PRODUCTION OF METHANOL

(CH3OH)
)TON/YEAR 200,000(
Project Design Research
Submitted to Faculty of Engineering / Chemical Engineering
Department in Partial of Fulfillment of the Requirements for the
Degree of Bachelor of Chemical Engineering

Supervised by: Dr. Adil H.Rashid

:Prepared by
Tariq Fareed Abdullah
Hassan Ali Younis
Alaa Rahim Awad

2019-2020
 Chapter 1
Introduction

1.1 INTRODUCTION
Methanol is an Alcohol whose chemical formula can be written as
CH3OH. It is a clear , colourless liquid with a mild odour, and diss olves
readily in most common organic solvents Methanol is one of the largest
volume chemicals produced , with a world wide annual production of
about 13. Million tons .

In their embalming process, the ancient Egyptians used a mixture of

substances, including methanol, which they obtained from the pyrolsis of
wood. Pure methanol, however, was first isolated in by Robert Boyle,
who called it spirit of box , because he 1661 produced it via the
distillation of boxwood . In 1834, the French chemists Jean- Baptiste
Dumas and Eugene Peligot determined its elemental composition. They
also introduced the word methylene to organic chemistry.

The term methyl was derived in about 1840 by back-formation from

methylene, and was then applied to describe methyl alcohol . This was
shortened to methanol in 1892 by the International Conference.

1.2 Physical Properties

Methanol (CH3OH) is an alcohol fuel. Methanol is the simplest alcohol,
containing one carbon atom. It is a colorless, tasteless liquid with a very
faint odor and is commonly known as "wood alcohol."As engine fuels,
ethanol and methanol have similar chemical and physical characteristics.
Methanol is methane with one hydrogen molecule replaced by a hydroxyl
radical (OH).

Table 1.1: physical properties of (CH3OH)

Chemical Formula CH3OH
Molecular Weight 32.04 g/mol
Boiling point 64.7°C
Vapor pressure 97 Torr at 20°C
Freezing point -97.68°C
Refractive index 1.3284 at 20°C
Density 0.7913 g/mL (6.603 lb/gal) at20°C
Viscosity 0.59 cP at 20°C
Surface tension 22.55 dyn/cm at 20°C
Solubility in water Miscible in all proportions
Melting Point -97.7 0C
Flash point 11 oC
Critical temperature 512.6 K
Critical pressure 81 bar absolute
Critical volume 0.118 m³/kmol
Heat of Vaporization 35278 kJ/kmol

1.3 CHEMICAL PROPERTIES OF METHANOL:

1.3.1 Combustion of Methanol:
Methanol burns with a pale-blue, non-luminous flame to form carbon
dioxide and steam.

2CH3OH + 3O2 2CO2 + 4H2O

1.3.2 Oxidation of Methanol:

Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or
with acidified Sodium Dichromate, Na2Cr2O7, or with acidified Potassium
Permanganate, KMnO4, to form formaldehyde.

CH3OH HCHO + H2O

Methanol Formaldehyde water

H2 + O2 2H2O
Hydrogen oxygen water

If the oxidizing agent is in excess, the formaldehyde is further oxidized

to formic acid and then to carbon dioxide and water.

HCHO HCOOH CO2 + H2 O

Formaldehyde Formic Acid carbon water

1.3.3 Catalytic Oxidation of Methanol:

The catalytic oxidation of methanol using platinum wire is of interest as
it is used in model aircraft engines to replace the sparking plug
arrangement of the conventional petrol engine.

1.3.4 Dehydrogenation of Methanol:

The heat of reaction is sufficient to spark the engine. Methanol can also
be oxidized to formaldehyde by passing its vapor over copper heated to
300 °C. Two atoms of hydrogen are eliminated from each molecule to
form hydrogen gas and hence this process is termed dehydrogenation..

°300C
CH3OH HCHO + H2
Methanol Formaldehyde Hydrogen

1.3.5 Dehydration of Methanol:

Methanol does not undergo dehydration reactions. Instead, in reaction
with sulphuric acid the ester, dimethyl sulphate is formed.

CONC H2SO4
CH3OH (CH3)2SO4 + H2 2
Methanol Dimethyl sulphate Water

1.3.6 Esterification of Methanol

.Methanol reacts with organic acids to form esters

CH3OH + HCOOH HCOOCH3 + H2 O

Methanol Formic Acid Methyl Formate water

1.3.7 Substitution of Methanol with Sodium

Methanol reacts with sodium at room temperature to liberate hydrogen.
This reaction is similar to the reaction of sodium with ethanol.

CH3OH + 2 Na 2CH3ONa + H2 2
Methanol sodium Sodium Methoxide Hydrogen
1.3.8 Substitution of Methanol with Phosphorus
Pentachloride
Methanol reacts with phosphorus pentachloride at room temperature to
form hydrogen chloride, methyl chloride, (i.e. chloromthane) and
phosphoryl chloride.

CH3OH + PCl5 HCl + CH3Cl + POCl3

Methanol phosphoric hydrogen chloride chloromethane Phosphoryl chloride

1.3.9 Substitution of Methanol with Hydrogen Chloride

Methanol reacts with hydrogen chloride to form methyl chloride (i.e
chloromethane) and water. A dehydrating agent (e.g. zinc chloride) is
used.

ZnCl2
CH3OH + HCl CH3Cl + H2O
Methanol Hydrogen chloride Methyl Chloride water
1.4 USES OF METHANOL
The major portion of the methanol produced is used for making
formaldehyde and a number of chemical derivatives. Other applications
include its use as solvents extractant and air automation antifreeze.

1.4.1 Methanol As A Solvent:-

Methanol is miscible with most organic liquids and is a solvent for
variety of substance like dyes, nitro cellulose, polyvinyl, butyl ethyl
cellulose, Shellac and modified resin. It is used in the manufacturing10 of
wood and metal polishes. Water proofing formulation, coated fabrics,
aniline, and other inks, and duplicator fluids.

Methanol As An Extractant 1.4.2

Methanol is employed in a large scale in many industrial chemical
processes as an extractant. In the refining of gasoline and heating oil.
Methanol is also uses for removing acid impurities from vegetable oils,
dewaxing dimmer gum, flash washing water soluble crystals, extracting
inorganic salt such as potassium iodide and barium and strontium halides,
purifying hormones and crystallizing steroid.

Methanol As A Cleansing Agent 1.4.3

Methanol is used in many cleansing operations such as in washing steel
surfaces before coatings are applied , rinsing the interiors of electronic
tubes before they are evacuated , cleaning resin sheets before further
processing , It is employed as a reducing agent in the vapor phase
cleaning of copper, the bright annealing of brass and in soldering fluxes.
Its is also used in special preparation for dry cleaning leather goods, in
glass cleaners and in flushing fluids for hydraulic brake system.

