Supervised by: Dr. Adil H.

Rashid
Prepared by:
Zainab Fadhil, Zainab Eyad, Asmaa Ali, and
Shumus Kamil
Academic Year 2018-2019
 CHAPTER ONE
INTRODUCTION
 Methyl tertiary butyl ether (MTBE):

• Methyl tert-butyl ether (also known as MTBE and tert-butyl

methyl ether) is an organic compound with a structural
formula (CH3)3COCH3.

• MTBE is a volatile, flammable, and colorless liquid that is

moderately soluble in water. It has a minty odor unclearly
reminiscent of diethyl ether, leading to unpleasant taste and
odor in water
The chemical structure of MTBE

(CH3)3COCH3
Why we Choose MTBE in our Project????

 Gasoline standards throughout the

world are continuing to move toward
cleaner burning gasoline.
 This includes mandating limits on
aromatics, benzene, sulfur and distillation
characteristics.
 All of these changes must be met while
maintaining or increasing gasoline octane
number.
Some of the possible blend stocks that fulfill
the abovementioned requirements are:
Methanol(MeoH)

Alcohols Ethanol(Etoh)

Isopropyl alcohol
Oxygenates (IPA)

n-butanol (BuOH)

Gasoline grade t-
Alkylates butanol (GTBA)
Methyl tert-butyl
ether (MTBE)
Tert-amyl methyl
ether (TAME)
isomerate Tert-hexyl methyl
ether (THEME)
Ethyl tert-butyl
ether (ETBE)
Iso-octane Tert-amyl ethyl
Ethers ether (TAEE)
Diisopropyl ether
(DIPE)
 Oxygenates refer to oxygenated fuels and they are
usually employed as gasoline additives to reduce
carbon monoxide and soot produced during the
burning of the fuel.

 As for oxygenates, Methyl-Tert-Butyle-Ether

(MTBE) became the single most widely used
oxygenate for enhancing gasoline octane number,
primarily for its superior blending characteristics and
economics compared to other oxygenates such as
ethanol , TAME and ETBE.

 This gives a reason for the increasing demand for

MTBE as a gasoline additive.
Production of MTBE in USA Global MTBE Demand by
Region (2014)
 Physical Properties:
The main physical properties of (MTBE) are illustrated in the
following table.

Properties Information
mp
bp
0.36 mpa.s

Heat of vaporization(at bp)

-314 kj\ mol
Heat of combustion -34.88 Mj/kg
Flash point (Abel-pensky)
Ignition temperature
Explosion limit in air 1.65- 8.4 %vol
 Chemical Properties:

Methyl tert-butyl ether (MTBE) is very

stable under alkaline, neutral, and weakly
acidic conditions.
 In the presence of strong acids, it is cleaved
to methanol and isobutene.

Property Explosion Ignition Henrys law Other

Limit temperatur constant at
e 25C
Information 1.65 to 8.4% 224 C 5.87x10^-4 MTBE is
in air (atm- unstable
m^3/mol) in acidic
solution
 Uses and Applications
The most important uses of MTBE are:
 MTBE is the most widely used fuel oxygenate, due
to its combination of technical advantages and
supply availability.

 MTBE delivers high octane value at relatively low

cost. In addition, MTBE offers low water solubility
(compared to e.g. alcohols), low reactivity and
relatively low volatility. These characteristics allow
refiners to overcome handling problems in the fuel
distribution system posed by alcohol oxygenates.

 Another important reason for the widespread use

of MTBE is feedstock flexibility thereby ensuring
ready availability and reducing dependence on
crude oil for the production of automotive fuels.
 Production Methods
Several Routes have been proposed to produce MTBE:

MTBE from Tetr-Butyl Alcohol.

MTBE from a Mixture of Methanol and Isobutanol.

MTBE from a Mixture of Methanol and Isobutene.

 Process Selection
 Due to its high purity product, low cost, high conversion
ratio, and ability to recycle & use of reactant material the
production method of MTBE from Isobutene and Methanol
has been selected.
 The overall reaction stoichiometry for MTBE synthesis is
quite simple: one mole of methanol is added to one mole of
isobutylene.
 This etherification reaction is catalyzed
in an acidic medium.

