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Energy Procedia 114 (2017) 7154 – 7161

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18

November 2016, Lausanne, Switzerland

Utilization of CO2 for Ethylene Oxide

Paul D. Mobleya, Jonathan E. Petersa, Nandita Akunuria, Joshua Hlebaka, Vijay Guptaa, Qinghe Zhenga, S. James
Zhoua, and Marty Lail*a
a
RTI Intenrational, 3040 Cornwallis Rd., Durham, North Carolina, USA, 27709

Abstract

A process for the utilization of CO2 for the conversion of ethylene to ethylene oxide has been studied for the greenhouse gas life
cycle analysis and compared to the commercial production of ethylene oxide which uses oxygen from an air-separation unit. Mixed-
metal oxides were identified and tested in a micro-reactor for ethylene oxide yield. The mixed-metal oxides were shown to produce
ethylene oxide under moderate conditions. Comparison of the single-pass yields of the CO2-utilizing route to the O2-utilizing route
shows that the CO2 utilizing route is similar in ethylene conversion and ethylene oxide yield.
© 2017
© 2017TheTheAuthors.
Authors. Published
Published by Elsevier
by Elsevier Ltd. Ltd.
This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of GHGT-13.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
Keywords: CO2 Utilization, ethylene oxide, ethylene

1. Introduction

A conventional hydrocarbon feedstock that could be of particular interest for CO2 Utilization is ethylene (Et).
Ethylene is produced at large scale and is converted into high value products with large markets.1 Researchers have
investigated its uses with CO2 in the past with both heterogeneous and homogenous catalysts. Early research efforts
found that it can be converted readily into propionic acid at high pressure.2 More recently it has been converted into
sodium acrylate at 80-100°C at moderate pressures (10-bar ethylene, 20 bar CO2).3-5 It has also been combined with
methanol and CO2 to make methylpropionate at approximately 40 bar and 160°C. 6 These carboxylation routes
represent promising utilization directions which incorporate the entire CO 2 moeity into an ethylene-derived product.
Alternatively, CO2 can be split by certain reduced metal complexes, resulting in a useful carbon monoxide product
stream and a metal oxide.7 Metal oxides can selectively oxidize ethylene to various products, ethylene oxide (EtO)

* Corresponding author. Tel.: +1-919-485-5703; fax: +1-919-541-8002.

E-mail address: mlail@rti.org

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.03.1878
 Paul D. Mobley et al. / Energy Procedia 114 (2017) 7154 – 7161 7155

being a particularly valuable one with a large market size.8 Major chemical makers worldwide (e.g., DOW Chemical,
Japan Catalytic Company, Shell International Chemicals, Sumitomo Chemical, BASF, Scientific Design)
manufacture EtO using several closely related industrial processes.9,10

2. Process Design and LCA

The chemical methodology by which EtO is currently produced is the partial oxidation of Et with oxygen (O2) using
a catalyst.11 Several mixed-metal oxides have been developed that can be used for Et epoxidation using CO2 instead
of O2. The mixed-metal oxides react with CO2 and remove an oxygen atom to produce EtO and carbon monoxide
(CO), which is a feedstock for many value-added chemicals.12,13 The general reaction scheme using the mixed-metal
oxide as an oxygen carrier is shown in Equations 1-3 below. Therefore, the two marketable product streams from the
process are EtO and CO, which are both valuable intermediates for the petrochemical industry.

Similar to the commercial process, an undesirable side reaction (Equations 4-6) in which Et is completely oxidized
to form CO2 and water was found to be unavoidable. The oxygen for non-selective combustion is derived from CO2,
so while the process ends up as a large consumer of CO2, it comes at the expense of the valuable Et feedstock. As a
result, this side reaction must be kept at a minimum to keep the techno-economics of the process favourable.

The reactions occur in a co-feed reactor, when both of the main reactants, CO2 and Et, are fed together into the main
reactor where the epoxidation and reduction reactions occur. The overall reaction is slightly endothermic. A process
model was developed using Aspen Plus with the aim of understanding the economic and technical feasibilities of the
process. The process flow diagram of the technology is shown in Figure 1. The process models were developed to
depict the overall process to produce 250,000 tonnes/yr of EtO.
7156 Paul D. Mobley et al. / Energy Procedia 114 (2017) 7154 – 7161

Figure 1. Process flow diagram for CO2 utilization approach for Et oxidation.

