Production of Fluorescent

Backbone Molecule
CME 431-1 Group 5
Bradley Siefker, RJ Schratz, David Devlin, Trevor Langton
April 26, 2017
 Table 1: Stream Table
Stream 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Solids
PCl5 DCPM Bottoms, Distillate, POCl3, DCPM, Nickle Magnectic
Chlorine PCl3 Benzophenone TPE Reator Chlorine Separation DPCM
Description Reactor Reactor Distillation Distillation After Heat After Heat Complex Separation
Make Up Feed Feed Effluent Recycle Screen Recycle
Effluent Effluent Column Column Exchanger Exchanger Recycle Product
Out
Pressure (psia) 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7
Temperature (C) 25 25 50 25 220 305 105.8 25 25 25 25 25 25 25 25
Vapor Fraction 1 0 0 0 0.53 0 0 0 0 0 0 0 0 0 0
Liquid Fraction 0 1 1 1 0.47 1 1 1 1 1 1 1 1 1 1
Total Flow (kmol/h) Trace 6.22 6.22 6.22 12.45 6.22 6.22 6.22 6.22 6.28 9.46 6.22 3.17 3.11 0.06
Component Flow Rates
(kmol/h)
Cl2 Trace - - - - - - - - - - 6.22 - - -
PCl3 - 6.22 - - - - - - - - - - - - -
PCl5 - - 6.22 - - - - - - - - - - - -
Benzophenone - - - 6.22 - - - - - - - - - - -
DPCM - - - - 6.22 6.22 - - 6.22 - 0.06 - 0.06 - 0.06
Phosphorus(V) Oxychloride - - - - 6.22 - 6.22 6.22 - - - - - - -
Nickel-Glyme Complex - - - - - - - - - 6.28 6.28 - - - -
TPE - - - - - - - - - - 3.11 - 3.11 3.11 -
Process Narrative

Gaseous chlorine (Cl2) is delivered via railcar at 150 psia to a liquid atomization reactor,
but chlorine gas from a future process is recycled back as the primary source. Liquid phosphorus
trichloride (PCl 3) is atomized with nitrogen gas and added to the reactor at an equimolar rate
with chlorine gas. Solid phosphorus pentachloride (PCl 5) precipitates from the droplet and vapor
reactions and exits bottom of the reactor.
Solid PCl5 exits the reactor vessel and is transported via screw conveyor into a second
reactor, then mixed with benzophenone. The reactor vessel raises the temperature of the reactants
to 220oC. The PCl5 and benzophenone melt inside and react to form diphenyldichloromethane
(DPCM) and a byproduct of phosphorous oxychloride (POCl 3) [1]. Reactant vapors formed
during this step are condensed to ensure no loss of reagents and ensure no hazardous material
may occur. Benzophenone and PCl 5 are entirely consumed by this reaction and DPCM and
POCl3 exit in the reactor effluent.
The products are fed to a distillation column to separate the POCl 3 and DPCM. The
overhead product from the distillation column contains POCl3 at purity greater than 99.99%. The
gaseous POCl3 is cooled in a concentric tube heat exchanger to 25 oC where it can be collected.
The POCl3 will be sold as a byproduct. The bottoms product contains greater than 99% DPCM
which is fed to a concentric tube heat exchanger to reduce the temperature to 25 oC and is fed into
an equilibrium reactor at 14.7 psia.
Nickel chloride powder dissolved in glyme is fed into the equilibrium reactor equimolar
to the DPCM and catalyzes the reaction [2]. Conversations with Dr. Mark Masthay and Dr.
Vladimir Benin [3] suggest chlorine gas as product of the reaction. Chlorine gas exits the reactor
and is recycled to the phosphorous pentachloride reaction vessel. The reaction yields solid TPE
which exits the reactor with trace amounts of DPCM and the nickel glyme complex. The TPE
and DPCM mixture is fed into a magnetic solids screen, also at 25C and 14.7 psia, where the
nickel glyme complex is recycled. TPE is separated from the DPCM by a centrifuge and DPCM
is recycled back to the equilibrium reactor. Solid TPE from the reactor effluent is packaged for
sale at a purity greater than 99.5%.
 Equipment Design Progress Table

Detailed
Unit Energy Materials of
Unit Mass Sizing Costing
ID Balances Construction
Balances
Spray Drying Complete Complete Complete
R1 Complete Complete
Reactor
DPCM Production Complete Complete Complete
R2 Complete Complete
Reactor
Catalytic TPE Complete Complete Complete
R3 Complete Complete
Production Reactor

Distillation Column D1 Complete Complete Complete Complete Complete

Magnetic Separator S1 Complete Complete Complete Complete Complete

Centrifuge S2 Complete Complete Complete Complete Complete

Phosphorous
Oxychloride Heat H1 Complete Complete Complete Complete Complete
Exchanger
DPCM Heat Complete Complete Complete Complete Complete
H2
Exchanger
Equipment Design Audit Sheets
Group #:_____5_____ Grading Iteration:_____3___________

Team Member with Primary Responsibility:_____David Devlin__________

Unit Op Name: _________Phosphorus Pentachloride Reactor_____________

2
PCl3
12
Chlorine Recycle
1
Cl2
1

Cooling Duty
-351 MJ/h

3
PCl5

Stream 1 2 3 12
Chlorine PCl5 Reactor Chlorine
Description PCl3 Feed Recycle
Feed Effluent
Pressure (psia) 14.7 14.7 14.7 14.7
Temperature (C) 25 25 50 25
Vapor Fraction 1 0 0 1
Liquid Fraction 0 1 1 0
Total Flow (kmol/h) Trace 6.22 6.22 6.22
Enthalpy (MJ/h) 0 -1886 -2237 0
Component Flow Rates
(kmol/h)
Cl2 Trace - - 6.22
PCl3 - 6.22 - -
PCl5 - - 6.22 -
Group #:_____5_____ Grading Iteration:_____3___________

Team Member with Primary Responsibility:_______RJ Schratz_____________

Unit Op Name: ________________DPCM Reactor_________________________

Unit Diagram and stream table

Cooling Duty
295 MJ/h

Heat Duty
930 MJ/h

Stream 3 4 5

PCl5 Reactor Benzophenone DCPM Reactor

Description
Effluent Feed Effluent

Pressure (psia) 14.7 14.7 14.7

Temperature (C) 50 25 220
Vapor Fraction 0 0 0.53
Liquid Fraction 1 1 0.47
Total Flow (kmol/h) 6.22 6.22 12.45
Enthalpy (MJ/h) -2971 -125 -2166
Component Flow Rates
(kmol/h)
PCl5 6.22 - -
Benzophenone - 6.22 -
DPCM - - 6.22
Phosphorus(V)
Oxychloride - - 6.22
Group #:__5________ Grading Iteration:___3_____________

Team Member with Primary Responsibility:__Bradley Siefker_____________________

Unit Op Name: ___Packed Distillation Column__________________________________

Unit Diagram and stream table

440 MJ/hr

308 MJ/hr

Stream 5 6 7 - - Net Balances

Bottoms, Distillate,
DPCM/POCl3
Description Distillation Distillation Condenser Reboiler
Mixture
Column Column
Pressure (psia) 14.7 14.7 14.7 14.7 14.7 -
Temperature (C) 220 305 105.8 - - -
Vapor Fraction 0.53 0 0 0 0 -
Liquid Fraction 0.47 1 1 1 1 -
Total Flow (kmol/h) 12.44 6.22 6.22 0.00 0.00 0.00
Enthalpy (MJ/hr) -2359 1039 -3534 308 -444 0
Component Flow Rates
(kmol/h)
DPCM 6.22 6.212 0.008 - - 0.000
Phosphorus(V) Oxychloride 6.22 0.008 6.212 - - 0.000
Group #:____5______ Grading Iteration:_______3_________

