Research Article

Cite This: ACS Sustainable Chem. Eng. 2018, 6, 10260−10272

Technoeconomic Analysis of Alternative Pathways of Isopropanol

Production
Warissara Panjapakkul† and Mahmoud M. El-Halwagi*,†,‡
†
Chemical Engineering Department, Texas A&M University, College Station, Texas 77843, United States
‡
Gas and Fuels Research Center, Texas A&M Engineering Experiment Station, College Station, Texas 77843, United States

ABSTRACT: Isopropanol is a widely used solvent and chemical. The growing

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demand for isopropanol, the declining supply of typical feedstocks for

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manufacturing isopropanol, and the increasing prices necessitate the search for
alternative, cost-effective, and sustainable pathways for the production of iso-
propanol. The objective of this work is to synthesize, screen, design, and assess
alternate pathways to produce isopropanol. First, biomass- and fossil-based raw
materials are considered along with plausible reaction pathways. A process
synthesis and integration approach is used to create and prune the alternatives
based on branching, matching, and prescreening. For the promising
candidates, process simulation, design, and technoeconomic assessment are
carried out to compare the options. Under the studied conditions, the results
show that propane dehydrogenation followed by direct hydration is the most
promising pathway based on profitability (while accounting for price volatility)
as well as technical and environmental benefits.
KEYWORDS: Design, Process synthesis, Process integration, Shale gas, Glycerin, Propane, Propylene

■ INTRODUCTION
Isopropanol (isopropyl alcohol or IPA) is an important chem-
Table 1. Chemical Reactions of Indirect Hydration Process
Step 1. Esterification
ical which is widely used as a solvent, a chemical intermediate, main reaction CH3CHCH2+H2SO4 ⇆ (CH3)2CHOSO3H
and an ingredient in personal care products and pharmaceut- (CH3)2CHOSO3H + CH3CHCH2⇆((CH3)2CHO)2SO2
icals. It is ranked third in lower-alcohol production (following Step 2. Hydrolysis
methanol and ethanol).1 The global production of isopropanol main reaction (CH3)2CHOSO3H + H2O ⇆ (CH3)2CHOH + H2SO4
is approximately 3 × 106 metric tons per annum (MTPA), with ((CH3)2CHO)2SO2 + 2H2O ⇆ 2(CH3)2CHOH + H2SO4
the US, Europe, and Asia each contributing about 30% of the side reactions (CH3)2CHOSO3H + (CH3)2CHOH ⇆ ((CH3)2CH)2O +
total production.2 The isopropanol market has been steadily H2SO4
growing. Its compound annual growth rate is approximately ((CH3)2CHO)2SO2 + (CH3)2CHO ⇆ (CH3)2CHOSO3H +
((CH3)2CH)2O
7%, and the growth is expected to continue especially in the
Asia-Pacific region primarily because of the increased use in
the pharmaceutical sector.3 Isopropanol has been largely pro- process used in Europe and Japan.2 The primary disadvantage
duced from propylene via two commercial routes: indirect of this method is the requirement for a high-purity feed
hydration of refinery-grade propylene and direct hydration of (at least 90 wt % propylene).4 Furthermore, to enhance the
chemical-grade propylene. Indirect hydration is a process with conversion and yield, the reaction is typically operated at much
two main reaction steps (esterification and hydrolysis) which higher temperature and pressure than those used in indirect
convert propylene to isopropanol. The conversion is about hydration. On a positive side, direct hydration has some advan-
93%, and the selectivity to isopropanol and its main byproduct tages over indirect hydration. The direct hydration process
(diisopropyl ether, DIPE) is above 98%.4 The main reactions uses water as a solvent instead of sulfuric acid, thereby reducing
for this process are provided in Table 1. Sulfuric acid is used as the corrosion and environmental problems. The stoichiometric
a solvent. Therefore, special materials of construction must be equation of the propylene hydration process is given by
used to avoid excessive corrosion. Care should also be given to CH3CHCH 2 + H 2O ⇆ (CH3)2 CHOH
the treatment and disposal of process wastes including waste-
water, waste sulfuric acid, spent soda, and off-gases. A key Similar to the indirect method, the main byproduct of this
advantage for this process is its ability to use low-purity propyl- process is diisopropyl ether (DIPE). There are three types of
ene feed (∼40−60 wt %). The indirect hydration process has
been common in the US. Received: April 9, 2018
The direct hydration process converts propylene to iso- Revised: June 5, 2018
propanol via a single-step reaction. It has been the common Published: July 9, 2018

© 2018 American Chemical Society 10260 DOI: 10.1021/acssuschemeng.8b01606

ACS Sustainable Chem. Eng. 2018, 6, 10260−10272
ACS Sustainable Chemistry & Engineering Research Article

Figure 1. Example of forward and backward branching, matching, and interception for sample pathways of isopropanol production.