In the process, Et and CO2 are heated and expanded from pipeline pressures, mixed, and then further heated to
325°C. Additional external heat is supplied to the reactors to provide the heat required for the reactions to take
place. The co-feed reactor was assumed to be isothermal in the process model, and the heat duty of the reactor was
considered in the GHG life-cycle analysis (LCA). The EtO yield for the CO2-EtO process was considered to be 5%,
and the side reaction conversion was assumed to be 7% based on the mixed-metal oxide performance data obtained
experimentally. CO2 input to the CO2-EtO process obviously has the most impact in terms of GHG emissions
avoided compared with the conventional process. Because CO2 is one of the main reactants of the CO2-EtO process,
the amount of CO2 avoided is around 2.82 tonnes per tonne of EtO produced when compared with the conventional
processes.
The outlet gas stream contains a mixture of products (CO, EtO, and H2O), as well as the unreacted CO2 and Et. This
stream is used for partial reheating of the feed gases and is sent to a scrubbing section that uses H2O as the scrubbing
agent. Product EtO is recovered in the water stream exiting this section, and the H2O and EtO mixture is distilled to
recover EtO as the product, similar to conventional EtO production. The gas stream leaving the scrubbing section
with CO, CO2, and unconverted Et is sent to a CO2 capture system, where CO2 is captured and recycled to the co-
feed reactor. The outlet gas stream is a mixture of CO and Et and is sent to a cryogenic separation unit to condense
Et from the mixture and obtain a pure product stream of CO. Unconverted Et is recycled to the co-feed reactor. The
energy required for each separation step is included in the GHG LCA table below.

Table 1. GHG life-cycle analysis of CO2-EtO process.

Conventional Production CO2-EtO Production CO2-EtO GHG Benefit

(tonne CO2-e/tonne EtO) (tonne CO2-e/tonne EtO) (tonne CO2-e/tonne EtO)

Air Separation Unit 0.067 -- 0.067

Carbon Dioxide 0.352 -6.270 6.622

Ethylene Input 1.283 3.000 -1.717

Electricity 0.123 0.540 -0.417

Natural Gas 0.390 2.387 -1.997

 Paul D. Mobley et al. / Energy Procedia 114 (2017) 7154 – 7161 7157

CO Product -- -3.810 3.810

CO Purification 3.552 -3.552

Total 2.822

3. Experimental

Catalysts for the transformation of CO2 and ethylene were tested and characterized in three systems to evaluate
their ability to abstract an oxygen from CO2 and to transfer an oxygen to ethylene to produce EtO. The three systems
used for testing included a TA Instruments Q500 atmospheric thermogravimetric analyzer, a Cahn TherMax 500
high-pressure thermogravimetric analyzer (HP-TGA), and an automated microreactor which was fabricated in
house. The microreactor system consists of four main sections: feed gas generation, gas-switching valve, packed-bed
reactor, and downstream and gas analysis. The feed gas generation system consists of four mass flow controllers
(MFCs) for gas inputs and one syringe pump to feed water. Nitrogen, CO2, CO, air, and ethylene are supplied to the
unit from gas cylinders. CO2 can be switched with air as the feed gas by using a powered three-way valve. Pressure
regulators are used to regulate the delivery pressure to the gas MFCs at 24 barg. Upon preheating, the gases are
mixed and then routed to a six-port gas-switching valve that is used to direct the flow either through the reactor or
through a bypass. The packed-bed reactor has been designed as a conventional, down-flow packed-bed consisting of
catalyst material sandwiched between two layers of quartz wool and silicon carbide particles used as diluent. The
microreactor system is designed with the vaporizer, reactor, and six-port switching valve inside a hot box heated to
150°C to prevent condensation in the transfer lines between these components. The packed-bed reactor is
constructed from a half-inch outside diameter by 8-inch long, 316 stainless-steel tube (0.035-inch wall thickness).
The reactor is covered with a brass sleeve that is used to conduct heat from the band heaters to the reactor tubing
uniformly along its length. The temperature of the bed is measured by using a thermocouple enclosed in a protection
tube, with the tip positioned at the center of the bed. The bed is heated by a set of three 200-W clamp heaters that
cover the brass sleeve along the length of the reactor tube. The clamp heaters use the sleeve temperature, measured
by using a thermocouple inserted in the sleeve, to control the heating. The effluent from the reactor is sent to a back
pressure regulator (BPR). The BPR is used to control the pressure of the system measured by a pressure transducer
placed just upstream. The effluent from the pressure regulator is diluted in nitrogen and sent to an MKS Instruments
Fourier transform infrared (FTIR) multigas analyzer to measure the effluent composition. A process flow diagram
for the microreactor test system is given in Figure 2 below.
7158 Paul D. Mobley et al. / Energy Procedia 114 (2017) 7154 – 7161

PRV HP/LT mode

102
1000 psig
PRV LP/HT mode
104
FI 170 psig
N2 Purge PI PT To vent
102 TE
102 To vent
101B
FIC FC FCV TSET
105 105 105 TE TIC
TIC
101A 101
Drain TSH
TE TE
103A 103B JE TY
101 101
TE
H2O 102B Set at 1000
TSET PRV psig
F-105 TE TIC
TIC TY
P-101 103
102A 102 TSH 102 To vent
FIC FC FCV JE TY
101 101 101 JE
104 104 102
PT
Gas 1 TSET
TE 103
N2 TIC
104 104
A
TE
TSH PIC PSET
103
F-101 104B R-101 PSH

V-101 PY
FIC FC FCV 103
102 102 102
Set at 1000
Gas 2 psig
Air PRV AI AI
101
101 101
To vent

F-102 V-104 MKS FTIR

To Vent

F-106 V-102 F-103

A-101
Gas 3
CO2
P-41 TE
PI PT 150B
101 101 TSET TE TE TE TE TE TE
TE TIC
TIC 101B 102B 103B 104B 105B 150B
150A 150
FIC FC FCV TSH
103 103 103
TSS JE
TE JE TY 100B 100B
Gas 4 LT LIC LSET 150 150
Ethene 105A 101 101
TSET TSS JE
TIC TE LSH
105A LY 100A 100A
TSH 105
HX-101 101
F-103 TY JE
Drain TSS TSS TSS TSS TSS TSS
105 105
101B 102B 103B 104B 105B 150B
FCV
V-103
FIC FC
100 100 100

Gas 5
CO

F-100

Figure 2. Microreactor process flow diagram.

