Universidad Peruana de Ciencias Aplicadas

Industrial Engineering
Tecnología y Automatización Industrial
“High Octane Additives- Ethyl tert-butyl
ether “
Final Report

Made by:
• Briceño Común, Diego u201320061
• Tapia León, Rosa u201412983
• Vásquez Tamayo, Walter u912570

Professor: George Power

INA2

2018-2
 Index
ABSTRACT...................................................................................................................................................... 3
Chapter 1 ....................................................................................................................................................... 4
1.1. Theoretical background ..................................................................................................................... 4
1.2. Objectives .......................................................................................................................................... 6
1.3. Product applications ........................................................................................................................... 6
1.4) Legal Framework ............................................................................................................................... 7
Chapter 2 ....................................................................................................................................................... 8
2.1. Process description............................................................................................................................. 8
2.2. Block diagram .................................................................................................................................... 9
Chapter 3 ..................................................................................................................................................... 11
3.1. Control loops.................................................................................................................................... 11
3.2. Piping and instrumentation diagrams ............................................................................................... 14
3.2. P&ID ................................................................................................................................................ 15
Chapter 4 ..................................................................................................................................................... 16
Chapter 5 ..................................................................................................................................................... 17
Chapter 6 – Conclusions and Recommendations ........................................................................................ 18
Bibliography ............................................................................................................................................... 18
 ABSTRACT

The increasing use of biofuels and fuel additives can potentially change the typical
contamination related to fuel in soil and groundwater. These products, fuel additive, are ethyl
tert-butyl ether (EtBE), as well as methyl tert-butyl ether (MtBE), benzene and tert-butyl alcohol
(TBA, a possible oxygenated metabolite).

In this essay, the production process of ETBE will be analyzed, with the purpose of being
able to identify the importance of the use of this additive in the fuel market and the components
required for its production. The necessary control loops will be thoroughly investigated so that
the quality of this product is the one required, as well as maintaining the risk, which implies its
production, under the standards regulated by the laws.
Chapter 1
1.1. Theoretical background
Oxygenated compounds are known to be important as components in the
formulation of automotive gasolines, not only as enhancers of gasoline octane ratings, but
also as reducers of carbon monoxide (CO) and unburned hydrocarbons (HC), minimizing
the emission of volatile organic compounds. The introduction of a minimal percentage of
oxygenated compounds in the formulation of gasolines has been required by law in most
countries which have areas of low air quality.

Alcohols and ethers are the oxygenated compounds most commonly used as
additives in automotive gasolines, since they possess the desired characteristics of octane
ratings and CO emission reductions . Some countries prefer ethers rather than alcohols due
to their mixing characteristics, such as low volatility and compatibility with the
hydrocarbons of gasoline . Alcohols are substantially more polar than the ethers and
hydrocarbons of gasoline, and may cause phase separation in the presence of a small
amount of water in the gasoline storage and distribution system.

One of the most consolidated fields of industrial application of acidic ion-exchange

resins (IER) as catalysts is the synthesis of tertiary alkyl ethers such as methyl tert-butyl
ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and, in less
extent, tert-amyl ethyl ether (TAEE). The framework of applications of IER is however
much wider, as they are also suitable catalysts for esterification, hydration, alkylation and
oligomerization reactions. The understanding of the relationship between catalytic activity
and morphological properties of IER is crucial for selecting the best catalyst and operating
conditions as well as for designing new catalysts able to improve the process efficiency.
(Meneses 2008 :10)
As organic polymers, resins properties depend on the nature of the monomers, the
polymerization method, the crosslinking degree and the nature of the functional groups
anchored to the polymeric matrix that confer catalytic activity. Resins synthesized by
copolymerization of styrene (S) and divinylbenzene (DVB) in aqueous suspension are the
most common porous support for IER catalysts.2But other aromatic vinyl compounds as
vinyl toluene, vinyl naphthalene, vinyl ethylbenzene, methyl styrene, vinyl chlorobenzene
and vinyl xylene can be used as co-monomers in the manufacture of polystyrene-based
resins. Two main types of porous structures can be created as a result of the porogens and
the amount of crosslinking agent (DVB) used during polymerization: microporous and
macroreticular matrix. The former is a closed-cell, also called gel-phase, containing
micropores, whereas macro-reticular resins present an open-cell with permanent
macropores apart from the gel-phase. Macroporous resins are agglomerates of gel-
microspheres with smaller nodules than microporous resins that are fussed together
forming permanent meso and macropores. Functionalization of such supports provides
catalytic activity to the resins. Depending on the foreseen application, functional groups
can be acid, basic, redox or even metallic complexes (transition metals). Acidic IER are
usually functionalized with sulphuric acid between 363 and 413 K. Sulfonic groups (-
SO3H) are therefore the functional groups eventually incorporated to the resin backbone.
Different functional groups can be used to give particular properties to the catalyst, for
instance, electron attracting groups such as halogens atoms can be used to enhance thermal
resistance. (Meneses 2008 :1150)
Tertiary ethers offer advantages over ethanol due to their low Reid vapor pressure
(RVP), low latent heat of vaporization, and low solubility in water. The most commonly
used of these ethers are MTBE and ETBE. It is worth pointing out that ETBE is considered
semi-renewable, since the raw material for its production – ethanol – is derived from
biomass.

