construction of distillation solvent recovery system
TRANSCRIPT
Scholars' Mine Scholars' Mine
Masters Theses Student Theses and Dissertations
1960
Construction of distillation solvent recovery system Construction of distillation solvent recovery system
Joseph Richard Aid III
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T\1..1 o C» ' \
CONSTRUCTION OF DISTILLATION SOLVENT
RECOVERY SYSTEM
BY
JOSEPH RICHARD AID, III
A
THESIS
submitted to the faculty of the
SCHOOL OF MINES AND METALLURGY OF THE UNIVERSITY OF MISSOURI
in partial fulfillment of the work required for the
Degree of
~ .f ~\ ·, .·. .. ' ,. ' ·. , ' /
\ ' . .I
'~.~
-ii-
TABLE OF CONTENTS
TIT!Ji; PAGE ••••••••••••••••••• o ..... o........ i
TABLE OF CONTENTS ~ O e O O O o O O O O e O O o o ' o • O O e O O o O O ii
I. INTRODUCTION•••••••••••••••••••••••••••••••
II. LITERATURE REVIEW ••••••••••••••••••••• ~ •••• 4
Chemical Processing .of Nuclear ·Fuel • • • 4
Introduction •••••••••••••••••••••• 4
Nuclear Fuel Elements ·······••ooo 6
Dissolution •••o~•o••~•oo~••••••o• 8
Phase contacting, Separation, and Purification 0000000•0•••. ••••••• 10
Oxide, Hexaflu.oride, and Metal Production 000000•00••0•.•oo.~o•oo 17
Distillation •o••o••o•••••••••••••o•oo• 18
Calculations 0 0 e O e O O O e O e O O O O O O O O O e 19
Tower Hydraulics •••• o. o •••••• o o o o o 19
Control and Instrumentation
Water-Methano.l~Tr:lchloroethylene .
000000 20
System o•·~··•o••o••o••o•••o••• :•••.o••o 21
Vapor-Liq~i~ _Equilibrium •••• o . _' ••• ;:··23
Enthalpy •••••••• ·- ~ .• • o .••••••• ~ • ~ • • • 23
Density ••••••o••••••o••••~~.o•••• 23
Refractive Index · •• ~ •••••••• o o ~ ••• o 23
Gas-Liquid Partition Chromatography o•• 23
Theory o o • o o • o • o • o o •••• _o • o • o • o o • • • 28
Equipme:r:it •00000•••0•••••••••••••• 29·
III.
-111-
Gas Flow Control ••••••••o•~ 29
Column and Thermostat 31
Sample Introduction • 0 •••••• 31
Component Detection 0 • • • • • • • 32
Applications • • • 0 • • • • • • • • • • • • • • • • 32
EXPERI:MENTAL • ••••• .••••••••••••••••••• 0 •• ~. 34
Purpose of Investi§ation ••••••••••••• 34
Plan of Investigation •••••••••••••••• 34
Literature Review •••••••••••• ~ •• 35
Redesign and Purchase Specifica-tions ••••••••• · •••••••••••••••• . 35 ;.., .:
Con~truction •••••••••••••••••••• 35
Analytica~ •••••••••••••••••••••• 35
Materials•••••••••••••••••••••••••••• 36
Construction and In~tallation ot Eguipment ••••••••••••• ~ •• . •.. • • • • • • • 37
Flow Sheet, · • • • • • • • • • • • • • • • • • • • • • • 37 ·
Equipment Placement••••••••••••• 37
Tanks ........... ·• .............. . Pumps . .
•••••••••••••••• 0 •••••••• . •.
Distillatiqn Column ·• ...........• Reboiler · •••• .•••••••• ~.~ •••••• ~ ••
37
41
43
47
Condenser •••••• ·• • · •.•••••••••••••• · 47
Feed H~ater ••••••.••••••••••• ~ ••• 50
Feed Prehea ter •••••• .•••••• ·• • • • • • 50
Distillate Cooler •••••••••••••• ~ 50 .,
Instrument Panel .......... • .• .... 53
IV.
-iv-
Control Instrumentation • ·• ••••••• 53
Instrument Air
Process Piping
O O O O • O O • O O • 0 • ~ O O O O
O O O O • • 0 0 • 0 0 0 O O O O O O
58
58
Vent System 00000••••0••0~•••0••• 60
Electrical Wiring·~·!· ······••••• 60
Operational. Procedure ••••••• o·• •••• ~.. 63
. Preliminary Procedure· • • • • • • • • • • • 63
Start-up Procedure· • • • • • • • • • • • • • • 65
Continuous Operation•••••••••••• 67
Shut-down Procedure ••••• ·•• • • • • • • 68
Sample Calculations • • • • • • • • • •.• • • • • • • • 69
Determination of Flow Rates and Heat Requirements •••• o ••• o ••.•• 70
Calculation-of Distilate Product Rate and the Re-flux Rate , ••••••• o •••• o • • • 71
Calculation of the Bottoms ·Rate •••••o••••••••••••••• 73
Calculation of the Heat Re-· quirements. · • • • • • • • • • • •. • • • • 74
Calculation of the Theoretical Plates ....................... ·•.•• 75-
Results of. the· Calculations .••• · •• 76
Calibration o.f Analytical I:astruments. 76
Westphal Balance •••••• ~. o... ... . . . 79
Dipping Refractometer••••••••••• 79
Gas Chromatograph .••••••••••••••• · 79
Unknown SamP,les •••••••••••••••.• ·,; 82
DISCUSS ION ••••• o : ••••••••• . •· o ••••• o •••• ~ ••• o
Discussion of Equipment O O O O O O O O O O O o O O
v. VI.
VII.
VIII.
IX.
-v-
Distillation Column••••••••••••• 85
Reboiler •••••••••••••••••••••••• 86
Condenser ••••••••••••••••••o•••• 87
Auxiliary Heat Exchangers ••••••o 88
Feed Heater ••••••••••o••••• 88
Feed Preheater ••••••••••••• 88
Distillate Cooler ••••o••••• 88
Process Pumps o•••••••••••••••••• 89
Tanks and Taruc Rack••••••••••••• 89
Vent System••••••••••••••••••••• 90
Discussion of Instrumentation •••••••• 90
Process Instrumentation••••••••• 91
Analytical Instrumentation •• -•••• 91
Recommendations • • • • • • • • • • • • • • • • • • 0 • • •
Distillation Column ••••o••••••••
Condenser • • • • • • • • • • • • • • • • • • • • • • •
Limitations • • • • • • • • • • • • • • • • • • • • • • • • • 0
CONCLUSIONS e • e e • • • • • • • • • • e • e • e • • • e O • • • 0 e • e
92
92
93
94
96
S~~RY •••••••••••••••••••••••••••• o.. . . . . 98
APPENDICES •••••••••o~•••••••••••••••••••• 100
Appendix A, Nomenclature•••••••••••• 101
BIBLIOGRAPHY ••••••••o•••••••••••••••••••• 102
ACKNOWLEDGEMENTS • • • • • • • • • • • • • • • • • • • • 0 • • • • 113
X. VITA •••••o••••••••••••••••••••••••••••••• 115
Figure 1.
Figure 2o
Figure 3.
. .
Figure 4.
Fig~re 5o
Figure 60
Figure 7.
Figure 80
Figure 9.
Figure 10.
Figure 11.
Figure 12.
Figure 13.
-Figure 14.
Figure 15.
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LIST OF. FIGURES ·
Block·Diagram Representing the Reactor Fuel Cycle with ·Sol-vent. Extraction Reprocessing ••• . 11
Block Diagram Representing the Reactor Fuel Cycle withrFlu~ oride Volatility Reprocessing · •• 12
Block Diagram Representing the Reactor Fuel Cycle with Pyrometallurgical Reprocessing ...... 13
Generalized ~olvent -Extraction Flow Sheet • • • • • • • • • • • • • • • • • • • • •. 1 5
.. Enthalpy Composition Chart for
Methanol-Water Solutions at 1 Atmosphere ••••••••••••••••o•• 25
Schematic Diagram of Gas Chromatography Apparatus -... o o ••••• o 30
Distillation Flow Sheet ~···•o•••·•• 38
The Distillation:· Unit showin·g the Distillation Column, the Control Valves, and the T.ank ,Farm •••••• 39
The · Distillation · Unit -showing;. the Bottom ·or the Column and the Re boiler • o·• ·• ••••••••••••.•• o.... 40
Rear View of· Tank Farm.and Tank. · Rack • • • • • • • • • ~ .• · • • • • • • . • . • • • • • • •• o 4 2
Process Pumps and Control Vailives. 44
The Distillation Column •••• o ••••• . 45
Distillation Column Installation Det_ails ·. 9 9·•· • .•••.••••••• .-; • .• ~ • • • .• • • 46
View of the Reboiler. from the South Side·· of · the Unit o •••••••• 48
View of the Reboiler from the · North Side· of the Unit •• ~ ••.••• ." 49 ·
Figure 16.
Figure 17.
Figure' 18.
Figure 19.
Figure 20.
Figure 21 •
Figure 22 .•
Figure 23.
Figure 24.
Figure 25.
Figure 26.
Figure 27.
Figure 28 •.
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The Product Condenser •••••••••••• 51
The Feed Heater •••••••••o•••••••• 52
. Front View of · the Instrument -Panel .-•••• · •••••• .•••.•••••• .•• ~ • • • 54
Rear View of the Instrument ~anel showing the ·Tel-0-Set Instruments., the Instrument Air Header, and the Electrical Wiring••••••••••••••••••••••••• ·55
Process Control Flow Diagram ••••• 56
Location and Numbering of Thermo-couple Leads •••••••••••••••• . • •• . 57
The Instrument Air Compressor •••• 59 . .
Vent System Flow Diagram·~······· 61
Wiririg Schematic••••••••••••••••• 62
Ponchon-Savarit Solution to· the Sample Calculations . • • • •.• • • • • • • • 72
Specific Gravity as a Function of Composition for the System . . . Methanol-Water at 25 oc •••••••• 80
Refractive Index as a Function of Composition for the S~stem . · ·Methanol-Water at 25 C • • • • •. • • • ~.1
Ratio of Areas of Methanol-Water Peaks as a Function of Compo- · si tion by Gas .. Chromatography·· -~ .o ~ 83
TABLE I.
TABLE II.
TABLE III.
TABLE IV.
TABLE V.
TABLE VI.
TABLE VII.
-viii-
LIST OF TABLES
Current Atomic .Energy Commission . . Assignment. of Fuel Processing
Responsibility by Fuel Types ••• 7
Table of Solvent ·Properties o o . : ••• 22
Vapor-Liquid Equilibrium Data for Methanol-Water at ·760 milli- · meters of _Mercury •o•••••••••••• 24
Density, Specific Gravity, and Composition Relationship of Mixtures of Methanol and Water at 25 °c .•••• 0 ••• .••• 0 •• · - •• .•••• 0 ~ 0 • 26
Refractive Index of· Mixtures of Methanol and Water at 25 oc . •• .•• 27
Effect of Reflux Ratio on the Theoretical Plates Required for Separation ••••••• · ••••••••• o •••• ·_ 77
Results of Theoretical Material and Energy Balances •••••.•• -••.• ·• • 78
TABLE VIII.· Analysis of Unknown Samples of Methanol-Water Mixtures as Per Cent Methanol •••• o.o ••••••••.•• -•• 84
TABLE IX. Limitations of Equipment • • • • • • • • .• 95
I. INTRODUCTION
When a nuclear fuel is uburnt 11 in an atomic
reactor it is not possible to completely utilize the
fissionable material present due to build-up of fission
products (which act as poisons), depletion of the fis
sionable material, and radiation damage to the fuel
elementao .Chemical processing of nuclear fuels is con-. .
earned with the recovery of the ·fissionable materials,
specif~cally uran1um,.pluton1um, and thorium, from the
spent fuel · elementao There are t\·10 general _metp.oda of
reprocessing nuclear f~~ls: aqueous and non-aqueouso·
The aqueo~~ methods· include solvent extraction, ion
exchange, and precipitationo Comprising the non-aqueous
methods are_fluoride volatility and pyrometallurgyo At
the present time only the aqueous method is. ·being· used
on a commercial a~ale by the Atomic Energy Comm1J:3Sion
in its reprocessing plants at O~k Ridge, tdaho Falls,
Savannah River, and Hanfor.do . .
Of the aqueous pro.ceases fo.r uranium purifi!)ation,
the most .comm.on is the 1/iq-µid-liqui~ extracti.on of ·Uranyl
nitrate, ~y m~ans or'~ organic soivent, ·from-a urany·~
nitrate-fission products solutiono The uranyl nitrate · ..
is then re-extracted from the organic phase by 1.·1ater and
· is further processed- to the uranium oxides, uranium
-2-
tetrafluor~de, and finally to the uranium metal. If an
enriched uranium is wanted, the tetrafluoride is conver
ted to the hexafluoride which is processed by gaseous
diffusion.
It is desirable .that students in chemical and
nuclear engineering have a sound theoretical and prac
tical background in the chemistry and chemi-cal engineer
ing involved in the aqueous process. 'ro support instruc·
tion in this field, a model of an aqueous nuclear fuels
reprocessing plant was designed and constructed in. the
Unit Operations Labo~atory of ·the University of Missouri
School of Mines and Metallurgyo Since safety considera
tions ruled out the use of radioactive materials and/or
heavy metals, the system water-.methanol-trichloroethylene
was chosen to represent the uranyl nitrate-organic solvent
system employed in the actual process. In this case,
methanol, representing the uranium, would be extracted
from a solution of methanol-trichloroethylene by water,
representing the organic solvent. The resulting mixture
of methanol and water then would be separated by frac
tional distillation, representing the re-extraction._: and
further purification stepso
The purpose of· this investigation was to construct
the neceisary equipment to isolate, by fractional dis- ·
tillation {separation by differential vapor pressure),
the products of a liquid~liquicl extraction {separation
-3-
by differen:tial solubility) unito The construction
of the distillation unit was an integral part of and
coordinated with the construction of the extraction -:
equipment.
-4-
II. LITERATURE REVIEW
The background material for this investigation
was considered from four points of view: (1) chemical
processing of nuclear fue~s, (2) · distillation,
(3) water-methanol-trichloroethylene system, and
(4) gas-liquid partition chromatography.
· · Chemical Processing of Nuclear Fue°ls
There has been a great deal of research and de
velopment work in the field of chemical processing of
nuclear fuels. This review ·1s concerned chie.fly with
the presentation of a broad basic background of the field.
Introduction. At the pre~ent time, the only prac
tical method of utilizing ·nuqlear power involves the gen
eration of.heat by nuclear fission(~ 1). In turn, the
heat is employed to produce steam from water. The steam
is then further used to drive a turbine in the production
of electric current. Thus~·the nuclear reactQr is actu
ally used only to replace the.boiler in the conventional
power s~ation, commonly referred to as the fossil fuel
power station~. The fossil fuels are petroleum gas, oil,
and coal.