 The reaction could be realized in an

homogeneous reactor with the reactants
being mixed with an acid to lower their
pH.

 The use of a liquid acid requires,

however, an additional separation step.

 Eventually, the use of solid acidic

catalysts easing the separation of the
catalyst from the liquid phase and this led
to the development of heterogeneous
reactors.
 CHAPTER TWO
MATERIAL BALANCE
Flow sheet
 BASIC CALCULATIONS
 Production of Methyl-Tert-Butyl-Ether
(MTBE) = 75,000 (ton/year)

 Actual operating year = 350 day

 75,000(ton/year)*1000(Kg/ton)*(year/350
day)*(1day/24hr) = 8928.571(Kg/hr)

 No. of moles of MTBE = wt / M.wt

= 8928.571/88.15
= 101.2884(Kmol/hr)
Material Balance on Reactor

MTBE
i-C4 i-C4
N-C4 N-C4
CH3OH 1 2 CH3OH
H2O H2O

Operating Conditions:
P = 1 Bar
T = 90 °C
Conversion = 97%
 The main equations applied in this section are:
 No. of moles = wt. / M.wt
 %conv.= ( reacted/input )
 %excess of (CH3OH) = [(input–reacted)/reacted)]
*100
 Mole of unreacted=(input–reacted)

 Total wt input=wt. (i-c4)+ wt.(N-c4)+wt. (CH3OH)+

wt. (H2O)
 Total wt. output= wt. (i-c4)+wt. (N-c4) + wt.
(CH3OH)+ wt. (H2O) +wt. (MTBE)
 Total moles input = n (i-c4) + n (N-c4)+ n (CH3OH)+
n(H2O)
 Total moles output= n(i-c4)+n(N-c4)+n(CH3OH)
+n(H2O)+ n(MTBE)
 Composition of the Input & Output Streams
of the Reactor:
Comp. Stream 1 Stream 2 Stream 1 Stream 2
(Kmol/hr) (Kmol/hr) (Kg/hr) (Kg/hr)

i-C4 104.421 3.1326 5858.749 175.7619

N-C4 85.43536 85.43536 4793.5219 4793.5219
CH3OH 111.41724 10.12884 3570.031 324.548
H2O 4.04765 4.04765 72.8577 72.8577
MTBE 101.2854 8928.571
 Material Balance On Distillation (1) :

MTBE

i-C4

4 N-C4
CH3OH

H2O
MTBE

i-C4
N-C4 2
CH3OH

H2O MTBE

i-C4
3
N-C4
CH3OH

H2O

Operating Conditions :
P= 760 mm
T= 120 °C
 The main equations applied in this section are:

• Antoine equation
𝑩
𝑨−𝑻+𝑪
𝒑° = 𝟏𝟎
• The heavy and light component
determine from Relative Volatility
𝐾𝑖
𝛼=
𝐾 𝑠𝑒𝑙𝑒𝑐𝑡
Kselect =MTBE
𝑲𝒊 = P sat. /P tot.
Where:
P °= the partial pressure of the component
A, B, C are Antoine Coefficients
α = Relative Volatility
Ki = coefficient representing
Comp. A B C K α
MTBE 5.096 708.69 179.9 3411 4.48 1
i-C4 6.84 923.1 240 18918 24.89 5.5
N-C4 6.84 926.1 240 18638 24.5 5.4
CH3OH 8.07 1574 238.8 4800 6.3 1.4
H2O 8.14 1810 244 1484.9 1.9 0.43

From the above Table:

1- MTBE and H2O are the heavy Keys.

