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1. INTRODUCTION
CH2O is the first of the series of aliphatic aldehydes. It is also known as methanal. In
formaldehyde, the carbonyl carbon in functional group of aldehyde is directly linked with one
hydrogen atom. Formaldehyde occurs in nature and it is formed from organic material by
photochemical processes in the atmosphere. Formaldehyde is an important metabolic product in
plants and animals (including humans), where it occurs in low but measurable concentrations. It
has a pungent odour and is an irritant to the eye, nose and throat even at low concentrations.
Because of its relative low cost, high purity, and variety of chemical reasons,
formaldehyde has become one of the world's most important industrial and research chemical. It
is not only an Important low cost chemical intermediate, it is also a synthetic tool like
hydrogenation, oxidation etc. Since pure monomeric formaldehyde is a gas at ordinary
temperature and cannot be readily handled in this state, it is marketed chiefly in the form of
aqueous solutions containing 37% to 50% formaldehyde by weight. In addition, solution of
formaldehyde in methanol, propanol and butanol are also available commercially. The standard
37% U.S.P solution contains sufficient methanol (2 - 15% by weight), to prevent precipitation of
polymer under ordinary conditions of transportation and storage. A 30-50% aqueous solution of
methanol containing about 2-15% methanol is called formalin, also used for the preservation of
biological specimens.
HISTORY:
2. PROPERTIES
a) Formaldehyde Gas
At ordinary temperatures, pure formaldehyde is a colorless gas that has a strong pungent odour is
extremely irritating to the mucous membrane of the eye, nose and throat. Formaldehyde gas is
combustible and forms explosive combinations with air in the range covering mixtures
containing about 7-72% vol. The auto ignition Temperature is reported as approximately
300C.The heat of combustion is 134.lkcal/gmol or 4.47kcal/g.
Values per gmol at 25 C are:
Ionization value, 10.88 volt is reported by Franklin. The dissociation energy is obtained by
Reed is equivalent to 75.l} 2.3 kcal/mol. At low temperatures, it condenses to a clear, mobile
liquid (F.P -118C, B.P. -19.2C). At ordinary temperature the formaldehyde gas is readily
soluble in water, alcohols and other polar solvents. Its heat of solution in water and the lower
aliphatic alcoho1s is approximate1y equal to 15 kcal/mo1.
4
o
Boiling point at 101.3 kPa = -19.2 C
o
Melting point = -118 C
o 3
Density at 80 C = 0.9151g/cm
o 3
At 20 C = 0 .8153 g/cm
Vapour density relative to air = 1.04
o
Critical temperature = 137.2 141.2 ( C)
Critical pressure = 6.784 6.637 Mpa
3 -1
Cubic expansion coefficient = 2.83 x 10 K
o
Heat of formation at 25 C = -115.9 + 6.3 kJ/mol
o
Heat of combustion at 25 C = 561.5 kJ/mol
o
Heat of vaporization at 19.2 C = 23.32 kJ/mol
o
Specific heat capacity at 25 C = 35.425 J/mol K
o
Heat of solution at 23 C
In water = 62 kJ/mol
In methanol= 62.8 kJ/mol
In 1-propanal = 59.5 kJ/mol
In 1-butanol = 62.4 kJ/mol
o
Entropy at 25 C= 218.8 + 0.4 kJ/mol
5
b) Formaldehyde Solution
In general, commercial formaldehyde solutions are of high purity capable of meeting high
product requirements. Formaldehyde is described as containing not less than 37% formaldehyde
(CH2O) with methanol added to prevent polymerization. It is clear, colorless liquid possessing
the characteristic pungent odour of formaldehyde. The properties of the formaldehyde solutions
vary with, formaldehyde content, methanol content and temperature.
It is colorless, pungent smelling gas readily soluble in water, alcohol and ether. It is a powerful
disinfectant and antiseptic. When condensed it yields a colorless liquid. It has following physical
properties.
CH2O Content 37 37 37 45 50
(%)
CH3OH Content 1 5 10 1 1
(%)
Boiling Point 210 208 206 211 211
o
( F)
Density at 18C: 9.29 9.29 9.09 9.47 9.70
(lb/gal)
Approx. 0.0005 0.0006 0.0006 0.0006 0.0006
expansion
coefficient
o
Flash Point F 185 171 147 177 175
Approx.Specific 0.8 0.8 0.8 0.6 0.6
Heat
o
(cal/g. C)
6
Formaldehyde is one of the most reactive organic compounds known. The various chemical
properties are as follows:
1. Decomposition
o
At 150 C formaldehyde undergoes heterogeneous decomposition to form methanol and CO2
o
mainly. Above 350 C it tends to decompose in to CO and H2.
2. Polymerization
o
Gaseous formaldehyde polymerizes slowly at temperatures below 100 C,
Polymerization accelerated by traces of polar impurities such as acids, alkalis or water. In water
solution formaldehyde hydrates to methylene glycol
H
H2C=O + H2O H C OH
Formaldehyde is readily reduced to methanol with hydrogen over many metals and metal oxide
catalysts. It is oxidized to formic acid or CO2 and H2O.