· A major difference between burning fossil.and
nuclear fuels is the "combustion products. 11 When fossil
-5-
fuels are burned, combustion is virtually complete; and
the ash is ready for immediate disposalo However, in
the case of the nuclear reactor, the fuel is not complete
ly utilized; and the "unburnt" fuel is usually too valua
ble to be wasted and too dangerous for disposai by ordin
ary means( 11,s1).
Chemical processing is concerned with the decon
tamination and recovery of fissionable materials from
the irradiated fuel elementso Many different.methods
have been proposed :for the processing of irradiated nu
clear. fuels; but they can be divided into two main clas-
sifications: aqueous and non-aqueouso The aqueous
methods basically involve liquid-liquid<.extraction;
however, seine work has been done .with ion exchange and
precipitation { 21 ' 69 ) o The. non-aqueous methods include
pyrometallurgy and fluoride volatilit/ 17 ' 44,.77 ). . The
major portion of the . reprocessing -done in the .United
States is by liquid-liquid .extr~c~ion< 66 ).
It is difficult to pr~dict f _uture trends .in the
chemical processing of nuclear fuels • . Of the processing
methods now in use, it appears that the developments
must come in the technology rather than in the chemistry -·
in order to make ~rem economic~lly feasible. The demand , .
will be for · substantial·,.reduction in fuel processing
cqsts and for closer integration of processing plant
and operating reactor( 55 )0
-6-
With this brief introduction it is the intent to
present _information on the essential aspects of chemical
processing of nuclear fuelso The following four principal
related topics are now presented: (1) different types of
nuclear fuel elements and ·the factors involved in their
design; (2) . dissolution of irradiated nuclear fuels to
convert them to a form suitable for further processing;
(3) separation, recovery, and purification of the fis- ·
. sionable materials from the fission products; - and (4)
preparation of the metal oxides, . tetrafluoride, an_d pure
metal from the product of the purification stepo
Nuclear Fuel Elementso A wide range of nuclear (32,53)
fuel types is possible • Some of the potential ( 38)
fuels include uranium metal . and its alloys with such ' (74) - -
metals as aluminum , chromium,. niobium, molybdenum, · ( 37)
and zirconium. Uranium dioxide _ and other. refrac-. - . { 42)
tory compounds of uranium are the basis for ceramic
and cermet fuelso Thorium {_a 4) . and plutonium ( 52 ) are
also used as fertile and fissionable materialso · Clad-
ding materials for the various fuels might be -aluminum, . - . . ~ · ( 68)
stainless steel, zirconium, or_ Zircaloy o The clad-
ding, or jacket, can. be metallurgically bonded to the
fuel; or a liquid-metal thermal bond_ with sodium may be
usedo The enrichment of the uranium used is also quite
important in determining the ··make-up of the fuel elemento
A summary of the various types of fuel elements currently
being processed is given in Table I.
-7-
TABLE I
Current Atomic Ener5y Commission Assi5nment of Fuel Processin5
Responsibility by Fuel Typesa
Idaho
U-Zr(Zr)-HF
U02-SS(SS)-H2S04
U-~l .(Al)-HN03
Handford
·U02(Zr)-NH4F
. U02 (SS) -H2 SO 4
_TIO(Al)-HN03
· ·u(Al)-HNo3
Oak Ridge
U-Mo(SS)-H2S04b . b .U02(SS)-H2S04
Th02-U02(SS)-H2S04b
U-Al(Al)-HN03
·· u-zr ( Zy )-~H4F
Savannah River
U-Mo(Zr)-HF
U(Al)-HN03
aThe ~ignificant dissolution agent is shown after each fuel type. The .core of the fuel element· is shown before the parenthesis and the cladding· is within the parenthesis. (SS-stainless.steel, Zy-zircalloy)
_bDarex alternate, decladding if sodium_bond~d.
-Baranowski, F-. P. : Scope ·or the ~ower: Fuel ;Broces·sing Program, "Pro- . · ceedin§s of ~h~- AEC · Symposium for Chemical Processing of Irradiated :: ·_ · Fuels, ·held· at Richl~nd ,- Washington, October 20 and 21 , 1959, p. 14.
Office of Technical Services, Department of Commerce, Washington 25, D • C • ," 1 960 •
-8-
An interesting review of the factors involved
in the design of reactor fuel elements appeared in the
literature recently< 76 ) o The factors included: {1)
nuclear physics, (2) reaction rate, {3) temperature,
and (4) heat transfero The primary design, which is
concerned with the reaction rate, the temperature de
sired, and the approximate shape and arrangement of the
fuel elements, is dictated principally by nuclear physic.so
After these restrictions have been decided upon, heat
transfer becomes quite important since there is the pos
sibility of the mill~on-degree temperature· of an uncon
trolled chain reactiono In a nuclear reactor the prob
lem is not the generation of heat, but its effective.re-
moval and utilizationo
Fuel elements as they are known today may become
obsolete in the future with the arrival of the homogene
ous reactor{g) o Instead of the fuel and moderator being
engineered separately, as is the case in the heterogene
ous reactor, they are intimately mixed in the homogeneous
reactoro Several homogeneous reactors have been built
for experimental purposes< 33) o One advantage of the
homogeneous reactor is that a aide stream of the fuel can
be continuously withdrawn for reprocessingo
Dissolutiono Dissolution is the process whereby
the heterogeneous reactor fue'l elements are converted
from solid fuel to liqu14 feed solution for reproceaaingo
-9-
The actual material used for the dissolution is deter-
mined by the particular type of fuel element to be re
procesaed(7) o The composition of the fuel can vary
widely, along with the ·possibility of many different
cladding, or jacketing,_ materialso In general, however,
nitric acid dissolution is used for uranium, urani'l.:Ull
aluminum alloys, and thoriumo Sodium hydroxide is used
for dissolution of aluminum jackets and uranium-aluminum
allojs; and fuel elements containing zirconium can be
dissolved in hydrofluoric acid or in solutions of ammo-
nium fluoride, singly or in mixture with ammonium nitrate( 85)o
During the dissolution, gaseous fission products are
often liberated and must be disposed ofo Also, quite fre
quently, oxides of nitrogen will be liberated; and these
may have to be removed from the effluent gas by scrubbing
with caustic(S)o
In some.cases it may be desirable to remove the
cladding before making the final product dissolution:
for example, if the cladding is not soluble in nitric
acid whereas the fuel is, or if the fuel requ~res a less
corrosive disso;J_ving agent than does the jacket(SB)o The
cladding may be removed by either mechanical or chemical
meanso The mechanical methods include sawing, shearing,
and pulverizing. The chemical methods are similar to
those used for the fuel dissolutiono
-10-
Batch dissolution .is satisfactory in most appli-
cations; however, continuous dissolution methods are
being studied< 54)0 Besides the obvious reasons in fa
vor of continuous dissolution, such as greater through~
put in smaller pieces of equipment and more uniform
product control, there is the criticality problem< 54 )0
In a system containing fissile material certain combi
nations of concentration and vessel geometry may result
in an accumulation of sufficient mass of the fissile
material to allow a chain reaction to progress { 14, .57) o
If continuous dissolution is employed, the vessel size
for~ given through-put will be smaller; a~d c~oser con
trol can be maintained over the concentrationar fissile
material.
Phase Contacting. Separation, and Purification.
Recovery a~d purification methods have been divided into
two main classes: aqueous and non-aqueouso The first
is characterized by the use of aqueous solutions for
reprocessing of the irradiated nuclear fuelso The non
aqueous methods include fluoride volat_ility and pyro
metallurgical processing.
The over-all react.or fuel cycles for the various . ( 45)
processi_ng methods are quite different o . The cycles
are shown a.ahematically in Figures 1, 2, and 3 for the
s~lvent extraction, fluoride. volatility, and pyrometal
lurgical processes. It is n~ted that the method employed
REACTOR COOLING
FABRICATION
REDUCTION HYDRO-
TO METAL FLUORINATION
REDUCT~ON GASEOUS {TO U~) DIFFUSION .
-11-
DlSSOLUT ION
REDUCTION
' ' '
FLUORIN·ATION
FIGURE 1.
HEAD END SOLVENT
EXTRACT I ON
SOLVENT
EXTRACTION
DE NITRATION
BLOCK DIAGRAM REPRESENTING THE REAC,:OR FUEL CYCLE WITH SOLVENT EXTRACTION
REPROCESSING
La:wroski, So: Non-Aqueoua Processi:gg - An Introduction, "Symposium on the Reprocessing of Irradiated Fuels, 11 Po· 4800 Technical In.formation Service Extension, Oa~ Ridge, Tenno, 19576
REACTOR
FABRICATION
COOLING
REDUCTION
TO METAL
-12-
DISSOLUTION
AND
FLUOR I NATION
REDUCTION
(TO UF4)
FIGURE 2.
FRACTIONAL
DISTILLATION
GASEOUS
DIFFUSION
BLOCK DIAGRAM REPRESENTING THE REACTOR FUEL CYCLE WITH FLUORIDE VOLATILITY
REPROCESSING
La.wroski, a.: N·on-aqueous Processi~ - An Introduction, "Symposium on the Reprocessing or Irradiated Fuels," p. 482. Technical Information Service Extension, Oak Ridge, Tenn., 1957,
-13-
MOLTEN REACTOR
REACTOR -- DE CLADDING - MAGNESIUM ~ BLANKET ~
EXTRACTION
H REACTOR
CORE
y REMOTE
FUEL -- OXIDE ~
FABRICATION d~ DROSStNG
~ 1
FIGURE 3.
BLOCK DIAGRAM REPRESENTl'NG THE REACTOR FUEL CYCLE WITH PYROMETALLURGICAL
REPROCESSING
-,.....-- (EXCESS
PRODUCT)
Lawroski, s.: Non-aqueous Processin~: - An Introduction, -"symposium on the . Reprocessing of Irradiated Fuels, p. 482. Technical Information Service
Extension, Oak Ridge, Tenn., 1957 •.
-14-
. for fuel recovery in the ,solvent extraction process is ..
. comparatively. complicated~ Many operations must -still
.be performed arter the chemical" purification step be:- ·
fore the recovered fuel can be re-introduced to the
nuclear reactoro An examination of the flow sheet for
the fluoride volatility method reveals that a lesser
number of operatingsteps is required for the reactor
-f~el cycleo A still further simplification of the fuel
cycle may·be obtained with a pyrometallurgical type of
processo
.. For the present at least, solvent extraction is .
the· most versa.tile method for complete decontamination
of plutonium, . thorium, and uranium fuels from fission ·
products and other contaminants. Descriptions of the
two major processes (Redox and Purex), as well as des
crip·tions ~f the _ solvent-extraction processes. mo~1f1ed
· to handle enriched ·ruels and fuels -containing .various · .-:' •-- •· · · · · ·· . .. · . ··. -· (11,1a·,7a,a6) _alloy.ing agents, have_ been publishe~ · · .. ~ A
A generalized solvent~extrac~ion flow sheet is shown . . .
· .inFigur~· 4 ·and is typical . f~r th(:f Red.ox pro~ess, which · . . . . ' . ' . . '. . .
· 1~ .· characte~ized .• by the use . of h~xone · (Diethyl isobutyl .< ket~~e)as ihe • sol Vento it could also al)pljr to the · . ..
Pur~x pr_ocess, which . uses . tributyl. phosphat~ '. diluted ..
· ·.· w~ tl'l. ~ydroc~rbon diluent for t}?.e s.olvento . · .· .. .. ·
OFF
GAS
DISSOLUTION OF
IRRADIATED URANIUM
IN HN03
ORGANIC EXTRACTION
ACTIVE
WASTE
STORAGE
NITRATE. SCRUB AND
SALTING AGENT
E x T R A c T I
0 N
-15-
DILUtE ACID
... REDUCING DILUTE
AGENT ACID
USED SOLVENT TO RECOVERY
p s A T R R T I I p T p
ADDITIONAL I I SOLVENT 0 N EVAP.
EXTRACTION N G CYCLES. I N G
.ORGANIC EXTRACTION
----- EVAP. t----c>ADDITIONAL SOLVENT EXTRACTION CYCLES
FIGURE 4.
GENERALIZE~::., SOLVENT-EXTRACTION FLOW SHEET
u. s. Atomic Energy Commission: Reactor Fuel frocessing, 1, No. 1, 7 (1958).
-16- .
The- fluoride volatility processes comprise ··a
group o·f non-aqueo~s reprocessing methods which exploit
the volatility of uranium and plutonium hexafluorides (12,78,86) · ·- . . . .
o Except for tellurium ( and molybdenum which_
is~ fission product -with a short.ha1:r:..11re), all of
the fission products form fluorides which are much.less
volatile than uranium hexafluorideo Uranium hexafluoride
and plutonium he~afluorid~ have nearly the same volatili
ties. However, it is difficult to fluorinate· p~utonium -
to the hexafluorid~; and the lower fluorides.of plutonium ..
are not volatileo Thus, the relative ease of fluorination ·.
of u~anium .and plutonium .. may be used for t1:1,ei~ separ~tion~· · .
The mos"t;t.important of the fluoride volatility methods are: ·
( 1) fused· salt processes, ( 2) ·continuous. dissolution
by inter-halogens, . and ( 3) a combination ·of aqueous
dissolutio;n. with fluorination and fluidization techniqueso
~he.major difficulties encountered a.re with techniques
and materials of -construction ·in the feed dissolution
stepo .. .
The.· pyrome.tallurgica.l proces_se~ have ah inherent
compactness wh.ichresults from avoiding chemical Qonver
sions dUI'ing th~- proces;ing . steps( 13,7i3,B6) 0 ·. .
' ·, . · , : .: :
the ·fuel ·· is ·retained.· in the ·metallic 'state . througho'Ut·;
howeyer, proces~~s i:n w~ich _the metallic state is lost
momeii.tar1iy . or -. -in .. whi cli it11e . 'inetai(t s ·conver.t 'ea into . the ·.- .•
salt in one •step and back in the ~exi ;r:e allio inci\lcie~{
-17-
·pyrometallurgical processes are characterized by high
temperatures and low decontamination factorso It is
believed that moderate decontamination will be suffi-
cient for fuels in power reactorso The pyrometallurgi
cal processes include:- ( 1) oxide dressing, also known
as oxide slagging or meld refining; (2) solvent·ex
traction, either with immiscible molten metals or fused
salts; and (3) methods such as zone refining, fractional
crystall1.zation, electrolytic refining, and fractional
distillationo
Ox1de 0 Hexafluoride 0 and Metal Productiono Fol
lowing the separation and purification steps in the re
processing scheme, the fuel must be converted to a re
usable form as a nuclear fuel(B 6)o The forms in which
uranium is used as a fuel are uranium dioxide, uranium
metal, and metal alloyso The product of the. aqueous
sol vent extraction process is usu_ally a uranyl nitrate
solution. The nitrate solution is denitrated to uranium
trioxide which is then reduced to uranium dioxideo The
uranium dioxide may be the desired fuel product, or it
may be fluorinated to uranium tetrafluoride from which
either uranium hexafluoride (for re-enrichment-) or ura 0
nium metal is produeedo In the fluoride vo_latility
processes, uranium hexafluoride is obtained directly
and is re-enriched by gaseous diffusion and/or is reduced
to uranium tetrafluoride for further processing to uranium
metalo
-18-
One of the important techniques receiving exten
sive attention is the fluidized bed( 86)o Fluidized bed
reactors are used for denitration and reduction of uranyl
nitrate to the oxides and for fluorination of the oxides
to the tetrafluoride and hexafluoride.
