Project Title

Production of
Toluene
Diisocyanate

1
Designing Team
Project Advisor:
 Prof Dr Mehmood Ahmed

Team members:
 CH M. Adnan Farooq
 Arshad Mehmood
 Amir Usman
 Liaqat Ali
 Saqib Islam

2
Introduction to Toluene
Diisocyanate
 Synonyms for Toluene Diisocyanate
 Introduction
 History
 Properties of TDI
 Safety and storage
 Uses

3
Synonyms for Toluene
Diisocyanate

TDI, Methylphenylene isocyanate

Toluene diisocyanate, Methyl-m-phenylene isocyanate
Benzene 1,3 iisocyanatomethyl, Toluene-1, 3-diisocyanate
Isocyanic acid Diisocyanates
Methyl phenylene ester Diisocyanatotoluene,
Methyl-m-phenylene ester Tolylene diisocyanate,
Methyl-meta-phenylene Tolylene isocyanate
Diisocyanate

4
Introduction
 Toluene Diisocyanate (TDI) is a member of the isocyanate family and
has the two most commonly available functionalities of structural
formula as shown below.

 Although there are many commercially available isomer mixtures but

the 80/20 and 65/35 isomer ratio mixtures of 2,4/2,6 TDI are of the
most importance.
 The above shown isomers differ in two ways.
1. The first reason is affiliated with the structure itself.
2. The second reason relates to the use of these isomers in
different applications.

5
 Toluene
crystalization Nitration crystalization

Mixture of mononitro-Toluene
isomers

Ortho- Nitration Para-nitrotoluene

nitrotoluene
80% 2,4 Dinitro-Toluene
Nitration Nitration
20% 2,6 Dinitro-Toluene

65% 2,4 dinotro-toluene Reduce

phosgenation 2,4 Dinitrotoluene
35% 2,6 dinitro-toluene
Reduce
Reduce Toluene Diisocyanate
phosgenation
phosgenation 80/20 isomer mixture

Toluene diisocyanate Toluene 2,4

65/35 isomer mixture Diisocyanate

The above diagram represents the basic steps involved in the

control of isomer ratio of TDI.
6
History
 The history of isocyanates is very strongly related to it use
and goes hand in hand with evolution of the polymeric foams.
 In Pakistan TDI is in much greater use than MDI as is the
case with most of the Asian countries. However the total
demand in the country is met by imports and no local
production is made.
 A major part of world's isocyanate production is shared by
the two isocyanates namely TDl and MDI. The production
capacity now stands over 2.5 million tones and a growth rate
of 3% per annum is forecast,
 Another reason for the slow growth of TDI market is its
hazardous nature.

7
General Physical and Chemical
Properties of TDI
 Physical state.
At room temperature liquid or crystals.

 Color.
Colorless to pale yellow.

 Odor.
Distinct pungent, sweet, fruity, odor detectable around
0.7mg/m3.

 Auto ignition temperature.

620°C.
8
General Physical and Chemical
Properties of TDI
 Explosion limits.
For 2,4 TDI Concentration (% v/v).
Lower 0.9%.
Upper 9.5%.
 Flash point
Open cup 135 (2,4-TDI)
132 (commercial mixture-2, 4-,
2,6-isomers)
Closed cup 127(2,4-TDI) 

9
General Physical and Chemical
Properties of TDI
Boiling point
At 760mmHg 251° C
At 10mmHg 120° C for 2,4-TDI
121° C for commercial mixture

 Density (g/cm3)
2,4-TDI 1.22g/mL 25/15
Commercial mixture (2,4-, 2,6-isomers)
Vapor pressure
Pa at 20° C: 1.3
Relative vapor density
6.0 10
Storage
 Optimal storage conditions of TDI dictate that the Storage of
toluene diisocyanate in polyethylene containers is hazardous
due to absorption of water through the plastic.
 Containers should remain closed as much as possible.
 Inside storage should be in a dry, fire-resistant, well-
ventilated storage room.
 If stored in tanks, it should be blanketed with inert gas, such
as nitrogen, or with dry air.
 Optimum Storage Temperature is 75 to 100 degrees F.
 TDI should be stored separate from amines, alcohols, bases
and acids.
 Apart from the above stated there are several useful
discussions of isocyanate toxicity and handling available,
and should be consulted before undertaking work with these
chemicals.

