ABDALLAH ALHARABAH

INTRODUCTION

INTRODUCTION
Problem Statement

This term's problem is to design an MTBE plant that produces

2000 tons MTBE per day.

MTBE is a gasoline additive used to increase octane number that is

produced from methanol and isobutylene. MTBE is produced by a
liquid-phase reaction over a catalyst. The reaction is between
isobutene and methanol as follows:
(CH3)2C=CH2 + CH3OH

(CH3)3C-O-CH3

INTRODUCTION
Problem Statement
Pure Methanol

The reactor
30 bar and 90 C

MTBE
2000 ton/day

Mixture :
-40% isobutylene
-55% isobutane
-5% propane
The isobutene and propane are inert. The conversion is
95% and the selectivity is one.

Outlines
INTRODUCTION
MTBE SYNTHSIS
- Raw Material
- Properties and Thermodynamics
MTBE PROCESSES
- Process Description
- Process Flow Diagram (PFD)
- Uses and Alternatives
- Safety

INTRODUCTION
known as methyl tertiary butyl ether
MTBE is a chemical compound with molecular formula C 5H12O.
It has been used since 1979 when it was first added to
gasoline to replace lead as an anti-knock agent and to boost
octane.
MTBE oxygenate has achieved a great economic importance
in recent years as a gasoline additive because of its ability to
enhance the octane value of unleaded motor gasoline while
increasing the oxygen content.
MTBE is produced by the reaction of isobutylene and
methanol in the presence of a cation exchange resin catalyst
Amberlyst 15.

INTRODUCTION
known as methyl tertiary butyl ether

MTBE is also used in organic chemistry as a relatively inexpensive

solvent with properties comparable to diethyl ether but with a higher
boiling point and lower solubility in water.
It is also used medically to dissolve gallstones.

Raw Material

RAW MATERIAL
known as methyl alcohol
its molecular formula is CH3OH.
Methanol was formerly produced by the destructive
distillation of wood.
The modern method of preparing methanol is based on
the direct combination of carbon monoxide gas and
hydrogen in the presence of a catalyst.
Most methanol is produced from the methane which is
found in natural gas.

RAW MATERIAL
known as methyl alcohol
Pure methanol is an important material in chemical
synthesis.
Methanol is a colorless liquid, completely miscible with
water and organic solvents and is very hydroscopic. It boils at
64.96 C (148.93 F) and solidifies at -93.9 C (-137 F).
It forms explosive mixtures with air and burns with a
nonluminous flame. It is a violent poison; drinking mixtures
containing methanol has caused many cases of blindness or
death. Methanol has a settled odor.

RAW MATERIAL
known as 2-methylpropene with a formula C4H8
It is called olefin because it contains a four-carbon
branched alkene.
It is colarless gas and on of the important hydrocarbon in
industrial.
Isobutylene is used as an intermediate in the production of
a variety of products.
It is reacted with methanol and ethanol in the manufacture
of the gasoline oxygenates methyl tert-butyl ether (MTBE)
and ethyl tert-butyl ether (ETBE), respectively. Alkylation with
butane produces isooctane, another fuel additive.

RAW MATERIAL
It is molecular formula C3H8

Propane is a colorless, flammable gas at atmospheric

pressure and normal temperatures.
It has a natural gas odor and is soluble in ether, alcohol and
slightly soluble in water.
Typical uses include vehicle fuel, home heating, and
refrigerant gas.

Properties and Thermodynamics

Properties and Thermodynamics

known as methyl tertiary butyl ether

MTBE properties
Molecular weight (g/mole)

88.15

Boiling Temperature ( C)

54

Specific gravity

0.74

Water solubility (mg/L)

50000

Vapor pressure (mm Hg)

251

Henry's Law

1.5E-3

Latent heat of vaporization (Cal/g)

81.7

Specific heat (Cal/g.C)

0.51

Properties and Thermodynamics

known as methyl alcohol with a formula
CH3OH

Properties and Thermodynamics

known as methyl alcohol with a formula
CH3OHMethanol properties
Molecular weight (g/mole)

32.04

Boiling Temperature (C )

65

Melting pint (C )
Relative Density
Specific gravity
Water solubility (mg/L)
Vapor pressure (mm Hg)
Heat of Formation (MJ/kmol)

-97.7
0.79
0.8
infinity
122
201.3-

Gibbs Free Energy

Tc (K)
Pc (bar)
Vc ( m/kmol)
Density ( kg/m)
Heat of Vaporization (kJ/kmol)

