University of Diyala

College of Engineering
Chemical Engineering Department

Production of formaldehyde
A project report Submitted to the Engineering Department
of Chemical of the University of Diyala in a partial fulfillment
for the Degree of [Link] in Chemical Engineering

By

Sajad jabar sabty

Muhanad asaad adham

Mohammad abdulljalel mudhafar

Supervisor:
Assist. prof. Dr. ahmed daham waheeb

2015 - 2016
 Table of Contents
Chapter one ……………………………………………………….. 1
1- Summary ……………………………………………………..... 2
1.1 - Introduction …………………………………………………...2
1.2 - Health effects …………………………………………………3
1.3 - Sources ………………………………………………………. 3
1.4 - Demand ……………………………………………………… 3
1.5 - Use of formaldehyde ……….………………………………...4

1.6- Physical and chemical properties ……………………………..4

1.6.1- Physical Properties of Formaldehyde ………………………4

1.6.2 - Chemical properties ………………………………………...5

1.7- Production methods …………………………………………...6

1.7.1- From methanol by silver catalysts process ………………….8

1.7.2- Metal oxide catalyst process ………………………………..10

1.7.3- Production of formaldehyde from other hydrocarbon gases ..12

1.8- Selection of process ……………………………………….…..13

Chapter two ……………………………………………………….14

2.1-Mass balance ……………………………………………….…..15

2.1.1- First run mass balance………………………………………..15

[Link]- Material balance on the reactor ……………………………15

[Link]- Material balance on the absorber…………………………...18

[Link]- Material balance on the distillation column…………………22

2.1.2- Second run mass balance ……………………………………..25

4
[Link]- Mass balance on the reactor ……………………………….25

[Link]- Mass balance on the absorber……………………………...26

[Link]- Mass balance on the distillation column …………………..27

2.2- Energy balance ………………………………………………...29

2.2.1- Mixing point between streams 2 , 3 and 15 …………………29

2.2.2- Energy balance on the heat exchanger E-101 ……………….30

2.2.3- Energy balance on the heat exchanger E-102 ……………….32

2.2.4- Mixing point between streams 6, 7 ………………………….33

2.2.5- Energy balance on the reactor ……………………………….33

2.2.6- Energy balance on the heat exchanger inside the reactor ……34

2.2.7- Energy balance on the absorber ……………………………...36

2.2.8 - Energy balance on the heat exchanger E-103………………...37

2.2.9- Energy balance on the distillation column T-101 …………….38

2.2.10- Mixing point of stream 17 , 18 and 19………………………40

2.2.11- Energy balance on the heat exchanger E – 106……………..42

Chapter three ………………………………………………………43

3.1- Introduction of design …………………………………………44

3.2- Reactor design………………………………………………….44

3.2.1- Reactor design equation ……………………………………..44

3.2.2 Mole balance …………………………………………………45

3.2.3 Net rate laws ………………………………………………....46

3.2.4 Rate laws …………………………………………………….46

3.2.5- Stoichiometry ……………………………………………….48

5
3.2.6- Combination ………………………………………………..49

3.2.7- Pressure drop ……………………………………………….50

3.2.8 – Result ……………………………………………………...52

3.3- Packed-bed absorber design…………………………………..56

3.3.1- Introduction ……………………………………………….56

3.3.2 -Packing material…………………….………………………56

3.3.3- Sizing of packed tower……………………………………..56

[Link]- Packed tower diameter …………….……………………..57

[Link] - Packing height (Z packing) ……….…………………….60

3.4 - Distillation column design …………….…………………...61

3.4.1 – Introduction ………………………….……………………61

3.4.2 – From material balance ……………………………………62

3.4.3 – Calculation number of plates ……………………………..63

3.4.4 – Column height …………………………………………..67

3.4.5 – Column diameter ………………………………………..67

Chapter four …………………………………………………….73

Control loop system on absorber …………………………………74

Chapter five ……………………………………………………..75

5.1- Safety & environment precaution ………………………….76

5.1.1- Methanol ………………………………………………….76

[Link]- Exposure ………………………………………………..76

[Link]- Reactivity ……………………………………………….77

[Link]- Storage…………………………………………………..77

6
5.1.2-Formaldehyde ……………………………………………77

[Link]- Fire hazards ……………………………………………78

[Link]-Exposure ……………………………………………….78

[Link]-Storage …………………………………………………78

5.2- Plant location ……………………………………………...78

5.2.1- Introduction……...………………………………………78

5.2.2 - CH2O plant location …………………………………...79

Chapter six …….………………………………………………80

6.1 – Introduction ………………………………………………81

6.2 – Raw material ……………………………………………..81

6.3 - Operating labor cost ………………………………………82

6.4- Equipment cost …………………………………………….83

Conclusion ……………………………………………………...84

Reference………..………………………………………………85

7
CHAPTER ONE
SUMMARY

8
1. Summary

1.1- Introduction

Formaldehyde is called Methyl aldehyde or Methylene glycol or Methylene

oxide it is a colorless, flammable gas or liquid that has a pungent, suffocating
odor. It is a volatile organic compound, which is an organic compound that
easily becomes a vapor or gas. It is also naturally produced in small, harmless
amounts in the human body. The chemical symbol for formaldehyde is CH2O.

Formaldehyde is released into the air by burning wood, kerosene, or natural gas;
from automobiles and diesel exhaust; and from cigarettes and other products. It
is found in the air at home, at work, and outdoors, especially in smog. It is also
found in some foods.

Formaldehyde occurs in forest fires, animal wastes, microbial products of

biological systems, and plant volatiles. It can also be formed in seawater by
photochemical processes .

Formaldehyde was discovered in 1859 by a Russian chemist named Aleksandr

Butlerov. Then in 1869, it was ultimately identified by the German chemist
August Hofmann. The manufacture of formaldehyde started in the beginnings of
the twentieth century. Between 1958 and 1968, the annual growth rate for
formaldehyde production averaged to 11.7%. In the mid-1970s, the production
was 54% of capacity. Annual growth rate of formaldehyde was 2.7% per year
from 1988 to 1997. In 1992, formaldehyde ranked 22nd among the top 50
chemicals produced in the United States. The total annual formaldehyde
capacity in 1998 was estimated by 11.3 billion pounds. Since then and the
production capacity around the globe is expanding exponentially reaching a
world’s production of 32.5 million metric tons by 2012. Due to its relatively low
costs compared to other materials, and its receptivity for reaching high purities,
formaldehyde is considered one of the most widely demanded and manufactured
materials in the world. It is also the center of many chemical researches and
alternative manufacture methods. This also explains the vast number of
applications of this material including a building block for other organic
compounds, photographing washing, glues, adhesives, paints, explosives,
disinfecting, tissue preservation and drug testing. formaldehyde is most
commonly produced in industry through the vapor- phase oxidation reaction
between methanol and air (Oxygen).

9
1.2- Health effects

The most probable route of human exposure to formaldehyde is inhalation .Non-

Cancer: Vapors are highly irritating to the eye and respiratory track. Acute
effects include nausea, headaches, and difficulty breathing. Formaldehyde can
also induce or exacerbate asthma, and throat irritation and Repeated exposure to
it cause skin irritation

1.3- Sources

Formaldehyde is both directly emitted into the atmosphere and formed in the
atmosphere as a result of photochemical oxidation of reactive organic gases in
polluted atmospheres containing ozone and nitrogen oxides. Photochemical
oxidation is the largest source (could be as high as 88 percent) of formaldehyde
concentrations in California ambient air. A primary source of formaldehyde is
vehicular exhaust Formaldehyde is a product of incomplete combustion. About
9 percent of direct formaldehyde emissions are estimated to come from the
combustion of fossil fuels mobile sources.

