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Production of Fluorescent

Backbone Molecule
CME 431-1 Group 5
Bradley Siefker, RJ Schratz, David Devlin, Trevor Langton
February 17, 2017
Stream 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
PCl5 Bottoms, Distillate, POCl3, After DCPM, After Magnetic Magnectic Solids
Benzophenone DCPM Reactor TPE Reator DPCM
Description Chlorine Feed PCl3 Feed Reactor Distillation Distillation Heat Heat Glyme Feed Separation Separation Separation
Feed Effluent Effluent Recycle
Effluent Column Column Exchanger Exchanger Out Product Screen Out
Pressure (psia) 150 35 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 25 220 278 105.8 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) 6.22 6.22 6.22 6.22 12.45 6.22 6.22 6.22 6.22 6.28 9.46 6.28 3.17 3.11 0.06
Component Flow Rates
(kmol/h)
Cl2 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 0.06 0.06 - - -
Spent Ni-Glyme Complex - - - - - - - - - - 6.22 6.22 - - -
TPE - - - - - - - - - - 3.11 - 3.11 3.11 -
Process Narrative

Gaseous chorine (Cl2) is delivered via railcar at 150 psia to a liquid atomization reactor.
Liquid phosphorus trichloride (PCl3) is atomized with nitrogen gas and added to the reactor at an
equimolar rate with chlorine gas. Solid phosphorus pentachloride (PCl5) precipitates from the
droplet and vapor interactions and exits bottom of the reactor.
Solid PCl5 exits the reactor vessel and is transported via screw conveyor into a second
reactor with equimolar benzophenone. The reactor vessel raises the temperature of the reactants
to 220oC. The PCl5 and benzophenone melt inside and react to form DPCM and a byproduct of
phosphorous oxychloride (POCl3) [1]. Reactant vapors formed during this step are condensed by
the reactor to ensure no release of hazardous material may occur. Benzophenone and PCl5 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 POCl3 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 25oC where it can be collected. A
cost analysis for POCl3 will determine whether the compound will be sold as a byproduct, or
disposed as hazardous waste. The bottoms product contains greater than 99% DPCM which is
fed to a concentric tube heat exchanger to reduce the temperature to 25oC and is fed into an
equilibrium reactor at 14.7 psia.
Nickel powder dissolved in glyme is fed into the equilibrium continuous reactor in
equivalent amounts to the DPCM and catalyzes the reaction [2]. 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 removed as waste. TPE is separated from the DPCM by a solid
separation screen 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%.
Table 1: Equipment Design Progress Table

Detailed
Unit Energy Materials of
Unit Mass Sizing Costing
ID Balances Construction
Balances

Spray Drying Reactor R1 Complete Complete Complete Complete TBD


DPCM Production
R2 Complete Complete Complete Complete TBD
Reactor
Catalytic TPE
R3 Complete Complete Complete Complete TBD
Production Reactor
Distillation Column D1 Complete Complete Complete Complete TBD

Magnetic Separator S1 Complete Complete In Progress In progress TBD

Solid Liquid
S2 Complete Complete In Progress In progress TBD
Separation Screen
Phosphorous
Oxychloride Heat H1 Complete Complete In progress TBD TBD
Exchanger
DPCM Heat
H2 Complete Complete In progress TBD TBD
Exchanger
Equipment Design Audit Sheets
Group #:_____5_____ Grading Iteration:________________

Team Member with Primary Responsibility:_____David Devlin__________

Unit Op Name: _________Phosphorus Pentachloride Reactor_____________


2
PCl3

1
Cl2
1

Heat Duty
-351000 kJ/h

3
PCl5

Stream 1 2 3
Chlorine PCl5 Reactor
Description PCl3 Feed
Feed Effluent
Pressure (psia) 150 35 14.7
Temperature (C) 25 25 50
Vapor Fraction 1 0 0
Liquid Fraction 0 1 1
Total Flow (kmol/h) 6.22 6.22 6.22
Enthalpy (kJ/h) 0.01221 -1886000 -2237000
Component Flow Rates
(kmol/h)
Cl2 6.22 - -
PCl3 - 6.22 -
PCl5 - - 6.22
Group #:_____5_____ Grading Iteration:________________

