MeOH and MH were 99.9 % and
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 28 of 35

1
2
3 38.5 %, respectively. The last stage temperature of the reactive stage was 422.4 K, which satisfied the
4
5 temperature constraint for the reactive zone. The reboiler duty was 1.34 MW with a bottom temperature
6
7 of 447.8 K, which used medium-pressure steam. The column diameter according to liquid holdup
8
9
calculation was 3.90 m. Figures 15a and 15b show the composition and temperature profiles of the RD
10
11
12 column, respectively.
13
14
15 A
16 1.0

17
18 0.8
Mole composition

19
0.6
20 Reactive Stages
21 (2-12) DME
0.4
22 MEOH
23 MH
0.2 MMH
24
MHOH
25
0.0
26 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36
27 RD column stages
28
29
30
31 B
32 448
33
440
34
Temperature (K)

35 432
36 Reactive Stages
(2-12)
37 424

38 416
39
40 408

41 400
42 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36
43 RD column stages
44
45
Figure 15 RD column (A) Mole composition profile, and (B) temperature profile.
46
47 12.2. Column C2
48
49
The distillate had a small flow rate of 0.518 kmol/h with 99.9 % DME purity. The condenser duty was
50
51
52
0.0045 MW with a reflux drum temperature of 318 K. The bottom stream was mostly excess MH with a
53
54 small amount of unreacted MeOH that was recycled back to the RD column. The reboiler duty was 0.72
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 29 of 35 Industrial & Engineering Chemistry Research

1
2
3 MW with a base temperature of 501.9 K. The column diameter according to Aspen tray sizing was 0.83 m.
4
5 Figures 16a and 16b show the composition and temperature profiles of column C2, respectively.
6
7
8
9 1.0 A
10
11 0.8
12
Mole composition
13 0.6
14
15 0.4
16 DME
17 0.2 MEOH
MH
18
19 0.0
20 0 2 4 6 8 10 12
21 Column C2 stages
22
23
24
25 B
26 500
27
28 450
Temperature (K)

29
30
31 400
32
33 350
34
35
300
36 0 2 4 6 8 10 12
37
Column C2 stages
38
39
40 Figure 16 Column C2 (A) Mole composition profile, and (B) temperature profile.
41
42 12.3. Column C3
43
44 Column C3 separated the bottom stream originating from the RD column into MMH and MHOH. The
45
46 distillate was 49.02 kmol/h with 99.9 % MMH. The condenser duty was 0.64 MW with a reflux drum
47
48 temperature of 352 K. The bottom stream was 0.49 kmol/h with 99.9 % MHOH. The reboiler duty was
49
50 0.18 MW with a base temperature of 401 K that was accompanied by low-pressure steam. The column
51
52
diameter was 1.42 m. The composition and temperature profiles of column C3 are shown in Figures 17a
53
54
and 17b, respectively.
55
56
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 30 of 35

1
2
3
4
5 1.0 A
6
7 0.8
8

Mole composition
9 0.6
10
11 0.4
12 MH
13 0.2
MMH
MHOH
14
15 0.0
16
0 2 4 6 8 10 12 14 16
17
18 Column C3 stages
19
20
21
410
22
B
23 400
24
25 390
Temperature (K)

26
27 380
28
370
29
30 360
31
32 350
33
0 2 4 6 8 10 12 14 16
34
35 Column C3 stages
36
37 Figure 17 Column C3 (A) Mole composition profile, and (B) temperature profile.
38
39
40
13. Economic Analysis
41
42
Economic analysis was carried out for the proposed RD configuration in terms of the TAC. For the
43
44
45 desired yield of MMH, the proposed RD configuration can reduce the energy consumption, and TAC by
46
47 up to 18.2, and 10.8 %, respectively. The results of the heat integration sequence demonstrated superior
48
49 performance for HI-sequence 1 that could further reduce the energy consumption, and TAC by up to 36.7,
50
51 and 21.8 %, respectively. Table 6 summarizes the economic analysis of the proposed RD configuration
52
53 and the different heat integration sequences applied.
54
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 31 of 35 Industrial & Engineering Chemistry Research

