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University of San Carlos

School of Engineering
Talamban, Cebu City, Philippines

CYCLOHEXANE MANUFACTURE
BY CATALYTIC HYDROGENATION OF BENZENE
(Design of a Slurry-phase Bubble Column Reactor and a Fixed-bed Finishing Reactor)

CHE 516N
Dynamics and Control of Processes

Submitted to:

Dr. Angelo H. Cabije


CHE 516N Instructor

Submitted by:

Alexis Margret M. Aberion


Kristian Gregg C. Banaag
Christine Jenica U. Dy
Alyssa Fay L. Go

October 18, 2016


Table of Contents
1. Overall Description of the Process .......................................................................................... 3
2. Mass and Heat Balances .......................................................................................................... 5
2.1. Input/Output Diagram ...................................................................................................... 5
2.2. Functional Block Diagram ............................................................................................... 6
2.3. Process Flow Block Diagram ........................................................................................... 7
2.4. Process Flow Sheet Diagram............................................................................................ 8
2.5. Process Stream Summary ................................................................................................. 9
3. Process Control Objectives .................................................................................................... 15
3.1 Hazard and Operability Study (HAZOP) Analysis of Slurry Bubble Column Reactor
and Multi-tubular Fixed Bed Reactor........................................................................................ 15
4. Dynamics and Control of Processes ...................................................................................... 27
4.1 Flow Controller Fresh Benzene Feed Flow Controller ............................................... 27
4.1.1. Parts of the Feedback Loop System and Block Diagram ....................................... 27
4.1.2. Transport Equations and Assumptions with PID Tuning ....................................... 31
4.1.3. Matlab Simulink Model and Response Graph ........................................................ 35
4.2 Concentration Analyzer Hydrogen Composition Analyzer ........................................ 36
4.2.1 Feedback Loop System, Block Diagram and Derived Process Transfer Function . 36
4.2.2 Transport Equations and Assumptions with PID Tuning ....................................... 39
4.2.3. Mathcad and Matlab Simulink Computation.............................................................. 42
4.3 Level Controller Liquid Level Controller in the Slurry Phase Bubble Column Reactor
43
4.4 Temperature Controller Temperature Controller Thermocouple of a Jacketed Reactor
52
5. Process Control Description and Diagnostics ........................................................................... 64
5. Process Instrumentation and Design...................................................................................... 66
6. Conclusion ................................................................................................................................ 70
6. References ............................................................................................................................. 70

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1. Overall Description of the Process

Cyclohexane is one of the most important industrial chemicals. It is the starting point for
the preparation of caprolactam and cyclohexanone which, in turn, are the precursors, respectively,
of Nylon-6 and Nylon-12. Cyclohexane is consumed largely for nylon 6 and 12 fibers, resins, and
films. For nylon manufacture, a typical purity specification of cyclohexane is 99.8%. Therefore,
the goal of this design project is to produce cyclohexane of 99.8% purity.

The cyclohexane manufacturing plant targets 150,000 tons of cyclohexane to be produced


each year with the available utilities from adjacent facility. The plant operates 350 days a year,
where 15 day-shutdown is allotted for plant maintenance, catalyst replacement and safety
evaluation. Generally, the process of producing cyclohexane involves two catalytic reactors with
partial hydrogenation occurring in the first reactor and complete hydrogenation in the second
reactor with excess hydrogen. Downstream processing utilizes a high-pressure separator followed
by a membrane separator for a hydrogen purification of the off-gas stream and a stabilizer to
produce a high purity product stream substantially free of hydrogen and light hydrocarbons.

In the slurry phase bubble column reactor (isothermal reactor), benzene, pumped to the
required pressure, enters near the bottom tangent line of the reactor. Fresh hydrogen and a
compressed recycle stream from a membrane separator are sparged into the bottom of the reactor.
The Raney nickel catalyst in the first reactor is kept in suspension by means of the high flowrate
of the incoming hydrogen strean. The conversion in this reactor is 95% (Klaus Weissermel, 2003).
The ratio of hydrogen to benzene in the mixture fed to the primary reactor may vary from a
stoichiometric 3:1 mole ratio to as much as about 15:1, but preferably is maintained at 3:1 mole
ratio. General reaction conditions are 160-235C and 10-40 atmospheres (A. Bertucco, 2001), to
provide optimum equilibrium conditions favoring high conversion to cyclohexane. Slurry phase
reactor is provided with an outer-recirculation heat exchanger/cooler which removes the heat of
reaction and low pressure steam generated. Optimum temperature and pressure in the primary
reactor are held at 204oC and 35 atm respectively for the recovery of a liquid phase product
containing cyclohexane, hydrogen and benzene (A. Bertucco, 2001). The second reactor is a
catalytic multi-tubular fixed bed reactor operating at 204oC and 1 atm. In this reactor the reaction
takes place in vapor phase, liquid phase product from the primary reactor containing amounts of

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unreacted benzene is first vaporized and then completely hydrogenated. The second reactor is
referred to as the finishing reactor which has a maximum conversion of 99.8% (Klaus Weissermel,
2003). The finishing reactor with a relatively smaller reaction volume contains a fixed bed of
alumina-supported nickel oxide catalyst.

Effluent from the fixed bed reactor is cooled to 160C (433 K) and then this gas-liquid
mixture is flashed to a vapor-liquid flash separator, operating at 310 K and 10 atm. The resulting
off-gas from the flash separator is sent to a membrane separator for hydrogen purification. The
permeate stream is composed of 0.98 mole% hydrogen and is recycled to the slurry phase bubble
column reactor. The retentate stream is a low hydrogen purity stream which contains the removed
impurities of benzene and methane. The feed side of the membrane is at 20 atm and 30oC (303 K)
while the permeate side, at 1 atm. At the said conditions, 85% recovery is achieved in the
membrane separator (Smith, 2005). The liquid stream product from the flash separator is fed to
the stabilizer column, operating at 355 K and 1 atm, to remove dissolved hydrogen. Liquid
cyclohexane product from the bottom of the stabilization column is cooled in a product cooler and
sent for final storage (A. Bertucco, 2001).

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2. Mass and Heat Balances
2.1.Input/Output Diagram

Retentate Gas sent to


External Recovery
73.60 kg/hr
INPUT 43.58 kg/hr Hydrogen (0.04%) OUTPUT
29.99 kg/hr CH4 (59.21%)
0.313 kg/hr Benzene (40.75%)

Stabilizer Column Overhead


Benzene Feed 33.6083 kg/hr
16,660.1002 kg/hr 1.2221 kg/hr Benzene (3.64%)
16,626.7800 kg/hr Benzene (99.8%) 29.0542 kg/hr Hydrogen (86.45%)
33.3202 kg/hr CH4 (0.20%) 3.3320 kg/hr CH4 (9.91%)

Hydrogen Feed Cyclohexane Product


17,919.4038 kg/hr
1,366.51 kg/hr 17,915.7682 kg/hr Cyclohexane (99.98%)
(Pure hydrogen) PROCESS 0.4074 kg/hr Benzene (0.0023%)
3.2282 kg/hr Hydrogen (0.0177%)

Catalyst Catalyst
9,200 kg Raney Nickel (2,000 9,200 kg Raney Nickel (2,000
hrs. catalyst cycle time) hrs. catalyst cycle time)
17,501 kg Ni/Al2O3 17,501 kg Ni/Al2O3

Cooling Water Cooling Water


1,270,296.34 kg/hr 1,270,296.34 kg/hr

Hydrogen Recycle
279.47 kg/hr
246.96 kg/hr Hydrogen (88.37%)
32.51 kg/hr CH4 (11.63%)
Total Input Total Output
18,026.61 kg/hr 18,026.61 kg/hr

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2.2.Functional Block Diagram

Retentate Gas sent to


Hydrogen Recycle External Recovery
279.47 kg/hr
` 73.6 kg/hr
0.03 kg/hr Benzene (0.04%)
246.96 kg/hr Hydrogen (88.37%)
43.58 kg/hr H2 (59.21%)
32.51 kg/hr CH4 (11.63%)
29.99 kg/hr CH4 (40.75%)

Benzene Feed
16,660.1002 kg/hr Stabilizer Column
16,626.7800 kg/hr Benzene (99.8%) Overhead
33.3202 kg/hr CH4 (0.20%) 33.6083 kg/hr
18,306.082 kg/hr 1.2221 kg/hr Benzene (3.64%)
1.663 kg/hr Benzene (0.009%) 17,953.012 kg/hr 29.0542 kg/hr Hydrogen
Hydrogen Feed 322.824 kg/hr Hydrogen (1.76%) 1.629 kg/hr Benzene (0.0091%) (86.45%)
17,915.768 kg/hr Cyclohexane 17,915.768 kg/hr Cyclohexane 3.3320 kg/hr CH4 (9.91%)
1,366.51 kg/hr (97.87%) (99.79%)
(Pure hydrogen) 65.827 kg/hr CH4 (0.361%) 3.3324 kg/hr CH4 (0.2009%)
REACTION SEPARATION PURIFICATION
Cyclohexane Product
17,919.4038 kg/hr
Catalyst Catalyst 17,915.7682 kg/hr Cyclohexane
9,200 kg Raney Nickel (2,000 9,200 kg Raney Nickel (2,000 (99.98%)
hrs. catalyst cycle time) hrs. catalyst cycle time) 0.4074 kg/hr Benzene (0.0023%)
17,501 kg Ni/Al2O3 17,501 kg Ni/Al2O3 3.2282 kg/hr Hydrogen (0.0177%)

