Chapter 2: Process Alternatives

2.1 Three Process Alternatives for MTBE Production

Methyl tert-butyl ether (MTBE) is produced through the reaction of isobutylene
withmethanol. There are different sources of the isobutylene feedstock, often
depending on thetype of MTBE producer. Unlike methanol, isobutylene is
generally not availablecommercially and thus must be either obtained from
process streams available in-house ormanufactured separately, generally
starting from butane. There are three primary
MTBE processes and the brief descriptions of the different sources of isobutylene
and of each process are shown below.
2.1.1 MTBE Production from Dehydrogenation of Isobutane
A typical etherification complex configuration is shown in figure 1 for the
production ofmethyl tertiary butyl ether (MTBE) from butanes and methanol.
Three primary catalytic processes are used in an MTBE complex:
1.Paraffin isomerization to convert normal butane into isobutane
2.Dehydrogenation to convert isobutane into isobutylene
3.Etherification to react isobutylene with methanol to make MTBE

Figure 1: MTBE Production Facility

Isomerization of n-butane:

Field butanes, a mixture of normal butane and isobutane obtained from natural
gascondensate, are fed to a deisobutanizer (DIB) column. The DIB column
prepares an isobutaneoverhead product, rejects any pentane or heavier material
in the DIB bottoms, and makes anormal butane side cut for feed to the paraffin
isomerization unit. The DIB overhead isdirected to the Oleflex unit. The oncethrough conversion of isobutane is approximately 50%.About 91% of the
isobutane conversion reactions are selective to isobutylene and hydrogen.On a
mass basis, the isobutylene selectivity is 88 wt%.[13]
The remaining normal butane is combined with dry makeup hydrogen will
channel tothe paraffin isomerisation unit at the temperature between
230 340oF (110 to 170oC) and 200 to 300 psig (1480 to 2170 kPa). The
function of hydrogen is to suppress polymerizationof the olefin that is formed as
intermediates. A small amount of promoter which is organicchloride is added to
maintain the stability of the catalyst activity and it will convertcompletely as
hydrochloric acid in the reactors.
The efficiency of stream will be increased when there are two reactors used
insteadonly one reactor. The reactor product which is isomerate will flow to a
stabilizer while hydrochloric acid will flow to the scrubber and the scrubber will
remove the hydrochloricacid from the light gases. The stabilized liquid product
contains almost same amount ofcomposition mixture of n-butane and isboutane.
The unconverted n-butane will be recycled back to isomerization unit to convert
it to isobutane in
order to achieve nearly totalconversion of n-butane to isobutane.[14]
Dehydrogenation of Isobutane:[15]
Isobutane undergoes dehydrogenation to produce isobutylene. Dehydrogenation
stepis carry out in the presence of catalyst which is platinum supported on
alumina. The Oleflexdehydrogenation process consists of three moving bed radial
flow reactors in series that feedstream is preheated in a furnace and send to the
first reactor. Since the temperature of outlet product drops due to
endothermic reactions, the inter-stage furnaces are placed betweenreactors to
increase temperature. The outlet product from the first reactor is heated in
thesecond stage inter-stage furnace and fed to the second reactor. Due to coke
formation on thecatalyst surface, the outlet catalyst from the third reactor is sent
to the regeneration section. Inthe regeneration reactor, the formed coke is burnt
and regenerated catalyst is recycled to thefirst reactor and turns along the
process. Figure 2 shows the schematic diagram of the Oleflex process.

Figure 2: Schematic Diagram of the Oleflex Isobutane Dehydrogenation Process

High temperature and low pressure will shift to isobutene dehydrogenation, but
also promote side reaction and catalyst deactivation. Thus, inter-stage furnaces f
unction to maintain the desired temperature required for dehydrogenation
reaction. The equation belowshows the dehydrogenation of isobutane.
iC4H10 iC4H8 + H2
Isobutane Isobutene + Hydrogen
Besides, there are 3 possible side reactions that might occur during
dehydrogenation of isobutane.
1.Isobutane Cracking:
iC4H10+H2 C3H8 + CH4
Isobutane + Hydrogen Propane + Methane
2.Propane Dehydrogenation:
C3H8 H2 + C3H6
Propane Hydrogen + Propene
3.Coke Formation
iC4H8 4C + 4H2
Isobutene Carbon + Hydrogen

Etherification Process:

The Ethermax process can be used to produce methyl tert- butyl ether (MTBE).
This process combines the Hls fixedbed etherification process with advanced R
WD catalyticdistillation technology from Koch-Glitsch, Inc. The combined
technology overcomes reactionequilibrium limitations inherent in a conventional
fixed-bed etherification process. TheEthermax process reacts isobutylene over an
acid resin in the presence of methanol to formMTBE. The reaction chemistry and
unit operating conditions are essentially the same as thoseof a conventional
ether process, such as the Hls MTBE process, except that
KataMax packing has been added to increase the
overall conversion. KataMax packing represents aunique and proprietary
approach to exposing a solid catalyst to a liquid stream inside adistillation
column. The reactive distillation zone of the RWD column uses KataMax
packingto overcome reaction equilibrium constraints by continuously
fractionating the ether productfrom unreacted feed components. As the ether
product is distilled away, the reacting mixtureis no longer at equilibrium. Thus,
fractionation in the presence of the catalyst promotes additional conversion of
the reactants. Isobutylene conversion of 99 for MTBE can beachieved in
this process.[16]
Figure 3 is a simplified flow diagram of the Ethermax process. Isobutylene and
smallexcess stoichiometric amount of methanol join a controlled quantity of
recycle from thereactor effluent and are cooled prior to entering the top of the
primary reactor. The combinedfeeds and recycle are all liquids. The resin catalyst
in the primary reactor is a fixed bed ofsmall beads. The reactants flow down
through the catalyst bed and exit the bottom of thereactor. Effluent from the
primary reactor contains MTBE, methanol and unreacted C4 olefins and usually
some C4 paraffins, which were in the feed.
A significant amount of the effluent is cooled and recycled to control the
reactortemperature. The net effluent feeds a fractionator with a section
containing catalyst. This is Kochs proprietary reaction with distillation (RWD)
column. The catalyst section, located above the feed entry, is simply structured
packing with conventional MTBE resin catalyst between
the corrugated mesh plates. MTBE is withdrawn as the bottom product, andunrea
cted methanol vapor and isobutylene vapor flow up into the catalyst reaction to
be converted to MTBE.
The advantages of an RWD column include essentially complete
isoolefinconversions. The excess methanol and unreacted hydrocarbons are
withdrawn from the RWDcolumn reflux accumulator and fed to a methanol
recovery tower. In this tower, the excessmethanol is extracted by contact with
water. The resultant methanol-water mixture is distilledto recover the methanol,
which is then recycled to the primary reaction.[17]

Figure 3: A simplified flow diagram of the Ethermax process