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LSU Historical Dissertations and Theses Graduate School

1956

Higher Alcohols in the Alcoholic Distillation From

Fermented Cane Molasses.
Herminio M. Brau
Louisiana State University and Agricultural & Mechanical College

Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses

Recommended Citation
Brau, Herminio M., "Higher Alcohols in the Alcoholic Distillation From Fermented Cane Molasses." (1956). LSU Historical
Dissertations and Theses. 166.
https://digitalcommons.lsu.edu/gradschool_disstheses/166

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HIGHER ALCOHOLS IN THE ALCOHOLIC DISTILLATION FROM

FERMENTED CANE MOLASSES

A D is s e r ta tio n

Subm itted to th e G raduate F a c u lty o f th e

L o u isian a S ta t e U n iv e rs ity and
A g ric u ltu ra l and M echanical C ollege
in p a r t i a l f u l f i l l m e n t o f th e
req u irem en ts fo r th e degree o f
D octor o f P hilosophy

in

The Departm ent o f Chemical E ngineering

by
Herminio M. Brau
B .S ., U n iv e rs ity o f P u e rto R ico, 1944
M.Chera.Eng., New York U n iv e rs ity , 1949
J u ly , 1956
 ACKNOWLEDGEMENT

The a u th o r w ishes to ex p ress M s s in c e re g r a titu d e to D r. A rth u r

G. K e lle r f o r h is sym pathetic guidance, a d v ice and i n t e r e s t in t h i s

work, to Mr. V ic to r R odrigues B e n ite s , T e ch n ical D ire c to r o f th e Run\

P i l o t P la n t o f th e A gricJtL tural E xperim ental S ta tio n o f th e U n iv e rs ity

o f P u erto Rico fo r v a lu a b le su g g estio n s and ad v ice d u rin g th e e x p e ri­

m ental phase o f t h i s re s e a rc h , and to th e A g r ic u ltu r a l E xperim ental

S ta tio n o f th e U n iv ersity ' o f P u e rto Rico whose f in a n c ia l a s s is ta n c e

made t h i s work p o s s ib le .
 TABLE OF CONTENTS
Page

ACKNOWLEDGEMENT ................................................................................................... ii

ABSTRACT.................................................................................................................... xi

CHAPTERS

I. ORIGIN AND COMPOSITION OF FUSEL OIL............................................ 1

G eneral C o n sid e ra tio n s and D e fin itio n o f Terms . . . . I
C o n s titu e n ts o f F u sel O il . 3
O rig in o f F u se l O il......................................................................... 6
R eaction Mechanism f o r th e Deamination o f Amino A cid s. 17
Composition o f F u sel O il From D iff e re n t S u b s tra te s . . 19
Y ields o f F u sel O il From D iff e re n t Raw M a te ria ls . . . 21
F u sel O il C ontent in A lco h o lic B e v e r a g e s .......................... 22

II. COMMERCIAL USES OF FUSEL OIL ....................................... 24

S p e c if ic a tio n s f o r F u se l O il and Am}-! A lc o h o l.................. 25
P ro d u ctio n and Im ports o f F u se l O il and Amyl A lcohol . 27
Uses o f Amyl A lcohols and F u se l O il. . . . . . . . . . . 28

III. ANALYTICAL METHODS FOR THE DETERMINATION OF FUSEL OIL. . 31

R ose-H erzfeld V olum etric Method. . . . . . . . . . . . 32
A llen-M arquardt V olum etric Method. . ...................... . . . 34
M ohler-Rocqucs C o lo rim e tric Method . . .............................. 37
K omarowsky-Fellenberg C o lo rim e tric M ethod.......................... 40
M o d ific a tio n s to Komarovsky's M e th o d ..................... 43
M iscellan eo u s M ethods..................................................................... 46

IV. EFFECT OF THE PRESENCE OF DIFFERENT CONCENTRATIONS OF

FUSEL OIL ON THE DETERMINATION OF ALCOHOL BY PICNOMETER,
REFRACTOMETER AND HYDROMETER ......................... 4S

V. SEPARATION AND PURIFICATION OF FUSEL OIL DURING THE

DISTILLATION PHASE OF THE PROCESS OF MANUFACTURE . . . . 56
O b je c tiv e s o f th e D i s t i l l a t i o n P rocess . . . . . . . . 5S
I n te r m i tte n t D i s t i l l a t i o n P ro c e sse s, . . . . . . . . . 61
C ontinuous D i s t i l l a t i o n P ro c e s s e s ........................................... 67
B ehavior o f F u se l O il in th e O peration o f th e
P u rify in g Column. . . . . . . . . . . . . . . . . . . 72
B ehavior o f F u se l O il in th e O peration o f th e
R e c tify in g C o lu m n ............................................... 82
P u r if ic a t io n o f th e F u se l O il T a k e - o f f ..................... 89

VI * AUTOMATIC CONTROLS IN THE ALCOHOLIC DISTILLATION . . . . 94

Q u a n tity C ontrol Systems ..................... 102
Composition C o n tro l S ystem s.............................................................109

iii
 Page

M o d ific a tio n s Developed in T h is Work

Com position C ontro l Sj'stem I I I . . . . . . . . . 119
Com position C o n tro l System IV..................... 123

V II i EXPERIMENTS DATA ON FUSEL OIL DISTRIBUTION IN THE

RECTIFYING COLUMN UNDER DIFFERENT OPERATING
CONDITIONS......................... 134
E xperim ental Procedure and Equipment U tilis e d . . . 134
R e s u lts .......................................................................................142
C o n c lu s io n s .............................................................................. 151

V III. COMPILATION OF EQUILIBRIUM DATA FOR THE SYSTEM

ETHANOL-WATER AT ATMOSPHERIC PRESSURE .............................. 159

BIBLIOCRAPHY................................................................................. 162
O rig in and Composition o f F u se l O i l ............................. 163
Commercial Uses o f F u sel O il......................................................... 173
A n a ly tic a l Methods f o r th e D eterm in atio n o f F u sel O il . . 174
S e p a ra tio n and P u r if ic a t io n o f F u se l O il During
D i s t i l l a t i o n ............................. 179
A utom atic C o n tro ls in th e A lc o h o lic D i s t i l l a t i o n .............. 183
C om pilation o f E q u ilib riu m Data f o r the System E th a n o l-
W ater a t Atm ospheric P r e s s u r e .....................................................1S5

APPENDIX - TABLES OF EXPERIMENTAL DATA........................................ 187

AUTOBIOGRAPHY................................................................................................ 259

iv
 LIST OF TABLES
Page
TEXT

1. Composition o f F u se l O il From D iff e re n t O rig in s . . . . 20

2. Y ields o f F u sel O il From D iff e re n t Raw M a te r ia ls . . . . 21

3. F u se l O il Content in A lco h o lic B everages. . . . . . . . 23

4. P ro d u ctio n and Im ports o f Amyl A lcohol and F u se l O il, . 27

5. A llo c a tio n s o f Amyl A lcohols From A p ril 1—June 30,

1935 ......................'............................................................................ 2S

6. F u sel O il and A lcohol D is trib u tio n by P la te s o f the

P u rify in g Column ......................................................................... 78

7. F u se l O il and A lcohol D is tr ib u tio n by P la te s o f th e

P u rify in g Column ................................................................ 79

8. O p eratin g C onditions in th e R e c tify in g Column in th e

V arious Experim ents Conducted a t D iff e re n t R eflire
R a tio s and Feed Com positions ............................. 139

9. L o cation o f P la te o f Maximum F u sel O il C o n cen tratio n

Under D iff e re n t O peratin g C onditions . . . . . . . . 150

10. F u se l O il C ontent in Main P roduct Under D if f e r e n t

O p eratin g C on d itio n s . .......................................... 151

: 1 1. F u sel O il C ontent in Top P la te o f th e R e c tify in g Column

Under D iff e re n t O peratin g C o n d itio n s . . . . . . . . 151

12. A pparent A lcohol C ontent in th e P la te o f Maximum F u se l

O il C o n c e n tra tio n ..................... 153

APPENDIX

I. E xperim ental D ata on th e E f fe c t o f th e P resen ce o f

D if f e r e n t C o n ce n tra tio n s o f F u se l O il on th e
D eterm in atio n o f A lcohol by P icnoineter, R e fra c -
to m cter and H ydrom eter................................. 188

II-X V . E xperim ental Data O btained in th e S tu d ie s on

A utom atic C o n tro ls in th e A lc o h o lic D i s t i l l a t i o n . 190

v
 Page

XVI-LX. E xperim ental Data on F u se l O il and A lcohol D i s t r i ­

b u tio n by P la te s o f th e R e c tify in g Colismi Under
D iff e re n t O peratin g C onditions ................................... 204

LXI. E q uilibrium C om positions fo r th e System E th an o l-

Water a t A tm ospheric P re s su re in Terms o f Per
Cent by W eightj Mol F ra c tio n and P er Cent by
Volume a t bO°F and 20°C. . ....................................... 249

vi
 LIST OK FIGURES
Page

1. E ffe c t o f P resence o f F u se l O il on th e D eterm in atio n o f

A lcohol by th e Picnom cter and Hydrometer Methods . . 54

2. E f fe c t o f P resence of F u se l O il on th e D eterm in atio n o f

A lcohol by th e R efracto m eter Method. .......................... 56

v ii
 LIST OF DRAWINGS
Page
DRAWING NUMBER

1. D i s t i l l a t i o n Flow S h eet . . . . . . . . . . . . . . . 68

2. Q uantify C ontrol System I ........................................................... 103

3. Q u a n tity C ontrol System I I ........................................106

4. Q u an tity C ontro l System I I I ....................................110

5. Composition C ontrol System I . . . . . . 112

5A. Composition C ontrol System l‘A ...........................................114

6. Composition C ontrol System I I . . . » 115

6A. Composition C ontrol System IIA ...........................................117

7. Composition C ontrol System I I I . . . . . . . . . . . . l'2 l

8. Composition C o n tro l S 3'stein IV . . . . . . . . . . . . 128

9. Flow Diagram and In s tru m e n ta tio n o f R e c tify in g

Column . . . . . . . . . . . . . . . . . 138

v iii
 ABSTRACT

F u se l o i l i s th e name given c o l l e c t i v e l y to a m ix tu re o f a lc o h o ls

h ig h e r in m o lecu lar w eight than e th a n o l, o b ta in e d a s b y -p ro d u cts in th e

a lc o h o lic fe rm e n ta tio n i n d u s t r i e s . Iso -a m y l, a c tiv e -a m y l, is o - b u ty l and

n -p ro p y l a lc o h o ls a re g e n e r a lly th e main c o n s titu e n ts o f f u s e l o i l w ith

n-am yl, n -b u ty l and is o -p ro p y l a lc o h o ls g e n e r a lly p re s e n t in l e s s e r

am ounts. In a d d itio n , m inute amounts o f a wide v a r ie ty o f o rg an ic sub­

sta n c e s appear as im p u r itie s in th e f u s e l o i l b y -p ro d u c t.

The main c o n s titu e n t a lc o h o ls o f f u s e l o i l a r c d e riv e d from amino

a c id s p re s e n t in th e mash and formed by a u to ly ti c breakdown o f th e p ro ­

te in s o f th e c e l l s th em selv es. The o r ig in o f n -b u ty l and is o -p ro p y l

a lc o h o ls i s tra c e d to th e a c tio n o f b u ty ric a c id b a c te r ia on su g ar.

The com position o f f u s e l o i l and th e amount produced in any p a r­

t i c u l a r fe rm e n ta tio n depends on th e k in d o f s u b s tr a te u t i l i s e d , n itro g e n

source p re s e n t, n a tu re o f th e m icroorganism employed, time and tem pera­

tu r e o f fe rm e n ta tio n p ro c e ss , and c o n tam in atio n s p re s e n t in th e mash.

F u se l o i l i s used com m ercially a s a s o lv e n t, f r o t h e r a g e n t, a n t i -

foaming a g e n t, and a s p ro c e ss m a te r ia l in th e chem icals in d u s tr y . Amyl

a c e ta te i s th e most im p o rta n t d e r iv a tiv e o f f u s e l o i l .

A review was made on th e v a rio u s methods o f a n a ly s is a v a ila b le

f o r th e d e te rm in a tio n o f f u s e l o i l . The A.O.A.C. p ro c e d u re, based on

th e A llcn-M arquardt m ethod, r e p o rts o n ly ab o u t 60^ o f th e tr u e f u s e l o i l

p r e s e n t. C o lo rim e tric m ethods, based on Komarowsky*s r e a c tio n , p o sse sse s

g r e a te r acc u ra cy and s e n s i t i v i t y and a re l e s s tim e consuming.

 The p re sen c e o f f u s e l o i l over c e r ta in l im i t s in a lc o h o lic b ev er­

ages and i n d u s t r i a l a lc o h o l d e tr a c ts from th e q u a lity o f th e p ro d u c t. In

con tin u o u s d i s t i l l a t i o n p ro c e ss th e o i l s a re se p a ra te d as a sid e -stre a m

from an in te rm e d ia te re g io n o f th e r e c t i f y i n g column.

In t h i s work ex p erim en tal d a ta have been g ath ered on f u s e l o i l

d i s t r i b u t i o n in the r e c t i f y i n g column under d i f f e r e n t o p e ra tin g condi­

tio n s . The d a ta can be used fo r d esig n purposes and f o r th e s e le c tio n

o f o p e ra tin g c o n d itio n s in commercial p r a c tic e in o rd e r to produce d i s - (

t i l l a t c s o f d e f i n i t e s p e c if ic a tio n s .

The ex p erim en tal r e s u l t s o b tain ed in d ic a te t h a t : (1) th e lo c a tio n

o f th e p la te o f maximum accum ulation i s a fu n c tio n o f th e r e f lu x r a t i o

u t i l i z e d and th e a lc o h o l c o n te n t in th e fe e d ; (2) under the. o p e ra tin g

c o n d itio n s s tu d ie d , a s in g le peak o f f u s e l o i l accum ulation o ccurs and

i t i s always above th e feed p la te in th e re g io n where th e a p p a re n t a lc o ­

hol c o n te n t i s from ab o u t 130° to 140° P ro o f; (3) th e w idth o f th e f u s e l

o i l band i s a fu n c tio n o f th e o p e ra tin g c o n d itio n s u t i l i z e d ; (4) d i f f e r e n t

c o n c e n tra tio n s o f fu s e l o i l occur i n p la te s o f s im ila r a lc o h o l c o n te n t

under d i f f e r e n t o p e ra tin g c o n d itio n s ; (5) v a r ia tio n s in th e c o n te n t o f

f u s e l o i l in th e feed do n o t cause a s h i f t in th e lo c a tio n of th e p la te

o f maximum c o n c e n tra tio n ; (o) r e f lu x r a t i o s o f 2:1 o r below do n o t p ro ­

d u c t predom inant accu m u latio n s in any re g io n o f th e column; d i s t i l l a t e s

v e ry high in f u s e l o i l a r e produced; (7) th e re i s no f u s e l o i l p re s e n t

in th e a lc o h o l-e x h a u ste d p la te s in th e bottom o f th e column.

An au to m a tic c o n tr o l system wns developed fo r th e o p e ra tio n o f

co ntinuous d i s t i l l a t i o n columns in th e a lc o h o lic d i s t i l l a t i o n , based on

v a ry in g th e r a t e o f feed to m a in ta in c o n sta n t a re fe re n c e tem p eratu re i n

the column.

Graphs were p re p a re d , based on e x p erim en tal d a ta , fo r d eterm in in g

tr u e a lco h o l c o n ten t i n samples c o n ta in in g la r g e c o n c e n tra tio n s o f f u s e l

o il •

Li q u id-vapor e q u ilib riu m d a ta f o r th e system e th a n o l-w a te r a t one

atm osphere was compiled in a s in g le ta b u la tio n which g iv e s th e e q u ilib ­

rium com positions fo r both phases in term s o f p e r c en t by w eig h t, mol

f r a c tio n and p e r c e n t by volume a t GO°F and 20°C. D ire c t co n v ersio n s

between the v a rio u s term s can be r e a d ily made.

 CHAPTER I

ORIGIN AND COMPOSITION OF FUSEL OIL

Whenever pure y e a s t i s allow ed to ferm ent in a su g ar c o n ta in in g

s u b s tr a te w ith the presence o f a s u ita b le n itro g e n o u s d i e t and th e p ro p er

m in e ra l s a l t s , th e liq u o r a t the end o f th e fe rm e n ta tio n c o n ta in s n o t

only a lc o h o l b u t a ls o m inute amounts o f a c o n sid e ra b le number o f o th e r

su b sta n c e s a r is in g from th e m etabolism o f th e c e l l .

Prom inent among th e g r e a t v a r ie ty o f su b sta n c es found in s o lu tio n

a rc in o rg a n ic s a l t s and a c id s , a lc o h o ls , a ld e h y d e s, k e to n e s, g ly c e r o l,

e s t e r s , o rg a n ic a c id s , e s s e n t i a l o i l s and g ases such as carbon d io x id e .

In a d d itio n , the mash c o n ta in s s o lid im p u r itie s c o n s is tin g in g r e a te r

p a r t o f n itro g e n compounds such as y e a s t c e l l s , album inoids and p e c tic

s u b s ta n c e s . Glycogen, y e a s t gum, complex o rg a n ic p h o sp h ates, as w e ll

as o th e r su b sta n c es a re a ls o p re s e n t (2 , 1 4 3 ).

The n itro g e n o u s compounds a re e a s il y decomposed when su b m itted to

h e a t in th e d i s t i l l a t i o n p ro c e s s , producing v o l a t i l e su b sta n c e s which,

i f n o t removed d u rin g th e d i s t i l l a t i o n , a re re s p o n s ib le f o r u n d e s ira b le

odor and f la v o r c h a r a c t e r i s t i c s in th e f i n a l p ro d u c t. In contam inated

m ashes, hydrogen and gaseous compounds o f su lp h u r a re fre q u e n tly found

due to pow erful b a c t e r i a l re d u c in g a c tio n on s u lp h a te s and s u lp h ite s

p re s e n t in th e mash. The im p u r itie s l i s t e d above e x i s t in v ery sm all

q u a n t i t i e s and in some c a se s mere tr a c e s .

The a lc o h o ls p re s e n t a s im p u ritie s i n ferm ented liq u o r s a re o f

s p e c ia l i n t e r e s t to th e chem ical e n g in eer re s p o n s ib le f o r th e d e sig n and

o p e ra tio n o f d i s t i l l i n g p l a n t s .

1
 2

Due to t h e i r p a r t i c u l a r b e h av io r in th e d i s t i l l a t i o n o f ferm ented

m ashes, t h e i r e lim in a tio n from th e p ro c e ss p re s e n ts some te c h n ic a l d i f ­

fic u ltie s . T h is group o f im p u ritie s c o n s is ts o f a number o f a l i p h a t i c

a lc o h o ls h ig h e r in m o le c u lar w eight th a n e th y l a lc o h o l. Isoam yl and

a c ti v e amyl (d-am yl) a lc o h o ls a re u s u a lly th e c h ie f c o n s titu e n ts p re s e n t,

follow ed by n -p ro p y l and is o b u ty l a lc o h o ls . In a d d itio n , is o p ro p y l,

n -b u ty l and n-am yl a lc o h o ls a r e p re s e n t in s m a lle r am ounts. Only prim ary

a lc o h o ls a r e b e lie v e d to be p r e s e n t. These a lc o h o ls accum ulate and a re

removed to g e th e r a s a b y -p ro d u ct d u rin g th e c o u rse o f th e d i s t i l l a t i o n

p ro c e s s . T his b y -p ro d u ct u s u a lly c o n ta in s a sm all p e r c e n t o f o th e r

im p u r itie s such a s h ig h b o ilin g e s t e r s , f a t t y a c id s , ald eh y d es and o th e r

s u b s ta n c e s . The h ig h e r a lc o h o ls ta k e - o f f i s d e sig n a te d c o l l e c t i v e l y w ith

th e name o f 'f u s e l o i l " . The term i s a p p lie d lo o s e ly to d e sig n a te th e

h ig h e r a lc o h o ls b y -p ro d u ct in v a rio u s degrees o f p u r i f i c a t i o n . I n th e

p la n t i t i s a p p lie d to th e stream withdrawn from co n tin u o u s d i s t i l l a t i o n

columns o r to a g iv en f r a c tio n from i n t e r m i t t e n t d i s t i l l a t i o n p ro c e s s e s ,

bo th o f which a r e r e l a t i v e l y r i c h i n h ig h e r a lc o h o ls , b u t c o n ta in in g

la r g e amounts o f e th y l a lc o h o l and w a te r. The c o n c e n tra te d p ro d u c t r e ­

s u ltin g a f t e r su b m ittin g th e raw ta k e - o f f to c o o lin g , e x tr a c tio n w ith

w a te r and d e c a n ta tio n i s d e sig n a te d a s d ecan ted o r crude f u s e l o i l .

F u r th e r , f u s e l o i l a ls o d e s ig n a te s a h ig h ly p u r i f i e d m ix tu re o f h ig h e r

a lc o h o ls o b ta in e d by dew atering and f r a c t i o n a l d i s t i l l a t i o n o f th e above

m entioned l e s s pure m ix tu re s . The l a t t e r i s c a lle d " r e f in e d f u s e l o i l "

i n o rd e r to d i f f e r e n t i a t e i t in th e m arketing o f th e b y -p ro d u c t.

C o n cen trated f u s e l o i l i s a y ello w o r brow nish, v o l a t i l e , o i l y

 3

l i q u i d w ith a d is a g r e e a b le , n a u se a tin g t a s t e and c h a r a c t e r i s t i c s u f f o c a t­

in g o d o r. The r e f in e d p ro d u c t i s a c o lo r le s s l i q u i d r e ta in in g m ost o f

th e t a s t e and odor c h a r a c t e r i s t i c s o f th e crude p ro d u c t. The term *f u s e l

o i l * * i s d e riv e d from th e German " F u s e l”, meaning bad s p i r i t s .

F u se l o i l was d is c o v e re d in 1785 by th e Sw edish p h a rm a c ist S c h e ele

and th e p h y sic ia n W estendorf (124, 1 4 3 ). The l a t t e r found t h a t i t co u ld

be s e p a ra te d from raw a lc o h o lic d i s t i l l a t e s by su b seq u en t d i s t i l l a t i o n ,

b u t a good number o f y e a rs e la p s e d front t h i s d isc o v e ry u n t i l a p r a c t i c a l

s o lu tio n to th e problem was o b ta in e d in th e a lc o h o l in d u s tr y . I t was

n o t u n t i l 1862 t h a t a r e a c tif y in g a p p a ra tu s from which f u s e l o i l was ob­

ta in e d sim u lta n e o u sly a s a b y -p ro d u c t, was i n s t a l l e d a t th e S te n g e l

a lc o h o l f a c to r y in L e ip z ig (1 4 4 ).

C o n s titu e n ts o f F u s e l O il

In 1834, Dumas s tu d ie d two sam ples o f f u s e l o i l s e p a ra te d from

commercial e th y l a lc o h o l by d i s t i l l a t i o n (2 4 ) . The samples were f r a c ­

tio n a te d by Dumas and th e f r a c t i o n s b o ilin g from 130* to 132*C a n aly z e d

f o r t h e i r c o n s titu e n t e le m e n ts. The r e s u l t s o b ta in e d were a s fo llo w s :

Sample I Sample I I C a lc u la te d f o r Amyl

% % A lc o h o l, %

Carbon 69.3 6 8 .6 6 8.2

Hydrogen 1 3 .6 1 3 .6 13 .6
Oxygen 1 7 .1 1 7 .8 18 .0
I
The c a lc u la te d v a lu e s f o r amyl a lc o h o l a r e in c lu d e d f o r com parison

(1 2 4 ).

I t was Cahours in 1839 who d is c o v e re d t h a t th e e s s e n t i a l c o n s titu e n t

o f f u s e l o i l produced from th e fe rm e n ta tio n o f p o ta to e s , which was th e same

 4

a s t h a t i s o l a t e d by Dumas by f r a c t i o n a l d i s t i l l a t i o n , co n tain ed th e r a d ic a l

C5 H1 Q- and t h a t i t was n o th in g e ls e th an th e h y d ra te o f axnylene o r amyl

a lc o h o l ( 1 0 ) . T h is f a c t was l a t e r confirm ed by Dumas and S ta s (2 5 ) .

B io t d isc o v e re d t h a t th e a lc o h o l is o la t e d by Dumas and l a t e r by

Cahours was o p t i c a l l y a c t i v e , b u t i t i s P a s te u r who proved th a t i t con­

s i s t s o f a m ix tu re o f two amyl a lc o h o l isom ers (104, 105)• The s tu d ie s

o f P a s te u r in d ic a te t h a t b o th a lc o h o ls a r e s im ila r in t h e i r chem ical p ro ­

p e r t i e s , d i f f e r b u t s l i g h t l y i n d e n s ity and b o ilin g p o in t, and y i e l d , under

s im ila r c irc u m sta n c e s, two p ro d u c ts which resem ble each o th e r i r i 'a l l

p r o p e r tie s ex cep t in o p t i c a l a c t i v i t y , th e a c tiv e a lc o h o l alw ays g iv in g

a c tiv e p ro d u c ts w hile th e in a c tiv e alw ays r e s u l t s in in a c tiv e p ro d u c ts .

P a s te u r found th e a c ti v e a lc o h o l to b o i l a t 127-128°C w h ile th e in a c tiv e

b o ile d a t 129°C under o rd in a ry atm o sp h eric p re s s u re . P r e s e n tly a cc e p ted

v a lu e s a re 128*C f o r th e a c ti v e d -a n y l, and 132*C f o r th e in a c tiv e isoam yl

(1 0 7 ).

The s t r u c t u r a l form ulas o f th e s e two a lc o h o ls a r e :

d -a n y l — CH3 • CH2 • CH(CH3) • CH2 • OH

isoarayl - CH3 . CH(CH3) . CH2 • CH2 • OH

P a s te u r found t h a t th e p ro p o rtio n o f th e a lc o h o ls i n f u s e l o i l

v a ry depending on i t s o r i g i n . T hat from fe rm e n ta tio n o f m o lasses con­

t a i n s ab o u t e q u al p a r ts o f th e two a lc o h o ls w h ile t h a t from th e fe rm e n ta tio n

o f g r a in s c o n ta in s ab o u t 1 /3 o f th e a c ti v e and 2 /3 o f th e in a c tiv e a lc o h o l.

The a t t e n t i o n o f numerous w orkers o f th e tim e was drawn tow ard

s tu d ie s d esig n ed to a s c e r ta in th e com position o f f u s e l o i l .

V artz d is c o v e re d , in 1852, the p re sen c e o f is o b u ty l a lc o h o l in

com m ercial f u s e l o i l (1 5 5 ).
 5

In 1853, Chancel d isco v e re d a new a lc o h o l in f u s e l o i l which he

i d e n t i f i e d a s n -p ro p y l a lc o h o l (1 4 ).

The work o f o th e r in v e s t ig a to r s confirm ed th e p resen ce o f n -p ro p y l,

is o b u ty l, a c tiv e amyl and isoam yl a lc o h o ls in f u s e l o i l (1 9 , 98, 1 5 2 ).

For some tim e th e s e fo u r a lc o h o ls accompanied w ith s m a lle r amounts o f

h ig h b o ilin g e s t e r s , a c id s , aldehydes and o th e r su b sta n c es were con­

s id e re d th e main c o n s ti tu e n ts o f f u s e l o i l .

In p ap ers p u b lish e d i n 1778 and 1880, Rabuteau re p o rte d th e p re s ­

ence o f is o p ro p y l, n -b u ty l an d n-amyl a lc o h o ls i n commercial f u s e l o i l s

(114, 1 1 8 ). These r e p o r ts w ere o r i g i n a l ly o v erlo o k ed . O ther a u th o rs

re p o rte d a n a ly s e s o f fu s e l o i l s in w hich th e s e a lc o h o ls had been found

amoung o th e r c o n s titu e n ts ( 1 8 , 49, 51, 1 0 3 ). I t was P ringheim , however,

who c a ll e d a t t e n t i o n toward th e overlooked work o f Rabuteau and o ff e re d

new e x p erim en tal fin d in g s which confirm ed th e s e r e s u l t s (114, 1 1 6 ). More

re c e n t d a ta has confirm ed t h e presence o f th e s e a lc o h o ls in some f u s e l

o i l s (2 6 , 59, 8 1, 119, 1 5 0 ).

Numerous w orkers have stu d ied th e n a tu r e o f th e group o f su b sta n c es

no rm ally p re s e n t in com m ercial fu s e l o i l and which c o n s ti tu te th e h ig h e r

b o ilin g f r a c tio n s and r e s id u e o b tain ed upon f r a c t i o n a l d i s t i l l a t i o n o f

th e o i l .

A lip h a tic a lc o h o ls o f m olecular w eight h ig h e r th a n amyl have been

i d e n t i f i e d in f u s e l o i l s from d i f f e r e n t o r ig in s ( 8 , 26, 60, 102, 103, 120,

136, 1 5 0 ). They c o n s is t o f isom ers o f th e h e x y lic , h e p ty li c , o c t y l ic ,

n o n y lic and d e c y lic s e r i e s . Swenarton has in d ic a te d t h a t in th e f r a c tio n

b o ilin g h ig h e r th a n decyl a lc o h o l th e r e a re sm all q u a n titie s o f a lc o h o lic

 6

m a te r ia l o f s t i l l h ig h e r m o le c u lar w eig h ts (1 3 6 ).

The a c id c o n s titu e n ts have been s tu d ie d e x te n s iv e ly and th e i s o l a ­

tio n and i d e n t i f i c a t i o n o f a la r g e number o f them have been re p o rte d in

th e l i t e r a t u r e . Form ic, a c e t i c , p ro p io n ic , b u ty r i c , v a l e r i c , c a p ro ic ,

e n a n th ic , c a p r i l i c , p e la r g o n ic , c a p r ic , l a u r i c , m y r i s tic , p a lm itic , and

o th e r f a t t y a c id s o f more th an 16 carbon atoms have been found ( 8 , 1 2 ,

13, 52, 58, 61, 69, 7 1, 8 0, 89, 120, 130, 1 4 8 ). I n a d d itio n , th e p re s ­

ence i n v ery sm all amounts o f l i n o l e i c and v a rio u s m o n o -eth y len ic a c id s

have been re p o rte d ( 1 1 2 ) .

E s te r s form a n o th e r im p o rtan t c o n s ti tu e n t o f th e h ig h e r b o ilin g

f r a c tio n s o f commercial f u s e l o i l . T h e ir p resen ce has been re p o rte d on

numerous o c ca sio n s ( 8 , 26, 27, 52, 58, 60, 69, 71, 103, 117, 148, 1 5 0 ).

In a d d itio n to a lc o h o ls , a c id s and e s t e r s , th e p re sen c e o f a r a th e r

la r g e number o f su b sta n c e s have been re p o rte d in th e l i t e r a t u r e . Among

them, th e fo llo w in g a re l i s t e d : ald eh y d es (6 0 , 117, 1 4 8 ), f u r f u r a l (2 6 ,

52, 58, 71, 1 4 8 ), low er k e to n e s (5 2 ), p y rid in e and o th e r b ases ( 8 , 1 6 , 26,

120, 1 2 5 ), te rp e n e s (1 0 2 , 1 2 0 ), SO2 and amines (1 4 8 ), hydrocarbons (2 6 ,

131) and o th e rs (103, 130, 137, 1 5 7 ).

O rig in o f F u se l O il

S e v e ra l th e o r ie s were o ff e re d to e x p la in th e fo rm ation o f h ig h e r

a lc o h o ls d u rin g th e c o u rse o f th e fe rm e n ta tio n . The o r ig i n o f th e se

a lc o h o ls was u s u a lly so ught in th e su g ar p r e s e n t i n th e mash to be f e r ­

m ented, from which th e y w ere b e lie v e d to be formed by th e y e a s t i t s e l f

o r by b a c te r ia p re s e n t w h ile o th e rs tr a c e d t h e i r fo rm atio n to th e d i r e c t

re d u c tio n o f f a t t y a c id s (5 , 50, 108, 110, 111, 112, 113, 1 1 6 ).

 7

I t was E h r lic h , however, who c o n c lu s iv e ly showed in h i s c l a s s i c a l

re s e a rc h e s t h a t th e main h ig h e r a lc o h o ls , and p ro b ab ly a ls o th e a ld eh y d e s,

c o n ta in e d in f u s e l o i l a re in r e a l i t y d e riv e d from th e am in o -acid s which

a re formed by th e h y d ro ly s is o f p ro te in s p re s e n t in th e mash and to a

l e s s e r e x te n t from th e p r o te in o f th e c e l l s i t s e l f .

The c lo s e r e la tio n s h ip between th e form ula o f le u c in e , which i s :

CH3 • CH(CH3 ) • CH2 • CH(NH2) • COOH

and isoam yl a lc o h o l,

CH3 • CH(CH3) • CH2 • CH2 • OH

had p re v io u s ly suggested t h a t some r e l a t i o n m ight e x i s t between th e s e

two s u b sta n c e s , b u t th e r e was no ex p erim en tal c o n firm a tio n o f th e id e a .

In 1903, E h rlic h d isc o v e re d t h a t p r o te in s a ls o y ie ld on h y d ro ly s is

a s iso m e rid e o f le u c in e , known a s is o le u c in e , which has th e c o n s titu tio n

CH3 • CH2 • CH(CH3) • CH(NH2 ) • COOH

and has to d-amyl a lc o h o l

CH3 • CH2 • CH(QH3) • CH2 • OH

th e same r e l a t i o n a s le u c in e to isoam yl a lc o h o l (2 9 , 30, 39, 3 7 , 38, 41,

47, 4 8 ).

T his f a c t a t t r a c t e d h is a t t e n t i o n to th e problem o f th e o r ig in o f

amyl a lc o h o ls in a lc o h o lic fe rm e n ta tio n . .

E h r lic h u t i l i z e d p u re y e a s t c u lt u r e s , th u s e lim in a tin g th e p a r­

t i c i p a t i o n o f b a c te r ia , to ferm ent s t e r i l i z e d su g ar s o lu tio n s to which

amino a c id s had been added. He found t h a t le u c in e r e a d ily y ie ld e d i s o -

amyl a lc o h o l and is o le u c in e gave d-amyl a lc o h o l (3 1 , 32, 3 6 , 37, 38, 4 0 ).

The fo llo w in g a r e ty p ic a l r e s u l t s o f th e experim ents conducted (6 5 ):

(I) I n an experim ent c a r r ie d o u t w ith o u t th e a d d itio n o f le u c in e th e

 8

amount o f f u s e l o i l produced was 0 .4 $ b ased on p u re e th y l a lc o h o l. ( I I )

When 6 grams o f s y n th e tic o p tic a l ly in a c tiv e le u c in e were added, 2 .11$

o f f u s e l o i l were produced which were a l s o i n a c t i v e . 2 .5 grams o f le u c in e

were re c o v e re d , th u s , th e f u s e l o i l produced was e q u iv a le n t to 87$ o f th e

t h e o r e t i c a l y i e l d o f isoam yl a lc o h o l. (Ill) I n th e p re sen c e o f 2 .5 grains

o f is o le u c in e , 1 .4 4 $ o f f u s e l o i l was produced c o rre sp o n d in g to 80$ o f th e

t h e o r e t i c a l y ie ld o f d-amyl a lc o h o l from th e is o le u c in e added (6 5 ) .

T his change, which E h r lic h has term ed th e a lc o h o lic fe rm e n ta tio n

o f amino a c id s , r e q u ir e s th e p re sen c e o f l i v i n g c e l l s . E h r lic h and

P ringsheim showed t h a t when e i t h e r zymin o r y e a s t ju i c e i s s u b s tit u te d

f o r th e i n t a c t organism th e change does n o t o c c u r ( 9 , 35, 1 1 2 ). E h rlic h

a ls o showed e x p e rim e n ta lly t h a t th e change i s n o t e f f e c te d even by l i v i n g

c e l l s i n th e absence o f fe rm e n ta b le su g ars (3 7 , 3 8 ).

O ther a-am ino a c id s undergo t h i s same ty p e o f r e a c ti o n . E h r lic h

showed t h a t is o b u ty l a lc o h o ls a re d e riv e d from v a l in e , i . e . , a-am in o -

is o v a l e r i c a c id (3 1 , 1 4 3 ).

The o r ig in o f n -p ro p y l a lc o h o l i s a t t r i b u t e d to a -a m in o -n -b u ty ric

a c id w h ile t h a t o f n-am yl a lc o h o l i s tr a c e d to n o rle u c in e , i . e . , a-am in o -

n -c a p ro ic a c id ( 5 9 ) . The fo rm atio n o f is o p ro p y l and n - b u ty l a lc o h o l , on

th e o th e r hand, does n o t p ro v e in from th e d eam in atio n o f amino a c id s ,

b u t i t s o r ig in i s tr a c e d to th e a c tio n on su g ar o f b u ty r ic a c id b a c t e r i a

p r e s e n t i n th e mash (5 1 , 114, 1 1 6 ). T h is p ro b a b ly e x p la in s th e r a t h e r

low c o n c e n tra tio n s o f th e s e a lc o h o ls g e n e r a lly found and i t s absence in

numerous c a s e s . The com position o f f u s e l o i l s from d i f f e r e n t so u rc e s w i ll

b e d is c u s s e d i n l a t e r p a ra g ra p h s .
 9

The chem ical r e a c tio n s in v o lv e d in th e deam ination o f th e amino

a c id s l i s t e d above a r e re p re s e n te d by th e fo llo w in g e q u a tio n s:

(1) CH3 *CH(CH3 )*CH2 *CH(NH2 )'COOH + H20 - CH3 *CH(CH3 )•CH 2 *CH2 *0H + C02 + NH3

Leucine isoam yl a lc o h o l

(2) CH3 -CH2 *CH(CH3 )*CH(NH2 )*C00H + H20 = CH3 ‘CH2 «CH(CH3 )«CH2 *0H + C02 + NH3

Is o le u c in e d-amyl a lc o h o l

(3) CH3 *CH(CH3 )*CH(NH2 )*C00H + H20 « CH3 «CH(CH3 )»CH2 *0H + C02 + nh3

V aline I s o b u ty l a lc o h o l

(4) CH3 *CH2 *CH(NH2 )*C00H + H20 = CH3 *CH2 *CH2 *0H + CX> 2 + nh3

a -a m in o -n -b u ty ric a c id n -p ro p y l a lc o h o l

(5 ) CH3 *CH2 *CH2 *CH2 *CH(NH2 ) -COOH + H2 0 - CH3 *CH2 , C H 2 , CH2 *CH 2*0H + C 0 2 + NH3

n o rle u c in e n-am yl a lc o h o l

O ther a-am ino a c id s undergo s im ila r changes and th e r e a c tio n ap­

p e a rs to be a g e n e ra l one. E h rlic h and P istsch im u ck a u t i l i z e d ty r o s in e ,

i.e ., 0 H, C6 H4 *CH2 , CH(NH2)'COOH to produce ty r o s o l,

which was f i r s t p re p a red in t h i s manner (43, 4 6 ). This su b stan ce has a

v e ry b i t t e r t a s t e and i s p ro b ab ly r e l a t e d to th e f la v o r o f b e e r. In a

s im ila r manner p h e n y la la n in e i s c o n v erted in to p h e n y le th y l a lc o h o l w hile

try p to p h an y ie ld s try p to p h o l which was f i r s t p re p a red in t h i s way by

E h r lic h (4 5 ).

The r e a c tio n i s c lo s e ly r e l a t e d w ith th e n itro g e n o u s m etabolism

o f th e c e l l and th e anmonia formed by t h i s p ro c e ss i s im m ediately

u t i l i z e d by th e y e a s t f o r b u ild in g up album inous m a tte r . No f r e e ammonia

i s d e te c te d in th e mash in th e co u rse o f th e fe rm e n ta tio n (3 7 , 3 8 ).

In th e co u rse o f h is s tu d ie s , E h r lic h proved w ith e x p erim en tal

 10

d a ta th a t i f a more r e a d ily a s s im ila b le n itr o g e n so u rce i s p r e s e n t,

such a s c o n ta in e d in ammonium s a l t s and a s p a rg in e , th e y e a s t ta k e s i t s

su p p ly o f n itr o g e n m ainly from them w ith o u t s p l i t t i n g up th e amino a c id s

to th e same e x te n t and co n seq u en tly l e s s f u s e l o i l i s formed (37, 3 8 ).

