1

1. INTRODUCTION

Formaldehyde is the simplest and most commercially important aldehyde. Formaldehyde

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.

Formaldehyde is an important industrial chemical and is employed in the manufacture of

many industrial products and consumer articles.
 2

HISTORY:

Formaldehyde was first synthesized in 1859, when BUTLEROV hydrolysed methylene

acetate and noted the characteristic odour of the resulting solution. In 1867, HOFMANN
conclusively identified formaldehyde, which he prepared by passing methanol vapour and air
over a heated platinum spiral. This method, but with other catalyst, still constitutes the principal
method of manufacture.

Industrial production of formaldehyde became possible in 1882, when TOLLENS

discovered a method of regulating the methanol vapour: air ratio and affecting the yield of the
reaction. In 1886 LOEW replaced the platinum spiral catalyst by more efficient copper gauze. A
German firm, Hugo Blank, patented the first use of a silver catalyst in 1910.In 1905, Badische
Anilin and Soda-Fabrik started to manufacture formaldehyde by a continuous process employing
a crystalline catalyst. Formaldehyde output was 30 kg/day in the form of an aqueous 30 wt%
solution. The methanol required for the production of formaldehyde was initially obtained from
the timber industry by carbonizing wood. The development of high-pressure synthesis of
methanol by Badische Anilin and Soda-Fabrik in 1925 allowed the production of formaldehyde
on a true industrial scale.
 3

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:

Heat of formation = -27.70 kcal

Free energy = -26.666 kcal
Heat capacity = 8.461 cal/c
Entropy = 52.261 cal/c

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

a.1) Physical Properties of Monomeric Formaldehyde

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

a.2) THERMAL PROPERTIES

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.

b.1) PHYSICAL PROPERTIES

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.

Table: Physical properties of typical aqueous commercial formaldehyde

solutions.

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

b.2) CHEMICAL PROPERTIES

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

This in turn polymerizes to polymethylene glycols, HO (CH2O)nH, also called polyoxy

methylenes.
 7

3. Reduction and Oxidation

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

4. Reaction with Ammonia

Formaldehyde reacts with ammonia to form hexamethylene tetra amine with the elimination of
water. It is important industrial chemical used in disinfecting urinary canal

6HCHO + 4NH3 (CH2)6N4 + 6H2O

Hexamethylene tetra amine

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:

2HCHO + NaOH HCOONa + CH3OH

 8

6. Condensation reactions

Important condensation reactions are the reaction of formaldehyde with amino groups to give
Schiffs bases, as well as the Mannich reaction.

CH3COCH2CH2N(CH3)2.HCl + H2O CH3COCH3 +

(CH3)2NH.HCl+ HCHO

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 condenses with urea, melamine, urethanes, cyanamide, aromatic sulfonamides

and amines, and phenols to give wide range of resins.
 9

3. COMMERCIAL USES OF FORMALDEHYDE

Formaldehyde resins are one of the major applications of formaldehyde. Some of the derivatives
are given below.

1 Urea-formaldehyde resins are produced by the controlled reaction of urea and

formaldehyde. Their major uses are as adhesives for particleboard, fibreboard and
plywood. They are also used for compression moulded plastic parts, as wet-strength
additives for paper treating, and as bonders for glass fibre roofing materials.

2 Phenol formaldehyde is produced by the condensation of phenol with

formaldehyde. The use of these resins is as an adhesive in waterproof plywood. These
resins are also used for binding glass fibre insulation.

3 Acetylenic chemical uses of formaldehyde involve the reaction with acetylene to

form butynediol, which in turn can be converted to butanediol, butyrolactone and
pyrrolidones. Their major applications are as specialty solvent and extractive distillation
agents.

4 Polyacetyl resins are produced from the anionic polymerization of formaldehyde.

These resins are used in plumbing materials and automobile components.

5 Pentaerythritol is formed by the reaction of formaldehyde, acetaldehyde and

sodium hydroxide. Its largest use is in the manufacture of alkyd resins for paints and
other protective coatings.

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.

2 The direct use of formaldehyde is to impart wrinkle resistance in fabrics.

3 Formaldehyde is used to inactivate bacterial products for toxoid vaccines (vaccines

that use an inactive bacterial toxin to produce immunity). It is also used to kill unwanted
viruses and bacteria that might contaminate the vaccine during production.

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.

Table. Annual production volume of main producers of formaldehyde

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

The following pie chart shows world consumption of 37% formaldehyde:

Construction/remodelling activity, vehicle and furniture production, and original equipment

manufacturer (OEM) account for most world consumption of formaldehyde. Demand for these
markets is greatly influenced by general economic conditions. As a result, demand for
formaldehyde largely follows the patterns of the leading world economies. Formaldehyde resins
are used predominantly in the wood products industry as adhesives. Growth of these resins is
strongly correlated to construction/remodelling activity (which accounts for over 50% of
consumption), and to a lesser degree, to the automotive industry.

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

1) Process Comparison and Selection Criteria

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.

i) Natural Gas Process

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

ii) Methanol Process

Formaldehyde is produced by vapor phase oxidation of methanol in excess of air followed by

absorption of water liquid methanol is vaporized in vaporizer then it is mixed with compressed
air. These mixed streams are then introduced into tubular reactor, filled with silver catalyst. Heat
is generated by oxidation of Methanol. In this process, 87.4% conversion of methanol to
formaldehyde takes place. In natural gas process, the conversion of low molecular weight
hydrocarbons in the oxidation step together with a complex separation system, results in energy-
intensive plant, which, with increasing fuel costs, suffers economically when competing with
newer, more selective manufacturing methods, Hence the methanol process is preferred. In
natural gas process, maximum conversion of methane to formaldehyde is 60% to 70% while in
methanol process, conversion of methanol to formaldehyde is 85%. That is why; methanol
process is preferred over natural gas process. No doubt, Pakistan is blessed with a large quantity
of natural gas which is a good raw material for the manufacturing of formaldehyde but we prefer
methanol to natural gas as it is fractioned from petroleum and is cheaper one though imported
from Middle East up to some extent. Also, natural gas sources are decreasing in Pakistan day by
day, that is why, nowadays instead of using natural gas process we prefer to import methanol and
methanol process is used in our country.

b) Catalyst Comparison for Methanol Process

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

i) METAL OXIDE PROCESS

Iron Molybdenum Oxide Catalyst

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.

2) SILVER CATALYST PROCESS

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:

CH3OH + O2 HCHO + H2O

CH3OH HCHO + H2
Methanol conversion is 65 75% per pass.

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 + 0.5 O2 HCHO + H2O

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

FIGURE: Process flow sheet

 20

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.

Abbreviations used in the calculations:

1 n : is the molar flow-rate (kmol/hr)

2 m : methanol
3 water: deionized water
4 H2: hydrogen
5 N: nitrogen
6 f: formaldehyde
7 O2: oxygen
8 x : is the mole fraction
9 nm: methanol flow rate, similarly for the rest components.

Known parameters:

1 Overall conversion of methanol: 0.874

2 Selectivity of desired reaction to undesired reaction = 9
3 Production of formaldehyde needed = 60000 ton per year
o
4 The outlet temperature from the reactor 343 C
o
5 The outlet temperature from the reactor 200 C
o
6 Recycled temperature and pressure is 68.3 C and 1.2 atm respectively.
7 Pressure of the absorber is 138 kPa with formaldehyde absorption recovery of
99%.
o
8 Exit liquid stream from absorber is heated to 102 C.
 21

st
1 run (without recycle): REACTOR

Reactor

BASIS: 10 kmol/hr of methanol.

Main reaction:

CH3OH + O2 HCHO + H2O

Side reaction:

CH3OH HCHO + H2

nM,9 = nM,8 z1 z2 (1)

nO,9 = nO,8 0.5 * z1 .. (2)

nH,9 = z2 . (3)
nw,9 = z1 (4)
 22

nF,9 = z1 + z2 (5)

Conversion = 0.874 = (nM,8 - nM,9)/nM,8 = (z1+z2)/10

z1 + z2 = 8.74 (A)

And we have,

Selectivity = 9 = (nF1 / nF2) = z1/z2

Or, z1- 9 * z2 = 0 (B)

From (A) and (B)

z1 = 7.866 kmol/hr

z2 = 0.874 kmol/hr

Substituting z1 and z2 in the equations:

From equation 1 ,

nM,9 = 10 - 7.866 - 0.874 = 1.26 kmol/hr

From equation 2,

0= nO,8 0.5 * z1

Or, nO,8= 3.933 kmol/hr

Similarly,

nN,9 = nN,9 = nO2,8 * (0.79/0.21) = 14.796 kmol/hr

nH,9 = z2 = 0.874 kmol/hr

nw,9 = z1 = 7.866 kmol/hr

nF,9 = z1 + z2 = 8.74 kmol/hr

nF1= nM1 = z1 = 7.866 kmol/hr

nF2= nM2 = z2 = 0.874 kmol/hr

 23

nm,8 = 10 kmol/hr, nO,8 = 3.933 kmol/hr, nw,8=0 kmol/hr

nH,8=0 kmol/hr, nf,8 = 0 kmol/hr, nN,8 = 14.796 kmol/hr

Stream 8 (n8) = ni = 28.729 kmol/hr

xm = 10/28.729 = 0.3481, xO = 3.933/28.729 = 0.1369, xN = 14.796/28.729 = 0.515

xi = 1

nm,9 = 1.26 kmol/hr, nO,9 = 0 kmol/hr, nH2O = 7.866 kmol/hr

nH,9 = 0.874 kmol/hr, nf,9 = 8.74 kmol/hr, nN,9 = 14.796 kmol/hr

Stream 9 (n9) = ni = 33.536 kmol/hr

xm = 1.26/33.536 = 0.03757, xO = 0, xw= 0.23455

xH = 0.02606, xf = 0.26062, xN = 0.4412

xi = 1

Mass Balance around the absorber: (assuming 99% absorption of formaldehyde)

nf,12 = xf,10 * (1 0.99) = 0.2606 * 33.536 * 0.01 = 0.0874 kmol/hr

o
Solubility at T = 89.4 C

Solubility of formaldehyde = 0.468 (kmol Formaldehyde)/(kmol water)

0.468 kmol of formaldehyde dissolves completely in 1 kmol of water

8.74 kmol/hr of formaldehyde requires (8.74)/0.468 = 18.675 kmol/hr of

water Lo= n11 = 18.675 kmol/hr

Solubility of methanol = 0.011255 kmol methanol / L of water

Therefore,
 24

0.011255 kmol of methanol dissolves in (1/18) = 0.0555 kmol of water

18.675 kmol/hr of water dissolves (18.675*0.011255)/ 0.0555 = 3.78 kmol/hr

Therefore, all of methanol dissolves in water

nm,13= nm,10 = 1.26 kmol/hr

Assuming all N2, H2 is separated:

Absorb
nN,12 = nN,10 = 14.796 kmol/hr er

nH,12 = nH,10 = 0.874 kmol/hr

nf,13= 0.26062 * 33.536 * 0.99 = 8.6528 kmol/hr

xw,12 = (68.5)/(138) = 0.496

nw,12 = (18.675 + 7.866) x 0.496 = 13.164

n12 = nf,12 + nN,12 + nH2,12 + nO2,12

n12 = 28.9214 kmol/hr

nw,13 = 18.675 + 7.866 13.164 = 13.378 kmol/hr

n13 = nf,13 + nm,13 + nw,13

n13 = 23.29 kmol/hr

Water inlet: (stream 11)

n11 = 18.675
kmol/hr xw = 1

Gas inlet: (stream 10):

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,

Gas outlet: (stream 12)

xm = 0, xo2 = 0, xw = 0.4552, xH2= 0.03022, xf = 0.003022, xN = 0.5116

xi = 1

Liquid outlet: (stream 13)

xm = 0.054, xO = 0, xw = 0.5744, xf = 0.3715

xi = 1

Mass Balance around the distillation column:

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

B = BxBi = 0.0038 + 13.244 + 8.65224 = 21.9

kmol/hr xM,D = 0.90355, xW,D = 0.09645
xM,B = 0.000174, xW,B = 0.60475, xF,B = 0.39508
 26

Species Mole fraction(xi) Mass fraction (xim)

HCHO 0.39508 0.52135

CH3OH 0.000174 0.000244

H2O 0.60475 0.4784
Total 1 1

nd
2 Run (with recycle):

Mass balance around mixing point of streams 2, 3 and 15:

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

Mass balance around mixing point of streams 6, 7 and 8:

n6 = n3:
x3,M = x6,M = n3,M/n3= 0.9868
x3,w = x6,w = n3,w/n3 = 0.0132

From first run we got n1,O2 and n1,N

n1,O = 0.5 * z1 = 3.933 kmol/hr

n1,N = 0.5 * z1 * (0.79/0.21) = 14.796 kmol/hr
n7= n5= n1= n1,O2+ n1,N=3.933+14.796=18.729 kmol/hr
n8 = n6 + n7=10.13387+18.729=28.86287 kmol/hr
 27

Mass balance around the reactor:

The feed to the reactor is n8 = 28.86287 kmol/hr

Where the composition is shown as follow:

xm=10
xO2=3.933
xw=0.13378
xN=14.796
z1 + z2 = 8.74
z1 z2 * 9 = 0; z1 = 7.866 kmol/hr; z2 = 0.874
kmol/hr and so,
n9,M (second run) = n9,M (first run) = 1.26 kmol/hr
n8,O (second run) = n8,O2 (first run) = 0.5 * z1 = 3.933 kmol/hr
n9,N (second run) = n9,N (first run) = 14.796 kmol/hr
n9,H (second run) = n9,H2 (first run) = 0.874 kmol/hr
n9,F (second run) = n9,F (first run) = z1 + z2 = 8.74 kmol/hr
n9,w (second run) = 0.13378 + z1 = 7.99978 kmol/hr

Mass balance around the absorber:

n10,F (second run) = n10, F (first run) = 0.0874 kmol/hr

n10,F= y10,F * (1- 0.99) = 0.2606 * 33.536 (1-0.99) = 0.0874 kmol/hr

From solubility:

n11(second run) = n11(first run) = 18.675 kmol/hr

Assuming that all N2 as well as H2 are streamed out through off gas (same as first run):

n13,N = n12,N = 14.796 kmol/hr

n13,H = n12,H = 0.874 kmol/hr
 28

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

Mass balance around the distillation column:

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

xM,D = 0.90335, xW,D = 0.09665

xM,B= 0.000173, xF,B= 0.39345, xW,B= 0.60637

Species Mole fraction(xi) mi (ni*Mwt) Mass fraction (xim)

HCHO 0.39345 259.5 0.51965

CH3OH 0.000173 0.12176 0.000244

H2O 0.60637 239.73 0.4801
Total 1 499.352 1
 29

Mass balance around mixing point at streams 17, 18 and 19:

In wt %:

Mf,19 = 0.37 = (mf,17)/(m17+m18)

Therefore,
M18 = 201 kg/hr
Hence,
N18 = 11.16667 kmol/hr

For Reactor:

Mass in = 8439.419 kg/hr Mass out = 8439.41 kg/hr

Reactor

For distillation column:

Mass in = 11726.783 kg/hr Mass out = 11726.4 kg/hr

Distillation
 30

For Absorber:

Mass in = 5302.29 kg/hr Mass out = 5302.13 kg/hr

Absorber
 31

For 60,000 Tons/Year of formalin production:

Let us consider the total working hour of the plant is 8760 hr

Therefore the production rate per hour = 6849.315 kg/hr

Avg. molecular weight = 0.37x30+0.63x18= 22.44 kg/kgmol

stream number
1 2 3 4 5 6 7 8 9 10

methanol 0 2740.783 3133.542 3133.542 0 3133.542 0 3133.542 394.8262 394.8262

oxygen 1230.8065 0 0 0 1230.8065 0 1230.8065 1230.8065 0 0

formaldehyde 0 0 0 0 0 0 0 0 2566.402 2566.402

water 0 0 23.54938 23.54938 0 23.54938 0 23.54938 1408.207 1408.207

hydrogen 0 0 0 0 0 0 0 0 17.09453 17.09453

nitrogen 4051.522 0 0 0 4051.522 0 4051.522 4051.522 4051.522 4051.522

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

methanol 0 0 394.8262 394.8262 394.8262 1.190746 1.190746 0 1.190746 1.190746

oxygen 0 0 0 0 0 0 0 0 0 0

formaldehyde 0 25.66402 2540.738 2540.738 0 2537.773 2537.773 0 2537.773 2537.773

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

Total mass balance:

Mass in = 116268.112 tons/yr Mass out = 116266.94 tons/yr

 33

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

methanol 0 85.54 97.79 97.79 0 97.79 0 97.79 12.32 12.32

oxygen 38.46 0 0 0 38.46 0 38.46 38.46 0 0

formaldehyde 0 0 0 0 0 0 0 0 85.47 85.47

water 0 0 1.31 1.31 0 1.31 0 1.31 78.23 78.23

hydrogen 0 0 0 0 0 0 0 0 8.48 8.48

nitrogen 144.70 0 0 0 144.7 0 144.70 144.70 144.70 144.70

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

methanol 0 0 12.32 12.32 12.30 0.04 0.04 0 0.04 0.04

oxygen 0 0 0 0 0 0 0 0 0 0

formaldehyde 0 0.85 84.62 84.62 0 84.52 84.52 0 84.52 84.52

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

Mixing point between 2, 3 and 15:

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

Nm = 97.79 Kmol/hr, Mm = 97.79 x 32.02 = 3131.236 Kg/hr

Nw = 1.31 Kmol/hr, Mw = 1.31 x 18 = 23.58 Kg/hr
o
At 30 C
m = 782 Kg/hr
3
w = 996 Kg/m

Pin = 111.456 KPa (1.1atm)

Pout = 303.975 KPa
Avg density:

From Bernoullis equation:

ws= 775.429/0.75 = 1033.905 kJ/hr

 36

Heat Exchanger E-101

Q = n Cp T
= (n Cp T)m + (n Cp T)w
=

= 4155051.3 + 62317.29 = 4217368.59 kJ/hr

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

Heat Exchanger E-102

Q = n Cp T
= (n Cp T)N + (n Cp T)O
=

= 477150 + 130580 = 607730 KJ/hr

 37

Mixing point between streams 6, 7 and 8:

Since the temperature of stream number 6 is same as the temperature of stream number, so
o
stream 8 also has same temperature which is 150 C.

TABLE:

Species nin(moles) Hin nout(moles) Hout

CH3OH 97790 H1 12320 H5
O2 38460 H2 0 H6
N 144700 H3 144700 H7
HCHO - - 85470 H8
H2 - - 8480 H9
H2O 1.31 H4 78230 H10

Where,








 38

H = ziHf + niHi,out - niHi,in

1= (-156 x 7.866 x 1000 85 x 0.874 x 1000) + 3679029.286 1290397.518
2= -1301386 + 3679029.286 1290397.518 = 1087245.768 KJ/hr

Heat exchanger inside the reactor

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

Using datas from table

17 = H = niHi,out - niHi,in
1= 1951994.104 - 3679029.286 = - 1727035.182 KJ/hr
The heat required to be removed from the system using cold water.

Absorption tower T-101

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

Qin= Qn10 + Qn11 = 4080729.58 126730 = 3954000 KJ/mol

Heat out at stream: T= (T-25)

Therefore,
o
Temperature at the outlet = 89.31 C

Heat Exchanger E-103

nM = 12320 moles, nW = 131490 moles, nF = 84260 moles

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

Distillation Column T-102

xMD = 0.9335 xWD =

0.0966 Distillate,

o
Tref = 25 C

HD = HDm + HDw = 48893.3 KJ/hr

We have,
V1 = L o + D
Assuming the reflux ratio:

Lo = 1.3 x D
Therefore,

V1 = 1.3D + D = 2.3 x 13.62

Bottoms,

For condenser,

 42

For Reboiler,

Heat Exchanger E-101:

Out* = 1227837.508 KJ/mole Steam in = 659758.043 KJ/mole

Heat exchanger

Feed in = 48911.384 KJ/mole Feed out = 616990.8491 KJ/mole

Total in = 1276748.892 KJ/mole Total out = 1276748.892 KJ/mole

(Out* = 0.7181 L + 0.2818 V)

 43

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.

(cool water in - steam out ) H = -1727035.182 KJ/hr

Reactor with
Heat exchanger

In=3679029.286 KJ/hr Out = 1951994.104 KJ/hr

H (out - in) = -1727035.182 KJ/hr

Absorption Tower T-101

In* = -126730 KJ/hr Out* = 3430828.30 KJ/hr

Absorption
tower

In =4080729.58 KJ/hr Out = 523171.23 KJ/hr

Total in = 3953999.58 KJ/hr Total out = 3953999.53 KJ/h
 44

Energy balance data sheet:

Equipment Energy balance load

specification (KJ/hr)
E-101 4217368.59

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

1. HEAT EXCHANGER E-101

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.

1. Heat balance = Q = 3997294.1521 Btu/hr

2. t:
Hot fluid Cold fluid Diff.
370.328 Higher temperature 302 68.328
370.328 Lower temperature 88.034 282.294
0 Difference 213.966 213.966

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,

From table 10 heat transfer area per feet

2
a = 0.1963 ft /lin ft

Therefore from table 9: we get,

OD tubes inch OD tubes on 1- in. triangular pitch

Shell ID = 10 inch
Number of tubes Nt = 52 (2 passes)

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)

Mass flow rate of steam,

m x = Q = 4217368.59 KJ / hr ( = 1984.31 KJ/kg)

Therefore, m = 2125.357 kg/hr = 4685.60 lb/hr
 47

1 shell & 2 tube passes

Tube side = Hot fluid Shell side = Cold fluid
2
(4) Flow area per tube: (4) as = (ID x C x B) / (144 x Pt) = 0.03472 ft
at= 0.302 Where,
at = (Nt x at)/144n B = ID/5 = 2 in (baffle spacing)
2
= 0.0545 ft C = 0.25 (tube clearance)
Therefore, Pt = 1.25 in (pitch)

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

(1) For Ret = 117558.1044 (1) For Res = 20146.02

2 2
f = 0.00014 ft / in. f = 0.0018 (Fig. 29)
From table 7, specific volume of s = 0.75 (specific gravity) (Fig. 6)
o
steam at 370 F Ds = 10 / 12 = 0.8333 ft
3
= 2.606 ft / lb (2) N + 1 = (12L)/B
s = 1 / (2.606 x 62.5) = 0.00613 N + 1 = 96

(2)

(12) Clean overall coefficient Uc = (hio x ho) / (hio + ho)

2
1= (230.256 x 1500) / (230.256 + 1500) = 199.614 Btu / (hr) (ft )
o
( F)

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

2. ABSORPTION TOWER T-101:

Some assumptions and conditions were design calculation based on:

1. G and L are representing the gas and liquid flow rates.

2. x and y are for the mole fraction of Methanol in liquid and gas respectively.
3. Assuming the column is packed with (2 Ceramic Raschig rings).

Packing diameter calculation:

The gas flow rate G= 329.2 kmol/hr = 8439.41 kg/hr

The liquid flow rate L= 182.63 kmol/hr = 3287.373 kg/hr

Now to calculate the value of abscissa :

Where: L and G = mass flow rates (kg/hr)

3
G & L = density of the gas and liquid stream (kg/m )
3
G = 1.62 kg/m
3
L = 998.2 kg/m
-1
Fp = 213.2 m (table 5.9 Dutta)

=1
-3
= 0.797 x 10
2
P gC = 9.8 m/s

 50

Using the flooding line: = 0.20

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

Therefore, Dtower = Dpacking x 1.25 = 0.736 x 1.25 = 0.9199 m

Packing Height:

Equilibrium data table:

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

We have, Z = HOG x NOG

NOG= number of transfer units based on an overall gas-film coefficient.

HOG= height of a transfer unit based on an overall gas-film coefficient,

m yA,in= mole fraction of solute in entering gas

yA,out= mole fraction of solute in exiting gas

[ ]
[ ]

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

Z = HOG NOG = 0.91 X 10.95 = 9.96 m

Zcolumn = Zpacking x (1.25) = 9.96 x 1.25 = 12.45 m

Wall thickness (for 2 in ceramic Raschig ring packing) = 6 mm with Porosity = 0.74 ()
 52

9. COST ESTIMATION & ECONOMICS

Fixed Capital Cost (FCI) = Rs 3700 lakhs

Estimation of Capital Investment Cost:

I. Direct Costs: material and labor involved in actual installation of complete facility (70-85% of
fixed-capital investment)

A) Equipment + installation + instrumentation + piping + electrical + insulation + Painting

(50-60% of Fixed-capital investment)

1. Purchased equipment cost (PEC): (15-40% of Fixed-capital investment)

Consider purchased equipment cost = 25% of Fixed-capital investment

i.e., PEC = 0.25 x 3700 = Rs. 925 lakhs

2. Installation, including insulation and painting: (25-55% of purchased equipment

cost.) Consider the Installation cost = 40% of Purchased equipment cost

1= 0.4 x 925 = 370 lakhs

3. Instrumentation and controls, installed: (6-30% of Purchased equipment

cost.) Consider the installation cost = 15% of Purchased equipment cost

1= 0.15 x 925 = 138.75 lakhs

4. Piping installed: (10-80% of Purchased equipment cost)

Consider the piping cost = 40% Purchased equipment cost

= 0.4 x 925 = 370 lakhs

5. Electrical, installed: (10-40% of Purchased equipment cost)

Consider Electrical cost = 25% of Purchased equipment cost

 53

= 0.25 x 925 = 231 lakhs

Hence total cost of (1+2+3+4+5) = 2034.75 lakhs (54.99% of FCI)

B) Buildings, process and Auxiliary: (10-70% of Purchased equipment cost)

Consider Buildings, process and auxiliary cost = 40% of PEC

1= 0.4 x 925 = 370 lakhs

3) Service facilities and yard improvement: (40-100% of Purchased equipment cost)

Consider the cost of service facilities and yard improvement = 62% of PEC

1= 0.62 x 925 = 573.5 lakhs

4) Land: (1-2% of fixed capital investment or 4-8% of Purchased equipment

cost) Consider the cost of land = 5% of PEC

1= 0.05 x 925 = 46.25

Thus, Direct cost = (A + B + C + D) = Rs. 3024.5 lakhs

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)

A) Engineering and Supervision: (5-30% of direct costs)

Consider the cost of engineering and supervision = 15% of Direct costs

i.e., cost of engineering and supervision = 0.15 x 3024.5 = Rs. 453.675 lakhs
 54

B) Construction Expense and Contractors fee: (6-30% of direct costs)

Consider the construction expense and contractors fee = 14 % of Direct costs

i.e., construction expense and contractors fee = 0.14 x 3024.5 = 423.43 lakhs

C) Contingency: (5-15% of Fixed-capital investment)

Consider the contingency cost = 10% of Fixed-capital investment

i.e., Contingency cost = 0.1 x 3024.5 = 302.45 lakhs

Thus, Indirect Costs = (A+B+C) = 1179.555 lakhs

III. Fixed Capital Investment: (actual)

Fixed capital investment = Direct costs + Indirect costs

= 3024.5 + 1179.555 = 4204.055 lakhs

IV. Working Capital: (WC) (10-20% of Fixed-capital investment)

Consider the Working Capital = 15% of Total capital investment

i.e., Working capital = (0.15/0.85) x 4204.055 = 741.892 lakhs

V. Total Capital Investment: (TCI)

Total capital investment = Fixed capital investment + Working capital

1= 4204.055 + 741.892

2= 4945.947 lakhs
 55

Estimation of Total Product cost:

9. Manufacturing Cost = Direct production cost + Fixed charges + Plant overhead cost.

A.) Fixed Charges: (10-20% total product 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

i.e. Depreciation = (0.10 x 4204.055) + (0.03 x 370) = 431.505 lakhs

ii) Local Taxes: (1-4% of fixed capital investment) Consider

the local taxes = 4% of fixed capital investment i.e. Local

Taxes = 0.04 x 4204.055 = 168.1622 lakhs

3) Insurances: (0.4-1% of fixed capital investment)

Consider the Insurance = 0.6% of fixed capital investment

i.e. Insurance = 0.006 x 4204.055 = 25.224 lakhs

4) Rent: (8-12% fixed capital investment)

Consider rent = 10% of fixed capital investment =

0.1 x 4204.055 = 420.4055 lakhs

Thus, Fixed Charges = i + ii + iii + iv = 1045.29 lakhs

B.) Direct Production Cost:

Now we have Fixed charges = 10-20% of total product charges

Consider the Fixed charges = 15% of total product cost

Therefore, Total product cost = Fixed charges/0.15= 1045.29/0.15 = 6968.646 lakhs

 56

i) Raw Materials: (10-50% of total product cost)

Consider the cost of raw materials = 30% of total product

cost Raw material cost = 0.3 x 6968.646 = 2090.594 lakhs

ii) Operating Labor (OL): (10-20% of total product cost)

Consider the cost of operating labor = 15% of total product

cost Operating labor cost = 0.15 x 6968.646 = 1045.297 lakhs

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

4) Utilities: (10-20% of total product cost)

Consider the cost of Utilities = 15% of total product

cost Utilities cost = 0.15 x 6968.646 = 1045.297

v) Maintenance and repairs (M & R): (2-10% of fixed capital investment)

Consider the maintenance and repair cost = 5% of fixed capital investment

i.e. Maintenance and repair cost = 0.05 x 4204.055 = 210.2027 lakhs

6) Operating Supplies: (10-20% of M & R or 0.5-1% of FCI)

Consider the cost of Operating supplies = 15% of M & R

Operating supplies cost = 0.15 x 210.2027 = 31.53 lakhs

7) Laboratory Charges: (10-20% of OL)

Consider the Laboratory charges = 15% of OL

Laboratory charges = 0.15 x 1045.297 = 156.79455 lakhs

 5
7

viii) Patent and Royalties: (2-6% of total product cost)

Consider the cost of Patent and royalties = 5% of total product cost

Patent and Royalties = 0.05 x 6968.646 = 348.4323 lakhs

Thus, Direct Production Cost = (i+ii+iii+iv+v+vi+vii+viii) = 5053.583 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

Plant overhead cost = 0.6 x (OL + OS + M & R)

1= 0.6 x (1045.297 + 31.53 + 210.2027)

2= 772.217 lakhs

9. Manufacture cost = production cost + Fixed charges + Plant overhead costs.

1= 6871.09 lakhs

II. General Expenses = Administrative costs + distribution and selling costs + research and
development costs

A) Administrative costs: (40-60% of operating labor)

Consider the Administrative costs = 55% of operating labor

Administrative costs = 0.55 x 1045.297= 576.0133 lakhs

B). Distribution and Selling costs: (2-20% of total product cost); Includes costs for sales offices,
salesmen, shipping, and advertising.
 58

Consider the Distribution and selling costs = 15% of total product

cost = 0.15 x 6968.646

= 1045.2969 lakhs

C) Research and Development costs: (about 3% of total product cost)

Consider the Research and development costs = 3% of total product cost

Research and Development costs = 0.03 x 6968.646 = 209.0593 lakhs

Thus, General Expenses = A+B+C= 1830.369 lakhs

61. Total Production cost = Manufacture cost + General Expenses

1= 6871.09 + 1830.369 = 8701.4595 lakhs

IV. Gross Earnings/Income:

Wholesale Selling Price of formaldehyde per kg = Rs. 19 /kg

Total Income = Quantity of product manufactured x Selling price

= 19 x 60000000 = 11400 lakhs

Gross Income = Total Income - Total Production cost = 2698.5405 lakhs

Let the Tax rate be 50%

Taxes = 50% of Gross income

= 0.5 x 2698.5405 = 1349.270 lakhs

Net profit = 1349.270 lakhs

Rate of Return:

Rate of return = (Net profit/Total Capital Investment) x 100

= (1349.27/4945.947) x 100 = 27.280 %

 59

Payback period:

Payback period = (Fixed capital investment) / (net profit + depreciation)

1= (4204.055) / (1349.270 + 431.505)

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

10. PLANT LOCATION & LAYOUT

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

Transport of raw materials and products is an important factor to be considered. Transport of

products can be in any of the four modes of transport. The transport of materials and products to
and from the plant will be an overriding consideration in site selection. If practicable, a site
should be selected that is close to at least two major forms of transport: road, rail, waterway or a
seaport.
Rail transport will be cheaper for long distance transport of bulk chemicals. Road transport is
being increasingly used and is suitable for local distribution.

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.

5. Environmental impact and effluent disposal

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

6. Local community consideration

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.

9. Political and strategic considerations

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

Items that should be located downwind of the plant

1 Blow down tanks
2 Settling tanks
3 Burning flares

The various units that should be laid out include

1. Main processing unit

2. Storage for raw materials and products
3. Laboratories for process control
4. Transportation
5. Fire stations and other emergency services
6. Utilities: steam boilers, compressed air, power generation, refrigeration
7. Effluent disposal plant
8. Offices for general administration
9. Canteens and other amenity buildings, such as medical centres
10. Car parks
 64

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

1.) Grouped layout

Grouped layout places all similar pieces of equipment adjacent. This provides for ease of
operation and switching from one unit to another. This is suitable for all plants.

2.) Flowline layout

Flowline layout uses the line system, which locates all the equipment in the order in which it
occurs on the flowsheet. This minimizes the length of transfer lines and therefore reduces the
energy needed to transport materials. This is used mainly for small volume products.

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.

b. Steam for process heating

The steam for process heating is usually generated in water tube boilers using the most
economical fuel available. The process temperature can be obtained with low pressure steam. A
competitively priced fuel must be available on site for steam generation.
 66

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.

d. Water for general use

Water is needed in large quantities for general purpose and the plant must be located near the
sources of water of suitable quality, process water may be drawn from river from wells or
purchased from a local authority.

7. Effluent disposal plant

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.

9. Canteen & Medical facilities

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.

10. Car parking

Sufficient land space must be provided near the exit for car parking.
 6
7

11. SAFETY & ENVIRONMENT CONSIDERATIONS

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:

1) Gloves of rubber or PVC should be worn.

2) Should there be any danger of spatters or leaks, protective glasses should be worn.
3) Methanol must be used or stored exclusively in rooms where there is sufficient ventilation.
4) If methanol is spilled, the spot in question must immediately be cleaned with a large quantity
of cold water. Clothes which have been splashed by methanol must be removed immediately. If
the eyes are spattered with methanol, they must be washed for at least 30 minutes. It is also
recommended to call for a doctor. In critical cases, first aid may be rendered. Take the patient out
into the open air; avoid further contact with methanol. Keep him-warm and calm. Give him
oxygen. In case breathing fails, give him artificial respiration. If methanol has entered the mouth,
give the patient an emetic consisting of salt and water.

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

Storage and transportation:

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.

With a decrease in temperature and/or increase in concentration, aqueous formaldehyde solutions

tend to precipitate paraformaldehyde. On other hand, as the temperature increases, so does the
tendency to form formic acid. Trace metallic impurities can boost the rate of formation of formic
acid. Therefore, an appropriate storage temperature must be maintained. Stabilizers can also be
added to prevent polymerization. Methanol is generally used as a stabilizer. Other compounds
used as a stabilizer for formaldehyde are ethanol, propanol, urea, melamine, hydrazine hydrate
and bismelamines.

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

1. Donald Q.Kern, PROCESS HEAT TRANSFER, McGraw Hill.

2. Harry Silla, Chemical Process Engineering: Design and Economics, Marcel Dekker,
Inc.
3. Max S Peters, Klaus D. Timmerhaus, Ronald Emmett West Plant Design and
th
Economics for Chemical Engineers, 5 Edition, McGraw-Hill Science.
4. Robert H. Perry, Don W. Green, James O. Maloney Perry's Chemical Engineers'
th
Handbook 7 Edition.
rd
5. Robert E. Treybal, "Mass Transfer Operation", 3 Edition, McGraw Hill
INTERNATIONAL EDITIONS.
6. Binay K. Dutta, Principles of Mass Transfer and Separation Processes, Eastern
Economy Edition.
rd
7. Phillip C. Wankat, Separation Process Engineering, 3 Edition
8. Formaldehyde: A Techno-Commercial Profile, chemical weekly, September 27, 2005.
9. "Formaldehyde Production from Methanol." McMaster University, 19 Dec. 2012. Web.
19 Sept. 2012.
10. Methods in Pathology, Histology without formalin, Ren J. Buesa, 12 (2008) 387396.
11. Allied Resins and Chemicals Ltd.