ABDALLAH ALHARABAH

INTRODUCTION
MTBE PLANT,
PRODUCTION

MASS AND
ECONOMICS The
ENARGY
ANALYSIS purpose BALANCE

EQUIPMENT
DESIGN,
SIZING
 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 MTBE

, 2000 ton/day
The reactor
30 bar and 90 °C

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
MTBE known as methyl tertiary butyl ether

 MTBE is a chemical compound with molecular formula C5H12O.

 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
MTBE 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
METHANOL 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
METHANOL 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
Isobutylene 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
Propane 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

MTBE 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
METHANOL known as methyl alcohol with a formula CH3OH

Liquid Vapor
Properties: Properties:

Heat capacity:
Viscosity: a = 21.152 b = 0.07092 c = 2.59E-05 d
= -2.85E-08
a = 555.3 b = 260.6
where Cp = a + b*T + c*T² + d*T³
where log(viscosity) =
Cp: kJ/kmol.K T: °K
a * ( 1/T - 1/b )
Vapour pressure:
viscosity: mNs/m² T: °K
a = 18.5875 b = 3626.55 c = -34.29
where ln(P) = a - b/(T+c) P: mmHg6 to
91°C
 Properties and Thermodynamics
METHANOL known as methyl alcohol with a formula CH3OH
Methanol properties
Molecular weight (g/mole) 32.04
Boiling Temperature (°C ) 65
Melting pint (°C ) -97.7
Relative Density 0.79
Specific gravity 0.8
Water solubility (mg/L) infinity
Vapor pressure (mm Hg) 122
Heat of Formation (MJ/kmol) 201.3-
Gibbs Free Energy -162.62
Tc (K) 512.6
Pc (bar) 81
Vc ( m³/kmol) 0.118
Density ( kg/m³) 791
Heat of Vaporization (kJ/kmol) 35278
Henry's Law 1.1E-4
Properties and Thermodynamics
Butenes Butenes properties isobutylene 1-butene

Molecular weight (g/mole) 56.11 56.107

Boiling Temperature (°C ) -6.9 -6.3
Melting pint (°C ) -140.3 -185.4
Specific gravity 0.59 1.998
Water solubility (mg/ml) insoluble 0.085
Vapor pressure ( kPa) 268.8 268
Flash point (°c) -76 -79
Tc (°c) -144.7 146.4
Pc (atm) 39.48 40.2
Vc ( cm³/mol) 239 -
Density ( g/cm³) gas 0.5879 2.72(kg/m³)
Latent Heat of Vaporization 94.3 390 (kj/kg)
(cal/g)
Specific heat (kj/kg.k) 1.487 0.083 (kj/mol.k)
Properties and Thermodynamics
Propane It is molecular formula C3H8
Propane properties
Molecular weight (g/mole) 44.1
Boiling Temperature (°C ) -42.09
Melting pint (°C ) -187.6
Specific gravity 1.5503
Water solubility (mg/ml) 0.07
Vapor pressure (psig) 109
Viscosity (centipoise) 0.008029
Gibbs Free Energy -162.62
Tc (°F) 206.2
Pc (psia) 617.4
Density ( kg/m³) gas 1.83
Density ( kg/m³) liquid 507.7
Heat of Vaporization (cal/g) 101.76
Specific heat (cal/g.°c) 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
MTBE Scrubber
Methanol Reactor

Methanol Recycle
Column
MTBE Column
Butenes
Waste
stream

MTBE
 Process Description

The Butenes stream contains 40% isobutylene, 55% isobutene and

and 5% light gases mainly propane

Butene waste
stream
Water

Methanol
MTBE Scrubber
Methanol Reactor

Methanol Recycle
Column
MTBE Column
Butenes
Waste
stream

MTBE
 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
MTBE Scrubber
Methanol Reactor

Methanol Recycle
Column
MTBE Column
Butenes
Waste
stream

MTBE
 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
MTBE Scrubber
Methanol Reactor

Methanol Recycle
Column
MTBE Column
Butenes
Waste
stream

MTBE
Process Flow Diagram (PFD)
Process Flow Diagram

R-901 T-901 T-902 T-903

MTBE MTBE Methanol Methanol
Reactor Column Scrubber Recycle
Column

11

8
9
process
water butene
waste stream
1 3

methanol 4

T-902
2

butenes

6
R-901

10
T-903

5 T-901 waste
water
12

MTBE

Figure 1: Process Flow Diagram for MTBE Production

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.