The primary stationary sources that have reported emissions of formaldehydeare

crude petroleum and natural gas extraction, manufacturers of miscellaneous
nonmetallic mineral products, and gas production and distribution services.

1.4- Demand

Demand for formaldehyde will grow with the development of the manufacturing
sector mainly the chemical industries such as disinfectants, cosmetics,
pharmaceuticals, insecticide & fungicides and the like. The demand for the
output of such establishments is in turn influenced by population growth,
urbanization, income rise and expansion of health services and the like.
Considering the combined effect of the above factors a growth rate of 10% is
taken to forecast the future demand.
PROJECTED DEMAND FOR FORMALDEHYDE (KG)

Year Projected
Demand
2012 143,000
2013 157,300
2014 173,030
2015 190,333
2016 209,366

10
1.5- Use of formaldehyde

Formaldehyde is an important industrial chemical because of its versatility as a

chemical intermediate (Gerberich et al. 1994). It primarily is used in the
production of urea-formaldehyde, phenol-formaldehyde, and melamine-
formaldehyde resins, which are used as adhesives in the production of particle
board, fiber board, and plywood. Formaldehyde is also used in the manufacture
of plastics, insulation, fertilizers, fungicides, biocides, corrosion inhibitors,
embalming fluids, disinfectants, and household cleaners, and it is used in the
textile industry .

1.6- Physical and chemical properties

Formaldehyde is a flammable, colorless gas at room temperature and has a

pungent, suffocating odor (Budavari et al. 1989). Odor thresholds ranging from
0.5 to 1.0 parts per million (ppm) (ATSDR 1999) and 0.06 to 0.5 ppm
(Gerberich et al. 1994) have been reported. Formaldehyde reacts readily with
many substances and polymerizes easily, making it one of the world's most
important industrial Compound. (Gerberich et al. 1994). Selected chemical and
physical properties are listed in TABLE

1.6.1- Physical Properties of Formaldehyde

Properties Formic aldehyde, methanal, methyl aldehyde,

methylene oxide, Oxo methane, ox methylene
CAS registry number 50-00-0
Molecular formula HCHO
Molecular weight 30.03
Boiling point –19.5°C
Melting point –92°C
Flash point 83°C (closed cup)
Explosive limits 7% to 73%
Specific gravity 1.067 with respect to air
Vapor pressure 3,890 mmHg at 25°C
Solubility Very soluble in water; soluble in alcohol and ether
Conversion factors 1 ppm = 1.23 mg/m3; 1 mg/m3 = 0.81 ppm
Vapor Pressure 3284 mm Hg at 20 0C
Vapor Density 1.03 for aq. soln.; 1.08 for gas
Density/Specific Gravity 1.067 (air = 1)
Log Octanol/Water 0.35
Partition Coefficient
Conversion Factor 1 ppm = 1.23 mg/m3

11
1.6.2 - Chemical properties

Formaldehyde is one of the most reactive organic compounds known. The

various chemical properties are as follows:

Decomposition
At 150 ºC formaldehyde undergoes heterogeneous decomposition to form
methanol and CO2mainly. Above 350 ºC it tends to decompose in to CO and H2.

Polymerization
Gaseous formaldehyde polymerizes slowly at temperatures below 100 ºC,
polymerization accelerated by traces of polar impurities such as acids, alkalis
orwater. In water solution formaldehyde hydrates to methylene glycol
H
H2C=O + H2O HO C OH
H
Which in turn polymerizes to polymethylene glycols, HO (CH2O)nH, also called
polyoxy methylenes.

Reduction and Oxidation

Formaldehyde is readily reduced to methanol with hydrogen over many
metaland metal oxide catalysts. It is oxidized to formic acid or CO 2 and [Link]
the presence of strong alkalis or when heated in the presence of acids
formaldehyde undergoes cannizzaro reaction with formation of methanol and
formic acid. In presence of aluminum or magnesium methylate,
paraformaldehyde reacts to form methyl formate (Tishchenko reaction)
2HCHO HCOOCH3

Addition reactions
The formation of sparingly water-soluble formaldehyde bisulphite is an
important addition reaction. Hydrocyanic acid reacts with formaldehyde to give
glyconitrile.
HCHO + HCN HOCH2 - C  - N

Resin formation
Formaldehyde condenses with urea, melamine, urethanes, cyanamide, aromatic
sulfonamides and amines, and phenols to give wide range of resins.

12
Chemical reaction of Formaldehyde

Number Reaction ΔHR,973 K(kJ/mol)

(1) CH3OH +1/2O2 → HCHO+H2O -156
(2) CH3OH →HCHO+H2 +85
(3) CH2O → CO+H2 +12
(4) CH3OH+2/3O2→CO2+2H2O −676
(5) CH2O+O2 → CO2+H2O −519
(6) CH2O+1/2O2→CH2O2 −314
(7) CH3OH → C+H2O+H2 −31
(8) CO+H2⇄ C+H2O −136

(9) CO+H2O ⇄ CO2+H2 −35

1.7- Production methods

Today two main processes are in use for the production of formaldehyde from
methanol, the silver process and the oxide process. The first can be divided in to
two processes, the methanol ballast process and the BASF Badische Anilin&
Soda-Fabrik process as shown in Figure 1.1.

Methanol
ballast
process
Silver
Process
Processes for
BASF
Production of
Process
Formaldehyde Oxide
Process

Figure 1.1. The different process types for production of formaldehyde from
methanol.

13
Figure 2.2. schematic overview of the silver process. The dashed square shows
what only exist in the methanol ballast process

Figure 2.3. A schematic scheme over the oxidation process (Table 1.1.)
]%[ Methanol BASF Oxide
Ballast
Conversion 77-88 97-98 95 – 98
Yield mol. 86-90 89.5-90.5 <92.5
Formaldehyde [wt] 42 40-55 <55
Methanol in product <1 < 1.3 0.5-1.5
[wt]

14
1.7.1- From methanol by silver catalysts process
Feed mixture of pure methanol vapor and blown in air is generated in evaporator
the mixture combined with steam and enter the reactor vapor passes through bed
to silver catalyst or silver gauze. The conversion is in completed and the reaction
takes place in 600-720 °C the reaction gases cooled in directly with water, the
remaining heat of bottom of a formaldehyde absorption column. In the water
cooled section of column, the bulk of a methanol, water, and formaldehyde
separate out a 42% formaldehyde solution from the bottom absorption column is
fed to distillation column, methanol recovered at top of column, and recycled to
the bottom of evaporator A formaldehyde and less than l%( wt) methanol
product containing up 5 is taken from, the bottom of distillation column and
cooled. Diagram(1) explains the process:

DIAGRAM 1

15
FORMALIN (FOLRMALDEHYDE 37 WT. % SOLUTION)

Flash point 64 °C

Autoignition temperature 430 °C

Explosive limits 36%
Lower Explosion Limit 6%
Upper Explosion Limit 36%
Products of Combustion Carbon monoxide (CO) and Carbon

16
1.7.2- Metal Oxide Catalyst Process

The Formax process developed by Reichhold chemicals to produce

formaldehyde through direct catalytic oxidation of methanol and some other 7
by-products such as carbon monoxide and dimethyl ether forms In 1921, the
oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was
introduced to and patented. Then in 1933, the iron-molybdenum oxide catalyst
was also patented and used till the early 1990’s. Improvements to the metal
oxide catalyst were done through the metal composition, inert carriers and
preparation methods. The first commercial plant for the production of
formaldehyde using the iron-molybdenum oxide catalyst was put into action in
1952. Unlike the silver based catalyst in this project, the iron-molybdenum
oxide catalyst makes formaldehyde from the exothermic reaction (1) entirely.
Under atmospheric pressure and 250 –350 ºC, methanol conversion inside the
reactor could reach 99% and a yield of 88% - 92%.