Total Input Total Output


18,026.61 kg/hr 18,026.61 kg/hr

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2.3.Process Flow Block Diagram

Hydrogen Recycle
279.47 kg/hr
Benzene Feed 246.96 kg/hr Hydrogen (88.37%)
16,660.1002 kg/hr 32.51 kg/hr CH4 (11.63%)
16,626.7800 kg/hr Benzene (99.8%)
33.3202 kg/hr CH4 (0.20%)
Catalyst <5>
<1>
9,200 kg Raney Nickel (2,000 Retentate Gas sent to
Hydrogen Feed Liquid Phase Reactor hrs. catalyst cycle time)
<2> External Recovery
1,366.51 kg/hr 477 K
73.6 kg/hr
(Pure hydrogen) 35 atm 18,306.082 kg/hr
0.03 kg/hr Benzene (0.04%)
831.339 kg/hr Benzene (4.54%)
43.58 kg/hr H2 (59.21%)
Catalyst 387.234 kg/hr Hydrogen (2.12%)
29.99 kg/hr CH4 (40.75%)
9,200 kg Raney Nickel (2,000 17,021.682 kg/hr Cyclohexane (92.71%) Membrane Separator
hrs. catalyst cycle time) 65.827 kg/hr CH4 (0.63%) 303 K
Permeate: 1 atm
<4>
Retentate and Feed: 20 <11>
atm

Finishing Reactor
477 K Catalyst
1 atm 17,501 kg Ni/Al2O3

<7> <8>
Catalyst
17,501 kg Ni/Al2O3
18,306.082 kg/hr
1.663 kg/hr Benzene (0.009%)
322.824 kg/hr Hydrogen (1.76%)
High Pressure Separator
17,915.768 kg/hr Cyclohexane (97.87%)
65.827 kg/hr CH4 (0.361%)
310 K Stabilizer Column Overhead
10 atm
33.6083 kg/hr
1.2221 kg/hr Benzene (3.64%)
<12> 29.0542 kg/hr Hydrogen (86.45%)
3.3320 kg/hr CH4 (9.91%)
17,953.012 kg/hr
1.629 kg/hr Benzene (0.0091%)
17,915.768 kg/hr Cyclohexane (99.79%) <17>
Stabilizer
3.3324 kg/hr CH4 (0.2009%) 355 K
1 atm <21>

Cyclohexane Product
17,919.4038 kg/hr
17,915.7682 kg/hr Cyclohexane (99.98%)
0.4074 kg/hr Benzene (0.0023%)
3.2282 kg/hr Hydrogen (0.0177%)

Total Input Total Output


18,026.61 kg/hr 18,026.61 kg/hr

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2.4.Process Flow Sheet Diagram

1 20
477 303
4 11

10
M-1 1 1
E-2 355 298
13 14
35 20 1
477 H-7 303 303 H-3
3 8 10 T-3
1
298
T-1 15

1 17
298 R-2 1 1 P-3
341 298
1 1 10
477 433 12 16
H-6
P-1 6 H-1 7
1
298
2
1
355
10
S-1
310 18 S-2
E-1
9
H-2
R-1 1 1
298 355
H-4
5 1 19
355
T-2 H-5 20

Equipment List 1
311
T-1 T-2 R-1 R-2 P-1 P-2 M-1
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Hydrogen Slurry Phase Multitubular
Benzene Benzene
Storage Bubble Column Fixed Bed Reflux Pump Membrane
Storage Tank Pump
Separator
Process Flow Scheme
Tank Reactor Reactor
Cyclohexane Manufacture by Benzene Hydrogenation
E-1 E-2 S-1 S-2 H-1 H-2 H-3 Project T-4
Reactor 2
(Design of Catalytic Reactors)
Hydrogen High Pressure Bottoms Stabilizer Project ID No. CHE514-03
Cyclohexan Stabilizer Effluent
Compressor Separator Exchanger Condenser
e Expander Cooler Completion Date 6-Oct-16
H-4 H-5 H-6 H-7 T-3 T-4 D e s ig n e rs
Stabilizer Recycle Reactor 1 Reactor 2 Stabilizer Cyclohexane A b e ri o n , A l e x i s M a rg re t M .
Reboiler Cooler Cooler Cooler Reflux Drum Storage Tank B a n a a g , K ri s ti a n G re g g C .
D y , C h ri s ti n e J e n i ca U .
Stream Number Temperature (K) Pressure (atm)
G o , A l y s s a F a y L.

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2.5.Process Stream Summary

The goal, as stated in the problem statement, is to produce the specified amount of 150,000 tons cyclohexane per year.
Considering that the plant is operational for 350 days per year, a production rate of 17,915.77 kg/hr cyclohexane must be achieved. In
order to meet the required production rate, the mass flow rate of benzene must be 16,660.10 kg/hr and the total hydrogen feed coming
from both the fresh feed and recycled feed must be supplied 25% in excess, with a combined mass flowrate of 1,645.98 kg/hr.

Table 2.5.1 Mass flowrates of Incoming and Outgoing Streams

Stream Number 1 2 3 4
Reactor 1 Product (From
Stream Name Benzene Feed Hydrogen Feed First reactor product
Expander)
Component kg/hr kg/hr kg/hr kg/hr
Benzene 16,626.78 - 831.34 -
Hydrogen - 1,366.51 387.23 -
Cyclohexane - - 1,7021.68 -
Methane 33.32 - 65.83 -
Stream Number 5 6 7 8
Reactor 2 Product (From
Stream Name Hydrogen Recycle Reactor 2 Product Off-gas from HP Separator
Cooler)
Component kg/hr kg/hr kg/hr kg/hr
Benzene - 1.66 1.66 0.03
Hydrogen 246.96 322.82 322.82 290.54

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Cyclohexane - 17,915.77 17,915.77 -
Methane 32.51 65.83 65.85 62.50
Stream Number 9 10 11 12
Retentate Stream for
Liquid Product from HP
Stream Name Permeate Stream for Hydrogen External Feed to Stabilizer
Separator
Hydrogen Recycle Recovery

Component kg/hr kg/hr kg/hr kg/hr


Benzene 1.63 - 0.03 1.63
Hydrogen 32.28 246.96 43.58 32.28
Cyclohexane 17,915.77 - - 17,915.77
Methane 3.33 32.51 29.99 3.33
Stream Number 13 14 15 16

Overhead Product of Condensed Overhead


Stream Name Reflux Stream Pumped Reflux Stream
Stabilizer Product of Stabilizer

Component kg/hr kg/hr kg/hr kg/hr


Benzene 1.22 1.22 1.22 -
Hydrogen 29.05 29.05 29.05 -
Cyclohexane - - - -
Methane 3.33 3.33 3.33 -
Stream Number 17 18 19 20

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Overhead Product of Reboiler Product to Bottom Product of Stabilizer
Stream Name Bottom Product of Stabilizer
Reflux Drum Stabilizer to Reboiler

Component kg/hr kg/hr kg/hr kg/hr


Benzene 1.22 0.41 0.41 0.41
Hydrogen 29.05 3.23 3.23 3.23
Cyclohexane - 17,915.77 17,915.77 17,915.77
Methane 3.33 - - -
Stream Number 21 - - -
Final Cyclohexane
Stream Name - - -
Product

Component kg/hr - - -
Benzene 0.41 - - -
Hydrogen 3.23 - - -
Cyclohexane 17,915.77 - - -
Methane - - - -

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Table 2.5.2 Process Stream Conditions

Stream Number and Name Stream Description Temperature (K) Pressure (atm)
(1) Benzene Feed High purity benzene feed 298 1
(2) Hydrogen Feed 100% pure hydrogen feed 298 1
(3) Reactor 1 Product Liquid-phase cyclohexane product
from the slurry phase bubble column 477 35
reactor
(4) Reactor 1 Product (From Vapor-phase cyclohexane product
Expander) (from an expansion turbine) for
477 1
complete benzene hydrogenation in
the multi-tubular fixed bed reactor
(5) Hydrogen Recycle High purity hydrogen recycle from a
298 1
membrane separator
(6) Reactor 2 Product Vapor-phase cyclohexane product
with traces of hydrogen and light
477 1
hydrocarbons which will be sent to a
cooler prior to downstream process
(7) Reactor 2 Product (From Liquid-phase cyclohexane product
Cooler) from a cooler which will be sent to a
high pressure separator for removal 433 10
of hydrocarbons and dissolved
hydrogen

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(8) Off-gas from HP Separator Off-gas sent to a membrane separator
303 20
for a final hydrogen purification step
(9) Liquid Product from HP Cyclohexane product with
310 10
Separator
(10) Permeate Stream for Permeate stream from membrane
Hydrogen Recycle separator containing hydrogen for 303 1
high purity hydrogen recycle
(11) Retentate Stream for Retentate stream from membrane
Hydrogen External Recovery separator for external hydrogen 303 20
recycle
(12) Feed to Stabilizer Cyclohexane product which will be
sent to a stabilization column to
341 1
remove dissolved hydrogen and other
hydrocarbons
(13) Overhead Product of Stabilizer Overhead product of stabilizer which
will be sent to a heat exchanger for 355 1
cooling
(14) Condensed Overhead Product Cooled and condensed overhead
298 1
of Stabilizer product of the stabilization column
(15) Reflux Stream Reflux stream from the reflux drum 341 1
(16) Pumped Reflux Stream Pumped reflux stream which will be
298 1
sent back to the stabilization column