commercial processes based on the reaction phase of direct recommended pathways. The following steps summarize the
hydration. proposed approach:
The recent substantial growth in shale gas production has Step i: Generating a Superstructure of Alternatives.
led to a decline in propylene production from oil refineries. The first step is the creation of a superstructure that embeds
This decline is attributed to the shift in ethylene production feedstocks and processing pathways of interest. The super-
through ethane dehydrogenation (which produces about 2% of structure was constructed based on the branching, matching,
propylene yield) instead of naphtha cracking (which produces and interception approach introduced by Pham and El-Halwagi.8
about 15% of propylene yield).5−7 The shortfall in naphtha- Branching is a strategy of gathering all of the pathway infor-
based propylene along with the rapid growth in propylene- mation by associating the chemicals with sources and main
based products caused market shortages and price increase. products. The branching approach can be achieved from either
Therefore, there is motivation to investigate various feedstocks a forward branching or a backward branching. The forward
and processing pathways for the production of isopropanol. branching is a method for searching intermediates from feed-
The objective of this work is to synthesize, screen, design, and stocks by forward approach. For example, in forward branching
assess alternate pathways to produce isopropanol from a variety biomass is a source of methanol, ethanol, etc. Likewise, the
of raw materials. Numerous pathways are first synthesized. backward branching is a method for generating intermediates
High-level technoeconomic screening is used to eliminate raw from products. For example, isopropanol can be made from
materials and processing pathways that are not economically propylene, acetone, and propane. Therefore, the backward
viable. Next, process simulation, design, and analysis tech- branching should list these chemicals and other species that
niques are used to compare the promising options and assess can be used to make isopropanol. After branching the chem-
their viability under various conditions. icals, connection of those chemicals or intermediates is needed
to form a continuous pathway. When identical chemicals are
■ PROBLEM STATEMENT
Isopropanol may be manufactured from various starting mate-
connected, it is called matching. On the other hand, when
different chemicals are connected via chemical reactions, the
rials and via different processing pathways. It is desired to develop step is called interception.8 Figure 1 is an illustration of the
a systematic approach for the generation and screening of forward and backward branching as well as interception.
plausible routes. Because of the need to include sustainability After generating the superstructure of alternatives for
of the supply and viability of the market, fossil-,and biomass- isopropanol production, the next step is screening the potential
based raw materials should be considered. Price volatility is pathways based on a high-level economic analysis. The Metric
also to be considered in the assessment. Specifically the fol- for Inspecting Sales and Reactants (MISR), an indicator of
lowing questions are to be addressed: stoichiometric-economic “stoichio-nomic” targeting method,9
is used for the preliminary screening. MISR9 is defined as
• What are the potential raw materials to be used?
• What are possible intermediates and byproducts? N
∑ p =products Fp × Sp
1
• What are the plausible processing pathways to produce MISR = N
isopropanol? ∑r =reactants
1
Fr × Cr (1)
• How can the numerous alternatives be quickly and effec-
tively screened? where Fp is the annual production rate of product p, Sp is the
• What are the recommended pathways and how suscep- selling price of product p, Fr is the annual feed rate of reactant
r, and Cr is the purchase cost of reactant r. Pathways with
tible is their profitability in light of possible price variability?
MISR values less than one are eliminated because they are not

■ APPROACH
Because of the potentially large number of alternatives for
economically viable (cost of raw materials exceeds value of
products). Pathways with MISR values slightly higher than one
are not likely to be profitable because of the additional costs
producing isopropanol, a systematic approach is proposed for associated with capital investment, utilities, labor, and other
generating a superstructure of alternative pathways, screening expenses. When multiple pathways had the same feed and
for potential pathways, synthesizing and simulating promising product, a pathway with the least number of steps is selected to
flowsheets, performing an economic analysis, and selecting promote process simplification.
10261 DOI: 10.1021/acssuschemeng.8b01606
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Table 3. Technology Legend of Isopropanol Production