17
The process begins by mixing of vaporized methanol and air prior to entering
the reactors. Inside the heat exchanger reactor, the feed is passed through the
metal oxide catalyst filled tubes where heat is removed from the exothermic
reaction to the outside of the tubes. Short tubes (1 – 1.5 m) and a shell diameter
2.5 m is the expected design of typical reactors. The bottom product leaving the
reactors is cooled and passed to the absorber. The composition of formaldehyde
in the absorber outlet is controlled by the amount of water addition. An almost
methanol-free product can be achieved on this process design. The advantage of
this process over the silver based catalyst is the absence of the distillation
column to separate unreacted methanol and formaldehyde product. It also has a
life span of 12 to 18 months, larger than the sliver catalyst.

18
1.7.3- Production of formaldehyde from methane and other hydrocarbon
gases

Another method of producing formaldehyde is through the oxidation of

hydrocarbon gases. An increase in the amount produced of formaldehyde is
expected in this process. However, the hydrocarbon formaldehyde is usually
obtained as dilute solution which is not economically concentrated accompanied
by other aldehydes and by-products. However, improvements have been effected
by the use of special catalysts and better methods of control. Wheeler
demonstrated that methane is not oxidized at an appreciable rate below 600°C.
The difficulty in this method is in controlling the oxidation of reaction. Ethylene,
ethane and propane oxidations can be controlled to yield formaldehyde und er
similar conditions to methane. Higher hydrocarbon gases can be oxidized at much
lower temperatures than methane and ethane. These methods have been described
by Bibb also reported by Wiezevich and Frolich, who used iron, nickel,
aluminum, and other metals as catalysts and employed pressures up to 135
atmospheres. The Cities Service Oil Company has developed a commercial
process using this method.

19
1.8- Selection of process

The oxide process has to think about how to let out their tail gas, which mostly
consist of nitrogen, oxygen ,CO and other compounds from the absorption tower
such as formaldehyde and methanol exist in the tail gas. Because of these
compounds the tail gas cannot be released into the air as it is, compared to the
silver processes that can let their tail gas go without consideration.
the disadvantage of The oxide process design is the need for significantly large
equipment to accommodate the increased flow of gases (3 times larger) compared
to the original silver catalyst process design. This increase in equipment sizing
clashes with economic prospect behind the design costs.
silver catalysts process

In this project formaldehyde is to be produced through a catalytic vapor-phase

oxidation reaction involving methanol and oxygen according to the following
reactions.
CH3OH + ½ O2 HCHO + H2O (1)
CH3OH HCHO + H2 (2)

The desired reaction is the first which is exothermic with a selectivity of 9,

while the second is an endothermic reaction. Operate of the process at
atmospheric pressure and very high temperatures (600°C – 650°C) .

20
 CHAPTER TWO
MATERAIL AND ENERGY BALANCE

21
2.1- Mass balance
kmol
The amount of input basis of methanol is 10
h

Definitions of all abbreviations used in our calculations:

n : is the molar flow-rate (kmol/hr)
m : methanol
water: deionized water
H2: hydrogen
N2: nitrogen
f: formaldehyde
O2: oxygen
x : is the mole fraction
nm: methanol flow rate, similarly for the rest components.

2.1.1- First run mass balance

[Link]- Material balance on the reactor
CH3OH + 1/2 O2 → HCHO + H2O …………………………. (1)
10 nO2,8 0 0
10 - £1 -1/2£ +£ +£
¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯ ¯¯¯¯¯¯

2.13 0 7.87 7.87

CH3OH → HCHO + H2 ………………………… (2)

2.13 0 0
2.13 - ɛ2 + ɛ2 + ɛ2
¯
¯¯¯¯¯¯ ¯¯¯¯¯ ¯¯¯¯¯
1.26 0.87 0.87

22
From the conversion :-
ε1+ε2 ε1+ε2
87% = =
nM ,8 10

ɛ1 + ɛ 2 = 8.7 ……………(1)

FROM the selectivity :-

ɛ1 = ɛ2 * 9
ɛ1 - ɛ2 *9 = 0 ……………...(2)
FROM (1) and (2) we get :-
ɛ1 = 7.87 𝑘𝑚𝑜𝑙/ℎ𝑟
ɛ2 = 0.87 𝑘𝑚𝑜𝑙/ℎ𝑟

nO2,8 = 1/2 ɛ1
= 3.935 𝑘𝑚𝑜𝑙/ℎ𝑟
79
nN2.9 = nO2.8 *
21

= 14.803 𝑘𝑚𝑜𝑙/ℎ𝑟

nH2,9 = ɛ2 = 0.87 𝑘𝑚𝑜𝑙/ℎ𝑟

nwater = ɛ1 = 7.87 𝑘𝑚𝑜𝑙/ℎ𝑟

nF,9 = ɛ1 + ɛ2
7.87 + 0.87 = 8.74 𝑘𝑚𝑜𝑙/ℎ𝑟
NM ,9 = nM ,8 - ɛ1 - ɛ2
10 - 7.87 - 0.87 = 1.26 𝑘𝑚𝑜𝑙/ℎ𝑟

STREM 8 (n8) = ∑ ni
= nM ,8 + nO2,8 + nH2,8 + nH2O,8 + nF,8 + nN2,8
10 + 3.935 + 0 + 0 + 0 + 14.803

23
= 28.738 𝑘𝑚𝑜𝑙/ℎ𝑟
nO2,9 = 0 𝑘𝑚𝑜𝑙/ℎ𝑟

STREAM 9 (n9) = ∑ ni
= nO2,9 + nN2.9 + nH2,9 + nH2O,9 + nF.9 + nM .9
= 0 + 14.803 + 0.87 + 8.74 + 1.26
= 33.543 kmol/hr
ni
Xi,8 = STREAM(8)
∑n

3.935
Xo2.8 = = 0.1369 XM = 0.347
28.738

10
XM ,8 = = 0.347 XO2= 0.1369
28.738

14.803
XN2,8 = = 0.515 XW = 0
28.738

1.26
XM ,9 = = 0.0357 XN = 0.515 REACTOR
33.543

0
XO2,9 = =0
33.543

7.87
XH20,9 = = 0.2346
33.543

0.87
XH2,9 = = 0.0259
33.543

8.74
XF,9 = = 0.2605 STREAM (9)
33.543

14.803
XN2,9 = = 0.4413 XM = 0.0375
33.543

X F =0.2605
XW = 0.2346
XH2 = 0.0259
XN2 = 0.4413

24
[Link]- Material balance on the absorber

STREAM (11) = n11 = ? STREAM (12) = n12 = ?