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(17) Overhead Product of Reflux Overhead product from reflux drum
Drum containing benzene, hydrogen and 298 1
methane
(18) Reboiler Product to Stabilizer Reboiler product which will be sent
355 1
back to the stabilization column
(19) Bottom Product of Stabilizer Total Bottom product of stabilizer
where a fraction will be sent to a heat 355 1
exchanger and reboiler
(20) Bottom Product of Stabilizer Fraction of bottom product which
to Reboiler will be sent to a reboiler then back to 355 1
the stabilization column
(21) Final Cyclohexane Product High purity cyclohexane free from
hydrogen and light hydrocarbons 311 1
sent for final storage

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Table 2.5.3 Total Mass Balance Around Major Equipment

INLET STREAMS OUTLET STREAMS


Mass EQUIPMENT Mass
flowrate Stream No. IDENTIFICATION Stream No. flowrate
[kg/hr] [kg/hr]
16,660.10 1
1,366.51 2 R-1 3,4 18,306.08
279.47 5
18,306.08 3,4 R-2 6 18,306.08
18,306.08 6 H-1 7 18,306.08
8 353.07
18,306.08 7 S-1
9 17,953.01
17,953.01 9 12 17,953.01
H-2
17,919.40 20 21 17,919.40
10 279.47
353.07 8 M-1
11 73.60
17 33.61
17,953.01 12 S-2
21 17,919.40
279.47 10 H-5 5 279.47

3. Process Control Objectives


3.1 Hazard and Operability Study (HAZOP) Analysis of Slurry Bubble Column Reactor and
Multi-tubular Fixed Bed Reactor

A hazard and operability study (HAZOP) is a structured and systematic examination of a


complex planned or existing process or operation in order to identify and evaluate problems that
may represent risks to personnel or equipment. The intention of performing a HAZOP is to review
the design to pick up design and engineering issues that may otherwise not have been found. The
technique is based on breaking the overall complex design of the process into a number of simpler
sections called 'nodes' which are then individually reviewed. Presented in the next Table 3.1 is a
HAZOP analysis of the primary and finishing reactors that were designed.

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Table 3.1 HAZOP Analysis for the Primary and Finishing Reactors
Cyclohexane Manufacture by Benzene Catalytic
Project Name: Date: September 15, 2016
Hydrogenation
Process Slurry Bubble Column Reactor (Primary Reactor) and
Equipment: Multi-tubular Fixed Bed Reactor (Finishing Reactor)
Section: Catalytic Hydrogenation Reaction
Element Process Possible Person/s
Deviations Possible Causes Action Required
(Study Node) Parameter Consequences Responsible
1. Closed inlet valve on 1. No reaction can 1. It must be
reactor vessel. occur or side made sure that
2. Valve blockage and reactions may occur. valves are
failure. 2. Valve rupture. opened as
No 3. Pump malfunction. 3. Fire hazard. Can intended for the
cause fire or smooth flow of
Plant Operators
Feed Stream to explosion upon reactants into
Flow and Process
Reactors contact with ignition the reactor
Engineers
sources. vessel.
1. Partially closed inlet 1. Lower production 2. Flowrate must
valve on reactor rate. be controlled
Less vessel. 2. Side reactions and and checked
2. Valve blockage and runaway reactions. regularly.
failure. 3. Valve ruptures.

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3. Leaking of pipelines 4. Fire hazard. Can 3. Regular
and storage vessels. cause fire or maintenance
4. Regulating pressure explosion upon and check-up of
too low. contact with ignition valves, pumps
sources. and piping
1. Valve Failure. 1. Spilling of reactants controls.
2. Sudden increase in in the reactor vessel. 4. In case of valve
flow rate. 2. Side reactions and blockage, valve
3. Regulating pressure runaway reactions. must be
too high (Pump 3. Excessive heat repaired
malfunction). formation, immediately.
More
4. Fire hazard. Can 5. In case of pipe
cause fire or or vessel
explosion upon leakage repair
contact with ignition must be done as
sources. soon as
possible.
1. Low supply of 1. Side reactions may 1. A temperature
Plant Operators
cooling water. occur in the reactor controller must
Temperature High and Process
2. Regulating pressure vessel. be installed to
Engineers
too high. monitor

17
2. Runaway reactions. temperature
Excessive heat is changes.
given off. 2. Temperature of
3. Fire hazard. the inlet
1. Temperature of 1. Side reactions may streams must be
cooling water is too occur in the reactor regularly
low. vessel. regulated and
Low 2. Regulating pressure 2. Low production monitored.
too low. formation. Final
product is not
favored.
1. Closed inlet valve on 1. No reaction can 1. It must be made
reactor vessel. occur or side sure that valves
Slurry Bubble 2. Valve blockage and reactions may occur. are opened as
Column Reactor failure. 2. Valve rupture. intended for the Plant Operators
Vessel / Multi- Flow No 3. Pump malfunction. 3. Fire hazard. Can smooth flow of and Process
tubular Fixed cause fire or reactants into Engineers
Bed Reactor explosion upon the reactor
contact with ignition vessel.
sources.

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1. Partially closed inlet 1. Lower production 2. Flowrate must
valve on reactor rate. be controlled
vessel. 2. Side reactions and and checked
2. Valve blockage and runaway reactions. regularly.
failure. 3. Valve ruptures. 3. Regular
Less
3. Leaking of pipelines 4. Fire hazard. Can maintenance
and storage vessels. cause fire or and check-up of
4. Regulating pressure explosion upon valves, pumps
too low. contact with ignition and piping
sources. controls.
1. Valve Failure. 1. Spilling of reactants 4. In case of valve
2. Sudden increase in in the reactor vessel. blockage, valve
flow rate. 2. Side reactions and must be
3. Regulating pressure runaway reactions. repaired
too high (Pump 3. Excessive heat immediately.
malfunction). formation, 5. In case of
More
4. Fire hazard. Can leakage of
cause fire or pipelines or
explosion upon storage vessels,
contact with ignition repair must be
sources. done
immediately.

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1. Low supply of 1. Side reactions may 1. A temperature
cooling water in the occur in the reactor controller must
heat exchanger. vessel. be installed to
High 2. Excessive release of 2. Runaway reactions. monitor
heat. Excessive heat is temperature
3. Cooling water given off. changes in the
temperature too high. 3. Fire hazard. reactor vessel.
Temperature
1. High supply of 1. Side reactions may 2. Pressure must
cooling water. occur in the reactor also be
2. Cooling water vessel. regulated to
Low temperature is too 2. Low production maintain
low. formation. Final specified
product is not temperature
favored. value.
1. Thermal 1. Side reactions may 1. A pressure
overpressure. occur in the reactor controlled must
2. Incorrect vent set vessel. be installed to
pressure. 2. Runaway reactions. monitor and
Pressure High
3. Chemical breakdown. Excessive heat is regulate
4. Pressure regulator given off. pressure
malfunction. changes.
5. Valve malfunction.

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3. Desired reaction may 2. Reactor vessels
not proceed as must have
designed. appropriate
4. Fire hazard. number and
(External fire) vent volume.
5. Overpressure may 3. Relief valves
cause vessel rupture must be
or explosion. regularly
(Imploding) checked.
1. Generation of vacuum 1. Side reactions may
conditions. occur in the reactor
2. Undetected leakage. vessel.
3. Chemical breakdown. 2. Runaway reactions.
4. Pressure regulator 3. Desired reaction may
malfunction. not proceed as
Low
5. Vessel drainage. designed.
6. Restricted 4. Vacuum conditions
pump/compressor may be formed.
line.
7. Blockage of
regulating valve.
No 1. Valve blockage.

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2. Low pump efficiency. 1. Side reactions may 1. Flow
3. Control faults. occur. regulator
4. Fouled gas 2. Fouling of gas must be
distributor. sparger and installed and
5. Leaking pipelines. contamination. checked
1. Valve blockage and 3. Pump and valve regularly.
failure. failure. 2. Pumps,
2. Low pump efficiency. valves and
Less
3. Fouled gas pipelines
distributor. must be
Plant Operators
Gas Sparger or Flow/Gas 4. Leaking pipelines. check. Pumps
and Process
Distributor Velocity 1. Increased pumping 1. Pump over-speed must not be
Engineers
capacity. and overheating. overheated.
2. Reduced delivery 2. Valve rupture and (replace if
head. pipe leakages. necessary)
3. Cross connection of 3. Spilling. 3. Leakages
More systems or running 4. Side reactions. must be
multiple pumps. repaired
4. Increased suction immediately.
pressure. 4. In case of
fouling, gas
distributor

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must be
cleaned and
regenerated.
1. Low supply of 1. Side reactions may 1. A temperature
cooling water in the occur in the reactor controller must
heat exchanger. vessel if temperature be installed to
High 2. Excessive release of is not controlled. monitor
heat. 2. Intense fire or temperature
3. Cooling water runaway reactions. changes in the
Cooling Jacket of Plant Operators
temperature too high. reactor vessel.
Slurry Bubble Temperature and Process
1. High supply of 1. Side reactions may 2. Pressure must
Column Reactor Engineers
cooling water. occur in the reactor also be
2. Cooling water vessel is temperature regulated to
Low temperature is too is not controlled. maintain
low. specified
temperature
value.
1. Closed inlet valve on 1. Side reactions may 1. It must be
reactor vessel. occur. made sure that Plant Operators
Product Steam of
Flow No 2. Valve blockage and 2. Damage to pump valves are and Process
Reactors
failure. and valves. opened as Engineers
3. Pump malfunction. intended for

23
1. Partially closed inlet 3. Damage to the smooth
valve on reactor pipelines. flow of
vessel. 4. Low production reactants into
2. Valve blockage and rate. the reactor
Less failure. vessel.
3. Leaking of pipelines 2. Flowrate must
and storage vessels. be controlled
4. Regulating pressure and checked
too low. regularly.
1. Valve Failure. 1. Side reactions may 3. Regular
2. Sudden increase in occur. maintenance
flow rate. 2. Separation unit may and check-up
3. Regulating pressure not be able to of valves,
too high (Pump accommodate the pumps and
malfunction). high flowrate. Thus, piping
More spilling and pipe controls.
rupture can occur. 4. In case of
3. Can cause valve
implosion of reactor blockage,
vessels and valve must be
separation units. repaired
immediately.