These r e s u l t s were confirm ed by Pringsheim (112, 1 1 3 , 1 1 6 ), and l a t e r

by Kurono ( 8 3 ) . E h r lic h found t h a t th e a d d itio n o f amnonium c a rb o n ate

to a mash low ered th e p ro d u c tio n o f f u s e l o i l from 0.70% t o 0.33% based

on p u re e th y l a lc o h o l. The a d d itio n o f le u c in e a lo n e r a is e d th e y ie ld s

o f f u s e l o i l from 0.70% to 2.78%. However, th e a d d itio n o f b o th , le u c in e

and ammonium c arb o n ate r e s u lte d in the fo rm atio n o f only 0.78% o f f u s e l

o il. The p ro d u c tio n o f f u s e l o i l , th e r e f o r e , a s w e ll as th e n a tu r e o f

i t s c o n s titu e n ts , depends on th e com position o f th e medium to be ferm en ted .

E h rlic h a ls o found in h is s tu d ie s t h a t th e y i e l d o f f u s e l o i l i s

a f f e c te d by th e c o n d itio n o f th e y e a s t in re g a rd to n itr o g e n . In s o lu ­

tio n s o f su g ar and le u c in e , y e a s ts poor in n itr o g e n produce c o m p arativ ely

more f u s e l o i l , due to th e more re a d y decom position o f amino a c id s th a n

i s th e case when y e a s ts w e ll s u p p lie d w ith n itro g e n o u s m a te r ia ls a r e

u tiliz e d . The n a tu re o f th e carbonaceous n u trim e n t and th e n a tu re o f th e

y e a s t u t i l i z e d proved to be o f g r e a t im portance (4 7 , 4 8 ).

A nother fin d in g which r e s u lte d from E h r li c h 's experim ents i s th e

f a c t th a t even in p u re su g ar s o lu tio n s and i n t o t a l absence o f amino a c id s ,

th e y e a s t alw ays produces some f u s e l o i l d u rin g .the co u rse o f th e ferm en­

ta tio n . I t s own album in i s p a r t l y s p l i t - u p T a u to ly s is i n t o amino a c id s

such a s le u c in e , is o le u c in e and v a lin e , w hich a r e , in tu r n , tran sfo rm ed

in to fu s e l o i l . The n itr o g e n th u s produced i s u t i l i z e d a g a in f o r th e

 11

c o n s tru c tio n o f th e p r o te in of th e c e l l (3 7 , 38, 6 5 ). H oussiau has

p o in te d o u t a lo n g th e s e same l i n e s t h a t , a s c e l l s d ie and new ones a re

form ed, th e r e s u l t i n g n itro g e n o u s compounds may ap p ear in subsequent

m etabolism in d is tin g u is h a b le from th o s e d e riv e d from a s p a rg in e , amino

a c id s , am ides, p r o te in s , e t c . , p re s e n t in m olasses o r o th e r medium, and

a re even used a g a in i n th e fo rm atio n o f c e l l s . T h is acco u n ts f o r th e

la c k o f p r o p o r tio n a lity i n th e y ie ld o f f u s e l o i l and th e n itro g e n con­

t e n t o f th e m o lasses o r s lo p s ( 7 0 ) .

Numerous w orkers have confirm ed th e fin d in g s o f E h rlic h in th e

c o u rse o f th e y e a r s .

Yomada, i n Jap a n , and G enovois, in F ran c e , have s tu d ie d th e e f f e c t

o f adding v a rio u s ammonium s a l t s and o th e r n itr o g e n n u trim e n ts to reduce

th e form atio n o f f u s e l o i l (6 2 , 1 5 7 ). U npublished r e s u l t s o b ta in e d a t

th e Rum P i l o t P la n t o f th e A g r ic u ltu r a l E xperim ental S ta tio n o f th e

U n iv e rs ity o f P u e rto R ico , u t i l i s i n g P u e rto R ican m o lasses have in d ic a te d

t h a t 2/3 l b . o f amnonium s u lp h a te , f e r t i l i s e r g ra d e , p e r 100 g a llo n s o f

mash a t a p p ro x im a te ly 24°B x., would y i e l d minimum c o n te n ts o f f u s e l o i l

i n th e ferm ented mash. A d d itio n o f l a r g e r amounts would n o t produce any

s i g i n i f i c a n t re d u c tio n i n th e p ro d u c tio n o f f u s e l o i l . The use o f s m a lle r

am ounts, on th e o th e r hand, n o t o n ly in c re a s e s th e y ie ld s o f f u s e l o i l ,

b u t a ls o in c re a s e s th e le n g th o f tim e re q u ire d f o r com pletion o f th e

fe rm e n ta tio n p ro c e s s .

Arroyo found, in P u e rto R ic o , w orking w ith cane m o la sse s, t h a t th e

amount o f f u s e l o i l produced i s sm a lle r i f a s p e c ia l y e a s t s t r a i n i s

s e le c te d , th e fe rm e n ta tio n i s perform ed a t 25-27*C and th e n itro g e n r e ­

q u ire d by th e y e a s t i s s u p p lie d i n th e f o r a o f amnonium hydroxide ( 4 ) .

 12

Z alesskaya and Konolev confirm ed t h a t th e form ation o f f u s e l o i l

depends on th e c o n te n t o f n itro g e n o u s su b sta n c e s in th e s u b s tr a te and on

th e a b i l i t y o f th e y e a s ts to u t i l i z e amino a c i d s . Removal o f supplemen­

t a r y n itr o g e n d u ring th e co u rse o f fe im e n ta tio n o f m olasses c o n trib u te s

to th e deam ination o f le u c in e w ith th e c o rresp o n d in g in c re a s e in f u s e l

o i l (1 6 4 ).

D ie tr ic h and K laranerth confirm ed t h a t in th e absence o f su g ar no

f u s e l o i l was formed from le u c in e ( 2 2 ) .

O ther w orkers have s tu d ie d o th e r f a c to r s re g a rd in g th e form ation

o f f u s e l o i l d u rin g fe rm e n ta tio n . S e g a l s tu d ie d th e i n h i b i ti n g e f f e c t s

o f th e h ig h e r a lc o h o ls in th e fe rm e n ta tio n p ro c e ss and found t h a t th e

in ju r io u s e f f e c t s a r e g r e a te r th e h ig h e r th e a lc o h o l in th e homologues

s e rie s . F u se l o i l sh a rp ly r e ta r d s fe rm e n ta tio n a t 0 .4 # and i n h i b i t s i t

co m p letely a t 0 .7 # to 0 ,8 # r e f e r r e d to th e mash (1 2 7 ). S h i c h i j i and

co-w orkers found t h a t f u s e l o i l added to th e mash in q u a n ti tie s over 0 .1 #,

r e f e r r e d to th e s o lu tio n , in h ib ite d fe rm e n ta tio n and re p ro d u c tio n o f y e a s t

(1 2 8 ).

There a r c s e v e r a l r e p o r ts in th e l i t e r a t u r e on s tu d ie s conducted

re g a rd in g th e sta g e o f th e fe rm e n ta tio n p ro c e ss a t which fo rm atio n o f

f u s e l o i l b e g in s (1 1 , 60, 63, 79, 82, 1 6 2 ). There a r e d is c re p a n c ie s

among th e p u b lish e d r e s u l t s . The fo rm atio n o f f u s e l o i l i n one case

was found to p reced e t h a t o f e th y l a lc o h o l w h ile i n o th e r c a se s th e r e ­

v e r s e was found to be tr u e (7 9 ) . In o th e r c a se s i t i s re p o rte d t h a t th e

fo rm atio n o f f u s e l o i l c o in c id e s w ith th e fo rm atio n o f e th a n o l ( 1 1 , 82,

1 6 2 ).

In re c e n t re s e a rc h e s , C asto r and Guyman o b ta in e d d a ta on th e

 13

r e la tio n s h ip betw een th e c o a rse o f f u s e l o i l fo rm atio n , m u ltip l ic a tio n

o f y e a s t c e l l s , u t i l i z a t i o n o f amino a c id s n a t u r a l l y p re s e n t in th e mash

and th e co n v ersio n o f s u g a r to e th a n o l i n th e a lc o h o lic fe rm e n ta tio n o f

grape j u ic e ( 1 1 ) .

The r e s u l t s o b ta in e d showed t h a t th e co u rse o f f u s e l o i l fo rm ation

was c o n c u rre n t w ith t h a t o f e th a n o l p ro d u c tio n , r a t h e r th an w ith amino

a c id d isap p e a ra n ce o r y e a s t c e l l m u l tip l ic a t io n . The g r e a t e r p a r t o f th e

t o t a l amount o f f u s e l o i l was formed a f t e r b o th r a p id c e l l m u ltip l ic a tio n

and ra p id lo s s o f amino a c id s had c e a se d . The amounts o f th e amino a c id s

p re s e n t dim in ish ed r a p id ly to low l e v e l s w ith in 18 to 37 h o u rs a f t e r s t a r t ­

in g th e fe rm e n ta tio n and t h e r e a f t e r th e r e were o n ly s l i g h t changes in

t h e i r c o n c e n tra tio n , in g e n e r a l, a slow , ste a d y in c r e a s e . Y east c e l l

m u ltip lic a tio n c ea sed between 45 and 50 hours a f t e r th e fe rm e n ta tio n was

s t a r t e d , whereas f o r a a tio n o f e th a n o l and f u s e l o i l c o n tin u e d up to ab o u t

170 h o u rs .

A t th e 3 7 th ho u r, when th e r a p id d e c re a se o f amino a c id s has c ea sed ,

o n ly a b o u t 34# o f th e t h e o r e t i c a l y i e l d o f f u s e l o i l had been o b ta in e d .

However, a t th e end o f th e ferm entation,* th e amount o f h ig h e r a lc o h o ls

found g r e a tly exceeded th e t h e o r e t i c a l y i e l d e x p ec te d . At th e 1 6 8 th h o u r,

th e a c tu a l y ie ld amounted t o 255# o f th e t h e o r e t i c a l .

The a u th o rs p o in te d o u t t h a t th e f a i l u r e o f a p p ro x im ately eq u iv a­

l e n t amounts o f h ig h e r a lc o h o ls t o a p p e a r c o n c u rre n tly w ith th e d isap p e a ra n ce

o f t h e i r amino a c id p re c u rs o rs m ig h t, a t f i r s t s i g h t , su g g e st t h a t th e

E h rlic h scheme—which p o s tu la te s t h a t by th e deam in atio n o f amino a c id s

am noniacal n itr o g e n i s fu rn ish e d f o r th e s y n th e s is o f p r o te in d u rin g

 14

y e a s t c e l l m u ltip l ic a tio n —was d i r e c t l y in v o lv e d o n ly to a lim ite d e x te n t

d u rin g th e y e a s t c e l l m u lti p l ic a ti o n s ta g e o f th e fe rm e n ta tio n p ro c e s s .

The id e a o f d i r e c t a s s im ila tio n by y e a s t o f i n t a c t amino a c id s , e a r l i e r

advanced by Thorne on th e b a s is o f ev id en ce n o t concerned w ith f u s e l o i l

fo rm a tio n , co u ld e x p la in th e fin d in g s (1 3 8 ). The l a t t e r p ro d u c tio n o f

la r g e amounts o f f u s e l o i l c o u ld , in t u r n , be e x p la in e d by th e id e a pos­

tu l a t e d by E h r lic h and Harden t h a t y e a s t can form f u s e l o i l by th e

a u t o l y t i c breakdown o f . i t s own p r o te in which y ie ld s th e amino a c id p re ­

c u rs o rs o f f u s e l o i l (3 7 , 6 5 ). The m easurable in c re a s e in th e c o n c e n tra tio n

o f amino a c id s d u rin g th e s ta g e o f a lc o h o lic fe rm e n ta tio n subsequent to

th e c e s s a tio n o f r a p id y e a s t m u lt ip l ic a t io n , su g g e sts t h a t d u rin g th a t

s ta g e o f th e fe rm e n ta tio n p ro c e s s , amino a c id s were b ein g produced a t a

somewhat f a s t e r r a t e th a n t h a t a t which th e y were c o n v erted i n t o h ig h e r

a lc o h o ls *

On th e b a s is o f th e Neubauer-Fromherz mechanism—which p o s tu la te s

t h a t th e m ost l i k e l y e a r ly in te rm e d ia te s i n th e fo rm atio n o f f u s e l o i l

a r e k e tn o ic a c id s , l a t e r d e c a rb o x y la te d t o ald eh y d es and su b se q u e n tly r e ­

duced to a lc o h o ls —and on th e fin d in g s t h a t , ( 1 ) th e r e i s a tim e la g

betw een th e a s s im ila tio n o f amino a c id s and th e app earan ce o f f u s e l o i l ,

(2 ) th e fo rm atio n o f e th a n o l and f u s e l o i l o ccu r c o n c u r re n tly , and (3)

th e c e s s a tio n s o f b o th p ro c e ss e s o ccu r s im u lta n e o u sly , th e a u th o rs o f f e r

a sim ple e x p la n a tio n f o r th e r e la tio n s h ip between th e c o n v ersio n o f su g ar

to e th a n o l and th e fo rm atio n o f f u s e l o i l . They su g g e s t t h a t i t i s l i k e l y

t h a t th e f i n a l s te p s o f b o th o f th e s e m e ta b o lic p ro c e ss e s make use o f one

o r more i d e n t i c a l enzyme sy stem s. The slow appearance o f th e h ig h e r

 15

a lc o h o ls could be ex p lain ed by c o m p etitio n between la r g e amounts o f su g ar

fe rm e n ta tio n i n te r a e d i a te s and sm all amounts o f f u s e l o i l in te r m e d ia te s ;

f o r th e carb o x y lase and th e h y d ro g e n -tra n s fe rrin g a lc o h o l dehydrogenase-

Coenzyme I system s o f th e zymase complex* When th e supply o f sugar

f e m e n ta tio n in te rm e d ia te s ; which y i e l d hydrogen t o Coenzyme I , f a i l e d be­

cau se o f th e d isap p earan ce o f su g a r; th e hydrogen t r a n s f e r system c o u ld

no lo n g e r reduce th e aldehyde p re c u rs o rs o f fu s e l o i l components; th u s

th e form ation o f b o th e th a n o l and h ig h e r a lc o h o ls would s im u lta n e o u sly

be te rm in a te d . The y ie ld o f f u s e l o i l i n excess o f t h e o r e t i c a l e x p e c ta ­

tio n s wouldi be ex p lain ed by id e a s d is c u s s e d in p re c e d in g p arag rap h s t h a t

y e a s t can form f u s e l o i l a t th e expense o f i t s ora p r o te in .

The e x p erim en tal r e s u l t s o f C asto r and Guyman confirm p re v io u s

o b s e rv a tio n s by w orkers on th e s u b je c t. In 1938; Z a le ssk a y a observed

t h a t th e m ost e n e r g e tic fo rm atio n o f f u s e l o i l c o in c id e s w ith th e b e g in ­

n in g o f th e main fe rm e n ta tio n o f su g ar when th e m u lti p l ic a ti o n o f y e a s t

and th e deam ination o f amino a c id s i s n e a r ly concluded (162) • With a

s tro n g y e a s t innoculum , which r e s u l t s in s h o r te r fe rm e n ta tio n tim e; th e

fo rm atio n o f f u s e l o i l was found t o s to p sim u lta n e o u sly w ith th e produc­

tio n o f e th a n o l a t th e end of 36 h o u rs. The s p l i t t i n g o f amino a c id s by

y e a s t took p la c e r a p id ly , up t o 70# o f them being consumed i n 1 2 h o u rs .

With c o n d itio n s which produced lo n g e r fe rm e n ta tio n tim e s th e y ie ld o f

f u s e l o i l was g r e a t e r . I t s form atio n took p la c e slo w ly and c o n tin u e d

u n ifo rm ly u n t i l th e main fe rm e n ta tio n was concluded. A u to ly tic breakdown

o f y e a s t c e l l p r o te in i n l a r g e r amounts e x p la in s th e g r e a te r y ie ld s o f

f u s e l o i l d u rin g lo n g e r fe rm e n ta tio n tim e s .

 16

In 1949, w h ile stu d y in g th e c a p a c ity o f y e a s ts to u t i l i z e n itr o g e n

from v a rio u s amino a c id s , Konovalov ob serv ed t h a t th e fo rm atio n o f f u s e l

o i l b e g in s o n ly a f t e r th e f i r s t s ta g e o f th e fe rm e n ta tio n p ro c e ss (8 2 ) .

The in flu e n c e o f tim e o f fe rm e n ta tio n on th e p ro d u ctio n o f f u s e l

o i l i n th e a lc o h o lic fe rm e n ta tio n has been th e s u b je c t o f s e v e r a l s tu d ie s .

I n a l l c a s e s , i t has been found t h a t th e amount o f f u s e l o i l produced i n ­

c re a s e s w ith lo n g e r fe rm e n ta tio n tim e (1 1 , 60, 63, 128, 1 6 2 ). Glimm,

stu d y in g th e - fe rm e n ta tio n o f b e e r , and S h i c h i j i , working w ith cane

m o la sse s, found t h a t th e form atio n o f f u s e l o i l v a r ie s w ith tim e re a ch in g

a l i m i t which rem ains unchanged t h e r e a f t e r (6 3 , 1 2 8 ). '

The d is c o v e r ie s o f E h r lic h , t h a t th e y ie l d o f f u s e l o i l co u ld be

in c re a s e d up to 7%, based on e th y l a lc o h o l, w ith th e a d d itio n o f s u i t ­

a b le p ro p o rtio n s o f amino a c id s , su g ar and y e a s t innoculum , gave r i s e , in

th e e a r ly y e a rs o f th e c e n tu ry , to s e v e ra l p a te n ts and proposed p ro c e sse s

f o r th e p ro d u c tio n o f la r g e amounts o f f u s e l o i l . At t h a t tim e th e com­

m e rc ia l u t i l i z a t i o n o f f u s e l o i l in s e v e ra l a p p lic a tio n s , e s p e c ia ll y f o r

th e p ro d u c tio n o f s o lv e n ts and th e su g g e stio n o f -its use a s raw m a te r ia l

f o r is o p re n e and b u ta d ie n e , needed in th e s y n th e tic ru b b er in d u s tr y , g r e a tly

in c re a s e d th e demand and th e p r ic e o f f u s e l o i l (1 4 3 ). E h r lic h o b ta in e d

p a te n ts in Germany, England and in t h i s Country f o r a p ro c e ss based on

h i s d is c o v e r ie s (3 2 , 36, 4 0 ). Darco S a le s C o rp o ratio n o b ta in e d a B r i t i s h

p a te n t f o r a p ro c e ss based on prom oting th e fe rm e n ta tio n o f f u s e l o i l

(and o th e r fe rm e n ta tio n s ) by ad d in g to th e ferm en tin g mash an a c tiv e

a b so rb e n t a g e n t a s a c tiv a te d v e g e ta b le c h a rc o a l to g e th e r w ith o rg a n ic .

n itro g e n o u s food su b sta n c es ( 2 1 ) . S u lta n and S te in p a te n te d a p ro c e ss

 17

in F ran c e , in 1907, based on adding le u c in e to th e ferm en tin g mash (134, 1 3 5 ).

Fem bach and S tra n g e o b ta in e d a B r i t i s h p a te n t on a p ro c e ss based

on producing h ig h e r a lc o h o ls by t r e a t i n g y e a s t, such a s t h a t rem aining

from a lc o h o lic fe rm e n ta tio n p ro c e s s e s , in th e p resen ce o r absence o f

c arb o h y d ra te s w ith a p r o te o ly tic ferm ent such a s t y r o t h r i x te n u is , and a

ferm ent such a s th e b u ty lic b a c il lu s o f F it z (5 7 ) .

S e v e ra l a u th o rs have review ed th e methods o f commercial p ro d u ctio n

o f f u s e l o i l (9 0 , 95, 139, 141, 1 6 1 ).

R eaction Mechanism f o r th e D eam ination o f Amino A cids

There have been s e v e ra l mechanisms proposed through which group—

CH(NH2 ) —could be c o n v erted in to th e te rm in a l group— OH—appear i ng

i n th e a lc o h o l.

(1) One way in which th e change may p o s s ib ly be e ffe c te d i s by th e

d i r e c t e lim in a tio n o f carbon d io x id e w ith subsequent h y d ro ly s is o f th e

r e s u l t i n g amine a s fo llo w s (6 5 ):

(a ) R*CH(NH2 )*C00H - R*CH2 (NH2) + C02

(b) R*CH2 (NH2) + H20 - R‘CH2 *0H + NH3

R eactio n (a ) h as been found to be a c t u a l l y e f f e c te d by some b a c te r ia

b u t th e r e i s no d i r e c t evidence t h a t i t can be e ffe c te d by y e a s t ( 6 6 ) .

E h rlic h and P istsch im u k a have found t h a t manyw ild y e a s ts a c t u a lly

b rin g ab o u t th e change re p re s e n te d by e q u a tio n (b ) in which th e amine i s

h y d ro liz e d to th e co rresp o n d in g a lc o h o l ( 4 6 ) . With o rd in a ry y e a s t c u l­

tu r e s o n ly tr a c e s o f amylamine a re co n v erted in to amyl a lc o h o l w h ile y e a s ts

which form s u rfa c e grow th, such a s w i l l i a anom ala. produce th e change
 18

r e a d ily i n th e p resen ce o f su g a r, g ly c e r o l o r e th y l a lc o h o l a s so u rc es o f

carbon.

(2 ) E h rlic h o r i g i n a l l y su g g este d a s a p o s s ib le mechanism th e f o r ­

m ation o f an a -h y d ro x y -a c id which was su b se q u e n tly decomposed in to an

a lc o h o l and carbon d io x id e o r in to an aldehyde and form ic a c id , th e

aldehyde b ein g reduced to th e a lc o h o l and th e form ic a c id d e stro y e d (3 4 ):

(a ) R*CH(NH2 )*C00H + H20 - R*CH(OH)*C00H + NH3

(b) R*CH(0H).COOH - R*CH2 »0H + C02 or

(c ) R*CH(OH) .COOH *= R.CHO + HCOOH and

(d) R’CHO + H2 - R*CH2 «0H

(3 ) Neubaucr and From hertz proposed a scheme which c o n s is ts o f th e

o x id a tiv e removal o f th e -NH2 group w ith th e form ation o f an a -k e to n ic

a c id (1 0 0 ). The a - k e to n ic a c id i s su b se q u e n tly decomposed in to carbon

d io x id e an d an a ld eh y d e , th e l a t t e r b ein g e i t h e r reduced to an a lc o h o l

o r o x id iz e d to an a c id :

(a ) R*CH(NH2 ).C00H + 1 /2 0 2 » R«C0»C00H + NH3

(b) R*CO*COOH - C02 + R*CHO

(c ) R*CHO + H2 - R«CH2 0H or

(d) R.CHO + 1 /2 0 2 - R.COOH

The re s e a rc h e s o f Neubauer e s ta b lis h e d t h a t amino a c id s a c t u a ll y

y i e l d th e c o rresp o n d in g a -k e to n ic a c id when t r e a t e d w ith y e a s t in a su g ar

s o lu tio n (1 0 0 ). He f u r th e r dem onstrated t h a t , under s im ila r c o n d itio n s , .

th e a -k e to n ic a c id produces good y i e l d s o f th e a lc o h o l c o n ta in in g one l e s s

 19

carbon atom w h ile th e c o rresp o n d in g a -h y d ro x y -a c id , c o n tra ry to E h r lic h 1s

s u g g e s tio n , y ie ld s o nly e x trem ely sm all amounts o f th e a lc o h o l. The r e - '

s e a rc h e s o f Neuberg have shown t h a t a l l ra c e s o f brew ers and wine y e a s ts

r e a d ily c o n v e rt a -k e to n ic a c id s i n to an aldehyde and carbon d io x id e , a s

d e p ic te d by e q u atio n ( b ) , by th e enzyme c a rb o x y lase (1 0 1 ). F u r th e r , th e

re a d y c o n v ersio n o f th e aldehyd e i n t o a lc o h o ls and a c id s by y e a s t has

been p roved. This would e x p la in th e many tim e s re co g n ized p re sen c e o f

th e v a l e r i c a c id and aldehyde (1 4 3 ).

Based on th e above m entioned f a c t s , Harden co n clu d es t h a t t h i s

mechanism f o r th e a lc o h o lic fe rm e n ta tio n o f amino a c id s i s th e m ost

p ro b ab le course ( 65 ) .

Com position o f F u se l O il from D if f e r e n t S u b s tra te s

I t has been m entioned in p re v io u s p arag rap h s t h a t th e com position

o f th e f u s e l o i l produced in a given fe rm e n ta tio n w i l l depend on a number

o f f a c to r s such a s th e n a tu r e o f th e mash, n itro g e n o u s su b sta n c e s p r e s e n t,

type and c o n d itio n o f th e y e a s t w ith re g a rd to n itr o g e n , tim e o f fermen­

t a t i o n and o th e r s .

Table 1 g iv e s th e com position o f v a rio u s f u s e l o i l s from d i f f e r e n t

o r ig in s re p o rte d in th e l i t e r a t u r e . The com position f ig u r e s a re based on

th e a lc o h o l-w a te r- fre e o i l . The re fe re n c e number o f th e so u rce o f i n f o r ­

ma tio n i s g iv e n .

I t can be observed from th e d a ta ta b u la te d t h a t th e r e a r e r a t h e r

wide v a r ia tio n s i n th e com position o f th e f u s e l o b ta in e d even when th e

same k in d o f s u b s tr a te was u t i l i z e d i n th e fe rm e n ta tio n . T h is i s a con­

firm a tio n t h a t th e n a tu r e o f th e carb o h y d rate so u rce used i s n o t th e only

f a c t o r a f f e c t i n g th e com position o f th e o i l produced. I t may a ls o be

 TABLE 1

COMPOSITION OF FUSEL OIL FROM DIFFERENT ORIGINS ON ALCOHOL-WATER-FREE BASIS

A cid s,
n- n- Iso - Hexyl
S u b s tra te A c tiv e Iso - Iso - n- + A id ., U n d eter- R ef.
Amyl Amyl Aiayl B u ty l B u ty l P ro p y l P ro p y l E s te r s , mined No.
H igher e tc .

1 Cane M olasses _ 55.3 j- UM-—m 4 .3 7 .4 8 .1 0 .6 24.3 — 59,81

2 Cane M olasses -------- 85 .0 -------- — ---- —- 2 .0 ---- —— 2 .8 8 .2 27
3 Cane M olasses —— 55.4 - —»- 4 .1 7 .4 8 .1 0 .7 24.3 ---- tr a c e ---- 119
4 Cane M olasses — -— 9 5 .4 — — ---- 0 .2 0 .4 2 .5 0 .3 0 .6 3 .8 —__ 132
5 Cane M olasses — — 65.3 ------- — 1 .9 5 .6 18.9 3 .4 0 .4 1 .7 2 .8 132
6 Cane M olasses ---- — 69.8 ------- 0 .2 0 .4 1 9 .4 0 .5 0 .4 3 .1 6 .2 132
7 B eet M olasses — — 59.8 ------- —- 1 4 .4 7 .2 —- 15 .1 0 .3 0 .3 2 .9 132
8 B eet M olasses 4 1 .4 26.3 8 .1 6 .1 6 .1 4 .0 ---- T race 3 .0 5 .0 " 8
9 Grapes 24.5 - - - - - — 63.8 U .7 ~~ 18,103
10 Grapes 34 .4 4 .5 49 .3 —^ M 11 .9 I z 18
11 Grapes 9 .6 54.0 tr a c e 18 .3 6 .8 --- - 4 .1 1 .5 5 .6 0 .1 150
12 Grapes -------- 6 3 .2 ------ - —- 7 .7 8 .9 — 1 5.7 0 .4 0 .2 3 .9 132
13 Grapes 8 5 .2 — — — 2 .8 ---- ---- 1 2 .0 — —. 143
14 P o ta to —■---- 3 4 .4 ------- 3 0 .4 4 .4 18 .8 3 .8 — 0 .8 7 .4 132
15 P o ta to —- — 68.8 — ---- ---- 2 4 .4 ---- ---- 6 .8 ___ aamm* ___ 5 8 ,5 9 ,8 1
16 P o ta to ------ - 3 1 .5 —---- 6 .9 5 .7 7 .4 1 7 .2 3 .4 ___ 8 .6 19.3 117
17 P o ta to -------- 68.7 -------- ---- 2 4.4 -— ---- 6 .9 ___ tr a c e 143,152
18 P o ta to 2 8 .6 24.0 0 .5 4 .2 ---- 6 .5 5 .2 0 .1 30.9 102
19 Corn 1 4 .6 36.3 -— 23.9 ---- ---- 2 0 .4 ___ —... 4 .8 59,81
20 Com 23.4 59.7 —- 1 2 .2 — ---- 11.7 ---- 3 .0 59,81
21 Corn ------- 8 7 .4 — ---- ---- 9 .8 WT _— 2 .7 —- 1
22 Corn -------- 64.3 — - — —- 1 7 .6 8 .4 ---- 4 .0 1 .3 0 .3 4 .1 132
23 B arley —•— - 47.7 --------- - —. 5 .6 5.9 35.7 0 .9 0 .3 3 .9 132
24 Rye ------- -- 79.8 --------- - — 15.7 —- ------ — ----- ___ 6 .5 59,81
25 Wood Sugar 68.8 ----- 1 5.9 —- ----- 2 .2 ----- ___ 1 3 .1 53
26 Wood Sugar --------- 74.4 2 0 .5 ----- tr a c e 0 .3 ----- 1 .0 3 .8 52
27 S u l f i t e Waste 9 .9 49.3 ----- 16 .9 2 .0 2 .0 2 .8 1 0 .4 6.7 69
28 Unknown ------ .— 67.4 ------— ----- 21.8 ----- — 1 0 .8 ----- ----- ----- 88
 21

observed t h a t in s e v e ra l c a s e s th e a n a ly s is was perform ed on o n ly a f r a c tio n

o f th e o r ig i n a l o i l c o n ta in in g th e main c o n s ti tu e n ts , w h ile in o th e r c a se s

th e com plete m ix tu re was a n a ly z e d .

Y ie ld s o f F u sel O il from D if f e r e n t Raw M a te ria ls

A ccording to th e in fo rm a tio n a v a il a b le in th e l i t e r a t u r e , th e

y ie ld s o f f u s e l o i l o b ta in e d in com m ercial p r a c tic e may v ary between 1

and 11 g a llo n s p e r 1000 g a llo n s o f a b s o lu te a lc o h o l produced, depending

upon th e s u b s tr a te u sed , n itro g e n o u s s u b sta n c e s added, c o n d itio n s o f th e

fe rm e n ta tio n and th e d i s t i l l a t i o n p ro c e ss u se d . Table 2 g iv e s average

f ig u r e s re p o rte d in th e l i t e r a t u r e .

TABLE 2

YIELDS OF FUSEL OIL FROM DIFFERENT RAW MATERIALS

F u s e l O il, G al.
Source p e r 1000 g a l. o f a lc o h o l R eferen ce No.

B la c k stra p m olasses 2 .6 67

B la c k s tra p m o lasses 4 -5 59, 81

H ig h -te s t m olasses 1 -3 59

E vaporated cane ju ic e 1 -2 59

Corn 4 -5 59, 81

Degerm inated corn 2 .5 - 3 59, 81

Wheat 2 -3 59, 81

Rye 2 -4 59, 81

G rains (mixed) 5.3 67

S u lp h ite liq u o r 2 -3 59

P o ta to e s 5 -11 59
 22

F u se l O il C ontent i n A lc o h o lic Beverages

F u se l o i l i s n o rm ally p re s e n t in v a ry in g amounts i n a l l k in d s o f

a lc o h o lic beverages* I t s p ro p o rtio n depends on th e n a tu re o f th e b ev erag e.

Much has been w r itte n re g a rd in g th e to x ic e f f e c t s supposedly p ro­

duced by th e f u s e l o i l p re s e n t i n beverages* to th e e x te n t t h a t th e b e l i e f

was lo n g h e ld th a t th e in ju r io u s e f f e c t s o f b ev erag es such a s w hiskey,

brandy and ru n were due m a in ly , i f n o t w h o lly , to t h e i r f u s e l o i l co n ten t*

As a r e s u l t o f re c e n t re s e a rc h e s on th e s u b je c t, i t i s now a cc e p ted t h a t

th e to x ic e f f e c t s o f f u s e l o i l , i n th e p ro p o rtio n t h a t i t e x is t s i n b e v er­

a g e s , have been g r e a tly e x ag g erated and t h a t i t i s p ro b a b le th a t th e

predom inating a g e n t in th e w hiskey which produces p h y s io lo g ic a l e f f e c t s

i s th e e th y l a lc o h o l (1 5 3 ).

Table 3 p re s e n ts d a ta on f u s e l o i l c o n te n t o f s e v e r a l co nm ercial

beverages t h a t have been re p o rte d in th e l i t e r a t u r e . The v a lu es giv en b e ­

low f o r s tro n g s p i r i t o u s b e v e ra g e s, such a s rum, brandy and w hiskey, have

been c o n v e rte d , when n e c e s s a ry , to a b a s is o f 100 m i l l i l i t e r s o f p ro d u ct

a t 86*P.
 23

TABLE 3

FUSEL OIL CONTENT IN ALCOHOLIC BEVERAGES

Kind o f Product T gs* R eferen ce No.

p e r 100 m l. o f p ro d u ct

1. Beer 1 .7- 3 132

2. S h e rry Wine 3- 5 132
3. M adeira Wine 5- 7 132
4. P o rt Wine 8- 1 0 132
5. C la r e t Wine 3- 5 132
6. W hite Wine 2- 4 132
7. Red Wine 4- 6 137
8. C a lifo rn ia W hite Table Wine 16 - 37 64
9. C a lifo rn ia Red Table Wine 14 - 42 64
10. C a lifo rn ia D e s s e rt Wine 16 - 90 64
11. C ider . 3 - 5 132
12. Gin 5-4 0 132
13. Gin 19 153
14. Cognac Grandy, 10 y e a rs old 54 153
15. Henessy Brandy, 2 y e a rs old 253 132
16. M a rte l Brandy, 10 y e a rs old 354 132
17. Jam aica Rum 95 - 108 132
18. P u e rto . Rican Rum 32 - 60 3 , Vi
19. Demerara Rum 50 153
20. Rum, unknown o rig in 39 132
21. Dewar Whiskey, 5 y e ars o ld 189 - 224 132
22. House o f Lords Whiskey 217 - 265 132
23. S c o tc h Whiskey 69 - 86 154
24. I r i s h Whiskey 88 154
25. Bourbon W hiskey, unknown o rig in 668 132
26. American Rye Whiskey 73 - 167 154
27. American Rye Whiskey 78 - 132 20
28. American Bourbon Whiskey 89 - 130 154
29. American Bourbon Whiskey 101 - 124 20
30. C ountry S p i r i t s 923 -1254 132
 CHAPTER I I

COMMERCIAL USES OF FUSEL OIL

For many* y e a rs f u s e l o i l was an alm o st v a lu e le s s b y -p ro d u ct o f th e

a lc o h o l in d u s tr y . I t was u t i l i z e d a s illu m in a tin g o i l and in o th e r m inor

a p p lic a tio n s * I t was l a t e r u sed a s a s o lv e n t i n th e e x p lo siv e and p a in t

i n d u s tr ie s b u t i t s use was abandoned in fa v o r o f cheaper s o lv e n ts (1 7 6 ).

D uring th e e a r ly y e a rs o f th e c e n tu ry , however, f u s e l o i l became a v ery

v a lu a b le s u b sta n c e . I t was l a r g e l y used a s a so u rce o f amyl a lc o h o l f o r

th e p ro d u c tio n o f amyl a c e ta te which in tu rn was used in la r g e q u a n titi e s

a s a s o lv e n t f o r n it r o c e l l u l o s e i n th e making o f v a rn is h e s , la c q u e r s , and

a r t i f i c i a l le a t h e r s having a n i t r o c e l l u l o s e co m p o sitio n . The u se o f f u s e l

o i l was extended to o th e r i n d u s t r i e s . In th e f r u i t essen ce in d u s tr y , i t

was s e p a ra te d in to i t s c o n s titu e n t a lc o h o ls by f r a c t i o n a l d i s t i l l a t i o n .

These, in tu r n , were su b se q u e n tly c o n v erted i n t o t h e i r co rresp o n d in g

e s t e r s o f s e v e ra l a c id s and used f o r fla v o rin g li q u o r s , j e l l i e s , sw eets

and th e l i k e . F u se l o i l and i t s c o n s ti tu e n t a lc o h o ls were employed f o r

th e p r e c i p i t a t i o n o f a s p h a lt from heavy m in e ra l o i l s (1 7 6 )•

As a r e s u l t o f th e methods worked o u t by P e rk in s , Mathews and o th e rs

f o r c o n v e rtin g isoam yl a lc o h o l i n t o is o p re n e and n - b u ty l a lc o h o l in to

b u ta d ie n e , th e u se o f f u s e l o i l a s raw m a te r ia l f o r s y n th e tic ru b b e r was

sugg ested (1 7 9 ).

I n 1900-1901, th e o i l was s o ld in Germany a t 50 M. f o r 100 k i l o s ,

o r 4 -1 /2 l b s . a s h i l l i n g . By 1910, i t s p r ic e had r is e n to 170 M. p e r 100

k i l o s and, in 1912, i t was quoted in England a t 140 pounds o f s t e r l i n g p e r

24
 25

ton* The w orld su p p ly , in 1912, was e stim a te d a t 3,500 to 6,000 to n s a

y e ar. With th e a d v en t o f F e m b a ch ’s p a te n t, d is c u s s e d in C hapter I , i t

was s ta te d t h a t i t could be produced in u n lim ite d amounts a t 35-40 pounds

s t e r l i n g p e r to n (1 7 6 , 1 8 6 ).

The U nited S t a t e s , in 1910, im ported 495,000 l b s . w ith a v a lu e o f

$598,000. No l e s s than 50,000 g a llo n s o f amyl a c e ta te were a n n u a lly con­

sumed in th e U nited S ta te s a t t h a t tim e f o r s o lv e n t purposes (176, 1 8 6 ).

Because th e .lim ite d su p p ly o f f u s e l o i l was i n s u f f i c i e n t to m eet

th e in c re a s in g demands f o r high b o ilin g s o lv e n ts f o r use in autom otive

la c q u e rs , th e p ro d u c tio n o f s y n th e tic amyl a lc o h o ls commenced in 1926 (1 7 3 ).

The p ro c e ss c o n s is ts o f c h lo r in a tin g in th e vapor phase a m ix tu re o f pen-

ta n e s from n a tu r a l gas g a s o lin e . In a d i s t i l l a t i o n u n i t th e amyl c h lo rid e

isom ers a re s e p a ra te d from any p o ly c h lo ro p e n ta n es as w ell a s from u n reacted

p entanes and hydrogen c h lo r id e . The amyl c h lo rid e s a re su b seq u en tly hydro-

li z e d to th e co rresp o n d in g a lc o h o ls (167, 169, 170, 1 7 4 ). The f i n a l pro d u ct

c o n ta in s a l l p o s s ib le amyl a lc o h o l isom ers w ith th e ex cep tio n o f 2 ,2 - d i -

m ethy1-1-propanol. S p e c if ic a tio n s fo r s y n th e tic amyl a lc o h o l a re a v a ila b le

i n the l i t e r a t u r e (166, 1 7 3 ).

S p e c if ic a tio n s f o r F u se l O il and Amyl A lcohol

F u se l o i l i s su p p lie d co m u ercia lly in a crude and r e f in e d g ra d e .

