Technology Profile

Ethanolamines from Ethylene Oxide and Ammonia

Ammonia (NH3i Steam reforming/
By Intratec Solutions Hydrogen,
nitrogen, ► synthesis/ NHt synthesis/
Naphtha, air.
ethylene oxide

thanolamines are a family of

ethylene oxide
1____£
alkoxylation alkoxylation

Steam reforming/ Partial oxidation/

E
compounds that are used Natural gas, air.
ethylene oxide
NH synthesis/ 3 NH synthesis/ 3
Coal, air,
ethylene oxide
alkoxylation alkoxylation
as feedstocks for emulsi­
fiers, detergents, corrosion Water, nitrogen,
inhibitors and chemical intermedi­
ethylene oxide
Electrotysjs/NH
synthesis/
alkoxylation
3
FT Oxygen-based
direct oxidation/
alkoxylation
Ethylene.
oxygen.
ammonia

ates, as well as used for scrubbing □ Raw material □ Process ■ Main product
carbon dioxide from exhaust gas. FIGURE 2. Several pathways exist for manufacturing ethanolamines, as shown here
The family includes monoetha-
nolamine (MEA), diethanolamine side reactions that generate some Production pathways
(DEA) and triethanolamine (TEA). heavy byproducts, which need to be Ethanolamines production is almost
As the names suggest, they can be separated in the purification section. exclusively based on the reaction of
thought as derivatives of ammonia The final product composition de­ ammonia with ethylene oxide, in such
in which the radical •CH2-CH2-OH pends exclusively on the molar ex­ a way that different ethanolamines
replaces one, two or three, respec­ cess of ammonia fed to the reactor. manufacturing routes are related to
tively, of the hydrogen atoms in the The reactor output comprises MEA, different sources of these raw materi­
base ammonia molecule. DEA and TEA, as well as unreacted als. Pathways for ethanolamines pro­
Ethanolamines combine interest­ ammonia dissolved in water and the duction are presented in Figure 2.
ing chemical properties exhibited by heavy byproducts.
both alcohols and amines. Under Ammonia recovery. The reaction Economic performance
acidic conditions, they may either product is fed to an ammonia strip­ The total operating cost (raw materi­
form acids, due to the presence of ping column for separating the ex­ als, utilities, fixed costs and depre­
a basic amine group, or esters, be­ cess ammonia present in the mix­ ciation costs) estimated to produce
cause of the hydroxyl group. MEA ture. Ammonia and water vapors ethanolamines was about $1,000
and DEA always yield salts if they are are recycled to the reaction, while per ton of ethanolamines (MEA :
in the presence of organic acids. the liquid bottom product is routed DEA : TEA, in a ratio of 1/3 : 1/3 :
to a two-stage evaporator and then 1/3) in the third quarter of 2015. The
The process to a dehydration column, where analysis was based on a plant con­
The following paragraphs describe a residual ammonia and water are structed in the U.S., with the capac­
process for ethanolamines produc­ separated from ethanolamines and ity to produce 120,000 metric ton
tion from ethylene oxide and am­ also recycled to the reaction area. per year of ethanolamines.
monia. The process comprises three Ethanolamines are withdrawn as the This column is based on "Etha­
major sections: (1) reaction, (2) am­ bottom product of the dehydration nolamines from Ethylene Oxide and
monia recovery, and (3) purification column and transferred to the purifi­ Ammonia - Cost Analysis,” a re­
(Figure 1). cation section. port published by Intratec. It can be
Reaction. Ammonia is mixed with Purification. The ammonia-free found at the following URL: www.
water to form an aqueous ammo­ ethanolamines are further separated intratec. us/analysis/monoethanol-
nia solution (45-55 wt.% ammo­ in three purification columns. Small amine-production-cost. ■
nia). Ammonia is supplied in excess amounts of MEA and DEA may also Edited by Scott Jenkins
to the reactor, so ethylene oxide is be recycled to the reactor to balance
Edfor's note: The content for this column is supplied
fully consumed in the reaction. Wa­ the desired output of each ethanol- by Intratec Solutions LLC (Houston; www.intratec.us) and
ter also plays an important role in amine — MEA : DEA : TEA ratios edted by Chemical Engineering. The analyses and models
accelerating the reaction. The reac­ of 1/3 : 1/3 : 1/3. A small stream of presented are prepared on the basis of publicly avaiable
and non-confidentral ntormation. The content represents
tions achieve yields in the range of heavy byproduct waste is separated the opinions of Intratec only. More information about the
98-99%. The balance is lost in minor in the TEA purification step. methodology lor preparing analysis can be found, along with
terms of use. at www.intratec.us/che.

:)f-A 1. Ammonia absorption

2. Alkoxylation reactor
Ammonia * * 3. Ammonia stripping column
4. Evaporator
5. Dehydration column
Water
© 6. MEA column
make-up
7. DEA column
Steam ► 8. TEA column
9. Cooling tower
Heavy
ends
10. Steam boiler
Ethylene
oxide cw * Q ® CW Cooling water
ST Steam

ST-0®
FIGURE 1. The production of ethanolamines from ethylene oxide and ammonia is shown here

32 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM SEPTEMBER 2019