24
4. Pump over-speed 5. In case of pipe
and overheating. or vessel
leakage repair
must be done
as soon as
possible.
1. Low supply of 1. Product may 1. A temperature
cooling water. contain undesirable controller must
High
2. Regulating pressure amounts of be installed to
too high. impurities. monitor
1. Temperature of 2. Separation unit may temperature
cooling water is too not be able to changes in the
low. efficiently separate reactor vessel.
2. Regulating pressure undesired 2. Pressure must
Temperature
too low. impurities from the also be regulated
desire product. Can to maintain
Low
strongly affect the specified
next operations or temperature
processes. value.
3. Fire hazard. If
temperature is too
high, a runaway

25
reaction may occur
and cause
explosions.

26
4. Dynamics and Control of Processes
4.1 Flow Controller Fresh Benzene Feed Flow Controller
4.1.1. Parts of the Feedback Loop System and Block Diagram
The flow of fresh liquid benzene to the slurry phase bubble column reactor is a critical aspect
of process control since the amount of benzene being fed to the reactor will affect the overall
conversion of benzene to cyclohexane via catalytic hydrogenation. With this, a closed-loop
feedback control system will be employed to control flowrate of incoming fresh benzene feed to
the slurry phase bubble column reactor.

There are various methods used to measure the flow rate of liquid streams. Since the
flowrate of all incoming and outgoing streams presented in the design project are in terms of mass
flowrates, a mass flow meter or an inertial flow meter would be highly sufficient. Generally, a
mass flow meter is a device that measures mass flow rate of a fluid traveling through a tube. The
mass flow rate is the mass of the fluid traveling past a fixed point per unit time. In industry, there
are two types of mass flowmeters namely: a thermal flowmeter and a Coriolis flowmeter.
Accordingly, we have chosen to use a Coriolis type of flow meter.

The thermal mass flowmeter operates independent of density, pressure, and viscosity.
Thermal meters use a heated sensing element isolated from the fluid flow path where the flow
stream conducts heat from the sensing element. The conducted heat is directly proportional to the
mass flow rate and the temperature difference is calculated to mass flow. The accuracy of the
thermal mass flow device depends on the calibrations reliability of the actual process and
variations in the temperature, pressure, flow rate, heat capacity and viscosity of the fluid.

Direct mass measurement sets Coriolis flowmeters apart from other technologies. Mass
measurement is not sensitive to changes in pressure, temperature, viscosity and density. With the
ability to measure liquids, slurries and gases, Coriolis flowmeters are universal meters. Coriolis
mass flowmeter uses the Coriolis effect to measure the amount of mass moving through the
element. The fluid to be measured runs through a U-shaped tube that is caused to vibrate in an
angular harmonic oscillation. Due to the Coriolis forces, the tubes will deform and an additional
vibration component will be added to the oscillation. This additional component causes a phase
shift on some places of the tubes which can be measured with sensors.

27
Coriolis meters are true mass meters that measure the mass rate of flow directly as opposed
to volumetric flow. Because mass does not change, the meter is linear without having to be adjusted
for variations in liquid properties. It also eliminates the need to compensate for changing liquid
viscosity, temperature and pressure conditions. The meter is especially useful for measuring
liquids whose viscosity varies with velocity at given temperatures and pressures. Presented in
Figure 4.1 is a photo of a basic Coriolis flow meter.

Figure 4.1 Mass Flow Meter of the Basic Double-Tube Coriolis Type

A Coriolis meter is a bidirectional flowmeter handling flow in either direction with no


adjustments. Coriolis meters are extremely accurate. In facts, a Coriolis meter is often used as a
standard for checking other flowmeters. A liquid mass flow accuracy of 0.10% is common and
0.05% is readily available. Moreover, liquid density accuracies up to 0.0002 g/cm 3 are available.
Newer Coriolis meters have onboard diagnostics such as meter verification, which allows the user
to confirm accuracy while the meter is operating (Emerson Process Management, 2015).

In order to accommodate the expected benzene mass flowrate of exactly 16,660.10 kg/hour,
a CMFS100M Model from the series of Micro Motion flowmeter products manufactured by
Emerson Process Management was chosen. CMFS100M is a basic dual-tube Coriolis flowmeter
constructed using Stainless Steel 316L that allows a maximum flowrate of 25,900 kg/hour (7.1944
kg/s) of liquid flow (See Table 4.1). Shown in Figure 4.2 is a schematic diagram of the Coriolis
flow meter.

28
Table 4.1 Nominal and Maximum Flowrates for Various Models of Coriolis Flow Meters

Figure 4.2 Schematic Diagram of a Coriolis Meter

For the control valve, a throttling valve will be used and will be pneumatically operated.
The valve is a controlled device that regulates the flow of a liquid the system. This regulation is
accomplished by the varying resistance that the valve introduces into the system as the valve is
stroked. As the valve modulates to the closed position the system pressure drop shifts to the valve
and reduces the flow in the system. The controller action depends upon the choice of control valve.
Pneumatic operated valves can be automatic or semi-automatic. They function by translating an
air signal into valve stem motion by air pressure acting on a diaphragm or piston connected to the

29
stem. Pneumatic actuators are fast-acting for use in throttle valves and for open-close positioning.
They are simple, dependable and direct acting. They can be used in demanding conditions because
of their integral positioner capability and high stem force output. For controlling mass flow of
benzene to the slurry phase bubble column reactor, the valve will be operated automatically to
reduce transport lag.

If an air to open valve is chosen then controller action should be reverse, as an increase in
flow must be countered by a decrease in valve opening. For an air to close valve the action must
of course be direct. In this case, the controller is set to be air-to-open. If an air to open valve is
chosen then controller action should be reverse, as an increase in flow must be countered by a
decrease in valve opening. Based on international standards, the valve positioner should be
calibrated to be fully open at an air pressure of 3 psig and fully closed at a pressure of 15 psig.

Presented in Figure 4.3 is the designed flow control loop for benzene mass flowrate to the
primary reactor. In the designed feedback control loop, a Coriolis flowmeter measures the mass
flowrate of fresh liquid benzene entering the slurry phase bubble column reactor (Denoted as R-
01). Generally, a Coriolis meter is partitioned into two sections: the flowtube and the transmitter.
The flowtube is essentially a mechanical component providing the pipework through which the
process fluid flows, including the measurement section which is able to vibrate, along with coil-
based sensors and drivers to monitor and maintain the flowtube vibration. The transmitter is
essentially an electronic device with electrical connections to the sensors and drivers of the
flowtube. The tasks of the transmitter are to initiate and maintain flowtube vibration and to extract
mass flow, density and possibly other process data from the sensor signals (Manus Patrick Henry,
2004). Typically, for this type of system the transmitter inside the flowmeter sends an electric
signal to a transducer, which converts the signal from electric to pneumatic. In the case of flow
controls, an I/P transducer is commonly used. Once the controller has calculated a position of the
actuator, it sends an electric current to the transducer, typically from 4 to 20 mA, which transforms
into a pressure between 3 to 15 psig. This is expected to send a signal to the flow controller to tune
the flowrate. Additionally, because the elements are close in proximity, it is assumed that there is
no transport lag. Based from literature data, the Coriolis flowmeter has a response time of about
0.04 to 1 second (Manus Patrick Henry, 2004).

30
FT
101

FC
101 FIT
Fresh Benzene Feed
101
To R-01
Benzene Feed
Pump

Control Valve

Benzene Storage
Tank

Figure 4.3 Design Flow Control Loop for Benzene Inlet Stream to R-01

With the above assumptions, the control loop of the system can be derived as transfer
functions, as shown in Figure 4.4.