Distillation
"Now I am come to the arts and I
shall begin from distillation, an invention
of later times, a wonderful thing to be
praised beyorid the power of men; not that
which vulgar and unskilled men use, for
they do but corrupt and destroy what is
good; but that which is done by skillful
artistSoooLet one that loves learning and
to search nature's secrets, enter upon this;
for a dull fellow will never attain to this
art of distilling."
Forta, 15890
The purpose of this section of.the literature
review is to provide information on recent advances in
the field of distillation to in.elude: { 1) calculations,
(2) tower hydraulics, and (3) control and instrumen
tationo A basic knowledge (as covered in the standard · ,
texts) of the theory and terminology of distillation is
assumed and will not be covered( 10, 56170 , 79 ).
-19-
Calculations. The emphasis of distillation cal-
culations has changed in recent years from empirical
correlations to rigorous calculations. Not that the
principles have changed, but with the use of analog and
digital computers the simplifying assumptions formerly
made are no longer necessary.. Computers are being used
successfully for (1) prediction of vapor-liquid equi
librium data< 15 ), (2) simulation of column behavior ( 42)
under varying conditions , (3) prediction of opti-
mum column design(l,75 >, (4) solution of multic9mpo
nent . distillation problems ( 25 , 28 , 48 ), an·d (5) many
oth~r types of distillation problems(31 , 49,72, 83). A
committee has been established by the American Institute
of Chemical Engineers for the .interchange of computer
programs.
Other work· on distillation calculations has been
concentrated on modification of existing methods and
development of short cuts ·for the solution of equations.
The McCabe-Theile method has received considerable atten
tion, with the emphasis on developing methods for reduc
ing the inherent error of assuming constant vapor-liquid
ratio throughout the co1umn< 82).
Tower Hydraulics. An investigation of the tray
efficiencies of distillation columns was recently com
pl~ted at the Universities ·of Delaware and Michigan and
the North Carolina State College. The research committee
-20-
of the American Institute of Chemical Engineers spon-.
sored the investigation and published the results in a
comprehensive booklet(S). Recent research has also in
creased our knowledge and understanding of: (1) the·
influence of surface phenomena and entrainment on tr~y
.. efficiencies ( 89), ( 2) mass .transfer between liquids· (36) .
and vapors in bubble-cap columns , and (3) pressure . (80)
drop through bubble-cap and packed columns •
New tray designs for use in distillation columns
have been proposed. The claims in favor of the new de-
signs .are lower initial cost and higher efficiency than
the.conventional bubble-cap tray. In general these trays
operate very well at the design specifications, but. they
lack the stability of operation which is inherent in the
bubble-cap tray.
Control and Instrumentation. Progress in control
and instrumentation of distillation columns ~as been very
rapid during the past few·years, and many instruments
which were merely laboratory. curiosities five rears ago
are today helping to control chemical processes.
Through the use of improved instrumentation, the
delay between measurement of the process variables .and
applic~tion of control to the process has ~een decreased.
Of particular importance is the use of in-line analy~ical . . ( 22)
instruments: for example, 'vapor phase chromatography o
-21-
Of especial interest today is the use of compu
ters. The possible steps in the integration of computers
into process control are: (1) use of digital data log
gers, (2) 11on-linett calculation of operating gui~e~,
(3) computer supervi~ion of processes, and (4) dynamic
· control of processes ( 27).
Water-Methanol-Triohloroethylene System
The system water-methanol-trichlo~oethylene has
been specified for use in the operation of the unit.
Originally, the system water-acetone-carbon tetrachloride
had-been considered( 25 ' 64); but owing to safety consider
ations, principally flash points and toxicity, this sys
tem was abandoned. A summary of the solvent properties
for the two systems is given in Table II.
The solubility of trichloroethylene in water is . 0
0.11 per cent at 20 C, and in a mixture of methanol and
water at the same temperature the solubility of trichloro
ethylene is only about one per cent when the concentration
of methanol is 37 per cen~( 59 , 73 >. The product.of the
extraction unit will be the feed for the distillation
unit and will contain from 15 to 20 per cent methano1( 6o).
The amount of trichloroethylene dissolved in the feed
stream to the distillation unit is subsequently assumed
as negligible, and this portion of the literature review
1 •
2.
3.
4.
TABLE II
Table of Solvent Properties
Name and· Synonyms Boiling Flash Fire Explosive Limits, Threshold % by Volume in Air Point, .Point, Hazard
OF OF Group,
Acetone 133 0 4 dimethyl ketone 2-propanone
Carbon Tetrachloride 171 * 0 tetrachloromethane
-Methanol 148 54 4 methyl alcohol wood alcohol
Trichloroethylene 189 * 0 eth1nyl trichlor1de e
(A) e
* LEL ·
American Conference of Industrial-Hygienists Can be vio1e·n·t1y decomposed· by aluminum fines Non-flammable Lower explosive limit Upper explosive limit
LEL
3.0
7.3
UEL ppm Parts of vapor per million parts of air, PY volume
Limit UEL Values,
ppm
1 1 1000
25
36 200
200
Fire Hazard Rating Fla.sh Points Non-flammable Above 140 °F 100 - 140 OF 73 ·- 100 °F Less than '73 °F
(A~
(A)
(A)
(A)
Group 0 1 2 3 4
"Handbook of Organic Industrial Solvents," pp. 25, 34, 51, 60. National Association of Mutual Casualty Companies, Chicago, Ill.
.-23-
is concerned chiefly wit~ the physical properties· of .the
me~hanol-wa.te:I' system •
. The following· .·_data. on the· me.~hanol-water system;
·were used for all calculations' and calibrations.
Vapor-Liguid .. Eguilibrium •. The vapor-liquid equi.; • ( : j •
librium data are.given in ~able III for a pressure of 760
millimeters of mercury( 2o.>. Enthalpy. The relationship bet.ween .th~ liquid
and vapor _enthalpies as a function of composition is shown·
in Figure 5~4
~. ·
.. ·. Density. · V~lues_ of density as a function of. com
p6alt1on at ae~er!!.1 temperatures are given 1:q Table IV(i 6>, Refractive Index. Values of .. the refraotive .. index
·for the methanol~water system at several different tem
peratures are giveri in Table vC34).
't}as-Liquid Partition Chromatography .
Initial operational procedure for the analysis
of a product by gas-liqu~d·chromatography ;s the intro
duction of a· measured sample into· a· ·controlled·-gas stream . • / .
The. gas' .. stream then· ·acts. as ·a. carrier :for the sample as
it transports· it _t};lrotigh a heated colµmn packed with -a· ..
partitioning agent. The partitioning agent, which must··
be esae·ntially ·non-volatile at the temperature· and pres
sure or·· oper_at1on:, is usually·. ·coated on: inert. granul_ar
-24-
TABLE III
Vapor-Liquid Equilibrium Data for Methanol-Water
at 760 millimeters of Mercury
Methanol Methanol Temperature in Liquid, in Vapor,
mole J{, mole% OC
3.21 19.0 95.3
3.72 22.2 Q4.0
5.23 29.4 92.5
5.95 30.8- 91.5
7.50 35.2 89.9
8.76 39.0 88.1
15.4 49.0 85 .1
15.8 51.6 83.9
18.2 55.2 82.9
22.5 59.3 82 .1
29.0 64.3 78.7
34.9 70.3 76· •. 7
81 .3 91 -.8 67.4
91 .8 96.3 65.6
Chu, J. C., S. L. Wang, S. L. Levi and R. Paul: "Vapor-Liquid Equilibrium Data, 1 p. 420. J. w. Edwards,Inc., Ann Arbor, Mich., 1956.
c.> 0 E D
,.: <'l)
0.
:j +-' dl
:2 :::, O'
-0
~ .Q. <U .c
+> c w
-25-
24200
21,800
21,400
21,000
20,600
20,200
1°9,800
sql 19,400 v,...c:1 t~
(/ J..-q 19,000 t:>o,...
18,600
18~200
17,800
17,400
Saturated 11. Uid ·
800 --400
0 0 0.1 0.2 o.3 0.4 ··o.5 o .6 o.7 o.e o.9 1.0 ·
Mole fraction niethan of FIGURE 5. ENTHALPY COMPOSITION CHART FOR METHANOL-WATER
. SOLUTIONS. AT 1 ATMOSPHERE
Ansell, L. s., H. Sammuels and w. c. Frishe; Enthalpy Concentration Chart for Methanol-Water Solutions, Chem. · Eng., 512., No. 4, 133 (1951);
~
0 E .ci
t.: c,) a.·
:J +-' co L~ 0 a. cu > -0
~ a. l'v .c ....... c
LLI
-26-
TABLE IV
Density, ·specific Gravity, and Composition R~lationship
of Mixture·s . of . Methanol and 'Water at 25 °c
Methanol, Methanol, · Density, . Specific . Gravity, __ ·
wt% vol .·% 25°/4° a : 25~/25° a' '
0 o.oo 0.99708 1 .0000 . 5 6.28 o.9887 0.9916
10 12.46 0.9804 0.9833 15 18.55 0 .,9726 0.9754 20 24.53 0:-96~9 0.9677 25 30.42 0.9572 0~9600 30 · 36.20 0.9492 ·0.9520, 35 41 .84 0.9405 0.9433 ·40 ·· 47 .37 0.9316 0.9343 45 52.74 o·.9220 0.9247. · ..
· 50 57.98 Ol9122 0.9.149 55 63.05 0.9019 O .9045 ,' · 60 · 67 .96 0 .·8910 0·~8936 65 72 .64' 0.8792 0.8818 70 77 .19 o.8675 0 .8790 . 75 81 .54 o.8553 0.8578 80 85.66 o.8424 o.8449 85 89 .·60' 0.8293 0 .8317 90 93.33 o.8l58 0.8182
.95 96.79 ·o .801-5 0.8038 100 100.00 'O ;7867 . _0.7890
Carr, C., and J. A. Riddick: :,Phy.sical Properties of Methanol Water System, !):_ijg.. Eng. Chem., i2,, .693 (1951).
-27-
TABLE V
Refractive Index of Mixtures of Methanol
and Water at 25 °c
Methanol Nn25
mole%
o.oo 1 .33232
21 .70 1 .33823
37.66 1 .34090
52.22 1.34163
54.23 1.34163
64.35 1 .34065
68.20 1 • 33984
80.44 1.33663
86.27 1.33505
92.48 1.33193
100 .oo 1.32773
Maximum Nn25 = 1.34170 at . 53 mole % Meth_anol
International Critical Tables, VI, p. 66. McGraw-Hill Book Co., Inc., New York, N. Y., 1929.
-28-
materials in amounts up to 40 per cent by weight·.. By
selection of the proper partitioning agent, the sample
may be separated into fractions consisting of pure com
pounds. The pure compounds arrive separately at the
exit of the column, w~ere they are measured by a suitable
'detector. Recordings obtained by measuring the d~tector
output result in a series of peaks, whose locations pro
vide qualitative information and whose. heights or areas
determine the quantitative analysis.
The possibility of gas-liquid chromatography was
first suggested by Martin and Synge(SO) in their paper
on liquid-liquid chromatography in 1941, for which they
received the Nobel Prize in 1952. The suggestion was
neglected until 1951, when Martin, together with James, ( 35)
proceeded to elaborate on it • Since then the tech-
nique of gas-liquid chromatography has been developed
into a powerful tool for analyzing volatile materials.
Theoryo As in distillation, a gas-liquid chroma
tographic column can be considered from the viewpoint of
containing a number of theo.retical plates ( 39_, 61 ) • The
separation per plate and the number of plates then deter
mine the over-all separation obtained in any one column.
The mechanism of separation is based on the varying
absorbability of the components of the sample in a non
volatile liquid impregnated: on an inert support·. Sepa
ration then takes place because the molecules of one
-29-
component spend more time in the carrier gas than those
of another, thus determining the residence time for each
component in the ~01umn< 43 ). Therefore, the · separation
obtained is a matter of the relative volatility, whic~
in turn is affected by the vapor pressure, adsorption
· and solute-solvent effects, and in some cases mol~cular
\'Teight of the sample components.
Equipment. The apparatus used in gas-liquid
chromatography can be divided into four categories(40):
(1) equipment for providing a controlled flow of carrier
gas, (2) the column and its thermostat; (3) the sys
tem employed for introducing the sample, and (4) the
apparatus used for detecting the components in the ef-
fluent. These four categories are discussed separately.
A generalized flow diagram for~ gas-liquid chromatograph
is shown in Figure 6.
Gas Flow Control~ The precise regulation
of the flow of the. carrier gas is not a necessary
requirement for the separation of the components of
a mixture by gas-liquid c~romatograp~y. However,
if the retention volume or the efflux t1mes are to
· be used for qualitative identif~catiori, accurate
control is necessary; and, if a quantitative analy
·sis is to be made, the flow must be substantially
constant. The usual method consists of a coarse
and fine pressure regulator to adjust the pressure
. I
I
I
L
FLOW.
METER
PRESSURE
GAUGE
CARRIER
GAS
NEEDL'E
VALVE
PREHEATER q)IL
L------
RECORDER
-30-
----------,
REF
THERMAL
CONDUCTIVITY
CELL
3WAY VALVE
COLUMN
I I L_ -
VENT
EXHAUST .----,-...-. SAMPLE I
I I CONSTANT_ T~"1~E~~R_§ ±I~ ~ATH__ _J L ____ _
FIGURE 6. SCHEMATIC t)IAGRAM OF GAS CHROMAT00RAPHY APPARATUS
Fi"sher-Gulr Partitioner,· Catalogue No.11 1 ~ ~130, p. 3. .F.1sher Scientific Co.,· Pittsburgh, Pa.
-31-
within a range of 0-30 pounds per square inch,
gage and a flow regulator. Also, the column it
self acts somewhat as a flow regulator and there-
fore helps control the flow.
Column and Thermostat. Chromatographic
columns usually consist of lengths of tubing,
four to eight millimeters inside diameter, either
straight or coiledo The tubing can be of any
suitable material, such as glass, copper, alumi-
num, or stainless steel. The advantage of a coiled
column is i~s co@pactness and hence the reduced
size of the thermostat, and metal coils are su
perior to glass in heat transfer and consta~cy of
temperature. As peak .height .is pa~ticularly sensi
tive to temperature variations, close control of
the temperature is important if analyti.cal results
are to be obtained; but it is not necessary for
good separation(41). Several different types of
thermostats have been used, including the follow
ing: (1) oil baths, (2) vapor baths, and
(3) an air thermostat with a sufficient gas ve
locity.
