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sc300121j Si 001
sc300121j Si 001
Number of Pages: 22
Number of Tables: 7
Number of Figures: 3
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Section A. Assumptions common to the simulations of the conventional PO/TBA, HPPO and
CEBC-PO Processes.
S2
Section B. Process Description of the Conventional PO/TBA Process
This process may be viewed in two parts (Figure S1) i-butane oxidation and propylene
epoxidation.
i-Butane oxidation reactor (Section A of Figure S1): Table S1 summarizes the mass flow rates of
the components entering and leaving i-butane oxidation and propylene epoxidation reactors and
the mass flow rates of components in the recycle streams. In Section A, recycled gases (i-butane,
butane) and make-up raw materials (i-butane and oxygen) are fed into six continuous stirred tank
reactors (CSTR) in parallel (total volume = 2143 m3).(6) i-Butane undergoes non-catalytic liquid-
phase oxidation to form t-butyl hydroperoxide (TBHP). Typical reaction conditions are 3 MPa at
135 °C with an average residence time of 10 h. Under optimized conditions, the i-butane
conversion is 37%, and the TBHP selectivity is 53 mol% based on i-butane consumption. A
major co-product of this step is t-butyl alcohol (TBA), with a selectivity of 41 mol% (based on i-
butane conversion).(7) The oxygen concentration in the liquid phase is kept below 4-7 mol%,
primarily for safety reasons.(8) Temperature control in the TBHP reactor is achieved by re-
The liquid phase containing product TBHP, t-butanol and dissolved i-butane and n-butane
exit the reactor from the bottom. The unreacted oxygen, nitrogen, undissolved i-butane and n-
butane exit the reactor through the overhead stream (vent gases). The vent gases are partially
condensed to recover and recycle (R1) the butanes (i-butane and n-butane) whereas the non-
condensable gases (nitrogen and small quantities of oxygen) are sent to a flare where the oxygen
is used to burn off the unrecovered light hydrocarbon gases. The liquid effluent stream exiting
the reactor is sent to the butanes column (P = 0.2 MPa, T = 78-134 °C) where the light ends (i-
butane, n-butane) and byproducts (acetone and methanol formed by the decomposition of TBHP)
S3
are separated from the TBA+TBHP mixture, which is sent to the propylene epoxidation
reactor.(9) The low concentration of methanol byproduct in the reactor effluent stream containing
TBHP may pose a safety concern. By preventing the build-up of methyl hydroperoxide in the
butane column (P = 0.6 MPa, T = 118-140 °C) are recycled whereas acetone and methanol are
separated by extractive distillation with water as the separation solvent.(11) Acetone is recovered
in the acetone column (P= 0.1 MPa, T= 56-84 °C) while methanol and water are separated by
simple distillation in methanol column (P= 0.1 MPa, T= 65-91 °C). In all these columns, cooling
Propylene Epoxidation (Section B): In the second step, the oxidant (TBHP dissolved in TBA,
from section A), make-up enriched propylene feedstock (propylene/propane ratio is 9:1), and
recycled gases (propylene/propane) are fed into four stirred tank reactors (total volume=1080 m3)
in parallel.(12), (13)
Propylene is selectively epoxidized by TBHP in the presence of a
homogeneous molybdenum-based catalyst at 121 °C and 3.5 MPa. For a residence time of 2 h,
the reported TBHP conversion is 98%, and the PO selectivity is 98.4% (based on converted
TBHP).(14), (15)
Temperature control in the propylene epoxidation reactor is achieved by
vaporizing and reflux-condensing the reaction mixture.(13) The non-condensable vapors from the
reflux condenser are sent for product separation to the propylene stripper.