The s p e c if ic a tio n s v a ry from case to c a s e . The fo llo w in g ty p i c a l s p e c i­

f i c a tio n s a re given i n th e l i t e r a t u r e :

1* Crude F u s e l O il (1 7 3 ):

C olor - - - - - - - - - - - - - - - - - - - - - - - - - y ello w
Odor - - - - - - - - - - - - - - - - - - - - - - - - - stro n g
 26

B o ilin g Range:
up to 1 2 2 “C - - — 34^
122-138*0 ------------ 61$
above 138*0 - - - - - - - - - - - - - - - - - - - - - - 3 .4 $
d2 0 ---- - ----------------------- --------------- ---------------------------- --- 0.83
20
S o l u b i l i t y in s a tu r a te d NaCl - - - - - - - - - - - - - - - - 3$
E th y l A lco h o l, $ by volume ---- - ------------- --- - 1 .7

2. R efined F u se l O il (173. 1 8 3 ):

C olor - - - - - - - - - - - - - - - - - - - - - - - - W ater-w hite

Odor - - - - - - - - - - - - - - - - - - - - - - - - - N o n resid u al
B o ilin g Range:
Below 110*0 - - - - - - - - - - - - - - - - - - - None
Below 120*0 - - - - - - — - - - - - - - - - - - Less th an 15$
Below 130*0 - - - - - - - - - - - - - - - - - - - Above 60$
Above 135*0 - - - - - - - - - - - - - - - - - - - None

d2 0 0 ,8 1 1 " 0 ,8 1 5
A c id ity a s a c e t i c a c id , maximum - - - - - - - - - - - 0 .02$
D ryness, m i s c i b i l i t y w ith 20 volumes o f 60*Be.
g a s o lin e a t 20*0 - - - - - - - - - - - - - - - - N o t u r b i d i t y
N o n v o la tile m a tte r, maximum - - - - - - - - - - - - - 0.005$

3. R efined F u s e l O il (1 7 7 ):

C o e f fic ie n t o f expansion p e r 1*F - - - - - - - - - — 0.00051

per 1*0 - - - - - 0.00092
C olor - - - - - - - - - - - - - - - - - - - - - - - - W ater-w hite
D ryness, m i s c i b i l i t y w ith 20 volumes o f 60*Be g a s o lin e
a t 20*0 - - - - - - - - - - - - - - - - - - - - - No t u r b i d i t y
E vaporation R ate a t 95“F ( in m in u te s ): 5$ - - - - - - 3 -1 /2
2 5 $ ----------------- 17
5 0 $ ----------------- 3 6 -1 /2
7 5 $ -----------------6 4 -3 /4
9 0 $ ----------------- 9 0 -1 /4
9 5 $ ------------ 1 0 3 -1 /2
F la sh P o in t - - - - — -------------------- --- - 108 “F (A pprox.)
R esidue on e v a p o ra tio n - - - - - - - - - - - - - - - - None
d2° ------------------------------------------------ 0.811 - 0.815
W eight p e r g a llo n a t 20*0 - - - - - - - - - - - - - - 6 .7 6 l b s .
A c id ity a s a c e t i c a c id , maximum - - - - - - - - - - - 0 .0 1 $
B o ilin g Range:
Below 100*0 - - - - - - - - - - - - - - - - - - - None
Below 110*0 - - - - - - - - - - - - - - - - - - - Not o v er 10$
Below 120*0 - - - - - - - - - - - - - - - - - - - Not o v er 30$
Below 130*0 - - - - - - - - - - - - - - - - - - - Not l e s s th an 90$
Above 145*0 - - - - - - - - - - - - - - - - - - - None
 27

N o n v o la tile m a tte r, maximum ---------- - 0.005$

4. R efined Amyl A lcohol (1 8 3 ):

C olor - - - — - - - — - - - - - - - - - - - - - - W ater-w hite

Odor ------- --- - — - - - - - - - - - N o n resid u al
D i s t i l l a t i o n Range:
Below 126 “C - - -------- - - - - - - - - - - - - None
Above 132°C - - - - - - - — - - - - - - - - - - None
d2 0 ---------- --------------------------------------------------- --- - 0.811 - 0.815
20
A c id ity a s a c e tic a c id , maximum - - - - — - - — - 0.02$
D ryness, m i s c i b i l i t y w ith 20 volumes o f 60“Be.
g a s o lin e a t 20°C - - - - - - - - - - - - - - - - N o t u r b i d i t y
N o n v o la tile m a tte r, maximum - - - - - - - - - - - - - 0,003$

P ro d u c tio n and Im ports o f F u se l O il and Amyl A lcohol

Data R eg ard in g th e p ro d u c tio n o f f u s e l o i l i s m eager. The i n f o r ­

m ation p re s e n te d in Table 4 , p u b lish e d by th e U nited S t a t e s T a r i f f

Coranission, in c lu d e s b o th f u s e l o i l and amyl a lc o h o l. Q u a n titie s produced

and im ported, a s w ell a s th e co rresp o n d in g v a lu e in d o ll a r s f o r s e le c te d

y e a r s between 1929 and 1947 a re given (1 8 5 ).

TABLE 4

PRODUCTION AND IMPORTS OF AMYL ALCOHOL AND FUSEL OIL

P ro d u c tio n Im ports
ar Q u a n tity , l b s . Value Q u a n tity , l b s . Value

1929 52,467 $ 10,737.00

1935 11,002,667 $ 1 ,4 3 0 ,3 4 7 .0 0 3,292 1 ,9 4 8 .0 0

1937 14,205,997 1 ,9 8 8 ,8 4 0 .0 0 2,605 699.00

1938 9,096,977 1 ,0 9 1 ,6 3 7 .0 0 179 69.00

1939 754 308.00

1943 14,250,000 1 ,9 9 6 ,0 0 0 .0 0

1946 15,475,000 2 ,3 2 1 ,0 0 0 .0 0 136,941 13,22 8 .0 0

1947 17,728,000 3 ,1 9 1 ,0 0 0 .0 0 32,511 1 ,9 4 9 .0 0

 28

The d a ta p re s e n te d in d ic a te s th e in c re a s in g tre n d i n th e p ro d u c tio n

o f f u s e l o i l and amyl a lc o h o ls . It can be observed t h a t th e v alu e o f the

im ports i s i n s i g n i f i c a n t a v e ra g in g le s s th a n 1 .0 # o f p ro d u c tio n . F u se l

o i l g e n e r a lly accounts f o r a predom inant p a r t o f th e im p o rts.

M ellan g iv e s th e d a ta p re s e n te d i n Table 5 in th e a ll o c a tio n s o f

amyl a lc o h o ls , in c lu d in g a l l g ra d e s and s o u rc e s , f o r th e p e rio d between

A p ril 1—June 30, 1945 (1 7 7 ):

TABLE 5

ALLOCATIONS OF AMYL ALCOHOLS FROM APRIL 1 —JUNE 30, 1935

Use Amount, l b s . P er Cent

T o ta l a llo c a tio n s 4 .630.000 1 0 0 .0

Amyl a c e t a t e , a l l grades 2,345,000 5 0 .7

Lacquers and s o lv e n ts 1 ,279,000 27.7

Ore f l o t a t i o n re a g e n ts 418,000 9 .0

Drugs and P h a rm a c eu tica ls 235,000 5 .1

A dhesives 180,000 3 .9

P etroleum r e f in in g 44,000 1 .0

M iscellaneous u ses 122,000 2 .6

Of th e amyl a c e t a t e produced, 20# was used i n th e p ro d u c tio n o f

p e n i c i l l i n , 73# i n la c q u e rs and 7% . i n o th e r a p p lic a tio n s .

Uses o f Amyl A lcohols and Fusel O il

The in d u s tr ie s in which f u s e l o i l and th e amyl a lc o h o ls fin d ap ­

p lic a tio n a r e l i s t e d in th e l i t e r a t u r e w ith v a ry in g degree o f com pleteness

(1 7 2 , 173, 176, 177, 178, 18 2 ). One o f th e most com plete a cc o u n ts i s

p ro b ab ly t h a t given by Gregory from which m ost o f th e in fo rm atio n p re s e n te d

 29

below i s ta k en (1 7 2 ). In a l l c ase s th e in fo rm a tio n a v a ila b le c o n s is ts o f

g e n e r a l i t i e s la c k in g s p e c if ic in fo rm a tio n re g a rd in g amounts u sed , poten­

t i a l m arket and s p e c if ic s ta g e o f th e p ro c e ss i n which u t i l i s e d .

In th e chem ical in d u s try f u s e l o i l and th e a lc o h o ls o b ta in e d from

i t f in d use a s g e n e ra l s o lv e n ts f o r a l k a l o id s , camphor, f a t s , io d in e ,

phosphorous, r e s i n s , su lp h u r and o th e r s . They se rv e a s s o lv e n ts m is c ib le

w ith e th y l a lc o h o l, e th e r and e s s e n t i a l o i l s . They a l s o s e rv e a s p ro cess

m a te r ia l in o rg a n ic s y n th e s is and a c t a s s t a r t i n g p o in t i n making amyl

a c e t a t e , amyl b u ty r a te , amyl fo rm ate, amyl o le a t e , amyl o x a la te , amyl

p h th a la te , amyl p ro p io n a te , amyl t a r t r a t e , and p h a rm a ce u tic a l chem icals

such a s amyl n i t r a t e , amyl v a l e r a t e , amyl form ate and amyl b a r b i t a l .

In th e perfume in d u s tr y , r e f in e d f u s e l o i l and amyl a lc o h o ls a re

used f o r th e p ro d u c tio n o f amyl b en zo ate and amyl s a l i c y l a t e .

In the. m anufacture o f c e llu lo s e p ro d u c ts , th e y fin d use a s in g re ­

d ie n ts o f s o lv e n t m ix tu re s f o r c e llu lo s e a c e t a t e , n i t r o c e ll u lo s e and

c e ll u lo s e e s t e r s and e th e r s .

Amyl a lc o h o ls f in d use in th e m ining in d u s tr y a s f r o th e r s f o r the

f l o t a t i o n o f n o n fe rro u s o r e s . A le in ik o v h a s found t h a t m ixing them w ith

e th y l x a n th a te g iv e s b e t t e r r e s u l t s and a f f o r d s c o n sid e ra b le sav in g s o f

th e o i l and e th y l x a n th a te in th e f l o t a t i o n o f q u a r t z i t i c co p p er s u lf id e

o re s (1 6 5 ).

The amyl a lc o h o ls and f u s e l o i l a re used a s a n tifo a m in g a g e n ts

and a re in te rm e d ia te in th e m anufacture o f p h o to g rap h ic ch em ica ls.

Due to t h e i r s o lv e n t power th e y a r e used a s d ilu e n ts f o r h y d ra u lic

f l u i d s o f th e c a s to r o i l ty p e , in r i f l e b o re c le a n e r s , gum i n h i b i t o r s ,
 30

p r in tin g in k s and in la c q u e rs (1 7 3 ).

F u sel o i l and amyl a lc o h o ls a re used a s s o lv e n ts in numerous o th e r

in d u s tr ie s in c lu d in g th e beverage in d u s try f o r th e p ro d u c tio n o f f la v o r ­

in g syrups and e x tr a c ts ; c o a tin g com positions in th e ceram ic i n d u s t r i e s ;

s o lv e n t f o r aro m atic a g e n ts and c e l l u l o s i c b ases in co sm e tic s; composi­

tio n s c o n ta in in g n i t r o c e l l u l o s e and r e s in s used f o r in s u la tin g and

c o a tin g in th e e l e c t r i c a l i n d u s t r i e s ; g e la t in i z i n g a g e n t and s o lv e n t f o r

n i tr o c e llu lo s e in th e m anufacture o f e x p lo s iv e s ; s o lv e n t f o r f a t s , e sse n ­

t i a l o i l and waxes; s o lv e n t in making f r u i t fla v o rin g syrups and e x tr a c ts ;

s o lv e n t in com positions c o n ta in in g n it r o c e l l u l o s e and r e s in s i n th e

p l a s t i c s , ru b b e r, t e x t i l e , p a i n t s , p a p e r, g la s s , l e a t h e r and m etal fa b ­

ric a tin g in d u s trie s . I t i s a ls o used as g lo s s im p a rte r and prom otor o f

good flow ing p r o p e r tie s in dopes, la c q u e r s , enam els, p a in ts and v a rn is h e s .

 CHAPTER I I I

ANALYTICAL METHODS FOR THE DETERMINATION OF FUSEL OIL

The m ost w idely used methods o f a n a ly s is f o r th e d e te rm in a tio n o f

f u s e l o i l can be grouped i n t o two g e n e ra l c l a s s i f i c a t i o n s . The f i r s t

group com prises th e v o lu m e tric methods which depend upon th e e x tr a c tio n

o f th e h ig h e r a lc o h o ls w ith an o rg a n ic s o lv e n t. The second group i n ­

clu d es th e c o lo rim e tric methods which a r e b ased on m easuring th e i n t e n s i t y

o f th e c o lo r produced by r e a c tio n s e x h ib ite d by th e h ig h e r a lc o h o ls b u t

n o t by e th y l a lc o h o l.

The b e t t e r known v o lu m e tric methods a r e th e R o se-H erzfeld method,

la r g e ly used in Germany, and th e A llen-M arquardt m ethod, g e n e r a lly em­

ployed in England and which forms th e b ase o f th e o f f i c i a l method o f th e

A ss o c ia tio n o f O f f i c ia l A g r ic u ltu r a l Chem ists in t h i s C ountry.

Among th e c o lo r im e tr ic methods t h a t o f M ohler-Rocques c o n s ti t u te s

th e o f f i c i a l French method w h ile t h a t based on Komarowsky*s r e a c tio n has

been used in American and th ro u g h Europe. I t c o n s t i t u te s th e o f f i c i a l

method in S w itz e rla n d (2 2 2 ). The in tr o d u c tio n o f r a th e r re c e n t m o d ific a ­

tio n s to Komarowsky*s method has r e s u lt e d in g r e a t e r p r e c is io n and ease

o f a p p lic a tio n w ith th e co rresp o n d in g in c re a s e in th e accep tan ce o f th e

method by th e a lc o h o l in d u s tr y (202, 216, 2 4 0 ).

S e v e ra l review s o f th e v a rio u s methods a re a v a ila b le in th e

l i t e r a t u r e (168, 205, 216, 222, 239, 240).

31
 32

V olum etric Methods

R o se-H erzfeld Method: T his method i s b ased on th e g r e a t e s t s o l u b i l i t y

o f th e h ig h e r a lc o h o ls in chloroform th a n in e th y l a lc o h o l i t s e l f . Ac­

c o rd in g ly , th e sample to be te s t e d i s shaken w ith a measured volume o f

chloroform and th e h ig h e r a lc o h o ls a re e stim a te d from th e in c re a s e in

volume o f th e chloroform . In th e o r i g i n a l method d e s c rib e d by R ose, th e

sample was a d ju s te d to 50$ a lc o h o l by volume co rresp o n d in g to a s p e c if ic

g r a v ity o f 0.96564 a t 15.5°C r e f e r r e d to w ater a t 15.5°C (2 4 5 ). One

hundred m i l l i l i t e r s o f th e sample 30 a d ju s te d were shaken w ith 20 m i l l i ­

l i t e r s o f chloroform i n a g rad u ated v e s s e l a t 15.0°C . W ith th e a i d o f a

t a b le and th e h e ig h t o f th e la y e r o f ch lo ro fo rm th e q u a n tity o f f u s e l o i l

i s d eterm in ed . In o rd e r to e lim in a te from th e sample su b sta n c es i n t e r -

f e r r i n g w ith th e method, S tu t z e r and R e itm a ir in tro d u c e d a p rocedure f o r

t r e a t i n g th e sample b e fo re th e a n a ly s is (2 5 4 ). The tre a tm e n t c o n s is te d

o f b o ilin g th e sample a t t o t a l r e f lu x w ith sm all amounts o f sodium o r

potassium hydroxide w ith subseq u en t d i s t i l l a t i o n o f th e r e s u l t i n g liq u o r

and com pleting th e d i s t i l l a t e to th e o r i g i n a l volume.

H erzfeld and W indish m o d ified R o se 's a p p a ra tu s fo r conducting th e

e x tr a c tio n p ro v id in g g ra d u a tio n s o f 0 .0 1 c e n tim e te r (2 2 2 ). The a lc o h o l

c o n c e n tra tio n in th e sample was m o d ified to 30$ by volum e.

The a n a l y t i c a l p ro c e d u re, w ith th e above m entioned m o d ific a tio n s ,

i s giv en a s fo llo w s by K ervegant (2 2 2 ):

To e lim in a te th e in t e r f e r r in g im p u r itie s , t r e a t 100 m i l l i l i t e r s

w ith s e v e ra l drops o f c o n c e n tra te d p o tassiu m hy d ro x id e; b o i l under t o t a l

r e f lu x f o r one hour and th e n d i s t i l l th e l a r g e s t p a r t o f th e l i q u i d and

 33

com plete th e volume o f th e d i s t i l l a t e t o th e o r ig i n a l 100 m i l l i l i t e r s .

A d ju st th e a lc o h o l c o n te n t o f th e sample to 30# by volume and c o o l to

15°C. Add pure chloroform a t ab o u t 15#C in to a m o d ified Rose tu b e up

to th e 20 m l. mark m a in ta in in g th e tu b e in to a w a ter b a th a t 15*C. Give

ab o u t 5 m inutes f o r b o th tube and chloroform to come to th erm al e q u ilib ­

rium and make su re t h a t e x a c tly 20 m l. o f chloroform have been ad d ed . At

t h i s moment add in to th e tube 100 m i l l i l i t e r s o f the sample a d ju s te d to

30% a lc o h o l by volume and a t 15°C. M aintain th e tube in s id e th e w ater

b a th a t 15°C a t a l l tim e s. Add one m i l l i l i t e r o f s u lf u r ic a c id d ilu te d

to a d e n s ity o f 1.286 and mix th o ro u g h ly the c o n te n ts o f th e tu b e . The

purpose o f the a c id i s to h e lp l a t e r i n th e s e p a ra tio n o f the ch lo ro fo rm .

A g ita te in s id e th e w ater b a th a t 15°C f o r 15-20 m inutes making s u re t h a t

in tim a te c o n ta c t i s o b ta in e d between th e two l i q u i d p h a se s. Leave th e

tube in th e b a th f o r one hour a t th e end o f which th e re a d in g i s ta k e n .

S im ultaneously w ith th e above o p e ra tio n , pure a lc o h o l d ilu te d to 30% by

volume a t 15*C i s tr e a te d w ith chloroform in i d e n t i c a l fa s h io n . The d i f ­

fe re n c e between th e in c re a s e in volume i n the two tu b es w il l determ ine

th e c o n c e n tra tio n o f h ig h e r a lc o h o ls p re s e n t in th e sam ple. For th a t

purpose, p re v io u s ly p rep ared ta b le s a r e used.

In o rd e r t o o b ta in r e l i a b l e r e s u l t s by th e R ose-H erzfeld method

g r e a t c a re i s re q u ire d in th e m a n ip u la tio n . Under th o se circu m stan ces

i t u s u a lly g iv e s r e s u l t s o f th e c o r r e c t ord er o f m agnitude (2 4 0 ). The

a lc o h o lic s tr e n g th should be c a r e f u l ly a d ju ste d sin ce v a r ia tio n s o f 0 .1 #

would produce a d iff e r e n c e o f 0.0199# i n the volume o f th e h ig h e r a lc o h o ls

(2 2 2 ). A d iff e r e n c e o f 1.0°C produces a v a r ia tio n o f 0 .1 m i l l i l i t e r s in

 34

th e chloroform la y e r w h ile a c o n c e n tra tio n o f one p a r t o f amyl a lc o h o l in

one thousand p a r ts o f sample a t 30# a lc o h o l and 15*C c o rresp o n d s to an

in c re a s e o f 0 .2 m i l l i l i t e r s . The p u r it y o f th e ch lo ro fo rm and th e c a l i ­

b r a tio n o f the a p p a ra tu s used a re a ls o f a c to r s o f g r e a t im p o rtan ce. The

in c re a s e i n th e volume o f chloroform produced by a g iv en c o n c e n tra tio n

o f f u s e l o i l depends on th e h ig h e r a lc o h o ls p re s e n t in any p a r t i c u l a r c a s e .

The r e l a t i v e c o e f f ic ie n ts o f expansion a t 30# e th y l a lc o h o l and 1S°C a re

a s fo llo w s (2 2 2 ):

Amyl a lc o h o ls 1 .0 0
n -B u ty l a lc o h o l 0.5 7
Is o b u ty l a lc o h o l 0 .5 0
n -P ro p y l a lc o h o l 0 .3 3
Is o p ro p y l a lc o h o l 0.1 3

The method has th e d isad v an tag e o f comparing th e in c re a s e in volume o f

chloroform to t h a t produced by pure e th y l a lc o h o l and n o t to t h a t o f a

f u s e l o i l sta n d a rd c o n ta in in g th e v a rio u s h ig h e r a lc o h o ls in a p ro p o rtio n

s im ila r to th e sam ple.

The p resen ce o f im p u r itie s in th e f u s e l o i l sample would a f f e c t

th e r e s u l t s . The p re tre a tm e n t o f th e l iq u o r to be t e s t e d does n o t remove

a l l im p u r itie s p o s s ib ly p r e s e n t. In a d d itio n , th e method i s tim e con­

suming, th e a d ju stm en t o f th e o r ig i n a l sample to e x a c tly 30# a t 15°C

b ein g v e ry te d io u s .

A llen-M arquardt Method: T his method i s b ased on th e e x tr a c tio n o f th e

h ig h e r a lc o h o ls by carbon t e t r a c h l o r i d e in w hich th e y a re more r e a d ily

s o lu b le th a n in e th y l a lc o h o l, washing th e carbon t e tr a c h l o r id e f r e e from

tr a c e s o f e th y l a lc o h o l, o x id a tio n o f th e e x tra c te d a lc o h o ls to th e c o r­

responding a c id s , d i s t i l l a t i o n and t i t r a t i o n o f the a c id s formed (2 6 3 ).

 35

In th e o r ig i n a l method d e sc rib e d by M arquardt, 150 m i l l i l i t e r s o f

th e brandy to be analyzed a re d ilu te d w ith an eq u al volume o f w a te r and

e x tra c te d th r e e tim es w ith carbon te t r a c h l o r id e u t i l i z i n g 50 m i l l i l i t e r s

o f th e l a t t e r in each e x tr a c tio n (1 8 9 , 2 3 6 ). The combined carbon t e t r a ­

c h lo rid e e x tr a c ts a re tho ro u g h ly washed w ith w a ter to remove any e th y l

a lc o h o l and th en h e a te d in a c lo se d f la s k f o r s i x ho u rs a t 85°C w ith 5

grams o f potassium b ichrom ate, 30 grams o f w ater and 2 grams o f s u l f u r i c

a c id . A fte r th e com pletion o f th e o x id a tio n , th e m ix tu re i s d i s t i l l e d ,

w ater added to th e re s id u e and th e d i s t i l l a t i o n c o n tin u e d . The d i s t i l l a t e

i s b o ile d f o r h a l f an hour w ith barium c a rb o n ate under t o t a l r e f l u x . The

carbon te tr a c h l o r id e i s then d i s t i l l e d o f f , th e re s id u e f i l t e r e d and th e

f i l t r a t e ev ap o rated to d ry n e ss. The re s id u e i s weighed and th en d is s o lv e d

in w a te r c o n ta in in g a few drops o f n i t r i c a c id . From t h i s s o lu tio n , th e

amount o f barium s a l t s o f f a t t y a c id s was determ ined and th e amount o f

f u s e l o i l p re s e n t in th e o r ig i n a l sample c a lc u la te d .

The A llen-M arquardt method has been e x te n s iv e ly m o d ified in th e

co u rse o f th e y e a rs and a t p re s e n t th e pro ced u re which c o n s t i tu te s th e

o f f i c i a l method o f th e A s s o c ia tio n -o f A g r ic u ltu r a l Chem ists i s a s fo llo w s

(190, 263):

To 50 m i l l i l i t e r s o f th e sam ple, in a 500 m i l l i l i t e r Erlenm eyer

f l a s k , add 50 m i l l i l i t e r s o f w ater and 20 m i l l i l i t e r s o f 0.5N , sodium

h y d ro x id e, and connect th e f la s k w ith a co n d en ser, u sin g sta n d a rd ta p e r

ground g la s s c o n n e c tio n s, and d i s t i l l o f f 90 m i l l i l i t e r s , slow ly a t f i r s t ,

then more v ig o ro u s ly tow ard th e end; add 25 m i l l i l i t e r s o f w ater and con­

tin u e th e d i s t i l l a t i o n u n t i l an a d d itio n a l 25 m i l l i l i t e r s a re c o lle c te d .

 36

I f aldehydes a re p re s e n t in excess o f 15 p a r t s in 100,000, add to th e

d i s t i l l a t e 0 .5 grams o f m etaphenylenediam ine h y d ro c h lo rid e , b o il under

r e f lu x condenser an hour, d i s t i l l 100 m i l l i l i t e r s , add 25 m i l l i l i t e r s

o f w a te r, and c o n tin u e th e d i s t i l l a t i o n u n t i l an a d d itio n a l 25 m i l l i l i t e r s

a r e c o lle c te d . A pproxim ately s a tu r a te th e d i s t i l l a t e w ith f i n e l y ground

sodium c h lo rid e and add s a tu r a te d sodium c h lo rid e s o lu tio n u n t i l th e

s p e c if ic g r a v ity i s 1 .1 0 . E x tra c t t h i s sodium c h lo rid e s o lu tio n fo u r

tim es w ith p u r if ie d carbon t e t r a c h l o r i d e , u s in g 40, 30, 20 and 10 m i l l i ­

l i t e r s , r e s p e c tiv e ly , and wash th e combined carbon te t r a c h l o r id e e x tr a c ts

3 tim es w ith 50 m i l l i l i t e r p o rtio n s o f s a tu r a te d sodium c h lo rid e s o lu ­

ti o n s , and tw ice w ith s a tu r a te d sodium s u lp h a te s o lu tio n . Then t r a n s f e r

th e carbon te tr a c h l o r id e la y e r to a f la s k c o n ta in in g 50 m i l l i l i t e r s o f an

o x id iz in g s o lu tio n p re p a red by d is s o lv in g 100 grams o f p o tassiu m b ichrom ate

i n 900 m i l l i l i t e r s o f w ater and ad d in g 100 m i l l i l i t e r s o f s u lf u r ic a c id ;

b o i l f o r 8 hours under a r e f lu x c o n d en ser. Add 100 m i l l i l i t e r s o f w ater

an d d i s t i l l u n t i l only ab o u t 50 m i l l i l i t e r s rem ain. Add 50 m l. o f w ater

and a g ain d i s t i l l u n t i l 35-50 m i l l i l i t e r s a r e l e f t . Use extrem e c a re to

p re v e n t th e o x id iz in g m ix tu re from b u rn in g and baking on th e s id e s o f th e

d i s t i l l i n g fla s k . D i s t i l l a t e should be w ater w h ite j i f i t i s c o lo re d ,

d is c a rd i t and r e p e a t d e te rm in a tio n . T i t r a t e d i s t i l l a t e w ith 0.1N sodium

h y d ro x id e , u sin g p h e n o lp h th a le in in d i c a t o r . 1 .0 m i l l i l i t e r s o f 0.1N

sodium hydroxide a re e q u iv a le n t to 0.0088 grams o f amyl a lc o h o l. Make a

b lan k d e te rm in a tio n on th e carbon t e t r a c h l o r i d e , b eg in n in g a t th e p o in t

i n th e procedure im m ediately a f t e r e x tr a c tio n and j u s t b e fo re th e carbon

t e t r a c h l o r i d e i s washed w ith th e sodium c h lo rid e s o lu tio n .

 37

T his method has lo n g been known to be s u b je c t to e r r o r s b u t th e

m agnitude o f th e s e e r r o r s has n o t been g e n e r a lly r e a li z e d (2 4 0 ). Dudley

made a com parative stu d y o f th e A U en-M arquardt and th e R o se-H erzfeld

methods and found t h a t th e r e s u l t s giv en by th e l a t t e r method were from

2 .0 to 2 .5 tim es th o se o b ta in e d by th e fo rm er. He concluded, however,

t h a t th e Rose method was g r e a t l y in e r r o r . The r e s u l t s o f Penniman and

co-w orkers, among o th e r s , have shown th e re v e rs e to be tr u e (2 4 0 ).

Penniman found t h a t th e A.O.A.C. method r e p o r ts an av erag e o f

about 60$ o f th e t o t a l f u s e l o i l a c t u a l l y p r e s e n t, a lth o u g h under c e r ta in

c o n d itio n s th e accu racy may be a s low as 40$. The r e s u l t s in d ic a te t h a t

th e e r r o r s i n t h i s method v a ry w ith th e com position and c o n c e n tra tio n o f

f u s e l o i l (2 4 0 ). The A.O.A.C. method i s a f f e c t e d by v a r ia tio n s in te c h ­

nique and by u n c o n tro lle d f a c to r s such as th e te m p e ra tu re a t which th e

e x tr a c tio n s a re conducted. In a given case in which amyl a lc o h o l was th e

o n ly a lc o h o l used , th e r e p o r ts o f elev en l a b o r a to r ie s on th e same sample

v a rie d from 42$ to 145$ o f th e t o t a l amyl a lc o h o l a c t u a l l y p re s e n t (2 4 0 ).

I n t h e i r s t u d i e s , Penniman and co-w orkers a ls o d eterm in ed t h a t th e e r r o r s

in the method p a r t l y occur in th e o x id a tio n s ta g e and p a r t l y in th e ex­

t r a c t i o n and w ashing s ta g e s . More re c e n t in v e s tig a tio n s by o th e r w orkers

have t o t a l l y confirm ed th e r e s u l t s o f Penniman (2 1 6 , 232, 2 6 2 ).

In a d d itio n to th e l i m i t a t i o n s l i s t e d , th e method i s la b o rio u s

and tim e consuming.

C o lo rim e tric Methods

M ohler-Rocques O f f i c i a l French Method: The e a r l i e s t form o f c o lo rim e tric

method f o r th e d e te rm in a tio n o f h ig h e r a lc o h o ls in e th a n o l l i q u o r s ,
 38

c o n s is te d o f tr e a tin g th e sample to be examined w ith s u lf u r ic a c id which

produced c o lo re d p ro d u c ts . T h is r e a c tio n , in d ic a te d by Dumas, was used

by S a v a lle f o r th e ra p id e stim a tio n o f im p u r itie s in a lc o h o l (2 2 2 ). It

was used by M ohler, G ira rd and Rocques f o r th e d e term in a tio n o f h ig h e r

a lc o h o ls a f t e r th e e lim in a tio n o f aldehydes and o th e r i n t e r f e r i n g sub­

s ta n c e s . S t i l l , to d ay , i t c o n s ti tu te s th e o f f i c i a l method in France f o r

th e a n a ly s is o f f u s e l o i l .

M ohler found t h a t th e r e l a t i v e c o lo r a tio n s produced by v a rio u s

h ig h e r a lc o h o ls in c o n c e n tra tio n s o f 0 .1 # in a 50# e th a n o l-w a te r s o lu tio n

were a s fo llo w s (2 2 2 ):

Is o b u ty l a lc o h o l 10
Amyl a lc o h o ls 3
P ropyl a lc o h o l 0

The d isad v a n ta g es o f th e method a r e obvious s in c e th e amyl a lc o h o ls

a re g e n e r a lly th e p r in c ip a l c o n s titu e n t o f f u s e l o i l and p ro p y l a lc o h o l

fr e q u e n tly e x i s t s in n o tic e a b le amounts.

Rocques found t h a t by a d ju s tin g th e e th a n o l c o n te n t o f th e s o lu tio n

to 67.7# th e r a t i o o f th e c o lo ra tio n i n t e n s i t i e s between is o b u ty l a lc o h o l

and amyl a lc o h o l was r a is e d to 10:6 in s te a d o f 10:3 o b tain ed w ith 50#

e th a n o l (2 2 2 ).

S e v e ra l im p u r itie s have been found to i n t e r f e r e w ith th e method

e s p e c ia lly aldehydes and te rp e n e s . I t h as been p o in te d out t h a t th e r e ­

s u ltin g c o lo r in i n d u s t r i a l sam ples i s due l a r g e ly to th e sm all and

v a r ia b le q u a n titie s o f f u r f u r a l n a t u r a lly o c c u rrin g in th e liq u o r an d ,

hence, th e method f a i l s to f u r n is h a r e l i a b l e m easure o f th e f u s e l o i l

c o n te n t (2 4 0 ).
 39

In o rd e r to s e p a ra te th e ald eh y d es p re s e n t i n th e s p i r i t s b e fo re

conducting the d e te rm in a tio n o f f u s e l o i l , s e v e ra l p ro ced u res have been

su g g este d . M ohler tr e a te d th e s p i r i t s w ith a n i l i n e a c id p h o sp h ate;

G ira rd and Rocques used m-phenylenediamene h y d ro c h lo rid e ; w h ile S ch id ro w itz

and Kaye found phenylhydrazine p -s u lfo n a te to be more e f f e c tiv e than th e

l a t t e r (222, 2 4 0 ). These su b sta n c es form n o n - v o la tile com binations from

which the h ig h e r a lc o h o ls and th e e th a n o l p re s e n t can be r e a d ily s e p a ra te d

by d i s t i l l a t i o n . The m ost e f f e c t iv e method, however, has been found to

be t h a t o f F e lle n b e rg , which c o n s is ts o f sa p o n ify in g th e s p i r i t s in th e

p resen ce o f c a t a l y t i c s i l v e r o x id e (210, 222, 2 4 0 ). By t h i s p rocedure

th e aldehydes polym erize and th e te rp e n e s a re decomposed.

W ith th e purpose o f in c re a s in g th e s e n s i b i l i t y o f th e r e a c tio n ,

S a g lie r sugg ested th e a d d itio n o f s e v e ra l dro p s o f 0 .1 # f u r f u r a l s o lu tio n

to th e m ix tu re o f s p i r i t s and s u l f u r i c a c id (2 2 2 ). T h is a u th o r re p o rte d

th e fo llo w in g r e l a t i v e c o lo ra tio n i n t e n s i t i e s f o r th e v a rio u s h ig h e r a l ­

cohols w ith th e a d d itio n o f 10 drops o f th e f u r f u r a l s o lu tio n to s p i r i t s

c o n ta in in g 0 .1 # o f th e p a r t i c u l a r h ig h e r a lc o h o l a t 50# e th a n o l (2 2 2 ).

I s o b u ty l a lc o h o l 1 0 .0
Isoam yl a lc o h o l 4 .5
n -B u ty l a lc o h o l 1 .0
Is o p ro p y l a lc o h o l 0 .5
n -P ro p y l a lc o h o l 0

The a n a l y t i c a l p ro ced u re f o r th e M ohler-Rocques method o f f i c i a l l y

used in France i s given by K ervegant a s fo llo w s (2 2 2 ):

P lace in a 250 m i l l i l i t e r round f la s k 100 m i l l i l i t e r s o f th e s p i r i t

to be analyzed p re v io u s ly d i s t i l l e d and a d ju s te d to 50# a lc o h o l. Add 1 .0

m i l l i l i t e r s o f pu re a n i l i n e , 1 .0 m i l l i l i t e r s o f s iro p y phosphoric a c id

and b o i l g e n tly a t t o t a l r e f lu x f o r one h o u r. At th e end o f t h a t tim e ,

 40

remove th e h e a t and a llo w to c o o l. P rovide th e f la s k w ith an adequate

condenser and g ra d u a ted r e c e iv e r and d i s t i l l th e s o lu tio n u sin g s u f f i ­

c i e n t r e f r i g e r a n t to produce a condensate a t am bient te m p e ra tu re . Recover

in th e re c e iv e r e x a c tly 75 m i l l i l i t e r s o f d i s t i l l a t e which w i l l c o n ta in

th e t o t a l i t y o f th e f u s e l o i l and e th a n o l p re s e n t i n th e sam ple. The

reco v ered d i s t i l l a t e w i l l c o n ta in 67.7/6 a lc o h o l. A g ita te to re n d e r th e

s o lu tio n homogeneous. P ip e tte and mix th o ro u g h ly , in a 100 m i l l i l i t e r

f la s k , 10 m i l l i l i t e r s o f pure s u lf u r ic a c id and th e reco v ered d i s t i l l a t e

o f the sam ple. S im u ltan e o u sly p ip e tte in a n o th e r 100 m i l l i l i t e r f la s k

10 m i l l i l i t e r s o f th e s u lf u r ic a c id and 10 mil l i l i t e r s o f a sta n d a rd

s o lu tio n c o n ta in in g 0.667 grams o f is o b u ty l a lc o h o l p e r l i t e r o f e th a n o l

a t 66.2%'. P la c e th e two sto p p e re d f la s k s in a calcium c h lo rid e b a th a t

120#C f o r one h o u r. At th e end o f t h i s tim e th e i n t e n s i t i e s o f c o lo r

o b ta in e d a r e measured in a c o lo rim e te r and th e f u s e l o i l c o n te n t d e te r ­

mined from a c u rv e .

The French method i s s u b je c t to s e rio u s o b je c tio n s . One o f th e

m ost im p o rta n t i s th e la c k o f s e n s i b i l i t y o f th e method (2 2 2 ). F u rth e r,

th e s ta n d a rd o f com parison t h a t i s used c o n s is ts o f is o p ro p y l a lc o h o l

which does n o t correspond to th e norm al com position o f f u s e l o i l . S e v e ra l

a u th o rs have found r e s u l t s o f th e o rd e r o f 2 5 % -5 0 % o f th e a c tu a l f u s e l o i l

c o n te n t (2 2 2 ).

K omarowsky-Fellenberg Method:

Modern c o lo rim e tric methods o f f u s e l o i l d e te rm in a tio n u t i l i z e

th e s o - c a lle d Komarowsky r e a c tio n by which c o lo re d p ro d u c ts a re formed

through th e i n te r a c t io n o f h ig h e r a lc o h o ls w ith c y c lic aldehydes in th e

 41

p resen ce of s u l f u r i c a c id (2 2 5 ). Nimerous ch em ists have s tu d ie d e x ten ­

s iv e ly th e Komarowsky r e a c tio n (1 9 8 , 201, 202, 206, 211, 216, 226, 228,

240, 247, 256). Some o f th e ald eh y d es which have been s tu d ie d in c lu d e

s a lic y la ld e h y d e , benzaldehyde, p-dim cthylam inobenzaldebyde, f u r f u r a l ,

v e r a t r i c ald eh y d e, and v a n i l l i n (2 4 0 ). I t has been g e n e r a lly c o n sid ­

e re d , a s a r e s u l t o f th e work o f von F e lle n b e rg , t h a t th e h ig h e r a lc o h o ls

a r e converted by the a c tio n o f s u lf u r ic a c id in to u n s a tu ra te d h y d ro car­

bons, which then combine w ith th e c y c lic aldehyde to form c o lo re d

p ro d u c ts (2 1 0 ). A ccordingly, s u b sta n c e s o th e r th an a lc o h o ls which

could y ie ld u n s a tu ra te d hydrocarbons w ith s u l f u r i c a c id would i n t e r f e r e .

In c lu d e d in t h i s group a re u n s a tu ra te d hydrocarbons and t h e i r d e r iv a tiv e s ,

a ld e h y d e s, k e to n e s , a c e t a l s , and te rp e n e s , b u t n o t a c id s (2 4 0 ). The most

e f f e c t iv e method fo r th e e lim in a tio n o f i n t e r f e r i n g su b sta n c es i s th a t

o f F e lle n b e rg in which th e sample i s s a p o n ifie d w ith s i l v e r oxide a s

c a t a l y s t (210, 2 4 0 ).

As a r e s u l t of r e c e n t i n v e s t ig a t i o n s , C oles and Tournay have

p o in te d o u t th a t a p p a re n tly th e r e a c tio n mechanism i s more complex than

g e n e r a lly a cc e p ted because p e n te n e -2 , even in h ig h c o n c e n tra tio n , does

n o t produce a c o lo r w ith p-dim ethylam inobenzaldehyde on prolonged b o ilin g .

I f c o n ce n tra te d s u l f u r i c a c id i s added to t h i s m ix tu re th e c o lo r develops

o n ly when the a c id re a ch e s a d e f i n i t e c o n c e n tra tio n . He concludes th a t

th e a c id i s n e c e ssa ry f o r th e r e a c tio n i t s e l f (2 0 2 ).

The g e n e ra l a n a ly t ic a l p rocedure o f t h i s method c o n s is ts o f p r e t r e a t ­

in g th e sample to be examined f o r th e rem oval o f i n t e r f e r i n g s u b sta n c e s .