(The Reference Following Each Technology Designates the
Source of Data and/or Flowsheet Info)
conversion technology (the number conversion technology (the number
before each technology represents the before each technology represents the
pathway arc on Figures 3 and 4) pathway arc on Figures 3 and 4)
1. fluid catalytic cracking12 20. fermentation22
2. fluid catalytic cracking12 21. syngas fermentation23
3. hydrogenation13 22. CO hydrogenation24
4. transesterification14 23. CO hydrogenation24
5. saponification14 24. CO hydrogenation24
6. hydrolysis14 25. syngas fermentation23
7. hydrolysis9 26. methanation24
8. pyrolysis15 27. CO hydrogenation15
9. gasification15 28. stream reforming25
10. landfill9 29. autothermal reforming25
11. digestion9 30. dry reforming25
12. prehydrolysis16 31. combined reforming25
13. fermentation17 32. partial oxidation25
14. IB, IBE fermentation18 33. pyrolysis26
Figure 2. Summary of the approach. 15. cellobiose degradation19 34. carbonylation27
16. ABE fermentation20 35. oxidative bromonation28
Table 2. Symbols and Prices of Chemical Species 17. hydrothermal21 36. stream cracking29
18. fermentation18 37. stream cracking29
symbol chemical price ($/kg)
19. gasification15 38. hydro-deoxygenation30
A naphtha 0.88 conversion technology (the number conversion technology (the number
B biomass 0.30 before each technology represents the before each technology represents the
C sugar/carbohydrate 0.57 pathway arc on Figures 3 and 4) pathway arc on Figures 3 and 4)
D syngas (H2:CO ∼ 2) 1.60 39. hydro-deoxygenation30 58. carbonylation27
E methane 0.14 40. hydrogenolysis31 59. hydrogenation39
F ethane 0.18 41. pyrolysis32 60. hydration35
G glycerol 0.004 42. fermentation33 61. hydroformylation and
H ethanol 0.78 hydrogenation4
I propane 0.48 43. anaerobic digestion33
J propanol 1.25 44. pyrolysis17 62. metathesis12
K methanol 0.30 45. gasification17 63. vapor phase oxidation27
L acetylene 0.68 46. stream reforming17 64. oxidation (Wacker process)35
M ethylene 0.39 47. dehydration34 65. oxidation27
N acetaldehyde 1.01 48. dehydrogenation35 66. oxidation27
O butane 0.49 49. oxidation35 67. cumene and hock process20
P benzene 1.21 50. oxidation36 68. ketonization40
Q acetic acid 0.84 51. direct oxidation37 69. esterification41
R propylene 0.95 (chemical grade: 94%) purity) 52. dehydrogenation38 70. indirect hydration4 (esterification
+ hydrolysis)
0.75 (refinery grade: 70% purity)
53. oxidative dehydrogenation38 71. direct hydration4
S acetone 1.12
54. dehydration31 72. oxidation20
T isopropyl acetate 1.38
55. MTP process6 73. hydrogenation4
U isopropanol 1.32
56. MTO process6 74. transesterification42
57. hydroformylation35 75. hydrolysis43
Step ii: Simulating and Designing Promising Path-
ways. For the pathways resulting from the prescreening step, considered before making a final recommendation on the
process synthesis, simulation, and design studies are carried out selected pathway. Figure 2 summarizes the steps involved in
to generate the mass and energy balance data for the process, the proposed approach.
equipment sizing, and key performance indicators. Next, an
economic analysis is performed to evaluate feasible pathways.
Capital and operating costs are estimates. The return on
■ CASE STUDY
It is desired to construct a production facility for the pro-
investment (ROI) is calculated as a measure of profitability. duction of 37 500 tonnes per year of isopropanol. Various
Sustainability and safety issues can also be included in the ROI renewable and fossil-based feedstocks as well as processing
calculations through the metric of sustainability-and-safety pathways should be considered. The aforementioned approach
weighted ROI.10,11 is applied as described in the following sections.
Step iii: Selecting the Recommended Pathway. Generating the Superstructure of Alternatives. Plau-
Processes meeting a minimum (threshold) ROI are considered sible feedstocks, intermediates, byproducts, and wastes were
in the final analysis. The margin of error associated with the generated along with the processing pathways for conversion.
cost estimation techniques and the impact of price volatility are The lists of chemicals and conversion technologies are given in
10262 DOI: 10.1021/acssuschemeng.8b01606
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Figure 3. Superstructure of pathways for isopropanol production.

Table 2 and Table 3, respectively. In general, numerous feed-

stocks may be considered based on availability, commercial
potential, sustainability, and safety. In this case study, the fol-
lowing fresh feedstocks were considered: acetone, benzene,
biomass, butane, ethane, glycerol, methane, methanol, naphtha,
and propane. Some of these fresh feedstocks may also be pro-
duced as intermediates. Other chemicals were considered to
only be intermediates produced within the network. The super-
structure of isopropanol production resulting from branching,
matching, and interception is demonstrated in Figure 3.
The process yield was set to the maximum theoretical value.9 Figure 4. Reduced superstructure after MISR prescreening and pro-
If a pathway is not economically viable when the yield is max- cess complexity constraint (no more than two major technologies).
imum, then it can be safely eliminated. For potentially viable
pathways, the actual process yield will be used. When the includes different routes for isopropanol production, which are
requirement for MISR to be greater than one is used and when the indirect hydration of propylene, direct hydration of
an additional constraint on process complexity is added to propylene, and acetone hydrogenation.
eliminate any process with more two major technology steps For each promising pathway, simulation was carried out
from the starting material to the product (isopropanol), the using ASPEN Plus. Whenever actual data for the reaction con-
superstructure shown by Figure 4 is obtained. version and yield were available (as will be discussed for the
Simulating and Designing Promising Pathways. Based individual pathways), RSTOIC model was used. Otherwise,
on the results from the prescreening step, the superstructure the reaction was modeled through the minimization of Gibbs
may be divided into two categories. The first category includes free energy (RGIBBS). The results for key pieces of equipment
different routes to produce propylene, which are the glycerol (pumps, compressors, heat exchangers, and distillation columns)
hydro-deoxygenation, propane dehydrogenation (PDH), and were exported to ASPEN Process Economic Analyzer to obtain
methanol to olefins (MTO) process. The second category the equipment cost. The cost of specialized reactors was
10263 DOI: 10.1021/acssuschemeng.8b01606
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Figure 5. Flowsheet of glycerol hydro-deoxygenation.