XW =1 XF =
XW =
XH2 =
XN2 =

ABSORBER

STREAM (10) STREAM (13)= n13

n10 = n9 = 33.543 XM =
XM = 0.0375 XF =
XF = 0.2605 XW =
XW = 0.2346
XH2 = 0.0259
XN2 = 0.4413

25
SOLUBILITY OF FORMALDEHYDE IN WATER AT T= 89.37C
EQUAL TO 0.78 KG F / KG WATER
0.78 KG F 1 Kmol F 18 KG WATER
= * *
KG WATER 30.02 KG F 1 KG WATER

Kmol F
= 0.468
Kmol WATER

0.468 kmol f 1 kmol water

=
8.7 kmol f x kmol water

X= 18.675 𝑘𝑚𝑜𝑙 𝑤𝑎𝑡𝑒𝑟/ℎ𝑟

n11 = 18.675 𝑘𝑚𝑜𝑙 / ℎ𝑟
from the solubility of methanol we find the amount of methanol which
dissolved in 18.675 of water
p(atm)∗fration ∗m.w
[Link] methanol =
Henry constant

1.362 ∗ 0.0375 ∗ 32 𝑔𝑚/𝑚𝑜𝑙

4.55 ∗ 10 − 6 𝑎𝑡𝑚 ∗ 𝑚3/𝑚𝑜𝑙

= 359208.7912 g 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙/𝑚3 𝑤𝑎𝑡𝑒𝑟
kmol kg
359208.7912 𝑔𝑚 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙/𝑚3 * * *1m3/1000 liter
33 kg 1000gm

= 0.011225 𝑘𝑚𝑜𝑙 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙/ 𝐿 of water

Molarity = 𝑘𝑚𝑜𝑙 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 / 𝑣𝑜𝑙𝑢𝑚𝑒

Molarity = 𝑤𝑒𝑖𝑔ℎ𝑡 / 𝑚. 𝑤𝑡
= 1/18
1 mole of water
=
18 1L

𝐾𝑚𝑜𝑙 of water = 0.0555

26
Thus ,
0.011225 kmol methanol 0.0555
=
x kmol methanol 18.675

X= 3.777 𝑘𝑚𝑜𝑙 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 / ℎ𝑟

So all the methanol dissolved in water because we have 1.26
𝑘𝑚𝑜𝑙 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 /ℎ𝑟 in the stream (10)

nM ,13 = nM ,10= 1.26 𝑘𝑚𝑜𝑙 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 /ℎ𝑟

all the 𝑘𝑚𝑜𝑙𝑒𝑠 of N2 and H2 out from stream (12)

so n2,12 = nN2,10 = 14.803 𝑘𝑚𝑜𝑙/ℎ𝑟

nH2,12 = nH2,10 = 0.87 𝑘𝑚𝑜𝑙/ℎ𝑟

nF,12 = nF,10 * (1- 0.99)

= 8.74 * 0.01
= 0.0874 kmol/hr
nF,13 = nF10 *0.99
= 8.74 * 0.99
= 8.6526 kmol/hr

P* (89.37c) = p * XH2O,12
P∗H2O ,12(89.37C)
XH2O,12 = …………………(1)
P

P*H2O = exp (A- B/T+C ) A=16.3872

P*H2O= exp (16.3872- 3885.7/89.37+230.17) B=3885.7
P*H2O = 68.5 𝑘𝑝𝑎 C =230.17
P = 138 𝑘𝑝𝑎

Substituting p *H2O and p in equation (1)

27
XH2O,12 = 68.15/138 = 0.496
METERAIL BALANE FOR WATER
nH2O,10 + nH2O ,11 = nH2O,12 + nH2O ,13 ……………….(2)
7.87 + 18.675 = nH2O ,12/XH2O,12
nH2O,12 = 26.545 * 0.496
nH20,12 = 13.116632 𝑘𝑚𝑜𝑙/ℎ𝑟
substituting nH2O in equation (2)
nH2O ,13 = 13.37868 𝑘𝑚𝑜𝑙/ℎ𝑟

n12= nF,12 + nN,12 + nH2.12 + nH2O,12

= 0.0874+ 14.803 + 0.87 +13.16632
= 28.92672 𝑘𝑚𝑜𝑙/ℎ𝑟
n13 = nF,13 + nM ,13 + nH2O ,13
= 8.6526 +1.26 + 13.37868
= 23.29 𝑘𝑚𝑜𝑙/ℎ𝑟
nF,12 0.0874
XF,12 = = = 0.00302
n12 28.92672

nN2,12 14.803
XN2,12 = = = 0.51174
n12 28.92672

nH2,12 0.87
XH2,12 = = = 0.03
n12 28.92672

nH2O,12 13.16632
XH2O,12 = = = 0.45516
n12 28.92672

nF,13 8.6526
XF,13 = = = 0.3715
n,13 23.29

nM,13 1 .26
XM ,13 = = = 0.0541
n,13 23.29

nH20,13 13.37868
XH2O,13 = = = 0.5744
n,13 23.29

28
[Link]- Material balance on the distillation column

D= n,15

n,14 = 23.29 𝑘𝑚𝑜𝑙/ℎ𝑟 XM =

DISTILLATION XW =
XM = 0.0541
XF = 0.3715
XW = 0.5744

B= n,16

XM =
XF =

XW =

from the boiling point of methanol and formaldehyde and water the assumption
is :-
1- light key : methanol
2- heavy key :H2O
n,14 = D + B

29
Fractional( 1) recovery for methanol = 99.7 %
Fraction (2 ) recovery for water = 99%
nM ,D = nM ,W + frac 1
nM ,D = 1.26 * 0.977
= 1.25622 𝑘𝑚𝑜𝑙 / ℎ𝑟
nM ,B = n,14 * (1- frac 1 )
nM ,B = 1.26 * (1- 0.997 )
= 0.00378 𝑘𝑚𝑜𝑙/ℎ𝑟

nH2O,B = nH2O,14 * frac 2

nH2O,B = 13.37868 * 0.99
nH2O.B = 13.2558 kmol/hr
nH2O,D = nH2O,14 * (1-frac2 )
nH2O,D = 13.37868 * ( 1- 0.99)
nH2O,D = 0.1337 𝑘𝑚𝑜𝑙 / ℎ𝑟

nF,B = nF,14 = 8.6526 𝑘𝑚𝑜𝑙/ℎ𝑟

D = ∑ ni,D = nW,D + n M ,D
D = 0.1337 + 1.25622
D = 1.38992 𝑘𝑚𝑜𝑙/ℎ𝑟

B = ∑ ni,B = nM ,B + nF,B + nW,B

= 0.00378 + 8.6526 + 13.2448
B= 21.9 𝑘𝑚𝑜𝑙/ℎ𝑟
nM,D 1.25622
XM ,D = = = 0.903
D 1 .38992

nW,D 0.1337
XW,D = = = 0.0961
D 1.38992

30
 nM,B 0.00378
XM ,B = = = 0.00017
B 21.9

nF,B 8.6526
XF,B = = = 0.395
B 21.9

nW,B 13.2448
XW,B = = = 0.6047
B 21.9

MATERIAL MOLE ni [Link] Mass Mass

FRACTION = ni * [Link] fraction
Methanol 0.00017 0.00378 32.042 0.1211 0.000243

Formaldehyde 0.395 8.6526 30.02 259.751 0.5212

Water 0.6047 13.2448 18 238.4064 0.4784

∑ 498.2785

Formaldehyde to water ratio = 0.5212

0.4784
= 1.089

Mass balance at mixing point of stream 2,3 and 15 : (second run )

nM ,3 = nM ,2 + nM ,15
10 = nM ,2 + 1.25622
nM ,2 = 10 – 1.25622 = 8.74378 𝑘𝑚𝑜𝑙/ℎ𝑟