Sample Introduction. The sample to be ana
lyzed should be introduced into the carrier gas
stream as close to the top of the column as pos-
sible. Gas samples are usually introduced by
-32-
trapping a definite volume of the sample and
then forcing it into the column by the carrier
gas. Some of the methods used in introducing
liquid samples are: (1) by syringe, (2) by
crushing a glass bulb, and (3) by use of a
special pipet.
Component Detection. The detector has to
sense and measure the amounts of components pres-
eht in the effluent gas. There are two basic
types of detectors: differential and integral( 23).
Integral methods include automatic titration of
acids and bases and detection by the ~onductivity
of a collecting solution. Differential methods
are characterized by the gas . density balance, ion
ization detectors., and thermal conduct! vi ty, which
is most widely used at the present t·ime.
Applications. The results of a gas-liquid chro-
matograph.le analysis is a 1:l"Gries of peaks on a strip of
chart papero Either the. p~ak heights or the ·a.reas w.1 thin
the peaks of the chromatogram may be. used to calculate
quantitative information about the sample. However, since
the areas are less sensitive· to small fluctuations of
temperature and carrier gas flow rate, they are usually
preferred( 41 ). The peak areas may be determined by ·graph-
. ical means or through use of an electronic or mechanical
integrator.
-33-
·The area obtained on a chromatogram is propor
tion.alto the a~ount of the component in the sampleo
However, it has been reported that the thermal conducti
vity detector does not respond equally t,o all" components ( 62 ).
Therefore, correction fact·ors .or calibration constant"s
must be determined which will put the relative·areas on
an equal·basis. There are seve~al ways of doing this:
( 1) equal amounts of the pure compound may be subje.cted l . . .
to chroma tographi,c analysis and the areas· compared, ( 2) .
r 'elative areas can be computed from analysis or known
mixtures, or ( 3.) calibration constants can be obtained
~rom publlshed lists<58 ).
Once the calibration constants have been deter
mined, ·quantitative results can be obtained by: (1) de
termining th~ areas under the respective peaks, (2) mul
tiplyi~g or diyiding.each area-by its respect.ive calibra
tion cor;istant, and (3) norm~llzing the __ (}orrected -~~.e.as
to give the percentage·coinpositiono
-34-
iii. EXPERIMENTAL
The experimental section of this thesis is divi
ded into the following sections:_ ( 1 ) purpose of inves
tigation, ( 2) plan of inve_stigation, ( 3) materials,
(4) construction and installation of equipment, (5)
operational procedure, (6) sample calculations, and
(7) cal-ibration of analytical instruments.
Purpose of Investigation
The purpose of this investigation was·to constru·ct
the necessary equipment to isolate, by fractional distil
lation (separation by differential vapor pressure), the
products of.a liquid-liquid extraction (separation by
differential solubility) unit. The construction of the
distillation unit was an integral part of and was coordi
nated with the construvtion of· the extraction equipment.
Plan of Investigation
The plan of procedure was: (1) to review the
literature, (2) to modify the proposed design of Puyear
( 63) and purchase additional necessary equipment, (-3) to
construct the unit, and ·(4) to calibrate the analytical
instruments.
-35-
Literature Review. The literature review .was
conducted for this investigation with the following
purposes in mind: (1) investigation of the methods
used in the reprocessing of nuclear fuels, (2) review
of the current literature for information on distillation
techniques, (3) acquisition of information on the phys
ical properties of the water-methanol-trichloroethylene
system, and (4) study of the methods of gas-liquid
chroma to.graphy •
Redesign and Purchase Specifications. During the
construction of the unit, the design( 63 ). was revised as
necessary changes became apparent. When additional
equipment was needed, it was obtained through the school
store room or the business office.
Construction. The proce.dure followed in construc
tion of the unit was: (1) erection of the structural
steel; (2) installation of the tanks, pumps, heat ex
changers, and control valves; (3) rough process piping;
(4) installation of the distillation column and reboiler;
( 5) installation of the process. instrumentation; ( 6)
completion of the process piping; and (7) installation
of the electrical wiring.
Analytical • . An investigation of the analytical
method's was made. The investigation involved preparation
of standard mixtures of methanol-water, analysis by the
various instruments(dipping refractometer, Westphal bal
ance, and gas chromatograph), and comparison of results~
-36-
Materials
The materials used in the construction of the
equipment are listed in the purchase specifications •.
These purchase specifications are found in two parts:
(1) Purchase specifications given by Puyear( 63), ·an4
(2) Purchase Orders Made Between July and December,
1958, and Purchase Specifications: January, 1959 to
January, . 1960 both presented by Okenf'us s ( ~O) .• A ·com
plete list of these purchase specifications, alon~ · with
lists of costs and .equivalents, is on file with the
Chairman of the Department of Chemical Engineering,
Missouri School of Mines and Metallurgy, Rolla, Missouri.
-37-
Construction and Installation of Equipment
This section deals with the construction and
placement of the equipment. Standard items have been
used where possible. Manufacturers and catalog numbers · ( 63) .
.. are listed in the materials list by Puyear and in
Appendix A and Appendix·B. Engineering drawings and pho
tographs are included where their use ._will clarify the
details of the construction.
Flow Sheet. A schematic flow diagram is presen
ted in Figure 7. The function of each piece of equip
ment is shown and each valve has been given a specific
number.
Equipment Placement. The equipment was installed
in the Unit Operations Laboratory of the Departme·nt of
Chemical Engineering at t~e University of Missouri School
of Mines ·and Metallurgy, Rolla, Missouri. Photographs of
the installation are shown ·in Figures 8 and 9.
Tanks. The ·tanks used were standard 55~ and 30-
gallon ICC-5 specification ·black steel drums. ·rn order
to have all of the d.v.ums readily accessible, yet using
the m1p.1mum amount of_ floor space, a tank rack was erec
ted. Standard structural steel members and an all bolted
construction were utilized to facili.tate future changes.
The ·tanks were not physicai~y attached to the tank rack
as they are held in place by their own weight. All flow
FROM EXTRACTION UNIT
•
DIS TILLATE 1
0-23 ------~ BOTTOMS 1
~~-D~-2_5~~~-
-----...a...D-27
BOTTOMS 3
DISTILLATE2
D-20
D-21
BOTTOMS
REJECT
D-24
BOT TOMS 2
D-26
D-28
BOTTOMS4
• D-30
,~-4--~~~-D_-3_3_j_~D-34
D-29
D-32 ~ 9RP
Fl FLOW I NDICAlOR FR FLOW RECORDER
DRP LLIC LEVEL INDICATOR CONTROLLER
FP
MTR MULTIPLE TEMPERATURE RECORDER
PR PRESSURE RECORDER PRC PRESSURE RECORDER
CONTROLLER
LEGEND
TRC TEMPERATURE RECORDER CONTROLLER
FPH FEED PREHEATER DC DISTIL LATE COOLER DR DRAIN D-1 thru 40 VALVES
TO VENT
/
BP BRP DP DRP FP RP
F R-3,4
MTR-1
BOTTqMS PUMP BOTTOMS RETURN PUMP DISTILLATE PUMP DISTILLATE RETURN PUMP FEED PUMP REFLUX PUMP·
BP
STEAM
TRC-1
TRAP
DR .
TRCV-2
DEPARTMENT OF CHEMICAL ENGINEERING MISSOURI SCHOOL OF MINES & METALLURGY
ROLLA, MISSOURI
DISTILLATION FLOW SHEET
SCALE: NONE DATE CASE NO: 60 DRAWN BY: J. RA . 2/23 60 FILE NO: 490 CHECKED BY: j:/, _ .. ~/h~/&/'J FIGURE NO: 7 APPROVED BY: ,t-_1-~ , .-/1~ / I .(f SHEET NO: 1 of 1
-39-
Figure 8. The Distillatio~ Unit showing the
D1st1ll~t1on Column, the Control Valves,
and the Tank Farm
Figure 9. The D1s·tillat1on Unit sho~ing
the Bottom of the Column
and the Reboiler
-41-
connections into or out of the tanks were made with
11 Swage.lok 0 fittings which allow the tanks to be removed·
from the system for repair or replacement with a minimum
of labor. Construction of the tank rack and installation
of the tanks is essentially as specified by Puyear(:65).
A photog~aph of the installation is shown in Figure 10.
Pumps. The pumps are Bell and Gossett booster
pumps. The pumps are driven by 1/6 horsepower, explosion
proof motors wound for 115 volts, 60 cycle, single phase
alternating current. These pumps are of a centrifugal
type with an enclosed impeller. The pumps, which are
located along the front of the tank rack, were placed on
a rack to which they.were securely bolted. The pump rack
consists principally of two pieces of 3 x 3 x 1/4-inch
angle iron laid back to back with a 3/4-inch spacer be
tween them. The pumps are used as follows: (1) feed
pump ( ~) , to pump the fee.d from the feed tank to the
column; (2) bottoms pump(~), to pump the bottoms
product from the reboiler to the bottoms storage tanks;
(3) reflux pump (B1:), to pump the reflux from the accu
mulator tank to the top of the column; (4) distillate
pump (Q!:), to pump the distillate ·product from the accu
mulator tank to the distillate storage tanks; . (5)
bottoms return pump (!ill!:), to pump the bottoms product
from th~ bottoms storage tanks t9 either the extraction
solvent tank or the distillation feed tanks; and ,. ,.
-42-
Figure 100 Rear · View of Tank Farm
and Tank Rack
-43-
(6) distillate return .pump (QB!:), to pump the distil
late product from the distillate storage tanks to either
the extra:cti-on or distillation feed tanks. A photograph
of the pump installation is shown in Figure 11.
Distillation Column. The distillation column is
an assembly of standard parts. The purpose of the dis- ·
tillation column is to separate, by differential vapor
pressure, the components of the feed mixture. The col
umn was constructed of glass pipe six inches in diameter
with nine plates spaced at 12- and .18-inch intervals.
The column.is supported by clamps which were mounted on
two pieces of 3-inch steel pipe extending from floor to
ceilingo The column as installed is shown in Figure 12 •
. The plates are formed from sintered gla~s, and
each plate contains one bubble ·cap. The bubble cap is
slotted around its periphery and is an integral part of
the plate. Each plate is ~lso provided with both a liquid
and a vapor sampling tap and a thermocouple well.
The plates were sandwiched between the sections
of glass pipe, and the entire assembly was held . together
by aluminum flanges. Th~ bo~tom section was rigidly
mounted to the s~pport clamps, while t~e other sections
were spring mounted to allow for expansion and contrac
tion of the column during. start-up and shut-down opera
tions. The details of the column suspension are shown
in Figure 13.
-44-
Figure 11. Process Pump~ and Control Valves
-45-
Figure 12. The ·Distillation Column
I
PLATE NUM.BER
9
8
7
6
5
4
3
2
1
DISTILLATION COLUMN
EAST VIEW
t°l l I
Fi I
:>ETAIL TWO SPRING MOUNTED PLATES
::~EE NOT[ Ot,IE
OETAI L C NE HIGI DLY M[:UNTE D
BOTTOM PLATE
SEE NOTE ONE
-4- SEE DETAIL TWO
0
DISTILLATION COLUMN
NORTH VIEW
TOP VIEW OF
BUBBLE CAP PLATE
CROSS SECTIONAL ViEW
0F BUBBLE CAP . PLATE
NOTE ONE : THE BOTTOM PLATE (No 1) IS RIGIDLY MOUNTED; ALL THE REST ARE SPR.ING MOUNTED.
DEPARTMENT OF CHEMICAL ENGINEERING MISSOURI SCHOOL OF MINES & METALLURGY
ROLLA, MISSOURI
DISTILLATION COLUMN . INSTALLATION DETAILS
SCALE: NONE DATE CASE NO: 60 DRAWN BY: J. R. A. 4/9/60 FILE NO: 490
CHECKED BY: 9:·f. S/IIJ/~~ FIGURE NO: 13
APPROVED BY: _"-·-~7. ~~-1,1~ ~ SHEET NO: 1 of 1
-47-
Optional feed sections were provided for in the
column. Numbering from the bottom, plates 3, 4, 5, and
8 have a tee section above them by which feed may be
introduced. The tee sections are 18 inches in ~ength,
while the straight_ sections of pipe comprising the re
mainder of the column are 12 inches in length. This
accounts for the unequal spacing of the bubble-cap plates
in the column.
Reboiler. The reboiler was fabri~ated from stain
less steel by the Nooter Corporation of St. Louis, Miss
ouri. It is fitted with a fully flanged head to which
the copper steam coil is attached. The steam coil was
built up from copper pipe and copper sweat fittings. The
purpose of the reboiler is to supply the heat input to
the distillation column. To _prevent undue heat loss to
the surroundings, the.reboiler is insulated with insula
ting cement. Photographs of the reboiler installation
are given in Figures . 14 and 15.
Condenser. The condenser consists of a V-shaped
double-pipe heat exchanger constructed f~om copper pipe
and copper fittings. The cooling water passes through
an inner one-inch tube, and the vapors condense in the
annulus between .this inner one-inch tube and the outer
two-inch tube. The purpose of the condenser is to con
dense the vapors from the top of the distillation column.
-48-
Figure 14. View of the Reboiler from the
South Bide of the Unit
-49-
Figure 15. View of the Reboiler from. the
North Side of the Unit
-50-
The condenser is mounted on the front of the tank
rack, and flow of the condensate from the condenser to
the accumulator tank is by gravity. The condenser as
installed is shown in Figure 16.
Feed Heater. The feed heater is a vertical, dou
ble-pipe heat exchanger fabricated from copper.pipe and
fittings in much the same manner as the product condenser •
. The purpose of this piece of equipment is to heat the dis
tillation feed stream to the boiling point prior to its
arrival at the distillation column. Steam is used in an
inner one-inch tube, and the distillation column feed
flows through the annulus formed by an outer two-inch
tube. This piece of equipment is mounted at the north
east corner of the unit. A photograph of the feed heater
is shown in Figure 17.
Feed Preheatero· The heat exchange! used to pre
heat the feed and to cool the bottoms product is a Graham
heliflow with a cast irpn shell and cojpper tubes 9 Cold
feed flows through the shell side,. and the bottoms product
flows through the tube side~ The feed preheater was
mounted on the southwest corner of the reboiler stand.
Distillate Cooler. The distillate cooler is iden
tical to the heat. exchanger used- for the feed preheater~
The distillate cooler is used to cool the distillate pro
duct from the accumulator.tank before it is pumped to the
product tanks. The cooling water used on the shell side
-51-
Figure 16. The Product Condenser
-52-
Figure 17. The Feed Heater
-53-
of this heat exchanger is obtained from the exit. side of
the product condenser.