-162.62
512.6
81
0.118
791
35278

Henry's Law

1.1E-4

Properties and Thermodynamics

Butenes properties
Molecular weight (g/mole)
Boiling Temperature (C )
Melting pint (C )
Specific gravity
Water solubility (mg/ml)
Vapor pressure ( kPa)
Flash point (c)
Tc (c)
Pc (atm)
Vc ( cm/mol)
Density ( g/cm) gas
Latent Heat of Vaporization
(cal/g)
Specific heat (kj/kg.k)

isobutylene

butene-1

56.11
6.9-

56.107
-6.3

140.30.59
insoluble
268.8
76144.739.48
239

-185.4
1.998
0.085
268
-79
146.4
40.2
-

0.5879
94.3

2.72(kg/m)
390 (kj/kg)

1.487

0.083 (kj/mol.k)

Properties and Thermodynamics

It is molecular formula C3H8
Propane properties
Molecular weight (g/mole)
Boiling Temperature (C )

44.1
-42.09

Melting pint (C )
Specific gravity
Water solubility (mg/ml)
Vapor pressure (psig)
Viscosity (centipoise)
Gibbs Free Energy
Tc (F)
Pc (psia)
Density ( kg/m) gas
Density ( kg/m) liquid
Heat of Vaporization (cal/g)
Specific heat (cal/g.c)

-187.6
1.5503
0.07
109
0.008029
-162.62
206.2
617.4
1.83
507.7
101.76
0.3885

Process Description

Process Description

(MTBE) is a gasoline additive used to increase octane number

that is produced from methanol and isobutylene.
Methanol is purchased but the isobutylene is obtained from
the isomerization and dehydrogenation of butane .
Butene waste
stream

Water

Methanol Recycle
Column

Butenes

MTBE
Reacto
r
MTBE Column

Methanol

Methanol
Scrubber

MTBE

Waste
stream

Process Description

The Butenes stream contains 40% isobutylene, 55% isobutene

and and 5% light gases mainly propane

Butene waste
stream

Water

Methanol Recycle
Column

Butenes

MTBE
Reacto
r
MTBE Column

Methanol

Methanol
Scrubber

MTBE

Waste
stream

Process Description

The MTBE produced is extracted from the reaction effluent via

distillation, while the unreacted methanol is absorbed by water
before it is separated from water via distillation. The recoverd
methanol is recycled back to the reactor.
Butene waste
stream

Water

Methanol Recycle
Column

Butenes

MTBE
Reacto
r
MTBE Column

Methanol

Methanol
Scrubber

MTBE

Waste
stream

Process Description

MTBE is produced by a liquid-phase reaction over a catalyst. The

reaction is between isobutylene and methanol as follows:

(CH3)2C=CH2 + CH3OH (CH3)3C-O-CH3

Butene waste
stream

Water

Methanol Recycle
Column

Butenes

MTBE
Reacto
r
MTBE Column

Methanol

Methanol
Scrubber

MTBE

Waste
stream

Process Flow Diagram (PFD)

Process Flow Diagram

R -9 0 1
M TBE
R e a c to r

T -9 0 1
M TBE
C o lu m n

T -9 0 2
M e th a n o l
S c ru b b e r

T -9 0 3
M e th a n o l
R e c y c le
C o lu m n

11

p ro c e s s
w a te r

b u te n e
w a s te s tre a m
3

m e th a n o l

T -9 0 2

b u te n e s

R -9 0 1

10

T -9 0 3
w a s te
w a te r

T -9 0 1
12

M TBE

F ig u r e 1 : P r o c e s s F lo w D ia g r a m fo r M T B E P r o d u c tio n

Process Flow Diagram

Kinetic Data and Uses

Process Flow Diagram

The catalyst used in this reaction is Amberlyst 15.

A kinetic model for the liquid phase reaction using
Amberlyst 15 as a catalyst is

Uses
MTBE has many properties that make it a good gasoline
component for technical and environmental reasons:
MTBE can be used as fuel that can supplement the
supply of gasoline components.
Its high octane rating makes it an ideal substitute for
other octane components, e.g. lead.
It is an oxygenate, which can be used in the
formulation of cleaner-burning gasoline.

Safety

Safety
Safety is very important in the plant because any small mistakes will
cost money. For example:
in reactor we should have a jacket or coil to cool the reactor
because the reaction is exothermic and isothermal. If we don't have
cooler the reaction temperature with time will increase and that will
lead to break the catalyst and explosion.
Also in the distillation column limit the maximum height to 53 m
because of wind load and foundation considerations

Safety
Also we need to use spare pump because if the primary pump is
not working we don't have problem.
Moreover we need to use PID tuning to control the process
conditions like temperature and pressure.

Also some safety factors will required in the design's calculation

to avoid problems.

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