nW,3 = nW,15 = 0.1337 𝑘𝑚𝑜𝑙 / ℎ𝑟

n3 = nW.3 + nM ,3
n3 = 0.1337 + 10 = 10.1337 𝑘𝑚𝑜𝑙/ℎ𝑟

31
Mass balance at mixing point of stream 6 , 7 and 8 :
n7 =n5 = n1 = nO2.1 + nN2,1
= 3.935 +14.803
= 18.738 𝑘𝑚𝑜𝑙/ℎ𝑟
n3 = n4 =n6 = 10.1337 𝑘𝑚𝑜𝑙/ℎ𝑟

n8 = n6 +n7
= 10.1337 + 18.738
= 28.8717 𝑘𝑚𝑜𝑙/ℎ𝑟

2.2- Second run mass balance

[Link]- Mass balance on the reactor

The feed to the reactor is n8 = 28.8717 𝑘𝑚𝑜𝑙/ℎ𝑟

Its composition is :-
XM ,8 = 10
XN2,8 = 14.803
XO2,8 = 3.935
XW,8 = 0.1067
nM ,9 (second run ) = nM ,9 (first run) = 1.26 𝑘𝑚𝑜𝑙/ℎ𝑟
no2,8 (second run ) = nO2,8 9 (first run) = 3.935 𝑘𝑚𝑜𝑙/ℎ𝑟

nN2,9 (second run ) = nN2,9 (first run) = 14.803 𝑘𝑚𝑜𝑙/ℎ𝑟

32
nH2,9 (second run ) = nH2,9 (first run) = 0.87 𝑘𝑚𝑜𝑙/ℎ𝑟
nF,9 (second run ) = nF,9 (first run) = 8.74 𝑘𝑚𝑜𝑙/ℎ𝑟

nW,9 (second run ) = 0. 1067 + ɛ1

= 0.1607 + 7.87 = 7.9767 𝑘𝑚𝑜𝑙/ℎ𝑟
n9 (second run ) = ∑ni ,9 = 37.5847 kmol/hr

[Link]- Mass balance on the absorber

nF,10 (second run ) = nF,10 (first run ) = 8.74 𝑘𝑚𝑜𝑙/ℎ𝑟

nf,12 (second run ) = nF10 (second run ) * (1-0.99)
nF,12 = 0.0874 𝑘𝑚𝑜𝑙/ℎ𝑟

nF,13 (second run ) = nF,10 * 0.99

nF,13 = 8.6526 𝑘𝑚𝑜𝑙/ℎ𝑟
nN2,13 = 14.803 𝑘𝑚𝑜𝑙/ℎ𝑟

nH2,13 = 0.87 𝑘𝑚𝑜𝑙/ℎ𝑟

XH2O,12 (second run ) = XH2O,12 (first run ) = 0.496
nH2O,12 = [ nH2O,10 (second run ) + nH2O,11 (second run )] * XH2O,12
= [ 7.9767 + 18.675] * 0.496
n12 = ∑ni ,12 = nF,12 + nN2,12 + nH2,12 + nH2O,12
= 0.6874 + 14.803 + 0.87 +13.219
= 28.988 𝑘𝑚𝑜𝑙/ℎ𝑟

nH2O,13 = nH2O,11 + nH2O,10 - nH2O,12

= 18.675 + 7.9767 – 13.219
= 13.432 𝑘𝑚𝑜𝑙/ℎ𝑟

33
nM ,13 = nM ,10 – nm,12
= 1.26 – 0 = 1.26 𝑘𝑚𝑜𝑙/ℎ𝑟
n13 = ∑ni.13 = nM ,13 + nH2O,13 + nF,13
= 1.26 + 13.432 + 8.6526
= 23.344 𝑘𝑚𝑜𝑙/ℎ𝑟

[Link]- Mass balance on the distillation column

n,14 = n13 = D + B
23.44 = D + B ………………….. ( 1)
nM ,D = nM ,14 * frac .1
= 1.26 * 0.997
= 1.256 𝑘𝑚𝑜𝑙/ℎ𝑟
nM ,B = nM ,14 * (1- frac .1)
= 1.26 * ( 1- 0.997)
= 0.00378 𝑘𝑚𝑜𝑙/ℎ𝑟

nH2O,B =nH2O,14 * frac .2

= 13.432 * 0.99
= 13.297 𝑘𝑚𝑜𝑙/ℎ𝑟
nH2O ,D = nH2O,14 * (1- frac.2 )
= 13.432 * (1-0.99 )
= 0.13432 𝑘𝑚𝑜𝑙/ℎ𝑟

nF,B = nF14 = 8.6526 𝑘𝑚𝑜𝑙/ℎ𝑟

D = ∑ni .D = nH2O,D +nM ,D
= 0.13432+ 1.256
= 1.39 𝑘𝑚𝑜𝑙/ℎ𝑟

34
 B = ∑ni,B = nH2O + nM ,B + nF,B
= 13.297 + 0.00378 + 8.6526
B = 21.953 𝑘𝑚𝑜𝑙/ℎ𝑟
nM,D 1.256
XM ,D = = = 0.903
D 1.39

nW,D 0.13432
XW.D = = = 0.0966
D 1.39

nM,B 0.00378
XM ,B = = = 0.000172
B 21.953

nF,B 8.6526
XF.B = = = 0.3941
B 21.953

nW,B 13.297
XW.B = = = 0.6057
B 21.953

MATERIAL MOLE ni [Link] Mass Mass

FRACTION = ni * [Link] fraction
Methanol 0.000172 0.00398 32.042 0.12118 0.000242

Formaldehyde 0.3941 8.6526 30.02 259.751 0.5203

Water 0.6057 13.297 18 239.346 0.4794

∑ 499.218

nF.19 = nF,17/n17+n18
nF,19 = 0.00378 𝑘𝑚𝑜𝑙/ℎ𝑟

35
 2.2- Energy balance
Table of (cp) for each compound in the system :-
Component Phase A B C D
Methanol Liquid 75.86*10-3 16.83*10-5 0 0
Gas 42.93*10-3 8.301*10-5 -1.87*10-8 -8.03*10-12
Water Liquid 75.4*10-3 0 0 0
Gas 33.46*10-3 0.688*10-5 0.7604*10-8 -3.593*10-12
Formaldehyde Gas 34.28*10-3 4.268*10-5 0 -8.694*10-12
N2 Gas 29 *10-3 0.2199*10-5 0.5723*10-8 -2.871*10-12
O2 Gas 29.1 *10-3 1.158*10-5 0.6076*10-8 1.311*10-12
H2 Gas 28.84*10-3 0.00765*10-5 0.3288*10-8 -0.8698*10-
12

CP = A+BT+CT2+DT3

2.2.1- Mixing point between streams 2 ,3 and 15

P=1.2 atm
T= 68.3°C
nw,15=0.1337 𝑘𝑚𝑜𝑙/ℎ𝑟
p= 1 atm nM ,15 = 1.25622 𝑘𝑚𝑜𝑙/ℎ𝑟
T= 25°C
n2 = 8.743kmol/hr

T= ??
nW,3 = 0.1377 𝑘𝑚𝑜𝑙/ℎ𝑟
nM ,3= 9.99922 𝑘𝑚𝑜𝑙/ℎ𝑟

XW,3= 0.0132
XM ,3 = 0.9868

at T = 68.3 0C and P = 1.2 Methanol is in liquid phase

Ein = Eout

36
 25 68.3 68.3
n2 ∫25 cp1 m2dt + nw,15 ∫25 cpW, 15 dt + nw,15 ∫25 cpM, 15 dt

T
= n3 ∫25 cp3dt

Ein = 0.1337 [ 75.4 *10-3T]68.3

25
+1.25622 [ 75.86*10-3 T + 16.83*10-3/2]68.3
25

Ein = 48.89 = Eout

T T
Eout = n3 ∫25 cp3 dt = ∫25(nW, 3 cpwi + nM, 3 cpMl)dt
T
= ∫25 7.517 + 0.01646 T dt
0.01646 T
= [ 7.517 T + T2 ]25
2