obtained from literature of similar or analogous units. Lang product and recycle unreacted hydrogen back to the reac-
factors were used to estimate the fixed and total capital invest- tor. A flowsheet and stream table of the glycerol hydro-
ments. The return on investment (ROI) is calculated through deoxygenation process are presented in Figure 5 and Table A1,
the following expression:9 respectively. A summary of the key information for economic
analysis is demonstrated in Table 4, and the economic results
annual net (after‐tax) profit
ROI = *100% of the glycerol hydro-deoxygenation process are shown in
TCI (1a) Table 5.
where TCI is the total capital investment of the process and
the net profit is given by9 Table 4. Key Information for the Glycerol Hydro-
deoxygenation Process
annual net (after‐tax) profit=
input/output unit value
(annual income − annual operating cost − depreciation) raw glycerol (62 wt %) kt/yr 1909
*(1 − tax rate) + depreciation hydrogen kt/yr 0.112
refinery-grade propylene (75 wt %) kt/yr 361
(2a)
fuel (from alcohols) kt/yr 830
=(annual income − total annualized cost) heating utilities MMBtu/h 652
cooling utilities MMBtu/h 847
*(1 − tax rate) + depreciation (2b) electricity kW 638
The tax rate was taken as 30% of the taxable income, and the
depreciation was carried out using a linear scheme over 10 years Table 5. Economic Results for the Glycerol Hydro-
and no salvage value. The process description and the results of deoxygenation Process
process simulation and economic analysis are provided in the description unit value
ensuing sections. fixed capital investment (FCI) MM$ 388
Glycerol Hydro-deoxygenation. Glycerol hydro-deoxy- total capital investment (TCI) MM$ 456
genation is a one-step catalytic propylene formation reaction annual income MM$/yr 349
with a conversion of 88% and a selectivity of 76%. A key annual operating cost MM$/yr 380
advantage of this reaction is that propylene is the only product ROI yr−1 −2%
in the gas phase so that the separation section is not required.30
This process is an enticing process because of its abundance Indirect Hydration. Refinery-grade propylene gas reacts with
and low-price glycerol feedstock. However, the main challenge sulfuric acid via an esterification reaction to generate a sulfate
of this process is that the glycerol from the biodiesel industry is solution in the absorber reactor. While spent gas is vented out
crude and impure, which can damage pipes and equipment.44,45 of the process from the top of the absorber reactor, the sulfate
Thus, an expensive glycerol purification technology is required. mixture from the bottom of the absorber reactor enters the
The process begins with purifying and sending raw glycerol to stripper reactor to react with water and form hydration reac-
the reactor to react with hydrogen. The reactor effluent comes tion. Unreacted sulfuric acid is removed from the bottom of
out as the vapor−liquid mixture. The mixture is then sent to the stripper reactor and recycled back to the absorber reactor
flash drum to separate propylene, which is the only product in for a further esterification reaction. Product from the hydration
the gas phase, from byproducts, which are all in the liquid reaction is fed to the scrubber to neutralize the residual acid
phase. The gas stream of propylene and hydrogen is sent to the with caustic. Although spent soda is discharged from the
pressure-swing adsorption section to purify the propylene bottom of the scrubber, a neutral product leaves the top of the
10264 DOI: 10.1021/acssuschemeng.8b01606
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Figure 6. Flowsheet of indirect hydration process.

scrubber as vapor stream. The vapor stream is condensed and Table 7. Economic Results for the Indirect Hydration
sent to the drum to separate propylene and propane gases from Process
the product stream. The liquid product stream from the drum
description unit value
is pressurized and fed to the first distillation column to separate
fixed capital investment (FCI) MM$ 135
DIPE and the remaining gas from the product stream. The
total capital investment (TCI) MM$ 159
distillate is sold as fuel. The product stream then enters the
annual income MM$/yr 497
isopropanol−water azeotropic distillation column which uses
annual operating cost MM$/yr 422
dimethyl sulfoxide (DMSO) to induce the separation. Isopropanol ROI yr−1 36%
with a purity of 99 wt % is concentrated in this distillation column
and is collected as the product stream. The heavy stream from Direct Hydration. Liquid chemical-grade propylene enters
the isopropanol−water distillation column is sent to the last the reactor and reacts with process water. The liquid effluent is
column to separate DMSO from the aqueous solution to cooled so that propylene and propane vaporize in a flash drum.
recycle it back to the azeotropic distillation column. Water is The vapor stream from the flash drum is condensed and sent
discharged from the process as a wastewater. A flowsheet of the to the propylene−propane distillation column to purify uncon-
indirect hydration process is presented in Figure 6. A stream verted propylene before recycling it back to the feed prepara-
table of the process is also presented in Table A2. A summary tion section. Liquid from the flash drum is sent to the separation
of the key information from the indirect hydration simulation section to purify the isopropanol product. The separation section
for an economic analysis is demonstrated in Table 6, and the consists of three distillation columns. The first column separates
economic results of the indirect hydration process are shown in DIPE from isopropanol. Distillate stream from this column is
Table 7. discharged from the process as fuel. The second column is an
azeotropic distillation column, which separates water from
Table 6. Key Information for the Indirect Hydration 99 wt % isopropanol by using DMSO as an extractive solvent.
Process The last column separates water from the solvent in order to
recycle water to the feed preparation section and DMSO to the
input/output unit value azeotropic distillation column. A flowsheet of the direct hydra-
refinery-grade propylene (70 wt %) kt/yr 452 tion process and stream table are presented in Figure 7 and
stream kt/yr 161 Table A3, respectively. A summary of the key information from
sulfuric acid aqueous (80 wt %) kt/yr 8.58 the simulation from the direct hydration process for an economic
caustic soda kt/yr 96.5 analysis is demonstrated in Table 8, and the economic results of
isopropanol (99.5 wt %) kt/yr 375 the direct hydration process are shown in Table 9.
fuel (from DIPE and light gas) kt/yr 35.1 Acetone hydrogenation. Hydrogen reacts with liquid ace-
vent gases with sulfuric acid MMft3/yr 52.6 tone in the reactor and gives the vapor−liquid phase product.
process wastewater MMm3/yr 0.06 The mixed-phase effluent is sent to drum to separate vapor from
spent soda MMm3/yr 0.289 the liquid product. The vapor mixture then enters a cooler to
ESP wastewater MMm3/yr 0.0596 condense all the chemicals but hydrogen. This condensed
heating utilities MMBtu/h 250 mixture enters the second drum in order to separate unreacted
cooling utilities MMBtu/h 285 hydrogen from the mixture. The liquid mixture from the
electricity kW 344 second drum combines with the liquid product from the first
clean water for ESP MMm3/yr 0.0015 drum and leaves the process as a 98.5 wt % isopropanol
10265 DOI: 10.1021/acssuschemeng.8b01606
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Figure 7. Flowsheet of direct hydration process.

