Swansea University: Ethanolamines Production Report, Process Analysis

This report, prepared by a team from Swansea University's College of Engineering, evaluates various routes for ethanolamines production, focusing on a plant with a capacity of 10,000 tonnes/year. The study compares three primary production methods: the Naphtha and Ammonia Route, the SRI process, and the Anhydrous Ammonia Route. The report delves into the specifics of each process, detailing steps such as naphtha desulphurization, cracking, oxidation, and reaction with ammonia. The SRI process is identified as the optimal route, based on parameters including reactants, product purity, plant costs, profit, cost management, and safety. The report includes detailed mass and energy balances, covering zones like ammonia stripping, evaporation, water dehydration, and MEA/DEA/TEA distillation. Safety considerations, such as handling ethylene oxide and implementing relief valve systems, are also discussed. The analysis incorporates figures, tables, and appendices with process flow diagrams, mass balance results, and HAZID analysis, providing a comprehensive overview of ethanolamines production.

College of Engineering
Swansea University
Team 6
Saeed Koleed 941727
Abdulla Alsaif 941890
Aisha Al-Kubaisi 942033
Will Smallwood 920942
Zaynat Awoyemi 876292
Production of 10,000 tonnes/year of ethanolamines
Date of Report: 10/12/2019
Date of Report: 10/12/2019

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Summary
Ethanolamine are organic substances that used in various industry depending on the type;
it is used in manufacturing detergents, personal care products, gas purification, as emulsifiers,
preservatives in wood industry, as construction chemicals and more other. However, 40% of its
uses falls under manufacturing of detergents. Ethanolamine was first produced in 1930 and the
global demand of the product has been growing every year. The growth of the ethanolamine
industry increased to $3.06 billion in 2016 and is expected to hit $4.91 billion in 2026. These
increased market demand is as a result of increasing demand of personal care products and
detergents in different parts of the world with Asia countries taking the largest share because of
the anticipated increase in disposable income in Asian countries.
Ethanolamine is produced in various countries with North America, China and Europe
being the leading manufacturers of the product. The three regions are also the leading
consumers. However, China and other Asian countries are expected to lead in consumption of
Ethanolamine in the next 3 years.
In this report, the study objective is to compare routes for manufacturing the product. The
routes used to produce Ethanolamine Are Naphtha and Ammonia Route, SRI process and
anhydrous ammonia route. Naphtha has four steps of producing Ethanolamine; Desulphurization
of Naphtha where Naphtha is pre-treated to remove Sulphur that affects the working of catalyst,
Cracking of Naphtha to ethylene ¸ Oxidation of ethylene to ethylene oxide and lastly reacting
ethylene oxide with ammonia to give Ethanolamine. The second route SRI Production Route;
the process involves production of Ethanolamine by mixing ethylene oxide with ammonia. The
third route is Anhydrous Ammonia Route where Ethanolamine is produced through reacting an
excess of an anhydrous ammonia solvent and ethylene oxide with a recycle of MEA and
ammonia in ratio of 1:15-30:1-5 with reaction temperatures of 40-700C.
The study determined the best route using 5 parameters namely; reactants, purity of
products, plants cost, profit and cost management of the process and safety concerns of the
method. The study used a table to compare the three routes by ranking every parameter as either
1, 2 or 3 based on the reactions process and analysis. SRI process appeared the best route to use
in production of Ethanolamine. The routes proved to be economical, safe and has the best purity
of the Ethanolamine.