The reactor effluent stream containing the unreacted reactants and products are recovered in
a train of distillation columns. The spent catalyst solution is recovered as bottom product from
the separation column (P = 0.4 MPa, T = 9-140 °C). The overhead stream from the separation
column is sent to a propylene stripper (P = 0.6 MPa, T = 3-70 °C) where propylene and propane
S4
are separated from PO, t-butanol and TBHP. The mixed propylene/propane stream is sent to a
propane stripper (P = 20 MPa, T = 50°C). The enriched propylene stream is recycled back to the
reactor (R2). PO is separated from the t-butanol and TBHP in the crude PO column (P = 0.2
MPa, T = 5-85 °C). The crude PO is further purified by distillation in a PO purification column
(P = 1.9 MPa, T = 54 °C). The condensers in the propylene stripper and crude PO column are
cooled with chilled water whereas the condensers in the separation column, propane column and
PO purification columns are cooled with ordinary cooling water. The byproduct/product weight
Figure S1: Process flow diagram for the conventional PO/TBA process: (A) i-Butane
oxidation; (B) Propylene oxide production. (7), (13), (12) Table S2 lists the simulation
parameters employed in this simulation and the compositions of the recycle (R1-2)
S5
Table S2: Simulation parameters for the conventional PO/TBA process.(7), (15), (16), (14)
Input/Output stream flow rates (lb/h) from the TBHP and PO reactors obtained from
HYSYS® simulation
TBHP production
Reaction Reactor: Six CSTRs in parallel
Conditions P= 3 MPa, T= 135 °C; Conversion (i-butane)= 36.9 mol%,
LHSV (Liquid Hourly Space Velocity)= 2.5 h-1
Catalyst Non-Catalytic
Product Selectivity TBHP= 53.4 mol%; TBA= 40.2 mol% (based on i-butane fed)
Propylene Epoxidation
Reaction Reactor: Four CSTRs in parallel
Conditions P= 3.5 MPa, T= 121 °C; Conversion (TBHP)= 98 %
Liquid Hourly Space Velocity (LHSV)= 5 h-1
Feed Composition : Propylene/Propane: 9/1
Catalyst 1.5% Mo Solution in TBA (165 ppm Mo in reaction mixture)
Product Selectivity PO= 98.4 mol% (based on TBHP consumed), 100 mol% (based on C3H6
consumed)
i-Butane Oxidation Propylene
Epoxidation
Mass Flow Rates Input Output Input Output R1 R2
Top Bottom
i-Butane 307340 757 193172 - - 193172 -
n-Butane 2640 167 2406 - - 2574 -
Oxygen 51700 440 - - - - -
Nitrogen 176 176 - - - - -
Methanol 33 - 3750 - - - -
Acetone 66 - 6765 - - - -
t-Butyl Alcohol 352 - 57590 136840 224940 350 -
t-Butyl 572 - 99770 99770 1995 570 -
Hydroperoxide
Propylene - - - 155980 110264 - 110264
Propane - - - 18898 18898 - 18898
Propylene Oxide - - - 1716 55200 - -
Refer to Figure S1 for stream identification (Rj)
S6
Section C. Process Description of the HPPO process
Due to the lack of published information on the amylanthraquinone process, this analysis
assumes that the oxidant (H2O2) is procured from an external supplier. The process flow diagram
of the modified HPPO process (hereafter referred to as HPPO process) is shown in Figure S2.
into three fixed-bed catalytic reactors connected in parallel (total volume = 900 m3).(18) The mass
flow rates of components entering and leaving the reactor are summarized in Table S3. A
and 2 MPa (Figure S2). The activity of the TS-1 catalyst gradually declines from an initial H2O2
conversion of 96% to 63% after two weeks, necessitating catalyst regeneration.(19) In this
analysis, roughly 90% of the H2O2 is utilized in the reactor for epoxidation while the remaining
10% unreacted H2O2 is safely decomposed. The selectivities toward PO and propylene glycol
(PG) are 95.5% and 4.5%, respectively.(16) In addition to PG, trace quantities of acetone, acetic
acid and formaldehyde are also formed as byproducts.(19) Temperature control in the PO reactor
is achieved by re-circulating part of the reaction mixture through a series of heat exchangers.
