OLEFIN ETHERIFICATION

PGS.TS. Trương Hữu Trì

 CONTENTS

1 Main ethers used in refining

2 Fundamentals of olefin etherification

3 Feed and raffinate treatment

4 Operating conditions

5 Process flow schemes

2
 Main ethers used in refining
 Ethers (tertioalkylethers) are mainly produced by reacting a tertiary iso-
olefin on an aliphatic mono-alcohol.
 Today MTBE is the most important of the industrially produced ethers.
It is produced by reacting the isobutene in C4 cuts with methanol in the
presence of an ion-exchange resin acid catalyst.
 TAME (tertioamylmethylether), produced by reacting the isopentenes
also called Iso-amylenes - in C5 cuts with methanol, has also become
increasingly successful. This is because of its low vapor pressure, but
also and above all because it allows a decrease in the light olefin content
In gasolines.
 Olefins have very high photochemical reactivity and cause smog
formation via ozone. For these reasons, it is even superior to MTBE
from the standpoint of reformulated gasolines.
 Main ethers used in refining

 ETBE (ethyltertiobutylether), produced by reacting isobutene on

ethanol, is now recognized for its valuable contribution as a gasoline
pool component: a high octane number and a low vapor pressure. It
offers all the advantages of its homologue MTBE. By analogy, TAEE
(tertioamylethylether) can be mentioned. It is produced by reacting
isopentenes on ethanol.
 Another potential source of oxygenated compounds is DIPE
(diisopropylether). It is produced by IPA (isopropyl alcohol)
etherification by an ethylene molecule in the presence of an ion-
exchange resin acid catalyst. It exhibits properties similar to those of
MTBE and TAME with the disadvantage, however, of readily becoming
peroxided into unstable, even explosive, compounds.
Main ethers used in refining

 Properties of Ethers

The major
advantage of
oxygenated
compounds
(alcohols and
ethers)
 Main ethers used in refining
Properties of Ethers
Ethers offer a series of advantages:
 High octane numbers, sometimes in excess of 100 (MON) and 115
(RON);
 Properties very close to those of the hydrocarbon components of the
gasoline pool;
 low vapor pressures (allowing more butane to be incorporated in the
gasoline pool);
 Pollution control properties: 10 to l5% ethers in motor fuels cause a 10
to 15% drop in carbon monoxide and a 5 to 10% reduction in unburned
hydrocarbons in exhaust gases.
 Main ethers used in refining
 Properties of Ethers

The octane
number rises by
approximately 2
to 5 points for
MTBE
concentrations
of 10 to 15%in
the gasoline

Properties of oxygenated compounds

 Fundamentals of olefin etherification
 Reaction Mechanism
• Ethers are produced by adding alcohol to an iso-oleflnin the presence of an ion-
exchange resin.
• The MTBE synthesis reaction occurs according to the reversible reaction below:

First step: Protonation of base species, with iso-olefin among them. This forms a
tertiary carbocation, which is more stable than a secondary carbocation, formed
with n-olefins:

Second step: Rapid reaction of the tertiary carbocation, stabilized by the acid
group, with excess methanol:
 Fundamentals of olefin etherification
 Side Reactions
 Etherification reactions are very selective for production of ethers
(MTBE, TAME, ETBE).
 In MTBE synthesis. selectivity (isobutene conversion into MTBE) is
higher than 99%.
The main side reactions are:
• production of TBA (tert-butyl alcohol) by iso-butene reacting with the
water present in the feed (resulting from saturation of the C4 feed after
washing):

• production of dimers (dlisobutylene) by isobutylene reacting with itself:

 Fundamentals of olefin etherification
 Side Reactions
The main side reactions are:
• production of MSBE (methylsecondarybutylether) by n-butenes reacting
with methanol

• production of DME (dimethylether) by methanol reacting with itself:

• production of codimers by isobutylene reacting with n-butenes:

 Fundamentals of olefin etherification
 Catalysts
 The etherification reaction is catalyzed by an ion-exchange resin of the
macrocrosslinked sulfonic type (copolymer of polystyrene and
divinylbenzene).
 The resin's particular feature is that its volume increases and its
crosslinked structurecomes apart in contact with water or methanol at
temperatures of approximately 100 to 110°C (mechanical strength limit
of the resin).
 Fundamentals of olefin etherification
Catalysts
Main physical and chemical properties are:
• shape: bead
• size: 0.35 to 1.2mm
• pore diameter: 250 oA
• specific surface area: 45m2/g
• pore volume: 0.3 cm3/g
• water retention: 50 to 54%
• density: 770 g/l
• acid site concentration: 1.8 meq/rnl (4.9 meq/g)
 Feed and raffinate treatment
Feed treatment
 Because of the acid and anionic nature of the resin, any feed
impurities: basic and cationic impurities, but also peroxides and
diolefins - will poison the resin and shorten its lifetime.
 Basic impurities are the result of feed production processes
(acetonitrile and propionitrile respectively for C4 and C5 cuts
from catalytic cracking).
 Impurities also come from the alcohols used: ammonia in the
methanol, esters and aldehydes in the ethanol.
 For C4 and C5 feeds, the most usual method of removing these
basic impurities is washing with water.
 Feed and raffinate treatment
Feed treatment
 Treatment on molecular sieves is also used. Guard beds containing
resins are used to remove impurities from alcohols.
 Peroxides affect the resin's skeleton by destroying aromatic groups,
thereby causing a reduction in active sites and therefore a decrease in
catalytic activity, Peroxides are minimized by preventing contact
between hydrocarbons and air during intermediate storage.
 Cations such as the sodium ion act on acid sites to replace hydrogen
ions and make the site inactive. Iron in the presence of oxygencatalyzes
peroxide formation.
 Feed and raffinate treatment
Feed treatment
 Diolefins are detrimental only at high concentrations (e.g. an untreated
C4 feed from steam cracking).
 They lead to the formation of gums that foul the catalyst and shorten its
lifetime. This effect is particularly perceptible with the C5 cut, even for
low diolefin concentrations (isoprene, pentadiene and
cyclopentadiene).
 Diolefins also cause TAME to have a particular smell and color
because they combine with the sulfur present in the feed.
 Water will have a reversible passivation effect at concentrations higher
than 1 000 ppm.

Note that the resin's activity can be partially restored by increasing the
operating temperature.
 Feed and raffinate treatment
Raffinate treatment
 An appropriate C4 and C5 raffinate purification treatment -
elimination of diolefins and oxygenated compounds - is
necessary to meet the specifications required by the upgrading
processes downstream from etherification.
 Typical specifications for these raffinates are as follows:
• methanol: 50 to 100ppm
• DME: 300 to 500ppm
• water: 400 to 500 ppm (saturation)
• ether: 10 to 20 ppm
 Operating conditions

 The characteristics of etherification reactions can be summed up

as follows: liquid phase, exothermic, reversible reactions
 The main operating conditions for the MTBE process are as
follows:
• methanol/isobutene molar ratio: 1.1 to 1.2;
• temperature: 50 to 90oC in the main reaction section and 40 to
60°C in the finishing reaction section;
• pressure between 7 and 20 bar;
• space velocity: 4 to 6 h-l .
The operating conditions for other etherification processes are
similar.
 Process flow schemes
MTBE Process
The process flow schemes are of 2 types depending on the desired result
when treating the C4 cut:
• Conventional scheme to produce motor fuels, achieving
approximately 96 to 97% isobutene conversion.
• Scheme with reactive distillation to upgrade the Cc raffinate for
production of high purity butene-I by eliminating isobutene.
Conversion targets are very high, up to 99.9%. When this scheme
is applied to MTBE production for fuels, it achieves maximum
isobutene conversion
 Process flow schemes
MTBE Process: conventional flow scheme
Process comprises 4 sections: washing, reaction, MTBE fractionation,
methanol recovery.