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TABLE OF CONTENTS
Summary......................................................................................................................................ii
List of figures................................................................................................................................v
List of tables.................................................................................................................................v
Safety...........................................................................................................................................vi
1.0 Introduction to Product and Markets....................................................................................1
1.1 Location of Plant....................................................................................................................3
2.0 PROCESS SELECTION.......................................................................................................4
2.1 Desulphurization of Naphtha:................................................................................................5
2.1.1. Cracking of Naphtha to ethylene...................................................................................5
2.1.2. Oxidation of ethylene to ethylene oxide.......................................................................6
2.1.3. Ethanolamine production..............................................................................................6
3.0 SRI Production Route............................................................................................................6
3.1 Anhydrous Ammonia Route..................................................................................................9
3.2 Selection Best Production Method......................................................................................11
4.0 Mass balance........................................................................................................................13
4.1 Ammonia Stripper Zone......................................................................................................17
4.2 Ammonia Evaporation Zone................................................................................................19
4.3 Water Dehydration Zone.....................................................................................................21
4.4 Mixing Tank (V-101) Zone.................................................................................................23
4.5 MEA Distillation Zone........................................................................................................24
4.6 DEA and TEA Distillations Zone........................................................................................26
4.7 Scale up to achieve required operation................................................................................28

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5.0 Energy balance of SRI production method..............................................................................29
5.1 Thermal properties A.......................................................................................................29
5.2 Theory..............................................................................................................................29
5.3 Adiabatic mixer energy balance......................................................................................31
Reference...................................................................................................................................33
Appendix 1: Final Process Flow Diagram (PFD) of Ethanolamines plant................................34
Appendix 2: Actual Mass Balance Results................................................................................35
Appendix 3: Molar and Total Enthalpy Calculations Results for all streams...........................37
Appendix 4: HAZID..................................................................................................................41

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List of figures
Figure 1: The world consumption of ethanolamine products (IHS Markit, 2018).........................2
Figure 2: European ethanolamine prices between May 2012 and May 2013 (Meehan, 2013).......3
Figure 1: The ethanolamine reactor zone......................................................................................14
Figure 2: The ammonia stripper zone............................................................................................18
Figure 3: The ammonia evaporation zone.....................................................................................20
Figure 4: The water dehydration zone (ZAHEDI, & AMRAEI, 2011).........................................22
Figure 5: The ammonia absorption zone.......................................................................................23
Figure 6: The MEA distillation zone.............................................................................................25
Figure 7: The DEA and TEA distillations zone.............................................................................27
List of tables
Table 1: comparison between Naphtha and ammonia route, SRI process route and anhydrous
ammonia rout of producing ethanolamine(s).................................................................................11
Table 3: The summary result of molar flowrate of ammonia stripper zone..................................19
Table 4: The summary result of molar flowrate of ammonia evaporation zone...........................21
Table 5: The summary result of molar flowrate of water dehydration zone.................................23
Table 6: The summary result of the ammonia absorption zone.....................................................24
Table 7: the summary results of molar flowrate of the MEA distillation zone.............................26
Table 8: the summary results of molar flowrate of the EA and TEA distillations zone................28
Table 9: Thermal properties of all materials in the plant...............................................................29
Table 10: the result of heat flow enthalpies of inlet and outlet of each equipment and heat duty of
each equipment..............................................................................................................................31

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Safety
The system for reactions runs in various conditions driven by the economic factors and
needed product distribution. Safety considerations therefore is paramount. The first consideration
is the construction of pipe of ethylene oxide; EO is very reactive and it should be made in
location near the EO production facility in order to channel EO to the reactors directly. Another
concern is EO injection system which should be controlled by use of meter to avoid explosion.
The system should be fitted with a safe system to prevent a backflow of EO into ammonia
system. Gas blanket system must have N2 gas to prevent air from getting in to the tanks, CO2
reacts with Ethanolamine. Last consideration is the making of relief valve system to mitigate the
over-pressuring of the reactor system.