Team Member with Primary Responsibility:_______RJ Schratz_____________

Unit Op Name: ________________DPCM Reactor_________________________

Unit Diagram and stream table

Cooling Duty
X kJ/h

Heat Duty
930,000 kJ/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 (kJ/h) -2971000 -125000 -2166000
Component Flow Rates
(kmol/h)
PCl5 6.22 - -
Benzophenone - 6.22 -
DPCM - - 6.22
Phosphorus(V)
Oxychloride - - 6.22
Group #:__5________ Grading Iteration:___1_____________

Team Member with Primary Responsibility:__Bradley Siefker_____________________

Unit Op Name: ___Packed Distillation Column__________________________________

Unit Diagram and stream table

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 25 25 -
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 (kJ/hr) -2359000 1039000 -3534000 308000 -444000 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:_______1_________

Team Member with Primary Responsibility:____Trevor Langton___________________

Unit Op Name: __TPE Reactor______________________________

Unit Diagram and stream table

Stream 9 10 11 15
DCPM, After Glyme TPE Reator DPCM
Description
Heat Exchanger Feed Effluent Recycle
Pressure (psia) 14.7 14.7 14.7 14.7
Temperature (C) 25 25 25 25
Vapor Fraction 0 0 0 0
Heat
Liquid Fraction 1 1 1 1
Duty
Enthalpy (KJ/h) 352770 16476 1038347 3370 665730
Total Flow (kmol/h) 6.22 6.28 9.46 0.06
Component Flow Rates
(kmol/h)
DPCM 6.22 - 0.06 0.06
Phosphorus(V) Oxychloride - - - -
Nickel-Glyme Complex - 6.28 0.06 -
Spent Nickle Glyme Complex - - 6.22 -
Introduction
The developed process flow sheet and narrative was used to develop preliminary analysis
of the unit operation systems in the production of tetraphenylethylene (TPE). The three reaction
vessels have been sized per literature reaction times ensuring an adequate size and conversion.
Various separation systems of the reactive intermediate dichlorodiphenylmethane (DPCM) and
byproduct phosphorous oxychloride (POCl5) were analyzed to achieve cost effective and
efficient separation of the components. Additional work was conducted on the magnetic
separation, liquid solid separator, and heat exchangers to obtain preliminary balances of these
unit operations. Future work will refine the primary unit operation design and finish design of the
remaining unit operations including finalizing material selection and costing of all components.
For all operations mass balances were conducted using an analysis of the inlet and outlet
flow rates of the system. The mass balances of the individual units are found in the stream table
above. Energy balances on process streams were determined through ChemCad analysis.
ChemCad determines enthalpy of a stream based on the heat of formation of a gas at 298.15K
and the heat capacity of the components. Equations 1 below show the equation ChemCad utilizes
to conduct enthalpy calculations of streams.
298.15
298.15 +298.15 ( )
= + 298.15( ) + ( ) () (1)

Mass and energy balances for each of the processes in TPE production are outlined with the
relevant equipment.