2- CH3OH, i-C4, and N-C4 are the light Keys.
Composition of the Input & Output Streams
of the Distillation Column (1):

Comp. Stream 2 Stream4 Stream 3

(Kg/hr) (Kg/hr) (Kg/hr)
MTBE 8928.5 89.285 8839.215
i-C4 176 174.24 1.76
N-C4 4792.7 4749.773 47.927
CH3OH 324 320.76 3.24
H2O 72.67 0.07267 91.943
Material Balance On Distillation (2) :

i-C4

N-C4
5 CH3OH
H2O

MTBE

i-C4
N-C4 4
CH3OH MTBE

H2O i-C4

6 N-C4
CH3OH
H2O

* The same procedure in Distillation

Column (1) was applied in this Distillation
Column.
Composition of the Input & Output Streams
of the Distillation Column (2):

Comp. Stream 4 Stream 5 Stream 6

(Kg/hr) (Kg/hr) (Kg/hr)

MTBE 89.285 0 89.285

i-C4 174.24 172.4976 1.7424
N-C4 4749.773 4627.325 47.4477
CH3OH 320.76 317.552 3.2076
H2O 0.07267 0.000726 0.07194
 Material Balance on Absorber
i-C4
H2O 9 8 N-C4
CH3OH

i-c4
N-c4
H2O 5
CH3OH

H2O
7 CH3OH
 The main Equations applied in this
section are:
(L/G) act. = (L/G) theo. * 1.5
(L/G) theo. = 0.4588
L act. = G * 0.6882
𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒊−𝒄𝟒 𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒏−𝒄𝟒
G=( + )
𝑴.𝑾𝒕 𝑴.𝑾𝒕
PA= H*XA
XA = (0-1)
H = Hanary constant=0.28851

Y = [PA/ (PA-PT)]
PT = 760 mmHg
 Composition of the Input & Output
Streams of the Absorber :

Comp. Stream 5 Stream 9 Stream 8 Stream 7

(Kg/hr) (Kg/hr) (Kg/hr) (Kg/hr)

i-C4 172.42 0 172.42 0

N-C4 4697.325 0 4697.325 0

CH3OH 317.552 0 3.1755 314.376

H2O 0.000762 936 0 693.000762

 Material Balance on Stripper

CH3OH
H2O 10

CH3OH 11 H2O
H2O 7

CH3OH
H2O 9
Composition of the Input & Output Streams
of the Stripper:

Comp. Stream 7 Stream 11 Stream 10 Stream 9

(Kg/hr) (Kg/hr) (Kg/hr) (Kg/hr)

CH3OH 315 0 311.232 3.1437

H2O 693 315 6.28 622.4

Material Balance on Knock Out
i-C4
N-C4 14

i-C4
N-C4
CH3OH
6 MTBE
H2O

CH3OH
MTBE
13
H2O
Composition of the Input & Output Streams of
the Knock out:

Comp. Stream(6) Stream(14) Stream(13)

( Kg/hr) (Kg/hr) (Kg/hr)
MTBE 89.285 _______ 89.285
i-C4 1.7424 1.7424 _______
N-C4 47.447 47.447 _______
CH3OH 3.2076 _______ 0.07194
H2O 0.017194 _______ 3.2076
 Material Balance on Decanter

MTBE 14
CH3OH

13 MTBE
H2O

CH3OH
H2O 15
Composition of the Input & Output Streams
of the Decanter:

Comp. Stream Stream Stream

(13) (14) (15)
(Kg/hr) (Kg/ hr) (Kg/hr)

H2O 0.07194 _____ 0.07194

MTBE 82.285 82.285 _______

CH3OH 3.2076 _____ 3.2076

 Material Balance on Mixer (2)

CH3OH i-C4
12
H2O 16 n-C4

10
CH3OH 15
H2O
17
CH3OH
H2O
i-C4
n-C4
CH3OH
H2O
Composition of the Input & Output Streams
of the Mixer (2):

Comp. Stream Stream Stream Stream Stream

16 10 17 15 12

i-C4 0 0 1.74 0 1.7424

N-C4 0 0 47.49 0 47.447

CH3OH 3251.6 311.232 3564.8 0.07194 0

H2O 65.65 6.28 72 3.2076 0

Material Balance on Mixer (1)

i-C4
N-C4
i-C4
18 1 CH3OH
N-C4
H2O

17

i-C4
N-C4
CH3OH
H2O
Composition of the Input & Output
Streams of the Mixer (1):

Comp. Stream 18 Stream17 Stream 1

(Kg/hr) (Kg/hr) (Kg/hr)

i-C4 18084.4 1.74 18096

N-C4 5270 47.49 5270

CH3OH 0 3564.8 3564.8

H2O 0 72 72
 THANKS
FOR
YOUR ATTENTION