11
Safety
 All isocyanates are potentially hazardous and should be
handled with proper safety procedures.
 TDI is not very dangerous if it comes into contact with the
skin however it does cause lacerations, but the primary
health hazard related to TDI is the respiratory irritation it
causes.
 Spills of isocyanate should be decontaminated promptly with
care, i.e. using respiratory protection and rubber or PVC
protection of the skin. Both solid absorbents and liquid
formulation are used to neutralize isocyanate spills.
 The level of isocyanate detectable in air by odor is from 0.1-
1ppm. This is considerably above the current federal
standards, which require that the employees should not be
exposed to more than 0.02ppm ceiling limit.

12
Safety
 NIOSH has recommended a max exposure for all
diisocyanates of a 10-minute ceiling of 20 ppb and a time
weighted average for a 10-hour day/40 hour week of 5 ppb.
The micro g/m3 equivalents of these for several isocyanates
are given in the following table.

13
Safety
TWA Ceiling
Diisocyanate
5ppb 20ppb
Toluene diisocyanate(TDI) 35 140
Diphenylymethane diisocyanate 50 200

Hexamethylene diisocyanate(HDI)
45 140

Isophorone diisocyanate(IPDI) 35 180

Dicyclohexylmethane diisocyanate
(H-MDI) 55 210

14
Safety
 There is enough data available on TDI to grade it as a very
toxic material and very hazardous when inhaled so care must
be taken that the concentration of TDI in the general working
area of a plant do not rise above the stipulated safe limits.

15
Safety
 For the safety of the people working at a TDI plant the
following merit is designed.

 Workers exposed to airborne isocyanate merit:

1. Pre-employment examination.
2. Periodic examination routinely.
3. Re-examination on return to work following sickness
absence.
4. Instruction in the first-aid treatment of accidental
exposures and Contamination.

16
Uses
 Toluene diisocyanates are reactive intermediates that are
used in combination with polyether and polyester polyols to
produce polyurethane products.
 Polyurethane coatings represent the second largest market
for toluene diisocyanates. Toluene diisocyanates are also
used in the production of polyurethane elastomeric casting
systems, adhesives, sealants and other limited uses.
 The rigid PU foam is also used in for refrigerator insulation;
interior paneling, wing tips, insulation, radar covers etc. of air
crafts; car bumpers, instrument panels, steering wheels, roof
insulation of automobiles; and finally for a number of strategic
applications for naval equipment.

17
Manufacturing
Processes for TDI

18
Manufacturing Processes for
TDI
Laboratory Method of Preparation
Industrial Method of preparation
process variations in the production
Process Description

19
 Laboratory Methods of
Preparation
Many methods for the preparation of isocyanates have been
reported. These can conveniently be classified according to the
reaction involved, the most important and common methods
involve the reaction of an amine, or its salt and phosgene (cocl2).
Curtius, Hofmann, or Lossens rearrangement and double
decomposition reactions have also been widely used.
Phosgene reaction
In 1884 Hents’chel obtained an isocyanate by the reaction between
phosgene and a salt of a primary amine. Several modification of
this reaction have since been developed.

20
Curtius, Lossens and Hofmann rearrangement
reaction
Next to the phosgenation reaction the reaction that is most
commonly used is the Curtius rearrangement of an acid azide in a
neutral solvent. it was first developed by Schroeter, who prepared
several isocyanates in good yield by treating an acid chloride with
sodium azide and by warming the resulting solution in benzene.
-N2
R C N3 R C N RNCO
O O
 The Hofmann rearrangement and the Lossen’s rearrangement of
hydroxymic acids have been similarly used though less widely
NaOx
R C NH3 R C N RNCO
O O
-H2O
R C NHOH R C N RNCO
O O
21
Laboratory Methods of
Preparation
Metathesis (double decomposition).

 Wutz and more recently Slotta and Lorenz used the reaction
between organic halides and sulfates, and a salt of cyanic
acid for the preparation of alkyl isocyanates.

R2SO4 + 2KCNO 2RCNO + K2SO4

 Preparation from isocyanate derivatives.

 Preparation from isocyanic acid.
 Special isocyanate preparation.

22
Industrial Methods of
Preparation
 Due to economical constraints the only method that has been
so far successfully employed in the industry, is the
phosgenation method. Which employs phosgene to reduce
the desired amine or diamine to isocyanate.
 Another reason for this method to be employed industrially is
that this method is very suitable for the generation of high
boiling isocyanates and also for organic isocyanates.
 There has been much research on the phosgenation reaction
for the production of isocyanates and many process
variations have evolved however the basic reaction chemistry
remains the same.

