Ministry of Higher Education

and Scientific Research

Al-Muthanna University
Engineering College
Chemical Engineering Department

Name of Report: Production of Mythel Tertiary Butyl Ether (MTBE)

from methanol & Butylene

Prepared by student:Mohammed Hussein aati

Class:Fourth Stage
Subject:Petrochemical Industry

Supervised by:Dr.Hameed R.AL-amer

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Content of Report page
1.1-Introduction………………………………………………....3
1.2- History ……………………………………………………...4
1.3- Physical and chemical properties of MTBE ……………..5
1.4- MTBE applications ………………………………………..6
1.4.1- As anti-knocking agent ………………………………….6
1.4.2- As a solvent ………………………………………………6
1.4.3- Alternatives to MTBE as an anti-knock agent ………...6
2.1- MTBE production …………………………………………7
2.2- Production methods ……………………………………….7
2.2.1- UOP-Oleflex Process …………………………………….7
2.2.2- Philips Star Process ……………………………………...8
2.2.3- ABB LummusCatofin Process …………………………..8
2.2.4- Snamprogetti-Yartsingtez FBD (SP-Isoether)………….8
2.2.5- Amberlyst process ………………………………………..9
2.3- Process Description…………………………………………9
2.4- Reason of Selection production method………………….10
2.5- Process details……………………………………………...10
3-Reference……………………………………………………....11

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1.1-Introduction
MTBE is a commonly used acronym for the chemical compound methyl tertiary-butyl
ether. At room temperature e, MTBE is a volatile, flammable, colorless liquid that is
highly soluble in water. It is produced by the chemical reaction of methanol, generally
manufactured from natural gas, and isobutylene. MTBE has a very distinct taste and odor,
similar to turpentine.
MTBE has been used as a gasoline additive since 1979. However, MTBE was not widely
used as a gasoline additive in Connecticut until the mid-1980s and was not discovered in
our ground water until 1987. Initially, it was added to gasoline as a. replacement for
tetraethyl lead to increase the octane rating of the fuel.
This action has resulted in a. significant reduction in ambient air levels of lead. As an
octane enhancing additive, MTBE is blended into conventional gasoline at concentrations
ranging from approximately 3 to 5 percent, by volume. More recently, MTBE has also
been used as an oxygenate, an additive that increases the oxygen content of gasoline.
Oxygenates are added to gasoline to produce more complete fitel combustion, resulting in
reductions of carbon monoxide and ozone forming emissions.
As an oxygenate, MTBE is currently blended into gasoline at concentrations ranging from
2.0 to 2.7 percent weight oxygen, the equivalent of 11 to 15 percent MTBE.

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1.2-History
In the late 1970s and 1980s, oxygenates such as MTBE and ethanol were added to fuels
to improve efficiency while meeting lead phase-out requirements. The use of MTBE
became prevalent because of its low cost, ease of production, and favorable transfer and
blending characteristics. Other less commonly used oxygenates include methanol, ethyl
tertiary-butyl ether (ETBE), tertiary-amyl methyl ether (TAME), diisopropyl ether
(DIPE), and tertiary-butyl alcohol (TBA). In 1987, the Colorado Air Quality Control
Commission adopted the first regulations in the country requiring that oxygenated fuels
be sold along much of the Colorado Front Range. The purpose of the oxygenated fuels
program was to make gasoline burn more cleanly in order to reduce air emissions and
smog. Based in part on the successful oxygenated fuels program that had been ongoing
along the Colorado Front Range, the Clean Air Act Amendments of 1990 required that
oxygenated fuels be used at service stations and gasoline retail businesses in regions of
the United States where ozone or carbon monoxide air quality standards were exceeded.
Beginning in 1992, the winter oxygenated fuel program required 2.7% oxygen by weight
in gasoline (equivalent to 15% MTBE or 7.3% ethanol by volume) in 40 U.S. metropolitan
areas, including those located along the Colorado Front Range. In 1995, the U.S.
implemented Reformulated Gasoline Phase I, requiring 2.0% oxygen by weight in
gasoline year-round in 28 U.S. metropolitan areas. Reformulated Gasoline Phase II,
beginning January 1, 2000, continued to require 2.0% oxygen by weight. As a result of
concerns regarding MTBE, efforts have been made in several States to discontinue the use
of MTBE in gasoline.

FIGURE (1): atomic combination for MTBE

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 1.3-Physical and chemical properties of MTBE

Table 1. Physical and chemical properties of MTBE

Characteristic/Property Data

Chemical formula C5H12O

Molecular weight 88.2
Common Name Methyl tertiary-butyl ether
Synonyms MTBE, tert-butyl methyl ether
Physical state Colorless liquid with characteristic
terpene-like odor.
Vapor pressure 245 mm Hg @ 25°C
Density (water = 1) 0.7

Specific gravity 0.74

Solubility (in water) 4.8 g/100 ml at 20°C

Melting point -109 °C
Boiling point 55°C
Flash point -28°C
Conversion factors 1 mg/m3 = 0.28 ppm 1ppm= 3.61 mg/m3

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1.4- MTBE applications:
1.4.1- As anti-knocking agent
In the US it has been used in gasoline at low levels since 1979 to replace tetraethyl lead
and to increase its octane rating helping prevent engine knocking. Oxygenates help
gasoline burn more completely, reducing tailpipe emissions from pre-1984 motor
vehicles; dilutes or displaces gasoline components such as aromatics (e.g., benzene) and
sulfur; and optimizes the oxidation during combustion. Most refiners chose MTBE over
other oxygenates primarily for its blending characteristics and low cost.