Instrument Panelo The instrument panel consists
of a piece of 3/8-inch sheet steel attached to~ rrame·
constructed from two- and three~inch angle iron. ,The pan
el is located between the two main structural.columns in
the unit operations laboratory··,~ and the front of the
panel board is flush with the east·. side of these columns.
The face of the panel was cut out to acc9modate the vari
ous indicating and recording.instruments. The panel has
a graphic representation of the process flow diagram on
its face above the instruments. A photograph of the in
stallation is shown in Figures 18 and 19.
Control Instrumentation. Process control of .the
unit is maintained through t~e use of automatic instru
mentation •. A vari~ty.of control instruments was incorpo
rated in_ the design; .and these _are illustrated in the di_s- .
tillation flow sheet, ·::_Figure· 7, and in the process. control
flow diagram,. Figure 20. The transmitter po·rtion of ·each
instrument is located .close to the point .o~ measurement;
the recorders, con~roller, and in~icators a~e located on
the· instrument panel; and the control valves are located
on the control valv_e rack. All transmi.ssion of control . .
signals is by compressed air. The individual spe_cifica-
tions of all the process instruments have be~n given by
Puyear( 66 ). The location and· numbering system used on
the thermocoupie leads is shown in Figure 21.
-54-
Figure 18. Front View of the ·Instrument ·Panel
-55-
Figure 19. Rear View of the Instrument Panel
showing tne Tel-0-Set Instruments,
the Instrument Air Header,. and
the Electrical Wiring
0
c
LLIC-V2
TRC-Tt
D
FR 3,4
F·V
FR 1,2
R
c e
..... --•D
Pf-i -TI
LLIC 2
R 4
PR I
R
'3
Pi,C -Tl
PRC
i'
TRC.,.__.._.,. TRC 4 r
A
FRC 3
FRC ...... .._~ FRC. 2 I
TRC-V2
LLIC-T:1
LEGEND TRC-TFMPERATURE RECORDER CON
TkOLLER
LLIC- -UQUIO LEVEL tNDtCATOR CONTROLLER
FR-FLOW RECORDER
PR-·PRESSURE RECO,AOER
PRC-PRESSURE RECORDER CONTROLLER
FRC-FLOW RECORDER Ct,'NTROLLEfi F-fLOW
V-VALVE
T-TRANSMtTTER
-SUPPLY AIR
-- INPUT 6 OUTPUT PNEUMATIC $1GNJlL
DEPARTMENT OF CHEMICAL ENGINEERIN6 MISSOURI SCHOOL Of MINES & METALLURGY
ROLLA, MISSOURI
PROCESS CONTROL rLOW DIAGRAM
SCALE: NONE DATEl~E NO: 60 DRAWN IY: G G '5TAPLES FILI NO: 490
..._------------a:;a... C CHECKED IY: Fl6URE NO: 20 APPROVED BY: ~ '/rjt,o SHEET NO: 1 d 1
DISTILLATION
COLUMN
2 ~-
LEADS INSERTED INTO
WELLS ON EACH PLATE
LEADS INTO TERMINAL BOX
ROTATING
DISC
COLUMN
PULSE
COLUMN .
LEADS INSE4TED l"ITO WELLS IN
INLET AND EX~l FLOW STREAMS
NOTE;LEADS A AND B ARE
CONNECTED TO RECORDER-
CONTROLLERS TRC - 1 AND
TRC - 2 ON DISTILLATION
SYSTEM.
LE ADS PASS FROM
TERMINAL BOX INTO
MULTIPOINT TE ~PER AT URE
RECORDER.
DEPARTMENT OF CHEMICAL ENGINEERING MISSOURI SCHOOL OF MINES & METALLURGY
ROLLA, M_ISSOURI
LOCATION AND NUMBERING
OF THERMOCOUPLE LEADS
SCALE: N () /'J ( DATE
DRAWN SY: R.A.L. I, II, - t>O
CHECKED BY: /(. 'Ji t.ll . J. • /0 ·i," APPROVED BY: '\{, Sii'!/t,.l)
CASE NO: 60 FILE NO: <\(}0 FIGURE NO: 21
SHEET NO: 1 of 1
-58-
Instrument Air. The instrument air is supplied
by an air compressor equipped w~th an intercooler and
aftercooler. The compressed air is filtered and reduced
to about 50~60 pounds per square inch, gage. The piping
between the compressor and the instrument panel is gal
vanized iron. The air is distributed from the instrument
panel by a copper header. Further distribution is by cop
per pipe and polyethylene tubing. Extensive use was made
of polyethylene tubing for·pneumatic lines .interconnect
ing the varioµs instrument components. A photograph of
the instrument air compressor is shown in Figure 22.
Process Piping. The distillation column, heat
·exchangers, and tank farm were integrated by means of the
process piping. All piping was of standard copper water
pipe connected with standard fittings -and joined by solder
sweat joints. Threaded unions were placed in the piping . .
·wherever their use might be advantageous in removing sec
tions of piping or equipment for cleaning_, repair, or re
placement. The piping runs- were made perpendicular and
parallel to the walls and floor of the unit operations
1aboratory to assure a neat appearance. ·
After the process piping had ~een installed, it
was checked for leaks. This was accomplished by pumping
water through the system, repairing the leaks discovered
after draining the lines, and then rechecking with water.
-59-
Figure 22 •. The Instrument Air Compressor
-60-
The pieces of equipment were linked together as
specified by the distillation flow sheet, Figure 7. The
general piping pi·cture can be seen in the pho·tographs of
the various equ·ipment installations.
Vent System. ~ vent system was installed for the
purpose of venting the tanks and the column. The vent
system was fabricated from 1/2-inch copper pipe using
copper sweat joints. A schematic diagram of the vent
system is shovm in Figure ·23.
Electrical Wiring. The electrical wiring for the
pump motors, the instrument chart ~iv~s, and lights was
installed according to the standard electrical codeo The
·wires were run through electrical conduit utilizing stan
dard connections and ele-ctrical junction box~s. The unit
was connected into the Missouri School of Mtnes and Met
allurgy power plant system.by standard.male plugs into
female outlets. A wiring diagram is shown in Figure 24.
-61-
i TO VAPOR CONDENSER ·
' •
I l 1
EXTRACT 1
FEED FEED
TANK TANK1 TANK2
I I l
RAFFINATE DISTILLATE DISTILLATE
TANK T ANK1 TANK2
. I I I
EXTRACT2 REFLUX BOTTOMS
ACCUMU LA. REJECT TANK TANK TANK
'
I I I
FEED BOTTOMS BOT TOMS
TANK TAN K1 TANK2
..
I r l
SOLVENT BOTTOMS BOT TOMS
TANK TAN K3
TANK4
4 FROM CONTROL VALVE: PRC - V-1
NOTE: VENT SYSTEM IS MADE
O F ~·. C OP P E R P I P E DEPARTMENT OF CHEMICAL ENGINEERING
MISSOURI SCHOOL OF MINES & METALLURGY
ROLLA. MISSOURI
VE NT
FLOW SCALE: NONE
DRAWN BY: /f. w_ r)/. CHECKED BY: J R A
APPROVED BY: ~
SYSTEM
DIAGRAM DATE
J..-<f-1,0
4/9/60 S'/10/1. IJ
CASE NO: 60 FILE NO: 490 FIGURE NO: 2 3
SHEET NO: 1 of 1
.
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DEPARTMENT OF CHEMICAL ENGINEERING MI.SSOURI SCHOOL OF MINES & METALLURGY
ROLLA, MISSOURI
\,,\/ I R I N G, S'C. \-\ E. MA, 1 c..· . r.:'01'(
D \ S_TlLLRTIDN - E'XTRRC1IOA/ SYSTEM ..
SCALE: . HOA/E. DATE I/- 1./ CASE NO: (f_q DRAWN BY: MMIZ FILE NO: 490. CHECKED BY: ~.)Y.' d. / ;J.. -/'7. ~1' FIGURE NO: 2. 4 APPROVED BY: 1:1:f'._ / l- 17·-S'I SHEET. NO: l o+ 1
-63-
Operational Procedure
The basic procedure for the operation of . the dis
tillation unit is: (1) the attainment of operating
temperature, ( 2) the approach to a steady~st~te ·:; ·· :
equilibrium, (3) introduction of the column feed, ·and
( 4) establishment o.f appropriate operating conditions.
The recommended, det_ailed procedure for operation
of the distillation unit is presented in the following
order: ( 1) preliminary pro_cedure, ·c 2) start-up pro
cedure, . (3) continuo.us operation, and (4) shut-down
procedure. All equipment will be referred to as desig
nated on the disttllation flow sheet, Figure 7.
Preliminary Procedure. The following preliminary
operations should be performed in order to prepare the
unit for operation:
1. All valves, including flow valves and by-pass
valves, are closed.
2. Both feed tanks are filled with water by means
of a connection to the distilled water outlet.
3. The number l·distillate tank and the numbers
land g bottoms tanks are filled with feed mixture by
connections to the suction sides of the distillate pump
and the bo~toms pump.
4. Cooling· water for the condenser should be
available at the control valve TRC-4.
-64-
5. Steam for the feed heater and the reboiler
should be available at the control valves TRC~1 and
TRC-2o Any condensate is bled off .through the drain
valves.
6. Approximately half of the contents of feed
tank ~umber 1 is ·pumped to the distillation columno
This is accomplished by opening valve D-15, the_by-pass
valve at F-V-1, the flow valves through EB::.1., the desired
feed _plate valve (12.::.1.,- J2.::.g, D-3, Qr. 12.:!), and valve D.-5
and by turning on the feed pump. After the desired amount
of water has been transferred to the co-lumn from the num
ber l distillate tank, the by-pas_s valve at F-V-1 is
closed; and the feed pump is turned off.
7o At this point, the following instruments should
be turned on and checked for proper operation:
a. ~ should read room temperature for
all _points.
b. TRC-2 and TRC-3 should indicate room
temperature.
c. ~ should indicate atmospheric pres-
sure.
d·. PRC-1 should indic·ate atmospheric
pressure. This instrument may be set·to control
at atmospheric pressure.
e. LLIC-2 should indicate the liquid level
in the rebeller.
-65-
Start-up Procedure. The unit is brought up to
temperature with boiling water, and the column is then
run at total reflux on water until ·static equilibrium
is approached. This may be accomplished by the following
procedure:
. 1. TRC-v-·4 is set to control the flow of cooling
water to the condenser.· The temperature set-point at
this time is the boiling point of water at atmospheric
pressure.
2. The by-pass valve at TRC-V-2 is .slowly opened
to allow entrance of steam into. the steam coil of the
reboiler. The water .in the reboiler is·brought to the
boiling temperature, and the vapors are allowed to fill
the column. The liquid level in the reboiler shou~d be
main~ained at greater than half of total capacity. If
the level drops below this, additional water should be
added from feed tank number l· (It may be _desirable to
add this .additional water at an elevated temperature. To
incre~se the temperatur~, the by-pass valve at TRC-V-1 is
opened slightly to allow: steam to enter the fe·ed heater.)
3. The vapor from·the reboiler should fill the
column, pass overhead, and be condensed in the ·condenser.
The condensate will then collect in the reflux accumula
tor. Flow from th~ condenser to the reflux accumulator
should ·-be through FR-3. This is accomplished by opening
the flow valves on either side of FR-3.
-66-
4. When sufficient material has collected in the
reflux accumulator, reflux to the col'1Illn can be started.
The by-pass valve at TRC-V-3 is opened, and the reflux
pump is turned o·n. The flow valves. through ~ and .12::.§_
are opened, and the reflux rate is adjusted by use of the
by-pa~s valve at·TRC-V~3.
5. At this stage, the column should be approach
ing an equilibrium condition; and the following process
instruments can be checked f"Or operation:
a. -~ should show a small temperature
·decrease up the column. The temperature on the
top plate should be the boiling point of water
at the prevailing .atmospheric pressure.
b~· TRC-2 should indicate a temperature
intermediate to that shown on~ for the first
and third plates of t .he distillation column.
TRC-2 can now be-set to control the steam flow
to the reboiler. The set-point of the instrument
should be the temperature indicated.· ·The· flow·
valves at TRC-V-2 are opened, and the.by-pass
valve is closed.
c. PRC-1 should maintain atmospheric
pressure for the pressure at the :top·~ of the column.
d. PR-1 ·should indicate the pressure at - .
· the bottom of the columno Tl;l.e difference between
this reading and that given by PRC-1 is-the pressure ·,
drop through the column •.
-67-
e. LLIC-2 should show the liquid level in
the reboiler. .-
f. FR-3 and~ should indicate the liquid
rates of ·flow in their respective process lines.
Continuous Operation. The pro.cedure f'or c~nyertirig
to the methanol-water mixture from the refluxing water is
now given, and instructions for continuous oper~tion are
presented:
1. The excess water in the feed tanks is pump.ad
out through valve D-36 by opening valves D~15 and l2:.1..2. and turning on the feed pump. When the· tanks are empty,
valves Q::.15. and 12.:.1..Q. are closed.
2. The feed mixture from numbers land 2 bottoms
tanks is pumped into the feed tanks by opening valves
D-25_, D-26, D-9, and Q:1.g and turning on the distillate
return pump.
3. Feed is now slowly introduced into the column
in the following manner: TRC-1 is set to maintain the
feed temperature at it~ ~oiling· point, _valve ·D-15 is
opened, and the feed pump is turned on. The flow valves.
on either ~ide of F-V-1 are opened, F-V-1 i~ slowly opened,
and the flow is regulated at a rate ·or o.2-o.3·gallons per
minut~.
4. LLIC-2 is set to control the level in the
reboiler. The flow valves on either side of LLIC-V-2
and ~ ~nd valve ~ ar.~ opened. The excess of water
-68-
in the unit will collect in the reboiler and can be
pu,mped out.
s. A temperature gradient should now begin·to
appear on m. ·The reflux rate sho.uld be carefully .
controlled at this time to help regulate the top tempera
ture. As the top temperature approaches the operat·ion
temperature, TRC-3 may be set for automatic operation.
6. The level of liquid in the reflux accumulator
tank will now begin to build up. When the tank is approxi
mately half full, LLIC-1 can be activated to maintain this
level. · Valve Jl:.a, the flow valves through LLIC-V-1.and
El::l, and valve D-17 should be opened.
7. All or· the process instruments should now be .
functioning, and the unit is on continuous operation.
Minor adjustments should be made to the instruments to
maintain steady operation. ·
Shut-down Procedure. The following procedure is
presented for terminating operation of the unit:
l. Valves D-15, D-16, 12::,g, TRC-V-1, · and F-V-1 ·
are closed; and the feed pump is turned off. ·
2o Flow of steam to the reboiler is discontinued
by closing valve TRC-V-2.
3. Valves TRC-V-3 and~ are closed, and the
reflux pump is turned offo
4. The unit is now allowed to cool.
-69-
5. The remaining material in the reboiler is
pumped, through t~e bottoms pump and £::.gl, to the bottoms
reject tank.
