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Manufacturing Of Meta-Phenoxy Benzaldehyde
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Chapter -1
HISTORICAL PROFILE
1.1 INTRODUCTION
1.1.1 Meta-Phenoxy Benzaldehyde
Meta-Phenoxy Benzaldehyde (MPBAD) has a formula – (C13H10O2) consists of two groups: Phenoxy group
and Benzaldehyde group. Phenoxy- is a prefix to indicate the presence of the group '-OC6H5', composed of
phenyl and an atom of oxygen. Phenoxy compounds are precursors of antibiotics especially penicillin’s, plant
growth regulators, and herbicides. Benzaldehyde- ‘C7H6O’ (also called Benzenecarbonal) is the simplest
representative of the aromatic aldehydes. It is a colorless liquid aldehyde with a characteristic almond odor. It
boils at 180°C, is soluble in ethanol, but is insoluble in water. Meta-Phenoxy Benzaldehyde posses the
properties of both the groups and is used as an important agrochemical intermediate synthetic pyrethroids like
Decamethrin, Cypermethrin and Fenvalerate used as pesticides. [1]
1.1.2 Needs of Meta-Phenoxy Benzaldehyde
It is essential to establish solutions which provide less harm to the environment. Meta-Phenoxy
Benzaldehyde is used as intermediates for manufacturing pyrethroids, dyes, pharmaceuticals, fungicides, and
flavoring agents. Pyrethroids, being more potent to pest and less harmful to environment, are having
increasing demand. A forward looking approach is the use of such synthetic chemicals which do not harm the
harm most mammals or birds. [2]
1.1.3 The Various Products That Can Be Produced By Using Meta-Phenoxy Benzaldehyde As An
Intermediate:
Synthetic Pyrethorids – (Decamethrin, Cypermethrin).
Pharmaceuticals – (Permethrin ’anti-itching drug’).
Antibacterial, Antifungal and Insecticidal products – (Cyclic Sydnonimine Hydrochloride) [3].
Insecticides – (Fenvalerate).
Permethrin – (first-line treatment for scabies).
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1.2 NATURAL OCCURRENCE OF MPBAD:
Meta-Phenoxy Benzaldehyde is a intermediate used for manufacturing mainly ‘AGROCHEMICALS’ like Synthetic
Pyrethroids and Pharmaceuticals Industries. Meta-Phenoxy Benzaldehyde does not occurs naturally however its other
derivative (P-Phenoxy Benzaldehyde presence in bamboo shoots was investigated) [4]. Traditionally Meta-Phenoxy
Benzaldehyde is manufactured by benzaldehyde via bromination, and phenol. However, synthesis of this important
agrochemical intermediate from meta-cresol via meta-phenoxy toluene oxidation has now become commercially more
attractive.
1.3 TRADITIONAL APPLICATIONS OF MPBAD:
The traditional applications of meta-phenoxy benzaldehyde are as follows:
Pharmacy: Meta-phenoxy benzaldehyde used by the pharmaceutical industry must meet various stringent
requirements in terms of purity and neutrality. It is used for the production of ‘anti-itching’ medicines for the
treatment of ‘scabies’.
Agrochemical: Meta-phenoxy benzaldehyde is a important agrochemical intermediate which are used as
insects repellents agents like Decamethrin, Cypermethrin & Fevalerate used as pesticides [1].
1.4 MANUFACTURERS:
The current manufacturers of m-phenoxy benzaldehyde are [5]:
Gujarat Insecticides Limited: It has its plant located in the state of Maharashtra (48, Hill Road, Bandra
(West), Mumbai – 400050, INDIA).
United Phosphorus Limited: It has its plant located in the state of Gujarat (United Phosphorus Limited
117, G.I.D.C., Ankleshwar City - Bharuch District, 393 002, Gujarat, INDIA).
Hemani Intermediates Private Limited: It has its plant setup in Gujarat and Maharashtra (780/1,2,40 Shed
Area, GIDC VAPI, District – Bulsar - 396195, Gujarat, INDIA).
Shakti Bio Science Ltd: It has its plants located in the state of Maharashtra (A - 101, Surya Kiran, Opp.
Jain Temple, Near Chamunda circle, Borivali (West), Mumbai-400092, Maharashtra, INDIA).
Apin Chemicals Limited: It has its plant located in UNITED KINGDOM (43D Milton Park, Milton, and
Abingdon OX14 4RU, UNITED KINGDOM).
China langchem Incorporation: Has its plant located in CHINA (88, Cailun road, Zhangjiang high tech
park, Shanghai – 201203, CHINA).
Toronto Research Chemicals: Has its plant located in CANADA (2, Brisbane road, Toronto, Ontario
CANADA M3J 2J8).
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1.5 HISTORY OF THE PRODUCTS:
As MPBAD is used as an intermediate for the production of the synthetic pyrethroids which are used as insecticides
for example: Decamethrin, Cypermethrin and Fenvalerate. So the history of these insecticides basically relates the
invention of MPBAD. Synthetic pyrethroids was introduced lately in 1900’s by a team of Rothamsted
Research scientists following the elucidation of the structures of pyrethrin I and II by Hermann
Staudinger and Leopold Ruzicka in the 1920’s. The 1st generation synthetic pyrethroids, developed in the 1960s,
include bioallethrin, tetramethrin, resmethrin and bioresmethrin. By 1974, the Rothamsted team had discovered a 2nd
generation of more persistent compounds (EAST AFRICA): permethin, Cypermethrin and deltamethrin. They are
substantially more resistant to degradation by light and air, thus making them suitable for use in agriculture, but they
have significantly higher mammalian toxicities and hence by the history of the synthetic pyrethroids we can justify the
history of MPBAD [6].
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Chapter-2
APPLICATIONS AND GRADES
2.1 CURRENT APPLICATIONS OF THE PRODUCT:
The current applications of meta-phenoxy benzaldehyde are as follows:
2.1.1 Insecticides:
Cypermethrin: Cypermethrin is a synthetic pyrethroid insecticide. It is toxic and adequately stabile
in air and light. It has become one of the most important insecticides in a wide-scale use [7].
Fenvalerate: Is an insecticide. It is a mixture of four optical isomers which have different
insecticidal activities. The 2-S alpha (or SS) configuration, known as esfenvalerate, is the most
insecticidal active isomer. Fenvalerate consists of about 23% of this isomer. Fenvalerate is an
insecticide of moderate mammalian toxicity. Fevalerate has applications against a wide range of
pests. It is most commonly used to control insects in food, feed, and cotton products [8].
Etofenprox: is a pyrethroid derivative which is used as an insecticide. Also found as an ingredient
in flea medication for cats [9].
Phenothrin: Also called sumithrin, is a synthetic pyrethroid that kills adult fleas and ticks. It has
also been used to kill head lice in humans. D-Phenothrin is used as a component of aerosol
insecticides for domestic use. Phenothrin is often used with methoprene, an insect growth regulator
that interrupts the insect's biological life cycle by killing the eggs [10].
Deltamethrin: Is a pyrethroid ester insecticide. This pesticide is highly toxic to aquatic life,
particularly fish, and therefore must be used with extreme caution around water [11].
2.1.2 Pharmacy:
Permethrin: Is a first-line treatment for scabies (Itching problem); a 5% (w/w) cream is marketed
by Johnson & Johnson under the name ‘Lyclear’. In Nordic countries and North America, it is
marketed under trade name ‘Nix’, often available over the counter [12].
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2.2 PRODUCT SPECIFICATIONS:
Table 2.1 Product Specification of Meta-Phenoxy Benzaldehyde [13]
1. Origin East Africa
2. Color Light Yellow
3. Storage Liquid Form
4. Meta-Phenoxy Benzaldehyde content
(by mass GLC)
99% Minimum
5. Acidity as Meta Phenoxy benzoic acid
(by mass)
0.5% Maximum
6. Moisture content 0.2% Maximum
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Chapter-3
ECONOMIC SCENARIO
3.1 WORLD SCENARIO (MPBAD):
Meta-phenoxy Benzaldehyde is used as an intermediate for the production of some important agro based chemicals
mainly synthetic pyrethroids like: Decamethrin, Cypermethrin and Fenvalerate used as insecticides. Mainly the meta-
phenoxy benzaldehyde which is produced I the plants are generally not supplied/exported to other industries they are in
the process converted to the synthetic pyrethroids. So meta-phenoxy benzaldehyde is a captive product and its
economic scenario could be explained by the help of the insecticides scenarios of the synthetic pyrethroids. Here we are
considering Insecticides to explain the economic scenario of meta-phenoxy benzaldehyde.
3.1.1 Uses Of Various Pesticides All Over the world:
Fig 3.1 Uses Of Various Pesticides All Over the world
The whole world is second largest consumer of the insecticides (mainly the synthetic pyrethroids) which are
having there intermediate as MPBAD so if the demand of Insecticides would increase them the demand of
MPBAD would also increase. Here as we can see in the (Fig. 3.1) the consumption percentage of various pesticides
are [14]:
Herbicides: 60%
Insecticides: 27%
Fungicides, Disinfectants, Rodenticides, Molluscicides: 13%
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3.1.2 Forecast On Output/Production Of Insecticides In World, 2011 -2015:
Fig 3.2 Forecast On Output/Production Of Insecticides In World [15]
As by the above bar graph (Fig 3.2) we can see that globally the production of insecticides is increasing
every year due to the increase in the demands of pesticides now days. Thus, we can clearly suggest from the
data available that the production of MPBAD is also increasing with every progressing year.
3.1.3 Market Share Of World In The Production Of Insecticides:
Fig 3.3 Market Share Of World In The Production Of Insecticides [16]
From the above (Fig 3.3) we can clearly see that the production of insecticides is more in the western countries than in the eastern.
3.1.4 Manufacturing Capacities :
Japan is a major producer of MPBAD in the world. They manufacture approx. 4000 TPA of meta-phenoxy
benzaldehyde for conversion to pyrethroids [17].
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3.2 INDIA’S SCENARIO (MPBAD):
3.2.1 Forecast On Output/Production Of Insecticides In India, 2011 -2015:
Fig 3.4 Forecast On Output/Production Of Insecticides In India
As from the above bar graph its clearly visible that the production of the Insecticides in India is increasing with
every coming year and so as the production of meta-Phenoxy benzaldehyde [15].
3.2.2 Import and Export data of Insecticides over the years:
Years Quantity Unit Value Assessable (INR)
2009 14600 TON 26302293.61
2010 25700 TON 29830265.23
2011 36200 TON 32569826.33
2012 47400 TON 39878263.21
Table 3.1 Import Data of India [18]
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Years Quantity Unit Value Assessable
(INR)2009 23400 TON 17702748.20
2010 34690 TON 25268349.82
2011 45190 TON 31658498.32
2012 56410 TON 38826721.35
Table 3.2 Export Data of India [19]
3.2.3 Manufacturing Capacities [17]:
Hence, by the above Import and Export data we can see that India’s demand and supply gap is about 8800 TPA.
Therefore, we have selected capacity of our plant as 9000 TPA.
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Chapter – 4
PROPERTIES, HANDLING AND STORAGE
4.1 PROPERTIES:
4.1.1 Meta-Phenoxy Benzaldehyde (Mpbad)[20]:
Meta-Phenoxy Benzaldehyde is a pesticide intermediate to manufacture synthetic pyrethroid
insecticides.
It is also used as an intermediate for the manufacture of pharmaceutical products.
It is also used as an intermediate for the manufacture of Antibacterial, Antifungal and Insecticidal
products.
Structure:
Fig 4.1 Structure of MPBAD [21]
4.1.1.1 Physical Properties [20]:
Molecular Formula C13H10O2
Molar Mass 198.22 g /mol
Appearance Viscous, yellow-amber liquid
Density 1.147 g/cm3 (20° C)
Melting point 13° C
Boiling Point 140° C (0.1 mm Hg)
Solubility in water Insoluble
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4.1.1.2 Chemical Properties [20]:
MPBAD is readily soluble in most of the organic solvents such as methanol and ethanol.
Reactive in alkaline medium.
MPBAD IS stable under normal conditions (temperatures and pressures).
It should be protected from air as it is susceptible to oxidation.
Heat Of vaporization is 64.2 kJ/mole.
It is insoluble in water.
4.2 BIO ENVIRONMENTAL CHARACTERISTICS [22]:
4.2.1 Metabolic Fate In Human Beings And Other Organisms:
Synthetic pyrethorids can be considered to result from the esterification of an appropriate alcohol (MPBAD)
with an appropriate acid. Metabolism of pyrethorids proceeds by the hydrolysis of the ester bond to give the
constituent acid and alcohol components. Once these acid and alcohol components are formed their
metabolism and degradation is independent of the pyrethorids from which they are derived. Due to increased
global use, acute and chronic exposures to pyrethorids insecticides in humans are of clinical concern.
Pyrethorids have a primary mode of action that involves interference with the sodium and calcium channels
in excitable cells, which may include cardiac myocytes. Here, it was investigated that the possible cardiac
toxicity of Permethrin metabolites (METP), 3-phenoxy-benzyl alcohol (3PBA), 3-phenoxy-benzaldehyde
(3PBALD), and 3-phenoxybenzoic acid (3PBACID). Plasma membrane fluidity, polarity, lipid, and protein
oxidation were studied in isolated rat heart cells. Laurdan was chosen as probe to detect the lateral mobility
and polarity of its environment and thus water penetration into the hydrophobic part of the bilayer, while 1,6-
diphenyl-1,3,5-hexatriene permits to measure changes in fluidity in the inner part of the bilayer. Results show
that METP can change membrane fluidity at different depths of the bilayer according to their partition
coefficient. Consequently, 3PBA, at all concentration used, decreases membrane fluidity and polarity in the
hydrophilic-hydrophobic region of the bilayer, and similar effect was observed with 20 μM 3PBALD or 10 or
20 μM 3 PBACID. Membrane dynamics in the hydrophobic core resulted decreased by 3PBALD, while it
was increased by 20 μM 3PBACID. All METP increase protein and lipid oxidation, and the per oxidative
lipid damage decreases with the type of METP produced during the transformation pathway from parent
compound to 3PBACID. Consequently, 3PBA induced the highest lipid per oxidation, while 3PBACID was
the stronger inducer of protein damage.
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4.2.2 Environment fate:
Environmental fate for the MPBAD can be explained by the help of the example of Cypermethrin which is
a product formed by using MPBAD as an intermediate is as follows:
Air: Cypermethrin has a very low vapor pressure and is not readily volatilized into the atmosphere. A
low Henry’s Law Constant (H), 2.5x10-7 atm-m3/mol at 200oC, indicates that Cypermethrin has almost no
tendency to volatilize from an aqueous solution.
Soil: Cypermethrin occurs as a mixture of both the cis and trans isomers. The cis/trans ratio in technical
grade Cypermethrin is 1:1. The cis isomers are more active than trans by a factor of two. No significant
difference was observed between the photo degradation rates of the two isomers in soil, although the
trans-isomer was hydrolyzed 1.2-1.7 times faster. Hydrolysis and photolysis play major roles in the
degradation of Cypermethrin in soil.
Water: The water solubility of Cypermethrin is very low, 4 ppb at 200oC. Cypermethrin is extremely
hydrophobic and will quickly move from an aqueous solution to suspended particulates. Thus, relatively
small amounts of suspended matter in natural bodies of water may remove a significant amount of
Cypermethrin from the aqueous phase. Soils and sediment are the main environmental reservoirs for
Cypermethrin. Cypermethrin hydrolyzes slowly in water at pH 7 and below, with hydrolysis being more
rapid at pH 9.
4.2.3 Health Impacts:
Various health impacts caused by Meta –phenoxy benzaldehyde are:
Potential Health Effects Eye: Causes eye irritation. May cause chemical conjunctivitis.
Skin: Causes skin irritation.
Ingestion: May cause gastrointestinal irritation with nausea, vomiting and diarrhea..
Inhalation: Causes respiratory tract irritation.
Chronic: Effects may be delayed
4.3 HANDLING & STORAGE [23]:
Handling: Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep
container tightly closed. Use with adequate ventilation. Wash clothing before reuse. Avoid breathing dust.
Storage: Store in a cool, dry place. Store in a tightly closed container.
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4.4 SAFETY MEASURES [23]:
Engineering Controls: Facilities storing or utilizing this material should be equipped with an eyewash
facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety
goggles as described by OSHA's eye and face protection regulations.
Skin: Wear appropriate protective gloves to prevent skin exposure.
Clothing: Wear appropriate protective clothing to prevent skin exposure.
Respirators: NIOSH/OSHA or European Standard EN 149 approved respirator if exposure limits are
exceeded or if irritation or other symptoms are experienced.
4.4.1 First aid measures :
Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the
upper and lower eyelids. Get medical aid.
Skin: Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing
contaminated clothing and shoes. Wash clothing before reuse.
Ingestion: Never give anything by mouth to an unconscious person. Get medical aid. Do NOT
induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. Wash
mouth out with water.
Inhalation: Remove from exposure and move to fresh air immediately. If not breathing, give
artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Do NOT use mouth-to-
mouth resuscitation.
4.4.2 Fire fighting measures:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or
equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by
thermal decomposition or combustion. Use water spray, dry chemical, carbon dioxide, or chemical foam.
4.4.3 Accidental release measures:
Use proper personal protective equipments. During Spills/Leaks Vacuum or sweep up material and place into a
suitable disposal container. Clean up spills immediately, observing precautions in the ‘Protective Equipment
Section’. Avoid generating dusty conditions and provide ventilation.
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Chapter – 5
MANUFACTURING PROCESSES
5.1 LOCATION OF THE PLANT:
We have selected the location of our product ‘Meta-Phenoxy Benzaldehyde’ in ANKLESHWAR, GUJARAT.
The reasons for choosing it are:
GUJARAT and MAHARASHTRA are the 2 leading ‘Meta-Phenoxy Benzaldehyde’ producing states of
INDIA.
We have preferred Gujarat over Maharashtra because [25]:
Gujarat State has the longest sea coast of 1600 km in India. It has many ports like; Kandla
Port (is one of the largest ports serving Western India), Port of Magdalla, Port Pipavav, Port
of Porbandar and the privately owned Mundra Port which helps in transportation of raw
materials from abroad and export of our products to other countries i.e. helps in reducing
transportation cost.
Compared to Maharashtra, Gujarat’s level of industrial facilities like electricity and water supply
are better.
Raw materials are easily available.
It is situated near bharuch which has the dumping facilities for the solid waste.
Gujarat government provides water treatment facilities (Although water used in the
plant is treated before release but it is again treated by the facilities provided by the
government).
Have a per-capita GDP significantly above India’s average.
In Gujarat we prefer Ankleshwar because:
Ankleshwar has over 1000 chemical plants, producing products such as pesticides, pharmaceuticals,
chemicals, and paints.
Have a population of about 1, 50,000. Therefore, Labor is easily available.
Moderate Climatic conditions.
Infrastructure.
Location of plant in Gujarat (shown in Fig. 5.1)
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Fig 5.1 Location of Project in Gujarat [26]
5.2 MANUFACTURING PROCESS [27]:
The general process for the preparation of the meta-phenoxy benzaldehyde comprises of following steps:
1) Preparing a mixture of Meta-Phenoxy benzyl halide and Meta-Phenoxy benzal halide by halogenating Meta-
Phenoxy toluene gas with halogen at an elevated temperature with a free radical initiator.
2) Reacting the mixture of halides prepared in (Step 1.) with Ammonia and Formaldehyde, or
Hexamethylenetetramine.
3) Hydrolyzing the reaction product from (Step 2.) under acid conditions to form the meta-phenoxy benzaldehyde.
5.3 META-PHENOXY BENZALDEHYDE MANUFACTURING PROCESS:
The basic block flow diagram for the production of meta-phenoxy benzaldehyde is as follows:
Mixture of halides
Meta-Phenoxy Toluene Meta-Phenoxy Benzaldehyde
Fig 5.2 Block flow diagram for the manufacturing of MPBAD
Halogenation Reaction with NH3 & HCHO/HMTA
Hydrolyzing Under Acidic Condition
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5.4 VARIOUS PROCESS FOR THE MANUFACTURING OF META-PHENOXY BENZALDEHYDE ARE:
5.4.1 Process 1 (Bromination process)[27]:
3-Phenoxytoluene was treated with a stream of bromine under a nitrogen atmosphere in a vessel
containing a source of ultraviolet light and designed so that bromine is introduced close to the U.V.-
source and the Reactants vigorously circulated. The bromine was thus present in a excess amount over
the Phenoxy -toluene. When addition was complete (about 3 hours) the reaction mixture was allowed to
cool overnight whilst being flushed with a stream of nitrogen. This yield of bromination product having
the following composition:
phenoxy toluene (unconverted):2.1%
3- phenoxy benzyl bromide:61.5%
3- phenoxy benzal bromide:36.4%
The bromination mixture resulting from above step was added to glacial acetic acid and
hexamethylenetetramine, followed by water. After maintaining under reflux (105° C) for 4 hours,
concentrated hydrochloric acid were added followed 5 minutes later by water, and the mixture refluxed
for a further 15 minutes. After cooling to room temperature by immersion in ice water, the reaction
mixture was extracted with methylene dichloride.
The combined extracts were washed neutral (pH 7-8) with saturated sodium bicarbonate, and then
washed once with ice-cold hydrochloric acid and once with water. After drying over anhydrous sodium
sulphate the methylene dichloride was distilled off and the residual product degassed to constant weight
under high vacuum (0.1 mm Hg) to yield of 3-phenoxy benzaldehyde.