Formaldehyde 1.4.4
Worldwide, the largest amount of formaldehyde is consumed in the
production of urea-formaldehyde resins, the primary end use of which is
found in building products such as plywood and particle board .

1.4.5 ACIDS
Methanol carbonylation has become the process of choice for production
of this staple of the organic chemical industry, which is used in the
manufacture of acetate fibers, acetic anhydride, and terephthalic acid, and
for fermentation.

1.4.6 Methanol As An Alternative Fuel

Utilization of methanol as alternative fuel can be done through two
different ways that is by using directly in an internal combustion engine
or by implementing methanol fuel cell powered vehicle.
1.5 Methanol production methods
Qunch reactor-1

Method class gas reactors-2

Method of producing methanol from industrial gas shift-3

LURGI method(low-pressure process)-4

1-Qunch reactor
Consists of the reactor from several racks of the catalyst and injects part
of the gas interaction during the first rack after heated in a heat exchanger
using gas output when he came out from the shelf the last while pumping
the remaining portion of the gas through the shelves the other inside the
reactor continuously using a good distributor to offset the heat produced
there disparity temperature on the surface of the catalyst in the reactor up
to a maximum of 30 Celsius.

Using this type of reactor by ici English It is more economical and has a
high flexibility for large production capacities

2- Class gas reactors

( the chem. Systems three phase method process)
Provides synthetic gas at the bottom of the reactor Bjerian opposite to
Hedrocarbona inert liquid. Being flowing catalytic inhibitor b
Hedrocarbona which is based Kmalk absorb heat of reaction which gives
complete control of the temperature is separated whimsical gas, liquid,
and solid at the top of the reactor
3-Method of producing methanol from industrial gas shift
(the conversion of synthesis gas to methanol )
Methanol is produced in this way from natural gas using catalysts of raw
materials and copper and gases involved are unilateral carbon dioxide and
hydrogen, as in equation

CO+2H2 CH3OH

Where is the gas pump and then cooled chiller and enters the reactor and
after the piece to converter

And then to distillation , And retrieval are part of the product purity
incomplete

4-LURGI method(low-pressure process):

This is the way of the main roads, and methods to produce methanol
which is the introduction of raw materials, which could be natural gas or
syngas containing the following
percentages(H2=74%,CO2=15%,Co=8%,inert=3%) Where the gases
enter the compressor where pushing gas to the pressure of 5MPa and a
temperature of 419.5 K after the intervention of gases to the heat
exchanger by the outlet of the reactor to raise the temperature of the feed
to a temperature of 250 Celsius that the gases go to the reactor and after
that the temperature drops and the pressure then separate
(CO2,CO,CH4)and recycle them then the water and methanol by
distillation
 Choosing the best way
Has been selected the previous method (LURGI) To study for the
following reasons:

1- Less expensive in terms of raw material, which is natural gas

2- Less expensive in terms of hardware design, the spectrum of the
few in number and small size
3- Less loss of energy used, the spectrum for the use of fumes coming
out of the stomach and introduced to other heating stomach
4- High purity methanol due to isotropic don’t occur
5- Less pollution to the environment in terms of the gases are raised
and processed
 CHAPTER TWO

MATERIAL BALANCE
a)reacter ;b)heat exchanger ;c)compresser ;d)seperator ;

e)distillation column ;f)cooler

BASIC CALCULATIONS
Product capacity = 200,000 ton/year

Operating Time =300 day

Basis = 1 hr

Component M.wt.) kg/kmol)

CO 28
CO2 44
H2 2
CH 3 OH 32
H2O 18
CH4 16

200,000 ton/year ×(1000kg/1ton)×(1 year/300day)×(1 day/24 hr)

=27777.78 Kg/hr

M.wt of Methanol = 32 Kg/Kmol

wt 27777.78
No.of moles = M . wt = 32

No.of moles of CH3OH = 868.056 Kmol

Now :

Methanol Yield = 98.5 %

Methanol produt
Methanol Yield % = (CO +CO 2)

That is (CO+CO2) for reacted

868.056
0.985= (CO +CO 2) (CO+CO2) = 881.275 Kmol

881.275 = ( 0.73*CO +0.144*CO2)

 881.275−0.144∗co 2
CO = 0.73

The feed composition is shown below:

Componen %
t
CO 15
CO2 8
H2 74
CH4 3
Total 100%

Now :
881.275−0.144 (0.08∗Feed)
(0.15*Feed) = 0.73

Feed = 7282.06 Kmol

MATERIAL BALANCE ON REACTOR

R F2
F1
E
C
Co 15% Co
CO2 8% T CO2
H2 74%
H2
CH4 3% E CH4
CH3OH
R H2O
Reaction 1:

CO+ 2 H 2 ⇄ CH 3 O H

A12 A1 A1

Conversion=X 1=73 %

Reaction 2:
CO 2+3 H 2 ⇄ CH 3 OH + H 2 O

B1 3 B1 B1 B1

Conversion=X 2=14.4 %

M.B. ON CO
CO In = 0.15 F1 = 1092.309 Kmol = 30584.652 Kg

Reacted= Conversion × Input

Reacted CO = A1× X1 = 797.3856 Kmol = 22326.795 Kg

Unreacted CO =In CO – Reacted CO

Unreacted CO = 294.9234 Kmol = 8257.8552 kg

CO In = CO Out

30584.652 =22326.795 + 8257.8552

30584.652 Kg = 30584.652 Kg
M.B. ON CO2
CO2 In = 0.08 F1 = 582.5648 Kmol = 25632.8512 Kg

Reacted = Conversion × Input

Reacted CO2 = B1 × X2 = 83.89 Kmol

Unreacted CO2 =In CO2 – Reacted CO2

Unreacted CO2 = 498.6748 Kmol = 21941.6912 kg

CO2 In = CO2 Out

25632.8512 = 3691.16 + 21941.6912

25632.8512 Kg = 25632.8512 Kg

M.B. ON H2
H2 In = 0.74 F1 = 5388.7244 Kmol = 10777.4488 kg

Reacted= Conversion × Input

For reaction 1:

Reacted H2 = 2A1×X1 = 1594.77114 Kmol

For reaction 2:

Reacted H2 =3 B1 × X2 = 251.67 Kmol

Unreacted H2=In H2 – Reacted H2

Unreacted H2 =3542.28326 Kmol = 7084.56652 kg

H2 In = H2 Out

10777.4488 = 3692.88228 + 7084.56652

10777.4488 Kg = 10777.4488 Kg
M.B. ON CH3OH
For reaction 1:

Produced CH3OH = A1×X1

Produced CH3OH = 797.3856 Kmol

For reaction 2:

Produced CH3OH = B1 ×X2

Produced CH3OH = 83.89 Kmol

M.B.ON CH4
CH4 In = 0.03 F1 = 218.4618 Kmol = 3495.3888 Kg

CH4 Out = 3495.3888 Kg

CH4 In = CH4 Out

3495.3888 Kg = 3495.3888 Kg

M.B.ON H2O
Produced H2O = B1 ×X2

Produced H2O = 83.89 Kmol

Component In (Kmol) In (Kg) Out (Kmol) Out (Kg)

CO 1092.309 30584.652 294.9234 8257.8552

H2 5388.7244 10777.4488 3542.28326 7084.56652

CH3OH --- --- 881.2756 28200.8192

CO2 582.5648 25632.8512 498.6748 21941.6912

H2O --- --- 83.89 1510.02

CH4 218.4618 3495.3888 218.4618 3495.3888

Total 7282.06 70490.34 5519.50886 70490.34

OVER ALL MATERIAL BALANCE ON THE REACTOR

INPUT TO THE REACTOR = OUTPUT FROM THE REACTOR

70490.34 Kg = 70490.34 Kg
 MATERIAL BALANCE ON GAS-LIQUID
SEPARATOR
CO=8257.8552 Kg

CO2=21941.6912 Kg

H2=7084.56652 Kg

F3 CH4=3495.3888 Kg

SSNLK
JSSJ
S
E

F2 P
CH3OH=28200.8192 Kg
A
CH4=3495.3888 Kg

CO=8257.8552 Kg R
CO2=21941.6912 Kg
A
H2=7084.56652 Kg

H20=1510.02 Kg T
O
R
SS

F4

CH3OH=28200.8192 Kg

H2O=1510.02 Kg
 F2 = 70490.34 Kg

F3 = 40779.50172 Kg

F4 = 29710.8392 Kg

F2 = F3 + F4

29710.8392 + 40779.50172 = 70490.34

Kg = 70490.34 Kg 70490.34

In = Out

Component In (Kmol ) In (Kg) Out (Kmol) Out (Kg)

CO 294.9234 8257.8552 294.9234 8257.8552
CO2 498.6736 21941.6912 498.6736 21941.6912
H2O 83.89 1510.02 83.89 1510.02

H2 3542.2832 7084.56652 3542.2832 7084.56652

CH4 218.4618 3495.3888 218.4618 3495.3888
CH3OH 881.2756 28200.8192 881.2756 28200.8192
Total 5519.50886 70490.34 5519.50886 70490.34

OVER ALL MATERIAL BALANCE ON THE SEPARATOR

INPUT TO THE SEPARATOR = OUTPUT FROM THE

SEPARATOR

Kg = 70490.34 Kg 70490.34
 M.B ON THE FIRST DISTILLATION COLUMN

F5

D CH3OH=99%

I H2O=1%

T
F4
I
CH3OH=28200.8192 Kg

H2O=1510.02 Kg
L

1 +

F6

CH3OH=1%

H2O=99%
 The heavy key is H2O
The light key is Methanol
Total M.B
F4=F5+F6………1
Total M.B for methanol
28200.8192=0.99*F5+0.01*F6
28200.8192=0.99*F5+0.01*(F4-F5)
28200.8192=0.99*F5+0.01*(29710.8392-F5)
28200.8192=0.99*F5+297.108392-0.01*F5
27903.710808=0.98*F5
F5=28473.1742Kg sub in eq.1
F6=1237.665Kg
Methanol in F5 =28188.442458Kg/hr=880.8888Kmol/hr
Methanol in F6=12.37665Kg/hr=0.3867Kmol/hr
Total M.B for water
Water in F5=0.01*F5=284.731742Kg/hr=15.8184Kmol/hr
Water in F6=0.99*F6=1225.28835Kg/hr=68.071575Kmol/hr

IN Out
Componen (Kg) (Kmol) F5 (Kg) F5(Kmol) F6 (Kg) F6(Kmol)
t
CH3OH 28200.819 881.275 28188.44245 880.8888 12.37665 0.3867
2 6 8
H2O 1510.02 83.89 284.731742 15.8184 1225.2883 68.071575
5

OVER ALL MATERIAL BALANCE ON THE FIRST

DISTILLATION COLUMN:
 INPUT TO THE FIRST DISTILLATION COLUMN = OUTPUT
FROM THE FIRST DISTILLATION COLUMN

M.B ON THE SECOND DISTILLATION

COLUMN

F7

CH3OH= 99.5%

H2O=0.5%

F5
CH3OH=28188.442458Kg

H2O=284.731742Kg

CH3OH=0.5%

H2O =99.5%

F8
The heavy key is H2O
The light key is Methanol
So:
Total M.B
 F5=F7+F8……1
F5=F7+(F5-F7)
For methanol
28188.442458=0.99*F7+0.01*F8
28188.442458=0.99*(F5-F8)+0.01*F8
28188.442458=0.995*(28473.1742 -F8)+0.005*F8
28188.442458=28330.808329-0.995F8+0.005*F8
-142.365871= -0.99*F8
F8=143.8039Kg/hr sub in eq….1
F7=28329.3703Kg/hr
Methanol in
F7=28329.3703*0.995=28187.7234485Kg/hr=880.8663Kmol/hr
Methanol in F8=143.8039*0.005=0.7190195Kg/hr=0.0224Kmol/hr
Total water M.B
water in F7=28329.3703*0.005=141.646851Kg/hr=7.8692Kmol/hr
water in F8=143.8039*0.995=143.08488Kg/hr=7.9491Kmol/hr
Methanol produced =28329.3703x 300 x 24 x0.001 ≅ 200000 ton/year

Out
Comp. F5 (Kg) F5(Kmol) F7 ( Kg) F7( Kmol F8 (Kg) F8(Kmol)
)
CH3OH 28188.442458 880.8888 28187.723448 880.8663 0.7190195 0.0224
H2O 284.731742 15.8184 141.646851 7.8692 143.08488 7.9491

OVER ALL MATERIAL BALANCE ON THE FIRST

DISTILLATION COLUMN:
INPUT TO THE FIRST DISTILLATION COLUMN = OUTPUT
FROM THE FIRST DISTILLATION COLUMN
OVER ALL MATERIAL BALANCE
 TOTAL IN = TOTAL OUT

Componen In(Kmol) In(Kg) Out(Kmol) Out(Kg)

t
CO 1092.309 30584.652 294.9234 8257.8552

CO2 582.5648 25632.8512 498.6748 21941.6912

H2 5388.7244 10777.4488 3542.28326 7084.56652

CH4 218.4618 3495.3888 218.4618 3495.3888

CH3OH --- --- 881.2756 28200.8192

H2O --- --- 83.89 1510.02

Total 7282.06 70490.34 5519.50886 70490.34

 CHAPTER THREE

ENERGY BALANCE

Energy balance on Comperessor :

T1=35ᵒC=308K T2=?