Reaction Vessels

Phosphorous Pentachloride Reactor

DPCM Reactor

TPE Reactor

Separation Systems
Packed Distillation Column
The reactor effluent of DPCM and POCl3 at 220oC and 1 atmosphere is separated prior to
being fed into the catalytic TPE reactor. Boiling point differences in DPCM (305oC)[] and POCl3
(105.8oC)[] suggest the possibility of using volatility differences as a means of separation.
Preliminary ChemCad simulations did not suggest any formation of an azeotrope of the
intermediate reactant and byproduct. Vapor liquid interactions of the equimolar binary mixture
was modeled using UNIFAC modeling shown in equation xx[].
= + + 2 (xx)
Values A, B, and C are defined constants for ChemCad modeling the binary interactions
of two species. The interaction of the species ( ) is a function of these constants as well as the
temperature (K) of a mixture. The constants of DPCM were generated using a user generated
UNIFAC modeling where functional groups are assigned a different designation []. The
combination of those designations provides the constants upon which binary interactions are
based. Further benchtop experimentation and solution characterization is suggested to ensure no
azeotrope exists with a mixture before implementing a distillation separation system. Separation
system selection, sizing, mass and energy balances are conducted at 1 atmosphere and using the
conditions of the reactor effluent as the inlet streams of the separation system.
A series of flash tanks, a sieve tray distillation column, and a random packed distillation
column were explored as possible separation systems for the binary mixture. The flash tanks
provide a lower capital and spatial cost than any of the other systems due to the size and nature
of their operation. However, the separation effectiveness and the desired production rates made
this route unfeasible. Four flash tanks were required to achieve the desired reactive intermediate
purity of DPCM into the catalytic reactor during ChemCad simulation. Additionally, the vapor
phase from each flash tank removes desired DPCM with the POCl3. Reduced DPCM production
requires a greater use of raw materials and more waste. Sharper separation of the DPCM and
POCl3 allowed for lower capital material costs, as well as the potential to sell the POCl3 as a
byproduct decreasing waste.
The x-y diagram of the binary mixture was used to step off stages using the McCabe
Thiele method for distillation column design [x]. Equations were generated for the raffinate, feed
and stripping section operating lines and plotted to develop the Figure XX below using known
parameters of feed quality, desired outlet compositions, an optimized reflux ratio to reduce
energetic demands and decrease column size, and flow rates of all streams in and out of the
column.

Figure XX: McCabe Thiele Analysis


The McCabe Thiele method estimated the number of separation stages at 5 which was
validated as an adequate number of stages using ChemCad simulation.
The spacing between plates was selected to be a standard spacing of .6096 m (2 ft.) from
typical industrial applications. Using Figure XX below, the capacity factor of the system was
estimated

Figure xx: Capacity Factor for Flood of Sieve Trays []


The estimated capacity factor (Csb), solution densities (i), and the surface tension () of POCl3
were used to estimate a flooding velocity of the column. Further work needs to be conducted to
determine whether the surface tension of POCl3 alone provides a sufficient value in
determination of flooding velocity. Equation xx determined the flooding velocity which was
used to determine the approximate sieve tray column diameter in equation xx.

= C (20).2 (xx)

4( )( )()
= (xx)
3600( )

The f term in equation xx accounts for the operational vapor velocity, and represents the
fraction of the area of one downcomer in the column. The value of these parameters was selected
to be 0.75 and 0.90 respectively using literature recommendations. The resulting column
diameter using these values was determined to be less than 0.3 m. When the estimated column
diameter is less than 0.762 m literature suggests implementation of a packed distillation column.
Using the same values for number of trays and solution densities a packed column using
5/8 pall rings was sized. Literature suggests sizing the column diameter to be roughly
equivalent to the height of a theoretical plate (HETP) []. Using equation xx and xx below the
approximate height, diameter, and HETP of the column was determined.

= ( )() (xx)

= 28 ( )(. ) (2.4)1/3 (xx)

The packed column height is estimated at roughly 2.15 m with the HETP and column diameter
equaling 0.43 m. Pilot scale up of any separation system should be conducted prior to large scale
production.
Mass balances were conducted in ChemCad following the sizing of the column to
determine flow rates and compositions of streams exiting the distillation column. Table xx below
shows the composition and flow rates of individual species in and out of the column.
Table xx: Separation System Stream Table
Stream POCl3 Flow Rate DPCM Flow Rate POCl3 Mole Fraction DPCM Mole Fraction
(kmol/hr) (kmol/hr)
Inlet 6.220 6.220 0.5 0.5
Bottoms 0.008 6.212 0.001 0.999
Distillate 6.212 0.008 0.999 0.001
In-Out 0.0 0.0

With mass balances completed the enthalpy models based on the heat of formations and
heat capacities of the species used in previous unit operations was used to determine the
enthalpies of each stream as well as the determine the reboiler and condenser duties on the
distillation column. Table xx shows the enthalpies of each stream as well as ChemCad estimated
reboiler and condenser duties.
Table xx: Enthalpic Demands and Net Heating Requirements
Stream/Unit Enthalpy (kj/hr)
Inlet -2359000
Bottoms 1039000
Distillate -3534000
Net Enthalpy of Column -136000