A m easured volume o f c o n c e n tra te d s u l f u r i c a c id i s th en added w h ile s w irlin g

 42

th e f la s k i n a b ath o f co ld w a ter d u rin g th e a d d itio n . A m easured amount

o f a s o lu tio n c o n ta in in g th e c y c lic ald eh y d e i s then added, w h ile s t i l l

s w ir lin g th e f la s k in th e c o ld b a th . S im u ltan e o u sly a second f la s k i s

p re p a red c o n ta in in g a s ta n d a rd f u s e l o i l s o lu tio n . Doth f la s k s a re th en

p la c e d sim u lta n eo u sly i n a b a th o f v ig o ro u s ly b o ilin g w ater f o r a d e f i n i t e

le n g th o f tim e . A fte r th e end o f t h i s p e rio d o f tim e th e sam ples a re

c o o led to a given te m p e ratu re and d e f i n i t e amounts o f s u l f u r i c a c id a re

added. The s o lu tio n s a re then read y f o r com parison i n a c o lo rim e te r o r

a sp ec tro p h o to m ete r.

As a r e s u l t o f numerous s tu d ie s o f th e m ethod, i t has been e s ta b ­

lis h e d t h a t a la r g e number o f f a c t o r s would a f f e c t th e v a lu es o b ta in e d .

The fo llo w in g fa c to r s m ust be c o n tr o lle d (2 4 0 ): (1 ) amount o f sam ple;

(2) n a tu re and amount o f re a g e n t; (3) amount o f c o n c e n tra te d s u lf u r i c

a c id ; (4) c o n c e n tra tio n o f e th y l a lc o h o l; (5) te m p e ra tu re and tim e o f

h e a tin g to develop th e c o lo r ; (6 ) amount o f d i lu e n t added a f t e r te rm i­

n a tin g th e r e a c tio n and c o n c e n tra tio n o f s u l f u r i c a c id in th e d ilu e n t

s o lu tio n . S in c e th e r e a c tio n i s stopped a f t e r a d e f i n i t e le n g th o f tim e

by c h i l l i n g th e m ix tu re and d i l u t i n g , i t i s , th e r e f o r e , n e c e s sa ry to ru n

sta n d a rd s and samples to g e th e r u n d er e x a c tly s im il a r c o n d itio n s . When a

sp ectro p h o to m eter i s used f o r com paring th e c o lo r d ev elo p ed , th e wave

le n g th o f th e l i g h t so u rce and th e s l i t opening o f th e in stru m e n t a r e

a d d itio n a l f a c to r s to be c o n tr o lle d . In s p i t e o f th e numerous f a c to r s

which should be c a r e f u l ly c o n tr o lle d th e method i s cap ab le o f g iv in g

a c c u r a te , re p ro d u c ib le r e s u l t s and h ig h s e n s i t i v i t y . B e sid e s, i t r e ­

q u ir e s s h o r te r tim es th a n any o th e r m ethod.

 43

Penniman, Sm ith and Lawshc have su g g ested th e fo llo w in g a n a ly t ic a l

procedure a s a r e s u l t o f in te n s iv e in v e s tig a tio n s (2 4 0 ):

1. P re p a ra tio n o f th e sample: P la c e 75 c c . o f sample in a 500 c c.

round bottom ed f l a s k . Add 0 .5 gram o f s i l v e r s u l f a t e and 1 .0 c c . o f

(1+1) s u lf u r ic a c id , and make th e t o t a l volume up to 110 c c . R eflux

g e n tly f o r 15 m in u te s. Make th e s o lu tio n a lk a l in e w ith 5 c c . o f a

(1 + 1) sodium hydroxide s o lu tio n and r e f lu x f o r 30 m in u te s. Bumping

can be p rev en ted by th e a d d itio n o f sm all q u a n titie s o f g ra n u la te d z in c .

I f foaming o c c u rs, t h i s can be reduced by adding 15 grams o f sodium

c h lo r id e . A fte r th e s a p o n if ic a tio n th e sample i s d i s t i l l e d , 75 c c . o f

d i s t i l l a t e being c o lle c te d . This d i s t i l l a t e c o n ta in s a l l o f th e h ig h e r

a lc o h o ls o r ig i n a lly p re s e n t in th e sam ple. The c o n c e n tra tio n has been

reduced to o n e - th ir d t h a t o f the sam ple. T his re d u c tio n in c o n c e n tra tio n

i s made n e c e s sa ry by th e extrem e s e n s i t i v i t y o f th e c o lo r re a g e n ts .

2. P rocedure f o r th e c o lo r r e a c tio n w ith p-D im ethylam inobenzal-

dehyde o r S a lic y la ld e h y d e : P lace 200 c c . o f d i s t i l l a t e , o b ta in e d a s

d ir e c te d above, in a 125 c c . F lo ren ce f l a s k . Add 20.0 c c . o f c o n c e n tra te d

s u l f u r i c a c id , s w irlin g th e f la s k in a b a th o f c o ld w ater d u rin g th e ad ­

d itio n . Then add 2 .0 0 c c . o f a s o lu tio n o f th e re a g e n t in 95% e th y l

a lc o h o l (10 mg. p e r c c . ) , a g a in s w irlin g th e f la s k in th e c o ld b a th .

P rep a re a s im ila r f la s k c o n ta in in g 2.00 c c . o f a s ta n d a rd f u s e l o i l

s o lu tio n , a c id , and re a g e n t.

P la c e th e f la s k s sim u lta n eo u sly in a b a th o f v ig o ro u s ly b o ilin g

w a te r. A fte r 20 m inutes t r a n s f e r th e f la s k s to th e co ld b a th . When c o o l,

add 25 c c . o f (1 + 1) s u l f u r i c a c id and mix th o ro u g h ly by s w ir lin g . The

 44

s o lu tio n s a re then ready f o r com parison in th e c o lo rim e te r.

C oles and Tourney have in tro d u c e d s l i g h t m o d ific a tio n s to Penniman*s

method coupled w ith th e u se o f a sp ec tro p h o to m ete r. I t i s claim ed t h a t

th e y in c re a s e th e s e n s i t i v i t y o f th e method ab o u t one hundred tim es and

speed up th e d e te rm in a tio n (2 0 2 ).

A t th e Rum P i l o t P la n t o f th e A g r ic u ltu r a l Experim ent S ta tio n o f

th e U n iv e rsity o f P u erto R ico, a m o d ified procedure has been developed

f o r th e c o lo r r e a c tio n b ased on th e above m entioned m ethods. B enzalde-

hyd'e i s used as re a g e n t and th e c o lo r developed i s compared in a 9101-A

Beckman Q uarts S p ectro p h o to m eter, Model DU, P h o to e le c tr ic , range 320-1000

m illim ic ro n s . The method i s a p p lie d to samples o f d i s t i l l a t e s o f f e r ­

mented m o la sse s. The a n a l y t i c a l p ro ced u re i s a s fo llo w s:

P ip e tte 2 .0 m l. o f th e sample in to a 125 m l. Erlenm cyer f la s k and

add 20.0 m l. o f c o n c e n tra te d s u l f u r i c a c id w h ile s w irlin g in an ic e -w a te r

b a th . Add 2 .0 m l. o f a s o lu tio n o f s a ly c ila ld e h y d e (10 mg. o f c h em ica lly

pu re re a g e n t p e r m i l l i l i t e r o f 95% a lc o h o l, U .S .P .), a g a in s w irlin g in

th e ic e -w a te r b a th . T re a t sim u lta n e o u sly and in i d e n t i c a l manner a f la s k

c o n ta in in g a sta n d a rd s o lu tio n o f f u s e l o i l . P la c e th e f la s k s f o r 20

m inutes in a b a th o f w ater b o ilin g v ig o ro u s ly . A t th e end o f t h i s tim e

tr a n s f e r th e f la s k s to th e ic e - w a te r b a th . A fte r c o o lin g add 25 m l. o f

a (1 + 1) s o lu tio n o f s u l f u r i c a c id and mix th o ro u g h ly by g e n tle s w ir lin g .

Read th e p e r c en t o f tra n s m itte d l i g h t a s fo llo w s:

a. I f th e f u s e l o i l c o n te n t o f th e sample i s between 0-90 mg. p e r 100 m l.,

use a s s ta n d a rd a s o lu tio n o f pure a lc o h o l a t 86®P, s e t th e sp e c tro p h o to ­

m eter a t a wave le n g th o f 560 m u., a s l i t opening o f 0 .0 2 5 mm., and u se

th e phototube s e n s itiv e to u l t r a v i o l e t l i g h t .
 45

b. I f th e f u s e l o i l c o n te n t o f th e sample i s between 90-180 mg. p e r 100

m l., u se a sta n d a rd f u s e l o i l s o lu tio n o f 90 mg. p e r 100 m l., s e t th e

sp ectro p h o to m eter a t a wave le n g th o f -600 mu., a s l i t opening o f 0 .2 4 mm.,

and u se th e phototube s e n s itiv e to i n f r a r e d l i g h t .

The p e rc e n t o f tr a n s m itte d l i g h t i s co n v erted in to f u s e l o i l con­

c e n tr a tio n s by use o f c a l i b r a t i o n c u rv es p re p a red u sin g a s e r i e s o f

s ta n d a rd f u s e l o i l s o lu tio n s .

The f u s e l o i l s ta n d a rd used c o n ta in s 60.0# isoam yl a lc o h o l, 7.0#

n - b u ty l a lc o h o l, 5.0# n-am yl a lc o h o l, 1 2 .0 # is o b u ty l a lc o h o l and 1 6.0#

n -p ro p y l.

The c o lo rim e tric methods based on Komorowsky's re a c tio n p o ssesses

in h e re n t advantages which could be summarised a s fo llo w s (2 4 0 )s

1. Much g r e a te r speed o f d e te rm in a tio n .

2. The s e n s i t i v i t y i s f a r g r e a te r than any o th e r method.

3. By v ir t u e o f i t s s e n s i t i v i t y i t i s a p p lic a b le to lo w -proof
beverages such a s wines and b e e r s , in which f u s e l o i l
was n o t fo rm e rly d eterm in ed .

4. Two o r more c o lo r re a g e n ts can be used in th e case o f a b ­

norm al o r un u su al sam ples.

5. The method y ie ld s r e s u l t s o f th e c o r r e c t o rd e r o f m agnitude.

6. The accu racy o f th e r e s u l t s can be g r e a tly in c re a s e d by u sin g

a s s ta n d a rd a s y n th e tic f u s e l o i l o f s im ila r com position,
o r a c t u a l l y th e same f u s e l o i l a s t h a t c o n ta in e d in th e
unknown sam ple.

The method p o s se ss e s th e d isa d v a n ta g e t h a t when i n t e r f e r i n g sub­

s ta n c e s a r e p r e s e n t, a rig o ro u s p re tre a tm e n t should be g iv en to e lim in a te

them.
 46

M iscellaneous Methods o f A n a ly sis

A r a t h e r la r g e number o f a n a l y t i c a l methods have been su g g ested

from tim e t o tim e f o r the q u a n t ita tiv e and q u a l i t a t i v e d e te c tio n o f f u s e l

o i l in s p i r i t o u s liq u id s (1 8 7 , 191, 193, 200, 204, 208, 217, 221, 231,

237, 238, 241, 249, 250, 251, 252, 257, 258, 259, 2 6 4 ). T h e ir u s e , however,

has n o t been g e n e ra lis e d to any c o n sid e ra b le e x te n t.

A method which i s u sed in some co m nercial d i s t i l l e r i e s fo r rough

p la n t c o n tr o l i s t h a t o f s a l t i n g o u t th e h ig h e r a lc o h o ls w ith p otassium

c a rb o n a te . I t fu rn is h e s r e s u l t s which in d ic a te th e o rd e r o f m agnitude

o f the f u s e l o i l c o n c e n tra tio n . The method i s a p p lie d to samples o f i n ­

te rm ed iate p la te s o f the d i s t i l l a t i o n columns to determ ine th e p la te o f

peak f u s e l o i l c o n c e n tra tio n and th e approxim ate c o n te n t o f h ig h e r a lc o h o ls

in th a t p l a t e . A procedure which h a s been u sed c o n s is ts o f d il u ti n g th e

sample w ith w ater to an a p p a re n t a lc o h o lic s tr e n g th o f ab o u t 25°P by th e

hydrom eter m ethod. A m easured amount o f th e d i l u t e sample i s p la ce d in

a long g rad u ated c y lin d e r and s a tu r a te d w ith p o tassiu m c a rb o n a te . The

h e ig h t o f th e upper la y e r c o n ta in in g th e f u s e l o i l i s m easured in th e

c y lin d e r and th e p e rc e n t o f f u s e l o i l i s determ ined by d iv id in g t h i s

volume by th e o r ig i n a l volume of th e sam ple. A lthough th e upper la y e r

c o n ta in s su b sta n c e s o th e r th a n h ig h e r a lc o h o ls , th e e r r o r i s p a r t i a l l y

compensated by th e f a c t t h a t some f u s e l o i l rem ains in s o lu tio n in th e

low er l a y e r . I t i s claim ed t h a t w ith c a r e f u l m an ip u latio n s a t i s f a c t o r y

r e s u l t s a r e o b ta in e d fo r some c o n tro l p u rp o se s.

M cIntosh g iv e s a method f o r th e q u a l i t a t i v e d e te c tio n o f f u s e l

o i l in s p ir ito u s liq u id s which c o n s is ts o f a g i t a t i n g 5 c c . o f th e sample

w ith 6 c c . o f w a ter and 15 to 20 d ro p s o f ch lo ro fo rm . The chloroform

 47

s o lu tio n i s d ecanted and e v ap o rated , le a v in g th e f u s e l o i l . I t i s claim ed

t h a t ab o u t 0.05/S may be d e te c te d in t h i s manner (2 3 7 ).

The a c e ty la tio n method su g g ested by S ch ick tan z and E tien n e i s b ased

upon th e e x tra c tio n o f th e h ig h e r a lc o h o ls by su c c e ssiv e p o rtio n s o f c a r ­

bon te tr a c h l o r id e a s in th e A.O.A.C. p ro ced u re (249, 2 5 1 ). The w ater and

e th a n o l a re e lim in a te d from th e e x tr a c t by f r a c t i o n a l d i s t i l l a t i o n . The

h ig h e r a lc o h o ls e x tr a c te d a re determ ined by e s t e r i f i c a t i o n w ith a c e ty l

c h lo r id e . A fte r th e re a c tio n i s com pleted, th e excess a c e ty l c h lo rid e i s

decomposed and t i t r a t e d . The d if f e r e n c e in t i t e r between th e sample and

a blank a llo w s c a lc u la tio n o f th e amount o f a c e t y l c h lo rid e used in th e

e s t e r i f i c a t i o n r e a c tio n and su b se q u e n tly th e amount o f h ig h e r a lc o h o ls

p r e s e n t. The e s t e r i f i c a t i o n r e a c tio n o f th e h ig h e r a lc o h o ls w ith a c e ty l

c h lo r id e , in o rd e r to m easure q u a n ti ta tiv e ly th e fu s e l o i l p re s e n t,

m erely s u b s tit u te s th e o x id a tio n s te p in th e A.O.A.C. m ethod. I t is

p o in te d out by th e a u th o rs t h a t any a lc o h o l below b u ty l a lc o h o l w il l

be excluded from th e v a lu e s o b ta in e d (2 4 9 ). I t has been found e x p e ri­

m e n ta lly t h a t in most c a se s th e method g iv e s even low er v a lu e s th an th e

A.O.A.C. procedure (2 5 1 ).
 CHAPTER IV

EFFECT OF THE PRESENCE OF DIFFERENT CONCENTRATIONS OF FUSEL OIL

ON THE DETERMINATION OF ALCOHOL BY PICNOMETER,
REFRACTOMETER AND HYDROMETER

D uring th e course o f o p e ra tio n s in a commercial d i s t i l l e r y , i t

i s fr e q u e n tly n e c e s sa ry to determ ine th e e th y l a lc o h o l c o n te n t o f samples

from in te rm e d ia te p la te s o f th e d i s t i l l a t i o n columns which c o n ta in r e l a ­

ti v e l y la r g e amounts o f f u s e l o i l and sm a lle r amounts o f o th e r im p u r itie s .

I t i s d e s ir a b le to make t h i s d e te rm in a tio n w ith o u t r e s o r tin g to tim e con­

suming and com p licated methods o f a n a ly s is which a r e n o t r e g u la r ly

u t i l i s e d in d a ily p ro c e ss c o n tr o l. D eterm ination o f th e a lc o h o l b e in g

removed from th e column w ith th e f u s e l o i l s id e stream and e s ta b lis h in g

th e r e l a t i o n between a lc o h o l and f u s e l o i l com positions alo n g th e column

a r e examples o f th i s n eed .

.The methods o f a n a ly s is most commonly employed in d i s t i l l e r y

p r a c tic e f o r th e d e te rm in a tio n o f a lc o h o l a re th o se o f Picnom eter, R e-

fra c to m e te r and Hydrom eter. The l a t t e r i s by f a r th e m ost used . The

methods of P icnom eter and Hydrometer a r e based on th e s p e c if ic g r a v ity

o f pure a lc o h o l-w a te r s o lu tio n s a t re fe re n c e te m p e ratu res w hile th e r e -

fra c to m e te r method i s based on th e in d ex o f r e f r a c t io n o f pure s o lu tio n s

a ls o a t re fe re n c e te m p e ra tu re s . O bviously, th e p resen ce o f su b sta n c es

o th e r than a lc o h o l and w ater w i l l a l t e r th e p h y s ic a l p r o p e r tie s o f th e

s o lu tio n , in tro d u c in g e r r o r s in th e r e s u l t s o b ta in e d w ith any o f th e

above a n a ly t ic a l m ethods. F o r tu n a te ly , th e amounts o f im p u ritie s i n th e

raw p ro d u c ts o f th e f i r s t columns o f th e d i s t i l l a t i o n u n i t and e s p e c ia lly

in th e fin is h e d p ro d u c t from th e l a s t column a re so low t h a t th e e r r o r

48
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in tro d u c e d i s u s u a lly n e g lig ib le and f a l l s w ell w ith in th e p r e c is io n

l i m i t s o f th e v a rio u s a n a l y t i c a l m ethods. In th e case o f aged s p i r i t s

and fin is h e d beverage p ro d u c ts , th e e f f e c t o f im p u r itie s i s m inim ized

by d i s t i l l i n g th e sample in th e la b o r a to r y fo llo w in g e s ta b lis h e d p ro c e ­

d u res b e fo re m easuring i t s s p e c if ic g r a v ity o r r e f r a c t i v e in d e x . When

d e a lin g w ith samples from in te rm e d ia te p la te s o f th e r e c tif y i n g column,

in which th e a lc o h o l c o n te n t i s r e l a t i v e l y low w h ile th e f u s e l o i l con­

t e n t could be 10 to 20$ and in some c a se s h ig h e r, a sim ple d i s t i l l a t i o n

o f the sample would be i n e f f e c t i v e . Even c a r e f u l f r a c tio n a tio n o f th e

sample would n o t be s a t i s f a c t o r y s in c e a s u b s t a n t ia l p a r t o f the f u s e l

o i l would p ass in to th e overhead p ro d u ct i f a l l o f th e e th y l a lc o h o l

p re s e n t in th e sample i s to be reco v ered in th e d i s t i l l a t e . The d i f ­

f i c u l t i e s encountered in th e s e p a ra tio n o f f u s e l o il- a lc o h o l- w a te r by

d i s t i l l a t i o n w’i l l be d is c u s s e d in d e t a i l in su b seq u en t c h a p te rs . With

th e purpose o f p ro v id in g a method f o r c o r r e c tin g f o r th e e r r o r in tro d u c e d

by th e p re sen c e o f d i f f e r e n t c o n c e n tra tio n s o f f u s e l o i l a t d i f f e r e n t

a lc o h o lic s tr e n g th , a stu d y was made under th e d ir e c t io n o f th e w r ite r

a t th e Rum P i l o t P la n t o f th e A g r ic u ltu r a l Experim ent S ta tio n o f th e

U n iv e rs ity o f P u e rto R ico. S o lu tio n s o f known a lc o h o lic and f u s e l o i l

c o n te n ts were p re p a red and an aly zed f o r a p p a re n t a lc o h o lic c o n te n t by

th e methods o f P icn o m eter, Hydrometer and Ihm ersion R e fra c to m e te r. S o lu ­

tio n s c o n ta in in g 200, 500, 1000, 2000, 4000, 7000, 10,000, 15,000, 20,000

and 30,000 m illig ra m s o f f u s e l o i l a s amyl* a lc o h o l p e r 100 m l. o f sam ple,

a t 10$, 20$, 30$, 40$, 50$, 60$, 70$, 80$ and 90$ a lc o h o l by volume a t

60°F were p re p a re d .
 50

A bsolute a lc o h o l, re a g e n t g ra d e , was used a s th e source o f e th a n o l.

T h is a lc o h o l was an aly zed in t r i p l i c a t e by th e Picnom eter method and found

to c o n ta in 99.25# a lc o h o l by volume a t 60°F.

Commercial f u s e l o i l from a P u e rto R ican d i s t i l l e r y was used as

th e so u rce o f f u s e l o i l . The o i l had been c o n c e n tra te d by e x tr a c tio n

w ith w ater a t i t s o r ig in p la n t and co n tain ed about 60# f u s e l o i l . It

was f u r th e r e x tra c te d tw ice w ith o n e -h a lf i t s own volume each tim e o f

w a ter s a tu r a te d w ith commercial ta b le s a l t . A fte r thorough m ixing, th e

m ix tu re was allow ed to s e p a ra te d u rin g s e v e ra l hours and th e o i l y upper

la y e r d e ca n te d . The o i l was th en f r a c t i o n a l l y d i s t i l l e d a t atm ospheric

p re s s u re in a 1* g la s s column, s ix f e e t in h e ig h t, packed w ith g la s s

R aschig r in g s . P o rtio n s o f 1500 m l. were p la ce d in a 2 .5 l i t e r fla s k

and h e a t su p p lie d through a c o n s ta n t tem p eratu re m in e ra l o i l b a th . The

te m p e ratu re o f th e o i l b a th was re g u la te d to m ain tain an overhead r a t e

o f 30 m l. p e r hour a t a r e f lu x r a t i o o f 1 0 :1 . The r e f lu x r a t i o was a u to ­

m a tic a lly re g u la te d by an e l e c t r i c tim e r and a m a g n e tic a lly o p e ra te d flow

d iv id e r in th e g la s s column head. The column \ms m a in tain ed a t t o t a l r e ­

f lu x f o r a p e rio d o f two ho u rs b e fo re rem oval o f condensate was commenced.

A f i r s t f r a c tio n o f 150 m l., b o ilin g between 83#C and 87°C was

d is c a rd e d to in s u re com plete removal o f any e th y l a lc o h o l p r e s e n t. In

so d oing, w ater and some o f th e low er homologues o f th e h ig h e r a lc o h o ls

were removed.

A second f r a c tio n o f 1150 m l., b o ilin g between 87®C and 132°C,

was c o lle c te d a s p u r if ie d f u s e l o i l .

A t h i r d f r a c t i o n , c o n s is tin g ox the re s id u e rem aining i n th e f la s k

 51

was s to re d a p a r t. A fte r having enough r e s id u e , 1500 m l. were p laced

in th e f la s k and f r a c tio n a te d a s b efo re ex cep t th a t no f i r s t f r a c tio n

was d is c a rd e d . The re s id u e was p r a c t i c a l l y ev ap o rated to d ry n ess a t

136°C. The product o f t h i s d i s t i l l a t i o n was mixed w ith th e f u s e l o i l

f r a c tio n c o lle c te d in th e f i r s t f r a c tio n a tio n . The o i l m ix tu re was

analyzed in t r i p l i c a t e f o r s p e c if ic g r a v ity and f u s e l o i l c o n te n t

g iv in g v a lu e s o f S p e c if ic G ra v ity : 0 . 8 2 1 2 ~ ~ and 86,665 mgs. o f f u s e l

o i l as amyl a lc o h o l p e r 100 m l. The a p p a re n t d iscrep a n c y o f i t s con­

ta in in g over 100# f u s e l o i l by w eight i s due to th e f a c t t h a t th e f u s e l

o i l c o n ten t i s ex p ressed a s amyl a lco h o l w hile i t a c tu a lly c o n s is ts o f

a m ixture o f a lc o h o ls c o n ta in in g a p p re c ia b le p o rtio n s o f low er m olecular

w eight homologues. These f ig u r e s a re in d i c a tiv e o f th e high degree o f

p u r ity o f th e f u s e l o i l o b ta in e d .

The samples were p rep ared by p ip e ttin g p re v io u s ly c a lc u la te d

amounts o f p u r if ie d f u s e l o i l and a b s o lu te a lc o h o l in to 250 m l., c a l i ­

b ra te d , v o lu m etric f la s k s and com pleting to volume w ith d i s t i l l e d w a te r.

60 m l. g la s s picnom eters pro v id ed w ith in d iv id u a l therm om eter-caps were

u tiliz e d . The c a li b r a t io n o f th e hydrom eters used was checked w ith pure

w a te r-a lc o h o l s o lu tio n s o f known com p o sitio n . A Bausch and Lomb Immersion

R efra cto m e te r w ith a Type nAn d ip p in g p rism , range nD 1.32539 - nD 1.36640

was u t i l i z e d fo r m easuring th e in d ex o f r e f r a c t i o n o f th e sam ples.

The a n a ly t ic a l r e s u l t s o f t h i s work a re p re se n te d in T able I , in

th e Appendix. From them i t can be observed th a t numerous sam ples were

d is c a rd e d due to th e p resen ce o f two l i q u i d phase l a y e r s . The R efrac­

tom eter method was employed w ith samples o f an a p p aren t a lc o h o l c o n te n t

i
ii
 52

up to 100“P (50# a lc o h o l by volume) a t 60°F s in c e t h a t i s th e upper

l i m i t o f th e s c a le of th e in s tru m e n t. D ilu tio n s were n o t made sin c e

th ey would have been e q u iv a le n t to sam ples c o n ta in in g low er c o n c e n tra ­

tio n s o f a lc o h o l and f u s e l o i l . The r e s u l t s th u s o b ta in e d would have

been only a p p lic a b le t o i d e n t i c a l d il u tio n s in o rd e r to a cc o u n t f o r

c o n c e n tra tio n and c o n tra c tio n e f f e c t s .

The r e s u l t s show t h a t th e d if f e r e n c e s between a p p a re n t and tr u e

a lc o h o l c o n te n t o b ta in e d by th e Hydrometer and P icnom eter methods a re

alm o st i d e n t i c a l through th e range o f a lc o h o lic s tr e n g th and f u s e l o i l

c o n te n t s tu d ie d . T his e x c e lle n t agreem ent i s to be ex p ected sin c e b o th

methods a re based on th e s p e c if ic g r a v ity o f th e sam ple. The d iff e r e n c e

between a p p a re n t and tr u e a lc o h o l c o n te n t by b o th methods v a r ie s w ith

th e a lc o h o lic s tr e n g th a t any given f u s e l o i l c o n c e n tra tio n . At low er

a lc o h o l c o n te n ts th e e r r o r in c re a s e s a s th e a lc o h o lic s tr e n g th in c re a s e s

and a f t e r p a ss in g th ro u g h a maximum i t d e c re a se s w ith f u r th e r in c re a s e

in a lc o h o l c o n te n t. W ith th e h ig h e r f u s e l o i l c o n c e n tra tio n s th e m axi­

mum i s n o t shown s in c e a t th e low er a lc o h o lic s tr e n g th p a r t i a l s o l u b i l i t y

e x i s t s and two l i q u i d phases a re formed. This v a r ia tio n i s due to th e

com bination o f c o n tr a c tio n and c o n c e n tra tio n e f f e c t s . The e r r o r de­

c re a s e s a s th e a lc o h o l-w a tc r c o n te n t i s such t h a t i t s s p e c if ic g r a v ity

approaches t h a t o f th e f u s e l o i l . I f f u s e l o i l w ith a s p e c if ic g r a v ity

o f 0 .8 2 1 2 ~ ~ i s added to an a lc o h o l-w a te r s o lu tio n o f t h a t same s p e c if ic

25 C
g r a v ity , which co rresp o n d s to an a lc o h o lic s tre n g th o f ap p ro x im ately

185°P, no e r r o r would be in tro d u c e d in th e d e te rm in a tio n o f a lc o h o l by

th e methods o f picnom eter and h y d ro m eters, should th e c o n tra c tio n e f f e c t s

be n e g lig ib le . A cco rd in g ly , a t any g iv en f u s e l o i l c o n c e n tra tio n , th e

e r r o r would ten d to d e crea se a s th e a lc o h o l c o n te n t i s in c re a s e d . How­

e v e r, th e r e s u l t s o b ta in e d in d ic a te t h a t a t th e low er a lc o h o lic c o n te n t

t h i s e f f e c t i s more than o f f s e t p ro b ab ly by an expansion e f f e c t and th e

e r r o r in c re a s e s w ith in c re a s e d a lc o h o l c o n te n t up to a maximum which d e­

pends on th e f u s e l o i l c o n te n t. A fte r t h i s maximum th e e r r o r d e crea se s

w ith in c re a s e d a lc o h o lic s tr e n g th .

The ex p erim en tal r e s u l t s o b ta in e d by th e Picnom eter method have

been p lo tte d in F ig u re 1 . T his graph a llo w s ra p id d e te rm in a tio n o f

th e c o rre c tio n to be in tro d u c e d i f th e f u s e l o i l c o n te n t and th e a p p aren t

p ro o f o f th e sample a re known. The r e s u l t s in d ic a te t h a t a t any tru e

a lc o h o lic s tre n g th th e e r r o r produced i s d i r e c t l y p ro p o rtio n a l to the

f u s e l o i l c o n te n t. This f a c t a llo w s d i r e c t in t e r p o la tio n between th e

l i n e s through e x p erim en tal p o in ts o f v a rio u s f u s e l o i l c o n c e n tra tio n s .

S in c e , in F ig u re 1 , A pparent P ro o f a s a b s c is s a has been p lo tte d v ersu s

(A pparent P roof-T rue P roof) as o r d in a te , th e p o in ts o f c o n s ta n t tru e

a lc o h o l c o n te n t f a l l on a s t r a i g h t l i n e whose slo p e i s 1 .0 when equal

s c a le s a re used in th e a b s c is s a and in th e o r d in a te . In our case th e

o r d in a te s c a le i s tw ice a s la r g e a s th e a b s c is s a s c a le an d , th e r e f o r e ,

th e s lo p e s o f the fam ily o f l i n e s o f fix e d tr u e a lc o h o lic c o n te n t have

a slo p e o f 2. By in te r p o la tin g alo n g th e s e li n e s between d i f f e r e n t f u s e l

o i l c o n te n ts , l i n e s have been drawn in F ig u re 1 a t c o n c e n tra tio n i n t e r ­

v a ls o f 1000 mgs. o f f u s e l o i l a s amyl a lc o h o l p e r 100 m l. o f sam ple.

The f u s e l o i l c o n te n t l i n e s can be e x tra p o la te d , i f n e c e s sa ry ,

to co v er v a lu e s o f a p p a re n t a lc o h o l o u ts id e th e range covered by th e
ex p erim en tal v a lu e s p lo tte d . I t i s b e lie v e d th a t tr u e a lc o h o lic s tre n g th s

can be determ ined w ith th e a id o f F ig u re 1 w ith in an a ccu racy o f 0 ,5 to

1 ,0 % a lc o h o l by volume a t 60°F. A l a r g e r s iz e p lo t would improve th e

a c c u ra c y . F ig u re 1 can be used f o r d eterm in in g c o rre c tio n v a lu e s fo r

bo th th e Picnom ctcr and th e Hydrometer methods s in c e , a s was s ta t e d

above, th e e x p erim en tal v a lu e s o b ta in e d by both methods fo r th e d e v ia ­

tio n s caused by th e p resen ce o f d i f f e r e n t c o n c e n tra tio n s o f fu s e l o i l

a re in e x c e lle n t agreem ent.

The e x p erim en tal r e s u l t s o b ta in e d by th e R efracto m eter method

a re p re se n te d g r a p h ic a lly in F ig u re 2 . I t can be observed t h a t w ith

t h i s method th e d e v ia tio n s produced by a given c o n c e n tra tio n o f f u s e l

o i l a t any giv en tr u e a lc o h o l c o n te n t a re l a r g e r than th o se produced by

th e Picnom eter and Hydrometer m ethods. In c o n tr a s t w ith th e o th e r m ethods,

th e e r r o r in tro d u c e d by a given c o n c e n tra tio n o f f u s e l o i l d e c re a se s con­

tin u o u s ly w ith in c re a s in g a lc o h o l c o n te n t. The l i n e co rresp o n d in g to

a f u s e l o i l c o n c e n tra tio n o f 4,000 mgs. o f amyl a lc o h o l p e r 100 m l. o f

sample i s an ex ce p tio n showing an in c re a s e w ith in c re a s in g a lc o h o l con­

te n t. The r e s u l t s in d ic a te t h a t th e same l i n e a r r e l a t i o n does n o t e x i s t

between th e e r r o r in tro d u c e d and th e f u s e l o i l c o n te n t a t a given tr u e

a lc o h o l c o n te n t as was found w ith th e Picnom eter and Hydrometer m ethods.

Not enough d a ta i s a v a ila b le f o r p l o t t i n g l i n e s co rresp o n d in g to f u s e l

o i l c o n c e n tra tio n s over 4,000 mgs. p e r 100 m l. Most o f th e samples p re ­

p ared a t th e h ig h e r f u s e l o i l c o n c e n tra tio n f e l l o u ts id e th e maximum

s c a le re a d in g o f th e in s tru m e n t. In g e n e ra l, more e r r a t i c r e s u l t s were

o b ta in e d w ith t h i s m ethod. T h is f a c t , p lu s i t s r a t h e r s h o rt range o f

5555555555555555555555555555555555555555555555555555JH55

MI L L I M E T E R
p oi nt e d
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a p p lic a tio n , makes i t l e s s u s e f u l a s compared w ith th e o th e r m ethods.

F u sel o i l c o n c e n tra tio n s up to 200 mgs. o f f u s e l o i l p e r 100 m l.

o f sample in tro d u c e n e g lig ib le e r r o r s a t any t r u e a lc o h o lic s tr e n g th

w ith th e th r e e a n a l y t i c a l methods s tu d ie d .
 CHAPTER V

SEPARATION AND PURIFICATION OF FUSEL OIL DURING

THE DISTILLATION PHASE OF THE PROCESS OF MANUFACTURE

O b je c tiv e s o f th e D i s t i l l a t i o n P ro cess

D i s t i l l a t i o n o f ferm ented mashes i s one o f th e m ost im p o rtan t

s ta g e s in th e p ro c e ss o f m anufacture o f e th y l a lc o h o l by ferm en tatio n

o f s u b s tr a te s . As was in d ic a te d in C hapter I , th e ferm ented mash con­

t a i n s m inute q u a n titie s o f a v a r ie ty o f su b sta n c e s i n s o lu tio n , such a s

in o rg a n ic s a l t s and a c id s , g ly c e r o l, a lc o h o ls , a ld eh y d e s, k e to n e s , e s t e r s ,

o rg a n ic a c id s , e s s e n t i a l o i l s and g a s e s , such a s carbon d io x id e and hydro­

gen s u l f i d e . In a d d itio n , th e mash c o n ta in s s o lid im p u r itie s , c o n s is tin g

in i t s g r e a te r p a r t o f n itro g e n compounds such a s y e a s t c e l l s , album inoids

and p c c tic su b sta n c es which would produce th erm al decom position p ro d u cts

o f v o l a t i l e n a tu re when exposed to the te m p e ratu res p re v a ilin g i n th e

d i s t i l l a t i o n column.

The o b je c tiv e o f th e d i s t i l l a t i o n p ro c e ss in th e m anufacture o f

i n d u s t r i a l a lc o h o ls i s , b e s id e s re c o v e rin g th e e th y l a lc o h o l p re s e n t in

th e ferm ented mash, th e e lim in a tio n o f im p u r itie s to th e h ig h e s t p o s sib le

e x te n t so t h a t c o n c e n tra tio n s o f th e l a t t e r in th e f i n a l p ro d u c t does

n o t exceed e s ta b lis h e d l i m i t s . The n a tu re o f m ost o f th e s e im p u ritie s

i s such t h a t t h e i r p re sen c e in th e f i n a l d i s t i l l a t e , even in ex trem ely

low c o n c e n tra tio n s , i s s tro n g ly evidenced in th e odor and fla v o r o f th e

p ro d u c t.

In th e case o f a lc o h o lic b e v erag e s, i t i s d e s ir a b le to r e t a i n in

th e f i n a l d i s t i l l a t e some o f th e se s u b sta n c e s , such a s e s t e r s and a c id s ,

s in c e t h e i r p resen ce enhances th e q u a li ty and th e c h a r a c te r o f th e p roduct

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w hile th e p re sen c e o f o th e rs d e tr a c ts from i t s t a s t e and aroma. The

d i s t i l l a t i o n o f b e v erag e s, th u s , becomes a p ro cess o f s e le c tiv e s e p a ra ­

tio n whose o b je c tiv e i s th e s e p a ra tio n from th e ferm ented mash o f th e

e th y l a lc o h o l to g e th e r w ith some w a ter and th o se d e s ir a b le co n g en eric

bodies which a r e o f utm ost im portance s in c e i t i s t h e i r c h a r a c t e r i s t i c

body, aroma and t a s t e t h a t d i f f e r e n t i a t e a lc o h o lic b everages from i n ­

d u s t r i a l a lc o h o l (2 6 9 ).

The n o n v o la tile s a l t s and th e suspended im p u r itie s p re s e n t in th e

ferm ented mash can be r e a d ily removed by d i s t i l l a t i o n . However, th e

s e p a ra tio n o f th e l a t t e r by c e n tr ifu g in g p r i o r to fe e d in g th e mash to

the d i s t i l l a t i o n columns i s a most d e s ir a b le p r a c t i c e . I t has been

p o in te d o u t by A rroyo t h a t 75% o f th e fo u l odor o r ra n k in e ss which

u s u a lly accom panies f r e s h ly d i s t i l l e d s p i r i t s i s due to th e decomposi­

tio n by th e a c tio n o f h e a t o f th e n itro g e n o u s suspended im p u ritie s

p re s e n t in th e ferm ented mash (2 7 0 ). At l e a s t some o f the p ro d u c ts o f

decom position a r e h ig h ly v o l a t i l e p a ss in g over w ith th e main p ro d u c t and

even when u t i l i z i n g e la b o r a te and e f f i c i e n t equipm ent, t h e i r com plete

removal i s very d i f f i c u l t .

The v o l a t i l e im p u r itie s p re s e n t in th e ferm ented mash v a ry con­

s id e r a b ly in v o l a t i l i t y m ost o f them b ein g l e s s v o l a t i l e than e th y l

a lc o h o l, th e e x c e p tio n s c o n s is tin g m o stly o f some e s t e r s , ald eh y d es and

a c id s . T h e ir rem oval i s ach iev ed by th e use o f ad eq u ate r e c ti f y in g

columns. The p re sen c e o f su b sta n c es having r e l a t i v e v o l a t i l i t i e s v e ry

c lo se t o 1 .0 r e f e r r e d to e th y l a lc o h o l, and p o s s ib ly th e fo rm atio n o f

a z e o tro p ic m ix tu re s , makes th e ta s k o f co m p letely p u rify in g e th y l a lc o h o l

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by d i s t i l l a t i o n a d i f f i c u l t one. In th e case o f b ev erag es, th e s e le c tiv e

s e p a ra tio n o f d e trim e n ta l im p u r itie s , w h ile r e ta in in g th o se which a re de­

s i r a b l e , makes th e p ro c e ss even more complex.

The rem oval d u rin g d i s t i l l a t i o n o f f u s e l o i l , which e s s e n t i a l l y

c o n s is ts o f a lc o h o ls h ig h e r in m o le c u lar w eight th a n e th y l, i s o f g r e a t

im portance s in c e , due to i t s n a tu r e , i t i s la r g e ly re s p o n s ib le f o r th e

d e f e c ts found i n i n d u s t r i a l a lc o h o ls and a lc o h o lic b ev erag es e s p e c ia lly

th o se o f th e l i g h t e r ty p e s a s P u e rto R ican and Cuban ty p e rums.