P1=1bar P2=50bar

CP= A+ BT +C T 2 + DT 3 + E T 4

comp. A B C D E Cp YI%
CH4 34.942 -0.03996 1.9184E-04 -1.5303E-07 3.9321E-11 36.71656 0.03
CO2 27.437 0.04232 -1.9555E-05 3.9968E-09 -2.9872E-13 38.729 0.08

CO 29.556 -0.00658 -2.013E-05 -1.2227E-08 2.2617E-12 29.1018 0.15

H2 25.399 0.020178 - 3.5849E-05 3.188E-08 -8.7585E-12 28.809 0.74
CP=KJ/Kmol. k
Cp(CH4)in mix =36.71656*0.03=1.103

Cp(CO2)in mix=38.729*0.08=3.098

Cp(CO)in mix=29.1018*0.15=4.365

Cp(H2)in mix=28.809*0.74=21.31

Cp for mixture = Cp(CH4)in mix+ Cp(CO2)in mix + Cp(CO)in mix + Cp(H2)in mix

Cp for mixture=1.103+3.098+4.365+21.31=29.876

Mol % TC PC w
Comp .
y k ¯¿
0.714
H2 0.74 33.2+8 13.31+8
0.066
co 0.15 132.9 35
Co 2 0.228
0.08 304.2 73.8
0.011
CH 4 0.03 190.58 46.04

TC mix=∑TCi × yi

TC mix =80.903

Pc mix=∑ pci × yi

Pc mix = 28.304

w mix=∑wi × yi

w mix=0 .55683

Tr=T /Tc Tr =308/80.903 = 3.807

Pr = P/Pc Pr = 1/28.304 = 0.035

Pc Pr Pc Pr
Z for mix=1+ 0 .083−
( Tc 1 .6
× ( )) (
Tr
+w × 0 .139− 4 .2 ×
Tc ( ))
Tr

Z=1.001

PV=ZnRT
ZnRT 1.001 ×7282.06 × 8.314 ×308
V= = =51.84
P 100× 3600

Ep : Efficiency compressor =( 76%)

CP mix =∑ cpi × yi CP mix =29.876

Cp = CV−¿ R

R=8.314 J/mol.K

CV mix=29.876 – 8.314 = 21.562

CP 29.876
γ=
( mix )
= =1.3855
CV (mix )
21.562

γ−1 1.3855−1
m= = =0.366
E P × γ 0.76 × 1.3855

P2 m 50 0.366
T 2=T 1 × ( )
P1
=35 ×
1( ) =146.51° C =419.51°K

T 1+T 2 419.51+308
Tmean= = =363.755 ° K
2 2

Cp(CH4) at Tmean=1.17343

Cp(H2) at Tmean=21.47406

Cp(CO2) at Tmean=3.23424

Cp(CO) at Tmean=4.3914

Cp° for mix. At Tmaen = Cp(CH4) at Tmean+ Cp(H2) at Tmean+ Cp(CO2)

at Tmean+ Cp(CO) at Tmean
Cp° for mix. At Tmaen =30.27312

Cp-Cp°=1 From chart 3.2 vol 6

Cp=30.27312+1=31.27312

Cp 31.27312
γ= = =1.36
Cp−8.314 31.27312−8.314

γ −1 1.36−1
m≡ γ × Ep = 1.36 × 0.76 =0.34

1 1
n= = =1.517
1−m 1−0.34

n−1
n p2
Work (per kmol)= ZRT ( )[ ( )
n−1 p 1
n
−1]

Z = 1.0 01 , R = 8.314 kJ/kmol.K constant of gases

1.517 50 1.517−1
W =1.001× 8.314 ×308 ×( )×[( ) 1.517 −1]
1.517−1 1

W= 21009.03057kJ/kmol

KJ kmol hr
(21009.03057 × 7282.06 × )
kmol hr 3600 s
power=
0.76

power=55917.03989 Kw =55.91703989 Mw

Energy balance on Heat Exganger :

 F4

Co=8257.8552 Kg

Co2=21941.6912 Kg

CH4=3495.3888 Kg

H2=7084.56652 Kg

H2O=1510.02 Kg

CH3OH=28200.8192 Kg

T=?

F2 F1

Co2=25632.8512Kg Co2=25632.8512Kg

Co=30584.652 Kg Co=30584.652 Kg

CH4=3495.3888 Kg CH4=3495.3888 Kg

H2=10777.4488 Kg H2=10777.4488 Kg

T=250ᵒC T=146.5ᵒC

F3

Co=8257.8552 Kg

Co2=21941.6912 Kg

CH4=3495.3888 Kg

H2=7084.56652 Kg

H2O=1510.02 Kg

CH3OH=28200.8192 Kg

T=250ᵒC
 COMP. A B×10−2 C×10−4 d×10−7 E×10−11

CH4 34.942 -3.996 1.9184 -1.5303 3.9321

CO2 27.437 4.232 -0.19555 0.039968 -0.029872

CO 29.556 -0.658 0.2013 -0.12227 0.22617

H2 25.399 2.0178 -0.35849 0.3188 -0.87585

H2O 33.933 -0.84186 0.29906 -0.17825 0.36934

CH3OH 40.046 -3.8287 2.4529 -2.1679 5.9909

n Δ H ∈¿ n Δ H out
Tref =25 ᵒ C=298 K

Q1+Q3=Q2+Q4
419.5 523 523 T
∑∋ ∫ cpi dT +∑∋ ∫ cpidT =∑∋ ∫ cpidT +∑∋ ∫ cpi dT
298 298 298 298

Q=ncpΔT =n ¿
419.5
Q 1=∑∋ ∫ cpi dT
298

Q1 = QCO2 + QCO + QCH4 +QH2

QCO2 =582.5648 ¿
QCO2 =2849886.408 KJ/hr

QCO=1092.309 ¿
QCO =3884563.204 KJ/hr
QCH4=218.4618 ¿
QCH4=1033932.949KJ/hr
QH2=5388.7244 ¿
QH2=19209899.87 KJ/hr
Q1 = QCO2 + QCO + QCH4 +QH2
Q1 = 26978282.43 KJ/hr
523
Q 3=∑∋ ∫ cpi dT
298