1
2
3 Table 6 Economic comparison of RD configuration with the base case.
4
5
Heat Integration Sequences
6 Base Proposed RD
7 Economic Analysis
Case Configuration Seq-1 Seq-2 Seq-3 Seq-4
8
9 C1/RD Column
10
Reactor cost (106$) 0.1091 - - - - -
11
Catalyst Cost (106$) @ 10$/kg 0.120 0.073 0.073 0.073 0.073 0.073
12
Column Vessel Cost (106$) 0.095 0.968 0.968 0.968 0.968 0.968
13
14
Exchanger Capital Costs (106$) 0.128 0.187 0.156 0.159 0.183 0.183
15 Energy Costs (106$/year) 0.442 0.379 0.278 0.281 0.377 0.377
16 Add. Exchanger Cost (106$) - - 0.045 0.045 0.000 0.000
17 C2 Column
18 Column Vessel Cost (106$) 0.567 0.071 0.071 0.067 0.068 0.068
19 Exchanger Capital Costs (106$) 0.213 0.081 0.082 0.079 0.079 0.079
20 Energy Costs (106$/year) 0.224 0.225 0.225 0.216 0.217 0.217
21 Add. Exchanger Cost (106$) 0.000 0.000 0.000 0.006 0.005 0.005
22 C3 Column
23 Column Vessel Cost (106$) 0.249 0.156 0.153 0.154 0.153 0.153
24 Exchanger Capital Costs (106$) 0.128 0.079 0.048 0.078 0.048 0.054
25 Energy Costs (106$/year) 0.141 0.055 0.007 0.051 0.007 0.010
26 Add. Exchanger Cost (106$) 0.000 0.000 0.021 0.000 0.013 0.020
27 Total Capital Cost (106$) 1.608 1.615 1.616 1.629 1.588 1.601
28 Total Energy Cost (106$/year) 0.808 0.660 0.511 0.548 0.600 0.604
29
TAC (106$/year) 1.344 1.198 1.049 1.091 1.130 1.138
30
31
32
33 The performance comparison in terms of savings of the proposed RD configuration and heat integration
34
35 sequences with the base case is illustrated in Table 7.
36
37 Table 7 Performance comparison in terms of savings
38
39
40 Savings Base Case Proposed Heat Integration Sequences
41 in costs (%) Configuration Configuration compared to proposed RD configuration
42 Seq-1 Seq-2 Seq-3 Seq-4
43 Energy - 18.29 36.74 32.18 25.63 25.21
44 TAC - 10.82 21.89 18.81 15.90 15.32
45
46
47 14. Conclusions
48
49 The chemical 2-methoxy-2-methylheptane exhibits decreased solubility in water and has the ability to
50
51 replace MTBE as a fuel additive, which causes environmental contamination. To meet the growing
52
53
market demand for 2-methoxy-2-methylheptane, the design of an intensified configuration based on
54
55
56 reactive distillation was proposed. A desired yield of MMH in the conventional process is usually
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 32 of 35

1
2
3 obtained by maintaining a large reactor size or by using an excess of MH. Both strategies are expensive in
4
5 terms of capital and operating costs. The proposed configuration uses the RD technology to obtain the
6
7 desired MMH yield at significantly lower capital and operating costs. The results demonstrate that the RD
8
9
configuration can significantly reduce the energy consumption, and TAC by up to 18.2, and 10.8 %,
10
11
12 respectively, compared to the conventional reactor column sequence. Furthermore, different heat
13
14 integration sequences were investigated to further reduce the energy requirement. The heat integration
15
16 sequence (1) realized savings of 36.7, and 21.8 %, for the energy, and total annual cost, respectively.
17
18 Future work would include the development of an effective control structure for the proposed
19
20 configuration.
21
22 Acknowledgments
23
24 This work was supported by Engineering Development Research Center (EDRC), funded by the Ministry
25
26 of Trade, Industry & Energy (MOTIE) (No. N0000990), and by the Basic Science Research Program
27
28 through the National Research Foundation of Korea (NRF), funded by the Ministry of Education
29 (2015R1D1A3A01015621), and by the Priority Research Centers Program through the National Research
30
31 Foundation of Korea (NRF), funded by the Ministry of Education (2014R1A6A1031189).
32
33
34
35 References
36
37 (1) Srivastave, S. P.; Hancsok, J.; Fuels and Fuel-Additives; Wiley: New Jersey, 2014.
38
39 (2) Anderson, S. T.; Elzinga, A. A ban on one is a boon for the other: Strict gasoline content rules
40
41 and implicit ethanol blending mandates. J. Environ. Econ. Manage. 2014, 67, 285-273.
42
43 (3) Luyben, W. L. Design and Control of the Methoxy-Methyl-Heptane Process. Ind. Eng. Chem.
44
45 Res. 2010, 49, 6164-6175.
46
47
(4) Griffin, D. W.; Mellichamp, D. A.; Doherty, M. F. Effect of Competing Reversible Reactions on
48
49
50
Optimal Operating Policies for Plants with Recycle. Ind. Eng. Chem. Res. 2009, 48, 8037-8047.
51
52 (5) Kiran, B.; Jana, A. K. A hybrid heat integration scheme for bioethanol separation through
53
54 pressure-swing distillation route. Sep. Purif. Technol. 2015, 142, 307-315.
55
56 (6) Hussain, A.; Minh, L. Q.; Lee, M. Intensification of the ethylbenzene production process using a
57
58
59
60 ACS Paragon Plus Environment
Page 33 of 35 Industrial & Engineering Chemistry Research