Table 1-Mean molar composition of the industrial hydrocarbons load of the C4 cut

Compounds Concentration (molar%)

Isobutane 1.7
n-butane 7.6
2-transbutene 16.9
1-butene 33.2
Isobutene 36
2-cisbutene 4.6
Source: Menezes-Cataluña 2008
1.2. Objectives
The oxygenate additive, Ethyl tert-butyl ether has multiple objectives:

• Increase the gasoline octane.

• Enter the engine cylinders increasing the octane rating, improving combustion and
increasing the power
• Provide cleanness for all the injection system, avoiding the creation of sediments.
• Make a sustainable production cycle with an environmental focus.

1.3. Product applications

• The main application for Ethyl tert-butyl ether is the automobile industry and an
specific market is the engine. This octane additive has a lower vapor pressure than
MTBE (Yuan 2006 :10). Thus this component blends perfectly with mixed gasoline
and provides more efficient process.
• Definitely, one of the most common uses of high octane additives is engine
performance. When we add an additive for gasoline, the best combustion will increase
the power of the engine in a percentage way (Di Girolamo, Brianti &
Marchionna,2017). This is due to the fact that it increases the octane level we obtain
from the fuel, providing greater power to the engine, using the same fuel. As a final
result, having more engine power requires less fuel.

• When gasoline additives lubricate the internal parts of the combustion chamber of the engine,
they facilitate freer, frictionless operation. This, in the long run, prevents mud and grime from
accumulating inside the chamber, which also allows the free movement of all the pieces.
• The engine, either gasoline or diesel, can be supported by gasoline additives. But it is important
to remember that they are only supports and do not substitute in any way the elements of normal
maintenance, such as lubricating oil and antifreeze. These make the car work correctly.
• One using of these additives is to prevent the scheduled maintenance of your engine.
Because the additives generate a modification of the combustion chamber, the wear
and corruption caused by the same reaction of the fuels we use is significantly reduced.
 For example, traditional gasoline is an element that by its nature generates a lot of
corrosion inside the engine, during its combustion. The purpose of gasoline additives
is to prevent this deterioration of cylinders, rings, pistons, liners and even valves.

1.4) Legal Framework

ETBE is consider a Biofuel , that is the reason why the legal framework for the use of this
product is regulated by the normative of Biofuels in Perú .

Graphic: Evolution of the Normative in the Bio-combustible in Perú.

Source: “Los Biocombustibles: Desarrollos recientes y tendencias internacionales,2016”

Chapter 2
2.1. Process description
ETBE is produced by reacting a C4 stream containing isobutene with ethanol over an ion-
exchange resin catalyst. On an industrial scale, the conventional process of ETBE synthesis
consists basically of the following stages: pretreatment of the C4 hydrocarbon feed flow,
reaction, purification, and recovery of nonreacted products. Nowadays, to minimize
implementation and operating costs, reactive distillation (also called catalytic distillation)
is proposed as an alternative route for ETBE synthesis, offering high conversion and low
implementation/operating costs in comparison with conventional synthesis. The reactive
distillation process combines the reaction and purification stages in a single unit of the
process. In the ETBE production process, nonreacted ethanol forms an azeotropic mixture
with ETBE, which cannot be separated by distillation.