Table 8. Key Information for the Direct Hydration Process lower than the isopropanol price in other processes because of
its lower purity. The price of isopropanol with 98.5 wt % purity
input/output unit value
is approximated to be $1.2/kg. Based on the relatively low ROI
chemical-grade propylene (95 wt %) kt/yr 350 of 7% (which is less than the minimum acceptable ROI of 10%)
process water kt/yr 101 and the risk issues associated with the use of high-pressure
isopropanol (99.8 wt %) kt/yr 326 hydrogen, acetone hydrogenation was eliminated from further
fuel (from DIPE and light gas) kt/yr 82 consideration.
heating utilities MMBtu/h 495 Selecting the Recommended Pathway. Final selection
cooling utilities MMBtu/h 534 of propylene production: Since PDH has more potential for
electricity kW 1253 profitability compared to MTO,12 the pursued pathways of pro-
pylene production are PDH and glycerol hydro-deoxygenation.
Table 9. Economic Results for the Direct Hydration Process While the economic analysis of glycerol hydro-deoxygenation
description unit value was estimated from the simulation result, the economic analysis
of PDH process was adapted from a recent study.7 Based on the
fixed capital investment (FCI) MM$ 195
data and assumptions in this work, the ROI of the PDH process
total capital investment (TCI) MM$ 229
was calculated to be 20% (which can slightly increase when
annual income MM$/yr 432
sustainability issues are integrated7). Furthermore, the produced
annual operating cost MM$/yr 364
hydrogen can be integrated with adjacent facilities to foster
ROI yr−1 23%
industrial symbiosis and to reduce carbon footprint, water
uage, and energy utilization. The key information for economic
product. Unreacted hydrogen that leaves the second drum is evaluation of PDH process and its results are presented in
recycled back to the feed preparation section. Figure 8 and Table 12 and Table 13, respectively.
Table A4 present a flowsheet and stream summary of the ace- Based on the economic analysis of the glycerol hydro-
tone hydrogenation process. A summary of the key information deoxygenation, the annual ROI of the process was negative
from the acetone hydrogenation simulation for an economic (−2%), which indicates that it is not economically viable under
analysis is demonstrated in Table 10, and the economic results the studies conditions. Additionally, there are some issues of
of the acetone hydrogenation process are shown in Table 11. glycerol hydro-deoxygenation process such as insufficient
It should be noted the price of isopropanol in this process is amount of glycerol from biodiesel production and uncertainty
10266 DOI: 10.1021/acssuschemeng.8b01606
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Figure 8. Flowsheet of acetone hydrogenation process.

Table 10. Key Information on Acetone Hydrogenation Table 13. Economic Results for the Propane
Process Dehydrogenation Process
input/output unit value description unit value
acetone (98.7 wt %) kt/yr 359 fixed capital investment (FCI) MM$ 430
hydrogen kt/yr 20.8 total capital investment (TCI) MM$ 507
isopropanol (98.5 wt %) kt/yr 371 annual income MM$/yr 363
fuel kt/yr 11 annual operating cost MM$/yr 234
heating utilities MMBtu/h 7.48 annual ROI yr−1 20%
cooling utilities MMBtu/h 0.525
electricity kW 884 positive if the price of raw glycerol decreases and the price of
propylene increases. From the sensitivity analysis of hydro-
Table 11. Economic Results of Acetone Hydrogenation deoxygenation from raw glycerol in Figure 9a, the process can
Process
description unit value
fixed capital investment (FCI) MM$ 68
total capital investment (TCI) MM$ 80
annual income MM$/yr 444
annual operating cost MM$/yr 439
ROI yr−1 7%