Reboiler -444000
Condenser 308000
Net Enthalpy 0

A slight enthalpy difference in the column requires a secondary cooling system to remove a
small amount of heat from the system to prevent over heating of the column. Sizing of the the
heating system for the column will be conducted in future design steps.
Reboiler and condenser sizing from ChemCad ensures the desired outlet flow rates of the
components as in table xx are achieved and desired production rate of TPE will be achievable.
The area of the distillation columns heat transfer systems was preliminarily sized using
estimations of the overall heat transfer coefficients of similar heat transfer equipment. Sizing was
primarily done to determine approximate heat transfer area for future costing purposes of the
distillation column. Estimations at this stage in the design process are too imprecise to be truly
valid for costing. Future work will be conducted on these systems.
Material selection for pall rings, column, and the reboiler and condenser need to be
adequate to handle the hazardous components of DPCM and POCl3 flowing through the column.
Data on the corrosion resistances of materials to DPCM is extremely limited. All materials in
contact with DPCM must be adequately tested for corrosion resistance prior to any full-scale
implementation. For preliminary material selection, materials resistant to highly corrosive POCl3
will be assumed to be sufficiently resistant to DPCM. Few metals offer adequate POCl3
resistance, with most resistances being found in plastic based compounds like EPDM. To limit
corrosion of the distillation column components Hastelloy C is selected for all column
components. Hastelloy C is one of the few metals offering excellent corrosion resistance to
POCl3 while maintain the strength necessary for the column and packings. A hybrid of EPDM
and Hastelloy C may be plausible and used to cut down on costs, but material testing with both
DPCM and POCl3 must be conducted to ensure the column operates safely.
Using the information generated in distillation column sizing the material selection future
work will require costing of the various distillation column components. Prior to costing, column
heating systems will be appropriately sized. Reboiler and condenser heat transfer coefficients
will be further analyzed to ensure accurate sizing. Collection of this data will allow for
preliminary costing analysis. Before full implementation as in all systems material testing and
pilot scale-up of the specialized systems in this process must be conducted to ensure operations
perform as simulated and will operate in a safe manner.
Unit Operations List

Unit Operation PCl5 Reactor DPCM Reactor Packed Column TPE Reactor
Pressure (psi) 14.7
Inlet Temperature (oC) 220
Outlet Temperature (oC) Distillate - 105
Bottoms - 305
Heat Duty (kJ/hr) 440,000
Cooling Duty (kJ/hr) 308,000
Volume (m3) 0.309
Height (m) 2.15
Diameter (m) 0.428
Materials of Construction Hastelloy C
Packing 5/8 Pall Rings
(Packing Factor 70)

Heat Exchanger Table

Only preliminary design work has been conducted on the process heat exchangers. No
definitive design decisions have been made and therefore no table is included in this draft. Work
will be completed for heat exchanger sizing in future work.

Conclusion

Bibliography

[1]E. Barnett, The preparation of organic compounds. London: J. & A. Churchill, 1920.
[2]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.sigmaaldrich.com%2Fcatalog%2Fproduct%2Faldrich%2F262099%3Fl
ang%3Den [Accessed November 19, 2016]
Appendix A: Reactor Mass Balances and Purity Specifications
Chlorine and Phosphorous Trichloride Reactor
Atomic Balances around Reactor
Chemical Formula
Species Flow In Flow Out 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 In Flow Out 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 In Flow Out out - in C H Cl O Ni C out-in H out-in Cl out-in O out-in Ni out-in
DPCM 6.28 0.06 -6.22 13 10 2 0 0 -80.86 -62.2 -12.44 0 0
Ni-Glyme Complex 6.28 0.06 -6.22 4 10 0 2 1 -24.88 -62.2 0 -12.44 -6.22
TPE 0 3.11 3.11 26 20 0 0 0 80.86 62.2 0 0 0
Spent Glyme Complex 0 6.22 6.22 4 10 2 2 1 24.88 62.2 12.44 12.44 6.22
Net Atom Balances C H Cl O Ni
0.00 0.00 0.00 0.00 0.00