The process of ETBE purification occurs through the introduction of water into the system
and involves the separation of the ETBE, the C4 hydrocarbon mixture, ethanol and water.
The introduction of water into the purification process increases the costs of
implementation and production of ether. For this reason, some technologies use
pervaporative separation of the ethanol from the ETBE/alcohol mixture through special
membranes.

It has been demonstrated that the azeotropic mixture (ETBE/ ethanol) is less volatile than
ethanol and that its octane rating is higher and its production cost lower than ETBE, thus
presenting promising potential for application in gasoline formulations

The synthesis model proposed here eliminates the recycling of ethanol and suggests the
use of the azeotropic mixture (ETBE/ ethanol) as a direct additive in the formulation of
automotive gasolines.
 2.2. Block diagram
The reaction system consists of an adiabatic fixed bed reactor fed by two cylinders, one
containing the reagent ethanol (EtOH) and the other the C4 hydrocarbon mixture under a
pressure of 20 bar. The composition of the reagent mixture and the reaction system are
controlled by two electronic liquid flow gauges, one for ethanol, with a capacity of 405
mL/h, and the other for the C4 hydrocarbons mixture, with a capacity of 1380 mL/h. These
gauges allow the EtOH/i-C4 ratio and space velocity to be set as desired. The reagent
mixture is heated and fed into the reactor's lower portion. The temperature of the catalytic
stream bed and at the exit is monitored with thermocouples inside and outside the reactor
to ensure the reaction is in the steady state condition. The reactor's effluent is flashed into
a distillation column under atmospheric pressure, separating the C4 hydrocarbons into
vapor phase and the ethanol, ETBE and byproducts into liquid phase.

Fig.1 – Block Diagram of the ETBE synthesis

So in terms of process, the order is the next :

1. Mixture of C4 , EtOH and Nitrogen

2. Mix of the compound in the Reactor 1
 3. First Destillation and Reboil
4. Second Destilation and Reboil
5. Mix of the compound in the Reactor 2v
6. Third Destilation and Reboil
7. Final Product
By the way, the ETBE production process was carried out in a flow, using as reagents a
mixture of C4 hydrocarbons with 36 mol% of isobutene (i-C4) and 99.5 mol% of
anhydrous ethyl alcohol. Table 1 presents the mean molar composition of the industrial
load of C4 hydrocarbons. Amberlyst® 15 resin was used as catalyzer. The schematic
diagram in Fig. 2 depicts the production process.

The reaction system consists of an adiabatic fixed bed reactor fed by two cylinders, one
containing the reagent ethanol (EtOH) and the other the C4 hydrocarbon mixture under a
pressure of 20 bar. The composition of the reagent mixture and the reaction system are
controlled by two electronic liquid flow gauges, one for ethanol, with a capacity of 405
mL/h, and the other for the C4 hydrocarbons mixture, with a capacity of 1380 mL/h. These
gauges allow the EtOH/i-C4 ratio and space velocity to be set as desired. The reagent
mixture is heated and fed into the reactor's lower portion.
The temperature of the catalytic stream bed and at the exit is monitored with
thermocouples inside and outside the reactor to ensure the reaction is in the steady state
condition. The reactor's effluent is flashed into a distillation column under atmospheric
pressure, separating the C4 hydrocarbons into vapor phase and the ethanol, ETBE and
byproducts into liquid phase. The isobutene conversion was evaluated as a function of the
composition of the C4 hydrocarbons in the vapor phase. The concentration of liquid C4 at
the bottom of the column is negligible.
Chapter 3
3.1. Control loops

Raw Materials

Reactor 1
 Distillation column 1

Distillation column 2
 Reactor 2

Destilation Column 3
3.2. Piping and instrumentation diagrams
3.2. P&ID
Chapter 4
This chapter of the investigation details the controllers and actuators involve in the ETBE industrial
process .

• Transducers

o Pressure transducer
o Temperature Transducer

• Switches

o Level switch high

o Level switch low

• Alarms

o Level alarm High

o Level Alarm low

• Controllers
o Temperature Controller
o Pressure Controller

• Actuators

o Pneumatic Valve

o Reboiler ( heat exchanger) o Reactor

o Destilation Column
Chapter 5
The cost for the project are from 3 types. First, there are costs related to the instrumentation for
the control loops that implicate sensors, transmitters, indicators and controllers. Second, the next
category is related to the actuators and machines that work to the production of ETBE. Finally, the
project also included costs to install and prepare the company for this ETBE production.