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1.0 Introduction to Product and Markets
Ethanolamines are organic substances with chemical formula CxHyNOz where the values
of x, y, and z are dependent on the type of ethanolamine (i.e. mono-ethanolamine (MEA), di-
ethanolamine (DEA), and tri-ethanolamine (TEA)) (Zahedi et al., 2009). MEA and TEA are
viscous, flammable, corrosive, colourless, and clear liquids with an odour similar to ammonia at
room temperature, whereas DEA is a crystalline solid (Frauenkron et al., 2012).
Industrially, they were first manufactured in the 1930s, but larger-scale production was
not achieved until 1945. They are widely used in a variety of important applications: gas
purification (i.e., purification of natural gas or naphtha from sulphide compounds such as
hydrogen sulphide), excavation of oil wells, corrosion inhibitors, manufacturing textiles, wood
preservation, surfactants in personal care products, manufacturing detergent, emulsifiers in
drilling, construction chemicals, manufacturing pharmaceuticals, gas purification from carbon
dioxide, and as cement additives. Of all mentioned uses, manufacturing detergent and personal
care products are responsible for the largest share of consumption in 2016 with more than 40%,
whereas usage for gas purification is just 8% (Ball et al., 2018).
The global ethanolamine industry is anticipated to grow from $3.06 billion in 2017 to
$4.91 billion in 2026 at a compound annual growth rate of 5.4%. Increased disposable income in
Asia and some other developing economies will contribute towards rising ethanolamine demand
due to increased demand for detergents and personal care products, which are the largest market
for ethanolamines, particularly MEA. However, fluctuations in raw material costs may affect
producers’ margins and therefore have a negative impact on growth in the ethanolamine market
(Research and Markets, 2018). Increased demand for personal care products, oil and gas
treatment agents, and herbicides is anticipated to result in moderate growth in demand for
ethanolamines in North America between 2017 and 2022 (IHS Markit, 2018).
Many countries manufacture ethanolamine products such as Germany, Russia, Iran,
China, USA, Malaysia, South Korea, Mexico, Brazil, Saudi Arabia, India, Taiwan, Japan,
France, and Belgium. In 2023, the global production rate of ethanolamines is expected to be in
the region of 2,459 thousand tons (Business Wire, 2018). Production is concentrated in China,
North America, and Europe. China added significant new production capacity between 2012 and

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2017 and will continue to add more to reduce reliance on imports and to meet increased demand.
Global ethanolamine consumption is anticipated to experience continued growth, which will be
driven mainly by demand in China (IHS Markit, 2018). There has also been increased production
capacity in the Middle East in recent years, the most significant of which was the opening of
Sadara Chemical’s plant in Saudi Arabia in 2017, meaning that the Middle East has become a
significant exporter of ethanolamines (IHS Markit, 2018).
In 2017, the USA was the largest consumer of ethanolamines, followed by China and then
Western Europe as shown in Figure 1.

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Figure 1: The world consumption of ethanolamine products (IHS Markit, 2018).
DEA is the least valuable of the three ethanolamines, with a price in May 2013 of $1461-1526
per ton. MEA and TEA were both significantly more valuable in May 2013, with prices quoted
as $1,897-1,949 per ton and $1,923-2013 per ton, respectively (Meehan, 2013). Therefore, due to
the low price of DEA, the production of DEA should be minimized as much as possible. In
addition, one of the major challenges currently facing the ethanolamine industry is health and
safety regulations, which has resulted in The European Commission banning the use of DEA in
cosmetics (Pandey & Pulindi, 2016).
1.1 Location of Plant
Rising demand for ethanolamines is likely to be driven by demand in Asia, particularly in
China, where consumption of ethanolamines is anticipated to increase strongly until 2022.
Significant new production capacity has also been added in recent years to reduce reliance on
imports. Therefore, China would be a suitable location for a plant producing 10,000 tons of
ethanolamines per year. This total production value is only a small fraction of the 2,459 thousand
Figure 2: European ethanolamine prices between May 2012 and May 2013 (Meehan,
2013).