Table 12. Key Information for the Propane

Dehydrogenation Process
Figure 9. Sensitivity analysis for the annual ROI of hydro-
input/output unit value deoxygenation from raw glycerol (a) and from purified glycerol (b).
propane kt/yr 408
process water kt/yr 101 be operate economically with raw glycerol prices ranging from
propylene (95 wt %) kt/yr 350 $0.06/kg to $0.13/kg when the propylene price is high (more
hydrogen kt/yr 30 than $1.1/kg).
heating utilities MMBtu/h 1220 In order to compare the profitability of glycerol hydro-
cooling utilities MMBtu/h 733 deoxygenation from raw glycerol and from refined glycerol, the
electricity kW 21372 sensitivity analysis of the process from refined glycerol was also
performed. According to the sensitivity analysis shown in
in process scale-up. Therefore, it can be concluded that PDH is Figure 9b, the range of refined glycerol price for economically
the best pathway for propylene production. Although the ROI feasible scenario is between $0.32 and 0.45/kg, depending on
result of the glycerol hydro-deoxygenation using chemical the propylene selling price. However, it should be realized that
market prices are negative, the ROI of this process can be the market price of purified glycerol is $0.85/kg and the
10267 DOI: 10.1021/acssuschemeng.8b01606
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market price of propylene is in the range of $0.9−1.2/kg. This buying propylene were considered. The ROI for the “buy”
implies that propylene production from refined glycerol is scenario followed by direct hydration process is 23%. The ROI
hardly economically viable because the market price of refined for the “make” case, which was calculated based on the eco-
glycerol is about twice the highest feasible price of refined nomic analysis of direct hydration and PDH processes, was
glycerol for the propylene market price scenario. Therefore, it found to be 22%. A summary of economic results of purchasing
can be concluded that the using raw glycerol is preferred to and manufacturing scenarios is presented in Table 14.
using pure glycerol to produce propylene via hydro-deoxygena-
tion. Nonetheless, since the base case has a negative ROI, this Table 14. Summary of Economic Results of Two Possible
option is not pursued anymore. Scenarios
Final selection of isopropanol production: While the ROI of
the indirect hydration was equal to 36%, the ROI of the direct propylene “buy” propylene “make”
description scenario scenario
hydration was equal to 23%. As the margin of error in in these
types of conceptual design and economic studies is typically on fixed capital investment (MM 195 625
$/yr)
the order of 20−25%, it cannot be fully concluded which total capital investment (MM 229 736
pathway is the best pathway to produce isopropanol. Addi- $/yr)
tionally, other sustainability and safety issues should be considered. annual income (MM$/yr) 432 462
A sensitivity analysis was performed to assess the impact of varying annual operating cost (MM 364 262
propylene and isopropanol prices on ROI. The results of the $/yr)
sensitivity analysis for the indirect and the direct hydration ROI (yr−1) 23% 22%
processes are shown in Figure 10. The results from the
Due to the very close ROI values for the two scenarios, a
sensitivity analysis was carried out, as shown in Figure 11,

Figure 10. Sensitivity analysis for the annual ROI of indirect

hydration (a) and direct hydration (b) processes (the lines represent
the ROI for various selling prices of isopropanol). Figure 11. Sensitivity analysis for the annual ROI of (a) propylene
make scenario and (b) propylene buy scenario.
sensitivity analysis show that indirect hydration and direct
hydration processes are economically feasible with the iso- to assess the changes resulting from variations in propylene
propanol market price of $1.323/kg when the price of the (in the buy scenario) and propane (in the make scenario)
refinery−grade propylene drops below $0.93/kg and the price prices. The results illustrate that the ROI of the buy scenario is
of the chemical-grade propylene drops below $1.17/kg, respec- more sensitive to the changes in propylene price than the ROI
tively. Additionally, when the price of the refinery-grade of the make scenario to the propane price. Thus, it was conc-
propylene is reduced to a range of $0.61−1.03/kg, the minimum luded that it is more economically robust to produce make rather
acceptable level of ROI (10%) for the indirect hydration process than buy propylene. The sensitivity analysis of the make sce-
is achieved. Similarly, the minimum acceptable level of ROI of nario also reveals that such route can operate economically when
the direct hydration process is reached when the price of the the propane price is less than $0.95/kg at the isopropanol price
chemical-grade propylene is decreased to a range of $0.77− of $1.23/kg. Additionally, the minimum acceptable level of
1.24/kg for the different product selling prices. Comparing the ROI of 10% for the make case is achieved with the propane
impacts of the propylene price to the ROI of indirect hydration price between $0.45 and 0.83/kg, depending on the isopropanol
and direct hydration processes, the ROI of the direct hydration selling price. It is also worth noting that when sustainability issues
process is less dependent on its raw material price than the (including water usage, fuel consumption, carbon footprint,
ROI of the indirect hydration process. Hence, the indirect and volatile organic compound emission) are included, the
hydration process is much more sensitive to price volatility, sustainability weighted return on investment10 is enhanced by
and the ROI may easily drop below the minimum acceptable 1−6 yr−1% depending on the type of process modification under-
with plausible variations in prices. The direct hydration process taken to integrate and intensify the process.7 Further improve-
shows a lower slope of sensitivity and is, therefore, more econom- ments can also be made when the process is integrated with
ically robust under price-changing conditions. Furthermore, the adjacent facilities through an industrial symbiosis framework.46−49
indirect hydration process discharges wastewater streams that are
laden with sulfuric acid and caustic soda. As such, from an
environmental sustainability perspective, direct hydration offers
■ CONCLUSIONS
This work focused on the production of isopropanol from var-
key advantages. Therefore, while both routes are recommended, ious renewable and fossil-based feedstocks. A superstructure
the direct route is favored given the sensitivity and sustainability was created to embed a rich set of potential pathways. The super-
issues. structure was constructed based on the branching, matching,
Since propylene hydration is recommended as the primary and interception approach. Prescreening using high-level
route for isopropanol production, the options of making versus technoeconomic criteria was carried to eliminate infeasible or
10268 DOI: 10.1021/acssuschemeng.8b01606
ACS Sustainable Chem. Eng. 2018, 6, 10260−10272
ACS Sustainable Chemistry & Engineering Research Article

noncompetitive pathways. The remaining promising pathways that propylene production via propane dehydrogenation is
included the following: propylene direct and indirect hydration superior to glycerol hydro-deoxygenation and the most
(where propylene may be produced through glycerol hydro- profitable pathway to produce isopropanol is direct hydration
deoxygenation, propane dehydrogenation, or methanol to olefins of propylene. A sensitivity analysis was carried out to confirm
process) and acetone hydrogenation. The results of flowsheet the conclusions under potential scenarios of price volatility.
synthesis, process simulation, techno-economic analysis, and
other sustainability considerations were used to compare the
alternate pathways. Under the studied conditions, it was found
■ APPENDIX
Tables A1 , A2, A3, and A4 follow.