Instruments Unit Price Quantity Total price

Level alarm $ 125.00 4 $ 500.00
Level switch $ 50.00 4 $ 200.00
Flow controller $ 400.00 1 $ 400.00
Flow ratio controller $ 500.00 1 $ 500.00
Flow transmitter $ 620.00 2 $ 1,240.00
Pressure Controller $ 250.00 5 $ 1,250.00
Pressure Transmitter $ 350.00 5 $ 1,750.00
Pressure Indicator $ 129.00 4 $ 516.00
Temperature Controller $ 310.00 8 $ 2,480.00
Temperature
transmitter $ 420.00 8 $ 3,360.00
Temperature indicator $ 120.00 5 $ 600.00
Total $ 12,796.00

Actuator &
Machines Unit Price Quantity Total Price
Pneumatic needle
valve $ 80.00 15 $ 1,200.00
EtOH tank (100m3) $ 20,000.00 1 $ 20,000.00
C4 tank (100m3) $ 185,000.00 1 $ 185,000.00
Reactor $ 10,000.00 2 $ 20,000.00
Distillation Column $ 50,000.00 3 $ 150,000.00
Total $ 376,200.00

Others Total cost

Installation $ 58,500.00
Training $ 100,000.00
Workforce $ 60,000.00
Total $ 218,500.00

Finally, the total resulted as $607 496.

Chapter 6 – Conclusions and Recommendations
• ETBE is the product of an exothermic synthesis, which is obtained after the fusion of ethanol and
a hydrocarbon. This product has been chosen because it is less polluting than MTBE; In addition,
it is not prohibited in Europe.
• It is recommended to modify the implementation of the production system for ETBE depending
on the industrial magnitudes, since this research only covers the environment of a closed test.
• Through this research, it has been proven that the mass production of the high-octane additive
is profitably efficient and supports the reduction of the emission of greenhouse gases.
• It is recommended to consider the temperature and pressure levels at which the production of
ETBE will take place, since it depends on the proportion between ethanol and hydrocarbon.

Bibliography
• BILDEA, C., GYŐRGY, R., SÁNCHEZ-RAMÍREZ, E., QUIROZ-RAMÍREZ, J.,
SEGOVIA-HERNANDEZ, J., & KISS, A. (2015). “Optimal design and plantwide control of
novel processes for di-n-pentyl ether production. Journal Of Chemical Technology &
Biotechnology”, 90(6), 992-1001.
• DE MENEZES, E., & CATALUÑA, R. (2008). “Optimization of the ETBE (ethyl tert-butyl
ether) production process. Fuel Processing Technology”, 89(11), 1148-1152.
• DI GIROLAMO, M., BRIANTI, M., & MARCHIONNA, M. (2017). “Octane Enhancers.
Ullmann's Encyclopedia Of Industrial Chemistry”, 1-19.

• DOMINGUES, L., PINHEIRO, C., OLIVEIRA, N., FERNANDES, J., & VILELAS, A.
(2012).” Model Development and Validation of Ethyl tert-Butyl Ether Production Reactors
Using Industrial Plant Data. Industrial & Engineering Chemistry Research”, 51(46), 15018-
15031.

• HONG, Y. (2006). “ETBE as an additive in gasoline: advantages and disadvantages”. [ebook]

Sweden: The Tema Institute Campus Norrköping, pp.2-7. Available at: https://www.diva-
portal.org/smash/get/diva2:21941/FULLTEXT01.pdf [Accessed 23 Sep. 2018].

• MARCELLE J. VAN DER WAALS1,2 & CHARLES PIJLS3 & ANJA J. C. SINKE 4 &
ALETTE A. M. LANGENHOFF5 & HAUKE SMIDT 2 & JAN GERRITSE1 (2018)
“Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox
conditions”
 • SOTO, R., FITÉ, C., RAMÍREZ, E., IBORRA, M., & TEJERO, J. (2018). “Catalytic activity
dependence on morphological properties of acidic ion-exchange resins for the simultaneous
ETBE and TAEE liquid-phase synthesis. Reaction Chemistry & Engineering”, 3(2), 195-205.
• VAN DER WAALS, M., PIJLS, C., SINKE, A., LANGENHOFF, A., SMIDT, H., &
GERRITSE, J. (2018). “Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and
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https://www.liquidlevel.com/vertical-float-switches/
ANEXOS