An FTIR multigas analyzer (MKS Instruments) is used to analyze the gas effluent stream from the reactor. The
effluent is diluted by adding 750 sccm of nitrogen before the analyzer to allow for enough flow to purge the sample
cell and to not saturate the detector. A method was developed to quantify the effluent composition of the following
components: CO, CO2, ethylene, EtO, and H2O. Calibration data for CO, CO2, EtO, and H2O were available in the
MKS spectra library to develop calibration curves for each component within the expected volume percent ranges
and verified with known gas mixtures. Unique spectral bands were identified for each component to minimize
analytical interference with other components.

4. Results and Discussion

A large number of mixed-metal oxides have been screened and tested in a fixed-bed, high pressure reactor, for the
catalyst’s Et conversion and EtO selectivity. To our knowledge, no one has reported or investigated the utilization of
CO2 for EtO production before our work began in 2012 during Round 1 of the CCEMC Grand Challenge. Extensive
surveys of both the patent literature and the academic literature reveal no previously published work at all in this
area. Two primary formulations performed better than all others tested, and patents are pending for those
formulations.
Thermodynamically, several reduced metals can be oxidized by CO2 to make CO.14 Thermogravimetric analysis
was performed on mixed-metal oxides of metals which were thermodynamically favoured to observe the highest
capacities empirically. Tests were conducted by heating mixed-metal oxides to 800°C in 10 vol% flowing CO and 1
atm total pressure (balance Ar). After observing weight loss the gas was switched to CO 2 and weight gains were
observed. For the best performing materials, reduction resulted in loss of more than 10% of the oxygen in the
catalyst as shown in Figure 3 below, with approximately 7% of the weight regained upon exposure of the reduced
metal to CO2. These metal oxides were also able to show weight gain at 575°C and 19.3 barg (280 psig) CO2 in the
HP-TGA.
 Paul D. Mobley et al. / Energy Procedia 114 (2017) 7154 – 7161 7159

Figure 3. Thermogravimetric analysis of reduction and oxidation of mixed-metal oxide using CO reducing gas and CO2 oxidant.

The catalyst activity and performance was observed for a large number of process conditions (ethylene and CO 2
pressures, temperatures, flow rates, modes of reactor operation) using the micro-reactor described above. An
example raw data set is shown in Figure 4 Error! Reference source not found.to illustrate the trends observed for the
catalysts from automated micro-reactor screening. The chart in the middle is the ethylene oxide signal monitored
through an IR-based multi-gas analyzer. The data set shows 10 evaluations each at a different condition with a
catalyst regeneration step occurring in between. The catalyst was able to be regenerated between cycles and was
active for ~40 mins but the EtO production declined slowly indicating possible catalyst degradation, which needs to
be studied and addressed.

Figure 4. Example parametric test results from micro-reactor testing of the CO2-EtO catalysts. Middle graph shows multi-gas analyser detection
of EtO.
7160 Paul D. Mobley et al. / Energy Procedia 114 (2017) 7154 – 7161

Parametric testing was completed for the top performing catalysts from screening tests to optimize the reaction
conditions for the highest EtO yield. Figure 5 shows the single-pass yield of EtO as a function of percent conversion.
The EtO yield was highest at between 5.0 % and 7.5% between 300°C and 325°C. A comparison of the EtO yield
and Et conversion reported in academic studies and commercial processes using O 2 to RTI’s catalysts using CO2 are
presented in the figure.15-17 For both the conventional process using O 2 and the RTI process using CO2, the
remainder of the Et conversion is lost to the competing side reaction of Et oxidation to CO2. The CO2-utilizing EtO
process compares well with catalysts reported in the literature.

Figure 5. Comparison of literature data for conventional catalysts for O2-based ethylene oxide process compared to novel mixed-metal oxides for
CO2-based ethylene oxide process.

5. Conclusions

A CO2 utilization process for the transformation of CO2 and ethylene to ethylene oxide and CO has been identified.
A life cycle analysis of the process compared to the conventional ethylene oxide production process using oxygen
shows a GHG benefit of 2.822 tonnes CO2/ tonne EtO produced. Several catalyst compositions that can achieve the
conversion at temperatures below 400°C have been discovered. These materials compare well to catalysts which
require the use of oxygen for the process rather than CO 2.

Acknowledgements

The authors would like to acknowledge the Climate Change and Emissions Management Corporation (CCEMC) for
funding during Round 1 of the CCEMC Grand Challenge (Project Number K130115), and especially our Project
Advisor Mark Summers.

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