I t s s e p a ra tio n in th e d i s t i l l a t i o n p ro c e ss in tro d u c e s te c h n ic a l

c o m p le x itie s . These a lc o h o ls a re co m p letely s o lu b le in e th y l a lc o h o l

and being l e s s v o l a t i l e , can be s e p a ra te d by f r a c t i o n a l d i s t i l l a t i o n .

They a r e , however, e s s e n t i a l l y im m iscib le in w ater and by th e enhanced

vapor p re s su re phenomena, o r steam d i s t i l l a t i o n e f f e c t , t h e i r r e l a t i v e

v o l a t i l i t i e s , r e f e r r e d to e th y l a lc o h o l, a r e g r e a t ly in c re a s e d beyond

1 .0 when low a lc o h o l c o n c e n tra tio n s a re reach ed in th e d i s t i l l a t i o n

p ro c e s s . T his r e s u l t s in th e f u s e l o i l accu m u latin g i n f r a c tio n s o f

d e f i n i t e a lc o h o l c o n c e n tra tio n .

I t has been p o in te d o u t in C hapter I t h a t th e amount o f f u s e l

o i l produced a s w e ll a s th e p resen ce o f i t s v a rio u s c o n s titu e n ts in a

g iv e n fe rm e n ta tio n depends on a number o f f a c to r s such a s k in d o f sub­

s t r a t e u t i l i z e d , n itro g e n so u rce p r e s e n t, n a tu re o f th e m icro-organism

u t i l i z e d , tim e o f fe rm e n ta tio n and c o n tam in atio n s p re s e n t in th e m ash.

T h is u n c e r ta in ty in re g a rd to th e n a tu re and c o n c e n tra tio n o f th e sub­

s ta n c e s p re s e n t p re c lu d e s th e a p p lic a tio n o f p h y s ic a l chem ical methods

to p r e d ic t th e d i s t r i b u t i o n o f f u s e l o i l in th e co u rse o f th e a lc o h o lic

d is tilla tio n .
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D i s t i l l a t i o n P ro ce sse s Used Commercially

The d i s t i l l a t i o n p ro c e sse s u t i l i z e d f o r th e p ro d u ctio n of a lc o h o l

and a lc o h o lic beverages in th e fe rm e n ta tio n in d u s tr ie s can be broadly-

c l a s s i f i e d e i t h e r a s in te r m it te n t or c o n tin u o u s. A lthough t h i s work

d e a ls m ainly w ith th e b eh av io r o f f u s e l o i l in th e continuous a lc o h o lic

d i s t i l l a t i o n from ferm ented m o lasses, th e main fe a tu r e s o f the i n te r m it ­

te n t a lc o h o lic d i s t i l l a t i o n w i l l be d isc u sse d i n some d e t a i l .

I n te r m i tte n t D i s t i l l a t i o n P ro cesses

The f i r s t p ro c e sse s used fo r th e d i s t i l l a t i o n o f ferm ented liq u o r s

c o n s is te d o f sim ple d i s t i l l a t i o n and co n d en satio n u t i l i z i n g th e i n te r m it­

te n t p o t - s t i l l . The p o t - s t i l l c o n s is te d o f a k e t t l e o r p o t p ro v id ed w ith

steam c o i l s fo r h e a tin g the mash to be d i s t i l l e d o r b u i l t in brickw ork

over a fu rn a c e . The s t i l l head conducted th e vapors d i r e c t l y to a con­

d e n se r which c o n s is te d o f a copper c o i l immersed in a c o o lin g w a te r tan k .

The k e t t l e was p a r tly f i l l e d w ith th e ferm ented liq u id to be d i s t i l l e d

and h e a t was a p p lie d e i t h e r d i r e c t l y under th e k e t t l e o r through th e

steam c o i l s . The vapors produced c o n tain ed n o t only a lc o h o l and w a ter

b u t v i r t u a l l y a l l v o l a t i l e im p u r itie s p re s e n t. As th e c o n te n ts o f the

p o t - s t i l l become more exhausted o f a lc o h o l, steam d i s t i l l a t i o n e f f e c t

fo rc e s ov er th e h ig h e r b o ilin g c o n s titu e n ts o f f u s e l o i l and o th e r im­

p u r i t i e s o f low v o l a t i l i t y . Under norm al o p e ra tin g c o n d itio n s th e

ferm ented mash would c o n ta in from 5% to 10% a lc o h o l by volume. A ccord-

in g ly , th e d i s t i l l a t e o b ta in e d by t h i s method would be low in a lc o h o l

c o n te n t. In o rd e r to in c re a s e th e a lc o h o lic s tr e n g th o f th e f i n a l p ro d u c t,

th e f i r s t d i s t i l l a t e s were subm itted to subsequent sim ple d i s t i l l a t i o n s

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u n t i l th e d e s ir e d a lc o h o l c o n te n t was o b ta in e d . By th e use o f c o o lin g

c o i l s in th e head o f the p o t - s t i l l , which a c te d a s p a r t i a l condensers o r

dephlegm ators, th e r e c t i f y i n g c a p a c ity o f th e s t i l l was in c re a s e d . Im­

provem ents in th e q u a lity o f d i s t i l l a t e s produced by sim ple d i s t i l l a t i o n

and r e d i s t i l l a t i o n were a ch ie v e d by th e s e p a ra tio n o f " h e a d s" and " t a i l s "

f r a c tio n s r i c h in low er b o ilin g and h ig h e r b o ilin g im p u r itie s r e s p e c tiv e ly .

The main p ro d u c t th u s o b ta in e d c o n tain ed a low p o rtio n o f th e a lc o h o l

p re s e n t in th e ferm ented mash and a lth o u g h r e l a t i v e l y p u re r, i t s q u a lity

was poor compared to p re s e n t s ta n d a rd s .

W ith th e purpose o f producing d i s t i l l a t e s o f h ig h e r a lc o h o lic

s tr e n g th in a s in g le o p e ra tio n w ith o u t need o f r e s o r tin g to subsequent

r e d i s t i l l a t i o n s , P is to r i u s and Adam in tro d u c e d , in ab o u t 1800, th e th re e

chambered i n te r m it te n t d i s t i l l i n g s t i l l b ased on th e p r in c ip le o f Woulfe*s

b o t t l e (307, 32 1 ). T his a p p a ra tu s c o n s is ts o f a k e t t l e o r p o t which i s

p a r t l y f i l l e d w ith th e ferm ented mash to be d i s t i l l e d . Heat i s a p p lie d

d i r e c t l y o r through steam tu b e s and th e v ap o rs evolved a re conducted by

an in v e rte d "U" c o n d u it which p a sse s o u t o f th e c e n te r o f th e to p o f th e

k e t t l e , downward i n t o th e bottom o f a second v e s s e l. I n to t h i s v e s s e l i s

p la c e d a p a r t i a l l y exhausted m ix tu re o f heads and t a i l e s used in th e p re ­

v io u s ru n . The incoming vapor m ixes th o ro u g h ly w ith th e l i q u i d and i s

p a r t i a l l y condensed th e r e w ith th e co rresp o n d in g in te rc h a n g e o f h e a t.

The vapors evolved in t h i s v e s s e l, which a r e r i c h e r in a lc o h o l, a re con­

d u cted in a s im ila r manner in to a t h i r d v e s s e l c o n ta in in g a m ix tu re o f

heads and t a i l s f r a c tio n s o b ta in e d d u rin g th e p rev io u s ru n . The vapors

le a v in g t h i s t h i r d k e t t l e , which a r e r e l a t i v e l y s tro n g in a lc o h o l c o n te n t,
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a re conducted to a t o t a l co n d en ser. In some in s ta n c e s , th e y a re passed

through a p a r t i a l condenser f o r f u r th e r enrichm ent b e fo re b ein g le a d in to

th e t o t a l c o n d en ser. The cond en sate produced a t th e p a r t i a l condenser i s

re tu rn e d c o n tin u o u s ly to th e l a s t v e s s e l. At th e end o f each c y cle th e

c o n te n ts o f th e t h i r d v e s s e l a re tr a n s f e r r e d to th e second and p ro v id e th e

p a r t i a l l y exhausted l iq u id f o r th e n e x t o p e ra tio n . The high wines f o r th e

n e x t c y c le c o n s is t o f th o se f r a c tio n s heavy in im p u r itie s which were f r a c ­

t i o n a l l y s e p a ra te d from th e main p ro d u ct a s " h e a d s" a n d '" t a i l s " and a re

added in to th e l a s t v e s s e l.

The c y c le i s stopped when th e c o n te n ts of th e f i r s t and second

k e t t l e s a r e exhausted o f a lc o h o l w h ile th e liq u o r in th e l a s t v e s s e l

s t i l l c o n ta in s f a i r l y la r g e c o n c e n tra tio n s . A g r e a t v a r ie ty o f p r a c tic e s

have been u t i l i z e d by d i f f e r e n t m an u factu rers re g a rd in g th e ch arg in g o f

th e v e s s e ls and th e o p e ra tio n o f th e th r e e chambered s t i l l .

Adams an aly zed th e f r a c t i o n s o b ta in e d i n s e v e ra l c y c le s o f th e

conm ercial o p e ra tio n o f a th r e e chambered s t i l l and found t h a t th e f u s e l

o i l p re s e n t in th e ferm ented mash goes a s fo llo w s: 4 .7 # in th e heads

f r a c t i o n , 28.9# in th e t a i l s f r a c tio n and 6 6 .4 # in th e main p ro d u c t. No

f u s e l o i l was found in th e a lc o h o l- f r e e slo p s (2 6 8 ).

S t i l l s o f t h i s ty p e produced in one s in g le o p e ra tio n d i s t i l l a t e s

c o n ta in in g 86 to 90# a lc o h o l by w eig h t. A v e ry few o f them a re s t i l l

used to d ay in sm all i n s t a l l a t i o n s , b u t t h e i r u se i s g e n e ra lly lim it e d to

th e beverage in d u s tr y f o r th e p ro d u c tio n o f heavy bodied d i s t i l l a t e s which

a re su b se q u e n tly blended in r a t h e r sm all p ro p o rtio n s to produce s p e c ia l

c h a r a c t e r i s t i c s in th e f la v o r and aroma o f th e f i n a l p ro d u c t.
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Modem i n te r m it te n t s t i l l s c o n s is t o f a p la te column pro v id ed w ith

a k e t t l e s im ila r to th o se used in th e s t i l l s d e sc rib e d in th e p reced in g

p a ra g rap h s. The vapors evolved in t h i s k e t t l e a re passed to th e bottom

o f the column by a vapor c o n d u it. The column i s provided w ith t o t a l con­

d e n se rs and flo w d iv id e rs which re g u la te th e flow o f r e f lu x to th e column.

Some a u th o rs c laim t h a t t h e i r use i s v e ry d e s ir a b le fo r th e p ro d u c tio n o f

a lc o h o lic b ev erag es, where th e s e p a ra tio n o f im p u ritie s i s o f a s e le c tiv e

n a tu r e , becoming alm o st o b lig a to ry in th e c ase o f heavy bodied types (2 6 9 ).

The use o f i n te r m it te n t d i s t i l l a t i o n columns w ith a s u f f i c i e n t

number o f p la te s and o p e ra tin g a t ad eq u ate r e f lu x r a t i o s , r e s u l t s in

f i r s t d i s t i l l a t e s whose com position i s very c lo s e to th a t o f th e azeo -

tro p ic m ix tu re . The f i r s t f r a c tio n s would c o n ta in a ls o th o se im p u ritie s

more v o l a t i l e th an a lc o h o l. The m iddle f r a c tio n s u s u a lly c o n ta in l e s s

im p u r itie s and a r e c o lle c te d a p a r t a s h ig h g rad e a lc o h o l. As th e d i s t i l ­

l a t i o n p ro ceed s, the mash in th e k e t t l e becomes exhausted o f a lc o h o l and

r ic h e r in w a te r. The steam d i s t i l l a t i o n e f f e c t s t a r t s fo rc in g up th e

column those im p u r itie s which a re p a r t i a l l y so lu b le in w ater a t th e

o p e ra tin g c o n d itio n s . F u r th e r , th e te m p e ra tu re a t th e k e t t l e in c re a s e s

c o n tin u o u sly , and a t a c e r ta in sta g e o f th e d i s t i l l a t i o n p ro c e ss th e

p re sen c e of h ig h e r b o ilin g im p u r itie s in th e main p ro d u ct becomes no­

tic e a b le . At t h i s p o in t th e d i s t i l l a t e i s c o lle c te d in s e p a ra te re c e iv e r s

and th e s e c o n s ti tu te th e t a i l s f r a c t i o n s . Only a m inor p a r t o f th e a lc o h o l

p re s e n t in th e ferm ented mash i s reco v ered a s high grade a lc o h o l. Robinson

and G illila n d g iv e the r e s u l t s o f a r e c t i f i c a t i o n conducted in a modem

in te r m it te n t s t i l l o f a liq u o r o f u n id e n tif ie d o r ig in and such r e s u l t s

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in d ic a te t h a t th e f r a c tio n e n t i t l e d "H igh-grade a lc o h o l" c o n ta in s only

26# o f th e a lc o h o l p re s e n t in th e o r ig i n a l li q u o r an d , fu rth e rm o re , i t

i s f a r from b ein g pure a lc o h o l (3 1 4 ). T h is means t h a t 76# o f th e a lc o h o l

o r ig i n a lly - p re s e n t must be su b m itted to f u r th e r p u r i f ic a tio n b e fo re con­

v e r tin g i t in to h igh g rade p ro d u c t.

The b eh av io r o f th e f u s e l o i l p re s e n t d u rin g th e c o u rse o f the

i n t e r m i t t e n t d i s t i l l a t i o n w i l l be a f f e c te d by th e n a tu re o f i t s c o n s t i t ­

u e n ts . Should is o -p ro p y l a lc o h o l be p re s e n t i t would ap p ear in th e e a r ly

s ta g e s o f th e d i s t i l l a t i o n p ro c e s s . T h is p ro b ab ly a cc o u n ts f o r th e sm all

c o n c e n tra tio n s o f f u s e l o i l found in th e f i r s t f r a c tio n s o f in te r m it te n t

d i s t i l l a t i o n p ro c e s s e s . As th e a lc o h o l c o n te n t in th e k e t t l e i s red u ced ,

th e h ig h e r b o ilin g homologues w i l l s t a r t to a p p e a r. Adams has in d ic a te d

t h a t th e f u s e l o i l c o n te n t v a r ie s w ith th e p ro o f o f th e p ro d u ct and maxi­

mum c o n c e n tra tio n s a re found in th o se f r a c t io n s where th e a p p a re n t p ro o f

i s from 132 to 144°P (2 6 8 ). T his a u th o r has dem onstrated w ith e x p erim en tal

d a ta t h a t th e b e l i e f o f many t h a t f u s e l o i l would be found in th e s lo p s

from from a lc o h o l i s i n c o r r e c t . A ll f u s e l o i l p re s e n t in th e o r ig i n a l

mash ap p ears in th e d i s t i l l a t e f r a c tio n s re q u ire d to remove th e e th y l

a lc o h o l o r i g i n a l l y p r e s e n t. Foote has confirm ed t h i s f a c t (2 8 1 ). S e v e ra l

a u th o rs have em phasized th e dependence o f th e s e p a ra tio n o f f u s e l o i l in

th e d i s t i l l a t i o n p ro c e s s , on th e p ro p o rtio n s o f e th y l a lc o h o l-w a te r- fu s e l

o i l p re s e n t in th e liq u o r to be d i s t i l l e d . C arlso n , Sm ith and M o rre ll

have e x p e rim e n ta lly m easured th e v o l a t i l i t y o f, among o th e r s u b sta n c e s,

is o - p r o p y l, n -p ro p y l, i s o - b u ty l, n - b u ty l , 1 -P e n ta n o l and 2 -P en ta n o l r e l a ­

t i v e to e th y l a lc o h o l (2 7 7 ). I t was shown t h a t a l l th e s e a lc o h o ls a r e
 66

re n d e red more v o l a t i l e than e th y l a lc o h o l a f t e r a c r i t i c a l w ater concen­

t r a t i o n i s reached in each c a s e . As th e m o le c u lar w eight o f th e a lc o h o l

in c r e a s e s , th e c r i t i c a l w ater c o n c e n tra tio n becomes h ig h e r. The a p p ro x i­

mate c r i t i c a l w ater c o n c e n tra tio n f o r th e v a rio u s a lc o h o ls s tu d ie d i s as

fo llo w s:

A lcohol Mole # W ater

is o -p ro p y l 60
n -p ro p y l 91
is o - b u ty l 85
n - b u ty l 93
1 -p e n ta n o l 91
2 -p e n ta n o l 86

U n fo rtu n a te ly , no d a ta i s giv en fo r iso -am y l and a c tiv e amyl

a lc o h o ls which a re th e m ost im p o rtan t c o n s titu e n ts o f f u s e l o i l . The

v o l a t i l i t y o f 2 -p e n ta n o l r e l a t i v e to e th y l a lc o h o l was found to be from

2 .2 to 2 .7 when th e c o n c e n tra tio n o f w ater was 95.9 mole p e r c e n t.

Kervegant r e p o r ts e x p erim en tal v alu es d eterm ined by S o re l o f the

v a p o r-liq u id e q u ilib riu m c o n s ta n t "K" fo r iso -am y l a lc o h o l in m ix tu res

w ith w ater and e th a n o l. These r e s u l t s in d ic a te t h a t nKn v a r ie s from 0.25

when th e c o n c e n tra tio n o f a lc o h o l i s 95# by volume to 5 .5 when th e a lc o h o l

c o n te n t d e c re a se s to 25# by volume (2 9 0 ).

Luhder has re p o rte d t h a t th e v o l a t i l i t y o f fe rm e n ta tio n amyl a l ­

c o h o l, r e l a t i v e to e th y l a lc o h o l, v a r ie s from 0.23 when th e a lc o h o l

c o n te n t i s 95# by volume to 2.07 when the a lc o h o l c o n c e n tra tio n d e crea se s

to 25# by volume (3 0 3 ).

Data on f u s e l o i l d i s t r i b u t i o n under d i f f e r e n t o p e ra tin g c o n d itio n s

in i n t e r m i t t e n t d i s t i l l a t i o n p ro c e sse s i s v i r t u a l l y n o n - e x is te n t. I n th e

very few c a se s in which some in fo rm a tio n i s given in th e l i t e r a t u r e w ith

 67

re g a rd to f u s e l o i l c o n te n t o f v a rio u s f r a c t i o n s , th e re i s no in fo rm a tio n

a s to th e a c tu a l o p e ra tin g c o n d itio n s such a s r e f lu x r a t i o and number o f

p la te s in th e column u t i l i z e d in th e f r a c tio n a tio n (268, 291, 3 1 4 ).

Continuous D i s t i l l a t i o n P ro cess

In modern p r a c tic e , co n tin u o u s d i s t i l l a t i o n p ro c e sse s have sub­

s t i t u t e d a lm o st e n t i r e l y th e o ld e r i n te r m it t e n t m ethods. S in ce th e y a re

e s p e c ia lly w e ll a d ap ted f o r mass p ro d u c tio n , co n tin u o u s s t i l l s in tro d u c e

a number o f advantages o f economic n a tu r e . T h e ir com pactness, f lo o r

space economy, h ig h u n it c a p a c ity , sav in g s o f tim e, m a n ip u la tio n and f u e l

a re among th e m ost im p o rta n t. F u r th e r , th e a b i l i t y to produce n e u tr a l

s p i r i t s o f g r e a te r p u r it y have g e n e ra liz e d t h e i r use in th e a lc o h o l i n ­

d u s tr y . I n te r m i tte n t s t i l l s a re p r e s e n tly used to a m inor e x te n t in th e

beverage in d u s tr y . For th e m anufacture o f l i g h t ty p e b ev erag es, such as

P u e rto Rican and Cuban rum s, co n tin u o u s s t i l l s a r e u t i l i z e d alm o st

e x c lu s iv e ly .

Modem co n tinuous d i s t i l l a t i o n u n its c o n s is t o f a t l e a s t th re e

colum ns. A flow diagram o f th e o p e ra tio n o f such a u n i t i s p re s e n te d

i n Drawing No. 1 .

The f i r s t column, known a s th e *Beer* o r " E x h a u stiv e 11 column, lias

a s i t s c h ie f fu n c tio n th e rem oval o f a l l th e a lc o h o l p re s e n t in th e f e r ­

mented mash. The l a r g e s t p a r t o f th e column i s a c c o rd in g ly a s tr ip p in g

s e c tio n c o n ta in in g 15 to 25 s ie v e p la te s f o r s u i t a b l e h a n d lin g o f a s o lid s

c o n ta in in g stre a m . The upper s e c tio n o f th e column has a sm all number o f

b u bble-cap p la te s and th e s e a re u s u a lly s e p a ra te d from th e s tr ip p in g sec ­

t io n by an impingement p l a t e , whose fu n c tio n i s t o p re v e n t s o lid s from

 t V ent H
D r a w i n g No. 1
til j t o ,„ w
DISTILLATION F L O W S H E E T

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V en t

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B eer P u r f/ i/ Z /i j
fo a d . f u s e / O r/
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/e y e /
^ C o n fr o /^ r /.e v e /
feed C o /u r n n C o n /r o //e r L e y s / C o n fr o //e r ‘
P um p JT t n T eed 7 tfn £
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Fermented
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 69

e n te r in g th e to p o f th e column. S lo p s c o n s is tin g o f w ater w ith d is s o lv e d

and u n d isso lv e d s o lid s flow from th e bottom o f the to w er. This stream

can be f u r th e r p ro cessed f o r c a t t l e feed and y e a s t reco v ery i f p re v io u s

c e n tr if u g a tio n o f th e ferm ented mash i s n o t p r a c tic e d . A lcohol vapor o f

80-130 p ro o f s tr e n g th , c o n ta in in g v o l a t i l e im p u r itie s , le a v e s th e to p o f

th e column where i t i s condensed and d iv id e d between r e f lu x and to p p ro ­

d u c t s tre a m s. R eflux r a t i o s between 0 .5 :1 and 2:1 a re g e n e ra lly u sed .

The b e e r column p ro d u c t, d e sig n a te d as raw d i s t i l l a t e o r raw p ro d u c t,

p asses to re c e iv in g and m easuring ta n k s which a t th e same tim e se rv e as

feed ta n k s f o r th e p u rif y in g column, which i s th e n e x t s ta g e in th e

d i s t i l l a t i o n p ro c e s s e s . W ater may be added to th e b e e r column p ro d u ct

in th e re c e iv in g tan k s to r e a l i s e any d e s ir e d c o n c e n tra tio n i n th e

p u rif y in g column fe e d , u s u a lly from 40 to 100 p ro o f. In some i n s t a l l a ­

tio n s th e vapors from th e to p o f th e b e e r column p ass to a p a r t i a l

condenser where j u s t enough v apors a re condensed to supply th e r e f lu x

stream , th e r e s t b ein g fe d to th e p u rify in g column. The method o f

t o t a l l y condensing th e vapors and fe e d in g th e p u rif y in g column in th e

l i q u i d phase i s more favored in i n d u s t r i a l p r a c tic e s in c e i t s g r e a te r

f l e x i b i l i t y and ease o f c o n tr o l, r e s u l t i n g in a more uniform p ro d u c t,

more than o f f s e t s th e a d d itio n a l expense o f f u e l and condensing w a te r.

Feed i s added in th e m iddle s e c tio n o f th e p u rify in g column.

The fu n c tio n o f th e p u rif y in g column, which u s u a lly c o n ta in s

from 30 to 55 b u b b le-cap p l a t e s , i s to remove " h e a d s 11 c o n s is tin g o f low

b o ilin g c o n s ti tu e n ts . These a r e removed w ith th e overhead p ro d u c t which

may c o n ta in up to 10JS o f the e th y l a lc o h o l fed to th e column and whose

 70

com position i s v e ry c lo se to t h a t o f th e a lc o h o l-w a te r a z e o tro p e . The

vapors from th e to p o f th e column a r e condensed and a re d iv id e d in to

r e f lu x and p ro d u c t stre a m s. Very h ig h r e f lu x r a t i o s a re u t i l i z e d in com­

m e rc ia l p r a c t i c e . The w r ite r knows o f c ase s in which r a t i o s o f 50:1 and

100:1 a r e u se d . The " p u r i f i e d " a lc o h o l-w a te r s o lu tio n p a sse s from th e

bottom o f th e column to r e c e iv in g ta n k s which serv e a s feed ta n k s to th e

r e c t i f y i n g column. A c tu a lly th e term " p u r if i e d a lc o h o l" used in in d u s ­

t r i a l p r a c tic e i s f a r from b e in g tr u e s in c e the h ig h e r b o ilin g im p u r itie s

p re s e n t in th e raw p ro d u ct from th e b e e r column a re s t i l l p re s e n t.

The a lc o h o l bottom s o f th e p u rif y in g column a r e fe d in to th e

m iddle s e c tio n o f th e r e c t i f y i n g column which u s u a lly c o n ta in s from 40

to 75 b u b b le-cap p l a t e s . The purpose o f th e r e c t i f y i n g column i s to

c o n c e n tra te th e a lc o h o l to th e d e s ir e d s tr e n g th and to remove rem aining

im p u r itie s and a d d itio n a l im p u r itie s formed d u rin g r e c t i f i c a t i o n . Here

a g a in , "h ea d s* a r e removed from th e to p o f th e column. The to p vapors

p ass to th e condensers and th e condensate i s d iv id e d in to r e f lu x and

"heads". N orm ally, th e "h e a d s" p ro d u c t c o n ta in s a s m a lle r p e rc en ta g e o f

th e a lc o h o l fe d to th e column th a n in th e c ase o f th e p u rify in g column.

A lcohol o r beverage p ro d u ct o f th e d e s ir e d s tr e n g th i s removed a s a

l i q u i d s id e stream from th e up p er tr a y s o f th e column. Main p ro d u c ts r e ­

moved a s s id e stream s a re known a s " p a u s te r iz e d " p ro d u c ts . R eflu x r a t i o s ,

ex p ressed a s th e r a t i o o f th e o u ts id e r e f lu x stream to th e main p ro d u c t

sid e stream o f 3 :1 to 5 :1 a r e coranonly u s e d . I n some c a se s h ig h e r v a lu e s

a re u t i l i z e d . A lc o h o l-fre e s lo p s , c o n s is tin g o f w a ter and h ig h e r-b o ilin g

w ater s o lu b le im p u r itie s a r e removed. The f u s e l o i l accum ulates in th e

 71

in te rm e d ia te p la te s o f th e column and i s removed a s a liq u id s id e stream

a few p la te s above th e fe e d p l a t e . This stream p a sse s in to f u s e l o i l r e ­

c e iv e r s where i t i s co o led and g e n e ra lly d ilu t e d w ith w a ter which causes

th e f u s e l o i l to s e p a ra te in to a c o n c e n tra te d , o i l y , upper l a y e r . The

o i l i s d ecanted and th e low er la y e r i s re tu rn e d to th e p ro c e ss f o r r e ­

covery o f th e e th y l a lc o h o l p r e s e n t. I t i s u s u a lly u t i l i z e d to d i l u t e

th e raw p ro d u c t from th e b e e r column.

The p ro cess j u s t d e sc rib e d c o n s t i tu te s th e co re o f modem con­

tin u o u s a lc o h o l d i s t i l l a t i o n p ro c e sse s a lth o u g h numerous m o d ific a tio n s

and re fin e m e n ts a r e in use to d a y .

Unger lias review ed advances in a lc o h o l d i s t i l l a t i o n methods (3 2 4 ).

The o p e ra tio n o f th e b e e r column under vacuum a t low tem p eratu re was

su g g ested in o rd e r to reduce therm al decom position o f mash c o n s titu e n ts

which a re l a r g e ly re s p o n s ib le f o r u n p le a sa n t and o b je c tio n a b le fla v o r

and aroma o f th e p ro d u c t. T his problem i s more s u c c e s s fu lly and economi­

c a l l y e lim in a te d by c e n tr ifu g in g th e mash c o n tin u o u sly b e fo re fe e d in g i t

to th e b e er column.

One o f th e m ost im p o rta n t and s u c c e s s fu l re c e n t improvements con­

s i s t s o f o p e ra tin g th e p u rif y in g column a s an e x tr a c tiv e d i s t i l l a t i o n

column w ith th e a d d itio n o f w ater a t th e to p . A r a th e r com plete e lim i­

n a tio n o f im p u r itie s i s a ch ie v e d . In some in s ta n c e s , b o th an e x tr a c tiv e

d i s t i l l a t i o n and a c o n v e n tio n a l p u rif y in g column a re used in s e r i e s (3 2 4 ).

The o p e ra tio n o f th e e x tr a c tiv e d i s t i l l a t i o n column i s d is c u s s e d in l a t e r

p a ra g ra p h s.

In some in s ta n c e s th e " h e a d s " from th e p u rif y in g and r e c t i f y i n g

columns a re c h em ically tr e a t e d and r e d i s t i l l e d in a s e p a ra te b a tc h column

 72

ta k in g heads and t a i l s o f f and y ie ld in g second c l a s s s p i r i t (3 2 4 ). Unger

f u r th e r r e p o r ts t h a t a t Joseph E. Seagram and Sons th e "heads* p ro d u c ts

a r e fed to a continuous 75 p la t e column where th e y c o n c e n tra te to 1-2/S

a c e ta ld eh y d e and 10-20$ e th y l a c e ta te in a stream e q u iv a le n t to 0 .1 $ o f

th e t o t a l p ro d u c t. The re c o v ere d a lc o h o l i s re c y c le d . O perating d e t a i l s

f o r th e above p ro c e sse s a r e n o t a v a ila b le i n th e l i t e r a t u r e .

In some p la n ts , f u s e l o i l stream s a r e p r e s e n tly washed c o u n te r-

c u r r e n tly in co n tinuous packed e x tr a c tiv e colum ns. A f u s e l o i l r ic h

la y e r s e p a ra te s i n th e upper p a r t o f th e column and i s removed con­

tin u o u s ly a s f u s e l o i l b y -p ro d u c t. In o th e r in s ta n c e s f u s e l o i l stream s

a r e f u r th e r p ro cessed in c o n tin u o u s columns o f 50 to 6 0 ,p la te s from where

f u s e l o i l and h ig h b o ilin g e s t e r s a r e o b ta in e d (3 2 4 ).

K irk and Othmer d e s c rib e a number o f a lc o h o l d i s t i l l a t i o n u n its o f

in c re a s in g degree o f re fin e m e n t and com plexity (2 9 4 ).

B ehavior o f F u sel O il i n th e O p eratio n o f th e P u rify in g Column

The raw p ro d u ct to bo fed to th e p u rif y in g column c o n ta in s m ost

o f th e v o l a t i l e components p r e s e n t i n th e ferm ented mash. The h ig h e r

a lc o h o ls c o n te n t i n i t g e n e r a lly v a r ie s from 100 to 1100 m illig ra m s o f

f u s e l o i l a s amyl a lc o h o l p e r 100 m l. o f pure a lc o h o l. In th e c ase o f

l i g h t typ e rums, in which s p e c ia l y e a s t s t r a i n s a r e u sed , i t s c o n c e n tra ­

tio n can be even lo w e r.

The d i l u t i o n o f th e raw p ro d u ct w ith w a ter b e fo re fe e d in g to th e

p u rify in g column a id s in th e s e p a ra tio n o f im p u r itie s i n s a id column.

The v o l a t i l i t y o f most im p u r itie s r e l a t i v e to a lc o h o l i s g r e a tly i n ­

c re a se d a t reduced e th y l a lc o h o l c o n c e n tra tio n s . The amount o f d ilu tio n

 73

u sed i s lim ite d by economic c o n s id e ra tio n s s in c e i t r e q u ire s in c re a s e d

column c a p a c ity and g r e a te r expense o f steam . The d i r e c t in tr o d u c tio n

o f steam in to th e s t i l l , when u sed , produces an a d d itio n a l d ilu tin g

e f f e c t on the bottom s o f th e co lu im . In modem p r a c ti c e , however, th e

u se o f su rfa c e e v a p o ra to rs a s r e b o ile r s i s to be p r e f e r r e d s in c e th e use

o f open steam m ight r e s u l t in th e in tr o d u c tio n o f im p u r itie s , such a s

f r a c tio n s o f l u b r i c a tin g o i l s , which would ap p ear in th e f i n a l p ro d u ct

d e tr a c tin g from i t s q u a lity .

S ince a sm all p e rc e n ta g e o f th e a lc o h o l p re s e n t in th e feed i s

removed in the ■heads*1 p ro d u c t, th e a lc o h o lic s tr e n g th o f th e bottom s

from th e p u rify in g column i s v ery c lo se to t h a t o f th e feed when c lo se d

steam i s used. A cco rd in g ly , th e a lc o h o l c o n c e n tra tio n from th e feed

p la te to th e bottom o f th e column d e c re a se s b u t l i t t l e . F u rth e r, due

to th e presence o f a h y d r o s ta tic head g ra d ie n t which in c re a s e s tow ard

th e bottom end o f th e column, and to th e sm all a lc o h o l c o n c e n tra tio n g ra ­

d ie n t e x is tin g in th e o p p o site d ir e c tio n , th e te m p e ratu res p r e v a ilin g in

th e p la te s o f th e column under ste a d y o p e ra tin g c o n d itio n s show a g ra d ie n t

w hich in c re a s e s tow ard th e bottom o f th e column and re a c h e s a maximum a t •

th e r e b o i l e r . C onsequently, th e s o l u b i l i t y o f f u s e l o i l in th e l i q u i d

phase o f th e p la te s o f th e s tr ip p in g s e c tio n o f th e column i s n o t g r e a tly

a l t e r e d w ith th e r e s u l t t h a t no s i g n i f i c a n t steam d i s t i l l a t i o n e f f e c t

o c c u rs . The d i s t r i b u t i o n o f c o n c e n tra tio n s o f f u s e l o i l alo n g the s t r i p ­

ping s e c tio n i s r a t h e r uniform . The bottom s c o n ta in e s s e n t i a l l y a l l th e

f u s e l o i l e n te r in g w ith th e feed and c o n se q u e n tly th e r e i s no tendency

f o r any s tro n g accum ulation o f f u s e l o i l i n the in te rm e d ia te p la te s o f

 74

th e column. B a r b e t's diagram , given by Robinson and G ill ila n d , shows

th a t the f u s e l o i l c o n c e n tra tio n in th e bottom s o f a p u rify in g column

i s only s l i g h t l y h ig h e r than t h a t o f th e feed (3 1 4 ). T his i s caused by

th e f a c t th a t e s s e n t i a l l y a l l f u s e l o i l e n te rin g w ith th e feed would go

in to th e bottom s whose volume p e r u n it tim e would be somewhat sm aller

than t h a t o f th e fe e d . The d if f e r e n c e co rresp o n d s to the volume o f the

" h e a d s ” p ro d u ct which, in tu r n , a r e low in f u s e l o i l c o n te n t. B a r b e t's

d a ta a ls o confirm s th a t th e d i s t r i b u t i o n o f f u s e l o i l along the s t r i p ­

p ing s e c tio n of th e column i s r a th e r uniform .

S e v e ra l flow diagram s o f co n tin u o u s a lc o h o l d i s t i l l a t i o n p ro ­

c e sse s found in th e l i t e r a t u r e in d ic a te th a t f u s e l o i l s id e stream s a rc

removed from in te rm e d ia te p la te s o f the p u rify in g column where accum ula­

tio n s a re supposed to occur (2 6 5 , 266, 310, 3 1 3 ). U n fo rtu n a te ly , o p e ra tin g

c o n d itio n s a re n o t g iv e n . No in fo rm a tio n i s a v a il a b le re g a rd in g th e

a d d itio n o f w ater o r d i r e c t a d d itio n o f steam which would produce a r e ­

du ctio n i n th e a lc o h o lic c o n c e n tra tio n in the low er p la te s o f the column

to the e x te n t o f producing th e enhanced vapor p re s s u re phenomena w ith

th e co rresp o n d in g removal o f f u s e l o i l from th e bottom p ro d u ct and i t s

accum ulation in in te rm e d ia te p l a t e s .

In o rd e r to confirm B a r b e t's r e s u l t s and th e t h e o r e t i c a l c o n sid e ra ­

tio n s exposed above, two experim ents were conducted by th e w r i te r u t i l i s i n g

th e f a c i l i t i e s o f th e Rum P i l o t P la n t o f th e A g r ic u ltu r a l Experim ent

S ta tio n o f th e U n iv e rs ity o f P u e rto R ic o . The p u rify in g column o f i t s

d i s t i l l a t i o n u n it c o n ta in s 40 b u b b lc-cap p la te s o f 8 ” nom inal d iam eter

and a p la te sp acin g o f 1 0 ". The overhead v apors a re condensed in a t o t a l

 75

condenser and p ass to a r e f lu x c o l l e c t o r . From t h i s c o l l e c t o r th e con­

d e n sa te i s d iv id e d in to r e f lu x and nh e a d s w stream s by means o f au to m atic

flo w r a t e c o n tr o lle r s which a llo w th e s e t t i n g o f any d e s ir e d r e f lu x r a t i o .

A therm om eter b ulb i n s t a l l e d in th e p a th o f th e r e f lu x stream re g u la te s

th e i n l e t o f condensing w a ter to th e t o t a l condenser to m a in ta in any de­

s i r e d tem p eratu re in th e r e f lu x . The t o t a l condenser i s v e n ted through

a v e n t condenser which condenses any vapor p a ssin g over w ith th e non-

condensable g ases and r e tu r n s th e co n d en sate to th e r e f lu x c o l l e c t o r .

A tm ospheric p re s s u re p r e v a ils in th e to p p l a t e o f th e column d u ring

o p e r a tio n . Steam f o r h e a tin g i s added i n to th e s h e ll s id e o f an o u ts id e ,

v e r t i c a l , tu b u la r h e a t exchanger which c o n s t i tu te s th e r e b o i l e r o f th e

column. The b o il- u p r a te i s c o n tr o lle d by means o f a d i f f e r e n t i a l p r e s ­

s u re c o n tr o lle r w ith ta p s n e a r th e to p and bottom ends o f th e column.

In o rd e r to m a in ta in c o n s ta n t any s e t d i f f e r e n t i a l p r e s s u r e , th e con­

t r o l l e r r e s e t s an a u to m a tic steam flow c o n t r o l l e r which in tu rn r e g u la te s

th e supply o f steam to th e r e b o i l e r . The fe e d r a t e to th e column i s a ls o

re g u la te d by an a u to m atic flow c o n t r o l l e r . A fe e d -h e a te r provided w ith

an a u to m atic te m p e ratu re c o n t r o l l e r m a in ta in s th e te m p e ratu re o f th e feed

a t any d e s ir e d v a lu e . The flow o f b o tto m s-p ro d u ct o f f th e column i s

r e g u la te d by an a u to m atic l e v e l c o n t r o l l e r i n s t a l l e d in th e bottom o f th e

column. The a u to m a tic flow c o n t r o l l e r s used to r e g u la te th e flow o f feed

and p ro d u c ts to and from th e column co u ld be o p e ra te d , i f d e s ir e d , in

c o n ju n c tio n w ith a te m p e ratu re c o n t r o l l e r which would r e s e t one stream

flow c o n t r o l l e r to m a in ta in a c o n s ta n t re fe re n c e te m p e ratu re a t a given

p o in t in th e system . Next c h a p te r p re s e n ts a d e ta i le d d is c u s s io n on
 76

au to m a tic c o n tr o l system s f o r th e co n tin u o u s a lc o h o lic d i s t i l l a t i o n • The

c o n tr o l system u t i l i z e d f o r th e se experim ents c o n s is te d o f m anually r e ­

s e t t i n g the fe e d flow c o n tr o lle r to m a in ta in c o n sta n t a re fe re n c e tem p eratu re

in the p la te above th e feed p l a t e .

Every p la te in th e column i s p ro v id ed w ith ta p s which could serv e

a s a tem p eratu re w e ll. F if te e n therm ocouples a re i n s t a l l e d alo n g the

column f o r measurement o f te m p e ra tu re s. A larg e.n u m b er o f p la te s have

been m anifolded f o r a d d itio n o f feed and w ithdraw al o f s id e stream s, i f

d e s ir e d . A ll p la te s a r e provid ed w ith sample o u t l e t s .

Feed com positions o f 30$ and 40$ a lc o h o l by volume were s tu d ie d .