Team Member with Primary Responsibility:____Trevor Langton___________________

Unit Op Name: __TPE Reactor______________________________

Unit Diagram and stream table

Stream 9 10 11 12 15
DCPM, After
Nickel TPE Reactor Chlorine DPCM
Description Heat
Comp Effluent Recycle Recycle
Exchanger
Pressure (psia) 14.7 14.7 14.7 14.7 14.7
Temperature (C) 25 25 25 25 25
Vapor Fraction 0 0 0 1 0
Liquid Fraction 1 0 0 0 1
Enthalpy (MJ/h) 353 16 1038 0 3
Total Flow (kmol/h) 6.22 6.28 15.67 6.22 0.06
Component Flow Rates
(kmol/h)
DPCM 6.22 - 0.06 - 0.06
Phosphorus(V) Oxychloride - - - - -
Nickel-Glyme Complex - 6.28 6.28 - -
Chlorine Gas - - - - -
TPE - - 3.11 - -
Group #:____5______ Grading Iteration:_______2_________

Team Member with Primary Responsibility:____David Devlin___________________

Unit Op Name: __Magnetic Separator______________________________

Unit Diagram and stream table

10
Nickel Complex
Recycke

Stream 10 11 13
TPE Magnetic
Glyme
Description Reactor Separation
Recycle
Effluent Product
Pressure (psia) 14.7 14.7 14.7
Temperature (C) 25 25 25
Vapor Fraction 0 0 0
Liquid Fraction 1 1 1
Total Flow (kmol/h) 6.28 9.45 3.17
Enthalpy (MJ/h) 16.50 15.67 -0.83
Component Flow Rates
(kmol/h)
DPCM - 0.06 0.06
Nickel-Glyme Complex 6.28 6.28 -
TPE - 3.11 3.11
Group #:_____5_____ Grading Iteration:_____2___________

Team Member with Primary Responsibility:_______RJ Schratz_____________

Unit Op Name: ________________Solid Separator_________________________

Unit Diagram and stream table

Stream 13 14 15
Solids
Magnetic
Separation DPCM
Description Separation
Screen Recycle
Product
Out
Pressure (psia) 14.7 14.7 14.7
Temperature (C) 25 25 25
Vapor Fraction 0 0 0
Liquid Fraction 1 1 1
Total Flow (kmol/h) 3.17 3.11 0.06
Enthalpy (MJ/h) -0.083 -3.453 3.37
Component Flow Rates
(kmol/h)
DPCM 0.06 - 0.06
TPE 3.11 3.11 -
Individual Heat Exchangers Audit Sheet Streams

Hot Streams To be completed by students.

Heat Hot Stream Individual heat transfer

Exchanger ID coefficient
Stream ID Inlet T Outlet T Phase F (mol/s) Provide One Q (kW) Calculation
( )
(C) (C) FCp (kW/K) Method
(kJ/mol) (kJ/mol)
HX1 H1 220 106 V to L 1.78 - 46 - 81.9 1.75 Film HTC
HX2a H2a 136.7 105.8 V 1.73 0.159 - -- 4.96 0.05 Nusselt
HX2b H2b 105.8 105.8 V to L 1.73 - 68.6 - 118.7 2.12 Film HTC
HX3 H3 105 35 L 1.73 0.257 - - 18.0 0.138 Nusselt
HX4 H4 305 35 L 1.73 0.681 - - 183.9 1.23 Nusselt
HX5 H5 >315 >315 V 0.000278 - - 386700 123.3 - -

Cold Streams To be completed by students.

Heat Exchanger Cold Stream Individual heat transfer

ID coefficient
Stream ID Inlet T Outlet T Phase F (mol/s) Provide One Q (kW) Calculation
( )
(C) (C) FCp (kW/K) (kJ/mol) Method
(kJ/mol)
HX1 C1 25 40 L 72.7 5.47 - - 81.9 0.313 Nusselt
HX2a C2a 25 40 L 4.38 0.330 - - 4.96 2.29 Nusselt
HX2b C2b 25 40 L 105 7.91 - - 118.7 0.39 Nusselt
HX3 C3 25 40 L 15.9 1.20 - - 18.0 0.136 Nusselt
HX4 C4 25 25 S 1.73 - - 106 183.9 - -
HX5 C5 305 305 L to V 1.36 - 90.4 - 123.3 - -
Heat Exchanger Area Calculation Summary To be completed by students.

Heat HX Type Q Matl of , , , , LMTD A (m2)

Exchanger ID (kW) Construct. () () () Correction
( ) ( ) ( ) ( )
Factor

HX1 Shell & 81.9 Hastelloy C276 1.75 0.313 0.0389 0.34 220-40 106-25 119 1.0 2.00
Tube
HX2a Concentric 4.9 Hastelloy C276 0.05 0.341 5.57*10-5 0.04 136-40 105-25 86.0 1.0 1.41
Tube
HX2b Shell & 124 Hastelloy C276 2.12 0.340 0.059 0.38 105-40 105-25 72.2 1.0 4.53
Tube
HX3 Shell & 18.6 Monel 400 0.138 0.136 0.00971 0.08 105-40 35-25 29.6 0.9 7.77
Tube
HX4 Rxtr 194.5 Monel 400 1.23 - 0.00971 1.07 305-25 35-25 81.0 1.0 2.23
heating
coils
HX5 Fuel Fire 123.3 Chrome/Molly - - - - - - - - -
Reboiler Tubes

Heat Exchanger Detailed Design Summary: Shell and Tube Exchangers To be completed by students.

Heat Exchanger Tube Side Shell Side

ID
# of Tubes Tube Tube Diam. Tube Pitch Tube-Side Shell Diam. (m) Shell side
Length (m) (cm) Passes passes
HX1 14 4 1.91 2.54 2 1 1
HX2b 16 6 1.91 2.54 2 1 1
HX3 22 6 1.91 2.54 2 0.5 1

Heat Exchanger Detailed Design Summary: Other Types of Exchangers To be completed by students.

Heat Exchanger ID Inner Tube Outer Tube

Material Tube Length (m) Tube Outer Diameter Material Tube Inner Diameter (cm)
(cm)
HX2a Hastelloy C276 2.3 11.4 316 Stainless 12.8
HX4 Monel 400 19 1.91 Reaction Vessel N/A
HX5 Chrome/Molly - - N/A
Equipment Design

The sizing of major unit operation systems in the production of tetraphenylethylene

(TPE) is specified by material and utility demands necessary for industrial financial analysis.
Reaction vessels were sized per reaction times. A separation system exploiting volatility
differences of the reactive intermediate dichlorodiphenylmethane (DPCM) and byproduct
phosphorous oxychloride (POCl 3) was sized. Mass and volumetric flow rates determined the
appropriate size of the magnetic and centrifugal separators. Overall heat transfer coefficients
determined sizing of all heat transfer processes.
Atomic balances of the process units are found in Appendix A. Energy balances of
process streams were provided by ChemCad simulation. Closed energy balances of all major unit
operations are given in Appendix B.

Reaction Vessels
For all reactors, the enthalpies of each stream are calculated through ChemCad
simulations. CSTR volumes are calculated by the molar flow rate ( ) multiplied by the residence
time () and molar mass and divided by density (), shown in Equation 3.

= (3)

ChemCad simulates molar masses and densities of streams [4]. API Lus method calculates
densities of mixtures in solution [4]. The API method uses component densities and correlation
factors generated by ChemCad. This method is acceptable when a species is below the critical
temperature as are components in this process. Reaction residence times are from literature
values.
Phosphorous Pentachloride Reactor
Gaseous Cl2 is fed into the reactor at 6.22 kmol/h, 25C, and 14.7 psia. It is met by liquid
PCl3 at the same temperature, pressure, and flow rate dispersed by atomization with nitrogen gas
to increase contact area and facilitate the reaction. The reaction shown in equation 4 [4] produces
solid PCl5:

3 + 2 5 (4)
Minimizing the Gibbs free energy of the products in ChemCad yields a conversion over 99% [4],
with no side products [5]. The heat duty of the reactor is 351 MJ/h of heat to be removed.
 Literature suggests the residence time of the reaction is 0.5 hours [5]. The flow rate of
PCl5 is 6.22 kmol/h with a density of 1830 kg/m3, and so the volume of the phosphorous
pentachloride reactor is 0.360 m3. The reactor is 1 meter tall and 0.68 meters in diameter.
The primary criteria of material selection of the phosphorous pentachloride reactor are
adequate corrosion resistance to the materials in the reactor and the cooling water jacketing the
reactor. Stainless steel is subject to pitting in warm chloride environments above 50 C [6].
Monel 400 provides the corrosion resistance required for the process.
Reactor design heuristics suggest 2 mm of corrosion allowance for a non-pressurized
reaction vessel. Vessel walls 3/16 in thick provide 2 mm of corrosion allowance and an
additional 1.76 mm for vessel strength.
A cooling jacket removes 351 MJ/hr (97.5 kW) of heat to maintain reactor temperature at
50 C. The surface area of the reactor is 2.5 m2. Cooling water flows through a jacket at a
velocity of 2.5 m/s, entering at 25C and leaving 40C. The log mean temperature difference
from equation 5 below is 16.5C.

= (5)

The heat transfer coefficient of the cooling water in the jacket is 9320 W/m2K from the Nusselt
correlation in equation 6 [7].
0.027 .8 .33
= ( ) ( ) (6)

The thermal conductivity of Monel 400 is 21.8 W/mK [8]. The overall heat transfer coefficient
of the jacket is 3160 W/m2K from equation 7.
1
= (7)
ln( 2)
3 1
1 ( + )
3

129 kW of heat are removed from reactor by the cooling jacket from the general heat transfer
equation below [7].
= (8)
The heat removed is greater than the required heat removal from the reactor so the proposed
cooling jacket is sufficient for this process.

DPCM Reactor
 The second reactor generates DPCM and POCl3 by an equimolar reaction of PCl 5 and
benzophenone [9]. The liquid phase reaction occurs at 220C and 1atm within a continuously
stirred reactor. Equilibrium was simulated in ChemCad by minimizing the Gibbs free energy of
products. The equilibrium heavily favors the product, as reactant molar concentrations in the
effluent are less than 1 part per 10 million [4]. The products of the reaction are 53% vapor [4]. If
not removed, vapors would increase reactor volume by a factor of 100, as demonstrated in
Appendix H. Therefore, to reduce reactor size and thus capital costs, the vapor is condensed as it
is produced. The reactor contents have a density of 1060 kg/m3[4]. 6.22 kmol/hr of
Benzophenone flows into the reactor, which has a 4 hour residence time at 220C [9]. Assuming
a 20% allowance for vapor formation, the reactor volume is 11.0 m3.
The PCl5 and benzophenone must be melted and raised to a temperature of 220C, and
the reaction of these compounds is endothermic. Thus, 930 MJ/h of heating duty must be
provided to the reactor. To size a fuel fired reboiler, only energy demands are needed [10]. A
shell and tube heat exchanger is used to condense the vapor products by removing 295 MJ/hr of
heat. Specifications on the condenser are outlined in the heat exchanger equipment section.
Due to the presence of POCl 3, a strongly corrosive compound, steel was omitted from
consideration for reactor materials [11]. Hastelloy C276 [11] and PTFE [12] are compatible with
chemicals in the DPCM reactor. However, PTFE is only rated for temperatures up to 204C[8].
Hastelloy C276 allows for operation at high temperatures and provides sufficient corrosion
resistance. Dr. Douglas Hansen recommended use of Hastelloy C276 for vessels subjected to
highly acidic POCl3 [13].

TPE Reactor
The 35C DPCM stream is fed into the TPE CSTR with the DPCM recycle stream at a
total rate of 6.28 kmol/h. An ambient temperature nickel(II) chloride ethylene glycol dimethyl
ether complex (nickel-glyme complex) is fed into the reactor at a rate of 6.28 kmol/h as a
catalyst. The reaction forms TPE with a 99% yield over a 2 hour residence time [2]. 6.22 kmol/h
of chlorine gas are evolved and recycled back to the phosphorous pentachloride reactor at 25C
and 14.7 psi. The 25C reactor effluent contains of 3.11 kmol/h TPE, 6.28 kmol/h of the nickel-
glyme complex and 0.06 kmol/h of unreacted DPCM.
 The endothermic reaction is maintained at 25C and 14.7 psia with a heating coil. The
required heating duty of the coil is 666 MJ/hr from ChemCad stream simulation and equation 2
[4]. Heating of this reactor is achieved by heat transfer with the bottom product from the
distillation column. Specifications on the heating system for the reactor are outlined in the heat
exchanger equipment section.
Density and molar mass of the tanks contents are the same as the effluent stream in the
TPE CSTR. Equation 3 approximates reactor volume. The densities and individual volumes
needed for the total volume calculations can be found in Appendix I. this sums to a reactor
volume of 3.46 m3. The TPE reactor is constructed of glass lined stainless steel. Glass is
compatible with all reactants and products at the operating temperature and pressure. The
stainless steel is 3/16 in thick to provide necessary vessel strength.

Separation Systems
Distillation Column
The reactor effluent of DPCM and POCl 3 at 220C and 14.7 psia is separated prior to
being fed into the catalytic TPE reactor. Distillation is used due to boiling point differences in
DPCM (305C) [14] and POCl3 (105.8C) [15]. There is no azeotrope point in a ChemCad
generated vapor liquid equilibrium diagram. Vapor liquid interactions were modeled using
UNIFAC. An in-depth look at UNIFAC modeling and its implications in ChemCad can be found
in Appendix J.
An operating reflux ratio is found from iterating varying the reflux ratio, number of
stages, and feed stage and their effects on column height, feed stage, heat duty to the column,
composition and molar flow rate of distillate and bottoms product. The results of the study are
shown in Table 1 below.
Table 1: Reflux Ratio Determination
Feed Stage 2 2 3 3
Number of Stages 4 5 5 6
Reflux Ratio 1 4.66 0.5 1 2.65 0.5 0.75 1 0.5 0.68 0.75 1
Distillate Composition 0.973 0.998 0.956 0.984 0.999 0.987 0.999 1 0.992 0.999 0.999 1
Bottom Flow (kmol/hr) 6.06 6.22 5.94 6.12 6.22 6.15 6.22 6.23 6.18 6.22 6.22 6.23
Distillate Flow (kmol/hr) 6.38 6.22 6.50 6.32 6.22 6.29 6.22 6.21 6.26 6.22 6.22 6.21
Net Energy Needs (MJ/hr) 1067 2724 826 1011 1709 707 753 843 680 716 725 835
To achieve the annual production rate, distillate and bottoms flow rates must each be 6.22
kmol/h with a distillate composition greater than 0.999. 0.75 reflux ratio with a 5 stages and feed
stage on 3 meets these specifications with the lowest energy demands and number of stages.
The McCabe-Thiele method for distillation column design is applied to the vapor liquid
equilibrium diagram [16]. Known and desired feed quality, desired outlet compositions, a reflux
ratio to reduce energy demands and decrease column size, and flow rates of all streams in and
out of the column generate the various operating lines for the McCabe-Thiele method. Raffinate,
feed, and stripping section operating lines plotted on liquid vapor equilibrium diagram in Figure
2 below.

Figure 2: McCabe Thiele Analysis

The feed into the column is 12.44 kmol/h 53% vapor with a POCl3 mole fraction of 0.50.
Both the bottoms and distillate flow rate are 6.22 kmol/h. The mole fraction of DPCM in the
distillate and bottoms are 0.999 and 0.001. Table 2 below shows the slope and y intercept of the
ROL, SOL and q line.
Table 2: Column Operating Lines
Operating Line Slope Y-Intercept
Q-Line -1.12 1.06
SOL 2.24 -0.001
ROL 0.43 0.57
The McCabe-Thiele method estimated the number of separation stages at 5, the same as tested
during the determination of reflux ratio.
Standard tray spacing of 0.6096 m (2 ft.) from typical industrial applications determined
column height [16]. Figure 3 provides capacity factor for the tray distillation column.

Figure 3: Capacity Factor for Flood of Sieve Trays [16]

The capacity factor (Csb) of 0.1 m/s, liquid and vapor densities (i) of 962 and 5.06 kg/m3, and
surface tension () of POCl 3 of 25 dynes/cm2 were used to estimate a flooding velocity (uflood) of
the column [16]. Further work needs to be conducted to determine whether the surface tension of
POCl3 alone accurately predicts flooding velocity. Equation 8 gives a flooding velocity of 1.45
m/s; equation 9 approximates the sieve tray column diameter.

= C (20) .2
(8)

4
= 3600P (9)

Here, f is the fraction of the flooding velocity the column operates at, is the fraction of the area
of one downcomer in the column, R is the ideal gas constant, is the molar vapor flow rate, and
P is the system pressure [16]. Literature recommended values of these parameters are 0.75 and
0.90 respectively. The resulting column diameter is 0.254m. Due to a diameter less than 0.75 m
literature suggests implementation of a packed distillation column [16].
 Using the same values for number of trays from the McCabe-Thiele method and solution
densities a packed column with 6.0 mm glass Raschig Rings. Glass components keep cost lower
than more expensive alloys while maintaining necessary corrosion resistance. Literature suggests
sizing the column diameter to be roughly equivalent to the height of a theoretical plate (HETP)
[16]. Equations 10 -12 [16] give the approximate height, diameter, and HETP of the column.

= (10)

100
= + 0.01 (11)

= ( )( ) (12)

With an Ap of 1300 m-1, the HETP is 0.2 m, and the height the column is 1 m.
Column diameter can be found through the flooding curve in figure 4 [16].

Figure 4: Flooding and Pressure Drop Correlation for Packed Columns

A pressure drop of 0.25 in of water/foot height, liquid and vapor densities of 962 and 5.06 kg/m3
respectively, and liquid and vapor flow rates of 1.73 mol/s results in an x axis value of 0.107.
This results in a y axis value of 0.029. Equation 13 is the rearranged y axis, solved for gas flux
(G) [16].
1
2
0.029
=( ) (13)
0.2

Here, F is a function of the packing type and diameter. For 6 mm Raschig Rings F equals 19.5
[16]. The liquid viscosity, is 0.28 cp as determined by the stream report in ChemCad. Terms g
and represent and the gravitational acceleration and density of water. The correlation requires
the use of English units for all densities and gravitational acceleration. The gas flux (G) is equal
to 0.173 lb/(s-ft2). Equation 14 solves for the cross-sectional area of the column to be 1.25 m2
with the molar mass of the POCl3 vapor equaling 153.33 lb/lbmol.

= (14)

From the column area, the final column diameter is 0.63m.

The final column diameter of 0.63 m and height of 1 m results in a column volume of
0.309 m3, allowing for the 6.0 mm glass Raschig ring volume. The shell of the column is made
of Hastelloy C276 with a 5 mm shell thickness. High column temperatures and the highly
corrosive nature of POCl 3 require a high corrosion resistant material. Hastelloy C276 meets both
the temperature and corrosion demands while maintaining high yield strength. A shell thickness
of 5 mm provides the recommended corrosion resistance and strength during normal column
operations.
Previous enthalpy models provide the enthalpies of each stream and the duties of the
reboiler and condenser. The simulated reboiler and condenser energy requirements are 308 and
440 MJ/hr respectively. The distillate leaves the column at 305C and is heated by natural gas in
a tube fired reboiler. The condenser requires latent and sensible heat transfer which is sized as
two unique heat exchangers in the heat transfer section.

Magnetic Drum Separator

To ensure a metal-free product, the TPE product stream is sent through a magnetic drum
separator to remove any nickel-glyme catalyst. Puritan Magnetics, Inc. provided consultation on
necessary information for rotating magnetic drum separation. With a mass flow rate of 2400 kg/h
[4], Puritan Magnetics, Inc. recommended a rotating magnetic drum separator 12 inches in length
by 12 inches in diameter. Figure 5 provides a diagram of a Puritan Magnetics Inc. rotating drum
separator.
 Figure 5: Rotating Magnetic Drum Separation Schematic

Centrifugal Separator
A mechanical separation system must remove 0.06 kmol/h of liquid DPCM from 3.11
kmol/h of solid TPE, for TPE purity of at least 99.5%. The volumetric flow rate of this mixture,
as simulated in ChemCAD, is 0.91 m3/h [4]. Volumetric flow rates for centrifugal separators
relate to system bowl diameter, power requirement and weight [16]. The centrifugal separator
has a bowl diameter of 0.46 m. The system will weigh 1360 kg and require 11.2 kW during
operation.
Heat Exchanger Network
Change in enthalpy for process streams were identified by stream enthalpy differences in
ChemCad simulation [4]. Streams with both latent and sensible heat were isolated by phase
change or temperature. Table 3 displays the hot and cold process streams.

Table 3: Hot and Cold Process Streams

Stream Stream Q Tin Tout
ID Name/(#) (KW) (C) (C)
DPCM Reactor
H1 81.9 220 106
Condenser
Distillation Column
H2a 4.96 136.7 105.8
Condenser
Distillation Column
H2b 118.7 105.8 105.8
Condenser
H3 POCl3 (Stream 7) 18 105 35
H4 DPCM (Stream 6) 183.9 305 35
C5 Reboiler 85.5 305 305

A minimum approach temperature of 10C is necessary for heat integration. Figure 6 is the TQ
diagram for all heat exchange operations.

350

300

250
Temperature (C)

200
Cold Composite Curve
150 Hot Composite Curve

100

50

0
0 100 200 300 400 500 600
Q (kW)

Figure 6: Tetraphenylethylene TQ Diagram

The cold composite curve lies above the hot composite curve for all process streams so no pinch
point exists and heat integration is not possible with just process streams. However, the TPE
reactor consumes the same amount of heat as H4 releases, 183.9 kW. Cooling of stream H4
provides the heat to maintain the temperature of the endothermic TPE reaction at 25 C. Process
streams H1, H2a, H2b, and H3 are cooled with cooling water. Natural gas combustion provides
the heat necessary for partial vaporization of stream C5. Final utility consumptions after
integration of stream H4 are 224 kW of cooling and 85.5 kW of heating. These consumptions do
not account for a cooling water jacket around the PCl 5 reactor (97.5 kW) and natural gas heating
for the DPCM reactor (258.3 kW). With these unit operations, the total cooling consumption of
the entire process is 321.5 kW in cooling and 343.8 kW in heating. This translates to 18500 kg/h
of cooling water and 0.065 kg/h of natural gas.
Figure 7 displays the heat exchanger network. Further information on the exchangers can
be found in the heat exchanger table as well as the energy balance table in Appendix B.

Figure 7. Heat Exchanger Network Diagram

Heat Transfer Equipment

The type, dimensions, and cooling water duty of 5 heat exchangers were sized per the
equations in this section. Dimensions were adjusted to provide sufficient area (A) and overall
heat transfer coefficient to meet energy demands (Q). The general heat transfer equation in
equation 15 [7] gives the relationship between these values.
= (15)
Equation 16 provides the log mean temperature difference of all heat transfer systems.

= (16)

The overall heat transfer coefficient for each heat exchanger is the inverse of the sum of the
resistances as in equation 17.
1
= (17)
1 ( 1) 1
2
( + + )
1 2

Hastelloy C276 which is commonly used in this TPE production route has a thermal conductivity
of 15 W/mK [17].
Three convective fluid heat transfer coefficients, tube flow, shell flow, and condensation
of vapor, are necessary in this process. The Nusselt correlation [7] in equation 18 determines the
heat transfer coefficient of single phase flow through a tube.
1
= = 0.023 0.8 3 (18)

Equation 19 is a correlation for the heat transfer coefficient of condensing vapor in a tube [7].
1
3 2

4
= 0.729 ( ) (19)

All properties with an f subscript in equation 19 are liquid properties of the condensate film.
Terms , g, Do, and represent the solution heat of vaporization, gravitational acceleration,
tube diameter and temperature drop across the condensate film.
The Donoghue equations [7], listed below, calculate cooling water heat transfer
coefficients in each shell of a shell and tube heat exchanger.
0.6 0.33 0.14
= = 0.2 ( ) ( ) ( ) (20)

= ( ) (21)

= (1 ) (22)

2 2
= (23)
4 4
All shell and tube heat exchangers are double pass with standard properties of 1 inch tube pitch
( ), 1 foot baffle spacing ( ), and a 0.25 baffle cut. With a baffle cut of 0.25, is 0.1955.
Number of tubes in the baffle window, tube diameter and shell diameter are represented by ,
, and respectively. All shells are constructed using 316 stainless steel.
On the shell side, all cooling water has entrance and exit temperatures of 25 and 40C,
respectively. An energy balance, equation 24, determines cooling water flow rates.

= (24)

Shell and Tube Heat Exchanger

Liquid POCl 3 from the total condenser is sent through a shell and tube heat exchanger to
cool the liquid byproduct for sale. Cooling water flows at a rate of 0.287 kg/s in a 0.5 m diameter
shell. The heat transfer coefficient of the cooling water is 0.136 kW/m2K. Heat exchanger tubes
are constructed of BWG 11 Hastelloy C276. There are 22, 6 m tubes providing a total heat
transfer area of 7.77 m2. POCl3 enters the tubes at 105C and exits at 35C for a log mean
temperature difference of 29.6 C. The heat transfer coefficient of the POCl 3 in the tubes is 0.138
kW/m2K. The overall heat transfer coefficient of the heat exchanger is 0.081 kW/m2K. Cooling
water can remove18.6 kW of heat from POCl 3 satisfying the 18.0 kW demand.

Heat Exchangers for Condensing Vapor

The heat exchanger for the DPCM reactor must condense 1050 kg/h of vapor. The
saturated vapor is composed of 0.878 mol fraction POCl3, with the balance DPCM. The vapor is
sent through 14 BWG 11 Hastelloy C276 tubes which are 4 meters long. An equilibrium
phase change and temperature change from 220 to 105.8C requires a cooling duty of 81.9 kW.
The contents of the tubes are cooled with water sent through a 1 m diameter shell. The heat
transfer coefficient of the water in the shell is 0.313 kW/m2K. The heat transfer coefficient of the
condensing vapor is 1.750 kW/m2K. The overall heat transfer coefficient, log mean temperature
difference and heat transfer area of the system are 0.344 kW/m2K, 119C, and 2.0 m2
respectively. A cooling water flow rate of 1.31 kg/s with the proposed build has a sufficient
cooling capacity of 91.4 kW.
After cooling the packed column distillate product to 105.3 C, the vapor is condensed
before being refluxed through the column or transferred out as byproduct. Saturated vapor is sent
through 16 6 m BWG 14 Hastelloy C276 tubing, to condense 99.9% pure POCl 3. The heat
transfer coefficient of the condensing POCl 3 in the tubes is 2.12 kW/m2K. The heat transfer
coefficient of the water in the 1 m diameter shell is 0.34 kW/ m2K. The overall heat transfer
coefficient, log mean temperature difference and heat transfer area of the system are 0.379
kW/m2K, 72.2 C, and 4.53 m2 respectively. A cooling water flow rate of 1.89 kg/s is capable of
removing 124 kW of heat which is greater than the 118 kW required.

Concentric Tube Heat Exchanger

Cooling of the POCl 3 vapor to the saturation temperature from the packed column is
achieved via a countercurrent concentric tube heat exchanger. Cooling water in the outer pipe
enters a 316 stainless steel 5 inch schedule 40 pipe. POCl3 vapor travels within the interior 4 inch
schedule 160 Hastelloy C276 pipe. The length of the exchanger is 2.3 m for a total heat transfer
area of 0.83 m2. Vapor enters the pipe at 136 C and exits at 105C. The log mean temperature
difference of the system is 86C. The cooling water and POCl 3 vapor have heat transfer
coefficients of 0.046 and 0.34 kW/m2K, respectively, calculated from the Nusselt correlation.
The overall heat transfer coefficient of the system is 0.04 kW/m2K. The 4.93 kW of heat which
must be removed from the vapor prior to condensation is met with the above heat exchanger
design.

Reactor Heating Heat Exchanger

Liquid DPCM leaving the partial reboiler provides the heat to maintain the temperature
of the endothermic reaction in the TPE reactor at 25 C. The liquid DPCM enters at 305C and
14.7 psi and exits at 35C and 14.7 psi. The LMTD is 81.0, with a correction factor of 1.0.
DPCM flows at a rate of 1473 kg/h. The coil is constructed of 19 m BWG 11 Monel 400 with
a thermal conductivity of 21.8 W/mK. The heat transfer coefficient of the DPCM is 1.23
kW/m2K, using the Nusselt correlation, resulting in an overall heat transfer coefficient of 1.07
kW/m2K. DPCM transfers 183.9 kW of heat to the reactor. Cooling demands for the DPCM and
heating demands for the reactor are both 183.9 kW allowing for this heat integration. Heat
integration removes the need for 183.9 kW of heat removal via a 2.93 kg/s cooling water flow
rate.
Unit Operations List

Unit Operation PCl5 Reactor DPCM Reactor Packed Column TPE Reactor
Pressure (psi) 14.7 14.7 14.7 14.7
Inlet Temperature (C) 25 PCl5 50 220 25
Benzophenone -25
Outlet Temperature (C) 50 220 Distillate - 105 25
Bottoms - 305
Heating Duty (MJ/hr) - 930 440 666
Cooling Duty (MJ/hr) 351 295 308 -
Volume (m3) .360 11.0 0.310 3.46
Height (m) 1.00 7.44 1.00 1.64
Diameter (m) 0.64 1.38 0.63 1.64
Materials of Construction Monel Hastelloy C Hastelloy C Glass Lined
Steel
Packing - - 6 mm Raschig -
Rings

Unit Operation Magnetic Centrifuge

Drum
Pressure (psi) 14.7 14.7
Inlet Temperature (C) 25 25
Outlet Temperature (C) 25 25
Height (m) 0.31 -
Diameter (m) 0.31 0.5
Materials of Construction 316 Stainless 316 Stainless Steel
Steel
Power Requirement 0.373 kW 11.2 kW

Heat Exchanger Table

Heat Inlet T Outlet T Phase LMTD A

Stream ID Q (kW) U( )
Exchanger (C) (C) Change (K) (m2)
H1 220 106 V to L
HX1 81.9 0.35 119 2.00
C1 25 40 -
H2a 136.7 105.8 -
HX2a 4.96 0.04 86.0 1.41
C2a 25 40 -
H2b 105.8 105.8 V to L
HX2b 118.7 0.38 72.2 4.53
C2b 25 40 -
H3 105 35 -
HX3 18.0 0.08 29.6 7.77
C3 25 40 -
HX4 & H4 305 35 -
183.9 1.07 81.0 2.24
TPE Reactor C4 25 25 -
HX5 H5 >315 >315 -
123.3 - >10 -
C5 305 305 L to V
Equipment Design Conclusion

Equipment sizing within this section will drive estimates of capital equipment costs.
Energy demands and raw material costs supply necessary information for yearly operating
expenses. Return on investment analysis will be conducted for financial feasibility. Code review
will be conducted to ensure worker safety and compliance. Emergency plans for unplanned
chemical and energy releases will be developed.
Bibliography

[1] E. Barnett, The preparation of organic compounds. London: J. & A. Churchill, 1920.
[2] S. Inaba, H. Matsumoto and R. Rieke, "Metallic nickel as a reagent for the coupling of
aromatic and benzylic halides", Tetrahedron Letters, vol. 23, no. 41, pp. 4215-4216, 1982.
[Accessed: October 20, 2017]
[3] M. Mastay and V. Benin, personal communication. March 2017
[4] ChemCad. Version 7.1.09402. Chemstations, Inc., 2016.
[Accessed: October 20, 2016]
[5] H. Booth, Inorganic syntheses. New York: McGraw Hill, pp. 99-100. 1939.
[Accessed: October 20, 2016]
[6]Penn Stainless Production Inc., 2017. [Online] http://www.pennstainless.com/stainless-
grades/300-series-stainless-steel/316l-stainless-steel [Accessed: February 8, 2017]
[7] W. McCabe, J. Smith and P. Harriott, <>, 1st ed. Beijing: Chemical Industry Press, 2008.
[8] "MatWeb - The Online Materials Information Resource", Matweb.com, 2017. [Online].
Available: http://www.matweb.com/search/datasheet.aspx?matguid=1364d82317034
76b8c466cdd07be71b7&ckck=1. [Accessed: 10- Mar- 2017].
[9] E. Barnett, The preparation of organic compounds. London: J. & A. Churchill, 1920.
[Accessed: October 20, 2016]
[10]M. Peters, K. Timmerhaus and R. West, Plant design and economics for chemical engineers,
1st ed. Boston [u.a.]: McGraw-Hill, 2006.
[11] "Corrosion Resistance of Hastelloy Alloys," in Hayes International, Inc., 1980. [Online].
Available: http://www.parrinst.com/wp-content/uploads/downloads/2011/07/
Parr_Hastelloy-Corrosion-Info.pdf. Accessed: [Accessed: February 9, 2017]
[12] "Chemical Resistance Guide," in IPEX, 2004. [Online]. Available:
http://www.gwspipe.com/Chemical_Reisistance_Guide%5B1%5D.pdf.
[Accessed: February 16, 2017]
[13] D. Hansen, personal communication, March 2017
[14]Dichlorodiphenylmethane; MSDS No. 820439 [Online]; EMD Millipore Corporation:
Billerica, MA, August 22, 2013 http://www.emdmillipore.com/Web-US-
Site/en_CA//USD/ProcessMSDS-Start?PlainSKU=MDA_CHEM-820439&Origin=PDP
[Accessed October 14, 2016]
[15] Phosphorus Oxychloride; MSDS No. 262099 [Online]; Sigma-Aldrich: Saint Louis, MO,
May 24, 2015 http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country
=US&language=en&productNumber=262099&brand=ALDRICH&PageToGoToURL
=http%3A%2F%2Fwww.sigmaa{ldrich.com%2Fcatalog%2Fproduct%2Faldrich%2F262099%
3Flang%3Den [Accessed November 19, 2016]
[16] P. Wankat, Separation process engineering, 1st ed. Upper Saddle River, NJ: Prentice
Hall, 2012. [February 9, 2017]
[17] "HASTELLOY C-276 alloy", Haynesintl.com, 2017. [Online]. Available:
http://haynesintl.com/docs/default-source/pdfs/new-alloy-brochures/corrosion-resistant-
alloys/brochures/c-276.pdf?sfvrsn=6. [Accessed: 10- Mar- 2017].
 Appendix A: Reactor Mass Balances and Purity Specifications
Chlorine and Phosphorous Trichloride Reactor
Atomic Balances around Reactor
Chemical Formula
Species Flow into Reactor Flow out of Reactor out - in P Cl P out-in Cl out-in
PCl3 6.22 0 -6.22 1 3 -6.22 -18.66
Cl2 6.22 0 -6.22 0 2 0 -12.44
PCl5 0 6.22 6.22 1 5 6.22 31.1
Net Atom Balances P Cl
0 0

Heated DPCM Reactor

Atomic Balances around Reactor
Chemical Formula
Species Flow into Reactor Flow out of Reactor out - in C H O P Cl C out-in H out-in O out-in P out-in Cl out-in
PCl5 6.22 0 -6.22 0 0 0 1 5 0 0 0 -6.22 -31.1
Benzophenone 6.22 0 -6.22 13 10 1 0 0 -80.86 -62.2 -6.22 0 0
DPCM 0 6.22 6.22 13 10 0 0 2 80.86 62.2 0 0 12.44
POCl3 0 6.22 6.22 0 0 1 1 3 0 0 6.22 6.22 18.66
Net Atom Balances C H O P Cl
0 0 0 0 0

Catalytic TPE Reactor

Atomic Balances around Reactor
Chemical Formula
Species Flow into Reactor Flow out of Reactor out - in C H Cl O C out-in H out-in Cl out-in O out-in
DPCM 6.28 0.06 -6.22 13 10 2 0 -80.86 -62.2 -12.44 0
Glyme 6.28 6.28 0 4 10 2 2 0 0 0 0
TPE 0 3.11 3.11 26 20 0 0 80.86 62.2 0 0
Chlorine 0 6.22 6.22 0 0 2 0 0 0 12.44 0
Net Atom Balances C H Cl O
0.00 0.00 0.00 0.00
 Appendix B: Energy Balances

Unit Stream ID Inlet T Outlet T F (mol/s) FCp (kW/K) Q (kW)

Operation (K) (K) (kJ/mol) (kJ/mol)

PCl 5 Reactor 2 &3 50 50 1.73 - - 56.6 97.5

CW 25 40 4.50 6.50 - - 97.5
DPCM Gas N/A (>230) N/A (>230) 0.000668 - - 386677 258.3
Reactor 4&5 220 220 3.45 - - 74.9 258.3
HX1 H1 220 106 1.78 - 46 81.9
C1 25 40 72.7 5.47 - - 81.9
HX2a H2a 136.7 105.8 1.73 0.159 - 4.96
C2a 25 40 4.38 0.330 - - 4.96
HX2b H2b 105.8 105.8 1.73 - 68.6 118.7
C2b 25 40 105 7.91 - - 118.7
Reboiler Gas N/A (>315) N/A (>315) 0.000278 - - 386677 123.3
Reboiler 305 305 1.36 - 90.4 - 123.3
HX3 H3 105 35 1.73 0.257 - - 18.0
C3 25 40 15.9 1.20 - 18.0 18.0
HX4 & H4 305 35 1.73 0.681 - - 183.9
TPE Reactor C4 25 25 1.73 - - 106000 183.9
 Appendix C: PCl5 Reactor Stream Report

STREAM PROPERTIES
Stream No. 1 2 3
Name Cl2 PCl3 PCl5
- - Overall - -
Molar flow kmol/h 6.2200 6.2200 6.2220
Mass flow kg/h 441.0353 854.1926 1295.2527
Temp C 25.0000 25.0000 50.0000
Pres atm 1.0000 1.0000 1.0000
Vapor mole fraction 1.000 0.0000 0.8306
Enth kJ/h 0.012208 -1.8865E+006 -2.2371E+006
Tc C 144.0000 290.0000 242.9324
Pc atm 76.1020 55.9590 88.9321
Std. sp gr. wtr = 1 1.430 1.588 2.123
Std. sp gr. air = 1 2.448 4.742 7.188
Degree API -32.5290 -42.4010 -64.8549
Average mol wt 70.9060 137.3300 208.1723
Actual dens kg/m3 2.9327 1566.1466 1830.7853
Actual vol m3/h 150.3871 0.5454 0.7075
Std liq m3/h 0.3085 0.5379 0.6101
Std vap 0 C m3/h 139.4129 139.4129 139.4582
- - Vapor only - -
Molar flow kmol/h 6.2200 0.0034
Mass flow kg/h 441.0353 0.3290
Average mol wt 70.9060 97.9024
Actual dens kg/m3 2.9327 3.7556
Actual vol m3/h 150.3871 0.0876
Std liq m3/h 0.3085 0.0002
Std vap 0 C m3/h 139.4129 0.0753
Cp J/kmol-K 33998.7070 50105.2500
Z factor 0.9884 0.9832
Visc Pa-sec 1.343e-005 1.296e-005
Th cond W/m-K 0.0089 0.0090
- - Liquid only - -
Molar flow kmol/h 6.2200 0.0007
Mass flow kg/h 854.1926 0.0923
Average mol wt 137.3300 134.5868
Actual dens kg/m3 1566.1466 1512.5573
Actual vol m3/h 0.5454 0.0001
Std liq m3/h 0.5379 0.0001
Std vap 0 C m3/h 139.4129 0.0154
Cp J/kmol-K 115824.3516 114196.6484
Z factor 0.0035 0.0032
Visc Pa-sec 0.0005251 0.0004261
Th cond W/m-K 0.1290 0.1288
Surf. tens. N/m 0.0282 0.0246

Flow rates in kg/h

Chlorine 441.0353 0.0000 0.1434
Phosphorus Trich 0.0000 854.1926 0.2778
Phosphorus Penta 0.0000 0.0000 1294.8314

CHEMCAD 7.1.0 3/21/2017 3:09 PM

 Appendix D: DPCM Reactor Stream Report

STREAM PROPERTIES
Stream No. 1 2 3
Name Benzophenone DPCM, POCl3 PCl5
- - Overall - -
Molar flow kmol/h 6.2200 12.4400 6.2200
Mass flow kg/h 1133.4208 2428.5991 1295.2528
Temp C 25.0000 220.0000 50.0000
Pres atm 1.0000 1.0000 1.0000
Vapor mole fraction 0.0000 0.5135 0.0000
Enth kJ/h -1.2495E+005 -2.1657E+006 -2.9708E+006
Tc C 556.8500 493.3768 373.0000
Pc atm 33.0817 46.0802 6.8122
Std. sp gr. wtr = 1 1.110 1.381 0.872
Std. sp gr. air = 1 6.292 6.741 7.190
Degree API -4.0299 -29.0015 30.7559
Average mol wt 182.2220 195.2250 208.2400
Actual dens kg/m3 1100.5958 9.5647 842.8079
Actual vol m3/h 1.0298 253.9115 1.5368
Std liq m3/h 1.0210 1.7592 1.4852
Std vap 0 C m3/h 139.4129 278.8257 139.4129
- - Vapor only - -
Molar flow kmol/h 6.3877
Mass flow kg/h 1044.9686
Average mol wt 163.5900
Actual dens kg/m3 4.1368
Actual vol m3/h 252.6052
Std liq m3/h 0.6593
Std vap 0 C m3/h 143.1723
Cp J/kmol-K 125689.2188
Z factor 0.9774
Visc Pa-sec 1.204e-005
Th cond W/m-K 0.0107
- - Liquid only - -
Molar flow kmol/h 6.2200 6.0523 6.2200
Mass flow kg/h 1133.4208 1383.6305 1295.2528
Average mol wt 182.2220 228.6134 208.2400
Actual dens kg/m3 1100.5958 1059.2140 842.8079
Actual vol m3/h 1.0298 1.3063 1.5368
Std liq m3/h 1.0210 1.0999 1.4852
Std vap 0 C m3/h 139.4129 135.6535 139.4129
Cp J/kmol-K 252530.3594 363843.3438 304371.8438
Z factor 0.0078 0.0065 0.0274
Visc Pa-sec 0.01051 0.0003982 0.0004477
Th cond W/m-K 0.1915 0.1215 0.1078
Surf. tens. N/m 0.0435 0.0198 0.0041

Flow rates in kg/h

DPCM 0.0000 1474.8861 0.0000
Phosphorus OxyCl 0.0000 953.7124 0.0000
Phosphorus Penta 0.0000 0.0003 1295.2528
Benzophenone 1133.4208 0.0002 0.0000

