Department of Chemical Engineering

University of San Carlos – Technological Center

Nasipit, Talamban, Cebu City

A Separation System Design Project

for Production of Ethylhexanol from Propylene and Synthesis

in partial submission of the requirements of the course

ChE 421N Separation Processes

is submitted to

Dr. Camilla Flor Y. Lobarbio

Chemical Engineering Faculty

by

Cos, Syra Jeane R

Gollem, Babe Eden Joy.

Mondares, Mevicci

March 29, 2017

 I. Introduction

The most widely used workhorse or plasticizer alcohol for polyvinyl chloride (PVC),
mainly di-octyl phthalate (DOP) is 2-ehtylhexanol. It is a valuable intermediate product for the
chemical industries. It is used as a low volatility solvent for resins, waxes, animal fats, vegetable
oils, disinfectants and insecticidal sprays, and petroleum derivatives (ICIS, 2007).

2-ethylhexanol is a derivative of butyraldehyde made from propylene by hydroformylation

process. From the early 1940s until the early 1980s, the world’s major producers of 2-ethylhexanol
operated propylene hydroformylation processes for producing the required butyraldehyde using a
cobal catalyst system (Ashley & Tudor, 2007).

The design focuses on the production of the ethylhexanol from propylene and synthesis
gas. We need to design a plant in order to produce 40,000 metric tons per year of 2-ethylhexanol.
It is assumed to have an operating period of 8000 hours on stream. The design requirements will
include a material balance for the whole process, process flow scheme for the plant indicating the
general flow of the processes and equipment and energy balances for the hydroformylation reactor
and the cracking reactor. It also include both chemical engineering design and mechanical design
of the second distillation unit.

Process Description

(a) Hydroformylation

This is the first step of the process. The reactor operates at 130°C and 350 bar which uses
cobalt carbonyl as a catalyst in solution. Cobalt carbonyl catalyst is commercially used for
homogeneous hydroformylation.The feeds entering the reactor are synthesis gas, which is a
mixture of carbon dioxide and hydrogen mixture, and propylene in the molar ratio of 2 is to 1, and
the recycled products of isobutyraldehyde cracking. The main products are n- and
isobutyraldehyde with a ratio of 4:1. Three percent of the propylene feed is converted to propane.
In the reactor, 6% of the n-butyraldehyde product is reduced to n-butanol, 4% of the
isobutyraldehyde product is reduced to isobutanol, and other reactions occur to a small extent
yielding heavy ends to the extent of 1% by weight of the butanol mixture at the reactor exit.

(b) Gas-Liquid Separator 1 & 2

 Following the hydroformylation reactor is the gas-liquid separator which operates at 30
bar. The liquid phase is heated with steam. The second separator operates at 1 atm. The products
are composed of two separate streams – the liquid phase stream and the gas phase stream. The
liquid phase product stream consists of aldehydes, alcohols, heavy ends and water while the gas
phase stream consists of the propane, propylene, carbon monoxide, and hydrogen.

(c) Distillation Column 1

The liquid phase mixture passes to a distillation column which gives a top product of mixed
butyraldehydes and a bottom product of alcohols.

(d) Distillation Column 2

The mixed butyraldehydes enters the distillation column 2 which yields two separate
streams: (a) n-butyraldehyde having 1.2% mol isobutyraldehyde and (b) isobutyraldehyde having
1.3% mol n-butyraldehyde.

(e) Cracker

The isobutyraldehyde from distillation Column 2 enters the cracker unit which converts
80% of the feed to propylene, carbon monoxide and hydrogen. These cracked gas are recycled to
the oxo – reactor.

(f) Separator 3

The bottom product from the cracker enters a separator which separates water and the
unreacted isobutyraldehyde. The unreacted isobutyraldehyde is recycled to the cracker inlet.

(g) Aldolization Reactor

The n-butyraldehyde product stream from distillation column 2 and 2% by weight of NaOH
enter the aldolization reactor which yield products of 2-ethylhexanal and unreacted n-
butyraldehyde.

(h) Separator 4

The products from aldolization reactor enters the separator which separates unreacted n-
butyraldehyde and 2-ethylhexanal.
 (i) Hydrogen Reactor

The 2-ethylhexanal from the separator is reduced to 2-ethylhexanol by hydrogen and Raney
Ni catalyst. The percent recovery of 2-ethylhexanal is 99.8 % at purity of 99% by weight.