6. The product in the reflux accumulator is
pumped to the distillate tank-by the distillate pump~
7. The cooling water to the condenser is t~rned
off. ·
8. All proc~ss· valves, flow valves, and. by-pass
valves are closed.
Sample Calculations
Theoretical material and energy balances around
the distillation -column have been determined. The cal-
c~lations were based on the system meth~nol-water. The
feed for the distillation was the extract stream ·from the
extraction unit. The extract stream has· been specified
by Okenfuss(60) to con~ain approximately 20 mole per cent
methanol and 80 mole per cent water, with.leas . than one
~alf of one mole per cent trichloro~thylene. This a~ount
of trichloroethylene was considered negligible for these
calculations and was not taken into account.
The distillate.p~oduct was specified t~ be of such
a composition that by mixing it with a calc~_~ated .amount . .
.of the raffinate stream from the extraction ·unit (approx-
imate_ly 100 per - cent trichloroethylene) additional feed
for the extraction unit was obtained. The desired.feed·
-70-
for .the extraction unit wa~ 50 mole per cent methanol,
40 mole per cent trichl.oroethylene, and 1 O mole per. cent
w~ter ( 60) '.. Therefore, the required distillate ·product
composition was calculated by material balance to be · . .
83.3 mole per cent methanol and 16.7 mole per cent water.
The bottoms product was specified to be essentially pure
solve.nt for the extraction·unit (water).
With regard to the ~iscussion. above, the· following
variables were specified in order that the calculations
would be in agreement with those made for the extraction
unit:
1. A feed composition of.20.0 mole per .cent
methanol and 80.0 mole per cent water.
2. A diatillate product composition of 83.3 mole
per cent methanol and 16.7 mole per cent water.
3. A bottoms produc~ of 99.0 mol~ per cent water
and 1 .o mole per cent methanol.
The following variables were th~n chosen specif
ically for the sample calculations:
1 • A feed rate· of O. 25 gallons · per minute of
the above feed composition.
2. · The feed ·mixture to enter the column at the
bubble point ·.
3. An.external reflux ratio of 1025.·
.Determination of the Flow Rates and Heat Require
ments~ The method of Ponchon-Savar1t(9·39 9'M was used in
~71-
the determination of the material and energy balances.
The enthalpy-composition diagram, Figure 5, ~as obtained
from t4e data of Ansell, Samuels, and Frishe(4).
The solution as worked on the Ponchon-Savarit
diagram is shown in Figure 25. Point F was established
by the concentration (xF = 0.200) and the temperat~re
(bubble point) of the feed. Points D and B were located
on the saturated-liquid line at xn ~ o.833 and·xB = 0.010
respectively. Point D 1· was ·found from the specified
reflux ratio by use of the following equation(94):
in - 1y iy - in
The values of iy_and in can be read directly from the
( 1 )
enthalpy-composition diagram, Figure 25, at the compo-
sition of the -distillate product.
= 1 a,000· ~b-mol~ ·
Btu
= 2,200 Btu
lb-mole
therefore: 1' D = 1-.25 (18,000 - 2,2oq) + 18,000 (2)
1' 37,750 Btu (3) = D lb.-mole
iB an~ B' were then located analytically at -8,075 Btu
per ·lb~mole by a · line through D'. apd F, the feed point.
Calculation of the ·Distillate Product Rate
and the Reflux Rate. The feed rate was spec-ified
at 0.25 gallons per min~te for these calculations.
DJ., "'110
20,000
18,000 I; . //
..! 11 ,; ,, I I
I I ,, ,, I I
,, ,, , / I !I 16,000 ,: I,
!/ I
" // I ,, ,, I : I : 1! ,' r I· I I
,: I ;
// I I I
I
I I
,// I I
I II I ;
I I I I , I I
1' I 14,000 I I'. ,· I I
i I ; ,' I I
!i I
.. I I
// I
a, I I I I
g I • I I
12,0.00 r ! , i I I I·
£j I I ,, i I
I I; I I I I
" I ! I I :J
i ; ' i ,' I ti) I j I
I , I I; I I
, I I: I I ,' I I l I I I I I i l I , I , I
~ I . i ,' I I .'.).. I I I
I co j I I ,
I :r:. I
I I I I ..... I
c I I ! I I I
w I I I I I I i I I I I I I I I j
I I I
I I I I I . I I ., I . I
I I I I I
I I / I I I I 1· /,
I. I I I I I
1/ I
I /1 I , / I I
I
·x D L1
0.1 0.2 Q3 OA 0.5 0.6 0.7 0.8 0.9 Mole Fraction Methanol I -80<.)0i i' '. s· B
· FIGURE 25. PONCHON- SAVAR IT ~LUTION TO THE SAMPLE CALCULATtO NS
-73-
This ·1s equivalent to a feed rate of 5.627 lb-moles
per hour.· The distillate product is related to the
feed by the following equation ( ~90) :
where:
therefore:
D F
F
D
.D
= (4)
= 0.200 mole fraction methanol
= 0.833 mole fractio~ methanol
0.010 mole fraction methanol
= 5.627
= 5.627
= 1.300
lb-mole hr
0.200.- 0.010
0.$33 - 0.010 · lb-mole
hr
(5)
(6)
The average molecular weight of the distil
late product is 29.66 lbs per lb-mole. Therefore,
. the distillate rate was calculated as 38.6 lbs · per
houro Also, since the reflux ratio was 1 .25, the
reflux rate was calculated at 48.3 lbs per hour.
These rates can be easily converted to gallons per
minute.
D - 0.095 gal min
(7)
R = 0 .119 g~l . min
(8)
Calculation of the Bottoms Rate. The
bottoms rate was calculated from the feed and
product rates by the following material balance
equation(9~):
·B
where: F
D
B
B
-74-
= F - D
= 5.627
= 1.300
lb-mole ·hr
lq-µiole hr
= 5.627 - 10300
= 4.327 lb-mole
hr
(9)
(10)
( 11 )
Converting this value to gallons per minute gave
a rate of 0.157 gallons per m'inute.
Calculation of the Heat Requirements·. The
specific enthalpies of the overhead and _bottoms
were 2,200 and 3,150 Btu per lb~mole, respectively,
as read from Fiqure 25. The heat withdrawn in the
condenser was then calculat~d using the following
equation c9 2):
where:
D
= 37,750
= 2,200
Btu lb-mole
Btu lb-mole
lb-mole 1.300 .
· hr
( 1 2)
q 0 = 1.300 (37,750 - 2,~00) (13)
= 49,050 ~tu hr
(14)
-.75-
The heat a~ded in the reboiler is calculated
from the following equation(92):
qr = B (iB .. ) - l.B ( 15)
where:
iB 3,200 Btu = lb-mole
1' -8,075 Btu = B lb-mole
B 4.327 lb-mole =
hr
qr = 4.327 [3, 200 - (-8,075~ ( 16)
48,700 Btu (17) qr = hr
Calculation of the Theoretical Plates. The theo-
retical plates were stepped off on the Ponchon-Savarit
diagram, Figure 25, in the following manner. Since
xD = Y1, the point representing V1 is on the saturated
vapor line at x = 0.833. From point V1, the appropriate
tie l~ne establishes po.int L1 on the saturated- liquid
line. An operating line through points D' and ·L1 inter
sects the saturated-vapor line ·at point V2," and ·the tie
line through this point establishes point L2 ~ An oper
ating line through point~ ·D' and L2 intersects the sat
urated-vapor line at point L3 •
Since L3 is at the .left of line D'FB' ·, the next
operating line is drawn through point B', thus estab
lishing point V4 on the saturated-v:apor 11ne. From
point V4, point L4 is located by a tie line; V5 from
-76-
an operating line; L5 by a tie line; V6 from an oper
ating l~ne; L6 b~ a tie line; V7 from an operating line;
and Irr by a tie line. Since x7 is less than ~B' s~ven
steps are sufficient. A reboiler ·and ·six ideal plates
with feed admitted on the fourth plate are specified·.
Results of the Calculations. The results of the
theoretical material and energy balances are given in
Tables VI and VII. Calculations were made for a range
of feed rates from 0.20 gallons per minute to 0.50 gallons
per minute and for external reflux ratios of 1.00, 1.25,
1.50, 1 .75, and 2.00. In all cases, it was assumed that
the feed mixture entered the c_olumn at· the bubble point.
Calibration of Analytical Instruments
The instruments used for the analytical deter
minations were: {1) a Westphal balance·, (2) a dip
ping refractometer, and (3) ·a gas-liquid chromatograph.
A description of these instruments is given in. the mat
erials list. The instruments were cali.brated by firs.t
analyzing pr_epared sanipies of methanol-wa t ·er.. These ··.;
mixtures were prepared ·by carefully weighing .. the amount . . · · , : ..
of liquid contained in pipets of .various size~ at 25 °c, and then calculated amounts of methanol and water were
pipetted into glass st9ppered bottles. Calibration charts
were prepared for .each of the instruments from analysis
of these known samples. Unknown samples were than
-77-
TABLE VI
Effect of ·Reflux Ratio on the Theoretical Plates
Required for Separationa
External Theoretic~l Reflux Ratio Plates
1 .oo 9
1 .25 7
1.50 . 7
1 • 75 6
2.00 6
O<. 4
· aA feed of 20 .o mole per cent methanol and 80.0 mole per cent water into a distillate product of 83.3 mole per cent methanol and 16.7~mole per cent water and a bottoms of loO:mole per cent methanol and 99.0 mole per cent wa·ter.
-78-
TABLE VII
Results of Theoretical Material and Energy Balances
Feed Product Bottoms Condens·er Duty in Btu per hour Rate Rate Rate at Reflux Rates of:
1.00 1.25 1.50 1. 75 2.00 gal gal gal min min min
0.200 00075 0.126 32,900 37,000 41,200 45,200 49,300 ..
0.250 0.095 0.157 40,050 49,050 51,000 56,000· 61,000
0.300 0 0 113 0.169 49,300 55,400 61,600 67,700 73,800
0.350 0.133 0.219 57,000 64,500 72,000 79,000 86,000
o.4oo 0.152 0.251 65,800 73,900 82,200 90,200 98,500
o.450 0.170 0.278 73,500 83,000 92,750 101,500 110, 500
0.500 .0 .188 0 0·314 82,20~ 92,300 · 103,500 11 2, 500 123, 100
-~.19-
analyzed by° each.of the instruments and the.results
compared.
Westphal 'Balance. The specific gravity of the
known samples was deterIQ.ined at 25 °c by thermostating
the samples prior to analysis. The results obtained
are presented 1~ graphical form in Figure 26. For
purposes of comparison, the values of Carr and Riddick
as given in Table IV were also plot_ted.
Dipping R~fractometer. The dipping refractometer
was used in conjunction with a cons·tant temperature ·bath
which.regulated the temperature at 25.00 ·= 0.01 °c. Due to the volatile nature of· the mixtures, a.metal
beaker which pr~vided a vapor-tight compartment for the
sample was· used. · The calibration curve obtained for .
this instrument is shown in Figure 27. For comparison,
the values from the Intern~tiona~ Criti~al Tables were
also plotted.
Gas ~hromatography. _ A considerable amount of
literature search and experim~ntal work w~s ne~essary
before a calibrat~on ·curve·_ could be determined for the
gas chromatograph. Owing to its highly pol~r nature,
water is·stro~gly retained by most partitioning agents,
with the result that the water peak has a long tail.
This makes it very difficult .to obtain .a quantitative
measurement of the peak area and also g~eatly lengthens
the time of the analysis. Therefore, it was desirable .
>-t: > ~ 0:: (.!)
u u: u w a.. l/)
-80-
1.000r---....... --~---.--...... --.----.-----------
0.950
0.900
0.850 0
+
0.800
0 0.1
' '
experiment~, values
values of Carr and
\
'\ Riddick 0
\ \
\
0.2 0.3 o.4 o.5 o.6 o.7 o.e 0.9. 1.0 WEIGHT FRACTION METHANOL
F!Gl)RE 26. SPECIFIC GRAVITY AS A FUNCTION OF COMPOSITION
FOR THE SYSTEM METHANOL-WATER AT 25 °c.
acarr, c., and J. A. Riddick: Physical Properties ot· Methanol Water System, Ind. Eng. Chem., il, 693 ( 1951} •.
)( w a z
w > .... u <{ a: L1. w a::
-81~
1.34250,----T----...---..... ----..... ----..---..... ----..... --.... ----..---......
134000
1.33750
1.33500
1.33250
o experimental values
6 valu~s from lnh:rnational Critical Tables0
1:33000
1.32750
1·3 2500 o~---,"'."io--2-'o--...130---....i4L.o--5._0 ____ 6 ... o----.170--..1so-.--g1.o---'100.·
METHANOL. weight percent
_FIGURE 27. REFRACTIVE INDEX AS A FUNCTION OF COMPOSITION
FOR THE SYSTEM METHANOL-WATER AT 25 °c
a~!International Critio~l Tables," ll, p.66. McGraw. Hill Book Company, Ino., New York, N. Y., 1929.
!"982-
to find a suitable liquid phase and solid support which
w.ould g~v,e a measurable water peak.
Ethylene glycol, silico~e grease, tricresrJ phos
phate, and "Ucon" lubricants were tri·ed without satis
factory results. An article in ".The Laboratory11(30)
suggested the use of "Theed" (tetrahydroxyethylet:J:J;ylene~
dianiine) on "Chromasorb W" as a good combination far
analysis of polar liquids~ A column containing 35.5
per cent "Theed" by weight was prepared· and tested.· This
combination was found to give the best water peaks of the
materials tried. A calibration curve was· plotted and is
shown in Figure 28. It t~kes·approximately 30. minutes
for a sample to ~e completely eluted from the .column
at 101 °c with a helium flow rate of 110 milliliters per
minute. The retention times for methanol and water are
2.75 and 17.50-minutes respectively.
Unknown Samples. Unlmown samples were prepared
at approximately 25, 50, and 75 per cent by weight
methanol. These samples were ~hen_analyzed by each of
the three instruments. · The results obtained are tabulat-. .
ed in Table VIII.
~ <t
~ w <t -~ w CL _J
0 a:: z w <( ~ I <{
~ ~ w u ~
0 LL
<t 0 w <t a:: <{ w
a:: <t
8.0 7.0
6.0
50
4.0
3.0
2.0
1.0
0.8
0.6
0.5
OA
0.3
0.2
0.1
0.08
0.06
0.05
0.04
Q030
0
0.1
-83-
expet-imental values
extrapolated values
0..2 · 0.3 OA 0.5 0.6 0.7 WEIGHT FRACTION METHANOL
0.8
\
' ' ' ' 0.9
FIGURE 28. RATIO OF AREAS OF METHANOL- WATER PEAKS ..