Eout = 7.517 T +8.32*10-3 T-2 – [ 7.517 (25) + 8.32*10-3 (25)2]

48.89= 7.517 T +8.32*10-3 T-2 – 193.06875
T= 31.13°C

2.2.2- Energy balance on the heat exchanger E-101

Q = ∑ n cp ∆T
= (n cp ∆T)M + (n cp ∆T )W
64.7 150
= nM ,4 [ ∫31.3 cp M ,Liq dt + ∆HV + ∫64.7 CP M ,gas dt ]
100 150
+ nW,4 [ ∫31.13 CPW,liq dt +∆HV + ∫100 cpW,gas dt ]
64.4
= 9.99922 [ ∫31.13(75.86*10-3 + 16.83*10-5 T )dt +35.27
150
+ ∫64.7(42.93*10-3 dt + 8.301*10-3T- 1.87*10-8T2 – 8.03*10-12T3)dt]
100
+0.1337[ ∫31.13 75.4*10-3 dt + 40.6565
150
+ ∫100 (33.46*10-3 + 0.0688*10-5T + 0.7604*10-8T2 – 3.593*10-12T3)dt]

37
= 4155051.3+6231729 = 4217368.59 𝑘𝐽/ℎ𝑟
Q = m cp ∆T
110
-4217368.59 𝐾𝐽/ℎ𝑟 = m ∫150 cpw dt
100
-4217368.59 = m ∫150 (33.46*10-3 + 0.688*10-5 T + 0.7604*10-8 T2

- 3.593*10-12 T3) dt
-4217368.59 = m [ 33.46 *10-3 T + 0.688*10-5/2 T2 +0.7774*10-8 T3/3

- 3.593*10-12 T4/4 ]110

150

-4217368.59 = m [ (3.7004*10-3 T + 0.041624 + 3.373364*10-3 – 1.3151*10-4 )

– ( 5.019*10-3 + 0.0774 + 8.5545 *10-3 – 4.547*10-4)]
-4217368.59 = m [ (0.0596 )-(0.0905)]
-4217368.59 = m (-0.03453)
m= 12262971.04 𝑚𝑜𝑙/ℎ𝑟

= 12202.97104 𝑘𝑚𝑜𝑙/ℎ𝑟

38
2.2.3- Energy balance on the heat exchanger E-102
Q = ∑n cp ∆T
= (n cp ∆T )N2 + (n cp ∆T )O2
150
= 14.803 [∫25 (29*10-3 + 0.2199*10-5 T +0.5723*10-8 T2 – 2.871*10-12 T3) dt ]
150
+ 3.935 [∫25 (29.1*10-3 +1.158 *10-5 – 0.6676*10-8 T2 +1.311*10-12 T3 ) dt ]

= 14.803 [ (29*10-3 T + 0.2199*10-5 T2/2 + 0.5723*10-8 T3/3

– 2.87 *10-12T4/4]150
25
+3.935 [29.1*10-3T + 1.158*10-5T2/2

-0.6076*10-8 T3+ 1.311*10-12 T4/4]150

25

= 14.803 [(4.35 +0.0247 +6.4383*10-3 – 3.6336*10-4) –

(0.725 +2.4738*10-4 + 2.9807*10-5 – 2.8037 * 10-7)]
+ 3.935 [(4.365 +0.1302 – 6.8355 *10-3 +1.6592*10-4) –
(0.7275 +3.6187*10-3 -3.1645*10-5 + 1.2802*10-7 )]
=14.803 (4.3808 – 0.72276 ) + 3.935 (4.4885 – 0.731 )
= 54112.7 + 147857
= 68898.4 𝐾𝐽/ℎ𝑟

Q = m cp ∆T
110
-68898.4 = m ∫150 cp dt
110
3.593*10-12 -68898.4 = m ∫150 (33.46*10-3 + 0.688 *10-5 T +0.7604*10-8 T2 –
T3 ) dt
-68898.4 = m [33.46*10-3T + 0.688*10-5 T2/2 + 0.7604*10-8 T3/3

- 3.593*10-12T4/4]110
150

-68898.4 = m [(3.7004*10-3 + 0.041624 +3.37364*10-3 – 1.13151*10-4)

- (5.019*10-3+ 0.0774 +8.5545*10-3 – 4.547*10-4)]
-68898.4 = m [(0.0596 ) – (0.0905)]

39
-68898.4 = m (-0.03453)
m = 1995320.012 𝑘𝑚𝑜𝑙/ℎ𝑟

2.2.4- Mixing point between streams 6, 7 Since the temperature of 6,7

are the same (150 °C) so the stream 8 also have the same temperature.

2.2.5- Energy balance on the reactor

Species ni (mole) Ĥin nout (mole) Ĥout
CH3OH 10000 H1 1260 H5
O2 3935 H2 0 H6
N2 14803 H3 14803 H7
HCHO 0 - 8740 H8
H2 0 - 870 H9
H2O 1310 H4 7976.7 H10

150
H1 = ∫25 CPm,gas dt = 6.2522 𝑘𝐽/𝑚𝑜𝑙
150
H2 = ∫25 CP O2,gas dt =3.7575 𝐾𝐽/𝑚𝑜𝑙
150
H3 = ∫25 CPN2,gas dt = 3.6551𝐾𝐽/𝑚𝑜𝑙
150
H4 = ∫25 CPH2O,gas dt = 4.266 𝐾𝐽/𝑚𝑜𝑙
343
H5 = ∫25 CPM ,gas dt = 18.2296 𝑘𝐽/𝑚𝑜𝑙
343
H6 = ∫25 CPO2,gas dt = 9.854 𝑘𝐽/𝑚𝑜𝑙
343
H7 = ∫25 CPN2,gas dt = 9.418 𝑘𝐽/𝑚𝑜𝑙
343
H8 = ∫25 CPF,gas dt = 13.368 𝑘𝐽/𝑚𝑜𝑙

40
 343
H9 = ∫25 CPH2,gas dt = 9.2168 𝑘𝐽/𝑚𝑜𝑙
343
H10 = ∫25 CPH2O,gas dt = 11.133 𝑘𝐽/𝑚𝑜𝑙

The standard of the reaction (298 °C, 1 atm ) for the two reaction are given as :-
∆Hf1 = -156 𝑘𝐽/𝑚𝑜𝑙 methanol

∆Hf2 = -85 𝑘𝐽/𝑚𝑜𝑙 methanol

ΔH = Σɛ ΔHf + Σ Ĥi,out Σ Ĥi, in
= ( 156 x 7.87 *1000 – 85 * 0.87 * 1000) + 3679029.286 – 1290397.518
= -1301386 + 3679029.286 – 1290397.518= 1087245.768 𝑘𝐽/ℎ𝑟.