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tons, which is expected to be produced by 2023, and due to healthy increases in domestic
ethanolamine demand in China, international exports may be unlikely.
2.0 PROCESS SELECTION
ion
technology routes of ethanolamine (Mennella et al., 2019)
This report study and compare just three important routes to produce ethanolamine
products which are naphtha and ammonia route, SRI process route and anhydrous ammonia rout
of producing ethanolamine
Naphtha and Ammonia Route Generally, the process can be applied through 4 main steps that
can be described as the following:

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2.1 Desulphurization of Naphtha:
The presence of sulphur in Naphtha can cause the deactivation of used catalyst via
upstream processes. Thus the removal process is critical to pre-treat the Naphtha. This process
can be called also as Hydrodesulphurization (HDS) or Acid Gas Removal (AGR). The HDS or
AGR can be defined as a catalytic reaction technology that is used commonly to remove sulphur
from Naphtha. The first step is reacting H2 (Hydrogen) with CH3SH (methyl mercaptan) that
considered as one of sulphur compounds in a reactor where the reaction produces CH4
(methane) and (hydrogen sulphide) over the catalyst NiMo/Al2O3 at operating conditions (350
C and 10 bar) where the reaction can be shown as follows: (Huertas et al., 2011)
𝐶𝐻3𝑆𝐻+𝐻2→𝐻2𝑆+𝐶𝐻4
The hydrogen sulphide is removed via absorption tower using ethanolamine (i.e., solvent) as a
counter-current process at operating conditions (350 C and 1 bar) where the operation efficiency
is estimated at 75% (Huertas et al., 2011).
2.1.1. Cracking of Naphtha to ethylene
The first step is to pre-heating the feed stream of hydrocarbon in a heat exchanger and
mixed with steam. After that, the hydrocarbon with steam is heated to the initial cracking
temperature based on feedstock (500 ° C to 680 ° C). The third step is heating the feed inside the
reactor (commonly a fired tubular reactor) to the cracking temperatures (750° C to 875° C). In
this reactor, the hydrocarbon is cracked to smaller particles or molecules such as ethylene and
co-product. It is required to separate ethylene from other hydrocarbons products, so it is required
three distillations to separate other products from ethylene. The first distillation separates C4+
and C5+ components from inlet naphtha at operating conditions (50 ° C and 3 bar) as a bottom
stream, while the distillate that contains methane, hydrogen, and rest of naphtha components,
exits also at same operating conditions and inlet the second distillation. The second distillation
separates propane and propene from the inlet mixture as a bottom stream at operating conditions
(25 ° C and 5 bar), while the distillate stream contains methane, hydrogen, and rest of naphtha
components, exits also at same operating conditions and inlet the third distillation. The third one

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is used to separate ethylene from the inlet mixture as a distillate product where the operating
conditions of this distillation are (-20 ° C and 5 bar) (Haribal et al., 2018).
2.1.2. Oxidation of ethylene to ethylene oxide
The main target of this process is to produce ethylene oxide from ethylene; there are two
reactions occurred inside the reactor the first one is the main reaction (formation of ethylene
oxide), the second one is the side reaction (by-product). Silver metal is used as a catalyst, which
is unique in selectively catalyzing ethylene stimulation at high rates, and it is supported on
Alumina. The two reactions can be shown below: (Kestenbaum et al., 2002)
The required operating conditions of the reaction are (190 ° C and 19 bar), the ethylene reacts
with oxygen to produce ethylene oxide, and there are by-products (i.e., CO2 and water) and
some unreacted ethylene and oxygen due to the conversion is 20%. This product mixture exits
from, and then ethylene oxide separated from the mixture by introducing water inside a separator
at normal operating conditions (25 ° C and 1 bar) (Kestenbaum et al., 2002).
2.1.3. Ethanolamine production
In this step, ethanolamine is produced by the reaction between produced ethylene oxide
and ammonia, where the ammonia enters the reaction as aqueous ammonia with concentration
75% with pure ethylene oxide. The reaction occurs at high operating conditions (150 ° C and 180
bar), where the conversion of the reaction was found above 99% for ethylene oxide and 30% for
ammonia. After that, the product mixture passes through 5 distillations columns to separate
unreacted ammonia with water, MEA, DME, and TEA. The unreacted ammonia with water is
recycled again to the reactor (Hammer, & Reutemann, 1996).
3.0 SRI Production Route
SRI process for production is named after the Stanford Research Institute (SRI
International) that is an American nonprofit scientific research organization and institute. Also,
it is specialized to apply and perform client-sponsored developments and researches for private