IFP’s MTBE process: conventional flow scheme

 Process flow schemes
MTBE Process: conventional flow scheme
Washing:
The washing section eliminates basic impurities from the C4 feed.
Reaction:
The reaction section includes a main reactor where most of the
etherification reaction takes place (some 90%) followed by a finishing
reactor operating at lower temperature.
MTBE fractionation:
The MTBE is fractionated in an azeotropic distillation column. The C4
raffinate (unreaeted isobutene and nonreactive components) and the
methanol entrained byazeotropy (low-boiling point azeotropes with the
C4, whose methanol content increases with pressure) are recovered after
condensation at the top of the column. Meanwhile, the MTBE is
withdrawn as a bottom product.
 Process flow schemes
MTBE Process: conventional flow scheme
Methanol recovery
 The methanol recovery section includes 2 columns.
 The first is for washing with water circulated counter-currently to
extract the methanol from the C4 raffinate.
 It is followed by a water/methanol fractionating column, from which
the water is recycled to the washing column and the methanol to the
reaction section
 Process flow schemes
MTBE Process: flow scheme with reactive distillation

IFP's MTBE process: Flow scheme with catalytic distillation

 Process flow schemes
MTBE Process: flow scheme with reactive distillation
 The finishing reactor and the azeotropic distillation column are
replaced by a column system with a reaction section integrated in the
upper part.
 The produced MTBE is separated and at the same time the isobutene is
converted. It is an application of the Le Chatellier principle, which
states that in a reversible reaction, eliminating one of the components
moves the equilibrium toward formation of that same component (here
MTBE is the product that is eliminated continuously by distillation).
 The system includes several catalytic zones, and allows maximum
conversion to be achieved. It also permits integral recovery of the heat
of reaction and therefore minimizes energy consumption. The reactive
distillation process is being applied increasingly when the process is
adjusted to yield motor fuel.
 Process flow schemes
TAME Process
 The TAME and MTBE processes are similar, with the important
difference that the C5 cut is already incorporated in the gasoline pool,
contrary to the C4 cut.
 The C5 cut, light gasoline (IBP 60oC) from the wide-range gasoline cut
exhibits the following characteristics as compared with C4:
• A higher dlolefln content (isoprene, pentadiene and
cyclopentadiene) that will require installation of a selective
hydrogenation unit upstream from the TAME unit, the aim being
to improve the quality and quantity of TAME produced
• A less favorable equilibrium resulting in lower conversion.
 Process flow schemes
TAME Process

IFP's TAME process: high conversion (90-95%)

 Process flow schemes
ETBE Process
 ETBE and MTBE technology are very similar. The same plant without
any modification can be used interchangeably to produce MTBE or
ETBE.
 Isobutene conversion is approximately 92% with a conventional
scheme and around 95% with a reactive distillation reaction. The major
differences between the 2 processes are:
• a less favorable equilibrium and a lower ethanol/isobutene ratio (more
limited ethanol/hydrocarbon azeotrope), resulting in a lower conversion:
• a higher water concentration recycled with the ethanol (water/ethanol
azeotrope), resulting in a higher production of TBA (tert-butyl alcohol) - a
reaction by-product;
• a higher level of ethanol impurities, resulting in a shorter catalyst lifetime.
 Fractionating columns can be added to purify the ETBE product.
 Process flow schemes
DIPE Process
Because of the large amounts of propylene (more than isobutene and
isoamylenes) produced in refineries, diisopropylether and isopropyl
alcohol can significantly raise oxygenated compound production
 Process flow schemes
IFP’s Dimatol Process
 Reactor Design
Main Reactor
 MTBE synthesis is an exothermic reversible reaction. As such, 2
reactors are required to achieve high conversions: a main one working
at between 50 and 90oC and a finishing reactor operating at a lower
temperature, some 50°C.
 It is important to eliminate heat in the first reactor in order to minimize
side reactions and extend the catalysts lifetime.
 The difference between the various processes resides partly in the
design of the main reactor.
 Reactor Design
Finishing reactor
 Two types of reactor can be used: a fixed bed reactor, or a reactive
distillation column. The way the resin is placed in the column differs
according to licensors.
 CDTECH has proposed a system of bales containing the catalyst
placed in layers in several beds; Huels/UOP a system of structured
trays containing a catalyst patented by Koch; and IFP a system, called
Catacol, using "doublets", i.e, superposing a bed of catalyst in bulk in a
reactor with distillation trays above it.
 In contrast, TAME synthesis kinetics, as compared to MTBE and
ETBE, is slower and the approach to equilibrium more limited, The use
of an expanded bed reactor can not be considered, so fixed beds are
utilized.