The bulk of the unreacted propylene and propane is recovered by simple depressurization in
propane and propylene. The value of this enriched propane stream is credited in this analysis.
The presence of unreacted H2O2 in the reactor effluent stream poses safety concerns. Methanol
and H2O2 mixtures can form an explosive vapor phase mixture during distillation. For purposes
of this economic analysis, we assume that the unreacted H2O2 (10 mol%) is safely decomposed
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stripper 1. The effluent from the decomposer is a gaseous mixture of oxygen and propylene
whose composition (1 wt% propylene) lies below the lower flammability limit (LFL) of the
mixture.(8) The liquid effluent stream from the H2O2 decomposer containing PO, propylene
glycol, methanol, water and dissolved propylene/propane is fed to a propylene stripper 2 (P = 1.2
MPa, T = 50 °C) where propylene and propane are recovered. The liquid phase from this unit is
sent to a PO stripper (P = 1.2 MPa, T = 47 °C). The methanol recovery column (P = 0.4 MPa, T
= 66 °C) and the wastewater column (P = 0.5 MPa, T = 94 °C) help with the separation of
methanol and propylene glycol. The condensers in all the distillation columns utilize cooling
water. It is believed that the commercial process incorporates a proprietary H2O2 recovery and
recycle technology, details of which are not yet available in the public domain. H2O2 recovery
obviates the need for deliberate H2O2 destruction and should improve the process economics.
S8
Figure S2: Process flow diagram for the HPPO Process.(17), (16) Table S3 lists the simulation
parameters employed in this simulation and the compositions of the recycle (R1-2).
(*) The C3H8-rich stream exiting from the overhead of the propylene stripper 1
S9
Table S3: Simulation parameters for the Hydrogen Peroxide/Propylene Oxide (HPPO)
Propylene Epoxidation
S10
Section D. Process Description of the CEBC-PO Process
Propylene Epoxidation: Table S4 lists the mass flow rates of components entering and leaving
the reactor. Along with fresh (99.99%) and recycled propylene, nitrogen, aqueous H2O2, make-
up catalyst, promoter and methanol are fed into a continuous stirred tank reactor (total volume =
1057 m3) fitted with a nano-filtration membrane.(22) The assumption of a nearly pure propylene
feed is based on the fact that our initial tests with the MTO/H2O2 system utilized pure propylene.
While this assumption would appear to handicap the CEBC-PO process economics, it
nevertheless helps in assessing to what extent the use of pure propylene feed affects the
economics. The CSTR volume for 90% H2O2 conversion is estimated from reported kinetic
parameters and PO selectivity (based on propylene) values of 99% (see Section F of the
Supporting Materials for details).(23), (22) The liquid hourly space velocity (LHSV) is estimated to
be 5 h-1. We assume that the total volume is divided equally into four reactors connected in
parallel. It is further assumed that the Re-based catalyst is bound to a soluble polymer support
and that the activity and selectivity of the polymer-bound catalyst are similar to the unbound
MTO catalyst. The size exclusivity of the nanofiltration membrane effectively retains the
polymer-bound catalyst in the reactor while allowing only the passage of smaller components
The bulk of the unreacted propylene is recovered by simple depressurization from the reactor
pressure of 2 MPa to 0.4 MPa in propylene stripper 1 (Figure S3). The H2O2 in the reactor
effluent stream (approximately 10%) is safely decomposed at 50°C to avoid flammable vapors in
the distillation columns prior to secondary recovery of the remaining unreacted propylene (in
propylene stripper 2), product PO and methanol. The effluent from this decomposer is a gaseous
mixture of oxygen and propylene whose composition (2 wt% propylene) lies below the lower
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flammability limit (LFL).(8) The effluent from the decomposer is sent to a PO stripper where the