2.2.6- Energy balance on the heat exchanger inside the reactor

Heat exchanger is joined with the reactor to cool down the product
From 343 °C to 200 °C.
The enthalpies interring to the cooling section are :-
343
Ĥ5 = ∫25 CPM ,gas dt = 18.2296 𝑘𝐽/𝑚𝑜𝑙
343
Ĥ6 = ∫25 CPO2,gas dt = 9.854 𝑘𝐽/𝑚𝑜𝑙
343
Ĥ7 = ∫25 CPN2,gas dt = 9.418 𝑘𝐽/𝑚𝑜𝑙
343
Ĥ8 = ∫25 CPF,gas dt = 13.368 𝑘𝐽/𝑚𝑜𝑙
343
Ĥ9 = ∫25 CPH2,gas dt = 9.2168 𝑘𝐽/𝑚𝑜𝑙
343
Ĥ10 = ∫25 CPH20,gas dt = 11.133 𝑘𝐽/𝑚𝑜𝑙

The enthalpies out from the cooling section :-

200
ĤM ,9 = ∫25 CPM ,gas dt = 9.0946 𝑘𝐽/𝑚𝑜𝑙

41
 200
ĤO2,9 = ∫25 CPO2,gas dt = 5.3048 𝑘𝐽/𝑚𝑜𝑙
200
ĤN2,9 = ∫25 CPN2,gas dt = 5.13238 𝑘𝐽/𝑚𝑜𝑙
200
ĤF,9 = ∫25 CPF,gas dt = 6.8358 𝑘𝐽/𝑚𝑜𝑙
200
ĤH2,9 = ∫25 CPH2,gas dt = 5.0569 𝑘𝐽 /𝑚𝑜𝑙
200
ĤH2O,9 = ∫25 CPH2O,gas dt = 6.01 𝑘𝐽/𝑚𝑜𝑙

nm= 1260 moles , nO2 = 0 moles , nN2 = 14803 moles

nF = 8740 moles , nH2 = 870 moles , nH2O = 7976.7 moles
Q = ∆H = ∑ni Ĥi,out - ∑ni Ĥi,out
= [(1260 * 9.0940) + (14803*5.13238) + (8740*6.8358) + (7976.7*6.01 ) +
(870*5.0569 ) ] – [(1260 *18.2296 )+(14803*9.418) +(8740 *13.368)+
(7976.7*11.133) +(870*9.2168)]
= 199517.4231 – 376043.4871
= - 176526.064 𝑘𝐽/ℎ𝑟
This is the heat required to remove from the system using the heat exchanger or
using cold water .

Q = m cp ∆T

Q = ∫ cp dt
65
176526.064 = m ∫25 75.4*10-3 dt

176526.064 = m [75.4 * 10-3 T]65

25

176526.064 = m [75.4 *10-3 (65) – 75.4*10-3 (25)]

176526.064 = m [4.901 – 1.885 ]
176526.064 = m [3.016]

42
m = 58259.862607 𝑘𝑚𝑜𝑙/ℎ𝑟 (amount of water that used ).
2.2.7- Energy balance on the absorber
Energy in = Energy out
∑niĤn10(200 °C)+∑ niĤn11(30°C) =∑ niĤn12(T°C) +∑ niĤn13(T°C)
Reference Temp. is 25°C
Heat in stream 10 :∆T =(200-25) °C
Qn10=(n cp ∆T)nM ,10 +(n cp∆T)nW,10 + (n cp ∆T)nF,10+
(n cp ∆T)nH2,10 +(n cp ∆T)nN2,10
Qn10 = 4080729.58 𝑘𝑗/ℎ𝑟

Heat in the stream 11 : ∆T=(30-25) °C

Qn11 = (n cp ∆T)nW,11 = -126730 𝑘𝑗/ℎ𝑟
200 30
Qin =Qn10 +Qn11 = ∫25 ∑ni,10 cpi.10 dt +∫25 ∑ni,11 cpi,11

Qin = 3954000 𝑘𝑗/ℎ𝑟

T T
Qout = Qin = ∫25 ∑ni,B cpi,13 dt + ∫25 ∑ni,12 cpi,12 dt
T
=∫25[1260 (75.86 *10-3 +16.83 *10-5T)

+8652.6 (34.28 *10-3 +4.268 *10-5 T) +13378.68(75.4*10-3)] dt

T
+∫25[13166.32 (75.4 *10-3) +87.4(34.28 *10-3 +4.268 *10-5T)

+870 (28.84 *10-3 +0.00765 *10-5T +0.3288*10-8T2

-0.8698 *10-12 T3) +14803 (29 *10-3 +0.2199 *10-5 T +0.5723 *10-8 T2 – 2.871
*10-12 T3)] dt
T = 89.31 °C

43
2.2.8 - Energy balance on the heat exchanger E-103
nF =8652.6 𝑚𝑜𝑙𝑒𝑠 , nW = 13378.68 𝑚𝑜𝑙𝑒𝑠 , nM =1260 𝑚𝑜𝑙𝑒𝑠
89.31
ĤM ,13 = ∫25 cpM ,gas dt = 3.0615 𝑘𝐽/𝑚𝑜𝑙
89.31
ĤH2O,13 = ∫25 cpH2O,gas dt = 2.1788 𝑘𝐽/𝑚𝑜𝑙
89.31
ĤF,13 = ∫25 cpF,gas dt = 2.3613 𝑘𝐽/𝑚𝑜𝑙
102
ĤM ,14 = ∫25 cpM ,gas dt = 3.7048 𝑘𝐽/𝑚𝑜𝑙
102
ĤH2O,14 = ∫25 cpH2O,gas dt = 2.6126 𝑘𝐽/𝑚𝑜𝑙
102
ĤF,14 = ∫25 cpF,gas dt = 2.8480 𝑘𝐽/𝑚𝑜𝑙

Q= ∆H =∑niĤi,14 - ∑niĤi,,13
=[(1260*3.7048)+(13378.68*2.6126)+(8652.6*2.848)]
-[(1260*3.0615)+(13378.68*2.1788)+)]
=64263.79 -53438.3423
=10825.4477 𝑘𝐽/ℎ𝑟

Q = m cp ∆T
110
Q = m∫150 cp dt
110
-10825.4477 = m∫150 cp dt
110
-10825.4477 = m∫150 (33.46 *10-3 +0.688 *10-5T +0.7664 *10-8T2

-3.593 *10-12 T3) dt

-10825.4477 = m[33.46 *10-3T +0.688 *10-5T2/2
+0.7664 *10-8T3/3 -3.593 *10-12 T4/4]110
150

-10825.4477 = m[(3.7004 *10-3 T+0.041624 +3.37364 *10-3

- 1.3151*10-4)

44
 - (5.614 *10-3 +0.0774 +8.5545 *10-3 – 4.547 *10-4)]
-10825.4477 = [ (0.0596) – (0.0905)]
-10825.4477 = m (- 0.03453)
m = 313508.4767 𝑚𝑜𝑙/ℎ𝑟
2.2.9- Energy balance on the distillation column T-101
QR = hD – hB – QC – hFeed
XM ,D = 0.903 , XH2O,D = 0.0961
T T
hD = nM ,D ∫Tref cpM dt + nW,D ∫Tref cpW dt Tref = 25 ºC ,, T= 68.3 ºC
68.3
= 1.25622 𝑘𝑚𝑜𝑙/ℎ𝑟 *1000 𝑚𝑜𝑙/𝑘𝑚𝑜𝑙 ∫25 cpm,L dt + 0.13432 𝑘𝑚𝑜𝑙/ℎ𝑟
68.3
*1000 𝑚𝑜𝑙/𝑘𝑚𝑜𝑙 ∫25 cpW,L dt
68.3 68.3
= 1256.22 ∫25 (75.86*10-3 +16.83*10-5T ) dt + 134.32 ∫25 ( 75.4*10-3)dt