Q3 = QCO2 + QCO + QCH4 +QH2+ QH2O+ QCH3OH

QCO2=498.6748 ¿
QCO2=4680961.111 KJ/hr
QCO=294.9234 ¿
QCO=1957326.682 KJ/hr
QCH4=218.4618 ¿
QCH4=2043800.254 KJ/hr
QH2=3542.28326 ¿
QH2=23571234.84KJ/hr
QH2O=83.89 ¿
QH2O=650024.4334KJ/hr
QCH3OH=881.2756 ¿
QCH3OH=10416823.88 KJ/hr
Q3 = QCO2 + QCO + QCH4 +QH2+ QH2O+ QCH3OH
Q3 =43320171.2 KJ/hr
523
Q 2=∑∋ ∫ cpi dT
298

Q2 = QCO2 + QCO + QCH4 +QH2

QCO2=582.5648 ¿
QCO2=5468419.402 KJ/hr

QCO=1092.309 ¿
=QCO KJ/hr 5540261.836

QCH4=218.4618 ¿
QCH4=2043800.402KJ/hr

QH2=5388.7244 ¿
=QH2 35857917.53KJ/hr

Q2 = QCO2 + QCO + QCH4 +QH2

Q2 = 48910399.64KJ/hr

T
Q 4=∑∋ ∫ cpi dT
298

Q4 = QCO2 + QCO + QCH4 +QH2+ QH2O+ QCH3OH

QCO2=498.6748 ¿

QCO=294.9234 ¿
QCH4=218.4618 ¿
QH2=3542.28326 ¿

QH2O=83.89 ¿
QCH3OH=881.2756 ¿

:- Q1+Q3=Q2+Q4
Q4=Q1+Q3-Q2
Q4=21388053.99 KJ/hr
T
Q 4=∑∋ ∫ cpi dT
298
 Q4 = QCO2 + QCO + QCH4 +QH2+ QH2O+ QCH3OH
That is T=415 K =142 ᵒC

Energy balance on Reactor :

Q2
Co
CO2
H2
CH4
CH3OH
H2O
T=250°C

Steam
T=120°

water
T=25°

Q3
Co
CO2
H2
CH4
T=250°C

Qin=Qout

Q2+Qgen=Q3+Qsteam+Qacc.

(Steady state) Qacc.=0

 Q2+Qgen=Q3+Qsteam

523
Q 2=∑∋ ∫ cpi dT
298

Q2 = QCO2 + QCO + QCH4 +QH2

QCO2=582.5648 ¿
QCO2=5468419.402 KJ/hr

QCO=1092.309 ¿
QCO=5540261.836 KJ/hr

QCH4=218.4618 ¿
QCH4=2043800.402KJ/hr

QH2=5388.7244 ¿

QH2=35857917.53KJ/hr

Q2 = QCO2 + QCO + QCH4 +QH2

Q2 = 48910399.64KJ/hr

Qgen=ΔH (r 1+r 2)

Reaction1 :

CO+2H2 CH3OH
ΔH reaction 1=∑∋ Δh product −∑∋Δhf reacted
¿ [ ( 1×−201.3 ) ] −[( 2 ×0 )+ (−110.62 ) ]

kJ −90680 kJ
∗1000 mol ∗797.3856 kmol
mol kmol
¿−90.68 = =−72306926.208 kJ /hr
kmol hr

Reaction2 :

CO 2+3 H 2 CH 3 OH + H 2 O

ΔH reaction 2=∑ niΔhproduct −∑niΔh reacted

¿ [ ( 1×−241.815 )+ ( 1×−201.3 ) ] −[ ( 3 ×0 )+ (−393.51 )]

kJ
∗1000 mol
mol −496505 kJ kmol
¿−49.605 = ∗83.89 =−41651804.45 kJ /hr
kmol kmol hr

Q 2=ΔH 1+ ΔH 2

KJ
¿−72306926.208−41651804.45=−113958730.658
kmol
523
Q 3=∑∋ ∫ cpi dT
298

Q3 = QCO2 + QCO + QCH4 +QH2+ QH2O+ QCH3OH

QCO2=498.6748 ¿
QCO2=4680961.111 KJ/hr
QCO=294.9234 ¿
QCO=1957326.682 KJ/hr
QCH4=218.4618 ¿
QCH4=2043800.254 KJ/hr
QH2=3542.28326 ¿
QH2=23571234.84KJ/hr
QH2O=83.89 ¿
QH2O=650024.4334KJ/hr
QCH3OH=881.2756 ¿
QCH3OH=10416823.88 KJ/hr
Q3 = QCO2 + QCO + QCH4 +QH2+ QH2O+ QCH3OH
Q3 =43320171.2 KJ/hr
Qsteam=Q2+Qgen-Q3

Qsteam=48910399.64−113958730.658−43320171.2 ¿−108368502.218 kJ /hr the

energy from the reactor so the energy absorbed by the water is(
108368502.218 kJ /hr ¿

393

Qsteam=n∫ cp ∆ T
298

108368502.218=n∗¿

108368502.218=n∗3222.6215

n=26552.1965kmol

msteam =nsteam *Mwt

=33627.4372*18=605293.8696Kg/hr
 Energy balance on Cooler:

Co=294.9234 kmol/hr

Co2=498.6748 kmol/hr

CH4=218.41618 kmol/hr

H2=3542.28326 kmol/hr

H2O=83.89 kmol/hr

CH3OH=881.2756 kmol/hr

T=30 ᵒC

Q=1077175.2451kj/hr
H2O out=40°C

QC=20310878.7449KJ/hr

H2O in =25C

Co=294.9234 kmol/hr

Co2=498.6748 kmol/hr

CH4=218.41618 kmol/hr

H2=3542.28326 kmol/hr

H2O=83.89 kmol/hr

CH3OH=881.2756 kmol/hr

T=142 ᵒC
Q=21388053.99 kJ/hr
Qc=Q4-Q5

Q4=21388053.99 KJ/hr
303

Q5¿ ∑∋ ∫ cpiL +cpi V dT

298

Q5(for liquids)=QCH3OH +QH2O

QCH3OH=
3.1046∗10−1 ( 2 2 1.0291∗10−3 ( 3 3 1.4598∗10
881.2756 ×[40.152×(303−298)+ × 303 −298 −) × 303 −298 )+
2 3 4

QH2O=
3.9953∗10−2 ( 2 2 2.1103∗10−4 ( 3 3 5.4369∗10−7
83.89 ×[92.053×(303−298)− × 303 −298 )− × 303 −298 ) + ×
2 3 4

Q7=31771.1537+353082.3733=384853.527KJ/hr

Q5(for gases)=QCO+QCO2+QH2+QCH4
QCO=294.9234 ¿

QCO=42886.4858KJ/hr

QCO2=498.6748 ¿

QCO2=95680.7448KJ/hr

QH2=3542.28326 ¿

QH2=513966.5911KJ/hr

QCH4= 218.4618 ¿

QCH4=39787.9034KJ/hr

Qvap=42886.4858+95680.7448+513966.5911+39787.9034

Qvap=692321.7251KJ/hr

Q5= Qliq + Qvap

 Q5=384853.52+692321.7251
Q5= 1077175.2451KJ/hr
QC=Q4-Q5
QC=21388053.99 -1077175.2451
QC=20310878.7449KJ/hr
313

QH2O out=n ∫ CPH 2 O ∆ T

298

QH2O out =
3.9953 ×10−2 2.1103 ×10−4 5.4369 ×10−7
[
n × (92.053 × (313−298 )−
2
× ( 3132−2982 )−
3
× ( 3133−2983 ) +
4
×(3

20310878.7449=n× 1134.88746

NH2O=15989.48818Kmol/hr
mH2O=17896.8218 ×18=31838.7924 Kg/hr

Energy balance on Seperator :

Co=294.9234 kmol/hr

Co2=498.6748 kmol/hr

CH4=218.41618 kmol/hr

H2=3542.28326 kmol/hr

Co=294.9234 kmol/hr T=30 ᵒC

Co2=498.6748 kmol/hr Q6=692321.7251KJ/hr

CH4=218.41618 kmol/hr

H2=3542.28326 kmol/hr

H2O=83.89 kmol/hr

CH3OH=881.2756 kmol/hr

T=30 ᵒC
Qin=Q5=1077175.2521KJ/hr

Qout=Q6+Q7

Q6=QCO+QCO2+QH2+QCH4

QCO=294.9234 ¿

QCO=42886.4858KJ/hr

QCO2=498.6748 ¿

QCO2=95680.7448KJ/hr

QH2=3542.28326 ¿

QH2=513966.5911KJ/hr

QCH4= 218.4618 ¿

QCH4=39787.9034KJ/hr

Q6=42886.4858+95680.7448+513966.5911+39787.9034

Q6=692321.7251KJ/hr

Q7= QCH3OH+ QH2O

T=303K Tref=298K
QCH3OH=
3.1046∗10−1 ( 2 2 1.0291∗10−3 ( 3 3 1.4598∗10
881.2756 ×[40.152×(303−298)+ × 303 −298 ) − × 303 −298 )+
2 3 4

QH2O=
3.9953∗10−2 ( 2 2 2.1103∗10−4 ( 3 3 5.4369∗10−7
83.89 ×[92.053×(303−298)− × 303 −298 )− × 303 −298 ) + ×
2 3 4

Q7=31771.1537+353082.3733=384853.527KJ/hr

Qout=692321.7251+384853.527
Qout = 1077175.2521KJ/hr
Energy balance on Heat Exganger 2 :
H2O
T=40
℃

H2O=83.89Kmol/hr
H2O=83.89Kmol/hr
CH3OH=881.2756Kmol/hr
CH3OH=881.2756Kmol/hr
℃ T=30
℃ T=66.5

H2O
T=120

Q7= QCH3OH+ QH2O

T=303K Tref=298K
QCH3OH=
3.1046∗10−1 ( 2 2 1.0291∗10−3 ( 3 3 1.4598∗10
881.2756 ×[40.152×(303−298)+ × 303 −298 ) − × 303 −298 )+
2 3 4

QH2O=
3.9953∗10−2 ( 2 2 2.1103∗10−4 ( 3 3 5.4369∗10−7
83.89 ×[92.053×(303−298)− × 303 −298 )− × 303 −298 ) + ×
2 3 4

Q7=31771.1537+353082.3733=384853.527KJ/hr

Q8= QCH3OH+ QH2O

T=339.5°K Tref=273°K
QCH3OH=
3.1046∗10−1 ( 2 2 1.0291∗10−3 ( 3 3 1.459
881.2756 ×[40.152×(339.5−298)+ × 339.5 −298 ) − × 3 39.5 −298 ) +
2 3
QH2O=
3.9953∗10−2 2.1103∗10−4 5.4369∗1
[
83.89 × 92.053× ( 339.5−298 )−
2
× ( 339.52−298 2) −
3
× ( 339.53−2983 ) +
4

¿ 262 949.3206 KJ /hr

Q8= QH2O+ QCH3OH

Q8=262949.3206+2994663.6277
Q 8=3257612.9483 KJ /hr

Q=Q7-Q8

Q =384853.527-3249572.4068

Q = -2864718.8798kJ/hr

For steam Tin=120℃

QH2O=n*[33.933 (393-298)
−0.84186∗10−2 ( 0.29906∗10−4 ( 0.17825∗10−7
2 2
393 −298 ) +
3 3
393 −298 )− (
2 3 4
4 4 0.36934∗10−11 5 5
393 −298 ¿+ (393 −298 )¿
5

Tout=40℃

QH2O=n*[92.053 (313-298)
−3.9953∗10−2 ( 2.1103∗10−4 ( 5.4369∗10−7
2 2
313 −298 −) 3 3
313 −298 +) (
2 3 4
3134 −2984 ¿ ¿

Qin-Qout=n*2087.734kJ /hr

n=1372.1666kmol/hr

m=n*M=1372.1666*18=24698.9988kg/hr

Energy balance on Distillation Colomn 1 :

 D

S
CH3OH 99%
T
H 2O 1%
I

L
CH3OH=28200.8192 Kg
A
H2O=1510.02 Kg T

℃ T=66.5 I

H2O 99%

CH3OH 1%

QF +QR=QD +QW +QC

∝i∗xi . f
Σ =1−q ………….From (Vol.6)
∝ i−θ
Where
q=1 (feed at bubble point)
xi.f=𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑒𝑒𝑑 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡𝑠
∝i=𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡
θ=constant

XCH3OH = 0.913 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 CH3OH from M.B

XH2O =0.087 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 H2O from M.B

B
ln P= A−
T +C

Where:

P :vapor pressure(mmHg).

For the top of the dist.

Tdp=66.05O C

A,B,C:constant.