In 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
Formaldehyde reacts with ammonia to form hexamethylene tetra amine with the elimination of
water. It is important industrial chemical used in disinfecting urinary canal
5. Cannizzaro Reaction
The reaction which involves the self-oxidation and reduction of formaldehyde into acids and
alcohols in the presence of a strong base (e.g. NaOH) is called Cannizzaro reaction; the reaction
gives sodium formate and methanol:
6. Condensation reactions
Important condensation reactions are the reaction of formaldehyde with amino groups to give
Schiffs bases, as well as the Mannich reaction.
Formaldehyde reacts with ammonia to give hexamethylene teteramine and with ammonium
chloride to give monomethylamine, dimethylamine, or trimethylamine and formic acid,
depending upon reaction conditions. Aromatic compounds such as benzene, aniline, and
toluidine combine with formaldehyde to produce the corresponding diphenyl methanes. In the
presence of hydrochloric acid and formaldehyde, benzene is chloromethylated to form benzyl
chloride. Formaldehyde reacts with hydroxylamine, hydrazines, or semicardazide to produce
formaldehyde oxime, the corresponding hydrazones, and semicarbazone, respectively.
7. Resin formation
Formaldehyde resins are one of the major applications of formaldehyde. Some of the derivatives
are given below.
6 Some topical creams, cosmetics and personal hygiene products also contain
derivatives of formaldehyde as the active ingredients that prevent the growth of
potentially harmful bacteria
7 Urea-formaldehyde concentrates are used as controlled release nitrogen fertilizers.
1
0
1 Melamine resins are thermosetting resins produced from melamine and formaldehyde
and are primarily used for surface coatings.
4 Urinary tract infections are also often treated using a derivative of formaldehyde
(methenamine), a method often chosen because it prevents overuse of antibiotics and the
resultant development of bacterial resistance to them. In an acid environment
methenamine is converted in the kidneys to formaldehyde, which then has an
antibacterial effect in the urinary tract. (This is not safe for long term use due to the
carcinogenic effect of formaldehyde).
1
1
4. MARKET SURVEY
Annually some 26 million tons of formaldehyde, is used by companies all over the world. The
companies-producers of this chemical agent, by experts thoughts, are the largest consumers of
methanol in the world. In 2007, the enterprises from Western Europe purchased over 7 million of
formaldehyde. Thus, this indicator shows the volume of market of this agent, taking into account
a load-line of production facilities in the region, which was about 80%.
The principal manufacturers of formaldehyde in the world a company Dynea (the Netherlands),
BASF (Germany), Perstorp Formox (the Netherlands), Degussa (Germany), Ercros (Spain)
(Table 1). A traditional form of output of the matter (37% water solution) raises cost of
marketing of sellers.
Annual production
Name
volume, thousand t
Dynea, the Netherlands 720
BASF, Germany 650
Perstorp Formox, the Netherlands 550
Degussa, Germany 519
Ercros, Spain 400
Hexion, the Netherlands - Germany 390
Bayer, Germany 271
Sadepan Chimica, Italy 250
Ticona Polymerwerke, Germany 238
Dynochem, Great Britain 225
Caldic Chemie, the Netherlands 215
Krems Chemie, Austria 175
Chimica Pomponesco, Italy 160
Perstorp, Italy 140
Polioli, Italy 140
array of companies-producers replaced their
Recently, the subjects in the market of owners, a number of mergers increased. For
formaldehyde changed considerably. A wide example, one of
1
2
the leaders in the market Ercros bought the companies Derivados Forestalrs (Spain) and
Hexion-Arkema (Germany), and quite a few enterprises in Russia. Eastern market has become
one of the most interesting for the company owing to lots of modern organizations specialized in
production of methanol and a rapidly growing domestic demand for formaldehyde.
The European market of formaldehyde has a peculiarity the main part of the matter is used for
domestic use. Owing to this fact, there exists an internal European model of pricing. A price for
the chemical agent depends not on supply and demand; its price formed once a quarter and varies
sufficiently subject to a country. The price for formaldehyde is closely coupled with the price for
methanol.
DEMAND/CONSUMPTION
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 worlds production of 32.5 million metric tons by 2012.
Trends of development of the world formaldehyde market are easily predicted. This chemical
agent is quite widely used in the industry, therefore the market growth, by experts estimation,
will keep on growing at a slow pace compared to the increased of GDP. Specialists forecast a 2%
annual growth of European market, 1.7% - Japanese market, 1.5% - North America.
Asian markets (like Chinese) are going to exceed average rates owing to a growing demand from
the side of producers of agrochemical agents and paraformaldehyde.
Formaldehyde is usually produced close to the point of consumption since it is fairly easy to
make, is costly to transport and can develop problems associated with stability during transport.
As a result, world trade in formaldehyde is minimal.
1
3
China is the largest single market for formaldehyde, accounting for about 34% of world demand
in 2011; other large markets include the United States, Canada, Brazil, Germany, the
Netherlands, Spain, Italy, Belgium, Poland, Russia, Japan and the Republic of Korea. China is
forecast to experience fast growth rates (around 7% per year) and significant volume increases in
demand for 37% formaldehyde (formalin) during 20112016.
World consumption is forecast to grow at an average annual rate of almost 5% during 2011
2016. Continuing significant-to-rapid demand growth in Asia (mainly China) for most
applications will balance out moderate growth in North America, Western Europe, Africa and
Oceania. Central and South America, the Middle East, and Central and Eastern Europe are
forecast to experience significant growth in demand for formaldehyde during 20112016, largely
as a result of increased production of wood panels, laminates, MDI and pentaerythritol.
1
4
5. LITERATURE SURVEY
Today about all of the world's commercial formaldehyde is manufactured from methanol and air
by using metal or metal oxide catalyst but a portion is produced by the partial oxidation of lower
petroleum hydrocarbons. The former procedure gives essentially pure formaldehyde containing
methanol and traces of formic acid as a primary product, whereas the later gives a mixture of
lower aliphatic aldehydes, alcohols and acids which on refining yield an excessive group of
petro-chemicals.
Although, there are other miscellaneous methods for producing formaldehyde, including the
hydration of carbon oxides the pyrolytic decomposition of formates etc, but they do not appear to
have achieved commercial importance.
Normally three methods are used for the manufacturing of formaldehyde from natural gas:
1) Oxidation in gaseous phase by passing mixture of gas and air over catalyst.
2) Oxidation of natural gas by ozone.
3) Iodination with subsequent hydrolysis.
Formaldehyde is also synthesized by cracking of methane in electric discharge. Many types of
catalyst e.g. copper, nickel, cobalt, chromium, manganese, gold and silver are used for
production of formaldehyde. Maximum conversion of 60% to 70% of methane to formaldehyde
occurs in this process.
Most of the worlds commercial formaldehyde is manufactured from methanol and air either by a
process using a silver catalyst or one using a metal oxide catalyst.
1
5
Formaldehyde is manufactured commercially from methanol and air by an older process using a
metal catalyst and newer one using a metal oxide catalyst. Reactor feed to former is on the
methanol-rich side of a flammable mixture and virtually complete reaction of oxygen is obtained,
conversely, feed to metal oxide catalyst is lean in methanol and almost complete conversion of
methanol is achieved. Methanol process gives essentially pure formaldehyde containing traces of
formic acid as a primary product. Two types of catalysts are currently used for methanol
oxidation:
1) Iron Molybdenum oxide catalyst.
2) Silver or copper catalyst.
1
6
We normally use Iron Molybdenum oxide catalyst for best efficiency. Unreacted methanol
content in formaldehyde ranges between 0.5% - 1.0% in this case. Another reason is that we feed
a specific ratio of methanol and air in reactor. If this ratio is between 7.5-35 it produces an
explosive mixture. In case of iron molybdenum oxide catalyst this ratio is less, less than 7.5
therefore less methanol is used in this process. So this catalyst is more economical to use Initial
cost of this plant is although high but cost of product is low. A typical metal oxide catalyst' has an
effective life of 12 to 18 months. Compared to silver catalyst, it is much more tolerant to trace
contamination. It requires less frequent change-outs but a longer down time for each
replacement.
In this process formaldehyde is formed by oxidation process only. The reactions are:
CH3OH + O2 HCHO + H2O
HCHO + O2 CO + H2O
The reactions occur over a mixed oxide catalyst containing molybdenum oxide and iron oxide in
o
a ratio 1.5 to 3.The reaction is carried out at 250 350 C and essentially at atmospheric pressure.
Methanol conversion is 95 98% per pass.
We can also use silver or copper catalyst but in this case unreacted methanol content in
formaldehyde ranges between 4% to 7% Methanol and air ratio exceeds 35%, so large amount of
methanol is used in process. So although initial cost of this plant is low, cost of product will be
high. This catalyst poisons very rapidly. The silver catalyst has useful life of three to eight
months. It is easily poisoned by traces of transition group metals and by sulphur. By using silver
or copper catalyst, carbon monoxide and dioxide, methyl formate and formic acid are by-
1
7
products. In addition, there are also physical losses, liquid phase reactions, and small quantity of
methanol in the product, resulting in an overall plant yield of about 87% (based on methanol).
The silver catalyst processes for converting methanol to formaldehyde are generally carried out
at an atmospheric pressure and at 600 720C .The reaction temperature depends on the excess
of methanol in the methanol-air mixture. The composition of mixture must lie outside the
explosive limits. The amount of air used is also determined by the catalytic quality of the silver
surface. The following reactions take place:
It has been observed that although the conversion using Iron Molybdenum Oxide Catalyst but the
yield from the silver catalyst process is higher and hence we look into the silver catalyst process.
1
8
Process description:
The PFD shows a process to produce formaldehyde and water. Fresh methanol, Stream 2, at
30C and 14.7 psia mixes with recycled methanol, Stream 15, at 68.3C a 16 psia. Stream: 3
(recycled and fresh methanol) is at 31.13 C and 14.7 psia. Pump, P-101, raises the pressure up
to 35 psia. Stream 4 enters a heat exchanger where the methanol is vaporized. Stream 5 is then at
150C and 29 psia. Fresh air is available at 25C and 14.7 psia in Stream 1. Compressor, C 101,
raises the pressure to 35 psia in Stream 5. This stream is then heated by medium-pressure steam.
The temperature is raised to 150C in Stream 7. Stream 6 and Stream 7 mix at a pressure of 29
psia. The combined mixture is at 149.6C and 28 psia in Stream 8. The reactor converts 87.4% of
the methanol. The exit reactor temperature is 343 C. The metal oxide catalyst has approximately
uniform activity over a one year period, and catalyzes the oxidation reaction.
CH3OH HCHO + H2
Heat is removed by making high-pressure steam from boiler feed water. The outlet,
Stream 9, is at 343C and 25 psia. A valve drops the pressure of this stream to 5 psia before it
enters the absorber T -101. Fresh water is sent through the T -101 at 30C and 20 psia. T -101 is
set to absorb 99% of the formaldehyde that enters. Stream 13 is then heated to 102C before
entering T -102; the formalin distillation column T -102 recovers a 37 wt% solution of
formaldehyde in water. Most of the methanol is recovered in the distillate. Stream 15, the
distillate, is recycled back to the inlet of fresh methanol at 68.3C and 16 psia. The bottoms
Stream 16 is pumped, by P-103, up to 38.5 psia for storage. Deionized water at 30C in Stream
18 is added to achieve the 37 wt% solution of formaldehyde in water. Storage of formalin is
tricky. At high temperatures, undesirable polymerization of formaldehyde is inhibited, but formic
acid formation is favoured. At low temperatures acid formation is inhibited, but polymerization
is favoured. With 2 wt% methanol, the storage tank contents must be maintained between 35C
and 45C.
19
6. MATERIAL BALANCE
The methanol feed input is the basis of calculation throughout the chapter. The amount of input
basis of methanol was n3= 10 kmol/hr.
Known parameters:
st
1 run (without recycle): REACTOR
Reactor
Main reaction:
CH3OH HCHO + H2
nH,9 = z2 . (3)
nw,9 = z1 (4)
22
nF,9 = z1 + z2 (5)
z1 + z2 = 8.74 (A)
And we have,
z1 = 7.866 kmol/hr
z2 = 0.874 kmol/hr
From equation 1 ,
From equation 2,
0= nO,8 0.5 * z1
Similarly,
xi = 1
xi = 1
o
Solubility at T = 89.4 C
Therefore,
24
Absorb
nN,12 = nN,10 = 14.796 kmol/hr er
n11 = 18.675
kmol/hr xw = 1
n10 = 33.536 kmol/h, nm,10 = 1.26 kmol/h, nO,10 = 0 kmol/h, nw,10 =7.866
kmol/h nH,10 = 0.874 kmol/h, nF,10 = 8.74 kmol/h, nN,10 = 14.796 kmol/h
25
Thus,
xm = 0.03757, xO = 0, xw = 0.23455, xH= 0.02606, xf = 0.26062, xN = 0.4412
xi = 1
Similarly,
n14 =L1= D + B D
Fractional Recovery 1 = 99.7%
Fractional recovery 2 = 99 %
Distillati
on
Dx,M = frac.1 * n14 * xM,14 = 0.997 * 23.29 * 0.054 = 1.2534 kmol/hr
Bx,M = (1 frac.1) * n14* xM,14 = 0.0038 kmol/hr F
Bx,W = (frac.2)* n14 * xW,14 = 0.99 * 23.29 * 0.5744 = 13.244 kmol/hr
Dx,W = (1 frac.2) * n14 * xW,14 = (1 -0.99) * 23.29 * 0.5744 = 0.1338 kmol/hr
Bx,F = 0.3715 * 23.29 = 8.65224 kmol/hr B
D = DxDi = 1.2534 + 0.1338 = 1.3872 kmol/hr
nd
2 Run (with recycle):
n3,M = n15,M + N
N = n3,M n15,M = 10 1.3872 * 0.96355 = 8.7466
kmol/hr n3,w = 1.3872 * 0.09645 = 0.13378 kmol/hr
n3 = n3,M + n3,w = 10 + 0.13378 = 10.13378 kmol/hr
n6 = n3:
x3,M = x6,M = n3,M/n3= 0.9868
x3,w = x6,w = n3,w/n3 = 0.0132
From solubility:
xw = 0.495
n12,W= (18.657 + 7.99947) * 0.496 = 13.23 kmol/hr
n12 = nG1,F+ nG1,N + nG1, H2+ nG1,W= 0.0874 + 14.796 + 0.874 + 13.23 = 28.988 kmol/hr
nL1,W= n10 + n9,w (second run) n12,W = 18.675 + 7.99978 13.23 = 13.445 kmol/hr
nL1,M = 0 + n11,M n12,M = 0 + nGo 0 = 1.26 kmol/hr
n13 = nL1,M + nL1,F + nL1,W = 1.26 + 8.6526 + 13.445 = 23.358 kmol/hr
n14 = D + B
DxM= frac.1 * n14 * xM,n14 = 0.997 * 23.358 * 0.054 = 1.25755
kmol/hr BxM= (1 frac.1) * n14 * xM,n14 = 0.003784 kmol/hr
BxW = frac.2 * n14 * xW,n14 = 0.99 * 23.358 * 0.576 = 13.3197 kmol/hr
DxW= (1 frac.2) * n14 * xw,n14 = (1 -0.99) * 23.358 * 0.576 = 0.13454
kmol/hr BxF= 0.37 * 23.358= 8.6425 kmol/hr
D = DxDi= 1.25755 + 0.13454 = 1.39209 kmol/hr
B = BxBi= 0.0038 + 13.3197 + 8.6425 = 21.966 kmol/hr
In wt %:
For Reactor:
Reactor
Distillation
30
For Absorber:
Absorber
31
stream number
1 2 3 4 5 6 7 8 9 10
summation kg/hr 5282.3285 2740.783 3157.091 3157.091 5282.328 3157.091 5282.328 8439.419 8439.41 8439.41
Summation
46273.198 24009.26 27656.12 27656.12 46273.2 27656.12 46273.2 73929.31 73929.33 73929.33
tons/yr
32
stream number
11 12 13 14 15 16 17 18 19 20
oxygen 0 0 0 0 0 0 0 0 0 0
water 3287.373 2328.886 2366.732 2366.732 23.68317 2344.676 2344.676 1965.676 4310.352 4310.352
hydrogen 0 17.09453 0 0 0 0 0 0 0 0
nitrogen 0 4051.522 0 0 0 0 0 0 0 0
summation kg/hr 3287.373 6423.166 5302.297 5302.297 418.50 4883.639 4883.639 1965.676 6849.315 6849.315
Summation tons/yr 28797.39 56266.94 46448.12 46448.12 3666.142 42780.68 42780.68 17219.32 60000 60000
7. ENERGY BALANCE
Energy balance mostly depends on calculating the heat capacity (Cp) of each component present
on the system.
o
Where the units of the constants C1, C2, C3 and C4 are in KJ/ (mole. C)
stream number
1 2 3 4 5 6 7 8 9 10
summation kmol/hr 183.16 85.54 99.10 99.10 183.16 99.10 183.16 282.26 329.21 329.21
34
stream number
11 12 13 14 15 16 17 18 19 20
oxygen 0 0 0 0 0 0 0 0 0 0
water 182.63 129.38 131.49 131.49 1.32 130.26 130.26 109.20 239.46 239.46
hydrogen 0 8.48 0 0 0 0 0 0 0 0
nitrogen 0 144.70 0 0 0 0 0 0 0 0
summation kmol/hr 182.63 283.41 228.43 228.43 13.62 214.82 214.82 109.2 324.02 324.02
o
At the prevailing temperature (68.3 C) and pressure (1.2 atm), methanol is in liquid state
(stream 15).
Ein = Eout
35
Therefore,
o
T=31.13 C
Pump P-101
Q = n Cp T
= (n Cp T)m + (n Cp T)w
=
Compressor C-101
For air
Cp = 29.1 kJ/ (kmol.K), Cv = 20.78 kJ/ (kmol.K)
o
, Where , T1= 25 C, P5 = 3 atm, P1 = 1 atm, n(efficiency) = 0.75
o
= 34.218 C
o
T5 = 37.3 C
Q = n Cp T
= (n Cp T)N + (n Cp T)O
=
TABLE:
Where,
38
o
Heat exchange is joined with the reactor and so, the endpoint reaction is at 343 C and then
o
products will cool down to 200 C.
Heat Exchanger inside the Reactor: these are the enthalpies at the end of the reactor and before
interring the cooling section.
Also, these are the enthalpies at the end of the reactor and cooling
section. Enthalpy of the components in stream 9,
39
o
We have four streams, the temperature of the two inlets streams are 20 and 164 C for reaction
product and water stream respectively. The outlet temperature has calculated as follow:
INLET = OUTLET
1 nHin = nHout
o o o
2 nHn10 (165 C) + nHn11 (20 C) = nHn12 (89.31 C) + nHn13
o o
(89.31 C) Reference temperature is 25 C
o
Heat in at stream n10: T= (165-25) C
Qn10= (nCpT)n10M + (nCpT)n10W + (nCpT)n10F + (nCpT)n10H + (nCpT)n10N
= 4080729.58 KJ/hr.
Heat in at stream n11: T= (20-25)
o
C Qn11 = (nCpT)n11w = -126730
KJ/hr. So,
40
Therefore,
o
Temperature at the outlet = 89.31 C
And,
Thus,
Q = H = niHi,out - niHi,in
= [(12320 x 3.7048) + (131490 x 2.6126) + (84260 x 2.8480)] - [(12320 x 3.0615) + (131490 x
2.1788) + (84260 x 2.3613)]
Q = 629146.39 523171.23 = 105975.16 KJ/hr.
41
o
Tref = 25 C
Lo = 1.3 x D
Therefore,
Bottoms,
For condenser,
42
For Reboiler,
Heat exchanger
Reactor R-101
Since the reactor is merged with the Heat exchanger the inlet to the exchanger will be the outlet
from the reactor, and hence this part is considered in the energy balance.
Reactor with
Heat exchanger
Absorption
tower
E-102 607730
E-103 105975.16
E-104 -509157.15
E-105 571017.54
C-101
P-101 1033.905
45
8. EQUIPMENT DESIGN
o
Hot fluid = saturated steam at 370.2 F in tube
side Because,
Pressure:
Higher pressure fluid is placed in the tube
side. Viscosity:
Higher viscosity fluid placed in shell
side. Phase change:
The stream with phase change is assigned to shell side, in steam heated vaporizers the
condensing steam is placed in tube side.
o
Therefore, LMTD = 150.8258 F
For saturated steam Ft=1
o
Hence, t = 150.8258 F
3. Tc, tc avg. temperature of hot and cold fluid
o
respectively. Tc = 370.328 F
o
tc = 195.017 F
46
2 o
We assume UD=175 Btu/ (hr) (ft ) ( F)
Now,
2
a = 0.1963 ft /lin ft
2
Corrected Area = a x Nt x L = 0.1963 x 52 x 16 = 163.32 ft
So,
2 o
Corrected UD = Q / (A x t) = 162.273 Btu/ (hr) (ft ) ( F)
2 2
(5) Gt = w / at = 85974.311 lb/ (hr) (ft ) (5) Gt = w / at = 200466.1853 lb/ (hr) (ft )
o o
(6) At 370.328 F (Fig. 15) (6) at 195.017 F (Fig. 14)
= 0.03781 lb / (ft)(hr) = 0.25 Cp = 0.25 x 2.42 = 0.605 lb /
D = 0.62 / 12 = 0.0517 ft (ft)(hr)
Re = (D x Gt/ ) = 117558.1044 De = 0.73 / 12 = 0.06 in
Re = (De x Gt) / = 20146.02
(7) jH = 82 (Fig. 28)
2 o
(8) k = 0.114 Btu / (hr)(ft )( F/ft) (Table 4)
o
c = 0.6083 Btu/(lb)( F)
Therefore,
1/3
k((c x )/k) =
2 o 2 o
(9) hio = 1500 Btu / (hr)(ft )( F) 0.16848 Btu / (hr)(ft )( F/ft)
(9) ( )
ho / s = 230.256
(10) s = 1
2 o
ho = 230.256 Btu / (hr)(ft )( F)
48
Pressure Drop
(2)
2 o
(13) Dirt factor Rd = (Uc Ud) / (Uc x Ud) = 0.001152 (hr) (ft ) ( F) / Btu
Summary
1500 h outside 230.256
Uc 199.614
UD 162.273
Rd Calculated 0.001152
Rd Required 0.001
1 Calculated P 2.4634
Neg. Allowable P 10.0
49
=1
-3
= 0.797 x 10
2
P gC = 9.8 m/s
50
Where: G' = mass flow rate of gas per unit cross-sectional area of
column gc= gravitational constant
F = packing factor
= ratio of specific gravity of the scrubbing liquid to that of water
= viscosity of liquid
2
G flooding = 7.8776 kg / (m ) (s)
2
G operating = 0.7 (G flooding) = 5.514 kg / (m ) (s)
51
2
Area = D /4 = 0.425 Dpacking = 0.736 m
Packing Height:
Y X
0 0
0.1281 0.0204
0.2560 0.0416
0.3833 0.0638
0.5097 0.0869
0.6352 0.1111
0.7597 0.1363
0.8831 0.1627
1.0058 0.1904
NOG = 10.95
HOG is obtained from table 16-4 in Separation Process Engineering. For ceramic packing
with size 2 in, HOG = 3 ft = 0.91 m
Wall thickness (for 2 in ceramic Raschig ring packing) = 6 mm with Porosity = 0.74 ()
52
I. Direct Costs: material and labor involved in actual installation of complete facility (70-85% of
fixed-capital investment)
Consider the cost of service facilities and yard improvement = 62% of PEC
II. Indirect costs: expenses which are not directly involved with material and labor of actual
installation of complete facility (15-30% of Fixed-capital investment)
i.e., cost of engineering and supervision = 0.15 x 3024.5 = Rs. 453.675 lakhs
54
i.e., construction expense and contractors fee = 0.14 x 3024.5 = 423.43 lakhs
1= 4204.055 + 741.892
2= 4945.947 lakhs
55
9. Manufacturing Cost = Direct production cost + Fixed charges + Plant overhead cost.
i.) Depreciation: (depends on life period, salvage value and method of calculation- about
10% of FCI for machinery and equipment, and 2-3% for Building Value for Buildings)
Consider depreciation = 10% of FCI, and 3% for Building Value for Buildings
3) Direct Supervisory and Clerical Labor (DS & CL): (10-25% of OL)
Consider the cost for Direct supervisory and clerical labor = 12% of OL
Direct supervisory and clerical labor cost = 0.12 x 1045.297 = 125.4356 lakhs
C. Plant overhead Costs (50-70% of Operating labor, Operating supplies, and Maintenance or
5-15% of total product cost); includes for the following: general plant upkeep and overhead,
payroll overhead, packaging, medical services, safety and protection, restaurants, recreation,
salvage, laboratories, and storage facilities.
Consider the plant overhead cost = 60% of OL, OS, and M & R
2= 772.217 lakhs
II. General Expenses = Administrative costs + distribution and selling costs + research and
development costs
B). Distribution and Selling costs: (2-20% of total product cost); Includes costs for sales offices,
salesmen, shipping, and advertising.
58
= 1045.2969 lakhs
Rate of Return:
Payback period:
1= 2.36 years
CONCLUSION:
From mass balance and energy balance, the various equipments were designed and cost
estimation was made. The payout period was found to be 2.36 years. Hence the project is
feasible.
60
The economic construction and efficient operation of a process unit will depend upon how well
the plant and equipment specified on the process flow sheet is laid out and on the profitability of
the project with its scope for future expansion.
Plant location and site selection should be made before the plant layout.
Plant location and site selection:
The location of the plant has a crucial effect on the profitability of the project.
The important factors that are to be considered while selecting a site are:
1. Location, with respect to market area
2. Raw material supply
3. Transport facilities
4. Availability of Labour
5. Availability of utilities
6. Availability of suitable land
7. Environmental impact and effluent disposal
8. Local community considerations
9. Climate
10. Political and strategic considerations
1. Marketing area
For materials that are produced in bulk quantities, such as cement, mineral acids, and fertilizers
where the cost of product per tone is relatively low and the cost of transport a significant fraction
of the sales price, the plant should be located close to the primary product. This consideration
will be less important for low volume production, high-priced products, such as pharmaceutical.
6
1
2. Raw materials
The availability and price of suitable raw materials will often determine the site location. Plants
producing bulk chemicals are best located close to the source of major raw material, where this is
also close to the marketing area. For the production of formaldehyde the site should be
preferably near a methanol plant.
3. Transport
4. Availability of labour
Labour will be needed for construction of the plant and its operation. Skilled construction
workers will usually be brought in from outside the site area, but there should be an adequate
pool of unskilled labours available locally; and labour suitable for training to operate the plant.
Skilled tradesman will be needed for plant maintenance. Local trade union customs and
restrictive practices will have to be considered when assessing the availability and suitability of
the local labour for recruitment and training.
All industrial processes produce waste products, and full consideration must be given to the
difficulties and cost of their disposal. The disposal of toxic and harmful effluents will be covered
by the local regulations and the appropriate authorities must be consulted during the initial
survey to determine the standards that must be met.
62
The proposed plant must fit in with and be acceptable to the local community. Full consideration
must be given to the safe location of the plant so that it does not impose a significant additional
risk to the community on a new site, the local community must be able to provide adequate
facilities for the plant personnel.
7. Land
Sufficient suitable land must be available for the proposed plant and for future expansion. The
land should ideally be flat, well drained and have suitable loadbearing characteristics full site
evaluation should be made, to determine the need for piling or other special foundations.
8. Climate
Adverse climatic conditions, at a site will increase costs. Abnormally low temperatures will
require the provision of additional insulation and special heating for equipment and pipe runs.
Capital grants, tax concessions and other inducements are often given by governments to direct
new investment to preferred locations; such as areas of high unemployment. The availability of
such grants can be overriding consideration in the site selection.
After considering the location of the site, the plant layout is completed. It involves placing of
equipment so that the following are minimized:
1. Damage to persons and property in case of fire explosion or toxic release
2. Maintenance costs
3. Number of people required to operate the plant.
4. Construction costs
5. Cost of planned expansion.
wind. Wind direction will decide the location of
In plant layout first thing that should be done is
the plant.
to determine the direction of the prevailing
63
List of items that should be placed upwind and downwind of the plant is given down.Items that
should be located to the upwind.
1 Laboratories
2 Fire station
3 Offices building
4 Canteen and Change house
5 Storehouse
6 Medical facilities
7 Electrical substation
8 Water treatment plant
9 Water pumps
10 Workshops
1. Processing area
Processing area also known as plant area is the main part of the plant where the actual production
takes place. There are two ways of laying out the processing area
1.) Grouped layout
2.) Flowline layout
2. Storage house
The main stage areas should be placed between the loading and unloading facilities and the
process they serve. The amount of space required for storage is determined from how much is to
be stored in what containers. In raw material storage, liquids are stored in small containers or in a
pile on the ground. Automatic storage and retrieving equipment can be substantially cut down
storage
3. Laboratories
Quality control laboratories are a necessary part of any plant and must be included in all cost
estimates. Adequate space must be provided in them for performing all tests, and for clearing and
storing laboratory sampling and testing containers.