product PO is recovered (P = 1.2 MPa, T = 56 °C). Methanol is separated from water in the
wastewater column (P = 0.3 MPa, T = 27 °C). The condensers in all the distillation columns
Figure S3: Process flow diagram for the CEBC-PO Process.(24), (22), (23)
Table S4 lists the
recycle (R1-2)
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Table S4: Simulation parameters for the CEBC-PO Process.(22), (23) Input/Output stream flow
rates (lb/h) for the PO reactors obtained from the HYSYS® simulation
Propylene Epoxidation
Reaction Conditions Reactor: Four CSTRs in parallel
P= 2 MPa; T= 40 °C; Liquid Hourly Space Velocity (LHSV)= 5 h-1
Conversion (H2O2)= 90%
S13
Section E. Impact Categories considered in this analysis and their descriptions
Table S5. Impact Categories considered in this analysis and their descriptions
Greenhouse Gas Change in atmospheric temperatures caused by the buildup of chemicals that
Emissions trap heat from the reflected sunlight that would have otherwise passed
out to earth’s atmosphere
Acidification Quantifies the potential emissions (such as SO2 and NOx) that increase the
acidity of water and soil systems
Ecotoxicity Quantifies the potential ecological harm of unit quantity of chemical released
into an evaluative (soil, water and air) environment
Human Health Estimates the potential of a chemical released into an evaluative environment
Cancer to cause human cancer effects
Human Health Estimates the potential of a chemical released into an evaluative environment
Non-Cancer to cause human non-cancer effects
Smog Air Estimates the potential of a chemical released to air to cause smog via
photochemical reactions
Ozone Depletion Estimates the potential of chemical released to air to destroy ozone based on
Potential chemical’s reactivity and lifetime
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Section F. Estimation of reactor volume for the CEBC-PO Process
The reactor is modeled as a CSTR and epoxide formation (represented by the following
C 3 H 6 ( A) + H 2 O2 ( B ) → C 3 H 6 O (C ) + H 2 O ( D)
The rate of hydrogen peroxide (limiting reagent) consumption at the operating conditions is
given by(25)
− rB = k ' C BV (1)
The steady state conversion of hydrogen peroxide (XB) is obtained from a material balance as
follows:
vX B
V = (2)
k ' (1 − X B )
Pseudo first order rate constant for the propylene epoxidation (k’) = 0.04752 h-1
S15
Section G. Methodology to extract the Environmental Impact Factors for TRACI from GaBi
The potential adverse environmental impacts caused by the fugitive emissions at the plant
are estimated using empirical equations available in literature. TRACI, environmental impact
factors used in the estimation of environmental impacts are extracted from GaBi® software using
2. Create a new process in the plan rather than using the existing USLCI datasets.
3. Define the various components that constitute as fugitive emissions as process streams in the
process.
4. Input the estimated quantitative data in the process and execute the plan.
The differences in the predicted and reported data (total waste generated) may be attributed
to the increase in fugitive emissions with the aging of flanges and other connections. Such
temporal variations in fugitive emissions from various unit operations is not accounted for by the
S16
Table S6. Comparison of emissions obtained from Toxic Release Inventory data for
LyondellBasell’s Bayport, TX facility and those predicted by GaBi® software.(27)
DCP: Dichlorophenoxyace, Eq.: Equivalent, N/A: Data not available in the toxic release
inventory
S17
Section H. Predicted cradle-to-gate environmental impact assessment
Table S7. Predicted cradle-to-gate environmental impacts for producing propylene oxide by the
conventional PO/TBA, HPPO and CEBC-PO processes
k’ pseudo first order constant for propylene epoxidation includes catalyst concentration, h-1
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010&trilib=TRIQ1&FLD=&FLD=RELLBY&FLD=TSFDSP&OFFDISPD=&OTHDISP
D=&ONDISPD=&OTHOFFD=.
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