Table A1. Stream Table of Glycerol Hydro-deoxygenation

stream name units 1 2 3 4 5 6 7 8 9 10 11 12
temperature K 323 559 298 573 298 477 479 573 573 298 298 298
pressure bar 20 80 80 80 1 1 80 80 80 80 80 80
mass flows kg/h 7 7 161218 161218 238639 143723 143723 143723 304941 304941 201149 103792
mass fractions
hydrogen 1.000 1.000 1.000 1.000 0.000 0.000 0.000 0.000 0.512 0.512 0.776 0.000
propylene 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.144 0.144 0.217 0.002
methanol 0.000 0.000 0.000 0.000 0.335 0.000 0.000 0.000 0.000 0.000 0.000 0.000
2-propenol 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.008 0.008 0.001 0.022
1-propanol 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.022 0.022 0.002 0.060
2-propanol 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.008 0.008 0.001 0.021
water 0.000 0.000 0.000 0.000 0.000 0.003 0.003 0.003 0.217 0.217 0.004 0.629
propylene 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.017 0.017 0.000 0.050
glycol
1,3- 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.017 0.017 0.000 0.050
propanediol
glycerol 0.000 0.000 0.000 0.000 0.617 0.997 0.997 0.997 0.056 0.056 0.000 0.166
NaOCH3 0.000 0.000 0.000 0.000 0.027 0.000 0.000 0.000 0.000 0.000 0.000 0.000
triglycerides 0.000 0.000 0.000 0.000 0.020 0.000 0.000 0.000 0.000 0.000 0.000 0.000
protein 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000
stream name units 13 14
temperature K 298 298
pressure bar 80 80
mass flows kg/h 161211 45178.2
mass fractions
hydrogen 1.000 0.000
propylene 0.000 0.965
methanol 0.000 0.000
2-propenol 0.000 0.003
1-propanol 0.000 0.008
2-propanol 0.000 0.006
water 0.000 0.018
propylene glycol 0.000 0.000
1,3-propanediol 0.000 0.000
glycerol 0.000 0.000
NaOCH3 0.000 0.000
triglycerides 0.000 0.000
protein 0.000 0.000

Table A2. Stream Table of Indirect Hydration Process

stream name units 1 2 3 4 5 6 7 8 9 10 11
temperature K 363 363 363 372 367 342 407 407 406 422 363
pressure bar 6 6 6 6 6 1.01325 1.01325 3 1.01325 1.01325 1.01325
mass flows kg/h 1072 1072 56508.3 1672.86 89697.4 89697.4 89697.4 20170.1 87556.8 63956.3 63956.3
mass fractions
propylene 0.000 0.000 0.700 0.210 0.027 0.027 0.027 0.000 0.027 0.000 0.000
propane 0.000 0.000 0.300 0.664 0.177 0.177 0.177 0.000 0.181 0.000 0.000
dipe 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.014 0.000 0.000
isopropanol 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.577 0.003 0.003
diisopropyl sulfate 0.000 0.000 0.000 0.094 0.331 0.331 0.331 0.000 0.000 0.000 0.000
water 0.200 0.200 0.000 0.032 0.171 0.171 0.171 1.000 0.196 0.048 0.048
isopropyl hydrogen sulfate 0.000 0.000 0.000 0.001 0.248 0.248 0.248 0.000 0.006 0.000 0.000

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ACS Sustainable Chemistry & Engineering Research Article

Table A2. continued

stream name units 1 2 3 4 5 6 7 8 9 10 11
DMSO 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
sulfuric acid 0.800 0.800 0.000 0.000 0.047 0.047 0.047 0.000 0.000 0.949 0.949
caustic soda 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
sodium bisulfate 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
stream name units 12 13 14 15 16 17 18 19 20 21 22
temperature K 363 407 418 407 325 325 325 326 312 312 395
pressure bar 6 1.01325 1.01325 1.01325 1.01325 1.01325 1.01325 5.06625 4.053 4.053 4.32879
mass flows kg/h 63956.3 12064 85538.4 14531.7 85550.5 18172.1 67378.4 67378.4 3696.35 697.383 62984.6
mass fractions
propylene 0.000 0.000 0.027 0.001 0.027 0.106 0.006 0.006 0.100 0.024 0.000
Propane 0.000 0.000 0.184 0.005 0.184 0.698 0.045 0.045 0.782 0.228 0.000
DIPE 0.000 0.000 0.014 0.002 0.014 0.008 0.016 0.016 0.113 0.668 0.003
isopropanol 0.003 0.000 0.582 0.080 0.582 0.159 0.696 0.696 0.002 0.032 0.745
diisopropyl 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
sulfate
water 0.048 0.310 0.192 0.048 0.192 0.028 0.237 0.237 0.003 0.048 0.252
isopropyl hydrogen sulfate 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
DMSO 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
sulfuric acid 0.949 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
caustic soda 0.000 0.690 0.000 0.066 0.000 0.000 0.000 0.000 0.000 0.000 0.000
sodium bisulfate 0.000 0.000 0.000 0.798 0.000 0.000 0.000 0.000 0.000 0.000 0.000
stream name units 23 24 25 26 27
temperature K 345 355 424 371 474
pressure bar 1.31 1.03421 1.31 1.03421 1.31
mass flows kg/h 132838 46923.2 148891 16053.1 132838
mass fractions
propylene 0.000 0.000 0.000 0.000 0.000
propane 0.000 0.000 0.000 0.000 0.000
DIPE 0.000 0.004 0.000 0.000 0.000
isopropanol 0.000 0.995 0.001 0.011 0.000
diisopropyl sulfate 0.000 0.000 0.000 0.000 0.000
water 0.000 0.000 0.107 0.989 0.000
isopropyl hydrogen sulfate 0.000 0.000 0.000 0.000 0.000
DMSO 1.000 0.000 0.892 0.000 1.000
sulfuric acid 0.000 0.000 0.000 0.000 0.000
caustic soda 0.000 0.000 0.000 0.000 0.000
sodium bisulfate 0.000 0.000 0.000 0.000 0.000