Com A B C
CH3OH 18.5875 3626.55 -34.29
H2O 18.3036 3816.44 -46.13

3626.55
ln PCH 3 OH =18.5875−
339.05−34.29

PCH3OH=802.56 mmHg
3816.44
ln P H 2 O =18.3036−
339.05−46.13

PH2O=195.322 mmHg
yi
Ʃxi= P Ʃ pi =1

0.982 0.018
P ( 802.56 +
195.322 )
=1

P=760 mmHg(operating pressure)

pi
Ʃ × xi=1
p
Where P is the operating pressure

Pi is the vapor pressure of the component

Xi is the mile fraction of the component in the bottom

PCH 3OH × 0.096 PH 2O ×0.904
+ =1
760 760

By trial and error TBp for bottom=367.05°K

TBp for feed

PCH 3OH × 0.913 PH 2O ×0.087
+ =1
760 760

By trial and error TBp for feed=339.5°K

Relative volatility at top conditions

802.56
K CH 3 OH =
760

KCH3OH =1.056 hennery constant ofCH3OH

195.322
K H 2O =
760

KH2O =0.257 hennery constant of CH3OH (heavy key)

K CH 3 OH 1.057
∝CH 3OH = = =4.112 Volatility of CH 3OH at top conditions
KH 2O 0.257

K H 2O
∝ H 20= =1Volatility of H 2O at top conditions
K H 2O

Relative volatility at bottom conditions

2184.37
K CH 3 OH =
760

KCH3OH =2.874 hennery costant ofCH3OH

 608.739
K H 2O =
760

KH2O =0.8 hennery costant of CH3OH (heavy key)

K CH 3 OH 2.874
∝CH 3OH = = =3.59 Volatility of CH 3 OH at bottom conditions
KH 2O 0.8

K H 2O
∝ H 20= =1Volatility of H 2O at bottom conditions
K H 2O

∝i at top+ ∝i at bottom
∝ avg=
2

1+1
∝ avg for H 2 O= =1
2

4.112 +3.59
∝ avg for CH 3OH = =3.851
2

∝CH 3 OH∗X CH 3 OH ∝ H 2 O∗X H 2 O

+ =1−1
∝CH 3 OH−θ ∝ H 2 O−θ

3.851∗0.913 1∗0.087
+ =0
3.851−θ 1−θ

θ=1.2

For TOP:
∝i∗xi . d
Σ =R min+1 ………….From (Vol.6)
∝i−θ

Where
xi.d=concentration 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡
∝i=𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡
θ=constant
𝑅𝑚𝑖𝑛=𝑚𝑖𝑛𝑚𝑢𝑚 𝑟𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜
XCH3OH=0.982 concentration of CH3OH at Top
xH2O=0.018 concentration 𝑜𝑓 𝐻2𝑂 𝑎𝑡 𝑇𝑜𝑝
∝CH 3 OH∗X CH 3 OH ∝ H 2 O∗X H 2 O
+ =R min+1
∝CH 3 OH−θ ∝ H 2 O−θ

3.851∗0.982 1∗0.018
+ =R min+1
3.851−1.2 1−1.2
Rmin=¿0.336

Ract= 0.336*1.5= 0.504 Actual Reflux Ratio

D = 896.7072kmol From M.B

R=0. 504
V =L+ D
L
R=
D
L=RD
V =RD + D=( R +1 ) D

V = (0.504+1)* 896.7072=1348.6476kmol of vapor at top

Condenser Energy Balance:
Qc= -ΔH vap mix × V
LV mix = X CH3OH * LV CH3OH + X H2O * LV H2O ……..from (perry 1997)
Where
XCH3OH mole fraction of CH3OH at Top
X H2O mole fraction of H2O at Top
LVCH3OHLatent heat of CH3OH of Vaporization=34899.07 kJ/kmol
LV H2O Latent heat of Vaporization =40934.85 kJ/kmol
ΔH vap mix = 0.982 * 34899.07 +0.018* 40934.85
= 34270.88674+736.8273=35007.71404 kJ/kmol Latent heat for mixture
Qc=−35007.71404 ×1348.6476=−47213069.5215 KJ /hr

QD=QH2O+QCH3OH

Tout=339.05K Tref=298K

QH2O=
3.9953 ×10−2 2.1103 ×10−4 5
[
15.8184 × (92.053 × (339.05−298 )−
2
2 2
× ( 339.05 −298 )−
3
3 3
× ( 339.05 −298 ) +

QH2O =49045.0422KJ/hr

QCH3OH=
3.1046∗10−1 1.0291 ×10−3 1
[
880.8888 × 40.152× ( 339.05−298 )+
2
2 2
× 339.05 −298 −
( )
3
× ( 339.053−298 3 )+
QCH3OH =2960037.4174KJ/hr

QD=QH2O+QCH3OH

QD=49045.0422+2960037.4174=3155911.2816KJ/hr

QW=QH2O+QCH4OH

Tout=375°K Tref=298°K

QH2O=68.071575 ׿

QH2O=159017.3723KJ/hr

QCH3OH=0.3867 × ¿

QCH3OH=1260.8165KJ/hr
Qwt=QH2O+QCH3OH

Qw=159017.3723+1260.8165

Qw=160278.1888KJ/hr

QF=QH2O+QCH3OH

T=339.5°K Tref=273°K
QCH3OH=
3.1046∗10−1 ( 2 2 1.0291∗10−3 ( 3 3 1.459
881.2756 ×[40.152×(339.5−298)+ × 339.5 −298 −) × 339.5 −298 ) +
2 3

QH2O=
3.9953∗10−2 2.1103∗10−4 5.4369∗1
[
83.89 × 92.053× ( 339.5−298 )−
2
2 2
× ( 339.5 −298 ) −
3
3 3
× ( 339.5 −298 ) +
4

¿ 262949.3206 KJ /hr

QF= QH2O+ QCH3OH

QF=262949.3206+2994663.6277
QF =3257612.9483 KJ /hr
 QF +QR=QD +QW +QC

3257612.9483+QR=3155911.2816 +160278.1888−47213069.5215 QR=

-47154492.9994KJ/hr

Energy balance on Distillation Colomn 2 :

CH3OH 99.5%

H 2O 0.5%

CH3OH=27918.811 Kg

H2O=15.1002 Kg

T=66.05 O C
 D

I
+
O

H2O 99.5%

CH3OH 0.5%

QF +QR=QD +QW +QC

XCH3OH = 0.982 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 CH3OH in feed from M.B

XH2O =0.018 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 H2O in feed from M.B

For the top of the dist.