23
Industrial Methods of
Preparation
 The basic chemistry of the phosgenation reaction to produce
TDI is given in the form of an equation below

CH3 CH3
NO2
H2SO4
+ HNO3

NO2

CH4 + O2 CO + H2
CH3 CH3
Cl2
NH2 NCO
COCl2 +
NH2 NCO

24
 Industrial Methods of
Preparation
 The same phosgenation reaction can be used for
the production of aliphatic isocyanates the basic
reaction equation being as follows.
RNH2HCl
COCl2
RNH2
SOLVENT 100-200c
RNH2 + COCl2 -20 TO 80C
(RNHCOCl + HCl) RNCO + 2HCL
RNH2
RNH2

RNHCONHR

25
Process Description,
Block and Process
Flow Diagram

26
 Process FlowChart

Start
96.7% Pure TDI
(486.73 Kg/hr of TDI)
Recycle Solvent

Section 100 Phosgenation

125 deg C, 135 PSI Section 400 TDI Resicue (By-Product)
Yield:85.%
(Basic upon TDA feed) Evaporation (89.05 Kg/hr)

Section 200 Section 300

Degassing Fractionation

Gases

Section 500
Separation of By-Product
HCl 3% wt
The section shown
Gases
red is not discussed
or designed
CoCl2 for recycle
27
 18

10 10 19
7 F-210
7 REACTION PHASE
SEPARATOR

9
18
PURE SOLVENT 11 12
STORAGE TANK 9 F-211
11
14
L-113 E-113 SECONDARY 14
SEPARATOR
TOLUENE
DIAMINE E-312
REACTOR 13
STORAGE TANK 8
R-110
13
1 15
E-112
O- F-311 17
DICHLOROBENZE 6
NE STORAGE Distillation
TANK
5
column 16
E-311 D-310 16
4 5

3
2
2 3 E-111 HEAT
EXCHANGER PHOEGENE
L-111 21
L-112 STORAGE TANK
E-313

20 20
24
E-411 24

V-410
E-412
22
23 23 Heater

28
Legend for Process Flow
Diagram
 The no written in black represent the line no
 The numbers written in red represent the material
balance points
 The codes for the equipment are written by their side are
as follows
Reactor (Phosgenator) = R-110
Feed heaters = E-111, E-112, E-113
Rxn phase separator = F - 210
Flash separator = F - 211
Fractionator = E - 310
Pre-heater = E – 311
Condensor = E – 312
Reboiler = E - 313
29
Legend for Process Flow
Diagram
gas liquid separator = F – 314
Evaporator = V – 410
 Saturated steam is used as heating utility in the
heat exchangers and cooling water is used as
cooling utility.
 The temp, pressure and other conditions of the
material in each line is stated in the design details
of each of the equipment they are handled in.

30
Process Description
 TDA solution (20%) is mixed with the recovered
impure solvent and introduced into the reactor
through a nozzle.
 Liquid phosgene heated to an elevated temp is
introduced into the reactor through a sparger.
 The reactor temp and pressure is maintained at
1350c and 125 psi.
 The reaction being exothermic evolves heat which
completely used for the vaporization of the
phosgene and HCl.
 The reaction mixture forms a dispersion which is
transferred to the primary separator by the help of a
small difference of pressure.
 The separators serve to separate all the unreacted
phosgene and the HCl formed by the reaction.
 The final recovery of the TDI is done by fractional
distillation and consequently evaporating the crude
TDI mixture. 31
Material and Energy
Balance