CHEMCAD 7.1.0 3/20/2017 9:44 AM

 Appendix E: Distillation Column Stream Report
STREAM PROPERTIES
Stream No. 1 2 3
Name DPCM/POCl3 DPCM POCl3
- - Overall - -
Molar flow kmol/h 12.4400 6.2181 6.2219
Mass flow kg/h 2428.5989 1473.9208 954.6784
Temp C 220.0000 302.3562 105.3587
Pres atm 1.0000 1.0000 1.0000
Vapor mole fraction 0.5351 0.0000 0.0000
Enth kJ/h -2.3596E+006 1.0390E+006 -3.5341E+006
Tc C 493.3769 549.4889 329.8373
Pc atm 46.0803 26.0292 34.1327
Std. sp gr. wtr = 1 1.381 1.235 1.687
Std. sp gr. air = 1 6.741 8.184 5.298
Degree API -29.0015 -16.9450 -47.6154
Average mol wt 195.2250 237.0362 153.4390
Actual dens kg/m3 9.1786 965.7250 1513.0997
Actual vol m3/h 264.5933 1.5262 0.6309
Std liq m3/h 1.7592 1.1933 0.5660
Std vap 0 C m3/h 278.8257 139.3709 139.4549
- - Vapor only - -
Molar flow kmol/h 6.6572
Mass flow kg/h 1085.9153
Average mol wt 163.1193
Actual dens kg/m3 4.1239
Actual vol m3/h 263.3193
Std liq m3/h 0.6834
Std vap 0 C m3/h 149.2118
Cp J/kmol-K 123565.6797
Z factor 0.9776
Visc Pa-sec 1.207e-005
Th cond W/m-K 0.0107
- - Liquid only - -
Molar flow kmol/h 5.7828 6.2181 6.2219
Mass flow kg/h 1342.6836 1473.9208 954.6784
Average mol wt 232.1851 237.0362 153.4390
Actual dens kg/m3 1053.8817 965.7249 1513.0997
Actual vol m3/h 1.2740 1.5262 0.6309
Std liq m3/h 1.0758 1.1933 0.5660
Std vap 0 C m3/h 129.6140 139.3709 139.4549
Cp J/kmol-K 433111.2188 502179.9063 165437.4531
Z factor 0.0066 0.0062 0.0053
Visc Pa-sec 0.0003953 0.0002780 0.0005582
Th cond W/m-K 0.1210 0.1040 0.1972
Surf. tens. N/m 0.0202 0.0145 0.0219

Flow rates in kg/h

DPCM 1474.8864 1472.9675 1.9192
Phosphorus Oxych 953.7126 0.9534 952.7592
Tetraphenylethyl 0.0000 0.0000 0.0000

CHEMCAD 7.1.0 3/20/2017 9:32 AM

 Appendix F: TPE Reactor Stream Report
STREAM PROPERTIES
Stream No. 1 2
Name DPCM TPE
- - Overall - -
Molar flow kmol/h 6.2800 3.1700
Mass flow kg/h 1489.1136 1048.1460
Temp C 25.0000 25.0000
Pres atm 1.0000 1.0000
Vapor mole fraction 0.0000 0.0000
Enth kJ/h 3.5277E+005 1.3656E+006
Tc C 549.5643 549.5643
Pc atm 25.9848 25.9848
Std. sp gr. wtr = 1 1.235 1.156
Std. sp gr. air = 1 8.187 11.416
Degree API -16.9251 -9.1002
Average mol wt 237.1200 330.6454
Actual dens kg/m3 1225.1646 1155.9280
Actual vol m3/h 1.2154 0.9068
Std liq m3/h 1.2058 0.9067
Std vap 0 C m3/h 140.7577 71.0513
- - Liquid only - -
Molar flow kmol/h 6.2800 0.0600
Mass flow kg/h 1489.1136 14.2291
Average mol wt 237.1200 237.1200
Actual dens kg/m3 1225.1646 1225.1646
Actual vol m3/h 1.2154 0.0116
Std liq m3/h 1.2058 0.0115
Std vap 0 C m3/h 140.7577 1.3450
Cp J/kmol-K 297435.6875 297435.6875
Z factor 0.0099 0.0099
Visc Pa-sec 0.0007388 0.0007388
Th cond W/m-K 0.1548 0.1548
Surf. tens. N/m 0.0365 0.0365
- - Solid only - -
Molar flow kmol/h 0.0000 3.1100
Mass flow kg/h 0.0000 1033.9169
Enth kJ/h 0.00000 1.3623E+006
Average mol wt 332.4500
Actual dens kg/m3 1155.0295
Cp J/kmol-K 384418.4375

Flow rates in kg/h

DPCM 1489.1136 14.2291
Tetraphenylethyl 0.0000 1033.9169

CHEMCAD 7.1.0 3/23/2017 2:30

PM
 Appendix G: Centrifuge Volumetric Flow
STREAM PROPERTIES
Stream No. 1 2 3
Name DPCM TPE Mixture
- - Overall - -
Molar flow kmol/h 0.0600 3.1100 3.1700
Mass flow kg/h 14.2272 1033.9196 1048.1466
Temp C 25.0000 25.0000 25.0000
Pres atm 1.0000 1.0000 1.0000
Vapor mole fraction 0.0000 0.0000 0.0000
Enth kJ/h 3370.4 1.3623E+006 1.3656E+006
Tc C 549.5643 0.0000 549.5643
Pc atm 25.9848 0.0000 25.9848
Std. sp gr. wtr = 1 1.235 1.155 1.156
Std. sp gr. air = 1 8.187 11.479 11.416
Degree API -16.9251 -8.9925 -9.1001
Average mol wt 237.1200 332.4500 330.6456
Actual dens kg/m3 1225.1646 1155.0294 1155.9276
Actual vol m3/h 0.0116 0.8951 0.9068
Std liq m3/h 0.0115 0.8951 0.9067
Std vap 0 C m3/h 1.3448 69.7064 71.0513
- - Liquid only - -
Molar flow kmol/h 0.0600 0.0600
Mass flow kg/h 14.2272 14.2272
Average mol wt 237.1200 237.1200
Actual dens kg/m3 1225.1646 1225.1646
Actual vol m3/h 0.0116 0.0116
Std liq m3/h 0.0115 0.0115
Std vap 0 C m3/h 1.3448 1.3448
Cp J/kmol-K 297435.6875 297435.6875
Z factor 0.0099 0.0099
Visc Pa-sec 0.0007388 0.0007388
Th cond W/m-K 0.1548 0.1548
Surf. tens. N/m 0.0365 0.0365

Flow rates in kg/h

DPCM 14.2272 0.0000 14.2272
TetraPhnEthylene 0.0000 1033.9196 1033.9196
Ethyl Glyme 0.0000 0.0000 0.0000

CHEMCAD 7.1.0 3/23/2017 2:02

PM
Appendix H: Reactor Sizing Sample Calculation
Appendix I: TPE Reactor Sizing

Density at 25 C (g/cm3) Volume (m3)

DPCM 1.2 0.023
Nickel Glyme Complex 1.9 1.54
TPE 1.1 1.90
Total - 3.46
Appendix J: UNIFAC and ChemCad

The Vapor liquid interactions can be modeled UNIFAC, a binary phase model.
= + + 2
ChemCad constants A, B, and C are dependent on UNIFAC subgroup contributions. The
volatility interaction ( ) is a function of these constants and mixture temperature (K). POCl3
constants are preloaded into ChemCad. DPCM is not an installed component in ChemCad and
had to be generated using UNIFAC modeling where combinations of functional groups
determine total species behavior [3]. Figure 1 shows the molecule development screen i n
ChemCad.

Figure 1: UNIFAC Component Creation

Each carbon atom in DPCM is identified by bond types. The quantity of each group is input into
the sheet. ChemCad simulates and predicts physical properties of the user generated component.