1
2
3 column configured with a side reactor. Chem. Eng. Process. 2017, 122, 204-212.
4
5
(7) Harmsen, G. J. Reactive Distillation: The front-runner of industrial process intensification: A full
6
7
8 review of commercial applications, research, scale-up, design, and operation. Chem. Eng.
9
10 Process. 2007, 46, 774-780.
11
12 (8) Kiss, A. A.; Suszwalak, D. J. P. C. Innovative dimethyl ether synthesis in a reactive dividing-wall
13
14 column. Comput. Chem. Eng. 2012, 38, 74-81.
15
16 (9) Kumar, A.; Daoutidis, P. Modeling, analysis and control of ethylene glycol reactive distillation
17
18 column. AlChE J. 1999, 45, 51-68.
19
20 (10) Al-Arfaj, M. A.; Luyben, W. L. Plantwide control for TAME production using reactive
21
22 distillation. AlChE J. 2004, 50, 1462-1473.
23
24
(11) Jacobs, R.; Krishna, R. Multiple solutions in reactive distillation for methyl tert-butyl ether
25
26
27
synthesis. Ind. Eng. Chem. Res. 1993, 32, 1706-1709.
28
29 (12) Luyben, W. L.; Yu, C. C. Design of MTBE and ETBE reactive distillation columns: In reactive
30
31 distillation design and control; Wiley: New Jersey, 2008.
32
33 (13) Kiran, B.; Jana, A. K. Assessing the performance improvement of an intensified heat integration
34
35 scheme: reactive pressure-swing distillation. Appl. Therm. Eng. 2015, 76, 509-520.
36
37 (14) Novita, F. J.; Lee, H. Y.; Lee, M. Self-heat recuperative dividing wall column for enhancing the
38
39 energy efficiency of the reactive distillation process in the formic acid production process. Chem.
40
41 Eng. Proc. 2015, 97, 144-152.
42
43
(15) Harvianto, G.R.; Ahmad, F.; Lee, M. A thermally coupled reactive distillation and pervaporation
44
45
hybrid process for n-butyl acetate production with enhanced energy efficiency. Chem. Eng. Res.
46
47
48 Des. 2017, 124, 98-113.
49
50 (16) Novita, F. J.; Lee, H. Y.; Lee, M. Energy-efficient design of an ethyl levulinate reactive
51
52 distillation process via a thermally coupled distillation with external heat integration arrangement.
53
54 Ind. Eng. Chem. Res. 2017, 56, 7037-7048.
55
56 (17) Karinen, R. S.; Krause, A. O. I. Reactivity of some C8-alkenes in etherification with methanol.
57
58
59
60 ACS Paragon Plus Environment
 Industrial & Engineering Chemistry Research Page 34 of 35

1
2
3 Appl. Catal. A-Gen. 1999, 188, 247-256.
4
5 (18) Dow, P. D. S; Amberlyst 35Wet; Retrieved 20th, Sep, 2017, from http://www.dow.com/en-
6
7 us/water-and-process-solutions/products/ion-exchange-resins.
8
9
(19) Shah, M.; Kiss, A. A.; Zondervan, E.; De-haan, A. B. A systematic framework for the fesibility
10
11
12 and technical evaluation of reactive distillation processes. Chem. Eng. Process. 2012, 60, 55-64.
13
14 (20) Venimadhavan, G.; Buzad, G.; Doherty, M. F.; Malone, M. F. Effect of kinetics on residue curve
15
16 maps for reactive distillation. AIChE J. 1994, 40, 1814-1824.
17
18 (21) Wang, S.; Huang, K.; Lin, Q.; Wang, S. J. Understanding the Impact of Operating Pressure on
19
20 Process Intensification in Reactive Distillation Columns. Ind. Eng. Chem. Res. 2010, 49, 4269-
21
22 4284.
23
24 (22) Luyben, W. L. Distillation column pressure selection. Sep. Purif. Technol. 2016, 168, 62-67.
25
26 (23) Kaymak, D. B.; Luyben, W. L. Quantitative comparison of reactive distillation with conventional
27
28
multiunit reactor/column/recycle systems for different chemical equilibrium constants. Ind. Eng.
29
30
31
Chem. Res. 2014, 43, 2493-2507.
32
33 (24) Douglas, J. M.; Conceptual design of chemical processes; McGraw-Hill: New York, 1988.
34
35 (25) Turton, R.; Analysis, Synthesis, and Design of Chemical Processes; Prentice Hall: Michigan,
36
37 2012.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
Page 35 of 35 Industrial & Engineering Chemistry Research

1
2
3
4
Table of Contents (TOC)
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment