Dimethyl Aniline

MANUFACTURE OF DMA
MGMs College of Engineering & Technology Kamothe, Navi Mumbai (2011-12). Page 1

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MANUFACTURE OF DMA


Table of Contents

CHAPTER 1: INTRODUCTION 5
1.1 DIMETHYLANILINE 6
1.2 HISTORY 8
CHAPTER 2: PHYSICAL AND CHEMICAL PROPERTIES 9
2.1 CHEMICAL AND PHYSICAL DATA 10
CHAPTER 3: MATERIAL SAFETY AND DATA SHEET 12
3.1 MSDS 13
CHAPTER 4: APPLICATION 20
4.1 APPLICATION 21
CHAPTER 5: MANUFACTURING PROCESS 23
5.1 PROCESSES 24
CHAPTER 6: PROCESS DESCRIPTION 25
6.1 RAW MATERIALS 26
6.2 DETAILS OF SELECTED PROCESS 27
6.3 PROCESS FLOW DIAGRAM 32
CHAPTER 7: MATERIAL BALANCE 34
7.1 MATERIAL BALANCE 35
CHAPTER 8: ENERGY BALANCE 39
CHAPTER 9: EQUIPMENT DESIGN 41
9.1 HEAT EXCHANGER 42
9.2 DISTILLATION COLUMN 48
CHAPTER 10: PLANT LAYOUT 55
CHAPTER 11: HAZOP STUDY 58
CHAPTER 12: PROJECT COST ESTIMATION 62
CHAPTER 13: CONCLUSION AND REFERENCES
MANUFACTURE OF DMA


CHAPTER 1

INTRODUCTION

MANUFACTURE OF DMA


1.1 Introduction Of Dimethylaniline

N,N-Dimethylaniline (DMA) is an organic chemical compound, a substituted derivative of
aniline. It consists of a tertiary amine, featuring dimethylamino group attached to a phenyl group.
This oily liquid is colourless when pure, but commercial samples are often yellow. It is an
important precursor to dyes such as Crystal violet.
N, N- Dimethylaniline is used as an intermediate
in the manufacture of dyes and other products and
as a solvent for special purposes, a rubber
vulcanizing agent and a stabilizer. It has been
detected in ambient water and soil in the vicinity
of industrial facilities N, N-Dimethylaniline can
be detected in air by adsorption on silica gel,
desorption with ethanol and analysis by gas
chromatography and flame ionization detection.
The limit of detection is 10 l1g/sample Amines
can be liberated during the manufacture of rubber,
especially by vulcanization and by other thermal
degradations. A method was described for the
determination of free aromatic amines.
Including N,N-dimethylaniline, using high-temperature glass-capillary gas chromatography and
nitrogen-selective detection (thermionic specific detector), with detection limits of 10-20 pg.

MANUFACTURE OF DMA


A
BRIEF
HISTORY
MANUFACTURE OF DMA


1.2 HISTORY

DMA was first reported in 1850 by A. W. Hofmann, who prepared it by heating aniline and
iodomethane:
C
6
H
5
NH
2
+ 2 CH
3
I C
6
H
5
N(CH
3
)
2
+ 2 HI
DMA is produced industrially by alkylation of aniline with methanol in the presence of an acid
catalyst:
C
6
H
5
NH
2
+ 2 CH
3
OH C
6
H
5
N(CH
3
)
2
+ 2 H
2
O
Similarly, it is also prepared using dimethyl ether as the methylating agent.
Dimethylaniline undergoes many of the reactions expected for an aniline, being
weakly basic and reactive toward electrophiles. N, N-Dimethylaniline is produced commercially
by heating aniline at 300C with
Methanol in the presence of a catalyst at high pressure; sulfuric acid, phosphoric acid or
Alumina can be used as the catalyst (Northcott, 1978; Rosenwald, 1978; Budavari, 1989).
N, N- Dimethylanilne is produced by one company each in France, Germany, Hungary,Korea,
Spain and the USA, by two companies in Japan and The United Kingdom and by four companies
in India (Chemical Information Services, 1991).

MANUFACTURE OF DMA


CHAPTER 2

PHYSICAL
AND
CHEMICAL
PROPERTIES
MANUFACTURE OF DMA


2.1 Chemical and physical data

N,N-Dimethylaniline (DMA) is colourless or pale yellow to brown, oily liquid with
characteristic amine-like odor. DMA is less dense than water and insoluble in water. Freely
soluble in alcohol, acetone, benzene, chloroform, diethyl ether, ethanol and acid solution. Stable
under ordinary conditions of use and storage. Combustible. DMA is a weak base incompatible
with strong oxidizing agents, strong acids, acid chlorides, acid anhydrides, chloroformates,
halogens. It emits toxic fumes of nitriogen oxides, carbon oxides, and aniline when heated to
decomposition. (C8H11N) MoL. wt: 121.18.
Synonyms, structural and molecular data
Chem. Abstr. Sem Reg. No.: 121-69-7
Chem. Abstr. Name: N,N- Dimethyl benzenamine
IUPAC Systematic Name: N,N-Dimethylaniline
Synonyms: (Dimethylamino )benzene; N,N-dimethylaminobenzene; dimethylanilne;
dimethylphenylamine; N,N-dimethylphenylamine

Chemical and physical properties
(a) Description: Yellowish to brownish oily liquid (Sax & Lewis, 1987)
(b) Boiling-point: 192-194 C (ElIer, 1985; Lide, 1991)
(c) Melting-point: 2-2.45 C (ElIer, 1985; Lide, 1991)
(d) Density: 0.956 g/ml at 20C (Eller, 1985)
(e) Refractive Index: 1.5580
(f) Spectroscopy data: Infrared, ultraviolet and nuclear magnetic resonance spectral data have
been reported (Sadtler Research Laboratories, 1980; Pouchert, 1981, 11983; US Nation9al
Toxicology 9Pro 1)gram., 1989; Sadtler .Research Laboratories, if Solubilty: Insoluble in water
MANUFACTURE OF DMA


(2-14 g/l at 25C). Since N,N-dimethyl aniline is a basic compound, its solubility is dependent
on the pH of the aqueous medium: its solubility in water at pH ).
7 is lower than that in water of pH .: 5. The data on aqueous solubility reported in the literature
thus vary widely (US Environmental Protection Agency, 1986). Soluble in acetone, benzene,
chloroform, diethyl ether and ethanol (Amoore & Hautala, 1983; Dragun & Hellng, 1985; Sax &
Lewis, 1987; Lide, 1991)
(g) Volatility: Vapour pressure, 1 mm Hg (133 Pal at 29.5 C (Lide, 1991)
(h) Stability: Slowly oxidizes and darkens in air; can react with nitrous acid to form ring-
substituted nitroso compounds (US Environmental Protection Agency, 1986)
(i) Octanol/water partition coeffcient (P): 2.31 (Hansch & Leo, 1979)
(j) Conversion factor: mg/m3 = 4.95 x ppm1.

TRANSPORTATION
PACKING: 180 Kg in Drum
HAZARD CLASS: 6.1 (Packing group: II)
UN NO.: 2253

MANUFACTURE OF DMA


CHAPTER 3

MATERIAL
SAFETY
DATA
SHEET
(M.S.D.S.)
MANUFACTURE OF DMA


3.1 Material Saftey And Data Sheet

Section 1: Chemical Product and Company Identification
Product Name: N,N-Dimethylaniline
Catalog Codes: SLD3868
CAS#: 121-69-7
RTECS: BX4725000
TSCA: TSCA 8(b) inventory: N,N-Dimethylaniline
CI#: Not available.
Synonym: Xylidine
Chemical Formula: C8H11N

Section 2: Composition and Information on Ingredients

Composition:
Name CAS # % by Weight
{N,N-}Dimethylaniline 121-69-7 100

Toxicological Data on Ingredients: N,N-Dimethylaniline: ORAL (LD50): Acute: 1410 mg/kg
[Rat]. DERMAL (LD50): Acute:1770 mg/kg.

Section 3: Hazards Identification

Potential Acute Health Effects:
Very hazardous in case of ingestion. Hazardous in case of skin contact (irritant, permeator), of
eye contact (irritant), of inhalation.

Potential Chronic Health Effects:
Hazardous in case of skin contact (irritant, permeator), of eye contact (irritant), of inhalation.

MANUFACTURE OF DMA


CARCINOGENIC EFFECTS: Not available.

MUTAGENIC EFFECTS: Not available.

TERATOGENIC EFFECTS: Not available.

DEVELOPMENTAL TOXICITY: The substance is toxic to blood, kidneys, liver. Repeated or
prolonged exposure to the substance can produce target organs damage

Section 4: First Aid Measures

Eye Contact: Check for and remove any contact lenses. Immediately flush eyes with running
water for at least 15 minutes, keeping eyelids open. Cold water may be used. Do not use an eye
ointment. Seek medical attention.

Skin Contact: After contact with skin, wash immediately with plenty of water. Gently and
thoroughly wash the contaminated skin with running water and non-abrasive soap. Be
particularly careful to clean folds, crevices, creases and groin. Cold water may be used. Cover
the irritated skin with an emollient. If irritation persists, seek medical attention. Wash
contaminated clothing before reusing.

Serious Skin Contact: Wash with a disinfectant soap and cover the contaminated skin with an
anti-bacterial cream. Seek immediate medical attention.

Inhalation:
Allow the victim to rest in a well ventilated area. Seek immediate medical attention.

Serious Inhalation: Evacuate the victim to a safe area as soon as possible. Loosen tight clothing
such as a collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is
not breathing, perform mouth-to-mouth resuscitation. Seek medical attention.

MANUFACTURE OF DMA


Ingestion: Do not induce vomiting. Examine the lips and mouth to ascertain whether the tissues
are damaged, a possible indication that the toxic material was ingested; the absence of such
signs, however, is not conclusive. Loosen tight clothing such as a collar, tie, belt or waistband. If
the victim is not breathing, perform mouth-to-mouth resuscitation. Seek immediate medical
attention.

Serious Ingestion: Not available.

Section 5: Fire and Explosion Data

Flammability of the Product: Combustible.

Auto-Ignition Temperature: 371C (699.8F)

Flash Points: CLOSED CUP: 63C (145.4F).

Flammable Limits: LOWER: 1.1%

Products of Combustion: These products are carbon oxides (CO, CO2).

Fire Hazards in Presence of Various Substances: Not available.

Explosion Hazards in Presence of Various Substances:
Risks of explosion of the product in presence of mechanical impact: Not available. Risks of
explosion of the product in presence of static discharge: Not available.

Fire Fighting Media and Instructions:
SMALL FIRE: Use DRY chemical powder. LARGE FIRE: Use water spray, fog or foam. Do
not use water jet.

MANUFACTURE OF DMA


Special Remarks on Fire Hazards: Not available.

Special Remarks on Explosion Hazards: Not available.

Section 6: Accidental Release Measures

Small Spill: Dilute with water and mop up, or absorb with an inert dry material and place in an
appropriate waste disposal container.

Large Spill: Combustible material. Keep away from heat. Keep away from sources of ignition.
Stop leak if without risk. Be careful that the product is not present at a concentration level above
TLV. Check TLV on the MSDS and with local authorities.

Section 7: Handling and Storage

Precautions: Keep away from heat. Keep away from sources of ignition. Ground all equipment
containing material. Do not ingest. Do not breathe gas/fumes/ vapour/spray. Wear suitable
protective clothing In case of insufficient ventilation, wear suitable respiratory equipment If
ingested, seek medical advice immediately and show the container or the label. Avoid contact
with skin and eyes

Storage: Flammable materials should be stored in a separate safety storage cabinet or room.
Keep away from heat. Keep away from sources of ignition. Keep container tightly closed. Keep
in a cool, well-ventilated place. Ground all equipment containing material. Keep container dry.
Keep in a cool place.

Section 8: Exposure Controls/Personal Protection

Engineering Controls: Provide exhaust ventilation or other engineering controls to keep the
airborne concentrations of vapors below their respective threshold limit value. Ensure that
eyewash stations and safety showers are proximal to the work-station location.
MANUFACTURE OF DMA


Personal Protection: Splash goggles. Lab coat. Vapor respirator. Be sure to use an
approved/certified respirator or equivalent. Gloves.

Personal Protection in Case of a Large Spill: Splash goggles. Full suit. Vapor respirator.
Boots. Gloves. A self contained breathing apparatus should be used to avoid inhalation of the
product. Suggested protective clothing might not be sufficient; consult a specialist BEFORE
handling this product.

Exposure Limits:
TWA: 5 CEIL: 10 (ppm) from ACGIH (TLV) TWA: 25 CEIL: 50 (mg/m3) from ACGIHConsult
local authorities for acceptable exposure limits

Section 9: Toxicological Information
Routes of Entry: Dermal contact. Eye contact. Inhalation. Ingestion.

Toxicity to Animals: Acute oral toxicity (LD50): 1410 mg/kg [Rat]. Acute dermal toxicity
(LD50): 1770 mg/kg [Rabbit].

Chronic Effects on Humans: The substance is toxic to blood, kidneys, liver.

Other Toxic Effects on Humans: Very hazardous in case of ingestion. Hazardous in case of
skin contact (irritant, permeator), of inhalation.

Special Remarks on Toxicity to Animals: Not available.
Special Remarks on Chronic Effects on Humans: Not available.
Special Remarks on other Toxic Effects on Humans: Not available.

Section 10: Ecological Information

Ecotoxicity: Not available.
MANUFACTURE OF DMA


BOD and COD: Not available.

Products of Biodegradation:
Possibly hazardous short term degradation products are not likely. However, long term
degradation products may arise.

Toxicity of the Products of Biodegradation: The products of degradation are more toxic.

Special Remarks on the Products of Biodegradation: Not available.

Section 11: Disposal Considerations

Waste Disposal:

Section 11: Transport Information

DOT Classification: CLASS 6.1: Poisonous material.

Identification: N,N-Dimethylaniline : UN2253 PG: II

Special Provisions for Transport: Not available.

Section 12: Other Regulatory Information

Federal and State Regulations: Pennsylvania RTK: N, N-Dimethylaniline Massachusetts RTK:
N,N-Dimethylaniline TSCA 8(b) inventory: N,N-Dimethylaniline SARA 313 toxic chemical
notification and release reporting: N,N-Dimethylaniline CERCLA: Hazardous substances.:
N,NDimethylaniline

Other Regulations: OSHA: Hazardous by definition of Hazard Communication Standard
MANUFACTURE OF DMA


(29 CFR 1910.1200).

Other Classifications:

WHMIS (Canada): CLASS B-3: Combustible liquid with a flash point between 37.8C (100F)
and 93.3C (200F). CLASS D-1A: Material causing
Immediate and serious toxic effects (VERY TOXIC). CLASS D-2B: Material causing other
toxic effects (TOXIC).

DSCL (EEC):R21/22- Harmful in contact with skin and if swallowed. R36/38- Irritating to eyes
and skin.

HMIS (U.S.A.):
Health Hazard: 3
Fire Hazard: 2
Reactivity: 0
Personal Protection: h
National Fire Protection Association (U.S.A.):
Health: 3
Flammability: 2
Reactivity: 0
Specific hazard:
Protective Equipment:
Gloves. Lab coat. Vapor respirator. Be sure to use an approved/certified respirator or equivalent.
Wear appropriate respirator when ventilation is inadequate. Splash goggles.

MANUFACTURE OF DMA


CHAPTER 4

APPLICATIONS

MANUFACTURE OF DMA


4.1 Applications

DYES
N, N-Dimethylaniline is used in the manufacture of Michler's ketone which is a chemical
intermediate used in the synthesis of many dyes and pigments, particularly auramine derivatives.
These pigments are used to dye paper, textiles, and leather. The main types of the dyes that can
be manufactured from DMA are alkali light yellow, alkali purple 5BN, alkali light green, alkali
turquoise blue, bright red 5 GN, bright blue. DMA is a key precursor to commercially important
triarylmethane dyes such as Malachite green or Crystal (Gentian) violet used as a histological
stain and in Gram's method of classifying bacteria.

PROMOTERS
DMA serves as a promoter in the curing of polyester and vinyl ester resins. This compound can
be used on its own with benzoyl peroxide (BPO) type catalysts or in combination with cobalt 6%
promoters with methyl ethyl ketone(MEKP) type catalysts. These systems give rapid cure at
room temperature. DMA helps the catalyst to start the chemical reaction. Promoters must never
be mixed directly with catalyst since a violent explosive reaction results.

STABILISERS
DMA is used as a stabilizer for colorimetric peroxidase determination.

FRAGRANCE
N,N-Dimethylaniline is used as an intermediate to manufacture vanillin.

PHARMA
DMA is used to manufacture cephalosporin V, madribon, sulphormethoxine and flucytosine in
medical industry. It is used as an acid scavenger in the synthesis of penicillins and
cephalosporins and has been reported as a contaminant of commercial preparations of those
antibiotics at levels of up to 1500 ppm.

MANUFACTURE OF DMA


Other Uses:
Specialty industrial solvent and rubber vulcanizing agent.
Reagent in chemical synthesis.
Catalytic hardener in certain fibreglass resins.

N,N-Dimethylaniline is used as an intermediate in the manufacture of dyes, Michler's
ketone and vanilin. It is also used as a specialty industrial solvent, a rubber vulcanizing agent
(see IARC, 1982b, 1987b), a stabilizer and an acid scavenger

MANUFACTURE OF DMA


CHAPTER 5

MANUFATURING
PROCESSES

MANUFACTURE OF DMA


1] BY ALKYLATION OF ANILINE:

REACTION:

C6H5NH2 + 2CH3OH C6H5N(CH3)2 + 2H2O

Thus, aniline, with a considerable excess of methyl alcohol and a catalytic amount of sulfuric
acid, is heated in an autoclave at about 200
o
C for 5 or 6 hours at a high reaction pressure we get
dimethylaniline . Vacuum distillation is used for purification.
In the alkylation of aniline to dimethylaniline by heating aniline and methyl
alcohol, sulfuric acid cannot be used because it will form ether; consequently,hydrochloric acid is
employed, but these conditions are so corrosive that the steel used to resist the pressure must be fitted
with replaceable enameled liners.Thus in presence of Al
2
O
3
as a catalyst is used.

2] BY NITRATION OF BENZENE:

REACTION:

Benzene ring in presence of H2SO4 reacts with nitric acid to give nitrobenzene and water. The
obtained nitrobenzene is subjected to hydrogenation in presence of palladium catalyst and ethanol gives
aniline. And further, aniline on reacting with methyl chloride or chloromethane produces N, N-Dimethyl
aniline.

MANUFACTURE OF DMA


CHAPTER 6

PROCESS
DESCRIPTION

MANUFACTURE OF DMA


6.1 Raw Materials Used

ANILINE

Aniline, phenylamine or aminobenzene is an organic compound with the formula C
6
H
5
NH
2
.
Consisting of a phenyl group attached to an amino group, aniline is the prototypical aromatic
amine. Being a precursor to many industrial chemicals, its main use is in the manufacture of
precursors to polyurethane. Like most volatile amines, it possesses the somewhat unpleasant
odour of rotten fish. It ignites readily, burning with a smoky flame characteristic of aromatic
compounds. Aniline is colorless, but it slowly oxidizes and resinifies in air, giving a red-brown
tint to aged samples.

MANUFACTURE OF DMA


PROPERTIES OF ANILINE

Molecular formula:C
6
H
5
NH
2

Molar mass: 93.13 g/mol

Appearance: colorless liquid

Density : 1.0217 g/mL, liquid

Melting point: -6.3 C, 267 K, 21 F

Boiling point: 184.13 C, 457 K, 363 F

Solubility in water:3.6 g/100 mL at 20C

Basicity (pKb): 9.3

Viscosity: 3.71 cP (3.71 mPa s at 25 C

MANUFACTURE OF DMA


METHANOL

Derived from natural gas, methanol is a hydrocarbon, comprised of carbon, hydrogen and
oxygen. Its chemical formula is CH
3
OH.
Methanol is an alcohol and is a colorless, neutral, polar and flammable liquid. It is miscible with
water,alcohols, esters and most other organic solvents. It is only slightly soluble in fats and oils.
Detailed physical and chemical properties of methanol are provided in the following pages.

Methanex produces methanol using a catalytic process with natural gas and steam as the
feedstocks. The natural gas is catalytically reformed to carbon oxides and hydrogen. The
resulting synthesis gas mixture is circulated under pressure and moderate temperature in the
presence of a metallic catalyst and converted to crude methanol. The crude methanol is distilled
to yield commercial chemical grade methanol.

Other common names for methanol include methyl alcohol, methyl hydrate, wood spirit, wood
alcohol, and methyl hydroxide.
Methanol is used as a building block for many chemicals and products. Other uses include
windshield washer antifreeze, fuels, waste water treatment and biodiesel production.

MANUFACTURE OF DMA


PROPERTIES OF METHANOL

Molecular formula:CH
4
O

Molar mass : 32.04 g mol1

Appearance: Colorless liquid

Density: 0.7918 g cm3

Melting point: -98--97 C, 175-176 K, -144--143 F

Boiling point: 65 C, 338 K, 149 F

Vapor pressure: 13.02 kPa (at 20 C)

Acidity (pKa): 15.5[2]

Viscosity: 5.9104 Pa s (at 20 C)

Dipole moment: 1.69 D

MANUFACTURE OF DMA


6.2 MANUFACTURING OF DIMETHYLANILINE (DMA) BY
ALKYLATION OF ANILINE
- A method for the production of dimethylaniline which consist alkylation of aniline with
use of methanol.

- First methanol is passed through heat exchanger to rise the temperature to 260
0
C.

- Then it is passed to the reactor to convert it into dimethylether gas in presence of alumina
(Al
2
O
3
)a instead of sulphuric acid as a catalyst , because sulphuric acid is corrossive
towards the reactor vessel.

REACTION:

2CH
3
OH CH
3
-O-CH
3
+H
2
O

METHANOL DIMETHYLETHER

- The effluent from the reactor is passed to ETP and DME gas is passed to autoclave.

- Here, it is mixed with aniline at high temperature and high pressure of 540 psi (3.7
MPa)about 5 to 6 hours.

REACTION:

CH
3
-O-CH
3
+C
6
H
5
NH
2
C
6
H
5
N(CH
3
)
2
+H
2
O
DIMETHYLETHER ANILINE DIMETHYLANILINE

- At the end of reaction we get dimethylaniline , which we need to purify.

- To purify the mixture from autoclave, it is passed through series of vaccum distillation
MANUFACTURE OF DMA


- coloumn. Thus, pure dimethylaniline is formed and passed to further processes and
storage.

MANUFACTURE OF DMA


6.3 PROCESS FLOW DIAGRAM FOR DIMETHYLANILINE

CHAPTER 6
MANUFACTURE OF DMA


CHAPTER 6
MATERIAL
BALANCE

MANUFACTURE OF DMA


MATERIAL BALANCE
REACTION 1:
2CH
3
OH CH
3
-O-CH
3
+ H
2

2 kmole of Methanol = 1 kmole of Dimethyl ether + 1mole of water
64gm of CH
3
OH 46gm DME + 18gm H
2
O
Assume 80% Conversion
Methanol reacted=64 0.8 = 51.2 gm
Unreacted Methanol = 12 .8gm
64gm CH
3
OH 48gm DME
51.2gm CH
3
OH x gm DME
x = 36.8gm of DME

REACTION 2:
CH
2
OCH
3
+ C
6
H
5
NH
2
C
6
H
5
N(CH
3
)
2
+ H
2
O
1 mol DME+1mol Aniline DMA + 1 mol of water
46gm DME + 93 Aniline 121gm DMA+ 18gm water
46gm DME 93gm Aniline
Therefore ,
36.8gm DME + 74.4Aniline 96.8 gm DMA + 14.4gm H
2
O

Assume 80% conversion Based on DME
DME reacted = 0.8 36.8 =29.44gm of DME
Therefore DME unreacted = 7.36gm of DME
Aniline req.= 59.52gm of Aniline
DMA produced = 77.44gm = 34.44 kmol/hr
MANUFACTURE OF DMA


H
2
O produced = 11.52gm of water
Feed to Distillation Column
DME = 7.36gm
H
2
O =11.52gm
DMA =77.44gm=77.44 X 10
-3
kg

MANUFACTURE OF DMA


Basis : 100 tones /day
i.e. 4166.67kg/hr of DMA
34.44kmol/hr

- Material balance over reactor:
REACTION 1:
2 CH
3
OH CH
3
OCH
3
+ H
2
O
153.057 kmol/hr Methanol = 110.01kmol/hr of DME
i.e. 4897.824kg/hr of Methanol feed
1692.8kg/hr of DME gas produced

- Material balance over autoclave:
REACTION 2:
CH
3
OCH
3
+ C
6
H
5
NH
2
C
6
H
5
N(CH
3
)
2
+ H
2
O
110.01kmol/hr of DME = 34.44kmol/hr of DMA = 222.54kmol/hr of Aniline = 34.43kmol/hr of
H
2
O
i.e. Aniline feed = 222.54 93 = 20696.22kg/hr

MANUFACTURE OF DMA


- Material balance over distillation column:
b d f
Bx Dx Fx
B D F
+ =
+ =

|
|
.
|
\
|
=
f d
b f
x x
x x
B
D

F = feed flow rate (mol/hr)
D = distillate flow rate (mol/hr)
B = bottom flow rate (mol/hr)
x = mole fraction of corresponding stream

Component In(kg/hr) Top Product
(kg/hr)
Bottom Product
(kg/hr)
DMA 4167.24 41.6724 4125.5676
H
2
O 619.88 618.0203 1.8597
ANILINE 256.34 253.7766 2.5634
DME 1594.24 1594.24 _
Total
6637.7

MANUFACTURE OF DMA


CHAPTER 8
ENERGY
BALANCE

MANUFACTURE OF DMA


ENERGY BALANCE
Total feed=4898.24kg
Assume water used 500kg
Reactor 1
mxCpxT=mxCpxT
4898.24x(533-298)x2.51=mx4.187x(573-T)
Q=2889226.864kJ/kg
4896.24x(533-298)x2.51=5000x4.187x(573-T)
T(out) of Water=434.9K
Q=mxCpxT+Mx
=153.057x0.06143x(623-533)+34.4x153.057
=611.367kJ
Req. of steam for the autoclave
Q=mx
611.36=mx1736.2
=3.51kg
aniline=4.838kJ/kmolK
Cp(mix)=Cp(aniline)xmolar mass of aniline+Cp(DME)xmolar mass of DME
=12.115kJ/kmolK

Reactor 2
Q=mxCpxT+Mx
=332.55x12.11x(673-473)+222.5x4.838
=805545.148kJ
Req. of heat for total reactor
Q=mx
805545.148=mX1825.1
=441.37kg/hr

MANUFACTURE OF DMA


CHAPTER 9
EQUIPMENT
DESIGN

MANUFACTURE OF DMA


9.1 HEAT EXCHANGER
- Shell side
MOC: CS
No. of shells: 1
No. of passes: 1
Fluid: liquid
Working pressure: 0.33N/mm
2

Design pressure: 0.5N/mm
2

Temp. IN: 30
o
C
Temp OUT: 50
o
C
Segmental Baffles (25%) with tie rods & spacers

- Head
Crown radius: 400mm
Knuckle radius: 40mm
Shell Flange: female facing
Bolts: steel
Nozzles-inlet & outlet-75mm
Vent: 25mm
Drain: 25mm
Opening for relief valve: 50mm
Permissible stress for carbon steel: 95N/mm
2

Permissible stress for bolt: 140.6N/mm
2

MANUFACTURE OF DMA


- Tube and tube sheet material: stainless steel
No. of tubes: 54
Outside dia: 12mm
Length: 12m
Pitch (Square): 25mm
Fluid: gas
Working pressure:19N/mm
2

Design pressure: 21.5N/mm
2

Temp. IN: 150
o
C
Temp OUT: 55
o
C
Permissible stress: 100.6N/mm
2

- Channel and channel cover
MOC: CS
Joint: ring facing
Gasket: steel jacketed asbestos
Nozzles-inlet & outlet-75mm
Permissible stress: 95N/mm
2

MANUFACTURE OF DMA


- Shell side
Shell Diameter
a=S
2
T
=25
2=625mm2
a
n
=2x54x625=67500mm
2

A
s
=/4xD=a
n
/ =0.7
D
s
=(61500x4/0.7x)
0.5

=350.4mm

- Shell Thickness
t=pD
i
/(2fJ-p)
=0.5x400/(2x95x0.85-0.5)
=1.24mm

- Nozzle (Inlet & Outlet)
t
n
=pDi/(2fJ-p)
=0.5x75/(2x95x0.85-0.5)
=0.23mm

- Head Thickness
t
h
= [pR
c
W/(2fJ)]+c
= [0.5x400x1.54/(2x95x0.85)]+1.5
= 3.4mm

MANUFACTURE OF DMA


- Flange Thickness (male & female)
G
o
=440mm
G
i
=416mm
G=428mm
Gasket width (N)= 24
Basic gasket seating width
b
o=
N/2=24/2=12
b=2.5x b
o
0.5

=8.66
Seating stress(Y
a
)=53.4N/mm
2

Gasket factor(m)=3.75
W
m1
=bGY
a

=x8.66x428x53.40
=6.2x10
5
N
W
m2
=x2x8.66x428x3.75x0.5+(/4)x428
2
x0.5
=1.15x10
5
N
k=1/(0.3+(1.5W
m
h
G
/HG))
W
m
=6.2x10
5

h
G
=48.5
H=71936.6
G=428
k=0.565
t
f
=G(p/kf)
0.5
=428x(0.5/0.565x95)
0.5
=41.3mm
MANUFACTURE OF DMA


- Tube side
Thickness of tube
t
f
=pD
o
/(2fJ+p)
=(21.5x18)/(2x100.6+21.5)
=1.74mm

- Tube sheet
t=FGx(0.25p/f)
0.5
=1.25x380x(0.25x21.5/100.6)
0.5
=109.8mm

- Channel and channel cover
T=G
c
x(kp/f)
0.5

=380x(0.3x21.5/95)
=99.02mm
Flange joint between tube sheet and channel
G=380mm
Ring gasket width=22mm
b
o
=w/8=22/8=2.75mm
Y
a
=126.6N/mm
2

m=5.5
W
m1
=bGY
a

=x980x2.75x126.6
=4.16x10
5
N
MANUFACTURE OF DMA


W
m2
=x2x2.75x380x5.5x21.5+(/4)x380
2
x21.5
=32.14x10
5
N
Bolt area= W
m2
/f
=22859.2mm
2

No. of bolt=38/2.5
=15.2
The bolt diameter=(22859.2x4/x16)
0.5
=42.65mm

- Flange thickness
k=1/(0.3+(1.5W
m
h
G
/HG))
=1.47
- Tube sheet
t
f
=G(p/kf)
0.5
=145mm
- Nozzles
t
n
=pDi/(2fJ-p)
=9.6mm

MANUFACTURE OF DMA


9.2 DISTILLATION COLUMN
SHELL:
Diameter (Di ) 1.99 m
Working/Operating Pressure 1.0329 kg/cm
2

Design pressure = 1.1Operating Pressure 1.11.0329 = 1.1362 kg/cm
2

Working temperature 441 0K
Design temperature 457.8 0K
Shell material - IS: 2002-1962 Grade I Plain Carbon steel
Permissible tensile stress (ft) 950 kg/cm
2

Elastic Modulus (E) 1.88105 MN/m
2

Insulation material - asbestos
Insulation thickness 2= 50.8 mm
Density of insulation 575 kg/m
3

Top disengaging space 0.3 m
Bottom separator space 0.4 m
Weir height 50 mm
Downcomer clearance 25 mm

HEAD - TORISPHERICAL DISHED HEAD:
Material - IS: 2002-1962 Grade I Plain Carbon steel
Allowable tensile stress = 950 kg/cm
2

SUPPORT SKIRT:
Height of support 1 m
Material - Carbon Steel
MANUFACTURE OF DMA


TRAYS-SIEVE TYPE:
Number of trays = 9
Hole Diameter = 5mm
Number of holes:
Enriching section = 6981
Stripping section = 10726
Tray spacing:
Enriching section: 500 mm
Stripping section: 500 mm
Thickness = 3 mm

SUPPORT FOR TRAY:
Purlins - Channels and Angles
Material - Carbon Steel
Permissible Stress = 1275 kg/cm
2

1. Shell minimum thickness:
Considering the vessel as an internal pressure vessel.
ts = ((PDi)/ ((2ftJ)- P)) + C
where ts = thickness of shell, mm
P = design pressure, kg/cm
2

Di = diameter of shell, mm
ft = permissible/allowable tensile stress, kg/cm
2

C = Corrosion allowance, mm
J = Joint factor
MANUFACTURE OF DMA


Considering double welded butt joint with backing strip
J= 85% = 0.85
Thus, ts = ((1.13621990)/ ((29500.85)- 1.1362)) + 3 = 4.556 mm
Taking the thickness of the shell as minimum specified value= 6 mm

2. Head Design- Shallow dished and Torispherical head:
Thickness of head = th = (PRcW)/ (2fJ)
P =internal design pressure, kg/cm
2

Rc = crown radius = diameter of shell, mm=1990mm
W=stress intensification factor or stress concentration factor for torispherical head
W= (3 + (Rc/Rk)0.5)
Rk = knuckle radius, which is at least 6% of crown radius, m
Rk = 6% Rc = 0.061990 = 119.4 mm
W= (3 + (Rc/Rk)0.5) = (3 + (1/0.06)0.5) = 1.7706 mm
th = (1.136219901.7706)/ (29500.85) = 2.7538 mm
including corrosion allowance thickness of head is taken as 6 mm
Pressure at which elastic deformation occurs
P (elastic) = 0.366E (t/ Rc)
2

= 0.3661.88105 (6/1990)
2

= 0.6255 MN/ m2 = 6.3761kg/cm
2

The pressure required for elastic deformation, P (elastic)> (Design Pressure)
Hence, the thickness is satisfactory. The thickness of the shell and the head are made
equal for ease of fabrication.
Weight of Head:
Diameter = O.D + (O.D/24) + (2sf) + (2icr/3)
MANUFACTURE OF DMA


Where O.D. = Outer diameter of the dish, inch
icr = inside cover radius, inch
sf = straight flange length, inch
From table 5.7 and 5.8 of Brownell and Young
sf =1
icr = 1
Also, O.D.= 1990 mm = 78.35
Diameter = 78.35 + (78.35/24) + (21) + (21/3) =
d = 84.45 = 2144.97 mm

3. Shell thickness at different heights

Axial Tensile Stress due to Pressure:
fap = PDi/4(ts -c) = 1.13621990/4(6 - 3) = 188.38 kg/cm
2

This is the same through out the column height.

Compressive stress due Dead Loads:
3.2 a Compressive stress due to Weight of shell up to a distance X meter from top.
fds = weight of shell/cross-section of shell
=(/4)x(Do
2
- Di
2
)xpxX/(/4)x(Do
2
- Di
2
)
fds=0.85x Xkg/cm
2

MANUFACTURE OF DMA


3.2 b Compressive stress due to weight of insulation at a height X meter

fd(ins)= Dins tins ins X/ Dm (ts - c)

Where

Dins, tins, ins are diameter, thickness and density of insulation respectively.

Dm = (Dc+ (Dc+2ts))/2

Dins =Dc+2ts+2tins = 199+ (20.6) + (25.08) = 201.216 cm.

Dm = (199+ (199+ (20.6)))/2 = 199.6 cm.

fd(ins) = 201.216 5.08575X/ 199.6 (0.6 - 0.3)
= 9815.5 X kg/m
2

3.2c Stress due to the weight of the liquid and tray in the column up to a height X meter
fd, liq. = weight of liquid and tray per unit height X/ Dm (ts - c)
The top chamber height is 0.3 m and it does not contain any liquid or tray. Tray spacing is 500
mm.
Average liquid density = 984.67 kg/m
3

Liquid and tray weight for X meter
fliq-tray =[2X + 0.4] 3062.97 kg
fd (liq) = Fliq-tray 10/ (Dm (ts - c))
= [2X + 0.4] 3062.97 10/ (1996 (6 - 3))
fd (liq) = 3.26X + 0.653 kg/cm
2

3.2d Compressive stress due to attachments such as internals, top head, platforms and ladder
up to height X meter

fd (attch.) = weight of attachments per unit height X/ D
m
(t
s
- c)

Now total weight up to height X meter = weight of top head + pipes +ladder, etc., Taking the weight
of pipes, ladder and platforms as 25 kg/m = 0.25 kg/cm
Total weight up to height X meter = (170.19+25X) kg
MANUFACTURE OF DMA


fd (attch.)= (170.19+25X) 10/ 199 (6 - 3) = 0.907 + 0.133X kg/cm
2

Total compressive dead weight stress:
fdx = fds + fins +fd (liq) + fd (attch)
= 0.85X + 0.98155X + [3.26X+0.653] + [0.907 +0.133X]
fdx = 5.225X + 1.559 kg/cm
2

4. Tensile stress due to wind load in self supporting vessels:
fwx = Mw /Z
where Mw = bending moment due to wind load = (wind load distance)/2
= 0.7PwDX
2
/2
Z = modulus for the section for the area of shell
Now Pw = 25 lb/ft
2

= 122.06 kg/m
2

Bending moment due to wind load
Mwx = 0.7122.061.99X
2
/2 = 170.03 kg-m
fwx= 1.4122.06X
2
/1.99 (6-3) = 3.075X
2
kg/cm
2

5. Stresses due to Seismic load:
fsx = Msx /Dm
2
(ts-c)/4
Where bending moment M
sx
at a distance X meter is given by
Msx = [CWX
2
/3] [(3H-X)/H
2
]

Where C = seismic coefficient,
W= total weight of column, kg
H = height of column
Total weight of column = W= C
v
m
D
m
g (H
v
+ (0.8D
m
))t
s
10
-3
----- (eq
n.
13.75, page 743, Coulson and Richardson 6
th

volume)
Where W = total weight of column, excluding the internal fittings like plates, N
Cv = a factor to account for the weight of nozzles, manways, internal
supports, etc.
MANUFACTURE OF DMA


= 1.5 for distillation column with several manways, and with plate Support
rings or equivalent fittings
Hv = height or length between tangent lines (length of cylindrical section) g =
gravitational acceleration = 9.81 m/s
2
t = wall thickness
m = density of vessel material, kg/m
3
Dm = mean diameter of vessel = Di + (t 10
-3
)
= 1.99+ (6 10
-3
) = 1.996 m
W= 1.585001.9969.81 (4+ (0.81.996))610
-3
= 26341.28 N

Trays:
The trays are standard sieve plates throughout the column. The plates have 6981
holes in Enriching section and 10726.11 holes in the Stripping section of 5mm
diameter arranged on a 15mm triangular pitch. The trays are supported on purloins.

MANUFACTURE OF DMA


CHAPTER 11
PLANT
LAYOUT

MANUFACTURE OF DMA


PLANT LAYOUT

A preliminary site layout has been sketched. The layout of the plant is decided keeping the
following factors in mind.

- The safety regulation should be followed.
- There should be minimum possible distance between equipment to facilitate the
transfer of material.
- Economic considerations should be taken into account like optimum distribution
of equipment and services.
- Operational convenience is very important.
- Possibility for future expansion should be kept in mind.
- The main cabin room should be located away from the main plant.
- In order to improve the aesthetic look for the plant, a garden may be provided . It
also helps to maintain better work environment.
The utilities and storage facilities are segregated from the main body of the plant. A separate
gate may be provided in this area. This gate can be used for trucks and tankers carrying the raw
materials, cooling water.

The units in the plant are the main plant, administrative building, utilities, canteen etc. The
vessel should be located close to the entry and exit point of the plant to facilitate loading and un
loading. The fire engines have easy access to all parts of the plant in case of any accidents.
Prevailing the wind conditions should also be considered in the relative locations of equipment.

MANUFACTURE OF DMA


MANUFACTURE OF DMA


CHAPTER 12
HAZOP
STUDY

MANUFACTURE OF DMA


HAZOP
(Hazards and operability studies )
The HAZOP study is formal procedure to identify hazards in a chemical process faculty.
The procedure is effective in identifying hazards and is well accepted by the chemical industry.
The basic data is to let the mind go free in a controlled fashion in order to consider all
possible ways that process and operational failures can occur.
Before HAZOP study started , detailed information on the process must be available.
This includes up-to-date process flow diagrams (PFDs), process and instrumentation diagrams
(P & Ids).Detailed equipments specifications, MOC & Mass & energy balances.
Here as far as our project is concerns the main hazards can from reactor itself where the
endothermic reaction is carried out.

HAZOP Study Table For The Reactor
Guide
word
Causes Consequences Action
NO 1. Control
valve
fails.
2. Controll
er fails
and
closes
valve.
- Temperature in Reactor
Decreases.
- Temperature in Reactor
Decreases.
1. Install a buypass
valve.
2. Put a controller
in critical list.

MORE 1. Control
valve
fails to
- Temperature increases in Reactor
rapidly.
- Temperature increases in Reactor
1. Instruct operator
on procedure.
2. Instruct operator
MANUFACTURE OF DMA


open.
2. Controll
er fails
and
open
valve.
rapidly. on procedure.
LESS 1. Control
valve
fails to
respond
&partial
ly open.
2. Partial
steam
source
failure.

- Temperature decreases slowly.
- Temperature decreases slowly.

1. Install bypass
valve.
2. Install backup
boiler service.
AS
WELL
AS
1. Leak in
reactor
body.
2. Pressure
in
reactor
less than
pressure
in
jacket.
- Dilution of content.
- Temperature increase evaporation
of content.
1. Install high
pressure alarm .
2. Install proper
relief valves .
3. Check for
maintenance.
MANUFACTURE OF DMA


REVE
RSE
1. Reverse
flow of
reactant
2. Reverse
flow of
product
- Failure of coolant source resulting
backflow
- Backflow due to back pressure
- Use of non
return or check
valve in coolant
line
- Install high
temperature
alarm to alert
operator

Part of Partial cooling Covered under LESS --------

MANUFACTURE OF DMA


CHAPTER 13
PROJECT
COST
ESTIMATION

MANUFACTURE OF DMA


COST ESTIMATION
Acceptable plant design must present a process that is capable of operating under conditions,
which will yield profit. Since net profit equal total value minus all expenses, it is essential that
the chemical engineer be aware of the many different types of cost involved in the manufacturing
processes. Capital must allocate for the direct, plant expenses, such as those for raw material,
labor and equipment.
Money is worth hence must be spent where required in a definite foolproof manner. For any
project the cost is of prime importance. The cost estimation is required so as to study about the
financial requirements, so that no future financial crisis should occur, for any project.
Total investment = fixed capital + working capital
- FIXED CAPITAL:

A) LAND & BUILDING
Area of building = 1000 m
2

No. of building = 5
Therefore plant area = 5 x 1000
= 5000 m
2

The cost of plant area = plant area x Rs. 1500/m
2

= 5000 x 1500
= 75,00,000 Rs.

Cost per building = area of building x 2000Rs.
= 5000 x 2000
= 1,00,00,000Rs.

Total cost of land = 1,75,00,000Rs.
MANUFACTURE OF DMA


B) MACHINARY & EQUIPMENTS:
EOUIPMENT NUMBERS COST IN Rs.
REACTOR 1 30,00,000
CONDENSER 1 75000
DISTILLATION COLUMN 1 4,00,000
DAY TANK 1 1,00,000
AUTOCLAVE 1 30,00,000
HEAT EXCHANGER 1 2,00,000
PUMPS 4 40,000

TOTAL M/C COST = 68,15,000Rs.

C) OTHER FIXED AMOUNT :
Installation of equipments = 10% of m/c cost = 0.1 x 68,15,000
= 6,81,500 Rs.

Instrumentation and control = 7% of m/c cost = 0.07 x 68,15,000
=4,77,050 Rs.
Piping (ISA approval) = 9% of m/c cost = 0.09 x 68,15,000
= 6,13,350Rs.

MANUFACTURE OF DMA


Total cost = equipment cost + (A) + (B) + (C)
= 68,15,000 + 6,81,500 + 4,77,050 + 6,13,350
= 85,86,900Rs.

D) PRELIMINARY & PREVENTIVE EXPENSES:
- Training cost = 10,000Rs.
- Legal expenses =12000 Rs.
- Marketing expenses = 15000Rs.
- Production expenses = 10000 Rs.
- Telephone deposits = 10000Rs.
- Advertising = 10000 Rs.
- Electrification deposits = 10000 Rs.
- Fright & Insurance charges = 25000 Rs.
- Project report = 10000 Rs.
- ISO certificates = 25000 Rs.
- Miscellaneous = 10000 Rs.

TOTAL COST = 1,47,000 Rs.

TOTAL FIXED CAPITAL = 1,75,00,000 + 85,86,900 + 1,47,000
= 2,62,33,900Rs.

MANUFACTURE OF DMA


- WORKING CAPITAL:

A) ADMINISTRATIVE EXPENSES:
Position People required Salary (lakhs./annum)
Total
(lakhs./annum)
General Manager 1 12 12.0
Assistant Manager 2 7 14.0
Engineers 3 3 9.0
Chemists 1 2 2.0
Plant Operators 30 1.5 45.0
Typists 2 0.8 1.6
Clerk 2 1.0 2.0
Accountant 1 1.5 1.5
Receptionist 1 1 1.0
Store Keeper 3 1 3.0
Unskilled workers 20 0.8 0.8
Watchmen 3 0.8 2.4
Drivers 3 0.8 2.4
TOTAL = 96,80,000 RS.
MANUFACTURE OF DMA


B) RAW MATERIAL COST:

CHEMICAL QUANTITY(Kg.) RATE PER Kg. TOTAL COST
(Rs.)
METHANOL 52,64,304 32 16,84,57,728
ANILINE 34,75,964 25 6,43,13,852
CATALYST 12500 45.75 32,52,000
TOTAL COST 23,27,81,580

C) UTILITIES COST:
UTILITIES COST PER YEAR
(IN Lakhs)
ELECTRICITY 15
COOLING WATER 7.5
STEAM 10
TOTAL COST 32.5

TOTAL COST OF WORKING CAPITAL = 23,27,81,580 + 96,80,000 + 32,50,000
= 24,57,11,580Rs.

TOTAL INVESTMENT = FIXED CAPITAL + WORKING CAPITAL
= 2,62,33,900 + 24,57,11,580
= 27,19,45,480Rs.
MANUFACTURE OF DMA


SELLING PRICE OF PRODUCT (DMA):

Production per day of DMA = 100tonn = 100000 kg
Cost per kg = 95Rs.

- Selling price per annum = 100000 x 95 x 300
= 13,50,00,000 Rs.

- Net profit = selling price total investment
= 28,50,00,000 27,19,45,480
= 1,30,54,520 Rs.

- Rate of return = net profit / total investment
= 1,30,54,520 / 27,19,45,480
= 0.048

- Profit percent = 0.048 x 100
= 4.8%

- Payback period =
Total capital investment
Gross profit

=
= 20.83 year

- Profit margin
Assuming 100% capacity utilization

Profit margin =

100
= 4.83%

MANUFACTURE OF DMA


CHAPTER 14
CONCLUSION
&
REFERENCES

MANUFACTURE OF DMA


CONCLUSION

This report gives a pre-preliminary feasibility study of a plant manufacturing of Dimethyl
aniline to be set up in India. Alkylation of aniline is the manufacturing process selected which
gives good yield and purity.
As a part of this report, the basic Mass Balance, Energy Balance, Process and
Instrumentation, Process Designing was included to give an analysis of the feasibility of the
project.
The estimated cost of the project was found to be Rs. 27.18 Crores. A payback period of
20.83 yrs is expected with a return on investment (ROI) of 4.8 %, assuming 100% capacity
utilization. By seeing the payback period and the profits, it seems that the project is economically
attractive and profitable.
In this analysis several assumptions have been made including that of an ideal market
with all that is produced being sold. Also, product prices have been assumed to remain constant.
To get a clearer picture a detailed feasibility report has to be done. However the
preliminary study does provide sufficient reason to conduct a detailed analysis to come at exact
figures.
This pre-preliminary feasibility report thus calls for and justifies the need for a more
detailed and rigorous analysis of the project in terms of the market demand for the product, the
actual yields from the process and the saleability of the product.

MANUFACTURE OF DMA


Bibliography
- ROBERT THORNTON MORRISON AND ROBERT NEILSON BOYD,ORGANIC
CHEMISTRY,SIXTH EDITION.
- JAMES G. SPEIGHT, CHEMICAL AND PROCESS DESIGN HANDBOOK.
- Shreves Chemical process Industries
- Perrys Chemical Engineers Handbook, Robert H. Perry, Don W. Green 7th Edition.
- M. V. Joshi & V. V. Mahajani, Process Equipment Design
- Beigler, Grossman and Westerberg, Systematic Methods of Chemical Process Design.
- R.K.Sinnott, Coulson & Richardson, Chemical Engineering Design - Volume 6.

Webliography
- www.google.com
- www.wikipedia.com
- www.britannica.com
- www.compositesaustralia.com
- toxnet.nlm.nih.gov
- ScienceLab.com

Dimethyl Aniline

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