V,i V P V,f
kg/s
KM KC mA KT PT
KV
kg/s psig kg/s

V,M
kg/s KM

Figure 4.4. Control loop for the system

4.1.2. Transport Equations and Assumptions with PID Tuning


Flowmeter (Measuring Element)

It is further assumed that the residence time of the signals through the flowmeter is
negligible. It is assumed that the flow measuring device is linear and has negligible lag
(Coughanowr & LeBlanc, 2009). The sensitivity (or gain) of the measuring device is therefore
computed as:

20 4
=

7.1944 0

31

= 2.2240

, ()
=
, ()

, ()
= 2.2240
, ()

Transducer

A measuring device that changes the type of signal between its input and output is called a
transducer. Again, it is assumed that the residence time of the signals in the transducer is negligible
(Coughanowr & LeBlanc, 2009). Hence, the transfer function of the measuring element is equal
to the gain KT as given below.

15 3
=
20 4


= 0.75

()
=
()

()
= 0.75
()

Control valve

The air-to-open control valve selected for the process has the following characteristics. The
flow of fresh benzene through the valve varies linearly from 0 to 25 m3/hour (6.0833 kg/s) as the
valve-top pressure varies from 3 to 15 psig. The response time is approximately equal to the
residence time V of the valve. Such quantity is approximated by estimating the capacity of the
valve as a cylinder. The flowrate used is the maximum flowrate allowable. Based on the calculated
dimensions of the liquid benzene inlet feed pipe, the valve dimensions were accordingly selected
from pre-set sizes readily available in the market. The control valve has an orifice dimeter of about
2.5 inches or 63.5 mm, and a travel length of approximately 75 mm (Uniflo Co., Ltd., 2014).

32
2

= 4
,

3
(63.5 )2 1
(75 ) ( )
= 4 1000
3 1 1
25 ( ) ( 60 )
60 min

= 0.03420

The next calculations show the solution for finding KV.


6.0833 0
=
15 3


= 0.5069

With the obtained values of KV and V, the transfer function for the control valve can be
obtained.

()
=
() + 1


() 0.5069
=
() 0.03420 + 1

Controller

The transfer function for the controller is obtained using the PID Tuning feature of
Simulink. Shown in Figure 4.5 are the Simulink models of the process with: no control, P control,
PI control and PID control. After tuning, the respective gains of the proportional control (KC,P),
proportional-integral control (KC,PI) and proportional-integral-derivative control (KC,PID) were
obtained, as shown in Table 4.2.

33
Table 4.2. Gains obtained from controllers

KC,P, psis/kg 2.4158


KC,PI, psis/kg 1.2329
KC,PID, psis/kg 1.5820

From the PI control, the integral I was found to be 108.1881 psis2/kg. From here, the
response time can be computed, as shown below.


, =
,

psi s 2
108.1881
kg
, = = 87.75
psi s
1.2329

From the PID control, the integral I was found to be 92.4580 psis2/kg. From here, the
response time can be computed, as shown below.


, =
,

psi s2
92.4580
kg
, = = 58.44
psi s
1.5820

34
4.1.3. Matlab Simulink Model and Response Graph

Figure 4.5. Liquid Benzene Flow Controller Simulation Model

Figure 4.6. Liquid Benzene Flowrate Response as a Function of Time

35
Flow measurements by its very nature is noisy. Therefore, derivative action cannot be used
effectively in the controller because the noisy signals cause the loop to become unstable. Flow
control is one type of loop where an integral-only controller can be used. One drawback to integral-
only control is that it can greatly slow down the response of the loop, but the flow process is so
fast that this slowing down may not be significant. In actual industrial settings, the control modes
for controlling flowrate will be proportional plus integral. PI controllers are fairly common, since
derivative action is sensitive to measurement noise, whereas the absence of an integral term may
prevent the system from reaching its target value.

Based on the simulation control responses, both the PI and PID controller achieved the set-
point mass flowrate value of liquid benzene. Though the PI controller had a larger offshoot, both
the PI and PID controller reached the steady state value at near time intervals, while the P controller
did not achieve the set-point value. Therefore, the choice of controller selection boils down to
either using a PI or PID controller. Considering the capital and installation cost of the controller,
the PI controller is more economical and can deliver excellent performance comparable to a PID
controller. Therefore, the PI controller will be used to control mass flowrate of liquid benzene to
the slurry phase bubble column reactor.

4.2 Concentration Analyzer Hydrogen Composition Analyzer


4.2.1 Feedback Loop System, Block Diagram and Derived Process Transfer Function
The hydrogen feed stream into the bubble column slurry reactor is composed of a mixture
of the pure hydrogen stream with the recycled hydrogen stream coming from the membrane
separator. It this process, the purity of the hydrogen to enter the bubble slurry reactor is critical
because low purity of this stream would affect the conversion of benzene to cyclohexane thus, it
is desired to make a control system intended for this purpose.

A control scheme for controlling hydrogen purity of the feed comprises a hydrogen purity
analyzer that measures hydrogen purity of the resulting feed mixture to be supplied to the reactor.
The hydrogen analyzer measures the purity of the resulting gas, which is converted into a control
signal and is transmitted to the appropriate gas controller. As hydrogen purity decreases in the feed
stream, the gas control valve of the recycle stream is adjusted. As hydrogen purity fluctuates, the

36
recycle gas control valve will open and close to maintain the desired purity set point. The control
loop as suggested is shown in Figure 4.7.

Figure 4.7 Control loop for purity of Hydrogen feed

The steady state values of the mixing system are given below

F1 = 4.2223 m3/ sec C1 = 0.090 kg/m3


F2 = 0.8635m3/ sec C2 = 0.0794 kg/m3

Where,

F1 volumetric flowrate of pure hydrogen in kg/ sec

F2 volumetric flowrate of recycled hydrogen in kg/ sec

C1 hydrogen concentration of pure hydrogen stream in kg/m3

C2 hydrogen concentration of recycled hydrogen stream in kg/m3

Derivation of the process transfer function

Carrying out a mass balance across the mixing point,

37

= 1 1 + 2 2 (1 + 2 )


= 1 1 + 2 2 (1 + 2 )

The deviation variables in this case are C and F1. Linearizing the differential equation,


= (1 )1 (1 + 2 )

Taking the Laplace transform,

= (1 )1 (1 + 2 )

Rearranging to obtain the transfer function in standard form,

+ (1 + 2 ) = (1 )1

1
1 + 2
= =
+ 1
1 + 2 + 1

Where, K is the gain in kg/hr and time constant in hr.

Using the balance at steady state to calculate C,

0 = 1 1 + 2 2 (1 + 2 )

1 1 + 2 2
=
1 + 2

3 3
4.2223 (0.09 3 ) + 0.8635 (0.0794 3 )

= 3 = 0.0882 3

5.0858


1 0.09 3 0.0881 3
= = 3 = 3.7359104
1 + 2
5.0858

38
3
5.0858
= = =1
1 + 2 3
5.0858

By substitution, the transfer function at the mixing point is obtained.

4
3.735910
=
+1

4.2.2 Transport Equations and Assumptions with PID Tuning

Measuring Element

The measuring element is the continuous hydrogen analyzer (CHA) that measures hydrogen
concentration directly and specifically. The gas stream sample from the hydrogen feed is diverted
to the CHA and then returned to the process. Upon installation, the analyzer is calibrated for
measuring hydrogen concentration within a discrete, specified range. A transducer changes the
type of signal between its input and output where in this case, the concentration signal is changed
to a current signal. The analyzer features a 4-20 mA current loop output signal as the hydrogen
concentration varies from 0.08 to 0.1 kg hydrogen/ m3. To simplify, it will be assumed that the
concentration measuring device is linear thus the gain or sensitivity can be computed as follows.

20 4
= = 800

0.1 3 0.08 3
3

Since C, the set point is desired to be 0.0881 3 , the normal signal expected from the measuring

device can be computed as follows,


0.0881 0.08 3
3 (20 4) + 4 = 14.89

0.1 3 0.0881 3

The Hydrogen Analyzer is to be obtained from COSA+Xentaur Instrument Corporation. The CHA
sensors proton conducting membrane is platinum-coated on both sides, creating two electrodes.

39
One electrode is in contact with the sample gas stream, the other with a reference gas stream of
known hydrogen concentration. As hydrogen molecules dissociate, the resulting protons are
conducted from the stream with higher hydrogen partial pressure through the membrane to the
stream with lower hydrogen partial pressure. The resulting electrons do not pass through the
membrane, creating a charge imbalance across the sensor. By quantifying these electrons as
voltage across the electrodes, hydrogen concentration in the sample is then determined (COSA
Instrument Corporation, 2004). As specified from the company instrument specification sheets,
the CHA has a response time of 2 minutes therefore the transfer function for the analyzer is
obtained as follows,

= 2 = 120

() 800
= =
() + 1 120 + 1

Controller

Using the PID tuning in Simulink, the transfer function for the controller will be obtained and from
this the respective gains can be determined. The following schemes will be compared using
Simulink: no control, P control PI control and PID control.