Four Methods of Preparation

The methods of preparation are listed below:
(a) Acetaldehyde process
This route starts from ethylene. It operates at atmospheric pressure. First, oxidizing
ethylene to acetaldehyde is done. Then, it is converted to crotonaldehyde via aldol reaction and
hydrogenated to n-butyraldehyde.
(b) Oxo process
One of the processes that gained worldwide importance is the Oxo synthesis for the
production of aldehydes and alcohols. This process of producing 2-ethylhexanol includes three
steps of conversions which are the following: (1) hydroformylation, (2) aldolization, and (3)
hydrogenation.
(c) Aldox process
This process involves addition of co-catalyst to the hydroformylation catalyst. The purpose
of adding a co-catalyst is for it to favor the aldolization reaction. This co-catalyst may be zince
acetylacetonate or magnesium ethylate for unmodified cobalt base systems (Chauvel & Lefebvre,
1986).
(d) Shell variant process
This process operates at lower pressure and higher selectivity. However, it has lower
reaction velocity and part of the propylene is converted to propane. In this process, potassium for
cobalt or phosphine catalysts are employed (Chauvel & Lefebvre, 1986).
Selection of Process:
The oxo process is predominant among the four processes producing 2-ethylhexanol. Huge
production of ethanol is needed in the first process (acetaldehyde). However, it is only possible if
large scale production of ethanol from biological sources. Aldox and shell variant processes are
still under development.
In oxo process, the main products are normal butyraldehyde and iso-butyraldehyde. The n-
butyraldehyde is highly valued than the latter. One of the principal reasons for employing this
technique of hydroformylation is that of a second stage process using hydrogen can convert
aldehydes from the standard hydroformylation process into the so-called oxo alcohols, which are
of great industrial significance (Smith, 1975). A large quantity of oxo-aldehydes obtained
industrially via hydroformylation are converted to higher alcohols, used mainly for plasticizers.
Over 75% of the industrial units for oxo-aldehydes produce butyraldehydes using propylene as
feedstock (Optience, n.d.). The economic superiority of the oxo route compared to those based on
ethylene is due to the more favorable yields, the lower price of propylene compared to ethylene
and the low cost of n-butyraldehyde from large modern oxo plants (Dekker, 1984).
II. Material Selection for Distillation Column 2
A material has attributes: its density, strength, cost, resistance to corrosion and so forth. A
design demands a certain profile of these: a low density, a high strength and a modest cost. It is
important to start with the full menu of materials in mind. The tasks are to identify the desired
attribute profile and to compare it with those of real engineering materials to find the best match
(Ashby, 2005).

One method for selecting material is by Michael F. Ashby whose method includes
translation of the design requirements to specification of materials. The conditions for selecting a
material is defined by the function, constraints, objectives and free variables. It is then followed
by screening-out the materials that fail the constraints. The third step is the ranking of the materials
by their ability to meet the objectives. The last step is seeking the supporting information for the
material candidates.
 All Materials

Screening

Ranking

Supporting Information

Final Material Choice

Figure 1. The strategy for materials selection (Ashby, 2005)

A. Material Performance Requirements
The material performance requirements can be divided into five broad categories, namely
functional requirements, process requirements, cost, reliability, and resistance to service
conditions (Kutz, 2002).
B. Performance Requirements for Distillation Column
Distillation column 2 operates at atmospheric pressure and 72°C.
The material performance requirements considered for the design of the second distillation
column unit are shown in the following table.
Table 2. Performance requirements for the distillation column unit
Performance Requirements Properties to be considered
For separation of the different components in a fluid by
Functionalilty using their difference in boiling point; unit must be
inexpensive
Processability Machinability and shape
The availability of material for construction and a
Cost
minimized cost
Ability to withstand the internal pressure from the feed
Reliability
and column internals
High pressure, ambient temperature, noncorrosive
Resistance to service conditions
components inside the equipment
C. Quantitative Method for Initial Screening
The material performance requirements can be referred from the laid out service conditions of
our equipment.
Table 3. Service conditions of the distillation column unit
Primary Performance Secondary Performance
Service Conditions
Requirements Requirements

Operates at ambient pressure, Able to withstand pressures Resistant to corrosion

at round 72°C of at least 1 bar

Operates at high pressures: 1

atm

We, the designers, prioritize the distillation column’s one with a minimized cost-to-density
ratio.
Table 3. Design requirements for the distillation column
Function To contain pressure safety
Select material that is inexpensive but safe
Objective
Able to withstand wind load, feed load and column internal load
Constraints Size and geometry of distillation column
Free Variable To select choice of material

D. Screening
It is particularly critical to choose a material that is capable to withstand such operating
conditions since the reactions occurs at ambient temperature and relatively high pressure. The
design requirements also dictate the material to corrosion resistant.

