Oxidation based

https://www.industry.usa.siemens.com/automation/us/en/process-
instrumentation-and-analytics/solutions-for-industry/oil-and-
gas/documents/ethylenoxid-oilgas-e.pdf

Ethylene oxide, C2H4O, is a colorless, flammable gas or liquid. Because of its

molecular structure ethylene oxide is one of the most versatile chemical
intermediates. Industrial production started in 1925 using the chlorohydrin
process and was improved in 1931 by introducing the much more economic
direct catalytic oxidation method. Currently, almost all ethylene oxide
production plants are based on the direct oxidation process with air or
oxygen.

The determination of the oxygen content of the process gas up- and downstream
of the reactor (ca. 8 % resp. 6 % O2, see measuring points 3 and 5 in fig. 2) is of
particular importance. Plant efficiency increases proportionally to the oxygen
content of the process gas and therefore, for economical reasons, the plant shall
be run at oxygen contents as high as possible, close to the explosion limit, but
still reliably distant from that. The distance to the explosion limit can be kept so
smaller and the plant efficiency so higher the more accurate and reliable the
oxygen measurement is performed. 1 % higher oxygen content in the process
gas will easily correspond with an additional production rate of several hundreds
of tons ethylene oxide per year. Therefore, the use of the best available oxygen
measuring technology, as offered by the Siemens OXYMAT analyzer series, is a
very economic decision. Usually the oxygen measurement is performed
redundantly with, for instance, three separate analyzers installed at
one measuring point.

steps
Feed of ethylene and oxygen into the reactor and oxidation of ethylene by
passing through the reactor (bundles of tubes packed with the catalyst material)
at 200 to 300 C. Together with ethylene oxide, CO2, H2O, and heat is generated
as well.
Cooling of the gas that leaves the reactor by means of steam generation or
direct heating of the gas inlet of the reactor.
Removal of ethylene oxide and CO2 from the gas by scrubbing with first water
and second an aqueous potassium carbonate solution. The ethylene oxide
dissolves in the solution.
Desorption of ethylene oxide from the solution in the desorber and stripping of
its low-boiling components.
Final distillation with separation into water and ethylene oxide. The process runs
continuously using a recycled gas stream through the reactors driven by
compressors, and reloaded before entering the reactor again.
http://www.ugr.es/~tep028/pqi/descargas/Industria%20quimica
%20organica/tema_5/oxido_etileno_a10_117.pdf process,reactor (in pdf)

http://www.chemengonline.com/ethylene-glycol-production/?printmode=1

Ethylene oxide production. Ethylene and oxygen are fed to a multi-tubular reactor,
forming EO. This exothermic reaction, conducted in fixed beds in the reactor tubes,
occurs in the gaseous phase with the use of a silver catalyst supported on alumina.
Steam is generated by the heat of reaction.

Ethylene oxide recovery. The reactor product stream is fed to the EO absorber for
lights removal by water quenching. Part of this gaseous overhead stream is recycled to
the reactor, while the other part is sent to a carbon-dioxide-removal unit composed of an
absorber and a stripper. In this unit, CO2 is separated to be used in ethylene carbonate
production.

A diluted EO stream removed from the absorber is fed to the EO stripper, where it is
concentrated and recovered in the overheads. The crude EO stream is condensed.
Residual light gases are recovered from it and recycled to the reactor. The resulting EO
stream is directed to the next section.

Ethylene glycol production and purification. Ethylene oxide is reacted with CO2,
forming ethylene carbonate, which is then hydrolyzed to form MEG and CO 2. Both
reactions are carried out in the liquid phase using homogeneous catalysts.

CO2 streams from the reaction steps are recycled to the ethylene carbonate reactor. MEG
is purified in two distillation columns where water is removed, leading to the final MEG
product. The catalyst is separated and recycled to the ethylene carbonate reactors.

http://lup.lub.lu.se/luur/download?func=downloadFile&recordOId=7363439&fileOId=7368695
(in pdf file, as 3. Containing chlorohydrins disadvantages)
https://www3.epa.gov/ttnchie1/le/ethoxy.pdf
( in pdf file, as 4 , containing three technology)

http://nptel.ac.in/courses/103103029/17 (plant pic- air based)

Ethylene oxide is produced by the oxidation of ethylene using air.

Air and ethylene are separate compressed and along with recycle stream are sent
to the shell and tube reactor.

The reactor is fed on the shell side with Dowtherm fluid that serves to maintain the
reaction temperature. A dowtherm fluid is a heat transfer fluid , which is a mixture of
two very stable compounds, biphenyl and diphenyl oxide. The fluid is dyed clear to
light yellow to aid in leak detection.

The hot dowtherm fluid from the reactor is sent to a waste heat recovery boiler to
generate steam.