32
Material Balance
From TDA From DLB To From CoCl2 To E-213 or
Component
Storage Storage E-111 Storage R-110

TDA 4086 4086

DLB 16344 16344 18063.5

CoCl
2 25140 10.86

TDI 28.9

HCL

Res

33
Material Balance
To To Section 500 To To Section 500 To
Component
D-210 or from D-210 D-211 or from D-211 D-310

TDA

DLB 34711 3609.4 3110116 295 30806.6

CoCl
2 18644 12820 5824 5805.8 18.2

TDI 5000 45.012 4987.7 26 4961.7

HCL 4675 4349.1 325.9 325.9

Res 643.3 643.3 643.3

34
Material Balance
To
To E-312 To Section To TDI To V-410
Component Residue
or D-314 500 Storage Or E-313
Storage

TDA 12712.5

DLB 30776 30.6 30.6

CoCl
2 18.2 7.34

TDI 49.6 20.7 62.08 4850 4912.08

HCL

Residue 643.3 643.3

35
Energy Balance
Heat Load T or ΔT
Unit Unit Name Utility
Kg/hr C

E-111 TDA solution Heater 9.8x105 105-145 Saturated Steam

E-112 CoCl2 Heater 7.5x105 65-90 Saturated Steam

E-113 Recycle Solvent Heater 2.5x105 165-190 Saturated Steam

Column feed
E-311 2.7x106 115-190 Saturated Steam
Pre-heater

E-312 Reflux Condenser 3.6x107 165 Cooling Water

E-313 Re-boiler 1.9x107 252-22 Thermal Fluid

V-410 Evaporator 1.5x106 252-22-270 Thermal Fluid

Product
E-411 1.3x106 270-252-22 Cooling Water
Condenser
36
Separator Design

37
Separator Design
 Selection of a separator
 Design principals
 Designing procedure
 Final selection
 Mechanical specifications

38
Selection of a Separator
 Basic objectives that dictate the selection procedure.
1. Separate the gases from the liquid as efficiently as
possible.
2. Minimize the liquid carryover and maximize the liquid in the
separator.
 There are many types of commercial separators available
i.e.
Vertical separators.
Horizontal separators.
Spherical separators.
 A basic comparison for these different types of separators
and a preliminary selection is given ahead.

39
 Vertical Horizontal Spherical
Function
configuration configuration configuration
For small
For low gas For high gas leases at
Usage
liquid ratio liquid ratio moderate
pressure
Large fluid Large gas Capacity rated
Capacity
capacity capacity low
Handling
foreign Rated no 1 Rated no 2 Rated no 3
materials
Separation
Rated no 2 Rated no 1 Rated no 3
efficiency
Maintenance
Very difficult Accessible Average
and inspection
Coast/ unit & Average & Least &
Highest & easy
installation most difficult average
Overall ranking Rated no2 Rated no 1 Rated no3 40
Selection of a Separator
 The basic selection states the use of a horizontal
separator.
 The following factors point towards the use of a horizontal
separator.
1. Horizontal separators are more suitable for two phase
separation than any other type.
2. They can handle the highest gas liquid ratio.
3. They have larger gas capacities.
4. They are rated no1 on the bases of their efficiency.
5. They are rated no1 in relation to their maintenance and
inspection.
6. They have the lowest coast per unit.
7. The installation coast is not prohibitively high.

41
Design Assumptions
The basic assumptions of design are as follows.
 No foaming takes place or the retention time is drastically
increased.
 The cloud point of the liquid and the hydrate point of the gas
are below the operating temperature.
 The smallest separable liquid drops are spherical ones
having a minimum diameter of 100microns.
The above assumptions are necessary owing to the reason that
otherwise the design equation become too complex without
any effective improvement in the design accuracy.

42
Design Principles
 The liquid droplets that settle through the gas fall to the liquid
interface against the drag of the rising gas hence considering
that the drop falls with terminal velocity imply

Fg  Fd
 Using respective expressions for drag force and gravity force
an expression for the droplet settling velocity is found that is

1

 l   g  d m 
2

U sv  0.01186   

 g  C
  d 

43
Design Principles
 The volumetric flow rate of gas processed by a separator is
directly related to its cross-sectional area and the max
allowable gas velocity. Hence an equation for the max
allowable gas velocity can be derived from
Qg  AgU g
 Using mathematical expressions for Qg and Ag an expression
for velocity comes out as follows

 
U g  0.327Qg 
 TZ p 
 1 A 
  g 

44
Design Principles
 For a vertical separator the upward gas velocity should not
exceed the downward terminal velocity of liquid. Hence the
final design equation achieved is.
1

  l   g  d m 
2

D  437.496Qg 
2 TZ 
  
 p   g  C
  d 

 The above equation combined with the liquid capacity
constraint equation.

D 2 H  2200.16Ql t
are used to calculate the minimum allowable height and
diameter of a separator for a vertical separator.