1.4.2- As a solvent
Despite the popularity of MTBE in industrial settings, it is rarely used as a solvent in
academia with some exceptions. MTBE forms azeotropes with water (52.6 °C; 96.5%
MTBE) and methanol (51.3 °C; 68.6% MTBE). Although an ether, MTBE is a poor Lewis
base and does not support formation of Grignard reagents. It is also unstable toward strong
acids. It reacts dangerously with bromine.

1.4.3- Alternatives to MTBE as an anti-knock agent

Other oxygenates are available as additives for gasoline including ethanol and other ethers
such as ETBE. Ethanol has been advertised as a safe alternative by agricultural and other
interest groups in the US and Europe. In 2003, California was the first US state to start
replacing MTBE with ethanol. An alternative to ethanol is ETBE, which is manufactured
from ethanol and isobutene. Its performance as an additive is similar to MTBE, but due to
the higher price of ethanol compared to methanol, it is more expensive. Higher quality
gasoline is also an alternative, so that additives such as MTBE are unnecessary. Iso-octane
itself is used. MTBE plants can be retrofitted to produce isooctane from isobutylene.

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2.1- MTBE production:
MTBE is an oxygenated fuel additive that is blended with gasoline to promote CO2
formation over CO formation during combustion. The facility manufactures MTBE from
methanol and isobutylene. Isobutylene is obtained from a refinery cut, and it also contains
1- butene and 2-butene, both of which do not react with methanol. Process Selection
MTBE is produced via direct addition of methanol to isobutylene using sulphonated ion
Exchange resin as catalysts.

2.2- Production methods

The MTBE plants actually consist of six units: Isomerization Unit (including
deisobutanizer), Dehydrogenation Unit, MTBE Unit, Methanol Recovery Unit,Oxygenate
Removal Unit and Olefin Saturation Unit. A common offsite utility system will be
incorporated to distribute the required utilities to each unit. There are five method of
producing MTBE implemented under license as the following [3]:
 UOP-Oleflex Process
 Phillips STAR Process
 ABB LummusCatofin Process
 Snamprogetti-Yarsingtez FBD (SP-Isoether) Process.
 Amberlyst Process.

2.2.1- UOP-Oleflex Process

The UOP-Oleflex process uses multiple side-by-side, radial flow, moving-bed reactors
connected in series. Preheated feed and interstage heaters supply the heat of reaction. The
reaction is carried out over platinum supported on alumina, under near isothermal
conditions. The catalyst system employs UOP's Continuous Catalyst Regeneration (CCR)
technology. The bed of catalyst slowly flows concurrently with the reactants and is
removed from the last reactor and regenerated in a separate section. The reconditioned
catalyst is then returned to the top of the first reactor. The typical processes involved are
the deisobutenization, the isomerisation and the dehydrogenation process.

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2.2.2- Philips Star Process
The second one is the Philips Steam Active Reforming (STAR) Process. The Phillips
Steam Active Reforming (STAR) Process uses a noble metal-promoted zinc aluminate
spinel catalyst in a fixed-bed reactor. The reaction is carried out with steam in tubes that
are packed with catalyst and located in a furnace. The catalyst is a solid, particulate noble
metal. Steam is added to the hydrocarbon feed to provide heat to the endothermic reaction,
to suppress coke formation, and to increase the equilibrium conversion by lowering partial
pressures of hydrogen and propane.

2.2.3- ABB LummusCatofin Process

The ABB LummusCatofin Process uses a relatively inexpensive and durable chromium
oxide alumina as catalyst. This catalyst can be easily and rapidly regenerated under severe
conditions without loss in activity. Dehydrogenation is carried out in the gas phase over
fixed beds. Because the catalyst cokes up rapidly, five reactors are typically used. Two
are on stream, while two are being regenerated and one is being purged. The reactors are
cycled between the reaction and thereheat/regeneration modes, and the thermal inertia of
the catalyst controls the cycletime, which is typically less than 10 minutes. The chromium
catalyst is reduced from Cr+6 to Cr+3 during the dehydrogenation cycle. The raw
materials used to produce MTBE by using this method are butanes, hydrogen and as well
as recycled isobutene from the system itself. In this process, there is an isostripper column,
which separatesthe heavies, and the light ends from which then could produce MTBE.