Table A3. Stream Table of Direct Hydration Process

stream name units 1 2 3 4 5 6 7 8 9 10 11

temperature K 316 323 395 308 308 311 543 508 437 437 437
pressure bar 17.51 17.51 151.99 1.01 1.01 151.99 151.99 151.99 151.99 17.37 17.37
mass flows kg/h 43703.8 54918.3 54918.3 12610.7 50010.4 50010.4 50010.4 104928 104928 16374.8 88553.7
mass fractions
propylene 0.948 0.754 0.754 0.000 0.000 0.000 0.000 0.118 0.118 0.280 0.089
propane 0.052 0.046 0.046 0.000 0.000 0.000 0.000 0.024 0.024 0.051 0.019
DIPE 0.000 0.047 0.047 1.000 1.000 1.000 1.000 0.384 0.384 0.158 0.425
isopropanol 0.000 0.148 0.148 0.000 0.000 0.000 0.000 0.468 0.468 0.495 0.463
water 0.000 0.005 0.005 0.000 0.000 0.000 0.000 0.006 0.006 0.015 0.004
DMSO 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
stream name units 12 13 14 15 16 17 18 19 20 21 22 23
temperature K 328 316 446 316 316 403 345 356 416 374 474 308
pressure bar 17.37 17.24 17.51 5.07 5.07 5.34 1.31 1.03 1.31 1.03 1.31 1.01
mass flows kg/h 16374.8 5160.17 11214.6 10020.5 226.813 78306.3 221015 40779.4 258415 37399.7 221015 37399.7
mass fractions
propylene 0.280 0.888 0.000 0.777 0.244 0.000 0.000 0.000 0.000 0.000 0.000 0.000
propane 0.051 0.112 0.023 0.169 0.064 0.000 0.000 0.000 0.000 0.000 0.000 0.000

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ACS Sustainable Chemistry & Engineering Research Article

Table A3. continued

stream name units 12 13 14 15 16 17 18 19 20 21 22 23
DIPE 0.158 0.000 0.231 0.003 0.079 0.480 0.000 0.002 0.145 1.000 0.001 1.000
isopropanol 0.495 0.000 0.723 0.020 0.462 0.520 0.000 0.998 0.000 0.000 0.000 0.000
water 0.015 0.000 0.022 0.032 0.151 0.000 0.000 0.000 0.000 0.000 0.000 0.000
DMSO 0.000 0.000 0.000 0.000 0.000 0.000 1.000 0.000 0.855 0.000 0.999 0.000

Table A4. Stream Table of Acetone Hydrogenation Process

stream name units 1 2 3 4 5 6 7 8
temperature K 323 380 365 373 293 295 373 373
pressure bar 20 30 30 30 1.01325 30 30 30
mass flows kg/h 2623.95 2623.95 3352.72 3352.72 44876.2 44876.2 44876.2 48228.9
mass fractions
hydrogen 1.000 1.000 1.000 1.000 0.000 0.000 0.000 0.038
acetone 0.000 0.000 0.000 0.000 0.987 0.987 0.987 0.001
isopropanol 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.948
water 0.000 0.000 0.000 0.000 0.013 0.013 0.013 0.012
2-hexanol 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001
stream name units 9 10 11 12 13 14 15 16
temperature K 373 373 313 313 313 313 313 368
pressure bar 30 30 30 30 30 30 30 30
mass flows kg/h 6223.04 42005.9 6223.04 2103.13 4119.91 728.773 1374.35 46125.8
mass fractions
HYDRO-01 0.289 0.000 0.289 0.855 0.000 1.000 0.77851 0.000
ACETO-01 0.002 0.001 0.002 0.002 0.002 0.000 0.00237 0.001
ISOPR-01 0.697 0.986 0.697 0.140 0.981 0.000 0.21405 0.985
WATER 0.012 0.012 0.012 0.003 0.017 0.000 0.00507 0.012
HEXYL-01 0.000 0.001 0.000 0.000 0.000 0.000 5.5 × 10−09 0.001

■ AUTHOR INFORMATION
Corresponding Author
IChemE/Elsevier: Amsterdam, 2017; DOI: 10.1016/B978-0-12-
809823-3.00002-3.
(10) El-Halwagi, M. M. A return on investment metric for
*E-mail: [email protected]. incorporating sustainability in process integration and improvement
ORCID projects. Clean Technol. Environ. Clean Technol. Environ. Policy 2017,
Mahmoud M. El-Halwagi: 0000-0002-0020-2281 19 (2), 611−617.
(11) Guillen-Cuevas, K.; Ortiz-Espinoza, A. P.; Ozinan, E.; Jiménez-
Notes Gutiérrez, A.; Kazantzis, N. K.; El-Halwagi, M. M. Incorporation of
The authors declare no competing financial interest. safety and sustainability in conceptual design via a return on

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