S im ila r r e f lu x r a t i o s , b o il up r a t e s and p er c e n t o f a lc o h o l in feed

going in to "heads " w e re u t i l i z e d . These fig u re s were 2 5 :1 , 10.4 g a llo n s

p er hour and 3$, r e s p e c tiv e ly . P la te 16, from bottom up, was th e feed

p la te in both experim ents.

The r a te s o f flow o f th e fe e d , r e f lu x and " h e a d s " stream s f o r th e

experim ent w ith th e 30$ a lc o h o l feed were r e s p e c tiv e ly 4 0 .0 , 1 0 ,0 , and 0 .4

g a llo n s per h o u r. The co rresp o n d in g f ig u r e s f o r th e experim ent w ith th e

40$ a lc o h o l feed were 3 3 .3 , 1 0 .0 and 0 .4 g a llo n s p e r h o u r. The re fe re n c e

te m p e ratu res m ain ta in ed c o n sta n t in th e vapor space o f th e p la te above

th e feed p la te were 183°F f o r th e 30$ a lc o h o l feed and 186°F f o r th e 40$

a lc o h o l fe e d . The column was m ain ta in ed a t t o t a l r e f lu x o f 1 0 .4 g a llo n s

p er hour u n t i l enough accum ulation o f a lc o h o l in th e column o ccu rred to

b rin g th e re fe re n c e te m p e ratu re to th e d e s ir e d v a lu e . At t h a t moment

w ithdraw al o f " h e a d s " p ro d u c t was coiranenced and th e r e f lu x stream a d ju s te d

to 1 0 .0 g a llo n s p e r h o u r. Samples were ta k en from p l a t e s 4 0 , 38, 35, 3 2 ,

29, 26, 23, 20, 1 7, 14, 11, 7 and 3 a t 0 , 8 , 16 and 24 h o u rs a f t e r rem oval
 77

o f " h e a d s " p ro d u ct began.

The r e s u l t s o f th e s e experim ents a re p re se n te d in T ables 6 and 7.

These d a ta confirm th e r e s u l t s o b ta in e d by B a rb e t. There i s no s i g n i f i ­

c a n t accum ulation o f f u s e l o i l in the in te rm e d ia te p la te s o f th e p u rify in g

column when o p e ra tin g by c o n v en tio n al m ethods and u t i l i z i n g c lo se d steam .

The f u s e l o i l c o n te n t o f th e bottom p ro d u c t o f th e column i s s l i g h t l y

h ig h e r than t h a t o f th e fe e d . The f u s e l o i l c o n te n t in th e to p p la te s

i s somewhat h ig h e r than ex p ected . T h is i s p ro b ab ly due to th e p resen ce

o f is o -p ro p y l a lc o h o l i n the ferm ented m olasses mash and co n seq u en tly in

th e d i s t i l l a t e from th e b e er column. At f u s e l o i l c o n c e n tra tio n in th e

" h e a d s " o f 25 mgs. o f f u s e l o i l p er 100 m i l l i l i t e r s o f s a m p le ,.th e f u s e l

o i l removed in th e "h ead s* i s e q u iv a le n t to ab o u t 0 .5 # o f th e f u s e l o i l

p re s e n t in th e fe e d . The d a ta p re s e n te d in C hapter I on com positions o f

f u s e l o i l from d i f f e r e n t so u rces in d ic a te s t h a t f u s e l o i l o r ig i n a tin g in

ferm ented sugar cane m olasses u s u a lly c o n ta in s above 0 .6 # o f is o -p ro p y l

a lc o h o l.

The r e s u l t s o b ta in e d le a d to th e obvious co n clu sio n t h a t no f u s e l

o i l s id e -s tre a m should be withdrawan from th e p u rify in g colunn when

u t i l i z i n g co n v en tio n al methods o f o p e ra tio n and c lo se d steam . M o d ifica­

t io n s to th e c o n v e n tio n a l o p e ra tin g pro ced u re which would r e s u l t in producing

c o n s id e ra b le d e crea se in a lc o h o l c o n te n t a t th e low er p la te s o f th e column

w h ile m a in ta in in g high a lc o h o lic s tre n g th s i n th e to p p l a t e s , would p ro ­

duce accum ulations o f f u s e l o i l in th e in te rm e d ia te p l a t e s . These could

be accom plished only i f a la r g e p e r c e n t o f th e a lc o h o l in th e feed were

ta k en in th e overhead p ro d u c t and by d i l u t i n g w ith w ater and open steam

 TABLE 6

FUSEL OIL AND ALCOHOL DISTRIBUTION BY PLATES IN PURIFYING COLUMN

Feed - 80°P; R eflu x R a tio - 25:1

F u se l O il C o n c e n tra tio n Given a s rags, o f Amyl A lcohol p er 100 m l. o f Sample

A lcohol C o n ten t Given i n Degrees P ro o f a t 60°F

Time o f
Sampling 0 hrs. 8 h rs. lb h r s . 24 h r s .
F u se l F u se l F u sel F u se l
P la te O il A lcohol O il A lcohol O il A lcohol O il A lcohol

40 25 189.7 30 190.0 40 190.0 40 190.1

38 20 189.1 25 . 189.6 25 1S9.7 35 189.7
35 20 188.1 25 188.7 20 188.7 30 189.0
32 25 186.8 25 187.3 25 187.3 25 187.5
29 40 184.2 30 185.3 25 185.4 25 185.6
26 50 181.2 45 182.1 35 132.7 30 182.7
23 20 177.2 55 177.6 40 177.8 40 178.0
20 55 171.3 70 1 71.1 60 171.7 45 171.3
17 75 87.3 70 87.8 70 89 .5 45 87.5
14 90 80.2 85 79.7 80 79.0 45 79.2
11 75 7 9 .2 85 78.7 85 79.7 45 79.0
7 100 79.0 90 78.7 85 79.6 50 79.3
3 79.3 110 79.0 95 78.7 60 7 9.1

F u se l
O il A lcohol

Composite Sample o f Feed 70 82.3

Composite Sample o f Heads 35 189.9
Composite Sample o f Bottoms 75 79.5
 TABLE 7

FUSEL OIL AND ALCOHOL DISTRIBUTION BY PLATES IN PURIFYING COLUMN

Feed - 60°Pj R eflu x R a tio - 25:1

F u se l O il C o n c e n tra tio n Given as mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

A lcohol C o n ten t Given in Degrees P ro o f a t 60°F

Time o f
Sampling 0 h rs. 8 h rs. 16 h r s . 24 h r s .
F u se l F u se l F u sel F usel
P la te A lcohol' A lcohol A lcohol A lcohol
O il O il O il ' O il

40 189.4 20 189.6 30 190.0 30 190.0

38 5 188.4 20 188.9 25 • 1 8 9 .4 30 189.5
35 5 187.6 15 188.5 20 188.5 30 188.6
32 20 185.1 30 186.5 35 186.6 30 186.8
29 25 182.2 45 183.3 30 133.6 35 182.7
26 35 179.7 65 179.1 35 179.2 65 179.5
23 55 174.0 80 174.6 35 174.9 75 173.9
20 95 160.6 170 151.3 95 162.7 160 161.3
17 40 68.3 50 72.3 60 67.0 65 67.8
14 45 59.8 70 5 9 .6 65 59.0 75 60.3
11 65 59.8 75 5 9.6 85 59.0 85 59.0
7 65 59.6 85 59.7 85 59.3 70 59.6
3 60 59.5 95 5 9 .4 95 59.3 95 5 9.4

F u sel
A lcohol
O il

Composite Sample o f Feed 40 60.1

Composite Sample o f Heads 30
Composite Sample o f Bottoms 50 58.6
 80

th e low er p la te s o f th e column. S in ce f u s e l o i l can be v e ry e f f e c t iv e ly

removed in th e r e c t i f y i n g column o r by o p e ra tin g th e p u rify in g column by

th e e x tr a c tiv e d i s t i l l a t i o n method to be d e sc rib e d i n th e n e x t p a ra g ra p h s,

no need i s found f o r th e economic burden o f s e p a ra tin g la r g e amounts o f

a lc o h o l in th e "heads* which would have to be re p ro c e s s e d to re c o v er th e

e th a n o l and c o n v e rt i t in to f i r s t c la s s p ro d u c t.

O b jectio n s to th e use o f open steam a re b ased , as m entioned b e fo re ,

o n -c o n s id e ra tio n s o f th e q u a lity o f th e f i n a l p ro d u c t. I t s u se , however,

would produce s i g n i f i c a n t d ilu tio n s i n th e bottom p ro d u c t. There i s no

f u s e l o i l d i s t r i b u t i o n d a ta in th e l i t e r a t u r e fo r such c a s e s . Some ac­

cum ulation along th e column should be e x p ec te d . However, sin c e th e

presence o f sm all q u a n titie s o f e th y l a lc o h o l g r e a tly in c re a s e th e s o lu ­

b i l i t y o f f u s e l o i l in w ater s o lu tio n s , i t s e x te n t i s u n c e r ta in and would

depend to a high degree on th e p a r t i c u l a r o p e ra tin g c o n d itio n s .

I t was m entioned in p re v io u s p arag rap h s t h a t one o f th e most suc­

c e s s f u l modern m o d ific a tio n s o f t h e ’c o n v e n tio n a l co n tin u o u s d i s t i l l a t i o n

p ro c e ss i s th e o p e ra tio n o f th e p u rify in g column as an e x tr a c tiv e d i s ­

t i l l a t i o n column u t i l i s i n g w ater a s th e e x tr a c ti v e a g e n t. T his p ro cess

i s based on th e p r in c ip le t h a t a t reduced a lc o h o l c o n c e n tra tio n s most

im p u r itie s p re s e n t in th e raw d i s t i l l a t e s become more v o l a t i l e th an

e th y l a lc o h o l. A cco rd in g ly , w ater i s added in th e to p p l a t e o f th e

column to produce a d e c re a se in a lc o h o l c o n c e n tra tio n th ro u g h th e column.

The low c o n c e n tra tio n o f a lc o h o l o b ta in e d i n th e bottom o f th e column

f o r c e s th e im p u r itie s o f f th e bottom p ro d u c t. Much low er a lc o h o lic

s tr e n g th s a re produced a ls o in th e vapor le a v in g th e to p o f th e column

 81

due to a d d itio n o f w ater i n th e to p p la te and to th e use o f l e s s p la te s

i n th e e n ric h in g s e c tio n By fe e d in g a t a h ig h e r p l a t e . Economic con­

s id e r a tio n s in d ic a te th e convenience o f adding th e minimum amount o f

w ater re q u ire d f o r e f f e c t iv e p u r i f i c a t i o n . O therw ise e x ce ssiv e column

c a p a c ity and steam consum ption would be re q u ire d in th e fo llo w in g stag e

o f th e p ro c e ss . D ata a v a ila b le in th e l i t e r a t u r e on th e o p e ra tin g con­

d itio n s o f t h i s p ro cess a re m eager.

I n t e r e s t i n g r e s u l t s have been o b ta in e d by th e w r ite r on p r e lim i­

n a ry experim ents designed to e s t a b lis h optimum c o n d itio n s f o r the

p u r if ic a tio n o f raw d i s t i l l a t e s from ferm ented m o lasses. The same p u r i­

fy in g column d e sc rib e d above was u t i l i s e d .

In one experim ent a raw d i s t i l l a t e was d ilu te d to about 100°Proof

and fed to th e column a t p la te 15. W ater a t 2026F was added in th e to p

p la te o f th e column in s u f f i c i e n t amounts to y ie ld a bottom p ro d u c t o f

about 30°P. .The a n a ly t ic a l r e s u l t s o f com posite sam ples o f th e fe e d ,

nh ead s" and bottom p ro d u ct o f th e column a rc g iv en below. The a c id s ,

a ld eh y d es, e s t e r s and f u s e l o i l c o n c e n tra tio n s a re ex p ressed in mgs. o f

a c e tic a c id , a c e ta ld e h y d e , e th y l- a c e ta te and amyl a lc o h o l, r e s p e c tiv e ly ,

p er 100 m l. o f sam ple. The a lc o h o l c o n te n t i s ex p ressed i n d eg rees p ro o f

a t 60°F.

Aldehydes E s te rs A cids F u se l O il A lcohol

Feed 1 5 .5 32.0 0 .6 90 9 8.1
Heads 470.5 183.0 1 .4 2000 75.7
Bottom P roduct 1 .6 0 0 20 33.2

In a second experim ent th e same feed was d ilu te d to 40°P and fed

a t p la te 32 o f th e column. W ater a t 202°F was added a t th e to p p la te

 82

to produce a bottom product o f ab o u t 10°P. The a n a ly s is o f th e bottom

p ro d u ct ob tain ed was as fo llo w s:

Aldehydes 0 .8
E s te rs 0 .0
Acids 0 .0
F usel O il 0.0
A lcohol 1 1 .3

These experim ents were o f an e x p lo ra to ry n a tu r e . The d a ta ob­

ta in e d , although incom plete and r e q u ir in g c o n firm a tio n , in d ic a te s th a t

t h i s p ro c e ss i s v e ry e f f e c t i v e . Com pletion o f th e se s tu d ie s i s planned

f o r th e n e a r f u tu r e .

As i s i n f e r r e d from th e r e s u l t s p re se n te d above, t h i s method o f

o p e ra tio n would n o t be s u ita b le f o r th e p ro d u c tio n o f a lc o h o lic b everages

sin c e i t r e s u lts i n a com plete e lim in a tio n o f a l l co n g en eric su b stan ces

p re s e n t i n th e raw d i s t i l l a t e r e s u l t i n g in a n e u tr a l m ix tu re o f e th y l

a lc o h o l and w ater i n which th e s u b sta n c e s re s p o n s ib le fo r th e c h a r a c te r ­

i s t i c s and q u a lity o f genuine b everages a re a b s e n t.

B ehavior o f Fusel O il in th e O p eratio n o f th e R e c tify in g Column

The a lc o h o l bottom s from t h e ‘p u rify in g column a rc fe d to th e

r e c t i f y i n g column where, b e s id e s c o n c e n tra tin g th e a lc o h o l to th e d e s ire d

a lc o h o lic s tr e n g th , rem aining im p u r itie s a re e lim in a te d a s w e ll a s th o se

formed in th e column d u rin g th e r e c t i f i c a t i o n p ro c e s s . The e n ric h in g

s e c tio n o f th e column u s u a lly c o n ta in s from 30 to 50 p l a t e s . The to p

d i s t i l l a t e com position i s v ery c lo s e to t h a t o f th e a lc o h o l-w a te r

a ze o tro p e which i s 95.58# a lc o h o l by w eig h t. A sm all stream c o n ta in in g

2% to 5% o f the a lc o h o l fe d to th e column i s removed a s h ead s. The main

p ro d u ct i s removed as a l i q u i d s id e -s tre a m s e v e ra l p la te s below th e to p

 83

p la te . By t h i s procedure th e c o n te n t o f low b o ilin g im p u r itie s in th e

main pro d u ct i s reduced to a minimum. The c o n c e n tra tio n o f th e s e im­

p u r i t i e s in c re a s e s s u c c e s s iv e ly tow ard th e upper end o f th e column and

re a c h e s a maximum c o n c e n tra tio n in th e overhead d i s t i l l a t e .

The bottom product o f t h i s column c o n s is ts o f w ater and w ater

s o lu b le im p u r itie s . The c o n c e n tra tio n o f a lc o h o l in th e in te rm e d ia te

p la te s v a r ie s between zero and th e a z e o tro p ic co m p o sitio n .

F u sel o i l i s com pletely s o lu b le in e th y l a lc o h o l and, being le s s

v o l a t i l e , i t i s fo rce d down th e column by r e c t i f i c a t i o n . As th e o i l s

p ass down to th e bottom , th e y become im m iscible in th e h ig h e r w ater

c o n c e n tra tio n s and steam d i s t i l l a t i o n fo rc e s them to r i s e . Not being

a b le to escap e, due to th e two opposing e f f e c t s , by e i t h e r end o f th e

column, th e f u s e l o i l accum ulates a t some in te rm e d ia te p l a t e s . The lo c a ­

tio n o f th e p la te o f maximum accum ulation and th e d i s t r i b u t i o n o f f u s e l

o i l along th e column a re fu n c tio n s o f such v a r ia b le s a s r e f l u x r a t i o

u t i l i z e d , a lc o h o l c o n te n t in th e feed and number o f p l a t e s . During th e

f i r s t hours a f t e r a d i s t i l l a t i o n run i s s t a r t e d , f u s e l o i l i s p e rm itte d

to accum ulate u n t i l a given c o n c e n tra tio n i s o b ta in e d i n th e p la te o f

maximum accu m u latio n . At t h i s p o in t, w ithdraw al o f th e f u s e l o i l s id e -

stream i s commenced. The volume o f th e s id e -s tre a m should be such as to

produce a m a te ria l balance between th e f u s e l o i l e n te r in g w ith th e feed

and t h a t le a v in g w ith th e main p ro d u c t, th e wh e a d s M a n d th e o i l s id e -

stream i t s e l f . The maximum f u s e l o i l c o n c e n tra tio n allow ed i n th e

p la te o f g r e a te s t accum ulation depends on th e s p e c if ie d c o n te n t o f fu s e l

o i l in th e main p ro d u c t. Should th e f u s e l o i l s id e stream n o t be w ith ­

drawn, th e h ig h e r a lc o h o ls w ill c o n tin u e to accum ulate in th e column w ith

 84

a co rresp o n d in g in c re a s e in th e f u s e l o i l c o n te n t in th e main p ro d u c t.

T his accum ulation w ill c o n tin u e u n t i l a f u s e l o i l c o n te n t in th e main

p ro d u c t i s reached which produces a m a te r ia l b alan ce between th e o i l en­

t e r in g th e column w ith th e feed and t h a t le a v in g in the v a rio u s stre am s.

I f in th e course o f normal o p e ra tio n th e f u s e l o i l c o n te n t in th e

feed v a r ie s , th e r e w ill be e i t h e r an in c re a s e o r a d e p le tio n o f th e f u s e l

o i l accum ulated in th e column u n t i l such c o n c e n tra tio n s a re o b ta in e d a t

th e p la te s from which th e f u s e l o i l s id e -stre a m and th e main pro d u ct a re

being removed t h a t produces th e re q u ire d o i l b alan ce in th e column.

In a c tu a l d i s t i l l e r y o p e ra tio n in th e m anufacture o f i n d u s t r i a l

a lc o h o l and a lc o h o lic b ev erag es, i t i s n e c e ssa ry on some o ccasio n s to

a l t e r th e o p e ra tin g c o n d itio n s o f th e p u rify in g and r e c ti f y in g columns

due to v a r ia tio n s in th e q u a lity o f th e ferm ented mash and co n seq u en tly

in th e raw d i s t i l l a t e from th e b e e r column. F u r th e r , in th e p ro d u ctio n

o f a lc o h o lic beverages i t i s a common p r a c tic e to produce d i s t i l l a t e s o f

d i f f e r e n t c h a r a c t e r i s t i c s under d i f f e r e n t o p e ra tin g c o n d itio n s which,

a f t e r ag in g , a re p ro p e rly blended to produce a w e ll balanced p ro d u c t.

Very o fte n p u b lic p re fe re n c e fo r c e s m an u factu rers to a l t e r th e c h a r a c te r ­

i s t i c s o f t h e i r pro d u ct which in tu rn r e q u ir e s a l t e r a t i o n s in th e

c o n d itio n s o f o p e ra tio n in th e d i s t i l l a t i o n phase o f th e p ro c e s s . As an

example o f t h i s i t may be m entioned t h a t in li n e w ith th e in c re a s in g

tre n d toward th e consumption o f l i g h t ty p e beverages in th e U nited S ta te s ,

s e v e ra l m an u factu rers o f medium and heavy bodied rums in th e C aribbean

Area have been fo rce d to m odify t h e i r form er p ro c e sse s o f o p e ra tio n , in

some c ases in v o lv in g rearrangem en t o f th e com plete d i s t i l l a t i o n u n i t , in

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o rd e r to su p p ly th e new m arket demands.

There i s no p u b lish e d d a ta on f u s e l o i l d i s t r i b u t i o n alo n g th e

r e c t i f y i n g column under d i f f e r e n t o p e ra tin g c o n d itio n s . A gain, as f o r

th e case o f i n te r m it te n t d i s t i l l a t i o n p ro c e s s e s , due to u n c e r ta in tie s

re g a rd in g th e c o n s titu e n ts o f f u s e l o i l p re s e n t and t h e i r r e s p e c tiv e

c o n c e n tra tio n s in any s p e c if ic c a s e , no a tte m p t has been made to p r e d ic t

i t s d i s t r i b u t i o n by th e o r e t i c a l c o n s id e ra tio n s .

A v a ila b i lity o f d i s t r i b u t i o n d a ta under d i f f e r e n t o p e ra tin g con­

d itio n s would h e lp th e o p e ra to r in th e s e le c tio n o f th e l a t t e r . These

d a ta would a s s i s t in e s ta b lis h in g th e p la te from which th e main p roduct

should be w ithdraw n. I t would a ls o in d ic a te th e p la te o f maximum con­

c e n tr a tio n from which th e f u s e l o i l s id e -s tre a m should be removed. It

would in d ic a te what maximum c o n c e n tra tio n could be p e rm itte d on th e p la te

o f maximum accum ulation w ith o u t s u rp a ssin g th e s p e c if ie d l i m i t o f f u s e l

o i l c o n te n t in th e main p ro d u c t. O peration a t th e h ig h e s t a llo w a b le con­

c e n tr a tio n o f f u s e l o i l in th e p la te o f maximum accum ulation would be

advantageous s in c e a sm aller f u s e l o i l s id e -s tre a m would be re q u ire d to

m ain tain a m a te ria l b alan ce between th e f u s e l o i l e n te r in g th e column

w ith a given feed and t h a t le a v in g w ith th e p ro d u c ts . S m aller and r ic h e r

f u s e l o i l stream s would r e p r e s e n t sm a lle r lo s s e s in e th y l a lc o h o l. In

la r g e f a c t o r i e s where th e f u s e l o i l i s s u b je c te d to f u r th e r p ro c e ssin g

f o r th e re c o v e ry o f e th y l a lc o h o l and f o r in c re a s in g th e c o n c e n tra tio n

o f h ig h e r a lc o h o ls in th e f i n a l f u s e l o i l b y -p ro d u c t, th e h a n d lin g o f a

sm a lle r and r i c h e r f u s e l o i l stream would r e p r e s e n t sav in g s i n th e c o s ts

o f o p e ra tio n and in equipm ent in v e stm e n t.

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In th e d esig n o f commercial d i s t i l l a t i o n p la n ts , f u s e l o i l d is ­

t r i b u t i o n d a ta should be examined b e fo re e s ta b lis h in g th e re q u ire d r e f lu x

r a t i o f o r a given p ro d u ct s p e c i f ic a ti o n . The r e f l u x r a t i o in tu rn w ill

determ in e th e d iam eter o f th e column f o r a given o u tp u t c a p a c ity . Be­

s id e s being used in p r e d ic tin g th e p la t e s from which th e main product

and th e f u s e l o i l s id e -s tre a m should be w ithdraw n, i t would p ro v id e a

b a s is f o r e s tim a tin g th e amount o f f u s e l o i l stream to be produced and

th e c o n c e n tra tio n s o f e th y l a lc o h o l and f u s e l o i l in i t . T h is inform a­

t i o n , in tu r n , w ill be th e b a s is f o r th e d e sig n o f th e e th y l a lc o h o l

re c o v e ry u n i t . At p re s e n t d esig n o f t h i s equipment i s based on h ig h ly

e m p iric a l methods.

The absence o f d i s t r i b u t i o n d a ta under d i f f e r e n t o p e ra tin g con­

d i t i o n s r e s u l t s in th e u t i l i s a t i o n in most c a se s o f e m p iric a l methods

o f o p e ra tio n which c i t h e r y ie ld p ro d u c ts o f low q u a lity o r in v o lv e th e

s e p a ra tio n from th e p ro c e ss o f v e ry la r g e Mheads* and f u s e l o i l c u ts .

The l a t t e r r e s u l t s i n e x c e ssiv e lo s s e s o f e th y l a lco h o l o r in th e need

f o r e x te n s iv e re -p ro c e s s in g o f bjr-p ro d u c t stream s o r b o th .

Robinson and G ill i l a n d p re s e n t a s e t o f d i s t r i b u t i o n d a ta c re d ite d

to B arb et (3 1 4 ). The o p e ra tin g c o n d itio n s , however, a re n o t given in

fu ll. There i s no in fo rm a tio n re g a rd in g th e r e f l u x r a t i o u t i l i z e d and

th e v a lu e s fo r th e v a rio u s stre am s. A ccording to t h i s d a ta , peak con­

c e n tr a tio n s o f f u s e l o i l occur in two d i f f e r e n t p l a te s r e q u ir in g th e

w ithdraw al o f two d i f f e r e n t s id e -s tre a m s . The upper p o in t o f maximum

accum ulation f a l l s in th e f o u r th p la te over th e feed p la te w h ile th e

low er co rresp o n d s to th e s ix th p la t e below th e fe e d p l a t e . The in fo rm a tio n

 87

i s c o n tr a d ic to r y re g a rd in g the n a tu r e o f th e h ig h e r a lc o h o ls p re s e n t a t

each o f th e two p la te s o f peak c o n c e n tra tio n . The c o n c e n tra tio n diagram

p re se n te d in d ic a te s th a t th e upper accum ulation c o n s is ts o f th o se a lc o h o ls

more so lu b le in w ater w hile th e lo w er p o rtio n i s formed by th e most i n ­

s o lu b le ones such as amyl a lc o h o l. The t e x t , however, say s th a t th e o i l s

l e s s so lu b le in w ater c o l l e c t h ig h e r up i n the column th an th o se more

s o lu b le . In th e o p e ra tin g c o n d itio n s g iv en i t i s s p e c if ie d th a t th e

a lc o h o l c o n te n t in th e fe e d i s 40$ by volume. The c o n c e n tra tio n c h a r t

in d ic a te s t h a t th e a lc o h o l c o n te n t in th e li q u id phase o f th e feed p la te

i s 80$ by volume. Should th e fe e d have been added a t th e p la te c o n ta in in g

40$ a lc o h o l by volume, i t seems th a t' th e maximum accum ulation would have

been produced a t some p o in t above th e fe e d p la te . F u rth e r, i t i s b e lie v e d

t h a t th e d ilu tio n e f f e c t o f the f e e d , which c o n ta in s l e s s f u s e l o i l than

th e l iq u id on th e p l a t e s , may have produced th e re g io n o f low er f u s e l o i l

c o n c e n tra tio n between th e two p e ak s. In i n d u s t r i a l p r a c tic e th e o i l

stream i s n o rm ally withdrawn from a s in g le p o in t above th e feed p l a t e .

A ccording to th e c o n c e n tra tio n diagram and th e in fo rm a tio n given i n th e

t e x t , th e r a t i o o f f u s e l o i l c o n c e n tra tio n s between th e fe e d and th e

l i q u i d in th e two p la te s o f peak c o n c e n tra tio n i s o f th e o rd e r o f 4 :1 .

D ata found in th e l i t e r a t u r e and th e ex p erim en tal r e s u l t s p re s e n te d i n

C hapter VII in d ic a te t h a t r a t i o s o f th e o rd e r o f 100:1 and h ig h e r a re

o b ta in e d in commercial p r a c tic e (2 8 0 ). A ccording t o th e in fo rm a tio n

g iv e n , th e f u s e l o i l c o n te n t in t h e raw d i s t i l l a t e from th e beer column

i s 2 grams p er h e c t o l i t e r o f liq u o r c o n ta in in g 50$ a lc o h o l by volume

which corresponds to 2 .0 m illig ra m s per 100 m i l l i l i t e r s o f raw p ro d u c t

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o r a p p ro x im ately 0.004$ o f th e a b s o lu te a lc o h o l p r e s e n t. The ran g e o f

com position o f f u s e l o i l in th e raw d i s t i l l a t e , however, i s u s u a lly from

0 .1 $ to 0 .7 $ o f a b s o lu te a lc o h o l o r 25 to 175 tim es h ig h e r (316, 3 2 4 ).

The f u s e l o i l c o n c e n tra tio n given fo r th e l i q u i d in th e p la te s o f maximum

accum ulation i s about 15 grams p er h e c t o l i t e r o r 15 m illig ra m s p er 100

m illilite rs . The c o n c e n tra tio n s o b ta in e d in p r a c tic e a rc u s u a lly 500

to 1200 tim es g r e a te r .

A ccording to th e c o n c e n tra tio n diagram , th e a p p a re n t a lc o h o l con­

t e n t o f th e p la te where th e upper peak c o n c e n tra tio n f a l l s , i s ab o u t 172°P.

Again t h i s i s in d isc re p a n c y w ith th e r e s u l t s found in p r a c tic e which

in d ic a te t h a t f u s e l o i l accum ulates in th e ran g e o f 132-144° a p p aren t

p ro o f (316, 322, 32 4 ).

Fertm an, P o k ro v sk ii and U ishnevskaya have s tu d ie d th e f u s e l o i l

c o n te n t by p la te s o f a d i s t i l l a t i o n column b ein g o p e ra te d by a p ro c e ss

which d e p a rts from c o n v e n tio n a l co n tin u o u s d i s t i l l a t i o n (2 8 0 ). A lthough

th e o r ig i n a l a r t i c l e docs n o t d e s c rib e th e d i s t i l l a t i o n p ro c e ss used nor

g ive th e v a lu e s o f th e o p e ra tin g v a r ia b le s , i t can be in f e r r e d t h a t th e

column i s i n s t a l l e d over a k e t t l e and th e fe e d i s added, a p p a re n tly i n a

con tin u o u s manner, d u rin g th e f i r s t p o rtio n o f th e o p e ra tin g c y c le .

F u r th e r , th e f u s e l o i l c o n te n t by p la te s i s re p o rte d a s p er c e n t by volume

o f a b s o lu te a lc o h o l p re s e n t b u t th e a lc o h o l c o n te n t by p la te s i s n o t g iv e n .

In view o f th e la c k o f d a ta on f u s e l o i l d i s t r i b u t i o n under d i f ­

f e r e n t o p e ra tin g c o n d itio n s and i t s p o te n ti a l v a lu e in th e d e sig n and

o p e ra tio n o f c o n tin u o u s d i s t i l l a t i o n u n i t s , i t was d ecid ed to conduct

a s e r i e s o f experim ents a t d i f f e r e n t fe e d co m p o sitio n s and r e f l u x r a t i o s

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c o v erin g th e normal range o f o p e ra tio n found in commercial p r a c t i c e . The

r e s u l t s o f th e s e s tu d ie s a re p re se n te d in C hapter V II.

P u r if ic a t io n o f th e F u sel O il Take-O ff

The f u s e l o i l stream , as removed from th e r e c t i f y i n g column, con­

ta in s r a th e r la r g e c o n c e n tra tio n s o f w ater and eth)rl a lc o h o l and a sm all

per c e n t o f hig h b o ilin g su b stan ces such as f a t t y a c id s and e s t e r s . D ata

a v a ila b le in th e l i t e r a t u r e and th e r e s u l t s p re se n te d in C hapter VII

in d ic a te t h a t th e h ig h e r a lc o h o ls c o n te n t in th e r u n - o f f u s u a lly v a r ie s

between 7.0$ and 20$ by w eight (2 8 0 ). The c o n te n t o f im p u r itie s i s o f

th e o rd e r o f 0 .1 $ to 1 ,0 $ . Large p la n ts w ith e f f i c i e n t equipment and

c o n tro l methods should be a b le to o p e ra te s te a d ily c lo s e to th e upper

l i m i t and even a t a somewhat h ig h e r c o n c e n tra tio n . S m aller i n s t a l l a t i o n s

w ith l e s s e f f i c i e n t equipm ent, and v e ry o fte n la c k in g adequate c o n tro l

system s and te c h n ic a l s u p e rv is io n , produce f u s e l o i l stream s c o n ta in in g

f u s e l o i l c o n c e n tra tio n s much low er th an 7 .0 $ . Based on th e r e s u l t s o f

C hapter V II, and n e g le c tin g th e c o n te n t o f h ig h e r b o ilin g s u b sta n c e s, a

ty p ic a l com position by w eight f o r f u s e l o i l ta k e - o f f from m olasses o r ig in

could be given as fo llo w s;

Higher a lc o h o ls 12$
E th y l a lc o h o l 47$
Water 41$

The a p p aren t p ro o f o f such a m ix tu re would be ab o u t 135°P a t 60°F.

In i n d u s t r i a l p r a c tic e th e f u s e l o i l stream i s p ro c e ssed to re c o v e r

as much as p o s s ib le o f th e e th y l a lc o h o l c o n tain ed in i t . In l a r g e r i n ­

s t a l l a t i o n s th e f u s e l o i l f r a c tio n i s f u r t h e r p u r if ie d u n t i l re q u ire d

s p e c if ic a tio n s a re o b ta in e d f o r i n d u s t r i a l p u rp o se s. In sm a lle r p la n ts ,
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e s p e c ia lly th o se lo c a te d in la n d s f a r removed from i n d u s t r i a l c e n te r s ,

th e e n ric h ed f u s e l o i l produced, which s t i l l c o n ta in s some a lc o h o l and

w a te r, i s g e n e r a lly d is c a rd e d . Numerous a p p a ra tu s have been d e sc rib e d

i n th e l i t e r a t u r e f o r th e s e p a ra tio n and p u r i f i c a t i o n o f f u s e l o i l (267,

271, 272, 274, 286, 293, 300, 305, 309, 316, 317, 3 2 2 ). G e n e ra lly th e s e

a p p a ra tu s , alth o u g h d if f e r i n g in s p e c if ic d e sig n f e a tu r e s , b a s i c a lly con­

s i s t o f d e v ic e s which cool th e f u s e l o i l stream and b rin g i t in c o n ta c t

w ith co ld d ilu tin g w ater in such p ro p o rtio n s a s to produce alm o st com­

p le te s e p a ra tio n o f th e h ig h e r a lc o h o ls in to an o i l y , upper la y e r which

i s d e ca n te d . Ullmann r e p o r ts t h a t by d il u tin g to 15 % a lc o h o l by volume,

th e f u s e l o i l s e p a ra te s r e a d il y (3 2 0 ). Much low er a lc o h o l c o n c e n tra tio n s

a re used i n many c a s e s . S u c c essiv e e x tr a c tio n s w ith w ater re d u c e th e

a lc o h o l c o n te n t and in c re a s e th e c o n c e n tra tio n o f h ig h e r a lc o h o ls in th e

f u s e l o i l b y -p ro d u ct (2 7 6 ), A pparatus f o r use w ith c o n tin u o u s and i n t e r ­

m itte n t d i s t i l l a t i o n u n its have been d e v ise d . M o d ific a tio n s o f th e

c o n v e n tio n a l method in v o lv e removing th e f u s e l o i l ta k e - o f f in th e vapor

phase and b u b bling i t through c o o lin g w ater (271, 2 8 6 ).

D ata i s a v a ila b le in th e l i t e r a t u r e on th e a n a ly s is o f e n ric h e d

f u s e l o i l s from numerous so u rc e s which in d ic a te s d i f f e r e n t d e g re es o f

enrichm ent (273, 288, 302, 311, 312, 316, 3 2 3 ). W ater c o n te n t v a r ie s from

about 6% to 20% w h ile e th y l a lc o h o l v a r ie s from ab o u t V% to 11% ,

V arious methods have been used to enhance th e s e p a ra tio n o f a lc o h o l

and w ater from f u s e l o i l b y -p ro d u c ts . S a tu ra te d s o lu tio n s o f sodium

c h lo r id e , potassium c a rb o n a te , calciu m c h lo rid e and o th e r s a l t s , in s te a d

o f w ater have been used in i n d u s t r i a l p r a c tic e (284, 295, 32 2 ).

 91

K r a s n its k ii has p a te n te d a method in R u ssia i n which i t i s claim ed

t h a t by in tro d u c in g a s o lu tio n o f sodium c h lo rid e in to th e f r a c tio n a tio n

to w er, th e s e p a ra tio n o f f u s e l o i l i s improved (2 9 5 ).

K ie fe r has p a te n te d , in t h i s C ountry, a d i s t i l l a t i o n a p p a ra tu s ,

c o n s is tin g o f two con tin u o u s packed columns, fo r c o n v e rtin g low p ro o f

wash c o n ta in in g f u s e l o i l in to liigh p ro o f e th y l a lc o h o l (2 9 3 ).

Sw allen and T in d a ll have p a te n te d a p ro cess fo r th e p u r if ic a tio n ,

o f c i t h e r g ra in o r m olasses f u s e l o i l , which in v o lv e s b rin g in g th e crude

f u s e l o i l , in th e p resen ce o f c e r ta i n amounts o f e ith e r s u lf u r ic o r phos­

p h o ric a c id s , in to c o n ta c t w ith an e s t e r o f amyl a lc o h o l having a b o ilin g

p o in t s u b s ta n tia lly h ig h e r than t h a t o f th e f u s e l o i l to be tr e a te d (3 1 8 ).

The e s te r should be p re s e n t in s u f f i c i e n t amount to r e t a i n th e im p u ritie s

p re s e n t in th e f u s e l o i l , th e l a t t e r bein g removed by d i s t i l l a t i o n a t a

te m p e ra tu re which i s ap p ro x im ately eq u al to o r s l i g h t l y above th e b o ilin g

p o in t o f amyl a lc o h o l, b u t s u b s t a n t i a l l y below th e b o ilin g p o in t o f th e

e s te r. Amyl p h th a la te , s t e a r a t e , b o ra te and phosphate, among o th e r s , may

be u sed .

C ontinuous f u s e l o i l ra s h e rs a r e used in modern d i s t i l l a t i o n u n its

(2 9 4 ). In th e se a p p a ra tu s , th e f u s e l o i l ta k e - o f f i s e x tr a c te d c o u n te r-

c u r r e n tly w ith w ater in a packed column which i s p ro v id ed in th e to p r a th

d isen g a g in g s e c tio n from where th e c o n c e n tra te d f u s e l o i l upper la y e r i s

d e ca n te d .

In an o th er process, d e sc rib e d in th e l i t e r a t u r e , th e f u s e l o i l stre am s,

removed from th e p u rify in g and r e c t i f y i n g columns, a re d i r e c t l y fe d in to a

co n tinuous bubble cap p la te column (2 6 6 ). The overhead p ro d u ct o f t h i s

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column c o n ta in s m ost o f th e a lc o h o l and some o f th e w ater p re s e n t i n th e

feed* A c o n c e n tra te d f u s e l o i l stream i s removed from th e in te rm e d ia te

p la te s and p a ss e s to a d e c a n te r. The upper la y e r i s d ecan ted and forms

th e f u s e l o i l b y -p ro d u c t. The lo v e r la y e r i s re tu rn e d to th e low er

p la te s o f th e column.

Subsequent p u r i f i c a t i o n o f f u s e l o i l f o r commercial use i s g e n e ra l­

ly ach iev ed by means o f e i t h e r co n tin u o u s o r i n t e r m i t t e n t d i s t i l l a t i o n s .

The purpose o f t h i s o p e ra tio n i s to remove an y e th y l a lc o h o l and w ater

rem aining i n th e m ixture* a s w e ll a s th e h ig h e r b o ilin g f r a c tio n s con­

ta in in g im p u r itie s o f low v o l a t i l i t y . S e v e ra l p ro c e sse s o f f r a c tio n a tio n

have been sug g ested i n th e l i t e r a t u r e .

K hshanouskii d e s c rib e s a f r a c tio n a l d i s t i l l a t i o n method i n which

a l l f r a c tio n s up to 97-98#C, which* a cco rd in g to him* c o n ta in a l l th e

lo v e r b o ilin g su b sta n c e s n o t allo w ed i n f u s e l o il* have v o l a t i l i z e d (2 9 2 ).

The m ain d i s t i l l a t i o n i s th en conducted to 135-7°C . The f r a c tio n rem ain­

in g above t h i s te m p e ratu re i s d is c a rd e d .

Ullmann r e p o r ts on a method i n which th e f u s e l o i l to be p u r if ie d

i s f i r s t d e -v a te re d w ith calcium c h lo r id e and su b se q u e n tly f r a c t i o n a l l y

d i s t i l l e d and s e p a ra te d in to th e d e s ir e d f r a c tio n s (3 2 0 ).