B
ln P= A−
T +C

Where:

P :vapor pressure(mmHg).

Tdp=65.35°C

A,B,C:constant.

Com A B C
CH3OH 18.5875 3626.55 -34.29
H2O 18.3036 3816.44 -46.13
3626.55
ln PCH 3 OH =18.5875−
338.35−34.29

PCH3OH=780.87 mmHg
3816.44
ln P H 2 O =18.3036−
338.35−46.13

PH2O=189.32 mmHg
yi
Ʃxi= PƩ p i =1

Where P is the operating pressure

Pi is the vapor pressure of the component

Yi is the mole fraction of the component in the top

YCH4OH=0.991

YH2O=0.009
0.991 0.009
p ( + )
780.87 189.32
=1

P=760 mmHg (operating pressure for the second distillation column)

For the bottom of the dist.

pi
Ʃ × xi=1
p

Where P is the operating pressure

Pi is the vapor pressure of the component

Xi is the mile fraction of the component in the bottom

PCH 3OH × 0.0028 PH 2O ×0.9972
+ =1
760 760

By trial and error TBp of bottom=373°K

PCH 3OH × 0.982 PH 2 O ×00.018
+ =1
760 760
By trial and error TBp of feed =339.05°K

Relative volatility at top conditions

780.87
K CH 3 OH =
760

KCH3OH =1.027 hennery constant ofCH3OH

189.32
K H 2O =
760

KH2O =0. 249 hennery constant of CH3OH (heavy key)

K CH 3 OH 1.027
∝CH 3OH = = =4.12 Volatility of CH 3 OH at topconditions
KH 2O 0.249

K H 2O
∝ H 20= =1Volatility of H 2O at top conditions
K H 2O

Relative volatility at bottom conditions

2645.33
K CH 3 OH =
760

KCH3OH =3.48 hennery constant ofCH3OH

755.88
K H 2O =
760

KH2O =0. 994 hennery constant of CH3OH (heavy key)

K CH 3 OH 3.48
∝CH 3OH = = =3.5 Volatility of CH 3 OH at top conditions
KH 2O 0.994

K H 2O
∝ H 20= =1Volatility of H 2O at bottom conditions
K H 2O
 ∝i at top+ ∝i at bottom
∝ avg=
2

1+1
∝ avg for H 2 O= =1
2

3.5+ 4.12
∝ avg for CH 3OH = =3.81
2

∝CH 3 OH∗X CH 3 OH ∝ H 2 O∗X H 2 O

+ =1−q
∝CH 3 OH−θ ∝ H 2 O−θ

∝CH 3 OH∗X CH 3 OH ∝ H 2 O∗X H 2 O

+ =1−q
∝CH 3 OH−θ ∝ H 2 O−θ

3.81∗0.982 1∗0.018
+ =0
3.81−θ 1−θ

θ=1.013

For TOP:
∝i∗xi . d
Σ =Rmin+ 1 ………….From (Vol.6)
∝i−θ

Where

xi.d=𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡

∝i=average 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡

θ=constant

𝑅𝑚𝑖𝑛=𝑚𝑖𝑛𝑚𝑢𝑚 𝑟𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜

XCH3OH=0.991 concintration of CH3OH at Top

xH2O=0.009 concentration 𝑜𝑓 𝐻2𝑂 𝑎𝑡 𝑇𝑜𝑝

∝CH 3 OH∗X CH 3 OH ∝ H 2 O∗X H 2 O
+ =Rmin+1
∝CH 3 OH−θ ∝ H 2 O−θ

3.81∗0.991 1∗0.009
+ =Rmin+1
3.81−1.013 1−1.013

Rmin=0.049

Ract= 0.049*1.5 =0.0735Actual Reflux Ratio

D = 888.7355 kmol/hr From M.B

R=0.0735
V =L+ D

L
R=
D

L=RD

V =RD + D=( R +1 ) D

V = (0.0735+1)* 888.7355 =954.0575kmol/hr of vapor at top

Condenser Energy Balance:
Qc= -ΔH vap mix× v
LV mix = X CH3OH* LV CH3OH + X H2O * LV H2O ……..from (perry 1997)
Where
XCH3OH mole fraction of CH3OH at Top
X H2O mole fraction of H2O at Top
LVCH3OHLatent heat of CH3OH of Vaporization=35153.652kJ/kmol
LV H2O Latent heat of Vaporization =41077.692kJ/kmol
ΔH vap mix = 0.991* 35153.652+0.009*41077.692
34837.269132+369.699228
= 35206.96836 kJ/kmol Latent heat for mixture
Qc=−35206.96836∗954.0575=−33589472.2161 KJ /hr

QD=QH2O+QCH3OH

Tout=338.35K Tref=298K

QH2O=
3.9953× 10−2 2.1103 × 10−4 5.
[
7.8692× (92.053 × ( 338.35−298 )−
2
2 2
× ( 338.35 −298 )−
3
3 3
× ( 338.35 −298 ) +

QH2O =23982.96KJ/hr

QCH3OH=
3.1046∗10−1 1.0291 ×10−3 1
[
880.8663 × 40.152× ( 338.35−298 )+
2
× ( 338.352−2982 ) −
3
× ( 338.353−298 3 )+
QCH3OH =2908185.8629KJ/hr

QD=QH2O+QCH3OH

QD=23982.96+2908185.8629=2932168.8229KJ/hr

QW=QH2O+QCH4OH

Tout=373K Tref=298K

QH2O=7.9491× ¿

QH2O =20183.8884 KJ/hr

QCH3OH=0.0224 × ¿

QCH3OH =79.6563 KJ/hr

Qwt=QH2O+QCH3OH

Qw=20183.8884+79.6563

Qw=20263.5447KJ/hr

QF=QH2O+QCH3OH

Tin=339.05K Tref=298K

QH2O=
3.9953 ×10−2 2.1103 ×10−4 5
[
15.8184 × (92.053 × (339.05−298 )−
2
2 2
× ( 339.05 −298 )−
3
3 3
× ( 339.05 −298 ) +

QH2O =49045.0422KJ/hr

QCH3OH=
3.1046∗10−1 1.0291 ×10−3 1
[
880.8888 × 40.152× ( 339.05−298 )+
2
2 2
× 339.05 −298 −
( )
3
× ( 339.053−298 3 )+

QCH3OH =2960037.4174KJ/hr

QF=QH2O+QCH3OH

QF=49045.0422+2960037.4174=3155911.2816KJ/hr
QF +QR=QD +QW +QC
3155911.2816+ QR=2932168.8229+20263.5447−33589472.2161

QR= -33792951.1301KJ/hr