2.2.4- Snamprogetti-Yartsingtez FBD (SP-Isoether)

The Snamprogetti-Yarsingtez SP-Isoether (FBD) Process uses a chromium catalyst in
equipment, which is the fluidized bed that resembles conventional fluidized catalytic
cracking technology used in the oil refinery. The catalyst is recirculated from the reactor
to the regeneration section on a 30–60-min cycle. The process operates under low pressure
and has a low-pressure drop and uniform temperature profile. Snamprogetti has been
presenting and marketing their hydrogenation technology, ISOETHER 100, since 1997.
This process is to be used to convert MTBE units by utilizing Snamprogetti’s MTBE
Water Cooled Tubular Reactor Technology. In this SPIsoether Process, the products are
MTBE and isooctagenas (iso octane gas). In this SPIsoether Process the catalyst used in
the isoetherification reactor is the same as those other typical processes, which is
Platinum.Four method processes of the MTBE above are favorable among the
petrochemical firms.
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2.2.5- Amberlyst process
Methanol and mixed butelynes feed (23 wt% iso-butelyne,20%wt 1- butelyne, 57 %wt 2-
butelyne) is pumped and heated at reaction conditions(30 bar and 85 Co ). The reactor is
a fixed bed type reactor and operating adiabatically at liquid phase over acidic ion-
exchange resin catalyst according to the following reaction:
CH3OH+C4H8 C5H12O
Methanol side reactions are minimized by using an excess of methanol. The reactor
effulent is distilled with MTBE as the bottom product. Methanol is recovered from the
mixed butelynes in a water scrubber and the methanol is subsecuently separated from
water so that unreacted methanol can not be recycled , unreacted butelynes are sent to the
refinery for further processing.the product stream must contain at least 94% mol MTBE.

2.3- Process Description

Methanol and the mixed butylenes feed is pumped and heated to reaction conditions. Both
the methanol and the mixed butylenes are made in on-site units, and are sent to this unit
at the desired conditions. The reactor operates in the vicinity of 30 bar, to ensure that the
reaction occurs in the liquid phase. The reaction is reversible. The feed temperature to the
reactor is usually maintained below 90°C to obtain favorable equilibrium behavior. Any
side reactions involving 1-butene and 2-butene form small amounts of products with
similar fuel blending characteristics, so side reactions are assumed to be unimportant.
Other side reactions are minimized by keeping the methanol present in excess. The reactor
effluent is distilled, with MTBE as the bottom product. Methanol is recovered from the
mixed butylenes in a water scrubber, and the methanol is subsequently separated from
water so that unreacted methanol can be recycled. Unreacted butylenes are sent back to
the refinery for further processing. The MTBE product is further purified, mostly to
remove the trace amounts of water. The product stream from Unit 900 must contain at
least 94 mol % MTBE, with the MTBE portion of the stream flowrate at specification.

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2.4- Reason of Selection production method
1-Lower capital investment from other processes.
2-Conversion isGreater than 98%.
3-Advantages are:
 the process operate under low pressure and the temperature is not high,this mean that
the process is not as dangerous as other high temperature operated process.
 the product of the process is only MTBE and other effulent and as wel as flue gas which
are not harmfull to the environment.
4- Disadvantages are:
Waste water which contain 99 wt% water must be treated to remove the trace amount of
impurities , this added to the utility cost.

2.5- Process details

Stream 1: Methanol – stored as a liquid at the desired pressure of the reaction.
Stream 2: Mixed butene stream – 23% isobutene, 20% 1-butene, 57% 2-butene.
Stream 8: MTBE product – must be 95 wt% pure.
Stream 11: Process water – see utility list for more information
Stream 12: Waste butenes – returned to refinery – contains 1-butene and 2- butene with
less than 1 wt% other impurities.
Stream 16: Waste water – must be treated – must contain 99 wt% wate

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3-Reference
1-"Glass Online: The History of Glass". Archived from the original on April 15, 2011.
Retrieved 2007-10-29
2-Kenoyer, J.M (2001). "Bead Technologies at Harappa, 3300-1900 BC: A Comparative
Summary". South Asian Archaeology (PDF). Paris. pp. 157–170.
3- Karklins, Karlis. "Simon Kwan -- Early Chinese Faience and Glass Beads and
Pendants".
4-BEADS: Journal of the Society of Bead Researchers
5-Werner Vogel: "Glass Chemistry"; Springer-Verlag Berlin and Heidelberg GmbH &
Co. K; 2nd revised edition (November 1994), ISBN 3-540-57572-3
6-The dilatometric softening point is not identical with the deformation point as
sometimes presumed. For reference see experimental data for Td and viscosity in: High
temperature glass melt property database for process modeling; Eds.: Thomas P. Seward
III and Terese Vascott; The American Ceramic Society, Westerville, Ohio, 2005, ISBN
1-57498-225-7
7-B. H. W. S. de Jong, "Glass"; in "Ullmann's Encyclopedia of Industrial Chemistry";
5th edition, vol. A12, VCH Publishers, Weinheim, Germany, 1989, ISBN 3-527-20112-
2, pp. 365–432.
8- Jump up to:a b "The Blow and Blow Method". Eurotherm. Retrieved 2013-05-20
9-"Glass-Forming Machine". Farlex. Retrieved 2013-05-20.

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