1.0
AS A FUNCTION OF COMPOSITION BY GAS-LIQUID CHROMATOGRAPHY
-84-
TABLE VIII
Analysis.of Unknown Samples.of Methanol-Water
Mixtures as Per Cent Methanol
Analysis by Sample
No. Westphal Dipping Gas-Liquid Balance* Refractometa~* Chz,.oma. tqgr.aphy
wt% wt % wt %
21.5 :t OoO 23o0 ± O.O 2_?. oO : o.o 2 41 o5 + 0.2 45.3 :!: Oo5 45.~ ± 1.0 -3 70.0 :f: 0.2 69.6 :i: o.s 67..0 :I: 0 o5
*Analysis determined at 25 °c.
-85-
IVo DISCUSSION
The discussion section is divided into the fol
lowing categories: (1) discussion of equipment, (2)
discussion of instrumentation, ( 3) recommenda-tions,
and (4) limitations .•
Discussion of Equipment
The distillation equipment has been installed for
the express purpose of serving as an instructional aid.
The discussion of the equipment will be made with this
in mind and wil~ cover the following items: (1) distil
lation column, ( 2) reboiler, · ( 3) condenser, . (·4)
auxiliary heat ·exchangers, (5) proces$ p~ps, (6)
tanks and tank rack, and (7) . vent system.
Distillation Columno _ The distillation column has
several desirable :features -~which enhance its instructional
value:
1. The column has been constructed of glass so
as to provide an unobstructed view of the phenomena occur
ring within.
2o Multiple feed plates were provided so the stu
dent can observe the effect produced by ~hanging the feed
plate·.
-86-
3. Each plate was provided with a thermocouple
well and liquid and vapor sample taps, enabli;ng .the stu
dent to obtain a temperature and .composition pro.file of
the column.
In the material and energy balance calcula~ions,
it was assumed .that the heat loss from the column .walls
was negligible. However, since the column ·Wa~ not insu
lated, this :. as· sumption was far from true; but the actual
amount of heat lost is unknown. It is believed that the
heat loss will not be a hindrance to successful operation
and that it will be compensated by the instructional value
obtained.
It has been noted that the feed plates were spa·ced
unequally in the distillation columno · While this is not
a particularly desirable feature, it was unavoidable.
Twelve-inch tee sections of six-inch glass pipe were not
available, and the use of 18-inch sections only would
have made the column too tall for the space ava+-lable.
Therefore, rather than reduce ·the number of plates in
the column, the unequal spacing was used. 'It is not ·felt,
however, that this will.be a critical fac~or for proper
operation of the column. The main· objection ·probably is
a less attractive appearance.
Reboiler. The . purpose of the reboiler is to supply
the q.riving force for operation of the column. · This is
accomplished by heat tra~sfer from steam in a copper coil
-87-
to ·the bottoms material. Copper was chosen for the steam
c_oil because of its high thermal con~uctivity and mechani- ·
cal strength. One end of the reboiler is flanged -so_ that
the steam coil ·can be removed inta_ct from the reboiler for
inspection and cleaning. Also, when the steam coil is
in place in the -reboiler, it is attached only to the flange
face. A metal support in the reboiler allows free expan-
sion or contraction of the steam coil in a horizontal di-
rection. This should effectively relieve strain from the
coil during expansion and contraction.
· Condenser. The condenser contains approximately
3.9 square feet of heat -transfer surface. The cooling
medium is water flowing inside the inner tube. Assuming
an over-all coefficient of heat transfer between the con
d~nsing vapors and the cooling water of 200 Btu per (hour) {o .
(square foot) (°F), at a temperature difference_ of 64°F,
the· heat transfer rate is calculated to be 49,920 Btu per
hour. .By reference to Table VII, it is seen that this will
limit the feed rate and the reflux ratio used. · rt is felt
that the size of the condenser will seri~usly limit the
effectiveness of the distillation unit as an. ·instructional
aid. However, · the conde_nser is adequate at selected feed .
rates and reflux ratios; and it .can be used .as ·1nstalled
to condense the product vapors from the distillation col-
umn.
--88-
·Auxiliary Heat Exchangers. The auxiliary heat
exchangers are: (1) the feed heater, (2) the feed
preheater, and ( 3) the disti·llate cooler. The purpose
of these heat exchangers is to supply or remove hea·t
from the process streams.
Feed Heater. The purpose of the feed
heater is to regulate the temperature of the feed
to the distillation column. This is a highly de
sirable instructional feature as the effect caused
by changing the feed temperature ~an be easily
predicted theoretically, and the empirical results
can thus be compared with the calculated ones.
Feed Preheater. The most important fun<:~·
tion of the feed preheater is to cool the bottoms
product, which .has a temperature very close to its
boiling point upon exit from the reboiler. If
no attempt is made to cool the bottoms product,
it is very likely that "vapor locking" will occur ' . . .
in the bottoms pump. •ivapor locking" is a co.ndi-
tion which occurs in a centrifugal -pump when a volatile material · vaporizes in the impeller hous
ing and prevents the pump from operating effi
ciently.
Distillate Cooler. The purpose of the
distillate cooler is essentially the same as that
of the feed prehe~ter: to cool the distillate
-89-
product so that it can be pumped and stored.
The cooling medium used in this case ·is the. cool
ing water from the exit side of the cond~nser.
This serves as an example _to illustrate the . con
servation of cooling water in the unit. If neces
sary, a . separate source of cooling water could be
supplied in order to more effective~y cool the
distillate product.
Process Pumps. The process pumps are of the cen
trifugal type, allowing placement of valves for flow con
trol·on th~ discharge side. With no .load, the pumps
have a maximum head of 17-1/2 feet. The head· drops to.
approximately 17 feet at a delivery rate of five gallons
_per minute. The pumps are of explosion-proof constrµc
tion as a safety precaution since they are located on
the floor in front of the ·tank rack. If any leaks were
to develop from the t~nk rack, the vapors would concen
trate .near the floor since the vapors of.both methanol
and trichloroethylene are heavier than air. For the
purpose of preventing any such concentration of vapors,
a window fan has been installed on the west ·side of the
·unit Operations Laboratory.
Tanks and Tank Rack. The tanks use~ as storage
and surge tanks in the unit were not intend~d to be per
manent. They were designed and installed so as to be
easily removable. For this reason, the tanks were not
-90-
physically attached to the tank rack; and all connections . .
into and out of the tanks were made with 11 Swageloku fit-
tings. The tank rack has an all-bolted construction in
order that mod.ifications may be e~sily made when ne_cessary.
The capacity of the tank farm is such that it lim
its the length .of time which the unit can be run without
either obtaining additional feed from the extraction unit
or making up feed from the distillation and bottoms prod-
uct. For this reason, it may prove desirable at some
future time to increase the capacity of the tank farm.
Vent System. It was necessary.for safety reasons
to maintain a closed system. However, whenever material
i_s pumped into or out of the tanks on the tank rack, they
must be vented. Therefore, a vent system -was employe_d to
provide a safe means for venting the tanks. All of the
tanks were tied together with a common vent system which
passes first through a condenser and then is piped out
side the building. Any volatile material is then condensed
and recovered while noncondensable gases are carried-out-
side.
.Discussion of Instrumentation
Two different types of instrumentation were incor
porated for use o;n the distillation unit: (1) process
instrumentation and (2) analytical instrumentation.
-91-
Both types of instrumentation have a functional and
necessary use in the operation of the distillation unit;
but they both also serve the purpose of providing· ·an
instructional benefit to the student by offering ·~ him
practical experience in the use and mode of operation
of the two type.s of instruments.
Process Instrumentation. The primary function of
the process instruments . is to control automatically the
unit operation and to provide information on the physical
conditions of the unit. Flow rates, temperatures, and
pressures are measured and indicated qr recorded. This
information can be used in conjunction with re·sults ob;.;;;
tained from analytical determinations to . calculate mat~
rial and energy balances for the system.
Analytical Instrumentation~ Whereas the process
instruments provide information on the pliysical condi
tions of the distillation unit, the analytical instru
ments serve to provide information on the· chemical con
ditions of the system. Three analytical instruments ._ are
used to perform the necessary chemical analyses: (1) a
w.estphal balance, for determination of specific gravity;
(2) a dipping refractometer, for,q.etermination of re
fractive index; and· (3) a gas chromatograph, · for sepa
ration, detection, and measurement of the various com
pone~ts of a sample. Thus, a sample receives three sepa
rate analyses,-< through the use. of three different ana.lytical
.-92-
instruments. Analyses performed in this triplicate manner
provide a basis for comparison of the potential accuracy
of each set ·or results.
The most beneficial and informative analyses would
be those of samples obtained from the feed tank, product
tank, bottoms tank, and each plate of the distillation
column. As has been noted, the analyses can b~ used in
the calculation of material and energy balances for the
system.
Recommendations
The distillation unit is to be used in conjunction
with the extracti'6n unit to support instru~tion, specifi
cally in the various aspects of the aqueous reprocessing
of nuclear fuels, of stude~ts in chemical and nuclear en
gineering. These recommendations are made with this in
mind.
Distillation Column. It is recommended that the
following variables be studied during ·the operation of
the distillation unit:·
1 • The effect of changing the feed plate.
2. The effect of varying the reflux ratio.
3. The effect of feed rate and temperature.
4. The effect of the top and bottom column tem-·
perature.
-93-
It would ·also be desirable to study the effect of . .
insulating the column. Insulation which would still af-
ford some visibility of the interior of the column could
be applied. For example, two slits in the insulation
could run the full length of the column opposite each
othero
Condenser. It. i-s strongly recommended that the
size of the product condenser be in.creased or supplemen-
ted. It is estimated that, in· order to provide the de
sired flexibility of operation which should be inherent
in this unit, at least 25 square feet.of heat transfer
surface be provided. A graphite heat exchanger might be
investigated. Graphite offers good corrosion resistance,
and heat exchangers which have a large amount of heat
transfer surface in a small volume can be fabricated.
The author has had some experience with.such a heat ex-
changer and has found ~t to be quite adequate •
. The present condenser as designed and constructed
is a total condenser. It may prove desirable to have
available a partial condenser for instructio~al purposes.
One could be installed to. operate either in conjunction
with or completely separate from the present condenser.
Another modification could be the conversion of one of
the feed sections to a side stream draw-off. This could
be aocomplished by disconnecting the feed section from the
feed manifold and substituting a condenser. A multiple
component mixture could then be run through the column.
-94-
Limitations
The distillation equipment is limited by materi
als of construction and by size. A list of the limits (86)
of each piece of equipment has been presented by Puyear ,
and it is also presented here in Table IX.
-95-
TABLE IX
Limitations of Equipmenta
Item Capacity or Limiting Feature
Distillation Column Approx1ma·tely 50 gal feed per hr, maximum
Reboiler Approximately 6.2. sq ft of heat transfer surface
Condenser
Feed Heater
Feed Preheater
Distillate Cooler
Feed Tanks
Overhead Product . Tanks
Approximately 3.9 sq ft
Approximately 1 .o sq f ·t
Approximately 2.5 sq .ft
Appro~imately 2.5 sq ft
110 gallons total
110 gallons total
of .heat transfer surface
of heat transfer surface
of heat transfer surface
of heat transfer surface
Accumulator Tank 30 gallons
Bottoms Reject Tank . 30 gallons
Bottoms Product Tank 220 gallons total
Pumps
Feed Line
Approximately ·17 ft of head, maxim~
Limited to tw·o ~al per min by flow recorder
Bottoms Product Line Limited to two gal per min by flow recorder
Distillate Product Line
·Reflux Line
Limited to one gal per min by flow recorder
Limited to one gal per min by flow recorder
Materials of Construction
Pyrex glass
Steel tank c·opper coil
Copper tube
Copper tube
Brass tube in cast iron case
Brass tube in cast · iron case
Sheet Steel
Sheet Steel
Sheet Steel
Sheet Steel
Sheet Steel
Bronze
Copper tul;>e
Copper tube
Copper tube
Copper tube
aPuyear, D. E.: Design of Distillation Solvent Recovery System, p. 134, Unpublished M. Sc. Thesis, Library, Missouri .. School ~t Mines and Metallurgy, Rolla, Mo. (1958).
-96-
V. CONCLUSIONS
The construction of the distillation portion of
the model of a nuclear fuels reprocessing plant has led
to the following conclusions:
1. The distillation column, condenser, reboiler,
feed heater, auxiliary heat exchangers, tanks, rotameters,
control valves, and process piping have been installed;
and preliminary testing has indicated that thi~ equip
ment will function properly.
2. The process instruments with the necessary
pneumatic lines, regulation equipmen~, and air compressor
have been installed. This _equipm~nt is _now reasonably
free from air leaks and is ready for operational checks.
3o · Theoretical material and energy balances have
indicated that, at a reflux ratio of 1o25 and using a
reboiler and six ideal plates, 0.25 gallons .of feed at
the bubble point and consisting of 20o0 mole·per cent
methanol and 80.0 mole per cent water can be separated
into the following:
a. A distillate product consisting of
83.3 mole per cent methanol and 16.7 mole per
cent water.
b. A bottoms pr_oduct consisting of ·1 .o
mole per cent methanol and 99.0 mole per cent
water.
-97-
4. The analytical instruments have been calibra
ted and have been used to analyze .unknown samples of
methanol-water mixtures. The analytical instruments
consist of the following items of equipment:
ao A Westphal balance for determining the
specific gravity of the sample.
b. A dipping refractometer for determina
tion of the index of refraction of the sample·.
c. A gas-liquid chromatograph for both
qualitative and quantitative analysis of the sample.
-98-
VI. SUMMARY
The Department of Chemical Engineering of the
University of Missouri School of Mines and Metallurgy,
Rolla, Missouri, received a grant f~om the Atomic Energy
Commission for the construction of a model of a nuclear
fuels reprocessing plant. The construction of a complete
ly nonhazardous system has now been completed. The system
consists of an extraction unit· and a distillation unit . .
which can be operated either concurrent+Y or separatelyo .
The ternary liquid system water-methanol-trichloroethyl
ene has been designated for use in the unit. Usi.ng the
principle of differential solubility, me~ha~ol is to be
extracted by water from a methanol-trichloroethylene
mixture in the extraction unit. The meth~ol-water mix-
ture thus obtained as the extract stream is then separated
in the distillation unit because of differential vapor
pressure. The system was constructed as an instructional
~id for students of nuclear ·and chemical engineering
rather than as a research tool.
The distillation unit consists of a s-ix-inch,
glass, bubble-cap.column and accessory equipment. The
feed plate, the rate and condition·of the feed, the re
flux ratio, the top and bottom.column temperatures; and,
to a certain degree, the column· pressure can all be
-99-
s·elected as required to illustrate their effect on the
operation of the unit.
The distillation unit was instrumented with both
process and analytical instruments. The process i~stru
ments serve the · dual purpose of controlling the distil
lation process and providing a record of the c9nditions
of temperature, pressure, and flow throughout the system.
The analytical instruments can be used to determine .the
composition of the feed stream, of the top and bottom
product, and of the material on each plate of the column.
The primary objective in the design and construc
tion of the distillat~on equipment was to provide maxi~
mum instructional benefit. This goal has been attained
in that:
1. The glass column allows visual understanding
of internal operations· and phenomena.