The vapour stream is cooled using a integrated heat exchanger using the
unreacted vapour stream generated from an absorber.

The vapour stream is then sent to the heat integrated exchanger and is then sent
back to the reactor and a fraction of that is purged to eliminate the accumulation of
inerts such as Nitrogen and Argon.

The product vapors are compressed and sent to a water absorber which absorbs
ethylene oxide from the feed vapors. Eventually, the ethylene oxide rich water
stream is sent to a stripper which desorbs the ethylene oxide + water as vapour and
generates the regenerated water as bottom product. The regenerated water reaches
the absorber through a heat integrated exchanger.

The ethylene oxide + water vapour mixture is compressed (to about 4 - 5 atms)
and then sent to a stripper to generate light ends + H 2O as a top product and the
bottom product is then sent to another fractionators to produce ethylene oxide as
top product. The heavy ends are obtained as bottom product.

http://www.owlnet.rice.edu/~ceng403/gr1599/finalreport3.html

The oxygen-based process is chosen due to its many advantages. For all plant capacities and a given
type of catalyst, the oxygen-based reactor yields a higher selectivity and requires less catalyst (10).
Although the air-based process may cost lower to run (for small to medium-sized plants), the initial
building costs of the air-based plant is much more than the oxygen-based plant (10). While the
oxygen-based process requires a carbon dioxide removal section, more stainless steel, and some
expensive instrumentation, the air-based process requires more catalyst, more reactors (to achieve a
comparable selectivity), a multi-stage compressor, air purification units, a vent gas treating system,
and two to three reactor train in series (12).

This basic design contains the following parts: the reaction system, absorption system, CO2 Removal
Section, and EO purification system. This proposal focuses on developing and optimizing the reactor
system. (HAVE DETAILED )

https://hub.globalccsinstitute.com/publications/ccs-roadmap-industry-high-purity-
co2-sources-sectoral-assessment-%E2%80%93-final-draft-report-2

In direct oxidation, ethylene, compressed oxygen and recycle gas are mixed and fed to a multi-
tubular catalytic reactor. The mixture is passed over a silver oxide catalyst supported on a porous
carrier at 200300oC and 1030 bar. The reaction is highly exothermic and the heat removed can
be used to generate steam. The gases from the reactor are first cooled and passed through a
scrubber where the ethylene oxide is absorbed as a dilute aqueous solution. This process of
reactor gas stream clean up includes the removal of the CO2 using physical sorbents, Hot
Potassium Carbonate process such as the Benfield process, or cryogenic separation techniques
(see Section 2.4). The resulting high purity CO2stream is typically vented. The resulting ethylene
oxide can then go straight to ethylene glycol manufacture or purified by fractionation for use in
other ethylene oxide derivatives (Figure 9).

There is extremely limited data on the rates of CO2 generation in the production of ethylene
oxide. The stoichiometry of the process suggests it is produced at a ratio of 6/2 ethylene oxide to
CO2, which would mean that CO2 generation is about a third of total ethylene oxygen production.
In this case, around 6.2 Mt of high purity CO2 is produced annually from ethylene oxide
production. Other literature suggests that the concentration of CO 2 in the reactor gas is around
8% (Metz et al. 2005; see Table 8), suggesting around 1.5 Mt high purity CO2 production per
annum (see Section 3.1.3).
The dilute aqueous solutions of EO, CO2, and other volatile organic compounds
(VOC) from the absorbers are combined (Stream 9) and fed to the desorber
where the EO and dissolved inerts are distilled under reduced pressure. The
desorber water, virtually free of EO, is recirculated to the absorbers (Stream 10).
The crude EO from the desorber is then sent to a stripper for removal of CO2 and
inert gases and then sent to a final refining column. (Note that in some plants
the EO from the absorbers [Stream 9 in Figure 3] may go first into a stripper and
then into a light ends refractory column. The nomenclature is different but the
basic operations are the same.) Light gases separated in the stripper are vented
overhead (Vent B). The final product (Stream 11), 99.5 mole percent EO, is
stored under a nitrogen atmosphere in pressurized tanks. In some plants, crude
EO is sent directly to a glycol plant rather than undergoing complete refining.

Stripper

The stripper removes all of the remaining light gas impurities. It is a 24-tray
column with a condenser and reboiler. The distillate contains all of the gas
contaminants while the bottoms contains only water, EO and acetaldehyde. One
major problem with this column is that the condenser must be operated at -64.5C
in order to provide the necessary reflux for the separation. This means that
refrigerated water cannot be used. Due to time and project scope limitations, only a
preliminary investigation into coolants was conducted. Lewin et. al. suggest that
ethylene is a suitable refrigerant, but it would unfortunately increase costs.