= 1256.22 [75.86*10-3 T+16.83*10-5 T2/2 ]68.3

25
+ 134.32 [75.4*10-3 T]68.3
25

= 1256.22 [ 3.26482 + 0.015777 ] + 438.536

= 4299.528514 + 438.536
hD = 4738.0591 𝐾𝐽/ℎ𝑟

XM ,B = 0.00017 , XF,B = 0.0395 , XW,B = 0.6037

T T T
hB = nM ,B∫Tref cpM ,gas dt + nF,B∫Tref cpF,gas + nW,B∫Tref cpW,gas

T = 25 °C
Tref = 110 ºC
110 110
h B = 0.00378 𝑘𝑚𝑜𝑙/ℎ𝑟 ∫25 cpM ,gas dt + 8.6526 𝑘𝑚𝑜𝑙/ℎ𝑟 ∫25 cpF,gas dt
110
+ 13.2978 𝑘𝑚𝑜𝑙/ℎ𝑟 ∫25 cpW,GAS dt

= 3.787 [ 42.93*10-3 T + 8.301 *10-5T2/2 – 1.87 *10-8 T3/3 – 8.03*10-12T4/4 ]110

25
+ 8652.6 [{34.28*10-3 T + 4.268*10-5T2/2} – 8.694*10-12T4/4]110
25

45
+ 13297.8 [33.46*10-3T + 0.688*10-5T2/2 + 0.76*10-8T3/3

– 3.593*10-12T4/4]110
25

= 14.93966 +26544.329 +38170.8414

= 64730.11009 𝑘𝐽/ℎ𝑟

QC = hD – heat reflux
heat reflux = HM ,reflux +HW,reflux
68 102 T
= nM ,reflux [ ∫Tref cpL dt + ∆HV,M + ∫68 cpL dt ] +nw,reflux [∫Tref cpW,L +∆HV,W +
102
∫100 cpgas dt ] ……………(1)

V1 = R + D
ASSUM. R / D = 1.3
R = 1.3 D
V1 =1.3 D +D

V1 = 3.197 𝑘𝑚𝑜𝑙/ℎ𝑟
nM ,reflux = XW,D * V1
= 0.903 * 3.197 = 2.8868 𝑘𝑚𝑜𝑙/ℎ𝑟 ……… (2)

nW,reflux = XW,D * V1
= 0.0966 * 3.197 = 0.3088 𝑘𝑚𝑜𝑙/ℎ𝑟 …….....(3)
Sub. (2) , (3) in (1)

Heat reflux = 2.886.8 {[(75.86*10-3T +16.83 *10-5T2/2]68

25
+ 35.27 + [42.93*10-
3
T +8.301*10-5T2/2 – 1.87*10-8T3/3 – 8.03 *10-12T4/4]102
68
}

+ 308.8 {[75.4 *10-3 T ]100

25
+ 40.656 + [33.46*10-3T + 0.688*10-5T2/2

+ 0.7604*10-8 T3/3 – 3.593 *10-12 T4 / 4 ]102

100
}

= 116034.4968 +14321.5059
= 130356.0027 𝐾𝐽/ℎ𝑟

46
Qc = hD – heat reflux
= 4738.0591 – 130356.0027
= - 125617.9436 kJ/hr
T T T
h = nM ∫Tref CPM ,gas + nF ∫Tref cpF + nW ∫Tref cpW,gas

= 1260 *3.7048 + 8652.6 *2.8480 +13378.68 *2.612

= 64263.79 𝑘𝐽/ℎ𝑟
QR = hD – hB – QC – hFeed
= 4738.0591 + 64730.11009 – (- 121617.9436) – 64263.79
= 130822.3228 𝑘𝐽/ℎ𝑟

2.2.10- Mixing point of stream 17 , 18 and 19

nF,17 = 8.6226 𝑘𝑚𝑜𝑙/ℎ𝑟 nF,19 = 8.6226

nW,17=13.297 𝑘𝑚𝑜𝑙/ℎ𝑟 nM ,19 = 0.00376 𝑘𝑚𝑜𝑙/ℎ𝑟

nM ,17 = 0.00376 𝑘𝑚𝑜𝑙/ℎ𝑟 nW,19 =?? = 14.67764 𝑘𝑚𝑜𝑙/ℎ𝑟

nW,18 = ??= 1.38064 𝑘𝑚𝑜𝑙/ℎ𝑟

0.37 = nF,19 /n19

0.37 = 8.6226/n19
n19 = 23.304 𝑘𝑚𝑜𝑙/ℎ𝑟

n19 = nF,19 +nW,19 +nM ,19

23.304 = 8.6226 + nW,19 + 0.00376
nW,19 = 14.67764 𝑘𝑚𝑜𝑙/ℎ𝑟
nW,18 +nW17 = nW,19

47
nW,18 = 14.67764 – 13.297
= 1.38064 𝑘𝑚𝑜𝑙/ℎ𝑟
Qin = Qout
110 110 110
nW,17 ∫25 cpW dt + nM ,17 ∫25 CPM dt + nF,17 ∫25 CPF
30 T T T
+ nW,18 ∫25 CPW dt = nW,19 ∫25 CPW dt + nM ,19 ∫25 CPM dt + nF,19 ∫25 CPF dt
110 110
13.297 ∫25 75.4*10-3 dt + 0.00376 ∫25 (75.86 * 10-3 + 16.83*10-5 T )dt
110
+ 8.6226 ∫25 34.28 *10-3 + 4.268 *10-5T – 8.694*10-12 T3)dt
30
+ 1.38064 ∫25 75.4 *10-3 dt
T T
= 14.67764 ∫25 75.4 * 10-3 dt + 0.00376 ∫25(75.4 * 10-3 + 16.83 *10-5 T )dt
T
+ 8.6226 ∫25(34.28 *10-3 + 4.268 * 10-5 T – 8.694 * 10-12 T3) dt

112.2204 = 14.67764 [75.4 * 10-3T – 75.4 *10-3 (25)]

+ 0.00376 [(75.4 *10-3T + 16.83 *10-5T2/2) – (75.4 *10-3 (25)
+16.83 *10-5 (25)2 /2 )] + 8.6226[(34.28 *10-3T +4.268*10-5 T2/2
+ 8.694*10-2 T4/4 ) – ( 34.28 10-3 (25) + 4.268 *10-5(25)2 /2
+ 8.694 *10-12 (25)4/4)]
112.2204 = 1.106694 T – 27.66735 + 2.835 *10-4 T + 3.164 *10-7 T2
- 7.0876 * 10-3 – 3.955*10-4 + 0.29558 T +1.84006 *10-4 T2

+1.8741 *10-11T4 - 7.3895 – 0.115003 – 7.3207 * 10-6

147.39974 = 2.102 T + 1.843 *10-4 T2 + 1.88741*10-11 T4
T = 68.22 °C

48
2.2.11- Energy balance on the heat exchanger E – 106
Q = ∑ n cp ∆T
= (n cp ∆T )F + ( n cp ∆T)H2O
30
= 8622.6 [ 34.28 *10-3 T+ 4.268*10-5 T2/2 – 8.694 *10-12T4/4 ]68.22
30
+ 14677.64 [75.4*10-3T ]68.22

= 11565.5 + 42297.846
= -53 863.4 KJ/hr (heat that must be removed from the heat exchanger )

Q= m cp ∆T
65
53863.4 = m ∫25 75.4 *10-3 dt

53863.4 = m [ 75.4 * 10-3 T ]65

25

53863.4 = m [(75.4 * 10-3 *65 )] – [(75.4*10-3 *25)]

53863.4 = m [ 4.901 – 1.885 ]
53863.4 = m [ 3.016]
m = 17859.21 𝑘𝑚𝑜𝑙/ℎ𝑟

49