N.M.R. analysis of this product established its purity as 95%, and G.L.C. analysis showed that all the
benzyl bromide and benzal bromide had reacted. The yield of 3-phenoxy benzaldehyde was 93% based
on the starting 3-phenoxytoluene.
5.4.2 Process 2 (Chlorination process by using carbon tetrachloride)[27]:
A mixture of 3-phenoxybenzyl chloride and 3-phenoxy-benzal chloride obtained from chlorination of 3-
phenoxy toluene by chloroform in the presence of free radical initiator catalyst, Azobisisobutyronitrile
‘AIBN’ under refluxing conditions (containing 60% mono chloride and 40% dichloride) was added to a
solution of hexamethylenetetramine dissolved in acetic acid .Water was added and the mixture heated
under reflux for 4 hours. Concentrated hydrochloric acid was then added and the mixture refluxed for a
further 15 minutes.
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After cooling to room temperature the reaction mixture was extracted with methylene chloride. The
combined extracts were washed neutral with aqueous sodium bicarbonate solution, and then evaporated
to give 3-phenoxybenzaldehyde (yield 97%).
5.4.3 Process 3(Chlorination process by using chloroform) [27]:
A solution of formalin was cooled to 10° C and then treated with aqueous ammonia solution over 15
minutes. A mixture of 3-phenoxybenzyl chloride and 3-phenoxybenzal chloride containing 70% mono
chloride and 30% dichloride mixture, obtained from chlorination of 3-phenoxy toluene by chloroform in
the presence of free radical initiator catalyst, Azobisisbutyronitrile ‘AIBN’ under refluxing conditions
was added and the mixture stirred under a nitrogen blanket for 3 hours. The mixture was then acidified
with acetic acid, stirred for a further 3 hours in the cold, and then refluxed for 4 hours.
After cooling, the reaction mixture was extracted with toluene and the extract washed neutral with
sodium bicarbonate solution. The toluene solution of crude 3-phenoxybenzaldehyde was diluted with an
equal quantity of ethanol and then stirred with a saturated aqueous solution of sodium bi-sulphite.
The resulting bi-sulphite adduct was filtered off and washed with toluene. After vacuum drying, this
gave purified 3-phenoxybenzaldehyde bi-sulphite compound which on treatment with dilute mineral acid
yielded the pure 3-phenoxybenzaldehyde. Yield based on chloride mixture was 95%.
5.5 COMPARISION OF VARIOUS PROCESS FOR THE MANUFACTURING OF META- PHENOXY
BENZALDEHYDE ARE:
As all the above processes are from Halogenation of 3-phenoxy toluene, the comparisons between the above processes
can be only being done on the basis of:
Raw materials used.
Operating Conditions (Halogenation of 3-Phenoxy Toluene).
Free Radical Initiator.
Yield (Shown in table 5.1).
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Table 5.1 Comparison of selected processes for the manufacturing of meta-phenoxy benzaldehyde.
Thus by comparing all the above process of manufacturing of meta-phenoxy benzaldehyde on the basis of:
Raw Materials used.
Operating Conditions (Halogenation of 3-Phenoxy Toluene).
Free Radical Initiator.
Yield (Shown in table 5.1).
We have selected ‘PROCESS 2’ because in all the process stated above have almost the same raw materials so the
cost for the raw materials would be same, but ‘PROCESS 2’ is operating at the temperature just above 50oC while
the other process are operating between the range of (195oC to 235oC). So, risk factor is much lesser in ‘PROCESS 2’
as compared to the (PROCESS 1). ‘PROCESS 3’ also operates on a temperature just above 50oC but the yield of
‘PROCESS 2’ is 97% which is much higher than other process including ‘PROCESS 3’.
S.NO PROCESSES RAW MATERIALS OPERATING
CONDITIONS
FOR
HALEOGINAT
ION
FREE
RADICA
L
INITIAT
OR
%
YIELD
1. Process 1. 3-Phenoxy Toluene, Bromine, Glacial Acetic
Acid, Methylene Di-Chloride,
Hexamethylenetetramine (HMTA),
Concentrated Hydrochloric Acid, Anhydrous
Sodium Sulphate.
195oC To 235oC UV
LIGHT
93
2. Process 2. 3-Phenoxy Toluene, Acetic Acid,
Hexamethylenetetramine (HMTA),
Concentrated Hydrochloric Acid, Aqua’s
Sodium Bicarbonate Solution, Anhydrous
Sodium Sulphate, AIBN/ Benzoyl Peroxide.
Above 50oC AIBN 97
3. Process 3. Formalin Solution, Ammonia Solution,
Nitrogen, Acetic Acid, Sodium Bi-Sulphide,
Toluene, Aqua’s Sodium Bicarbonate
Solution, AIBN/ Benzoyl Peroxide.
Above 50oC AIBN 95
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Manufacturing Of Meta
SELECTED PROCESS
6.1 FLOWSHEET:
The simplified flow diagram of the manufacturing of meta
Fig 6.1 Simplified Flow sheet for the production of MPBAD
Manufacturing Of Meta-Phenoxy Benzaldehyde
Chapter-6
SELECTED PROCESS
The simplified flow diagram of the manufacturing of meta-phenoxy benzaldehyde is given below:
Simplified Flow sheet for the production of MPBAD
19
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Manufacturing Of Meta-Phenoxy Benzaldehyde
20
6.2 PROCESS DESCRIPTION:
6.2.1 Raw Materials [27]:
3- Phenoxy toluene: The most widely used raw material for the manufacturing of meta-phenoxy
benzaldehyde.3- Phenoxy toluene undergoes halogenation with chloroform in presence of AIBN
(Azobisisobutyronitrile) to give rise 3- phenoxy benzyl chloride (mono chloride) and 3- phenoxy benzal
chloride (dichloride) which are further converted to meta-phenoxy benzaldehyde.
Hexamethylenetetramine in acetic acid: The reaction mass containing 3- phenoxy benzyl chloride and
3- phenoxy benzal chloride react with hexamethylenetetramine in acetic acid to give rise MPBAD.
Water: Water used to make the solution of Hexamethylenetetramine in acetic acid aqua’s in nature
because reaction of Hexamethylenetetramine with acid is highly exothermic reaction. So as to remove
the heat of reaction water is added to the mixture and it is also used for the hydrolysis reaction.
Concentrated Hydrochloric Acid: Concentrated Hydrochloric Acid is added towards the end of the
hydrolysis reaction to regenerate acetic acid from acetate formed in hydrolysis reaction.
Methylene Chloride: Methylene chloride is used to extract the meta-phenoxy benzaldehyde from the
reaction mass formed after the hydrolysis.
Aqueous Sodium Bicarbonate: Are used for the final neutralization and distillation of the meta-
phenoxy benzaldehyde.
6.2.2 PROCESS [28]:
Chlorination of m-phenoxy toluene. This step involves side chain chlorination of m-phenoxy toluene in a
medium of CCl4 in the presence of a free radical initiator catalyst, Azobisisobutyronitrile (AIBN), under
refluxing conditions. Meta-phenoxy benzene chloride and m-phenoxy benzal chloride are formed as major
products.
Reaction:
C6H5.O.C6H4.CH3 + Cl2 C6H5.O.C6H4.CH2 CL + HCL
C6H5.O.C6H4.CH2Cl + Cl2 C6H5.O.C6H4.CHCl2 + HCL
Hydrolysis of m-phenoxy benzyl and benzal chlorides. Conversion of the mixed chlorides into m- phenoxy
benzaldehyde is done by modified ‘Sommelet Reaction’ which involves reaction between m-phenoxy benzal
chloride and hexamine in the presence of aqueous acetic acid under boiling conditions leading to the formation
of m-phenoxy benzaldehyde and HMTA degradation products. The HMTA, acetic acid and water are mixed,
and then the benzyl/benzal halide is added thereto. In the preferred practice the HMTA is supplied as an
aqueous solution, which is directly mixed with the acetic acid.
AIBN
AIBN
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Manufacturing Of Meta-Phenoxy Benzaldehyde
21
Since the acid reacts exothermically with the HMTA, it is necessary to remove sufficient of the heat of
reaction to attain the necessary low mixing temperature before the halide mixture is added. The benzyl-benzal
halide mixture then is added slowly to the thoroughly stirred mixture and the stirred mixture is slowly (usually
over a period of 30-60 minutes, preferably about 40 minutes) heated to a temperature of from about 105° C. to
about 120° C. and held within that temperature range for a period of about 3 hours to about 4.5 hours.
Concentrated hydrochloric acid is added to the mixture for recovering the acetic acid and t he reaction mixture
is refluxed for about (15 minutes), this provides a temperature of from about 110° C. to about 120oC,
depending upon the particular proportions of the Ingredients used, and on the autonomic pressure in the
reaction system. The process is conveniently conducted at essentially atmospheric pressure or slightly above-
i.e., at the autonomic pressure of the reactor system.
Reaction:
3-C6H5.O.C6H4.CH2CL + (CH2)6.N4 3-C6H5.O.C6H4.CH2[(CH2)6.N4]+ CL-
3-C6H5.O.C6H4.CH2[(CH2)6.N4]+ CL- 3-C6H5.O.C6H4.CHO + CH3NH3
+ CL-
+ 3NH3 + 5HCHO
After cooling to room temperature the reaction mixture is extracted with methylene chloride. The combined
extracts were washed neutral with aqueous sodium bicarbonate solution, dried over anhydrous sodium
sulphate, and then evaporated to give 3-phenoxy benzaldehyde (yield 97%).
6.3 PLANT CAPACITY:
The plant capacity which we have decided is 9000 tons per annum i.e. 30 tons per day or 1250 kg/hr and this is the
overall plant capacity of production of meta-phenoxy benzaldehyde.
Aq. Acetic Acid
6H2O
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Manufacturing Of Meta
7.1 MATERIAL BALANCE FOR THE PRODUCTION OF
BASIS: 30 tons per day of meta-phenoxy benzaldehyde
7.1.1 Distillation Column:
Assumptions:
99% pure mpbad is formed.
Percentage of mpbad in feed=
Fig 7.1 Material balance
Streams:
Feed (15): Mixture of meta
Distillate (17): Volume %
Bottom (16): Volume %
Calculations:
Overall material balance: F=D+R
F= 140.638 kmol/hr.
Therefore, 140.638 =D+R
Component balance over distillation column for
F*f=D*d + R*r
Manufacturing Of Meta-Phenoxy Benzaldehyde
Chapter-7
MATERIAL BALANCE
MATERIAL BALANCE FOR THE PRODUCTION OF MPBAD:
phenoxy benzaldehyde from the evaporator column (99% pure
99% pure mpbad is formed.
in feed=4.52%
Material balance across Distillation column
meta-phenoxy benzaldehyde, solvent (methylene chloride)
Volume % meta-phenoxy benzaldehyde (Xd).
Volume % meta-phenoxy benzaldehyde (Xr).
Overall material balance: F=D+R
F= 140.638 kmol/hr. F=Feed
D=Distillate
R=Residue/Bottom
Component balance over distillation column for mpbad:
22
(99% pure).
).
/Bottom
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Manufacturing Of Meta
Meta-phenoxy benzaldehyde in bottom product is: 1250/198.22 = 6.306 kmol/hr.
Feed of the distillation column:
Meta-phenoxy benzaldehyde in distillate product is:
Value of methylene chloride
Methylene chloride in bottom product: (1
So, R=6.306 + 1.342 = 7.648
Then, D= 140.638-7.647 =
140.638*0.0452 = 7.647*0.824 + 132.991*X
Xd = 4.78*10-4
Methylene chloride in distillate product: 134.296
Kmol/hr(Inlet)
134.296
6.369 Meta
140.63
Table 7.1
7.1.2 Decanter:
Fig 7.2 Material balance across
Streams:
13: It contains mpbad, aqua’s ammonia, formaldehyde, sodium bicarbonate, methylene chloride.
14: It contains aqua’s ammonia,
15: It contains methylene chloride, mpbad.
Manufacturing Of Meta-Phenoxy Benzaldehyde
phenoxy benzaldehyde in bottom product is: 1250/198.22 = 6.306 kmol/hr.
Feed of the distillation column: 6.306/0.99 = 6.369 kmol/hr.
phenoxy benzaldehyde in distillate product is: 6.369-6.306 = 0.064 kmol/hr.
Value of methylene chloride for feed we have calculated from EXTRAXTER UNIT.
Methylene chloride in bottom product: (1-0.99)*134.296 = 1.342 kmol/hr.
7.648 kmol/hr.
7.647 = 132.991 kmol/hr.
140.638*0.0452 = 7.647*0.824 + 132.991*Xd
Methylene chloride in distillate product: 134.296 – 1.342 = 132.9 kmol/hr.
Components Distillate Products Bottom
Kmol/hr(Outlet)
Methylene Chloride 132.922
Meta-phenoxy benzaldehyde 0.06369 6.30
Total 140.63
Table 7.1 Material Balance across Distillation Column
Material balance across Decanter
It contains mpbad, aqua’s ammonia, formaldehyde, sodium bicarbonate, methylene chloride.
aqua’s ammonia, formaldehyde, sodium bicarbonate.
15: It contains methylene chloride, mpbad.
23
= 0.064 kmol/hr.
we have calculated from EXTRAXTER UNIT.
Distillate Products Bottom Products
Kmol/hr(Outlet)
1.34
0.06369 6.306
3
It contains mpbad, aqua’s ammonia, formaldehyde, sodium bicarbonate, methylene chloride.
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Manufacturing Of Meta
Calculations:
Molar flow rate of stream 15: 140.638 kmol/hr.
Molar flow rate of stream 14:
Kmol/hr(Inlet)
6.369
0.1817
0.3347
19.108
134.269
160.259
Table 7.
7.1.3 Neutraliser:
Assumptions:
Sodium bicarbonate to feed ratio is: 3:1
Fig 7.3 Material balance across
Calculations:
Sodium bicarbonate feed to neutraliser:
Manufacturing Of Meta-Phenoxy Benzaldehyde
Molar flow rate of stream 15: 140.638 kmol/hr.
Molar flow rate of stream 14: 160.259-140.638 = 19.621 kmol/hr.
Components Kmol/hr(
Meta-phenoxy benzaldehyde
Ammonia 0.1817
Formaldehyde 0.3347
Sodium bicarbonate 19.108
Methylene chloride 134.269
Total 160.259
Table 7.2 Material Balance across Decanter
Sodium bicarbonate to feed ratio is: 3:1
Material balance across Neutralyser
Sodium bicarbonate feed to neutraliser: 6.369*3 = 19.108 kmol/hr.
24
Kmol/hr(Outlet)
6.369
0.1817
0.3347
19.108
134.269
160.259
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Manufacturing Of Meta-Phenoxy Benzaldehyde
25
Kmol/hr(Inlet) Components Kmol/hr(Outlet)
6.369 Meta-phenoxy benzaldehyde 6.369
0.1817 Ammonia 0.1817
0.3347 Formaldehyde 0.3347
19.108 Sodium bicarbonate 19.108
134.269 Methylene chloride 134.269
160.259 Total 160.259
Table 7.3 Material Balance across Neutralyser
7.1.4 Extractor:
Assumptions:
Feed to solvent ratio is: 2:1
By products are completely immiscible in solvent.
Extract phase composition: mpbad: 95% , ammonia 0.9 % , formaldehyde 1%.
Fig 7.4 Material balance across Extractor
Streams:
18: Fresh methylene chloride + Recycled methylene chloride.
7: aqua’s ammonia, methyl ammonium chloride, formaldehyde, mpbad, unconverted oil (meta-phenoxy
benzyl chloride & meta-phenoxy benzal chloride).
11: It’s a raffinate stream having: aqua’s ammonia, methyl ammonium chloride, formaldehyde, and
mpbad, unconverted oil (meta-phenoxy benzyl chloride & meta-phenoxy benzal chloride).
10: It’s an extract stream having: aqua’s ammonia, formaldehyde, mpbad and methyl ammonium
chloride.
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Manufacturing Of Meta-Phenoxy Benzaldehyde
26
Calculations:
Reaction mixture coming out from the hydrolyser: 67.148 kmol/hr.
Solvent feed to the extractor: 67.148*2 = 134.269 kmol/hr.
Meta-phenoxy benzaldehyde in extract phase: 6.369 kmol/hr.
Feed:
Volume % of components of feed:
Ammonia: 30.08 %
Formaldehyde: 49.86 %
Mpbad: 9.97 %
Methyl ammonium chloride: 9.97 %
Unconverted (meta-phenoxy benzyl chloride + meta-phenoxy benzal chloride): 0.1.004 %.
Kmol/hr of components of feed:
Ammonia: 67.148 *0.3008 = 20.198 kmol/hr.
Formaldehyde: 67.148 *0.4986 = 33.479 kmol/hr.
Mpbad: 67.148 *0.0997 = 6.6946 kmol/hr.
Methyl ammonium chloride: 67.148 *0.0 997 = 6.6946 kmol/hr.
Unconverted (meta-phenoxy benzyl chloride + meta-phenoxy benzal chloride): 67.148 * 1.004*10-
3 = 0.0674 kmol/hr.
Extract:
Mpbad in extract phase: 6.6946*0.95 = 6.369 kmol/hr.
Methylene chloride (Solvent): 134.269 kmol/hr.
Formaldehyde: 33.479* 0.01 = 0.3347 kmol/hr.
Ammonia: 20.198* 0.009 = 0.1817 kmol/hr.
Raffinate:
Ammonia: 20.198 - 0.1817 = 20.0163 kmol/hr.
Methyl ammonium chloride: 6.6946 kmol/hr.
Mpbad in raffinate phase: 6.6946- 6.369 = 0.3256 kmol/hr.
Formaldehyde: 33.479- 0.3347 = 33.1442 kmol/hr.
Unconverted (meta-phenoxy benzyl chloride + meta-phenoxy benzal chloride): 0.0674 kmol/hr.
Volume % of components of raffinate :
Ammonia: 20.0163/60.2481 = 33.22%
Methyl ammonium chloride: 6.6946/60.2481 = 11.1%
Mpbad in raffinate phase: 0.3256/60.2481 = 5.4043*10-3%
Unconverted (meta-phenoxy benzyl chloride + meta-phenoxy benzal chloride): 0.0674/60.2481 =
0.1118%
Formaldehyde: 33.1442/60.2481 = 55.01%
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Manufacturing Of Meta
Therefore, Total Raffinate: 60.2481 kmol/hr
Total Extract: 141.154 kmol/hr
Kmol/hr(Inlet) Components
20.198 Ammonia
33.479 Formaldehyde
6.6946 Mpbad
6.6946 Methyl ammonium chloride
0.0674 Unconverted Mixture
134.269 Methylene chloride
201.40
Total
Table 7.
7.1.5 Hydrolyser:
Assumptions:
98% feed will convert to product.
Feed to Acetic acid ratio is 1:2.
Fig 7.5 Material balance across
Streams:
4: It contains mixture of meta
5: It is a water stream.
6: It contains acetic acid & hexamethylene tetra
7: It contains mixture of mpbad, aqua’s ammonia, formaldehyde and methyl ammonium chloride.
Manufacturing Of Meta-Phenoxy Benzaldehyde
60.2481 kmol/hr
al Extract: 141.154 kmol/hr
Components Raffinate Kmol/hr(Outlet) Extract
20.0163
Formaldehyde 33.1442
0.3256
Methyl ammonium chloride 6.6946
Unconverted Mixture 0.0674
Methylene chloride
60.24
201.40
Table 7.4 Material Balance across Extractor
98% feed will convert to product.
ratio is 1:2.
Material balance across Hydrolyser
4: It contains mixture of meta-phenoxy benzyl chloride and meta-phenoxy benzal chloride.
6: It contains acetic acid & hexamethylene tetra ammine.
7: It contains mixture of mpbad, aqua’s ammonia, formaldehyde and methyl ammonium chloride.
27
Kmol/hr(Outlet)
0.1817
0.3347
6.369
134.269
141.16
phenoxy benzal chloride.
7: It contains mixture of mpbad, aqua’s ammonia, formaldehyde and methyl ammonium chloride.
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Manufacturing Of Meta-Phenoxy Benzaldehyde
28
Calculations:
Overall Reactions:
3-C6H5.O.C6H4.CH2CL + (CH2)6.N4 3-C6H5.O.C6H4.CH2[(CH2)6.N4]+ CL-
3-C6H5.O.C6H4.CH2[(CH2)6.N4]+ CL- 3-C6H5.O.C6H4.CHO + CH3NH3
+ CL-
+ 3NH3 + 5HCHO
Molecular weights of reactants and products:
Mol. Wt. of Meta Phenoxy benzal chloride = 254.13
Mol. Wt. of Meta Phenoxy benzyl chloride = 218.68
Mol. Wt. of HMTA (Hexamethylenetetramine) = 140.186
Mol. Wt. of acetic acid = 60.07
Mol. Wt. of MPBAD = 198.22
Mol. Wt. of formaldehyde = 30.031
Mol. Wt. of CH3NH3CL = 67.57
Input:
Desired product is Meta Phenoxy benzaldehyde = 6.7048 kmol/hr.
Oil mixture of Meta Phenoxy benzal chloride and Meta Phenoxy benzyl chloride reacted = 6.7048 kmol/hr.
Moles of oil mixture fed = 6.7048/0.98 = 6.8416 kmol/hr.
Oil mixture reacted to acetic acid ratio = 1:2
Acetic acid fed = 6.8416*2 = 13.68 kmol/hr.
Water fed = 6.7048*6 = 40.228 kmol/hr.
Hexamethylenetetramine (HMTA) fed = 6.7048 kmol/hr
Output:
Meta Phenoxy benzaldehyde (MPBAD) in Product stream = 6.7048 kmol/hr.
Moles of ammonia in product streams = 3*6.0748 = 20.214 kmol/hr.
Moles of formaldehyde in product = 5* moles of MPBAD = 33.524 kmol/hr.
Moles of CH3NH3CL in Product stream = 6.7048 kmol/hr.
Unconverted oil mixture 2% = 0.02*6.8416 = 0.136832 kmol/hr.
6H2O
Aq. Acetic Acid
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Manufacturing Of Meta-Phenoxy Benzaldehyde
29
Kmol/hr(Inlet) Component kmol/hr(Outlet)
6.8416 Oil mixture
13.68 Acetic acid
40.228 Water
6.7048 HMTA
MPBAD 6.7048
Aqua’s ammonia 20.284
Formaldehyde 33.624
Methyl ammonium chloride 6.7048
Unconverted oil mixture 0.136832
67.45 Total 67.45
Table 7.5 Material Balance across Hydrolyser
7.1.6 Reactor:
Assumptions:
98% pure product is formed.
Product contains 60% benzyl chloride and 40% benzal chloride.
CCl4 75% excess then MPT (meta-phenoxy toluene).
Fig 7.6 Material balance across Reactor
Streams:
1: It contains meta-phenoxy benzaldehyde (MPT).
2: It contains Carbon tetra chloride (CCL4).
3: It contains HCL vapors and (unconverted MPT and unconverted CCL4).
4: It contains meta-phenoxy benzal chloride and meta-phenoxy benzyl chloride.
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Manufacturing Of Meta-Phenoxy Benzaldehyde
30
Calculations:
Overall Reactions:
C6H5.O.C6H4.CH3 + Cl2 C6H5.O.C6H4.CH2 CL + HCL
C6H5.O.C6H4.CH2Cl + Cl2 C6H5.O.C6H4.CHCl2 + HCL
Molecular weights of reactants and products:
Mol. Wt. of Meta Phenoxy toluene (MPT) = 184.23
Mol. Wt. of Meta Phenoxy benzal chloride = 254.13
Mol. Wt. of Meta Phenoxy benzyl chloride = 218.68
Mol. Wt. of HCL = 36.46
Mol. Wt. of CL2 = 70.90
Overall material balance: F= P+R F: Feed
F= 6.981 kmol/hr (MPT) + 11.97 kmol/hr (CCL4) P: Product
Total Feed=18.95kmol/hr R: Residue
Therefore,
18.95kmol/hr = P+R
Inlet:
Product of reactor is oil mixture of Meta Phenoxy benzal and benzyl chloride =6.8416 kmol/hr
Meta Phenoxy toluene reacted = 6.8416 kmol/hr
0.98 = 6.8416 kmol/hr /moles of MPT fed
Meta Phenoxy toluene fed = 6.9812 kmol/hr.
Moles of CCL4 are 75% excess of MPT.
Moles of CCL4 = 1.75*6.9812 =12.2171 kmol/hr.
Outlet:
From above reactions the product mixture contains 60% M- Phenoxy benzyl chloride and 40% M- Phenoxy benzal chloride.
Moles of Meta Phenoxy benzal chloride in product is = 0.40*6.8416 = 2.73664 kmol/hr
AIBN
AIBN
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Manufacturing Of Meta-Phenoxy Benzaldehyde
31
Moles of Meta Phenoxy benzyl chloride in product is: 0.60*6.8416 = 4.10496 kmol/hr.
Moles of HCL formed = moles of HCL formed in reaction 1 + moles of HCL formed in reaction 2
= 4.10496 + 2.73664 = 6.8416 kmol/hr
Moles of CCL4 Unreacted = moles of CCL4 used - moles of HCL formed.
= 12.2171-6.8416 = 5.3755 kmol/hr.
Unconverted toluene 2% = 0.02*6.9812 = 0.139624 kmol/hr
Kmol/hr(Inlet) Component kmol/hr (Outlet)
6.9812 MPT
12.2171 CCL4
M- Phenoxy benzal chloride 2.73664
M- Phenoxy benzyl chloride 4.10496
HCL 6.8416
CCl4 Unconverted 5.3755
Toluene Unconverted 0.13624
19.19832 Total 19.19832
Table 7.6 Material Balance across Reactor
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Manufacturing Of Meta-Phenoxy Benzaldehyde
32
Chapter- 8
ENERGY BALANCE
Formulas Used:
Empirical heat capacity equation:
Cp/R = A+BT+CT2+DT-2 (Kelvin)
R = 8.314 J/kg*K
Energy Balance:
Q-Ws=∆HºR+H
Ws=0 (when no moving parts)
H = n*Cp*∆T
8.1 REACTOR:
Stoichiometric Equation:
C6H5.O.C6H4.CH3 + Cl2 C6H5.O.C6H4.CH2 CL + HCL
C6H5.O.C6H4.CH2Cl + Cl2 C6H5.O.C6H4.CHCl2 + HCL
T = 323K (assuming isothermal conditions)
Tstd. = 298K (standard temperature)
Components A B C D
Meta Phenoxy toluene 15.133 6.76*10-3
16.35*10-6 -
Carbon tetra chloride 21.155 -48.28*10-3
101.19*10-6 -
Hydrochloric acid 3.512 1.623*10-3 - -0.156*10
-6
Meta Phenoxy benzyl chloride 11.278 32.86*10-3-31.90*10
-6 -
Table 8.1 Values of A, B, C, and D for empherical heat capacity equation [29]
Hr = (n*Cp*∆T)reactants = [(6.9812*7731.9)+(2*12.2171*338.673)] = 62253.1441 KJ/hr.
Hp = (n*Cp*∆T)products = [(2*6.8416*1537.11)+(6.8416*3031.48)] = 41772.7512 KJ/hr.
Q = Hr +Hp +Ws+(ni∆HºR)
ni: molar flow rate of limiting reactant.
Q = 28.89+Ws+ ni∆HºR
AIBN
AIBN
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Manufacturing Of Meta-Phenoxy Benzaldehyde
33
Standard Enthalpies of formation [30]:
∆Hformation (HCl) = -92.3KJ/mol
∆Hformation (MPT) = 120.0 KJ/mol
∆Hformation (CCL4) = -139.5KJ/mol
∆Hformation (Meta-phenoxy benzal chloride) = -36.3 KJ/mol
∆HºR = [-36.3+2*(-92.3)]-[2*(-139.5)+12.0] = 46.1 KJ/mºol
ni∆HºR = 6.9812*46.1 = 321.833 KJ/hr
Q = 28.89+Ws+321.833
Assumption:
Power input = 1.6 watt/Kg of input
Total input = 3165.38 Kg/hr
Ws = 3165.38*1.6 = 5.06460 KW
Therefore;
Q = 28.89+5.06460 + (321.833/3600) = 34.043 KW
8.2 HEAT EXCHANGER:
Utility calculation:
Assumption:
∆T = 75ºK
Amount of water (utility) used in heat exchanger: m
Q = m*Cp*∆T
34.043 = m*(4.816)*75
Therefore, Water required, m = 339.29 KJ/hr
8.3 HYDROLYSER:
Stoichiometric Equation:
3-C6H5.O.C6H4.CH2CL + (CH2)6.N4 3-C6H5.O.C6H4.CH2[(CH2)6.N4]+ CL-
3-C6H5.O.C6H4.CH2[(CH2)6.N4]+ CL- 3-C6H5.O.C6H4.CHO + CH3NH3
+ CL-
+ 3NH3 + 5HCHO
T = 425K (assuming isothermal conditions).
Tstd. = 298K (standard temperature).
6H2O
Aq. Acetic Acid
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Standard Enthalpies of formation [30]:
∆Hformation (NH3) = -46.2 KJ/mol
∆Hformation (HMTA) = -66.97 KJ/mol
∆Hformation (HCHO) = -108.57 KJ/mol
∆Hformation (H20) = -285.8KJ/mol
∆Hformation (CH3NH3+ CL-) = -22.97KJ/mol
∆Hformation (MPBAD) = 64.20 KJ/mol
∆Hformation (Acetic acid) = −483.5KJ/mol
∆Hformation (Meta-phenoxy benzyl chloride) = -36.3 KJ/mol
∆HºR = [64.20+22.97+(4*-46.2)+(5*-108.57)]-[(6*-285.8)-483.5-66.97-36.3] = 1661.09 KJ/mol.
ni∆HºR = 6.8416*1661.09 = 11364.51 KJ/hr = 3.156 KW
Ws=0 (when no moving parts)
Q = Hr +Hp +Ws+(ni∆HºR)
Q = Hr +Hp +0+3.156
Hr = (n*Cp*∆T) reactants = [(907598) Meta-phenoxy benzyl chloride + (-449.02) HMTA+ (173714.11) H20 + (-6614.28) Acetic acid ]
= 1074248.81 KJ/hr.
Hr = (n*Cp*∆T) products = [(123899.331) NH3+ (-3650.55) HCHO+ (430.44) MPBAD + (-154.00) CH3NH3+ CL-]
= 120525.221 KJ/hr
Q = 1074248.81 +120525.221+0+3.156 = 1194777.187 KJ/hr = 331.88 KW
8.4 DISTILLATION COLUMN:
Assumptions:
Temperature of distillate = 115ºC Boiling point of MPBAD = 392ºC Boiling point dichloromethane =39ºC Feed enters at = 25ºC
Calculation:
For CH2CL2 in distillate
ΔH = ΔHv + ∫ (102.3 ∗ 10^ − 395 )dt
ΔH = 28.6 + ∫ (102.3 ∗ 10^ − 3)95 dt = 32.6 KJ/mol
For MPBAD in distillate
ΔH = ΔHv + ∫ (172.0 ∗ 10^ − 395 ) dt +∫ (172.0 ∗ 10^ − 3)99 ∗
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ΔH = 64.2 + 67.467 – 60.716
= 70.951 kJ/mol.
For CH2CL2 in residue :
ΔH = ΔHv + ∫ (102.3 ∗ 10 ) ∗95 = 28.6 + (102.3*10^
-3)*dt
= 66.1441 kJ/mol.
MPBAD in Residue:
ΔH = ΔHv + ∫ Cp ∗ dt 95 = 64.2 + (172.0*10^
-3)*(392-25)
= 127.32 kJ/mol.
Components Feed N in (kmol/hr)
Hin (KJ/mol)
Distillate
N out (mol) H(out) (kJ/mol)
Residue
N out (mol) H out (kJ/mol )
CH2CL2 134.296 - 132.922 32.6 1.34 66.144
MPBAD 6.369 - 0.06369 70.951 6.306 127.32
Table 8.2 Energy Balance across Distillation Column
∆H=5229.288 KJ
Q=m*Cp*∆T=∆H
Cp=4.186kJ/KgºK
∆T=75ºK,
Therefore; Steam required, m=16.65 kg/s
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Chapter-9
CONTROL STRATEGY
Table 9.1 Control Strategy of Distillation Column [31]
Where:
SP: Set Point.
LC: Level Controller.
FC: Flow Controller.
TC: Temperature Controller.
PC: Pressure Controller.
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REFERENCES
1. http://www.chemicalland21.com/lifescience/agro/m-PHENOXY%20BENZALDEHYDE.htm
2. http://books.google.co.in/books?id=8OT-
Nj0RmmwC&pg=PA105&dq=meta+phenoxy+benzaldehyde&hl=en&sa=X&ei=lUpIUqnrKoSIrAec94CYBw&ve
d=0CDAQ6AEwAA#v=onepage&q=meta%20phenoxy%20benzaldehyde&f=false
3. www.sadgurupublications.com/ContentPaper/2009/9_7(2)2009.pdf
4. http://www.ncbi.nlm.nih.gov/pubmed/21981589
5. http://dir.indiamart.com/cgi/catprdsearch.mp?ss=meta+phenoxy+benzaldehyde
6. http://en.wikipedia.org/wiki/Pyrethroid
7. http://en.wikipedia.org/wiki/Cypermethrin
8. http://en.wikipedia.org/wiki/Fenvalerate
9. http://en.wikipedia.org/wiki/Etofenprox
10. http://en.wikipedia.org/wiki/Sumithrin
11. http://en.wikipedia.org/wiki/Deltamethrin
12. http://en.wikipedia.org/wiki/Permethrin
13. http://www.gharda.com/products/intermediates/meta-phenoxy-benzaldehyde.html
14. https://www.google.co.in/search?q=uses+of+pestisides+in+the+world&oq=uses+of+pestisides+in+the+world&aqs
=chrome..69i57j0.11093j0&sourceid=chrome&espvd=210&es_sm=93&ie=UTF-8
15. www.cnchemicals.com/.../Alpha-cypermethrin%20China%20Report%20
16. http://panjiva.com/trends/cypermethrin+technical
17. http://www.amazon.com/Industrial-Chemical-Downstream-Derivatives-Industries/dp/0824759540
18. http://www.cybex.in/india-imports-data/Cypermethrin-Imports.aspx
19. http://www.zauba.com/eport-data-cypermethrin-hs-code.html
20. http://www.chemicalbook.com/ProductMSDSDetailCB1697209_EN.htm
21. http://www.gharda.com/products/intermediates/meta-phenoxy-benzaldehyde.html
22. www.cdpr.ca.gov/docs/emon/pubs/fatememo/cyperm.pdf
23. http://www.ncbi.nlm.nih.gov/pubmed/21598078
24. www.ispharm.com/download/MSDS/I01-0736%20MSDS_I01-0736.pdf
25. http://en.wikipedia.org/wiki/Gujarat
26. http://origin-ars.els-cdn.com/content/image/1-s2.0-S0921800905002430-gr1.jpg
27. http://www.google.co.in/patents/US4085147
28. http://f3.tiera.ru/3/Chemistry/Chemical%20engineering/OrganicProd/Mukhopadhyay%20A.K.%20Industrial%20C
hemical%20Cresols%20and%20Downstream%20Derivatives%20(Dekker,%202005)(ISBN%200824759540)(232s
29. Mass Transfer Operation , 3rd edition by Robert E.Treybal.
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30. Chemical Engineering Thermodynamics, 6th edition by J.M Smith , H C Van Ness, M M Abbott.
31. Chemical-process-control by George Stephanopoulos.