A set of possible materials can withstand the temperature, pressure and the load of the
wind, feed and column internals with the given operating conditions of the distillation column.
Shown in Table 4 are the options of material selection for the construction of the column.

Table 4. Possible materials for the construction of distillation column

Aluminum alloy Lead alloy Stainless steel
Carbon steel Low alloy steel Titanium alloy
Cast iron Magnesium alloy Tungsten alloy
Copper alloy Nickel alloy Zinc alloy
 The largest pressure is carried by the material with the greatest value of:

𝑀1 = 𝐾1𝑐

A greater security is obtained by requiring that the crack will not propagate even if the
stress reaches the general yield stress. The vessel will deform stably in a way that can be detected.
The leak-before-break criterion is given by the equation below:

𝐾1𝑐 2
𝑀2 =
𝜎𝑦

The maximum pressure is carried most safely by the material by meeting this criterion. M1
and M2 could be made large by making the yield strength of the wall 𝜎𝑦 , very small. The reason
for this is because the column wall must be thin as possible for economic purposes and for it to be
kept light.

The thinnest wall is that with the largest yield strength, 𝜎𝑦 . This is achieved by meeting the
criterion below:

𝑀3 = 𝜎𝑦
 These selection criteria are explored by using the chart in Figure 1.

M3
M1

M2

Figure 1. Fracture toughness against yield strength chart (Design, 2009)

In Figure 1, the indices M1, M2, and M3 appear as lines of slope 0, 1, ½. The search region
marked as in the figure suggests that the materials appropriate for the process include low alloy
steels, stainless steels, copper alloys and nickel alloys. From the figure, these materials appropriate
for the process lie towards the upper left hand corner of the intersection of the lines. The rest of
the candidate metallic materials are eliminated in the process of screening.
E. Ranking

The economical aspect should be considered as well together with the material integrity.
The chart below served as a guide for the selection process into choosing the optimum
material.

Figure 1. Ashby chart: approximate cost per unit mass against material class (Design, 2009)

The data presented in the figure above is translated into numerical values. These values are
tabulated in Table 6 applying the cost per unit property method.
Table 6. Cost of each material per unit mass
Material Price, US $/kg
Low Alloy Steels 0.3 – 1.0
Stainless Steels 2.6 – 10.1
Copper Alloys 2.0 – 5.0
Nickel Alloys 4.2 – 22.0

F. Selection of Appropriate Material

Low alloy steel is the suitable material of construction for the distillation column unit of
butyraldehyde mixture from the analysis and screening of the possible materials. A specific type
of low alloy steel was chosen to account for the effect of pressure. The selected type of low alloy
steel must be of the highest maximum allowable stress which is expressed in terms of MPa.
Among the types of low alloy steel, 980 Grade X low alloy steel has a maximum allowable
stress of 552 MPa and is the selected optimum material of construction.
References
Ashby, M. (2005). Materials Selection in Mechanical Design. Oxford: Elsevier Buttterworth-
Heinemann.
Ashley, M., & Tudor, R. (2007). Development of the LP OXO process to the commercial stage.
Enhancement of Industrial Hydroformylation Processes by the Adoption of Rhodium-
Based Catalyst: Part 1, 116-126.
Chauvel, A., & Lefebvre, G. (1986). Petrochemical Processes: Technical and Economic
Characteristics. France: Editions Technip.
Dekker, M. (1984). Encyclopedia of Chemical Processing and Design. New York: Marcel
Dekker, Inc.
Design, G. (2009, January). Granta Design . Retrieved from Granta Design :
www.grantadesign.com/download/pdf/teaching.../2-Materials-Charts-2010.pdf
ICIS. (2007, November 5). ICIS. Retrieved from ICIS:
https://www.icis.com/resources/news/2007/11/05/9075782/2-ethylhexanol-2-eh-uses-
and-market-data/
Kutz, M. (2002). Handbook of Materials Selection. New York: John Wiley & Sons.
Optience. (n.d.). Optience. Retrieved from Optience Web Site:
www.optience.com/sitefiles/rex/examples/Propylene-Hydroformylation.pdf
Smith, F. (1975). Rhodium-Based Catalyst System for OXO Process Plants. New Technology for
Industrial Hydroformylation, 93-95.