2. Versatility incorporated into the unit allows . .
control of the operating variables, making possible obser-
vation of the effect of these variables on the operat'ion
of the unit.
3. Instrumentation employed within the system
allo~s practical experience in the use and mode of opera
tion of the process and analytical instrumentso
-100-
VII. APPENDICES
The nomenclature used in the thesis is listed
in Appendix A.
-101-
Appendix .A..
Nomenclature
The symbols used in this thesis are defined as
follows:
B Bottom product, lb-mole per hr
D Overhead product, lb-mole per hr
F Feed, lb-mole per hr
1 Specific enthalpy, Btu per lb; i _B, of bottom product; in, of over~ead product; iy, of v_apor from top plate; 113, of bottom product, corrected for heat effect qr; in, of overhead product, corrected for heat effect_ -qc
q Rate of heat flow, Btu per hr; qr, . heat· added -a~ rebo1ler; -qc, heat rejected at condenser
R Reflux ratio; Rn= L/D
x Mole or .mass fraction of component A in liquid; xB, in.bottom product! xn, in overhead product; XF, in feed to column
y Mole or mass fraction of component A in vapor; YB, in bottom product; Yn, in overhead product; YF, in feed to column .
-102-
VIII. BIBLIOGRAPHY
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'Z(. Freilich, A.: Computers in Process Control, Chem.
Eng., §i, No. 6, 280-4 (1957).
28. Greenstadt, J., Y. Bard and B. Mors.e: Multicompo
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Ind. Eng •. . Chem., ~' 1644 ( 1958).
29. 11Handbook of Organic Industrial Solvent.s, 11 pp. 25, . .
34,· 51, 60. National Association of Mutual Casu-
alty Companies, Chicago, Ill., 1958.
30. Here 1 s a More Effectiv? Support for Chromatography
of Polar Compounds, The Laboratory,~' No. 4,
1 1 8-9 ( 1 9 59 ) •
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neering Des.ign on a Computer, Ind·. Eng. Chem.,
5Q, 716 ( 1958).
· 32. Howe, J.P.: Reactor Fuel Metallurgy, 0 Proceedings . t
of the Inter. Conf. on the Peace·ful Uses of· Atomic
Energy, 11 2., p. 179. United Nations Puolications,
New York, N. Y., 1956.
33. Hurst, R., et al:. The Homogeneous Aqueous Reactor,
J. Brit. Nucl. Energy Conf., g, ·395-405 ( 1957).
34. "International Critical Tables," Il, p. 66. McGraw
Hill Book Co., Inc., . New York, N. Yo., 1929.
---1.06-
35. James, A. T. and A. J.P. Martin: Gas-Liquid-Parti
tion Chromatography: The Separation and Micro
Estimati~n of Volatile Fatty Acids from ·Formic
Acid to Dodecanoic Acid, Biochem. : J., 5Q., 679
(1952).
36. Johnson, A. I. and c. w. Bowman: Can. J. Chern. Engr.,
.1§., 253 (1958) ~
37. Johnson, J. R. and C. E.. Curtis: T~chnology of uo2 and Th02, 11Procee.dings of the In-ter. Conf. on
the Peaceful Uses of Atomic Energy," 2., p. ·169.
United Nations Publications, New York, N. Y.,
1956.
38. -Kaufmann, A. R.: Fabrication of Uranium Alloys,
"Proce.edings of the· Inter. Conf. on the Peaceful
Uses of Atomic Energy, 11 2., p. 210. · United Na
tions Public_ations, New York, N·_. · Y,,, · 1956~
39. Keulemans, A. I_. M.: -"Gas . Chromatogr.~phy, 11 p.· 9~. ·
Re~nhold Publishing Corp., New York, N. Y., 1957.
40. ibid, p. 55.
41-. ibid, p. 32.
42. Kling, H •. P. and B. Kopelman: Ceramic Fuels, "Mate-,.
rials for Nuclear Reactors 11 (B. Kopelman, Editor),
pp. 90-108. McGraw-Hill Book Co.; Inc., New York,
N. Y., 1959 •
43. Knight, H. S.: Mechanism of Separation, 11Principles
and Practice of Gas Chromatograp~y" (R. L. Pecsok,
-107-
Editor), pp. 21-8. John Wiley & Sons, _Inc.,
New Y~rk, N. Y., 1959.
44. Lawroski, s.: Non-Aqueou·s Processing - 1m In~roduc-.•
tion, "Symposi~ on the R~processing· . of Irradia
ted Fuels, 11 held at Brussels, Belgium, May 20-
25, 1957, pp. 479-97. Te·chnical Information Ser~
vice Extension, Oak Ridge, Tenn., 1957.
45. ibid, p. 479 •
. 46. ibid, p. 480.
47 •.. ibid, p. 482.
48. Lyster, w. N., D.S. Billingsley, et al: 38th.Nat.
Meeting, Am. Inst. Chem. Engro ,: Salt Lake City,
Utah, Sept. 1958.
49. Maddox, R. N. : · Use Digital Comput.ers .as · ·nistillation
Column Design Aid, Petrol. Engr., 3.Q., No. 4, - 15-8
( 1958) 0
50. Martin, A. J.P. and R. L. -M. Synge: A New Form of
C~omatography Employing Two Liquid'Phases. I.
A Theory of Chromatography: II. Application of
the Microdetermination of the Higher Monoamino-
acids· in Proteins, Biochem. J., J.!2., 1358-68
(1941).
51. Martin·, F. s. and' G. L. Miles: 11 Chem1cal Processing
of Nuclear Fuels, 11 . pp. 3-13. Butterworths Scien
tific Publications, London~ 1958.
52.
53.
54.
55.
56.
-1.08-
i .bid, p. 15.
ibid, pp •. 19-25.
ibid, p. 98. ·
ibid, pp. 223-231.
McCabe, W. L. and J. C. Smith: 11Unit Operations of
Chemical Engineering, u pp·. 665-755. McGraw-Hill
Book Co., Inc., New York, N. Y., 1956.
57. McKay, H. A. C. and c. M. Nicholls: Criticality in
Producing Fissile Materials: ttProceedings of the . .
Inter. Conf. on the Peaceful Uses of Atomic Ener-
gy,u U, pp. 311-4. United Nations Publications,
New York, No Y. ,. 1956 •.
58. Messner, A. E., D. M. Rosie and P.A. Argabright:
Correlation of Thermal Conduct.ivity Gell Response
with Molecular Weight and Structure, Anal. Chem.,
.ll, 230-3 (1959).
59. 0 Nialk Trichloroethylene," p. 9. Niagara Alkali Com-
pany, 1953.
60. Okenfuss, R.H.: Redesign and Construction of Ro
tating Di~c Contaotor, p. 108, Unpublished M. Sc.
Thesis, Library, Missouri School of Mines and
Metallurgy, Rolla, Mo. · (1960).
61. Patton, H. W.: Fundamental Principles, 11Principles
and Practice of Gas Chromatography!' (R. L~ Pecsok,
Editor), pp. 8-20. John Wiley & Sons, New York,
N. Y., 1959.
62. (Seep. 112).
-109-
63. Puyear, D. E.: Design of Distillation Solvent Re
covery System, Unpublished M. Seo Thesis·, Li
brary, Missouri School of Mines and Metallurgy,
Rolla, Mo~ (1958).
64. ibid, p. 65.
65. ibid, pp. 83-87.
66. ibid, pp. 93-107.
67. ibid, pp. 1 33-1 34.
68. Raiklen, H. and W. Go Lidman: Cladding and Bonding
Techniques, .. Materials for Nuclear Reactors 1.1
(B. Kopelman, Editor), pp. 157-76. McGraw-Hill
Book Co., Inc., .New York, N. _Y., 19590
69. Richards, R. B.: Aque·ous Reprocessing - An Introduc
tion, "Symposium on the Reprocessing of Irradia~ . ted Fuels," held at Brussels, B~lgium, May 20-
25, 1957, pp. 3-21. Technical Information Ser
vice Extension, Oak Ridge, Tenn., 1957.
70. Robinson, c. S. and E. -R. Gilliland: "Elements of . Fractional Distillation," McGraw-Hill Book Co.,
Inc.,· New York, N. Y., 1950. 4 ·ed.
71. Rosenbrook, H. H.: . Calculation of the Transient
Behavior of Distillation Columns, Brit. Chem.
Engr., l, 364:.7, 432-5, 491-4 (1958) • .
-72. Rose, A. and R. F. Sweeny: Ternary Batch Distilla
tion Calculation for Rectification of Naphtha-
lene Tar Acid Oil, Ind. Eng. ~he~., -5.Q_, 1687 (1958).
-110-
73. Rothlin, S., J. L. Crutzen and G. R. · Schultze:
Gleic~gewichte Flussiz/flussiz in Einegen T~r~
naren System und Gegenstrom-Extrakin in Einem
Horizontalen Rohr, Chemie_. Ing. Techn., ~' ?11-
9 (1957). (in German) .
7 4. Saller, H. A.: . Aluminum-Uranium Alloys, 11Proceed
ings of the Inter. Conf. on the Peaceful Uses of
Atomic Energy·, u 2., ·p. 214. United ~ations Pub
lications, New York, N. Y., · 1956.
75. Sargent, R. W • . H.: Trans. Inst. Chem. Engr. (London),
.22., 20 1 - 1 4 ( 1 9 58 ) •
76. Schumar, ·J. R.: Reactor Fuel El~ments, Scientific
American, 200, No. 2, 37 (1959).
77 • . Steunenberg, R. K. and R. _c. Vogel: Survey of Fluo~
ride Volatility Pro_cesses, 11Proceedings of the .. Inter. Conf~ on the Peaqeful Uses of Atomic
Energy, 11 11., pp. 438-51 • . United.Nations. Publi
cations, New York, N. Y.j 1959~ ·
78. 11 Symposium on the Reprocessing of Irradiated Fuels, 11 .
held .at Brussels, _Belgium, May 20-25, 1957, Books
1, 2,' and . 3 •. Technical . Information Service ·Ex
tension, Oalc Ridge, Tenn., 1957.
79. Weissberger, A.: · "Technique of Organic Chemistry, 11
4. Interscience Publishers, Inc., New York,
N. Yo, 1951.
-1·1.1-
80. Welch, H. T.: Pressure Drop Through Bubble Caps,
Petr~l. Refiner, 21., No. 8, 127 (1958). ·
81. Whitman, c. 'I.: Fuel Reprocessing, 11Materials for .. Nuclear Reactor.a" (B. Kopelman, Editor), pp.
337-4o. McGraw-Hill Book Company, Inc., New
York, N. · Y., 1959.
82. · Wing, R.H.: Rethink Your Distilla~ion Design,
Chem. Eng., .2§., No~ 21, 185-8 (1959) •
. 83. Winn, R. W.: . New Relative Volatility Method for
Distillation Calculations, Petrol. Refiner,.
:fl.·, No. 5, 215-8 (1958) • .
84. Witt, R·.: Th~rium, . 11Materials f<;>r Nuclear Reactors II . (B. Kopelman, Editor), pp. 45-58. McGraw-Hill
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85. · Wymer, R. G. and D. L. _Foster: Nuclear Reactor Fuel
Dissolution~· "Progress in Nuclear Energy, S~ries . III, Process Chemistrytt (F • . R. Bruce, et ~l., .
Editors), pp. 85-96. McGraw-Hill Book Company,
Inc., New York, N. Y., 1956.·
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-112-
89. Zuiderway, F. J. and A. Harmons: Chem.~ Eng. Sci.,
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Addenda
90. McCabe, W. L. and J. c. Smith: 11Uni t Operations of
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920
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ibid, P• 719.
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. Foust, A. S. and associates: "Principles of Unit
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94. Savarit, R.: Arts et· Metiers, 65ff ( 1-922).
Foust, A. s. and associates: "Principles of .Unit
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62 0 Pecsok, R. L.: Analytical· Methods, '~Principles and . Practice in Gas Chromatography'~ (Ro L. Pecsok,
Editor), pp. 142-143. John Wiley & Sons, Inc.,
New York, N. Y., 1959.
-113-
IX. ACKNOWLEDGEMENTS
The author of this thesis wishes to thank Dr.
Dudley Thompson, Major Adviser for this project, for his
patient and understanding assistance in the completion
of this research project.
Mr. R.H. Okenfuss and Mr. c. J. Vetter, who were
responsible for the construction of the extraction por
tion of the project, were of invaluable assistance in
coordinating their work with the work of the author.
The indebtedness of the author is gratefully acknowledged.
A special "thank youtt is extended to the under
graduate students who put in many hours of labor on the
unit. while enrolled in Chemical Engineer~ng 300. Their
assistance in the construction· of the unit is . greatly
appreciated.
The author's wife, Lucene, has given noble service
in proof reading the draft and assisting in the compila
tion of the final thesi·s. To her the author 1·s warmest
appreciation is extended~
The services, in the fabrication of equipment, of
Mr. Russell Welch and Mr. Elmer Giddens of the Chemical
Engineering Staff·are genuinely appreciated.
The assistance of the members of the staff and
graduate students of the Chemical Engineering Department
is appreciated and hereby acknowledged.
-114-
The author is also indebted to the Atomic Ene_rgy
Commission for the funds which made this project po~si
ble and · to Mr. D. E. Puyear and Mr.· Mo R. Fard for the
original design work on the unit.
X. VITA
The author of this thesis was born on October 16,
1935, in West Plains, Missouri. He received his elemen
tary and high school educations in the West Plains public
school system. His high school education was completed
in May, 1953. He entereo.· Westminster College in Fulton,
Missouri", in September, 1953, and was enrolled during the
scho9l years 1953-54 and 1954-55. He attended.summer
school at the University of Colorado in Boulder, Colorado,
during the summer of 1954. At thi~ time~ he transferred
to the ~niversity of Missouri School of Mines . and Metal
lurgy in Rolla, Missourio He was enrolled during the
-116- -
school years 1955~56 and 1956-57. He accepted a job
with Columbia-South~rn Chemical Corporation, Corpus ·
Christi, Texas, .~s a Project Engineer in the Development
Departm~nt in June, 1957, and remained. with them until
February, 1958. _During the summer of 1957 he was·e~
rolled in the night·school ·of Del Mar University, Corpus
Christi. He then returned . to the University of. ·Missouri
School of Mines and Metallurgy and completed the require
ments for a Bachelor of Science Degree in Chemical Engi
neering in June, 1958.
Upon graduation, the author worked for Oolumbia
Southern Chemical Corporation during the summer of 1958.
He returned to the Univers.ity of Missou~i S_chool of Mines
and Metallurgy in September, 1958, to_ begin work -on the
requirements for the Master . of Sci.ence Degree in Chemical
Engineering. He served as a Graduate Assistant in Chem~
ical Engineering from September, 1958, to-August, 1959;
as an Assistant Instructor in qhemical Eng~neering from
September, 1959, to January, 1960; and· as an Instructor
in Chemical Engineeri~g from February, 1960 to June, 1960 •
...... / (/