6
5
4. Transport
Road area is also used for firefighting equipment and other emergency vehicles and for
maintenance equipment. This means that there should be a road around the perimeter of the site.
No roads should be a dead end. All major traffic should be kept away from the processing areas.
It is wise to locate all loading and unloading facilities, as well as plant offices, personnel
facilities near the main road to minimize traffic congestion within the plant and to reduce danger.
5. Fire station
Fire station should be located adjacent to the plant area, so that in case of fire or emergency, the
service can be put into action
6. Utilities
The word Utilities is now generally used for the services needed in the operation of any
production process. These services will normally be supplied from a central site facility and will
include:
1. Electricity
2. Steam for process heating
3. Cooling water
4. Water for general use
5. Inert gas supplies
a. Electricity
Electrical power will be needed at all the sites. Electrochemical processes that require large
quantities of power need to be located close to a cheap source of power.
Transformers will be used to step down the supply voltage to the voltages used on the purpose.
c. Cooling water
Chemical processes invariably require large quantities of water for cooling. The cooling water
required can be taken from a river or lake or from the sea.
All industrial processes produce waste products, and full consideration must be given to the
difficulties and coat of their disposal. The disposal of toxic and harmful effluents will be covered
by local regulations, and the appropriate authorities must be consulted during the initial site
survey to determine the standards that must be met.
8. Offices
The location of this building should be arranged so as to minimize the time spent by personnel in
travelling between buildings. Administration offices, in which a relatively large number of
people are working, should be located well from potentially hazardous process.
Canteen should be spacious and large enough for the workers with good and hygienic food.
Medical facilities should be provided with at least basic facilities giving first aid to the injured
workers. Provision must be made for the environmentally acceptable disposal of effluent.
Sufficient land space must be provided near the exit for car parking.
6
7
Formaldehyde:
Liquid or gaseous formaldehyde is extremely toxic. Because of its sharp smell and its tear-
inducing, effects, formaldehyde can easily be discovered before the concentration becomes
dangerous. All rooms in which work with Formaldehyde is done must have good ventilation to
avoid collection of gases. Liquid formaldehyde can be -absorbed by skin and has a dangerous
effect. Each spatter on the skin should therefore be washed away at once and with care. An
appropriate skin cream should be applied. If there is any risk of splashing, protective glasses
should be worn. If nevertheless formaldehyde gets into the eyes, they must carefully be washed
by means of clean water. Afterwards a doctor should be consulted. Formaldehyde may cause
eczema. Most people working with formaldehyde at first feel only Slight reaction, which
normally means a slight reddening of the skin and dryness of the hand. Its sensitivity varies in
each case and it usual1y disappears after 2 to 3 weeks. By frequent washing with super fat soap
and application of protective cream, as well as by wearing rubber or PVC gloves, eczema can be
avoided. All persons having formerly suffered from eczema are discouraged from working with
formaldehyde. Formaldehyde gas irritates the mucous membranes of the eyes, nose and throat.
Its solution has a hardening or tanning action on the skin. Some persons are hypersensitive to
formaldehyde and even a slight exposure may lead to severe reaction in such cases. For optimum
safety, formaldehyde solution should be handled in closed equipment where ever possible.
Danger of Fire:
Formaldehyde is inflammable under certain conditions, e.g. as vapours from strong
formaldehyde solution or par formaldehyde. Throughout the Formaldehyde factory smoking and
open fires are therefore prohibited. The management of the factory must consent to any welding
work to be carried out in the factory premises.
68
Methanol:
Methanol is toxic, methanol in liquid or gaseous form is easily absorbed by the body. It can
penetrate the body in following ways:
1) As vapours by heating.
2) Through the mouth.
3) Through skin (particularly in case of cuts & scratches)
Once absorbed by body, methanol in increasing doses may lead to nausea, blindness, mental
disorder & finally to death. There is no safe dosage, and individual sensibility differs to a high
degree. When working with methanol the following should be observed:
Reactivity
Methanol has an explosive nature in its vapour form when in contact with heat of fires. In the
case of a fire, small ones are put out with chemical powder only. Large fires are extinguished
with alcohol foam. Due to its low flash point, it forms an explosive mixture with air. Reaction of
methanol and Chloroform + sodium methoxide and diethyl zinc creates an explosive mixture. It
boils violently and explodes.
69
Formaldehyde solutions can be stored and transported in containers made of stainless steel,
aluminum, enamel or polyester resins. Iron containers lined with epoxide resin or plastic may
also be used, although stainless steel containers are preferred, especially for higher formaldehyde
concentrations. Unprotected vessels of iron, copper, nickel and zinc alloys must not be used.
o
Formaldehyde content, wt % Methanol content, wt % Storage temperature, C
30 <= 1 7 10
37 <1 35
37 7 21
37 10 12 67
50 1 2 60 65
50 1 2 45
70
12. BIBLIOGRAPHY