Table 4.3. Controller gains determined using Simulink

Controller gain value


KC,P [psis/m3] 19.28
KC,PI, psis/m3 11.00
KC,PID, psis/m3 13.81

Control Valve

The air to close valve specifically, a throttling pneumatic operated valve is selected for the
process where the flow of recycled hydrogen gas is controlled through the valve. When selecting
control valves for gas applications, pressure drop through the valve is dependent upon operating
temperature, pressure, and fluid composition. Therefore, when selecting a valve for any particular
gas application, it is highly recommended that each valve be sized. Based on the calculated

40
dimensions of the hydrogen inlet feed pipe, the valve dimensions were accordingly selected from
pre-set sizes readily available in the market. The control valve has an orifice dimeter of 7.8 inches
or 198.12 mm, and a travel length of approximately 540 mm. Also, the valve varies linearly from
3
0 to 18,313 as the valve top pressure varies from 3 to 15 psi. (Uniflo Co., Ltd., 2014). The

transfer function for the valve is obtained with pressure and flow being the deviation variables
(Coughanowr & LeBlanc, 2009). Using these given information, the valve gain and response time
are computed as follows,

3 3 3
18,313 0
= = = 1887.5833 = 0.5243
15 3

The response time of the valve can be approximated by taking the capacity of the valve using the
maximum allowable flowrate where, r is the radius of the cross-sectional area of the valve and l is
the valve travel length.

2
= =

3
198.12 2 1
( ) 540 ( )
= 2 1000 (3600 ) = 3.2725103
3 1
18,313

The transfer function for the control valve is given by the following equation.

() 0.5243
=
() 3.2725103 + 1

Controller Transducer

The control valve requires a pneumatic signal of 3 to 15 psi and since the controller output is an
electronic signal of 4 to 20 mA range, a transducer will be needed to convert the controller signal
to the required pneumatic signal and the transfer function for the transducer can be represented by
a gain given by,

() (15 3)
= = = 0.75
() (20 4)

41
4.2.3. Mathcad and Matlab Simulink Computation

Figure 4.8. Hydrogen Feed Composition Controller Simulation Model

Figure 4.9. Hydrogen Composition Response as a Function of Time

42
Based on the simulated control system responses, both the PI and PID controllers achieve
the set point value. Both of their graphs appear to overlap each other while the P controller was
not able to achieve the steady state value. Therefore, the choice of controller boils down to either
selecting the PI or PID controller. Considering the cost of each controller, it would be more
economical to employ a PI controller. The PI controller deems sufficient to control and monitor
the changes in the Hydrogen concentration without any harmful safety drawbacks.

4.3 Level Controller Liquid Level Controller in the Slurry Phase Bubble Column Reactor
Level Control for Bubble Slurry Column
Slurry reactors are three-phase reactors, meaning they can be used to react solids, liquids,
and gases simultaneously. They consists of catalyst (solid) suspended in a liquid through which
gas is bubbled. The liquid in this case is benzene and it needs to fill up the whole reactor. With
this problem, a closed loop feedback control system is needed to control the height of the liquid in
the reactor given with the volumetric flowrate, cross sectional area of the reactor and set point
height.

Measuring Element
In all cases, some kind of instrument is measuring changes in the process and reporting a
process variable measurement. Measuring elements cause some changes in their properties with
changes in process fluid conditions that can then be measured. In our case, we used a typical
dynamic of a measuring element wherein it outputs a current as the height of the tank changes.
The typical electrical specification of most sensors have a current that varies from 4 mA to 20 mA.

Table 4.4. Comparison of common level sensors (OMEGA Engineering Inc. 2003-2016)

Sensor Advantages Disadvantages


Non-Contact Radar Sensors can detect the
Radar Level Continuous Level Measurement level under a layer of light dust
Transmitter/ Pushbutton or programmable or airy foam, but if the dust
Sensors calibration particle size increases, or if the
LVRD500 Series Operating temperature range: -40 foam or dust gets thick, they will
Radar Level to 60C no longer detect the liquid level
Transmitter This technology provides Internal piping, deposits on the
reliable, continuous pulse shapes antenna, multiple reflections, or

43
unaffected by environmental reflections from the wall can
factors such as temperature, interfere with the proper
vacuums, methane, steam, operation of the radar sensor
pressure, carbon dioxide, vapors, Rat holing and bridging of
and condensation. solids, as well as angled process
The antenna comes in material surfaces that can reflect
polypropylene or an optional the radar beam away from the
high resistance PTFE that can receiver
help protect against material Expensive and probe length
buildup must be the entire length of the
sensing range
When using the adaptors, a zero
offset is introduced into the
Liquid level output signal which must be
Immune to changes in viscosity,
transmitter/ float compensated for in the readout
density, or conductivity
sensor device and retainer clip pliers are
Resists vapor and turbulence
LVR20/30 Series required to remove the float
when using the adaptor system
Rugged construction
Rugged Construction
Capacitance Can operate at high temperature Housings must be compatible
Continuous and pressures with the requirements for
Level Unaffected by Coating media or hazardous, washdown, wet, or
Measurement aggressive products dusty environments
Probes Easy economical installation The active probe might need to
LV3000 and Compatible with both conductive be instrinsically safe or have an
LV4000 Series and nonconductive media intrinsic safety barrier
Max pressure 20 bar
All stainless steel casing
Submersible
Hermetically sealed housing
Pressure Limited to applications with low
Protective cap included
Transmitter for viscosity liquids with a specific
Moisture trap included
Level and Depth measuring range
0-35 bar operating pressure
Measurement
PXM78 Series Units work well with in liquid
with solids

44
Based from the table above, the best level sensor is the submersible pressure transmitter for level
and depth measurement. This type of level sensor has a time constant equal to 0.02 seconds
(Omega Inc, 2016).

In order to solve for the gain of the transfer function for our measuring element, we made these
assumptions:

1. The output of the measuring element varies from 4 mA to 20 mA as the height of the liquid
in the tank varies from 0 to 13.33m.
2. The level sensor is linear and has negligible lag compared to the process.

The sensitivity(gain) of the measuring device is therefore:

20 4
=
13.33 0
= 1.2

Controller Transducer
The output from the controller is an electronic current signal ranging from 4 to 20 mA
which is the same as the output signal for the measuring element. In this case, the transducer
transfer function is the same with the flow control. Again, it is assumed that the residence time of
the signals in the transducer is negligible. Hence, the transfer function of the measuring element is
equal to the gain KT as given below.

15 3
=
20 4


= 0.75

()
=
()

()
= 0.75
()

45
Control valve
The air-to-open control valve selected for the process has the following characteristics. The
flow of fresh benzene through the valve varies linearly from 0 to 19.07 m3/hr as the valve-top
pressure varies from 3 to 15 psig. The response time is approximately equal to the residence time
V of the valve. Such quantity is approximated by taking estimating the capacity of the valve as a
cylinder. The flowrate used is the maximum flowrate allowable.

In order to solve the transfer function for our measuring element, we made these assumptions:

1. The output of the control valve varies from 3 psig to 15 psig as volumetric flowrate of the
fresh liquid benzene varies from 0 to 19.07 m3/hr.

Based on the model specifications, the equivalent maximum volumetric flowrate is 25,900
L/hour or 19.07 m3/hr and the variables A and D correspond accordingly to the dimensions shown
in Figure 4.2.

2

= 4
,

(0.598 )2
(0.102 )
= 4
19.07 m3 /hr

= 1.5022 103

The next calculations show the solution for finding KV.


=

19.07 3 / 0
=
15 3

3
= 1.5892

With the obtained values of KV and V, the transfer function for the control valve can be
obtained.

46
()
=
() + 1

3
() 1.5892

=
() 0.00015 + 1

Process
Figure shows liquid flow in a pipe, with a restricting device (a valve) providing a hydraulic
resistance (Rh) to the flow.

When turbulent flow occurs from a tank discharging under its own head or pressure, the
flow is found by the following equation:
= 2

Where q0 is the flow rate (ft3/s), K is a flow coefficient, A is the area of the discharge
orifice (ft2), g is gravitation constant (ft/s2), and h is pressure head of liquid (ft).
We can define hydraulic resistance (R) to flow as follows:

=

Substituting qo, the instantaneous hydraulic resistance is:
2
= =

In a tank being filled with a liquid, the equation for the volume (V) of the liquid in the tank
is given by the following equation:
V (t) = A h(t)
where
V(t) = the volume of liquid as a function of time
h(t) = height of liquid
A = the surface area of the liquid in the tank

47
Note that the volume V of the tank and the liquid height or head are a function of time. The
flow of liquid into the tank, qi , and the flow liquid out of the tank, qo , vary with time. Rearranging
the previous equation, we get
()
= =
()
Comparing this equation to the equation for electrical capacitance (i.e., C=q/V) clearly
shows that liquid capacitance Cl is simply the surface area of the liquid in the tank, or Cl = A.
Furthermore, taking the derivative of the equation with respect to time yields
() ()
=

The volumetric output flow-rate qo, through the resistance R, is related to the head h and
can be given by a linear relationship as


0 =

The transient mass balance equation can be given as,
Mass flow-in Mass flow-out = Rate of accumulation of mass in the tank
In terms of variablesused in this analysis, the mass balance equation becomes

() 0 () = =


() 0 () =

By substituting and rearranging,

() =


() = +


() = +

Taking LaplaceTransform by assuming zero initial conditions,
( + 1)() = ()
Where,

48
()
=
() ( + 1)

If however, q0 is taken as the output ,the input being the same, then the transfer function is

0 () 1
=
() ( + 1 )

()
0 () =

To obtain the differential equation in terms of variable qo, dh/dt must be expressed in terms of
dqo/dt.
()
() 0 () =


=
0
From the previous description on R for turbulent flows,
= 2/

13.33
= 2( 3 )
19

= 1.398 /2
The lag time can be calculated by multiplying the resistance to the cross sectional area
=
(3.33)2
2
= 1.398/ ( )
4
= 12.175
So the transfer function is
()
=
() ( + 1)
() 1.398
=
() (12.175 + 1)

49
Controller

The transfer function for the controller is obtained using the PID Tuning feature of
Simulink. Shown in Figure XX are the Simulink models of the process with: no control, P control,
PI control and PID control. After tuning, the respective gains of the proportional control (KC,P),
proportional-integral control (KC,PI) and proportional-integral-derivative control (KC,PID) were
obtained, as shown in Table 4.3.