45
Design Principles
 For a horizontal separator the basic design equations vary
slightly owing to a difference in the area available for gas flow
and the parabolic path of a settling droplet. The gas and liquid
and gas capacity constraint equations for a horizontal separator
are as follows 1

 g  d m 
2

LD  422Qg  TZ  
   
 p    l   g  C 
  d 

liquid capacity equation

D 2l  1833.5 Ql t R

Gas capacity equation

46
Sizing of a Vertical Separator
The general procedure for sizing a vertical separator employs
the following points.
 Minimum allowable diameter is calculated from the equation
given previously.
 For diameters larger than the minimum the height of the
column is calculated from the liquid capacity equation(for
vertical sepa).
 The seem to seem length for each combination of D and H is
determined using the following equations.
,
H  76 H  D  40
Ls  for D  36in , Ls  for D  36in
12 12

47
Sizing of a Vertical Separator
 All the different combination of diameter and seem to seem
length are possible solutions of the design which give a
slenderness ratio between 3-5

48
Sizing of a Horizontal Separator
 The sizing procedure for a horizontal separator is
somewhat complex however the following points are
followed
1. Assume various values for the dia and calculate the
effective length of the separator using the gas capacity
equation and determine the seem to seem length from
D
Ls  Lg  ft
12
2. For each of the assumed values of D, determine the
effective length and the seem to seem length from the
liquid capacity equation, from

4
Ls  Lo ft
3

49
Sizing of a Horizontal Separator
 For each of the values of D used, compare the values of the
gas effective length and the liquid effective length to
determine whether gas constraint or liquid constraint governs
the design, the larger one will be the governing dimension.
 Select reasonable combination of D and L such that the
slenderness ratio is in the range of 3-5.

50
Separator Diagram
Gas outlet

Feed inlet
Assumed liquid level

Separator head Vortex breaker

51
Design Summary
1

 l   g  d m 
2

D2 
 437.496Qg  TZ 
   
 p   g  C 
  d 

Calculation of gas flow rate

yields Q g  12.214  ft 3 sec 
Calculation of compressibility factor using following EQ
1 4.9340  h  0.08664Pr
Z     where h 
1 h Tr
1.5
 1  h  ZTr
Z(phosgene) = 0.8764 yields Z=0.624
Calculation of gas and liquid densities

yields g  1 .1681  lb ft 3

and  l  75.01  lb ft 3  52
Design Summary
 Calculation of drag coefficient from the following sequence of
equations and employing an iterative technique.

3 24
Cd  0.34  
Re 0.5 Re
 g d mU
Re  0.0049
g
1

 l   g  d m 
2

U  0.01186   
 g  C 

  d 
yields drag coefficient = 0.4016
 Values for temperature and pressure are provided by the
process description as being
pressure = 110 psi
53
Temperature = 275 degree F
Design Summary
 All the variables once calculated were entered into the main
design equation and the minimum allowable diameter is
calculated
which yields D=2.556 ft
 Once the min allowable diameter was calculated the lquid
capacity equation was used to find out the min height and the
seem to seem length which yielded
H=19.24 ft
L=25.56 ft
 Values of diameter greater than the minimum value were used
to gain sets of D and L and to calculate the slenderness ratio
which yielded.
minimum affordable dia = 40.67 in where L/D=5.0
maximum affordable length= 17.67 ft
maximum affordable dia= 55.17 in where L/D=3.0
minimum affordable length= 13.89 ft
54
Mechanical Specifications for
Design
 There are many mechanical design specifications required for
the complete fabrication of a separator but the knowledge of
the entire field is out of our jurisdiction. However a slight
knowledge should be gathered for the primary coat estimation
of the separator and thus the final selection of the separator
ideal for use in a specific application.
 Note that however the final selection of a separator is in the
hands of a mechanical engineer. Since only he can the exact
estimation of the total capital investment on this particular
piece of equipment.

55
Specification Sheet
 Identification
item – separator
item no – F - 210
no required – 1
 Function
separation of gas liquid mixture from the reactor effluent
 Operation
continuous
 Design data
minimum affordable dia = 1.033m where L/D=5.0
maximum affordable length= 5.39m
maximum affordable dia= 1.41m where L/D=3.0
minimum affordable length= 4.23m

56
Specification sheet
 Identification
item – separator
item no – F - 210
no required – 1
 Function
separation of gas liquid mixture from the reactor effluent
 Operation
continuous
 Design data
maximum affordable dia = 1.37m where L/D=3.0
minimum affordable length= 4.11m
minimum affordable dia= 1.02m where L/D=5.0
maximum affordable length= 5.18m

57