Longinov and P ry an isb n ik o v have s tu d ie d th e f r a c tio n a t io n o f f u s e l

o i l i n commercial s c a le w ith o u t p re v io u s d e h y d ra tio n . Data i s g iv en on

th e amounts o f propyl* is o b u ty l and amyl a lc o h o ls which p a ss o v er w ith

th e e a r l y f r a c tio n s which c o n ta in th e w ater an d e th y l a lc o h o l p re s e n t i n

th e o r ig i n a l p ro d u c t (3 0 2 ).

A method has been p a te n te d i n Germany i n which m ix tu re s c o n ta in in g

 93

e th y l a lc o h o l, w ater and f u s e l o i l a r e f r a c t i o n a l l y d i s t i l l e d in th e

p re sen c e o f an a l k a l i o r a lk a l in e e a r th s a l t o f an a l i p h a t i c a c id , a s ,

f o r example, a m ix tu re o f sodium a c e ta te and potassium a c e ta te (2 7 9 ).

The s a l t may be added to th e m ix tu re in th e s t i l l o r th e vapor from th e

s t i l l can be passed in c o u n terflo w w ith an a lc o h o l s o lu tio n o r suspension

o f th e s a l t . I t i s c la m e d t h a t th e p ro c e ss y ie ld s a 95# a lc o h o l d i s ­

t i l l a t e and a re s id u e o f f u s e l o i l .

The d e s c r ip tio n s a v a ila b le in th e l i t e r a t u r e on th e above m entioned

a p p a ra tu s and p ro c e sse s c o n s is t o f g e n e r a l i t i e s . No s p e c i f ic v a lu e s o r

o p e ra tin g c o n d itio n s a r e given-. R eflu x r a t i o s and p ro p o rtio n s o f sub­

s ta n c e s added a rc n o t given in any c a s e . Tem perature ran g e f o r th e

v a rio u s f r a c tio n s in f r a c t i o n a l d i s t i l l a t i o n s a re giv en in v e ry few

cases.
 CHAPTER VI

AUTOMATIC CONTROLS IN THE ALCOHOLIC DISTILLATION

W hile p lan n in g th e re s e a rc h work, which load a s i t s o b je c tiv e th e

g a th e rin g o f experim ental d a ta on f u s e l o i l d i s t r i b u t i o n in th e r e c t i f y ­

in g column under d i f f e r e n t o p e ra tin g c o n d itio n s , th e need o f u t i l i z i n g an

adequate system fo r c o n tr o llin g the o p e ra tio n a l v a r ia b le s was prom ptly

re c o g n iz e d .

No in fo rm a tio n was found in th e l i t e r a t u r e re g a rd in g th e p e r f o r ­

mance o f au to m atic c o n tro l system s used in th e a lc o h o lic d i s t i l l a t i o n . ,

In view o f t h i s la c k o f in fo rm a tio n and c o n sid e rin g t h a t th e p resen ce o f

co n tin u o u sly changing c o n d itio n s would p re c lu d e th e c o lle c tio n o f r e l i a b l e

d a ta , a s e r i e s o f experim ents were conducted w ith th e o b je c tiv e o f e s ta b ­

li s h i n g a c o n tro l system which would f u l f i l l th e re q u ire m e n ts o f t h i s

p a r t i c u l a r d i s t i l l a t i o n p ro c e s s . The r e s u l t s o f th e s e s tu d ie s a re p re ­

se n te d in th e fo llo w in g p a ra g rap h s.

To o b ta in s a t i s f a c t o r y r e s u l t s in th e o p e ra tio n o f a d i s t i l l a t i o n

column, e i t h e r continuous o r i n t e r m i t t e n t , i t i s o f utm ost im portance t h a t

th e o p e ra tin g c o n d itio n s be r ig o r o u s ly c o n tr o lle d . A co n tin u o u s d i s t i l ­

l a t i o n u n i t , c o r r e c t ly designed and pro v id ed w ith an ad eq u ate c o n tro l

system i s cap ab le o f producing overhead d i s t i l l a t e s , bottom s, and s id e -

stream p ro d u c ts o f c o n sta n t com position and, co n se q u e n tly , o f uniform

q u a lity .

Once th e column has a tta in e d e q u ilib riu m c o n d itio n s and c o lle c tio n

o f th e p ro d u c ts has coinnenced, i t i s in d is p e n s a b le t h a t such c o n d itio n s o f

94
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e q u ilib riu m be m ain tain ed th ro u g h o u t th e whole co u rse o f th e o p e ra tio n .

In numerous d i s t i l l a t i o n p ro c e ss e s , a s in a lc o h o lic beverages and i n ­

d u s t r i a l a lc o h o l, th e im p u r itie s to be e lim in a te d d u rin g th e d i s t i l l a t i o n

p ro c e ss a re o f such a n a tu re t h a t t h e i r p re sen c e in th e f i n a l p ro d u c t,

even in v e ry sm all c o n c e n tra tio n s , g r e a tly d e tr a c ts from th e q u a lity o f

th e l a t t e r . U nstable c o n d itio n s in th e column fo r r e l a t i v e l y s h o rt

p e rio d s o f tim e may r e s u l t in th e p resen ce o f th e s e im p u r itie s in th e

p ro d u ct r e c e iv in g tan k in s u f f i c i e n t c o n c e n tra tio n s to make n e c e s sa ry

th e re p ro c e s s in g o f th e whole c o n te n t o f th e ta n k .

H a rb ert has p o in te d o u t t h a t , in most c a s e s , la c k o f ad eq u ate

c o n tro l system s and n o t d e fe c tiv e d e sig n , i s re s p o n s ib le f o r d e f ic ie n t

s e p a ra tio n s and d e v ia tio n s from th e o r e tic a l e x p e c ta tio n s (3 3 5 ). ■

In th e o p e ra tio n o f a co n tin u o u s d i s t i l l a t i o n column th e problem

o f c o n tro l would be g r e a tly s im p lifie d i f i t were p o s s ib le to m a in ta in

c o n sta n t th e com position, th e te m p e ratu re and th e r a t e o f th e feed

stream . Under th e s e c o n d itio n s , and u sin g au to m atic c o n tr o lle r s to f i x

th e o th e r v a r ia b le s o f th e p ro c e ss— such a s b o i l up r a t e ; r e f lu x r a t e ;

r e f lu x te m p e ra tu re ; p re s s u re ; r a t e o f overhead, bottom s and s id e - s tr e a m '

p ro d u c ts; and l e v e l s — th e o c cu rran ce o f v a r ia ti o n s and e r r a t i c c o n d itio n s

would be l e s s fre q u e n t and s e r io u s . In i n d u s t r i a l p r a c tic e i t i s pos­

s i b l e to m a in ta in th e tem p eratu re and th e r a t e o f th e feed v i r t u a l l y

c o n s ta n t. However, due to th e c h a r a c t e r i s t i c s and n a tu r e o f commercial

p ro c e s s e s , i t i s im p o ssib le to m a in ta in r ig o r o u s ly c o n sta n t th e compo­

s i t i o n o f th e fe e d . T his g iv e s o r ig in to most o f th e v a r ia tio n s and

u n s ta b le c o n d itio n s which develop d u rin g th e o p e ra tio n o f a co n tin u o u s

 96

colunn. V a ria tio n s in th e com position o f th e fe e d can be l a r g e l y red u ced ,

alth o u g h n o t com pletely e lim in a te d , by th e u se o f f a i r l y la r g e in te rm e ­

d ia te r e c e iv in g ta n k s between s u c c e ssiv e columns in th e p ro c e s s .

The c o n tr o l system u t i l i z e d should be cap ab le o f d e te c tin g d e v ia ­

tio n s from s te a d y c o n d itio n s and o f producing th e re q u ire d c o r r e c tiv e

a c tio n .

Numerous c o n tro l system s have been su g g ested fo r th e c o n tr o l o f

d i s t i l l a t i o n coluim s. A ll have th e comnon o b je c tiv e o f m a in ta in in g th e

dynamic e q u ilib riu m o f th e column in such a fa sh io n t h a t a p ro d u c t o f

hig h and uniform q u a lity i s o b ta in e d .

In a d d itio n to th e use o f te m p e ratu re as a fu n c tio n o f com p o sitio n ,

s e v e ra l o th e r p h y s ic a l and chem ical p r o p e r tie s o f p ro d u ct stream s have

been used a s a b a s is f o r c o n tro l sy stem s. Among o th e r s , e l e c t r i c a l con­

d u c tiv ity , in d e x o f r e f r a c t i o n and in f r a r e d r a d ia tio n s can be m entioned

(348, 352, 35 7 ).

Numerous a u th o rs have s tu d ie d th e e f f e c t o f c o n tr o llin g d i f f e r e n t

o p e ra tio n a l v a r ia b le s in th e perform ance o f a d i s t i l l a t i o n column.

Boyd h as d is c u s s e d i n s e v e ra l p u b lic a tio n s th e g e n e ra l p r in c ip le s

governing th e a p p lic a tio n <£ c o n tr o l system s to f r a c tio n a t in g colum ns.

The o p e ra tio n of c o n tro l system s, based on m a in ta in in g a c o n sta n t re fe re n c e

te m p eratu re in e ith e r th e r e c t i f y i n g o r th e s tr i p p i n g s e c tio n o f th e

column, has been s tu d ie d by t h i s a u th o r (327, 3 2 8 ).

Hartmand and Braun have d is c u s s e d th e f a c to r s and p r in c ip le s a f ­

f e c tin g th e u se o f c o n tro ls from t h e o r e t i c a l and p r a c t i c a l p o in ts o f

view (3 3 6 ).

U i t t i has stu d ie d th e optimum lo c a tio n o f te m p e ratu re c o n tr o l

 97

p o in ts and i t s e f f e c t on th e o p e ra tio n o f f r a c t io n a ti o n coluim s (354, 3 5 5 ).

The system s o f c o n tro l used in th e o p e ra tio n o f d i s t i l l a t i o n columns

can be c l a s s i f i e d a s e i t h e r 11q u a n tity c o n tro l sy stem s” o r "com position

c o n tr o l system s". In th e form er th e r a t e o f flow o f th e d i f f e r e n t stream s

to and from th e colunn, as w ell a s v a rio u s l e v e l s , a re m ain tain ed c o n s ta n t

w ith o u t any concern to v a ry in g com positions in th e p ro c e ss . In "com posi­

tio n c o n tro l system s" a t l e a s t one v a r ia b le i s a u to m a tic a lly o r m anually

a d ju s te d to m a in ta in c o n sta n t a re fe re n c e te m p e ra tu re , o r o th e r p ro p e rty ,

a t a given p o in t which in tu rn w ill m ain tain a c o n sta n t com position a t

t h a t p o in t and u ltim a te ly r e s u l t in th e p ro d u ctio n o f overhead or bottom

p ro d u c ts o f uniform co m p o sitio n . Bauer and O rr a p p lie d th e M cCabe-Tliiele

diagram to stu d y a n a ly t ic a lly th e use o f " q u a n tity c o n tro l" and "com posi­

tio n control** system s to c o rre c t fo r v a r ia t io n in th e com position o f th e

feed to a column o p e ra tin g a t h ig h r e f lu x r a t i o s (3 2 6 ). These a u th o rs

used a s c r i t e r i a o f th e adequacy o f th e c o n tr o l system s s tu d ie d , th e

a b i l i t y o f th e l a t t e r to m a in ta in c o n sta n t com positions in th e top and

bottom p ro d u c ts o f th e colunn. As ex p ected , th e y observed t h a t c o n tro l

system based on " q u a n tity c o n tr o l" a re n o t cap ab le o f d e te c tin g and p ro ­

ducing c o r r e c tiv e a c tio n s a g a in s t v a r ia tio n s in th e com position o f th e

p ro d u c ts and th e l i q u id in th e p l a t e s , produced by changes i n th e compo­

s i t i o n o f th e fe e d .

Most o f th e w orkers who have stu d ie d d i f f e r e n t methods o f c o n tro l

f o r d i s t i l l a t i o n columns have ta c k le d th e problem from th e p o in t o f view

o f m a in ta in in g c o n sta n t com position in one o f th e p ro d u cts from the ends

o f th e column; i . e . , th e overhead d i s t i l l a t e o r th e bottom s. Very l i t t l e

em phasis lias been given to th e a b i l i t y o f th e v a rio u s c o n tro l system s to

 98

m a in ta in c o n sta n t com positions a t in te rm e d ia te s e c tio n s o f th e column

from which s id e -s trc a m s would be w ithdraw n.

The o p e ra tio n o f a modem co n tin u o u s d i s t i l l a t i o n u n it f o r th e

p ro d u c tio n o f i n d u s t r i a l a lc o h o l and b everages was d e sc rib e d in C h ap ter V.

The behavior o f f u s e l o i l in th e p u rify in g and r e c t i f y i n g columns was

d is c u s s e d . I t was in d ic a te d t h a t under c o n v e n tio n a l o p e ra tin g c o n d itio n s

th e o i l would be removed as a s id e stream front th e r e c t i f y i n g column

s e v e ra l p la te s above th e feed p l a t e . I t was p o in te d o u t t h a t th e main

pro d u ct i s a ls o withdrawn as a s id e stream s e v e ra l p la te s below th e to p

p l a t e o f th e r e c t i f y i n g column. The o p e ra tio n o f th e b e er and p u rif y in g

columns o f th e u n it i s s im ila r to th e o p e ra tio n o f th e r e c t i f y i n g colunn

w ith th e e x cep tio n t h a t as m entioned above, two s id e -s tre a m s a re removed

from th e r e c t i f y i n g column in a d d itio n to overhead and bottom s p ro d u c ts .

The w ithdraw al o f s id e stream s from two p la te s n e a r th e two extrem es o f

th e r e c t i f y i n g s e c tio n , r e q u ir e s t h a t th e c o n tro l system employed be

cap ab le o f producing c o r r e c tiv e a c tio n s w ith o u t c au sin g a s h i f t in th e

d is t r i b u t i o n o f com positions alo n g th e whole r e c t i f y i n g s e c tio n . Con­

s t a n t com positions a r e re q u ire d n o t o n ly in th e main p ro d u c t b u t in a l l

p la te s o f th e r e c t i f y i n g s e c tio n .

C o n sid erin g t h a t th e c o n tr o l o f th e r e c t i f y i n g column i s more

complex th an th e c o n tro l o f th e b e e r and p u rify in g colum ns, from which

o n ly overhead and bottom p ro d u c ts a r e removed, our work tow ard th e de­

velopm ent o f an adequate c o n tro l system f o r th e a lc o h o lic d i s t i l l a t i o n

was conducted w ith th e r e c t i f y i n g column.

Once e q u ilib riu m com positio n s have been re a c h e d , i t i s in d is p e n s a b le

 99

t h a t th e s e be m ain tain ed throu g h o u t th e d u ra tio n o f th e o p e ra tio n . O th er­

w ise th e lo c a tio n o f th e f u s e l o i l accum ulation band would be d is p la c e d

alo n g th e column. Under e q u ilib riu m c o n d itio n s th e amount and com position

o f l i q u id and vapor in each p la te rem ains c o n s ta n t. C onsequently, th e

amount o f a lc o h o l hold-up in th e system i s c o n s ta n t. I f th e a lc o h o l con­

t e n t in th e feed d e c re a se s w hile th e same amount o f p ro d u ct i s being

removed, th e com position o f th e l a t t e r would n o t r e - a d ju s t i t s e l f in s ta n ­

ta n e o u s ly in o rd e r to produce th e re q u ire d a lc o h o l b alan ce in th e column.

For a r a th e r s h o rt p e rio d o f tim e th e com position o f th e main p ro d u ct in

th e upper p a r t o f th e column w ill rem ain s u b s ta n tia lly uniform w hile th e

a lc o h o l accum ulated in th e low er p la te s i s d e p le te d to such an e x te n t

t h a t th e com position o f th e pro d u ct i s a f f e c te d . During t h i s tim e -la g

th e tem perature o f th e low er p la te s would in c re a s e s te a d il y w hile th e

d is t r i b u t i o n o f c o n c e n tra tio n s o f f u s e l o i l i s d is p la c e d upward. If a

c o r r e c tiv e a c tio n i s n o t produced soon enough by th e au to m atic c o n tro l

system u t i l i s e d , th e d isplacem en t o f th e f u s e l o i l band would produce an

in c re a s e in th e c o n c e n tra tio n o f th e l a t t e r in th e upper tr a y s o f th e

column and c o n seq u en tly in th e main p ro d u c t. The upward d isp lacem en t o f

th e f u s e l o i l band would a ls o produce a low er c o n c e n tra tio n o f f u s e l o i l

in th e p la te where th e maximum accum ulation was form erly lo c a te d and from

where th e s id e -stre a m i s b ein g removed. T his in tu rn would o f f s e t th e

b a lan c e between th e f u s e l o i l e n te rin g and t h a t le a v in g th e column. Ac­

c o rd in g ly , th e o i l w i l l c o n tin u e to accum ulate in th e column u n t i l a

c o n c e n tra tio n i s reached a t th e p la te from which th e f u s e l o i l s id e -stre a m

i s bein g removed t h a t r e s to r e s th e o i l b a la n c e . A gain, t h i s would r e s u l t

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i n even h ig h e r c o n c e n tra tio n s o f f u s e l o i l in th e upper tr a y s and i n th e

main p ro d u c t.

Should th e a lc o h o l c o n te n t in th e feed in c re a s e under s im ila r

o p e ra tin g c o n d itio n s , th e a lc o h o l accum ulation would then b u ild up in

th e column to a p o in t where th e ex cess a lc o h o l fed to th e column would

be l o s t in th e bottom w aste p ro d u c t.

I t i s e v id e n t t h a t changes i n th e com position o f th e fe e d , i r r e ­

s p e c tiv e o f th e d ir e c tio n in which th e y o c c u r, should be prom ptly

c o u n te ra c te d by c o r r e c tiv e a c tio n s produced by th e c o n tro l system

employed in th e o p e ra tio n o f th e column.

The d i s t i l l a t i o n u n it o f th e Rum P i l o t P la n t o f th e A g r ic u ltu r a l

Experim ent S ta tio n o f th e U n iv e rs ity o f P u e rto Rico i s h ig h ly in stru m e n te d .

The c o n tro l system o f each column in c lu d e s au to m atic te m p eratu re c o n tro l­

l e r s to r e g u la te th e tem p eratu re o f th e feed and th e r e f lu x stream s a t

any d e sire d v a lu e . The b o il-u p r a t e in each column i s c o n tro lle d by an

au to m atic d i f f e r e n t i a l p re s su re c o n tr o l le r which in tu rn r e s e t s an a u to ­

m atic steam flow r a t e c o n tr o ll e r to th e r e b o i l e r . The d i f f e r e n t i a l

p re s s u re in stru m e n t i s tap p ed n e a r th e bottom and to p ends o f th e column.

The r a t e o f flo w o f th e feed and th e r e f lu x stream s a re a u to m a tic a lly

c o n tro lle d in a l l c a s e s . The r a t e o f flow o f th e fin is h e d main p ro d u ct in

th e r e c t i f y i n g colunn i s a ls o re g u la te d by means o f an au to m atic flow con­

tro lle r. The overhead pro d u ct stream in each column and th e f u s e l o i l

s id e -stre a m i n the r e c t i f y i n g column a re re g u la te d by means o f a p re c is io n

c a lib r a te d ro ta m e te r. I t should be r e c a lle d t h a t th e overhead p ro d u ct

o f th e beer column c o n s ti tu t e s th e raw p ro d u ct o f th e p ro c e ss and t h a t no

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p u r if ic a tio n i s in te n d e d a t t h i s coluim . The overhead p ro d u c ts o f th e

p u rif y in g and r e c t i f y i n g columns c o n s is t o f " h e a d s 11 stream s which c o n ta in

ab o u t 2% to 10$ o f th e a lc o h o l in t h e i r r e s p e c tiv e fe e d s . The flow o f

th e bottom product o f each column i s re g u la te d by an a u to m atic le v e l con­

t r o l l e r which m a in ta in s enough l i q u i d in th e column to cover th e tu b es

o f th e r e b o i l e r . A 48 p o in t push b u tto n tem p eratu re in d ic a to r and a

16 p o in t s t r i p c h a r t tempei*ature re c o rd e r , b o th o f e le c tr o n ic m easuring

c i r c u i t and a c tu a te d by c o p p er-co n sta n ta n therm ocouples, se rv e s f o r in ­

d ic a tin g and re c o rd in g te m p e ratu res a t s e le c te d p o in ts o f th e p ro c e ss .

A ll flow r a t e and le v e l c o n tr o lle r s a re o f th e pneum atic ty p e .

The flow r a t e c o n tr o lle r s a re p ro v id ed w ith a d ju s ta b le p ro p o rtio n a l band

and auto m atic r e s e t . These flow c o n tr o lle r s can be r e s e t by any o th e r

ty p e o f pneumatic c o n tr o lle r working w ith o u tp u t p re s s u re s from 3-15 p s ig .

In th e l a t t e r s ta g e s o f our e x p erim en tal work, a l i q u i d - f i l l e d tem pera­

tu r e c o n t r o l l e r was u sed to r e s e t a flow r a t e c o n tr o lle r to m ain tain

c o n s ta n t a re fe re n c e te m p e ratu re a t a s e le c te d p o in t o f th e system .

In a d d itio n to th e above l i s t e d in s tru m e n ts , p re c is io n c a lib r a te d

ro ta m e te rs a re i n s t a l l e d in s e r i e s w ith th e au to m atic flow c o n t r o l le r s in

th e fe e d l i n e s to th e th r e e columns and in th e main p ro d u c t ta k e - o f f .

These ro ta m e te rs a re in d ic a tin g in s tru m e n ts o n ly and serv e a s a check to

th e c a li b r a t io n o f th e a u to m a tic flow r a t e c o n t r o l l e r s . A ll in s tru m e n ts ,

w ith th e e x cep tio n o f th e in d ic a tin g ro ta m e te rs , a re i n s t a l l e d on a g rap h ic

c o n tr o l p an el in th e second f lo o r o f th e d i s t i l l a t i o n to w er. A photograph

o f th e p an el i s in c lu d e d in th e Appendix.

The fo llo w in g s e c tio n d e s c rib e s a group o f c o n tr o l system s which

have been su g g ested in th e l i t e r a t u r e fo r th e o p e ra tio n o f co n tin u o u s

 102

d i s t i l l a t i o n columns. Q u a n tity -C o n tro l System I I and Com position C o n tro l

System I I and IIA were t r i e d under a c tu a l o p e ra tin g c o n d itio n s . Composi­

tio n C o n tro l Systems I I I and IV r e p re s e n t m o d ific a tio n s developed d u ring

th e co u rse o f t h i s work.

During th e co u rse o f our s tu d ie s no in te n t io n a l v a r ia tio n on th e

com position o f th e feed was made. Hence, our work d e a ls w ith th e develop­

ment o f c o n tro l system s cap ab le o f producing c o n tro l a c tio n s to c o u n te ra c t

changes which a re in h e re n t to th e c h a r a c t e r i s t i e s o f th e p ro c e s s . P e rio d ic

d e te rm in a tio n s o f th e a lc o h o l c o n te n t o f th e feed showed v a r i a t io n s o f 5%

to 10% o f th e nom inal feed com position.

In a l l c ases o p e ra tio n s were conducted a t atm ospheric p re s s u re s .

QUANTITY CONTROL SYSTEMS

Q u a n tity C o n tro l System I : T his system , p a te n te d by Nelson i s a ty p ic a l

case o f q u a n tity c o n tro l methods (3 4 3 ). The d e t a i l s o f th e system are

shown in Drawing 2 . The r a t e o f flow and th e te m p e ratu re o f th e feed a re

m a in tain ed c o n sta n t by means o f au to m atic c o n tr o ls . The r a t e o f th e

bottom s p ro d u ct i s a ls o m ain tain ed c o n sta n t by means o f an a u to m atic flow

ra te c o n tro lle r. The b o il- u p r a t e i s v a r ia b le , bein g re g u la te d by an

a u to m atic le v e l c o n tr o lle r w hich, in o rd e r to m a in ta in c o n sta n t th e le v e l

o f l i q u i d in th e bottom o f th e column, v a r ie s th e r a t e o f flow o f steam

e n te r in g th e r c b o i l e r . The overhead d i s t i l l a t e i s condensed and passed

in to a re c e iv e r where i t i s d iv id e d in to r e f lu x and p ro d u ct stre a m s . The

te m p eratu re o f th e r e f lu x in th e p a te n te d p ro c e ss i s m ain tain ed c o n sta n t

by m anually c o n tr o llin g th e amount o f w ater e n te r in g th e co n d en ser. An

au to m a tic c o n tro l a c tu a te d by a therm ocouple i n s t a l l e d in th e r e f lu x l i n e ,

 D raw ing No. 2 . Vent

QUANTITY CONTROL S Y S TE M I
Water——A
Variable O v e r h e a d P r o d u c t R a t e
ifatei
( C o n d en ser

P roduct

R eflux

T Sfdestreom

—UP
Heater

F.RJC.
h R.C. — Flow R a te C ontroller
— L evel C ontroller
—Temperature C ontroller

F.R.C. - T h erm o sta t

103
R e b o i/e r D.P. C. —Differential: P ressure
'' Controller
RFC. Proportional Flow
Controller
 104

as s h o w in Drawing 1 , can be s u b s tit u te d f o r th e manual o p e ra tio n . The

r e f lu x r a t e i s m ain tain ed c o n s ta n t by means o f an autom atic flow r a t e

c o n tro lle r. The p ro d u c t r a t e i s v a r ia b le . I t le a v e s th e condensate r e ­

c e iv e r through an o verflow which, in tu r n , m a in ta in s c o n sta n t th e l i q u i d

le v e l in th e r e c e iv e r .

The o r ig i n a l draw ing a p p earin g w ith th e p a te n t.d o e s n o t show th e

removal o f sid c -stre a m s from in te rm e d ia te p l a t e s . These could be w ith ­

drawn, i f re q u ire d , and t h e i r flow c o n tro lle d by means o f au to m atic flow

ra te c o n tro lle rs .

I t i s e s s e n t i a l in th e a p p lic a tio n o f t h i s c o n tro l system t h a t th e

com position o f th e feed be m ain tain ed rig o r o u s ly c o n s ta n t. In th e case

o f v a r ia tio n s in th e l a t t e r , which in e v ita b ly o c cu r, t h i s system would

be in c a p a b le o f d e te c tin g and c o r r e c tin g f o r th e s e changes and, th e r e f o r e ,

o f producing a pro d u ct o f uniform q u a lity and com position.

I t could be used in th o se c a se s in which th e bottom p roduct o f th e

colunn c o n s is ts o f a pure su b sta n c e . To ach iev e t h i s , th e r a t e s o f flow

o f th e feed and th e bottom s p ro d u ct should be p ro p o rtio n ed in such a

fa s h io n t h a t th e amount o f th e bottom p ro d u ct be l e s s titan th e amount o f

th a t p a r t i c u l a r su b stan ce e n te r in g in to th e column w ith th e feed stream .

O bviously, i t i s assumed th a t th e column have th e number o f tr a y s re q u ire d

by th e p a r t i c u l a r s e p a ra tio n in c o n s id e ra tio n . In case o f v a r ia tio n s in

th e com position o f th e fe e d , th e r a t e o f flow' o f th e bottom p ro d u ct should

correspon d to th e minimum c o n c e n tra tio n p o s s ib le in o rd e r to in s u re th e

p u r it y o f s a id p ro d u c t. Whenever th e c o n c e n tra tio n o f t h i s su b stan ce in

th e fe e d i s over th e minimum, some o f i t w ill p ass w ith th e overhead

d is tilla te .
 105

Keeping in mind th e req u irem en ts f o r th e c o n tr o l o f th e a lc o h o lic

d i s t i l l a t i o n , we should conclude t h a t t h i s c o n tro l system i s n o t ad eq u ate

f o r t h a t p a r t i c u l a r p ro c e ss .

Q u a n tity C o n tro l System I I : T his system , shown in Drawing 3, d i f f e r s from

System I in t h a t th e b o il- u p r a t e and th e r a t e o f flow o f th e overhead

d i s t i l l a t e a re m aintained c o n s ta n t w hile th e r a t e o f flow o f th e bottom

p ro d u ct i s v a r ia b le . The l a t t e r i s re g u la te d by a l e v e l c o n tro l w hile

th e overhead p ro d u ct i s m ain ta in ed c o n sta n t by an au to m atic flow r a te

c o n tro lle r. The b o il-u p r a t e i s a u to m a tic a lly c o n tro lle d by m a in ta in in g

c o n sta n t a d i f f e r e n t i a l p re s s u re a c ro ss th e column, s in c e th e l a t t e r i s

a d i r e c t fu n c tio n o f the form er. A d i f f e r e n t i a l p re s s u re c o n t r o l l e r r e ­

s e ts th e steam flo w r a te c o n t r o l l e r which r e g u la te s th e e n tra n ce o f steam

in to th e r e b o i l e r . This p ro ced u re o f c o n tr o llin g th e b o il-u p r a t e i s

w idely used in d i s t i l l a t i o n p ro c e s s e s .

A gain, due to th e absence o f p ro v is io n s f o r d e te c tin g and producing

c o r r e c tiv e a c tio n s to c o u n terb ala n c e a l t e r a t i o n s produced by changes in

th e com position o f th e fe e d , t h i s system i s n o t cap ab le o f g iv in g p ro d u c ts

o f c o n sta n t com position and q u a lity .

I t could be employed in th o s e c a se s in which an overhead p ro d u ct

c o n s is tin g o f a pure su b stan ce i s d e s ir e d . T h is can be achieved by r e ­

moving th e overhead product a t a r a t e equal to th e minimum r a t e o f fe e d in g

o f t h i s p a r t i c u l a r su b stan ce w ith th e feed stre am . Whenever th e c o n te n t

o f t h i s su b stan ce in th e fe e d i s above th e minimum com position, some o f

i t w ill be p re s e n t in the bottom stream o f th e column.

T his system was used f o r th e o p e ra tio n o f our r e c t i f y i n g column

 C row ing N o. 3 •• Vent

0UANT1TY CONTROL SYSTEM I I

Water. n
Variable Reflux R a t e 3 >

Wa1
( C ondenser

T.R.

T.C.

.O f R e ceiver
L.C.

ru Reflux
o
FR.C.
= &

i I
F eed
»i I
K___ f Sldestream
I____
T .R . ■iLs!
— CO}- % -(m ) ■0- o
a a
FR.C.
Heater D.RC.

o
F.R.C. T.C.

o
L.C. a
S te a m Steam

Reboiler o
Cl

S lo p s
 107

in th e co u rse o f our s tu d ie s w ith th e purpose o f (1) d eterm in in g th e e f ­

fe c tiv e n e s s o f u sin g r a th e r la r g e in te rm e d ia te re c e iv in g tan k s between

columns to minim ize v a r ia tio n s in th e com position o f th e fe e d , and (2)

g a th e rin g ex p erim en tal d a ta which would in d ic a te th e e f f e c t o f u n stead y

c o n d itio n s in th e d i s t r i b u t i o n o f a lc o h o l and f u s e l o i l along th e column.

The c o n tro l system a p p lie d was id e n tic a l to t h a t shown in Drawing

2 a lth o u g h th e le v e l c o n tr o lle r shown in th e d i s t i l l a t e re c e iv e r was sub­

s t i t u t e d w ith an o v erflo w which produced i d e n tic a l r e s u l t s , i . e . , m a in ta in in g

a c o n sta n t le v e l in th e conden sate r e c e iv e r .

Our r e c t i f y i n g colunn has 50 bubble cap t r a y s , 15 in ch es nom inal

d iam eter a t 12 in c h es between p l a t e s . Feed, c o n s is tin g o f th e bottom

pro d u ct o f th e p u rify in g column and c o n ta in in g about 30 % a lc o h o l by volume

was added a t p la te l b . The main p ro d u ct was withdrawn from p la te 42 a s a

s id e stream . Heads c o n ta in in g 2% o f th e a lc o h o l fed were removed from th e

d i s t i l l a t e c o lle c to r. The b o il- u p r a t e was s e t to produce a r e f lu x stream

5 tim es as la r g e as th e main p ro d u ct stre am . The column was m ain ta in ed a t

t o t a l r e f lu x w hile feed was added c o n tin u o u sly u n t i l a tem p eratu re was

o b ta in e d in th e p la te above th e fe e d p l a te c o rresp o n d in g to th e com position

o f th e fe e d . Upon e n te r in g th e column, th e feed mixes in th e down-take

w ith th e l i q u id flow ing from th e immediate upper t r a y .

The experim ent was run f o r seven hours a f t e r w ithdraw al o f p ro d u c t

commenced. Every hour samples were tak en from p la te s 50, 46, 42, 40, 38,

36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 14, 12, 10, 8, and 6, c o u n tin g from

th e bottom up. No f u s e l o i l s id e stream was removed.

T ables I I and I I I in th e Appendix p r e s e n t, r e s p e c tiv e ly , th e a lc o h o l

 108

and f u s e l o i l c o n te n t i n th e v a rio u s p la te s o f th e column a t tim e i n t e r ­

v a ls . Table I I in d ic a te s a g ra d u a l ex h au stio n o f th e a lc o h o l h o ld -u p in

th e column. This w i l l happen whenever th e a lc o h o l c o n te n t in th e feed

f a l l s below th e v alu e on which th e m a te r ia l b a lan c e was b a se d . Under th e s e

c o n d itio n s more a lc o h o l i s removed in th e p ro d u c t than i s fed i n to th e

column. The d a ta p re s e n te d i n T able I I I in d ic a te s a g ra d u a l d isp lacem en t

o f th e f u s e l o i l c o n c e n tra tio n toward th e upper p la te s o f th e column. The

in c re a s e o f f u s e l o i l accum ulation w ith tim e i s due to th e f a c t t h a t no

o i l s id e -s tre a m was removed.

The upward d isp la ce m e n t o f f u s e l o i l i s a d i r e c t consequence o f th e

decx-ease i n a lc o h o l c o n te n t o f the p l a t e s . I t can be n o tic e d t h a t in th e

f i r s t sam pling p e rio d th e maximum c o n c e n tra tio n o f f u s e l o i l i s lo c a te d

a t p l a t e 26 where th e a p p a re n t a lc o h o lic s tr e n g th i s 129°P. At th e end

o f seven hours th e maximum c o n c e n tra tio n i s a t p l a t e 34 where th e a p p a re n t

a lc o h o l c o n te n t i s 1 3 l° P . A t th e b eg in n in g o f th e o p e ra tio n , th e f u s e l

o i l c o n te n t in p la te 42, from which th e main p ro d u c t was w ithdraw n, was

20 mg. p e r 100 m l. At th e end o f seven h o u rs, due to th e upward d is p la c e ­

ment o f th e f u s e l o i l band, th e f u s e l o i l c o n c e n tra tio n on t h i s p la te

reach ed a v a lu e o f 460 mg. p e r 100 m l., y ie ld in g a p ro d u c t o f v e ry i n ­

f e r io r q u a lity . These r e s u l t s d em o n strate th e i n a b i l i t y o f th e c o n tro l

system used to m a in ta in uniform c o n d itio n s th ro u g h th e co u rse o f th e

o p e ra tio n o f th e column.

As was m entioned in p re v io u s p a ra g ra p h s, th e feed to th e r e c t i f y i n g

column c o n s is ts o f th e bottom p ro d u c t o f th e p u rif y in g column and i t s com­

p o s itio n was n o t i n t e n t i o n a l l y v a r ie d . The changes produced in such

 109

com positions were in h e re n t to th e c h a r a c t e r i s t i c s o f th e p ro c e s s .

Q u a n tity C o n tro l System I I I : In t h i s system , shown in Drawing 4 , th e

te m p e ratu re and th e r a t e o f fe e d , a s w e ll a s th e tem p eratu re o f th e r e ­

f lu x stream and th e l i q u i d l e v e l in th e bottom o f th e column, a r e a g ain

m ain ta in ed c o n sta n t by means o f au to m atic c o n t r o l l e r s . The b o il-u p

r a te i s c o n tr o lle d in a manner i d e n t i c a l to t h a t d e sc rib e d f o r Q u a n tity

C ontrol System I I , based on a c o n sta n t d i f f e r e n t i a l p re s s u re a c ro s s th e

column. The r a t e o f flow o f th e bottom p ro d u c t i s v a r ia b le b ein g reg u ­

la te d by th e l e v e l c o n tr o lle r i n s t a l l e d in th e bottom o f th e c o l win.

In t h i s system , th e r a t i o between th e r e f lu x and overhead p ro d u c t stream s

i s m a in tain ed c o n sta n t by means o f a r a t i o - c o n t r o l l e r a c tu a te d by th e

l i q u id l e v e l in th e r e f lu x c o l l e c t o r .

By m a in ta in in g a c o n sta n t r e f lu x r a t i o i t i s in te n d e d to p re v e n t

d r a s t i c re d u c tio n s in th e r e c t i f y i n g c a p a c ity o f th e column which could

be produced by in d iv id u a lly re a d ju s tin g c i t h e r th e r e f lu x o r th e o v er­

head p ro d u c t stream s in o rd e r to c o r r e c t e r r a t i c c o n d itio n s in th e p ro c e s s .

As w ith a l l q u a n tity c o n tro l m ethods, t h i s system may be employed

when th e fe e d can be m a in ta in ed s u b s ta n t ia ll y c o n sta n t and when th e r a t e

o f flow o f th e v a rio u s stream s a r e p ro p o rtio n e d to in s u re th e p ro d u c tio n

o f a pure su b stan ce a s one o f th e p ro d u c ts . I f a l l th e p ro d u c ts from th e

column c o n s is t o f s o lu tio n s o f two o r more su b sta n c e s th e re i s no way o f

m a in ta in in g c o n s ta n t com positions in th e end p ro d u c ts when v a r ia tio n s in

th e com position o f th e feed o c c u r.

COMPOSITION CONTROL SYSTEMS

Wien i t i s d e s ir e d to o b ta in p ro d u c ts o f c o n s ta n t com position,

 Drawing No. 4 Vent

QUANTITY CONTROL SYS TEM 111

W ater
F i x e d Re f l ux R a t i o
Watei
C o n d en ser

T.C.
Receiver
L£.

R eflux

SP---------
F eed ________ 1
T.R. 1 1" 21
F.R.C.
D.P.C.

F.R.C. T.C.

I— St eam L.C. S te a m

110
Reboiler
 in

e i t h e r from th e ends o r from in te rm e d ia te p la te s o f th e column, i t i s

n e c e s s a ry to r e s o r t to th e p r in c ip le o f com position c o n tr o l. This ty p e

o f c o n tro l system , a s a p p lie d to d i s t i l l a t i o n p ro c e s s e s , in v o lv e s th e

d e te c tio n o f u n stead y c o n d itio n s as r e f l e c te d by changes in te m p eratu re

and th e p ro d u ctio n o f th e n e c e s sa ry c o r r e c tiv e a c tio n to m a in ta in con­

s t a n t one o r more re fe re n c e te m p e ra tu re s . The c o r r e c tiv e a c tio n u s u a lly

c o n s is ts o f a l t e r i n g th e r a t e o f flow o f a given stream o r stream s o r o f

r e a d ju s tin g th e b o il- u p r a t e .

Com position C o n tro l System I : T his system , sh o w in Drawing 5, d i f f e r s

from Q u an tity C o n tro l System I I I , d is c u s s e d above, in t h a t a te m p e ratu re

c o n t r o l l e r i s used to r e g u la te th e b o il- u p r a t e o f th e column in o rd e r to

m a in ta in c o n sta n t a re fe re n c e tem p eratu re a t a given p o in t o f th e column.

The p o in t a t which th e re fe re n c e te m p e ratu re should be m a in ta in ed c o n sta n t

can be lo c a te d anywhere along th e column depending on th e p a r t i c u l a r p ro­

c e s s under c o n s id e ra tio n . For th e s e le c tio n o f t h i s p o in t s e v e ra l f a c to r s

should be c o n sid ered in c lu d in g (1) tim e la g s , (2) c o e f f ic ie n t o f tem pera­

tu r e change w ith changes in com p o sitio n , and (3) re g io n o f th e column

where constancy in com position i s re q u ir e d .