Table 4.5. Gains obtained from controllers

KC,P, psis/kg 1.2113


KC,PI, psis/kg 0.6142
KC,PID, psis/kg 0.7901

From the PI control, the integral I was found to be 0.1255 psis2/kg. From here, the response
time can be computed, as shown below.


, =
,

psi s2
0.1504
kg
, = = 0.2449
psi s
0.6142

From the PID control, the integral I was found to be 0.1082 psis2/kg. From here, the
response time can be computed, as shown below.


, =
,

psi s2
0.1297
kg
, = = 0.1642
psi s
0.7901

50
Figure 4.10 Liquid Level Controller Simulation Model

51
Figure 4.11. Liquid level as a Function of Time

Based from the results, both the uncontrolled and proportional controller did not meet the liquid
height set therefore it is suitable to be used as the main system for the closed loop. On the other
hand, both the PID and PI controlled closed loop system did meet the liquid height set however,
PI has a higher overshoot than PID. Although PI has a higher overshoot, their difference in time
to reach their steady state values are almost equal therefore it is better to choose PI controller since
it is more economical than PID controller.

4.4 Temperature Controller Temperature Controller Thermocouple of a Jacketed Reactor


Derivation of the dynamic model of the reactor

Doing a mole balance across the reactor,


= ( )

Including the Arrhenius temperature dependence and a second order kinetic rate
expression for the rate of disappearance of the reactant followed by an energy balance accounting
for the reaction and heat transfer,

52

= = 0

Now, an energy balance is also performed.


= ( ) ( ) ( )

Since the reaction in this specific system of Benzene and Hydrogen is exothermic, the heat
of reaction HR will be negative and thus the rate of heat transfer Q will depend on the logarithmic
temperature difference where, T is the temperature of the well mixed tank and T c is the coolant
temperature.

( ) ( )
=

ln( )

The overall heat transfer coefficient depends on the film coefficients on the inner and outer
surfaces of the heat transfer barrier. Any conduction resistance in the barrier itself will be neglected
and since the temperature of the coolant supply Tci is stable, it will not be considered as a
disturbance. The outer film coefficient ho does not vary because the physical properties are taken
to be constant.

1 0 1
= ( + )
0


= Pr m

Rewriting this at a reference condition where for flow in tubes n is often taken to be about
0.8,


= ( )

1
Doing an energy balance on the coolant where, <Tc>=

< >
= ( ) ( ) +

53
The average temperature will be expressed in terms of the inlet and outlet temperatures
assuming that the heat exchanger outlet temperature adjusts quicker than the tank temperature T,
so that the accumulation term can be written as follows.

( ) =

The equations above describe how the outlet temperature and composition vary in time due
to disturbances in inlet temperature, inlet composition and coolant flow rate. The coolant outlet
temperature is an intermediate variable in the system. Since these equations are nonlinear, they
have to be simplified further by making a linear approximation to the material balance using the
Taylor series.

( ) ( )
= ( ) | ( ) | ( )

At the reference condition,


= 0 = ( )


( ) ( )
= | |

( )
=

( )
| =

( ) 2
| = =
2 2

Where, kr is the rate constant at the reference condition


= 0

Substituting into the linearized material balance and obtaining the first order lag equation
in the standard form,

54


=
2


+ = +

Where, is the residence time of the tank, is the time constant that characterizes the
dynamics of composition change and is the gain for he effect of temperature on the
composition in the reactor.


=
+


=
2

Similarly, the energy balance can be approximated as follows,

( )
= ( ) | ( )

( )
| ( )


| ( ) | ( )

At reference condition,


= 0 = ( )

Defining the deviation variables,

55
( ) ( )
= | | |


|

Eliminating the intermediate variable Tco,

0 1 0 1
= ( ) [1 exp { ( + ) }]
0

The partial derivatives are given by,

0 1 0 1
= [1 exp { ( + ) }]
0


| = [1 ]

0 1 0 1
= ( ) [1 exp { ( + ) }]
0

0 ( ) 1 0 1 0 1 0 1 1
( + ) exp { ( + ) }[(
0 0 0

0 1 0
+ ) ]

0 ( ) 0
| = [ ][1 ] [1 ]

1 1 0 0
Where, 0 = ( + 0 ) and = exp { }
0

By substitution into the linearized energy balance to obtain the first order lag equation,


+ = + + (0) = 0

Where,

56

=


=

1 + (1 ) + 2

( ) 0 0 0 0
= [ (1 ) (1 )]

Furthermore, we take the Laplace transforms of the derived energy and mole balances.


( + 1) () = () + ()

()
( + 1) () = + () + ()

These can be represented in the diagram below.

Figure 4.12. Block diagrams for temperature control

57
For the slurry bubble column reactor, the following values were used.

Table 4.6 Summary of values used for the calculations in the temperature control

V 115.7732 m3
F 1.833 x 104 m3/hr
E -12300 cal/mol
R 1.986 cal/ mol K
ko 0.18
Di 3.33 m
Do 3.39 m
873.6 kg/m3
Cp 4.181 kJ/ kg K
Uo 567.83 W/ m2 K
cp 993.965 kg/m3
Fc 874.194 m3/hr

Constants Calculations:

115.7732
= = = 0.006
1.833104
12300
= 0 = 0.18 (1.986477) = 4.134 107

Kinetic data for the system were given be (Kehoe & Butt, 1972).

115.7732
= = = 0.006
+ 1.83310 + 4.134 107 (115.7732)
4

4.134 107 (12300)(0.006)


= 2 = = 6.752 1011
1.986(4772 )

0 0 567.83(36)(103.933)
{ } { }
874.194(993.965)(4.181)
= e = = 0.942

The overall heat transfer coefficient was estimated by H&C Heat Transfer Solutions Inc.

58

=

1 + (1 ) + 2

0.006
=
874.194(993.965)(4.181)(1 0.942) 2639.88(115.7732)(4.143107 ) 12300
1+ 4 + ( 4 )( )
1.83310 (873.6)(0.1664) 1.83310 (873.6)(0.1664) 1.986(4772 )
= 0.006

206.2(115.732)(4.134107 )
= = 4
= 3.702109
1.83310 (873.6)(0.1664)

( ) 0 0 0 0
= [ (1 ) (1 )]

0.006(993.965)(4.184)(477 308) 0.942(567.83)(3.6)(106.604)
= [ (1
0.006(1.833104 )(873.6)(0.1664) (874.194)(994.965)(4.181)
567.83(3.6)(106.604)(0.8)
) (1 0.942)] = 0.134
104.615(2107094.009)

From these values, the constants needed can be calculated. They are summarized below.

Table 4.7 Summary of calculated constants for temperature control

0.006
4.134 x 10-7
0.006
6.752 x 10-11
0.006
3.702 x 10-9
0.134

59
Measuring Element (Thermocouple)

An important consideration in designing a measuring system is the dynamic response of a


sensor. The response of a temperature sensor is known as a thermocouple. It is commonly modeled
as a first-order system.

() 1
=
() + 1

1
() =
+ 1

Taking the inverse laplace of the equation above for a one-unit step change,



() = 1

The rate at which the response approaches the final value is obtained using the time
constant. The time constant or response time is the time that is required to reach 63.2% of an
instantaneous temperature change. This is depicted in the figure below.

Figure 4.13. Instantaneous temperature change as a function of t/

Since the operating temperature is not extremely high or low, a common thermocouple,
type K, can be used. The maximum service temperature of the type J thermocouple by Omega

60
Engineering, Inc. has a maximum service temperature of 871oC which is applicable since the set
temperature for this case is 204oC. As given by Omega Engineering, Inc., the time constant for a
thermocouple with 1/8 wire diameter is 12 seconds. Thus, for a one-unit step change, the transfer
function cab be directly expressed as.

1
() =
12 + 1

Transducer

The transducer will convert a range of signal 4 mA to 20 mA to a proportional linear


pneumatic output range of 3 to 15 psig. For this element, the transducer gain has been derived
above and is expressed as

() (15 3)
= = = 0.75
() (20 4)

Control Valve

The control valve use will be the same as that used in the flow control. The air-to-
open control valve selected for the process has the following characteristics. The flow of cooling
water through the valve varies linearly from 0 to 1000 m3/hour (241.3662 kg/s) as the valve-top
pressure varies from 3 to 15 psig. The response time is approximately equal to the residence time
V of the valve. Such quantity is approximated by estimating the capacity of the valve as a cylinder.
The flowrate used is the maximum flowrate allowable. Based on the calculated dimensions of the
inlet feed pipe, the valve dimensions were accordingly selected from pre-set sizes readily available
in the market. The control valve has an orifice dimeter of about 2.5 inches or 63.5 mm, and a travel
length of approximately 75 mm (Uniflo Co., Ltd., 2014).

2

= 4
,

3
(63.5 )2 1
(75 ) ( )
= 4 1000
3 1 1
1000 ( ) ( 60 )
60 min

61
= 0.8551

The next calculations show the solution for finding KV.


241.3662 0
=
15 3


= 20.1138

With the obtained values of KV and V, the transfer function for the control valve can be
obtained.

()
=
() + 1


() 20.1138
=
() 0.8551 + 1

Controller

The transfer function for the controller is obtained using the PID Tuning feature of
Simulink. Shown in Figure 4.14 are the Simulink models of the process with: P control, PI control
and PID control. After tuning, the respective gains of the proportional control (KC,P), proportional-
integral control (KC,PI) and proportional-integral-derivative control (KC,PID) were obtained, as
shown in Table 4.2.

Table 4.8. Gains obtained from controllers

KC,P 1.9135
KC,PI 0.1922
KC,PID 0.2290

62
Figure 4.14. Temperature Controller Simulation Model

63
PID
PI
P

Figure 4.15 Temperature Response as a Function of Time

Controlled temperature are crucial to obtaining desired end results. From the simulations,
both the PID and PI controller has achieved the steady-state point. However, the PID controller
has less overshoot than the PI controller. The PID controller combines proportional with integral
and derivative control. The addition of integral and derivative controls helps the unit compensate
for changes in the system. Although this type of controller is relatively the most expensive among
the others, it is required for this system where temperature plays a vital role. Therefore, the PID
controller is chosen to control the temperature for the slurry phase bubble column reactor.

5. Process Control Description and Diagnostics

General and equipment specific controls are provided for the purpose of monitoring the
key process variables during the plant operation and may be incorporated in manual monitoring or
automatic computer data recording systems. Monitoring instruments are critical process variables
and thus will be fitted with an automatic alarm accordingly to alert operators during critical
situations. For process variables that cannot be monitored directly, some dependent variable can
be monitored instead. In specifying instrumentation and control systems, the goal is to attain safer
plant operation. It is desired to keep the process variable within the limits of safe operation, detect
potential development of critical situations early with the use of alarms and automatic shutdown

64
systems. Another objective is to reach the desired product rate and quality where the target output
is attained without compromising the specified quality standard, maintaining product composition
consistently. In regards to economic consideration, it is also desirable to operate at lower
production cost.

Measuring elements are an integral part of a control system and will be used to measure
the following variables: pressure, temperature, flowrate and level. Controllers will be used to any
respond to error indications. The controllers will send signals to final control elements that will be
used to correct for changes to the process.

In the benzene hydrogenation plant, the controller and final control element will be
operated pneumatically with the advantages of pneumatic controllers being simple and low
maintenance. They are also considered to be safer in potentially explosive environments. Key
instruments will be set up with audible and visual alarms to alert operators in case of potentially
dangerous situations. Basically, the automatic system will operate as follows: A sensor will
provide an output signal whenever a preset variable measurement is exceeded then the signal is
transferred to the actuator consisting of a pneumatic system which carry out necessary actions such
as opening or closing of a valve or switching off of motors.

Based on the design and tuning of PID controllers, it was found out that for the control of
benzene mass flowrate, hydrogen feed composition, liquid level height and temperature in the
jacketed slurry phase bubble column reactor a proportional plus integral type of controller is
efficient. Using PI controllers, steady state errors were minimized thus achieving desired set-point
values for flow, composition, level and temperature. Though the PID controllers also showed
success in achieving desired operating conditions and process specifications, PID controllers are
very expensive thus a PI controller is selected. PI controllers are commonly used in actual
industrial settings.

P controller can stabilize only first-order unstable process. PI controller can be used to
avoid large disturbances and noise present during operation process. Whereas PID controller can
be used when dealing with higher order capacitive processes. With this reasoning, a PI controller
is indeed sufficient in the control of flow, composition, liquid level height and temperature as
supported by the plots obtained from PID tuning.

65
5. Process Instrumentation and Design

As what we have presented in Chapter 4 of this paper, we have designed four types of
controllers namely, a flow controller for the fresh liquid benzene feed entering the slurry phase
bubble column reactor, a composition controller to monitor and analyze hydrogen composition
entering the same reactor mentioned earlier, a level controller for the liquid height inside the slurry
phase bubble column reactor and a temperature controller to maintain desired operating
temperature of the jacketed slurry phase bubble column reactor.

The flow and composition of the benzene and hydrogen feed respectively will greatly affect
the conversion of benzene to cyclohexane via catalytic hydrogenation. It is always desired that the
mass flowrates of the incoming streams are constant and that the composition does not vary. The
composition of the hydrogen entering the reactor is very critical since it is a mixture of a fresh
hydrogen feed of 100% purity and a recycled hydrogen gas containing benzene and methane
impurities coming from a membrane separator (downstream process for hydrogen gas recovery).
There is a great possibility of composition variation at the mixing point of fresh and recycled
hydrogen feed. If the hydrogen composition is less than that of desired, there might be side
reactions occurring at the reactor due to the present impurities. This might also affect the activity
and catalyst performance. The catalytic activity of the Raney nickel catalyst is affected by the
purity of the hydrogen feed that will be adsorbed in the surface of the catalyst. Consequently,
benzene feed mass flowrate must be controlled because at higher flowrates there might be overflow
of liquid level in the reactor and at lower flowrates there might not be enough benzene feed to be
reacted with hydrogen. As the stoichiometry suggests, 1 mole of benzene is needed to react with
3 moles of hydrogen to form 1 mole of cyclohexane.

With regards to the level controller, it is required to employ a level controller as to reach
the optimal conversion of benzene (95% conversion) which corresponds to a liquid level height of
about 13.3 meters. This liquid level must be maintained in order to achieve 95% conversion of
benzene to cyclohexane. Moreover, the mechanism of the slurry phase bubble column reactor

66
solely occurs at the bulk of the liquid phase thus failures are probable when liquid level height is
not optimized.

Since the catalytic hydrogenation of benzene to cyclohexane is highly exothermic, a


temperature control is duely required to meet the desired operating conditions of the slurry phase
bubble column reactor which is where the primary catalytic hydrogenation of benzene to
cyclohexane occurs. The slurry phase bubble column reactor is a pressurized jacketed reactor
operating at 477 K and 35 atm. With these process conditions, it is greatly necessary to monitor,
control and maintain the optimal temperature of cyclohexane manufacture. Though we did not
present a detailed pressure control system, a pressure controller is also needed to maintain the
operating pressure of 35 atm.

Temperature is a critical factor in the design of a safe and efficient process design. In the
case of our reaction, at higher temperatures, there is a possibility of undesired secondary reactions
occurring such as hydrocracking and hydrogenolysis, formation of side-products (undesired
products like methycyclopentane) and runaway reactions. At higher temperature, the thermal and
structural stability of the catalyst used may be affected. At lower temperatures, cyclohexane
formation may not be favored (at lower temperature it is unstable). Presented in Figure 6.1 and
Figure 6.3 are the general piping and instrumentation diagram for the slurry bubble column reactor
and the multi-tubular fixed bed reactor respectively.

67
TO FLARE

Hydrogen

FC
TT TC

PC

TT
Benzene FC

P-7

Cyclohexane Product
(From R-01)

FC

Coolant Coolant

TT

Figure 6.1 Slurry Bubble Column Reactor Process Control & Instrumentation Diagram

68
TO FLARE

TT TC
Cyclohexane Product
(From R-01) FC

PC
TT

Cyclohexane Product
FC (From R-02)

Coolant P-15

Coolant

TT

Figure 6.2 Multi-tubular Fixed Bed Reactor Process Control & Instrumentation Diagram

69
6. Conclusion
In every process design, it is important to identify and establish a workable
conceptualization of process control instrumentation and to develop safety measures for the
equipment used in the process. Based on the design and tuning of PID controllers, it was found out
that for the control of benzene mass flowrate, hydrogen feed composition, liquid level height and
temperature in the jacketed slurry phase bubble column reactor a proportional plus integral type of
controller is efficient. Using PI controllers, steady state errors were minimized thus achieving
desired set-point values for flow, composition, level and temperature. Though the PID controllers
also showed success in achieving desired operating conditions and process specifications, PID
controllers are very expensive thus a PI controller is selected. PI controllers are commonly used in
actual industrial settings.

6. References
A. Bertucco, G. V. (2001). High Pressure Process Technology: fundamentals and applications.
Coughanowr, D. R., & LeBlanc, S. E. (2009). Process Systems and Analysis Control. New York,
NY: McGraw-Hill.
Kehoe, J. P., & Butt, J. B. (1972). Kinetics of Benzene Hydrogenation by Supported NIckel at Low
Temperature. J. appl. Chem. Biotechnol.
Klaus Weissermel, H.-J. A. (2003). Industrial Organic Chemistry.
Manus Patrick Henry, M. E. (2004). The dynamic response of Coriolis mass flow meters: Theory
and applications. 4th Annual Emerging Technologies Conference, ISA EXPO 2004.
University of Oxford.
Smith, R. (2005). Chemical process design and integration. Chichester, West Sussex, England:
Wiley.
Uniflo Co., Ltd. (2014). 8000 Series CV, FL Travel Chart. Retrieved from Uniflo Co., Ltd.:
http://uniflo.en.ec21.com/Globe_Angle_Control_Valve--9047018_9047020.html

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