T h is p a r t i c u l a r system g iv e s s a t i s f a c t o r y r e s u l t s s p e c i f i c a l l y when

th e com position o f one o f th e ends p ro d u c ts o f th e column i s d e s ir e d con­

s ta n t. The f a c t t h a t th e b o il- u p r a t e and th e r e f lu x r a t e a re v a r ie d ,

o f f e r s th e danger o f flo o d in g th e upper tr a y s o f th e co lu n n , should d r a s t i c

c o r r e c tio n s be e f f e c te d . E r r a t i c c o n d itio n s which would r e q u ir e a d r a s t i c

re d u c tio n o f th e b o il- u p r a t e may r e s u l t in a sudden d e c re a se i n th e r a t e

o f flow o f th e r e f lu x stream w ith th e p o s s i b i l i t y o f n o t having enough

 Drawing No. 5 Vent

COMPOSITION CONTROL SYSTEM I

Water
Fixed R e f l u x R a t i o *=4

C ondenser
BOI L UP R A t E R E G U L A T E D BY (
REFERENCE TEMPERATURE o
° °
IN S T R I P P I N G S E C T I O N T.C.
R e ceiver n
\l .c

■i
R e flu x
RFC.

j S id estrea m

FR.C.
H e a te r

F.R.C.

S te a m Steam

R eboiler
 113

l i q u i d flow ing down th e column a f t e r a r e l a t i v e l y la r g e s id e -s tre a m i s

removed in any given p ro c e ss such a s th e a lc o h o lic d i s t i l l a t i o n . One

a d d itio n a l d isad v an tag e o f c o n tro l system s based on v a ry in g th e b o il-u p

r a t e to produce th e re q u ire d c o r r e c tiv e a c tio n , i s th e f a c t th a t changes

i n th e amount o f e v ap o ratio n cause co rresp o n d in g changes in th e p re s su re

p r e v a ilin g in s id e th e column. T his e f f e c t , which i s g r e a te r in th e low er

p la te s o f th e column, produces subsequent re a d ju stm e n ts in th e vapor and

l i q u i d com positions by p la te s when th e re fe re n c e c o n tro l te m p e ratu re i s

m a in tain ed c o n s ta n t.

A m o d ific a tio n to t h i s system i s p re se n te d in Drawing 5-A a s

Com position C o n tro l System I-A . The o n ly d if f e r e n c e c o n s is ts o f r e ­

p la c in g th e au to m atic r a t i o c o n t r o l l e r , which in th e form er system

m a in tain ed a c o n sta n t r e f lu x r a t i o , w ith a sim ple flow r a t e c o n tr o lle r

which m a in ta in s c o n sta n t th e r a t e o f r e f lu x to th e column w hile th e

amount o f overhead d i s t i l l a t e i s v a r ia b le . The l a t t e r i s re g u la te d by

a le v e l c o n tr o lle r which m a in ta in s a c o n sta n t l i q u i d l e v e l i n th e r e f lu x

c o lle c to r.

Com position C o n tro l System I I : T h is system , shown in Drawing 6, i s ex­

te n s iv e ly used f o r th e c o n tro l o f co n tin u o u s d i s t i l l a t i o n columns (329,

33 8 ). As in th e p re v io u s ly d e sc rib e d system s, th e te m p e ratu re and th e

r a t e o f fe e d , a s w e ll as th e te m p e ra tu re o f th e r e f lu x stream a re m ain­

ta in e d c o n sta n t by means o f a u to m atic c o n t r o l l e r s . The r a t e o f flo w o f

th e bottom p ro d u ct i s a g ain r e g u la te d by a le v e l c o n tr o l le r t h a t m a in ta in s

a c o n sta n t l i q u i d l e v e l i n th e bottom o f th e column. The b o il up r a t e

i s c o n tro lle d by a s e t d i f f e r e n t i a l p re s s u re a c ro ss th e column. In te rm e d ia te

 Drawing No. 5A Vent

CO MP O S I TI O N CONTROL SYSTEM IA
W ater
5 1
Boil Up R a t e R e g u l a t e d by
W o le
Reference Tem perature in
( C ondenser
Stripping S e c t i o n
O
T.R. T.C.
R eceiver
0 L C .
r-P a

ru
R e flu x

' "I
TP 1
1
r i I
j
F eed ii____ i 9 k S id estrea m
•O'-
-------!£ jj
T.R.

H ea ter
6m)— o T.R
o - O
FJR.C.

T.C.

O
FR.C. T.C.

O
S te a m L.C. S te a m
J >
R e b o ile r

114
S to p s
 Drawing No. 6 Vent

COMP OSI T I ON CONTROL S Y S T E M II

Water
Reflux R a te R e g u lated by
Wafer
Reference Temperature at
( C ondenser
Feed P l a t e

R eceiver
L.C.

R eflux

uu - - O - j !
i
n _______ I
T.R. T.R.
H e a le r T.C.

F.R.C. T.C.

L S : S te a m L.C.

115
S to p s
 116

s id c -s tre a m s , i f p re se n t,* a re m ain tain ed c o n s ta n t by means o f au to m atic o r

manual flow r a t e c o n t r o l l e r s . The r a t e o f flow o f th e r e f lu x stream i s

re g u la te d by a te m p e ratu re c o n tr o lle r whose s e n s itiv e elem ent i n s t a l l e d

i n an in te rm e d ia te p o in t in th e column. The flow o f th e overhead d i s t i l ­

l a t e i s re g u la te d by a le v e l c o n t r o lle r i n s t a l l e d in th e r e f lu x c o l l e c t o r .

A m o d ific a tio n o f t h i s system , p re se n te d in Drawing b-A as Compo­

s i t i o n C o n tro l System II-A , c o n s is ts o f r e g u la tin g th e amount o f overhead

p ro d u ct by means o f th e te m p e ratu re c o n tr o l le r w h ile th e r a te o f r e f lu x

to th e column i s re g u la te d by th e le v e l c o n tr o l le r t h a t m a in ta in s a con­

s t a n t l i q u i d le v e l in th e r e f lu x c o l l e c t o r .

The two d e sc rib e d a l t e r n a t i v e s o f t h i s ty p e o f c o n tro l system were

used in s p e c ia l runs in which th e main p ro d u ct was o b ta in e d as th e o v er­

head d i s t i l l a t e o f th e column in s te a d o f removing i t a s a sid e stream

which c o n s ti tu te s th e co n v en tio n al p r a c tic e in modern continuous d i s t i l ­

la tio n u n its .

The lo c a tio n o f th e te m p e ra tu re re fe re n c e p o in t was th e s u b je c t o f

c a r e f u l s tu d ie s and p re lim in a ry ru n s . I t has been p re v io u s ly m entioned

t h a t t h i s p o in t should f a l l in a re g io n where r a t h e r la r g e changes in

tem p eratu re a re o b ta in e d w ith a given change o f com p o sitio n . F u rth e r,

when a l t e r a t i o n s to ste a d y c o n d itio n s o ccu r, th e y should be d e te c te d and

th e corresp o n d in g c o r r e c tiv e a c tio n b rought ab o u t b e fo re changes i n com­

p o s itio n a re produced in th e to p o f th e column from which th e main p ro d u ct

i s o b ta in e d in t h i s p a r t i c u l a r p ro c e s s . I t lias a ls o been p o in te d o u t th a t

in th e a lc o h o l d i s t i l l a t i o n i t i s n e c e s sa ry t h a t c o n sta n t com positions be

m ain tain ed a c ro s s th e whole r e c t i f y i n g s e c tio n o f th e column s in c e a f u s e l

 Drawing No. 6A Vent

C OMP OSI T I ON CONTROL SYSTEM H A

Water n o
O verhead*Product R e g u l a t e d by- TC)
Water
Reference Temperature a t C ondenser
Feed P late (

R e ceiver. o F.R.C.

O
L.C.

I I R e flu x
rv- -j1
J .A .

— — ------- —{JJ3— — — ---------- |

F eed n _ 1 l
l f o l ------------ *
“ ifto .
^ S id e s tr e o m
T.R. T.R.
-0 - O F.R.C.
O
Heater •
T.C.

i H O
F.R.C. T.C. O
D.RC.
[
o
team LC. S te a m

R e ta ile r

S to p s ' s n
 118

o i l s id c -stre a m i s withdrawn from p la te s o v er th e feed p l a t e . Having

th e s e f a c to r s i n mind, i t was d ecid ed t h a t th e re fe re n c e te m p eratu re on

which th e c o n tr o l system would be b ased , would be t h a t o f th e vapor space

o f th e p la te im m ediately over th e feed p l a t e . By s e le c tin g th e r i g h t

tem p eratu re v a lu e , th e l i q u id o f t h a t p l a t e , which mixes w ith th e fe e d

in th e downtake, would have th e same com position as th e feed i t s e l f .

The im portance o f in tro d u c in g th e feed on th e p l a te where th e l i q u i d has

a com position a s s im ila r a s p o s s ib le to t h a t o f th e -feed lias been p o in te d

o u t by a u th o rs on th e s u b je c t (330, 3 5 1 ). There a rc d e f i n i t e l i m i t s fo r

th e lo c a tio n o f th e feed p la te in o rd e r to g e t an o p e ra b le d e s ig n . Beyond

th e s e l i m i t s an i n f i n i t e number o f p la te s would be re q u ire d fo r th e de­

s ir e d s e p a ra tio n .

For our ex p erim en ts, h ig h q u a lity 1906P a lc o h o l was d il u te d w ith

w ater to a b in a ry m ix tu re o f 30% a lc o h o l. T h is m ix tu re was p ro cessed

thro u g h th e p u rif y in g column and th e bottom p ro d u c t c o lle c te d i n an i n ­

te rm e d ia te re c e iv in g tank from where i t was fed in to p la te 16 o f th e

r e c tif y in g column. A r e f lu x r a t i o o f 5:1 was u t i l i s e d i n th e l a t t e r .

The experim ents were run fo r f iv e hours a f t e r w ithdraw al o f p ro d u ct

commenced. Samples and te m p e ratu re re a d in g s were tak en ev ery hour

from p la te s 50, 42, 36, 30, 24, 20, 18, 14, 10, and 6. The sam ples were

a n aly se d fo r a lc o h o l c o n te n t. Manual c o n tro l was u t i l i z e d to m a in ta in

c o n s ta n t th e re fe re n c e te m p e ratu re in th e column.

T able IV and V i n th e A ppendix, p r e s e n t, r e s p e c tiv e ly , th e a lc o h o l

c o n te n t and th e te m p e ratu re by p la te s when u sin g th e c o n tro l system based

on v a ry in g th e r a t e o f th e r e f lu x stream to m a in ta in c o n sta n t th e re fe re n c e
 119

te m p e ratu re in th e column. T a b le s VI and V II p re s e n t s im ila r d a ta f o r th e

run in which th e c o n tr o l system based on v a ry in g th e d i s t i l l a t e stream was

u tiliz e d .

The d a ta o b ta in e d in d ic a te t h a t v ery s a t i s f a c t o r y r e s u l t s a re ob­

ta in e d when u t i l i z i n g th e c o n tro l sjrstem based on v a ry in g th e d i s t i l l a t e

stre am . A lthough a h ig h v a lu e was s e le c te d a s re fe re n c e te m p e ratu re w hile

tr y in g to account f o r th e p re s s u re p r e v a ilin g in th e column, th u s producing

r a th e r low a lc o h o lic c o n te n ts in th e feed p l a t e , th e r e s u l t s serv e v e ry

w e ll th e purpose o f in d ic a tin g t h a t t h i s c o n tro l system can m a in ta in u n i­

form com positions in th e r e c t i f y i n g s e c tio n o f th e column.

G re a te r v a r ia tio n s were observed when th e method o f a l t e r i n g th e

r e f lu x r a t e to c o n tro l th e o p e ra tio n was u sed . These a rc s p e c i f i c a l l y

n o te d i n th e in te rm e d ia te p la te s o f th e column where changes in feed

com position a re f i r s t r e f l e c t e d . Very good u n ifo rm ity was o b ta in e d ,

however, in th e upper tr a y s o f th e column and in th e to p p ro d u c t.

S in ce th e s iz e o f th e overhead p ro d u c t stream i s n o rm ally s e v e ra l

tim es s m a lle r th an th e r e f lu x stre am , l e s s d r a s t i c v a r ia tio n s occur i n

th e o p e ra tin g v a r ia b le s o f th e column when making p ro p o r tio n a l a d ju stm e n ts

to c o r r e c t t o r d e v ia tio n s w h ile u sin g System II-A .

C om position C o n tro l System I I I : The r e s u l t s o b ta in e d w ith com position

C o n tro l System II-A were v e ry s a t i s f a c t o r y . In th e a lc o h o lic d i s t i l l a ­

t i o n , however, th e overhead d i s t i l l a t e i s n o t th e main p ro d u c t. In tu r n ,

i t c o n s ti tu te s th e "heads*1 stream which i s v e ry sm a ll, b e in g u s u a lly from

100 to 300 tim es sm a lle r th an th e r e f l u x stre a m . I t i s e v id e n t t h a t a con­

t r o l system based on a l t e r i n g such a sm all stream would be in a d e q u a te .

 120

With th e o b je c tiv e o f s a ti s f y i n g th e req u irem en ts o f th e alco h o l

d i s t i l l a t i o n p ro c e ss a m o d ific a tio n was developed which i s p re se n te d in

Drawing 7 a s Com position C o n tro l System I I I . In t h i s system th e re fe re n c e

tem p eratu re i s m ain tain ed c o n sta n t by v a ry in g th e r a t e o f flow o f th e

main p ro d u ct which i s removed as a s id e stream s e v e ra l p la te s below the

top p l a t e o f th e column. The r a te o f ,th e r e f lu x stream i s m ain tain ed

c o n sta n t by means o f an autom atic flo w r a t e c o n t r o l l e r . S im ila r ly , the

r a t e o f ’’h ead s" ta k e - o f f i s m ain tain ed c o n s ta n t. T his o p e ra tio n re q u ire s

th a t th e d i f f e r e n t i a l p re s s u re a c ro ss th e colum n--w hich re g u la te s th e

r a t e o f ev ap o ratio n in th e colum n~bc s e t a t a s p e c if ic c o n tro l p o in t

which would produce a b o il-u p r a t e eq u al to th e r a t e o f r e f lu x p lu s the

r a t e o f ’’h e a d s” ta k e - o f f . T his s e t p o in t can be e a s ily e s ta b lis h e d in

p r a c tic e . I t i s our e x p erien ce t h a t , alth o u g h a p p a re n tly r i g i d , t h i s

c o n tro l system works v e ry w e ll in a c tu a l p r a c t ic e . The o b je c tio n to th i s

ap p aren t r i g i d i t y could be e lim in a te d by i n s t a l l i n g an autom atic liq u id

le v e l c o n tr o lle r in th e r e f lu x c o lle c to r wliich, in tu r n , would r e s e t the

c o n tro l p o in t o f th e d i f f e r e n t i a l p re s s u re c o n t r o l l e r .

F or c o n tr o llin g th e r a t e o f flow o f th e f u s e l o i l stream s a s well

as th e " h e a d s ” stream , v a r ia b le a re a ro ta m e te rs pro v id ed w ith n e e d le v alv es

f o r manual c o n tr o l, have been used w ith g r e a t su c c e ss.

Com position C o n tro l System I I I was t e s t e d in ex p erim en tal ru n s and

l a t e r used w ith g r e a t su cc e ss in th e ro u tin e o p e ra tio n o f th e p la n t u n til

Com position C o n tro l System IV , to be d isc u sse d in l a t e r p a ra g rap h s, was

developed.

T able V III and IX p r e s e n t, r e s p e c tiv e ly , th e a p p aren t a lc o h o lic

 Drawing No.. 7 Vent

COMPOSI TI ON CONTROL S Y S T E M III

W ater .
T.C.
R ate of S idestream Product
R e g u l a t e d by R e f e r e n c e
( C ondenser
T em perature a t Feed Plate

T.R.
R eceiver-
F.R.C.
F.R.C.

Reflux
Rum o r Industrial
A lcohol

O i F.R.C.
Feed
T.R.
— m
H e a le r
F.R.C. T.C.

F.R.C. T.C.

D.RC. F.R.C.
St—S te a m
[>>>, L.C. S te a m

R eboiler

S lo p s
 122

s tr e n g th and .th e f u s e l o i l c o n te n t by p l a te s o f th e column f o r one e x p e ri­

ment w hile T ab les X and XI g iv e s im ila r d a ta f o r a second experim ent. In

b oth cases a fe e d c o n s is tin g o f th e bottom p ro d u ct o f th e p u rif y in g column

and c o n ta in in g about 30# a lc o h o l by volume was in tro d u c e d a t p la te 16 o f

th e column; a r e f lu x r a t i o o f 5:1 was used; th e main product was w ith ­

drawn from p la te 42, and about 3% o f th e a lc o h o l fed to th e column was

removed in th e •’heads*1 stream . Samples were withdrawn from nisnerous

p la te s a t v a rio u s tim e i n t e r v a l s as shown i n th e ta b le s o f r e s u l t s . The

f i r s t experim ent was run f o r 12 hours a f t e r w ithdraw al o f main p roduct

commenced w hile th e second was run fo r 24 h o u rs. No f u s e l o i l sid c -stre a m

was removed in e i t h e r c ase d u rin g th e o p e ra tio n w ith th e purpose o f stu d y ­

in g th e e f f e c t o f c o n tin u o u sly in c re a s in g accu m u latio n s o f f u s e l o i l in

th e p la te s o f th e column.

Very good u n ifo rm ity was o b ta in e d in th e d i s t r i b u t i o n o f ap p aren t

a lc o h o l c o n te n t through th e column e s p e c ia lly in th e r e c tif y in g s e c tio n .

The in c re a s e n o tic e d in th e p la t e s n eig h b o rin g th e feed p la te i s due to

th e c o n tin u o u sly in c r e a s in g c o n c e n tra tio n o f f u s e l o i l around th e se p l a t e s .

These d e v ia tio n s , however, a re n o t r e f le c t e d in th e a lc o h o lic c o n te n t o f

th e upper 25 p la te s o f th e column producing a v e ry uniform main p ro d u c t.

The accum ulation o f f u s e l o i l in th e column in c re a s e s c o n tin u o u sly

d u rin g th e course o f th e o p e ra tio n s in c e , a s m entioned above, no o i l s id e

stream was removed. The d a ta in d ic a te s t h a t th e r e i s no d isplacem ent o f

th e band o f f u s e l o i l c o n c e n tra tio n d u rin g th e w'hole d u ra tio n o f th e ru n .

I t was c e n te re d around p l a t e 19 in b o th ex p erim en ts. The r e s u l t s o f a

s e r i e s o f experim ents s p e c i f i c a l l y d esig n ed fo r g a th e rin g d a ta on f u s e l

 123

o i l d i s t r i b u t i o n alo n g th e column a r c d isc u sse d in th e n e x t c h a p te r.

Com position C o n tro l System IV : The methods o f c o n tro l based on m a in ta in ­

in g c o n sta n t a re fe re n c e te m p e ra tu re by v a ry in g e i t h e r th e r e f lu x o r

p ro d u ct stream s a re capable o f producing s a t i s f a c t o r y r e s u l t s , e s p e c ia lly

when uniform com positions a r e d e s ir e d in th e p ro d u c ts from e i t h e r end o f

th e column.

In p re v io u s p a ra g ra p h s, i t has been in d ic a te d t h a t changes in th e

com position o f th e feed c o n s t i t u t e th e most common so u rce o f v a r ia tio n s

in th e e q u ilib riu m c o n d itio n s o f th e column. C onsequently a l t e r a t i o n s

w ill f i r s t occur in th e re g io n n e ig h b o rin g th e feed p l a t e . As m entioned

b e fo re , th e c o r r e c tiv e a c tio n u s u a lly c o n s is ts o f v a ry in g th e s iz e o f

e i t h e r th e r e f lu x o r the main p ro d u ct stream o r even a l t e r i n g th e b o il

up r a t e . N e c e s s a rily , th e e f f e c t o f t h is c o r r e c tiv e a c tio n would be

r e f le c te d a c ro ss a s e c tio n o f th e column s in c e by t h i s p ro c e d u re, we a re

try in g to c o r r e c t an unbalance o r ig in a tin g in a p o in t o f th e column by

a l t e r i n g th e o p e ra tin g c o n d itio n s a t a second p o in t p h y s ic a lly a p a r t from

th e f i r s t . While th e n e c e s sa ry a d ju stm en ts a re e ffe c te d to r e tu r n th e feed

p la te t o th e d e s ir e d e q u ilib riu m c o n d itio n s , a sequence o f sm all a l t e r a ­

tio n s would occur i n th e in te rm e d ia te p l a te s w hich, in tu r n , may produce

momentary d isp lacem en ts o f su b sta n c e s accum ulated on th o se p la te s from

which sid e -stre a m s a re n o rm a lly removed.

Should r a th e r la r g e f lu c tu a tio n s o ccu r in th e com position o f th e

fe e d , th e s e would be r e f l e c t e d in th e q u a lity o r in th e q u a n tity o f main

product produced. Assuming t h a t Com position C o n tro l System I I I i s b ein g

u t i l i z e d —which so f a r lias been shown to b e t t e r s a t i s f y th e re q u ire m e n ts

 124

o f th e a lc o h o l d i s t i l l i n g p ro c e s s —and t h a t th e a lc o h o l c o n te n t in th e

feed in c re a s e s s i g n i f i c a n t l y , th e au to m atic c o n tr o l in s tru m e n ts would

te n d to in c r e a s e th e s iz e o f th e main p ro d u ct stream to remove th e ad­

d i t i o n a l a lc o h o l e n te r in g th e column. In so d o in g , th e i n t e r n a l r e f lu x

r a t i o o f th e column, from th e main p ro d u ct ta k e - o f f p l a t e down, would be

reduced s in c e th e b o il- u p r a t e rem ains c o n s ta n t. T h is change in th e r e ­

f lu x to vapor r a t i o would o b v io u sly produce changes in th e d i s t r i b u t i o n

o f f u s e l o i l by p la te s which co u ld r e s u l t in a p ro d u ct r i c h in f u s e l o i l .

In th e n e x t c h a p te r i t w ill be shown th a t th e f u s e l o i l band i s d is p la c e d

upward w ith low er r e f lu x r a t i o s . In th e s i t u a t i o n j u s t d e s c rib e d , th e

a u to m a tic c o n tr o l system would p ro b a b ly n o t cause g re a t v a r ia t io n s i n th e

a lc o h o l d i s t r i b u t i o n in th e r e c t i f y i n g s e c tio n o f th e column s in c e i t s

a c tio n has been t h a t o f s e le c tin g a low er r e f l u x r a t i o to handle a r ic h e r

feed in a lc o h o l w h ile th e re fe re n c e te m p e ratu re i s m a in tain ed c o n s ta n t

j u s t above th e fe e d t r a y . The d a ta p re s e n te d i n th e n e x t c h a p te r shows,

however, t h a t th e d i s t r i b u t i o n o f f u s e l o i l and th e am p litu d e o f th e con­

c e n tr a tio n . band depends l a r g e l y on th e r e f l u x r a t i o u t i l i s e d . Much g r e a te r

c o n c e n tra tio n s o f f u s e l o i l would be found a t a p la te whose l i q u i d c o n ta in s

185°P when a r e f l u x r a t i o o f 3 :1 i s u t i l i s e d th a n would be found in a p l a te

whose l i q u i d i s a ls o 185°P b u t when a r e f lu x r a t i o o f 5:1 i s u se d . Fur­

t h e r , i t has been found e x p e rim e n ta lly t h a t below c e r ta in r e f lu x r a t i o s

th e re i s no sh arp accum ulation o f f u s e l o i l which r e s u l t s in r e l a t i v e l y

la r g e c o n c e n tra tio n s o f th e o i l i n th e upper s e c tio n o f th e column.

On th e o th e r hand, i f th e a lc o h o l c o n te n t in th e fe e d becomes lo w er,

th e c o n tr o l system would reduce th e s i s e o f th e main p ro d u c t stream , which

would, in tu r n , reduce th e p ro d u c tiv e c a p a c ity o f th e column, b e s id e s

 125

producing a l t e r a t i o n s in th e d i s t r i b u t i o n o f c o n c e n tra tio n s alo n g th e

column. Should i t be d e s ir e d to r e s to r e the? normal p ro d u ctio n c a p a c ity

t

o f th e column, i t would be re q u ire d then to v a ry a n o th e r group o f v a r i ­

a b le s such as th e feed r a t e and th e b o il up r a t e w ith consequent a l t e r a t i o n s

in th e e q u ilib riu m c o n d itio n s o f th e system .

I t i s n o t p robable t h a t ex trem ely la r g e changes would occur in th e

com position o f th e fe e d , e s p e c ia lly i f in te rm e d ia te re c e iv in g ta n k s o f

adequate c a p a c ity a re used between colum ns. In th e case i n which fe e d ,

.norm ally a t 40$ a lc o h o l by volume i s added to th e column, a d e crea se to ,

say, 38$ a lc o h o l, would be handled r e a d ily by th e c o n tro l system w ithout

cau sin g any n o tic e a b le s h i f t in th e d i s t r i b u t i o n o f f u s e l o i l . T h is,

however, would re p re s e n t a 5% d ecrease in th e p ro d u c tiv e c a p a c ity o f th e

p la n t, which would n o t be d e s ir a b le .

In none o f th e c o n tro l system s d e sc rib e d in th e l i t e r a t u r e and

sugg ested f o r th e o p e ra tio n o f co n tin u o u s d i s t i l l a t i o n columns i s i t

recommended t h a t th e feed stream be v a rie d as a c o r r e c tiv e a c tio n fo r

a l t e r a t i o n s in th e e q u ilib riu m c o n d itio n s o f th e system . I t lias been

re p e a te d ly m entioned, however, th a t in th e a lc o h o lic d i s t i l l a t i o n , due

to th e p re sen c e o f s id e -s tre a m s , i t i s re q u ire d t h a t th e com positions

in th e whole r e c t i f y i n g s e c tio n o f th e column, and n o t j u s t in th e upper

t r a y s , be m ain tain ed c o n s ta n t to in s u r e u n ifo rm ity in th e q u a lity o f th e

p ro d u c ts removed. W ith t h i s concept in mind, l e t us r e v is e th e eq u atio n

o f th e “ o p e ra tin g l i n e 11 which governs th e d is t r i b u t i o n o f com positions in

th e r e c t i f y i n g s e c tio n f o r th e s e p a ra tio n o f a b in a ry m ix tu re . T h is

e q u a tio n i s given by:

 w h ere:

yn = Com position o f th e v apors le a v in g p la te n j raol f r a c t io n

^hn+1 “ M° l es l i q u i d flow ing from p l a t e n+1

V = Moles o f vapor le a v in g p la te n

x ^ i =■ C om position o f l i q u i d flo w in g from p la te n + lj mol f r a c t i o n

D = Moles o f d i s t i l l a t e

x = Com position o f d i s t i l l a t e ) mol f r a c tio n

From t h i s e x p re ss io n , i t . can be seen th a t any c o n tro l system based

on a l t e r i n g th e v a r ia b le s in v o lv e d in th e eq u atio n would produce changes

i n th e com positions o f th e r e c t i f y i n g s e c tio n . The c o n tro l methods d e s­

c rib e d so f a r in v o lv e th e v a r ia t io n o f e i t h e r L, D o r V, When s id e -s tre a m s

a r e p re s e n t o th e r o p e ra tin g li n e s a re in tro d u c e d whose e q u atio n s a re o f

s im ila r form and in v o lv e th e co rresp o n d in g v a lu e s o f th e same v a r ia b le s

f o r th e s e c tio n under c o n s id e ra tio n .

I t can be concluded t h a t i f th e o p e r a tio n a l v a r ia b le s a re main­

ta in e d c o n s ta n t, th e com positions o f th e l i q u i d and th e vapor in th e

d i f f e r e n t t r y s o f th e r e c t i f y i n g s e c tio n would be c o n sta n t a s lo n g as

th e com position o f th e vapor e n te r in g s a id r e c t i f y i n g s e c tio n from th e

feed p la te i s c o n s ta n t. I t can be seen t h a t th e s iz e and th e com position

o f th e feed stream docs n o t ap p ear i n th e above given e q u a tio n .

The eq u atio n f o r th e s tr ip p in g s e c tio n o p e ra tin g l i n e i s giv en by:

 127

I f th e feed i s in tro d u c e d a t i t s b o ilin g p o in t and assum ing e q u i-

m olar l a t e n t h e a t o f v a p o ris a tio n f o r th e su b sta n c es p r e s e n t, we f in d t h a t :

W l = ^ * F
where:

Lm+i a L iq u id flow ing down th e s tr ip p in g s e c tio n ; mols

1^ = L iq u id flow ing from th e r e c t i f y i n g s e c tio n ; mols

• F = Feed, mols

B esides:

W « F - (D + Sx + S2 + Sn)

where:

W = Bottom p ro d u c t; mols

D = D i s t i l l a t e ; mols

S^, S2 , Sn = S id c -s tre a m s; mols

A ccordingly, changes in th e r a t e o f feed to com pensate fo r changes

in i t s com position, would produce v a r ia tio n s in th e com positions a t th e

d i f f e r e n t p la te s o f th e s tr ip p in g s e c tio n o f th e column. I t lias been i n ­

d ic a te d t h a t in th e a lc o h o lic d i s t i l l a t i o n no s id e -s tre a m s a re removed

from t h i s s e c tio n . F u r th e r , th e bottom p ro d u ct o f th e l a t t e r c o n s is ts o f

w ater and d is s o lv e d im p u r itie s b ein g d is c a rd e d . The o n ly req u irem en t i s

th e p re v e n tio n o f a lc o h o l lo s s e s in th e bottom w a ste s. T his can be

achieved by s p e c ify in g enough p la t e s in t h i s s e c tio n to h andle th e extreme

c o n d itio n s ex p ected .

In l i n e w ith t h i s re a so n in g , Com position C o n tro l System IV, p re ­

se n te d in Drawing 8, was developed and t e s t e d under a c tu a l o p e ra tin g

c o n d itio n s . This system d i f f e r s from Com position C o n tro l System I I I , in

 D r a wi n g No. 8 Vent

COMPOSI TION CONTROL S Y S T E M I V

W ater t ^( T.C.
Feed R a t e R e g u l a t e d by
Reference Temperature at
( Condenser
F ee d P l a t e

T.R.
R e c e iv e r

F.R.C.
H eads

fo
Reflux
Rum or Industrial L.C.
42 Alcohol
F.R.C.
F eed
O i F.R.C.
Fusel OH
T.C.
T.R.

Heater
F.R.C.

T.C.
o~
D.P.C. F.R.C.

S tea m S tea m

R eboiler
00

S lo p s
 129

t h a t th e a u to m atic te m p e ratu re c o n tr o l le r v a r ie s th e r a t e o f feed to th e

column in o rd e r to m a in ta in c o n s ta n t th e re fe re n c e tem p eratu re in th e

p la te above th e feed p l a t e . The r a t e o f flow o f th e main p ro d u ct s id e

stream i s m a in tain ed c o n sta n t by means o f an a u to m a tic flow r a t e con­

tro lle r. By t h i s procedure a l l v a r ia b le s e n te r in g i n th e eq u atio n o f th e

" o p e r a tin g l i n e " o f th e r e c t i f y i n g s e c tio n a re m ain tain ed c o n s ta n t.

E s s e n ti a lly , by v a ry in g th e r a t e o f feed to produce th e re q u ire d

c o r r e c tiv e a c tio n , we a re m a in ta in in g c o n sta n t th e in p u t o f a lc o h o l in to

th e column in s te a d o f th e feed in p u t. F u rth e r, s in c e in many c ase s i t i s

l i k e l y t h a t even when v a r ia tio n s in th e a lc o h o l c o n te n t o f th e feed o c c u rs,

th e r a t i o o f f u s e l o i l to a lc o h o l may be a p p ro x im ately c o n s ta n t, th e use

o f t h i s c o n tro l system r e s u l t s in m a in ta in in g a c o n sta n t in p u t o f f u s e l

o i l in to th e column which would add to th e s t a b i l i t y o f f u s e l o i l accumu­

l a t i o n in th e column a f t e r s te a d y s t a t e c o n d itio n s have been a t t a i n e d .

When v a r ia tio n s in th e com position o f th e feed o ccu r, th e composi­

tio n o f th e l i q u i d in th e feed p l a t e would a ls o v a ry producing c o rresp o n d in g

v a r ia tio n s in th e vapor le a v in g t l i i s p la t e and e n te r in g th e r e c t i f y i n g

s e c tio n o f th e column. T his w il l produce subsequent v a r ia tio n s in th e

com positions o f th e p la te im m ediately above th e feed p la te which in tu r n

w ill be r e f l e c t e d in i t s te m p e ra tu re . Upon d e te c tin g t h i s te m p e ratu re

v a r i a t i o n , th e a u to m atic te m p e ratu re c o n tr o lle r w a ll a l t e r th e r a t e o f

fe e d as re q u ire d to r e tu r n th e re fe re n c e te m p e ratu re to i t s s e t v a lu e and

co n seq u en tly r e s to r e e q u ilib riu m c o n d itio n s in th e r e c t i f y i n g s e c tio n o f

th e column.

Suppose t h a t w hile o p e ra tin g under e q u ilib riu m c o n d itio n s th e

 130

a lc o h o l c o n te n t in th e feed suddenly d e c re a s e s . T h is w ill produce a de­

c re a s e in th e a lc o h o l c o n te n t o f th e feed p l a t e which in tu r n w ill produce

subsequent a l t e r a t i o n s which w ill be r e f le c t e d in th e re fe re n c e tem p eratu re

on which th e c o n tro l system i s c e n te re d . The au to m atic tem p eratu re con­

t r o l l e r w ill r e s e t th e feed flow r a t e c o n tr o l le r to in c re a s e th e amount

o f feed e n te rin g th e column. By au ^n en tin g th e r a t e o f fe e d , th e i n t e r i o r

r e f lu x r a t i o o f th e s tr ip p in g s e c tio n , given by i s a ls o in c re a s e d .

From th e “ o p e ra tin g l i n e 11 equatio n f o r th e s tr ip p in g s e c tio n i t can be

seen t h a t a g r e a te r v alu e o f ljn+i/Vm re p re s e n ts an in c re a s e in th e en­

r ic h in g c a p a c ity o f th e p la te s o f t h a t s e c tio n . The c o n tro l system w ill

vary th e r a t e o f feed u n t i l such a v alu e o f I^n+i/V ra i s o b ta in e d t h a t com­

p e n sa te s f o r th e low er a lc o h o lic com position now p re s e n t in th e feed p la te

region and th e com position o f th e vapors e n te r in g th e r e c t i f y i n g s e c tio n

i s r e s to r e d to th e ste a d y s t a t e c o n d itio n s . T h is in tu rn w i l l b rin g th e

re fe re n c e te m p e ratu re to i t s s e t v a lu e .

In th e case o f an in c re a s e in th e a lc o h o l c o n te n t o f th e fe e d , th e

c o r r e c tiv e a c tio n produced would be th e in v e rs e o f t h a t j u s t d e s c rib e d .

I t can be observed t h a t t h i s c o n tro l system p o sse sse s th e d i s t i n c t

advantage o f d e te c tin g changes a t th e p o in t where th e y g e n e ra lly o r ig in a te

and proceed to c o r r e c t them l o c a l l y w ith o u t producing a s e r i e s o f su b se­

quent a l t e r a t i o n s along th e r e c t i f y i n g s e c tio n o f th e column. Time la g s

a re s u b s t a n t i a l l y red u ced .

T ables XII and X III , in th e Appendix, p r e s e n t, r e s p e c tiv e ly , th e

a lc o h o l c o n te n t and th e d i s t r i b u t i o n o f f u s e l o i l c o n c e n tra tio n a t s e v e ra l

tim e in t e r v a l s d u rin g 24 h o u rs. In t h i s experim ent 80° P ro o f a lc o h o l was

 131

in tro d u c e d a t p la te 18. A r e f lu x r a t i o o f 4:1 was u t i l i s e d . The feed

c o n s is te d o f th e bottom pro d u ct o f th e p u rify in g column. About 3% o f th e

a lc o h o l e n te r in g w ith th e feed was removed as a head stream in th e r e c t i ­

fy in g column. The main pro d u ct was removed from p la t e 42 a s a s id e stre am .

T ables XIV and XV p re s e n t s im ila r d a ta fo r a second experim ent conducted

under s im ila r c o n d itio n s w ith th e e x cep tio n t h a t a 3 :1 r e f lu x r a t i o was

u tilis e d . In b oth c a se s rem oval o f th e f u s e l o i l s id c -s trc a m was com­

menced a f t e r tw elve hours o f o p e ra tio n . The n in e horn’ sam ples were

a n aly se d to determ ine th e p la te o f peak c o n c e n tra tio n . The accum ulation

o f fu s e l o i l in th e column in c re a s e d s te a d il y d u rin g t h i s p e rio d . S in ce

th e r e i s no in s ta n ta n e o u s ' method o f a n a ly s is which w i l l in d ic a te th e con­

c e n tr a tio n o f f u s e l o i l in th e p la te o f peak accum ulation a t th e p re c is e

moment in which w ithdraw al o f t l i i s p ro d u ct i s to be s t a r t e d , a r a t e o f

0 .5 g a llo n s p er hour was s e le c te d f o r t h i s stre am . When removal o f t h i s

s id e -s tre a m i s commenced, th e r e w’ould be a d ju stm en ts in th e accum ulations

o f fu s e l o i l u n t i l a b alan ce i s e s ta b lis h e d betwTecn th e o i l e n te r in g and

t h a t le a v in g th e column. I f th e o i l ta k e - o f f stream i s to o sm all th e

c o n c e n tra tio n s w ill co n tin u e to in c r e a s e . On th e o th e r hand, i f th e

stream i s to o la r g e , th e c o n c e n tra tio n s o f f u s e l o i l i n th e p la te s w ill

d e crea se u n t i l th e n e ce ssa ry b a lan c e i s e s ta b lis h e d . V a ria tio n s in th e

f u s e l o i l c o n te n t o f raw d i s t i l l a t e from d i f f e r e n t fe rra e n te rs w ill produce

s im ila r a d ju stm e n ts . Manual c o n tro l was used in th e s e experim ents to v a ry

th e r a t e o f feed in o rd e r to m a in ta in c o n sta n t th e s e t re fe re n c e te m p e i'a tu re .

From th e d a ta o b ta in e d , i t can be observed th a t th e lo c a tio n o f th e

peak c o n c e n tra tio n rem ains on th e same p la te d u rin g th e whole o p e ra tio n .

 132

A part from sm all v a r ia tio n s i n th e re g io n a d ja c e n t to th e feed p l a t e , where

r e l a t i v e l y h ig h c o n c e n tra tio n s o f f u s e l o i l a r e o b ta in e d , e x c e lle n t s t a b i l ­

i t y in a lc o h o l c o n ten t by p la te s o f th e r e c t i f y i n g s e c tio n p re v a ile d a t a l l

times# The same a p p lie s to th e d is t r i b u t i o n o f f u s e l o i l . The u n ifo rm ity

o f th e com positions o f th e upper 25 p la te s a t a l l tim es i s s t r i k i n g .

The r e s u l t s o b ta in e d w ith t h i s c o n tro l system in th e se experim ents

and i n subsequent o p e ra tio n s o f th e Rum P i l o t P la n t were so s a t i s f a c t o r y

t h a t i t was adopted a s th e s ta n d a rd c o n tro l system f o r a l l r e s e a r c h work

a s w e ll as f o r ro u tin e o p e ra tio n s . A l i q u i d - f i l l e d au to m atic tem p eratu re

c o n tr o lle r has been i n s t a l l e d w h ic h a u to m a tic a lly r e s e t s th e fe e d flow

c o n tro lle r. The system was used fo r th e e x p erim en tal work on f u s e l o i l

d i s t r i b u t i o n p re se n te d in the n e x t c h a p te r and in a l l o p e ra tio n s o f th e

Rum P i l o t P la n t. I t s use was extended to th e p u rif y in g column. In th e

b eer column no p u r if ic a tio n i s e f f e c te d and th e o n ly p re c a u tio n s re q u ire d

i s th e p re v e n tio n o f a lc o h o l lo s s e s i n the bottom s lo p s . U su ally , t h i s

column i s o p e ra te d by s e t t i n g th e maximum r a t e o f feed allow ed by th e

feed c o n tr o lle r and by v a ry in g th e r a t e o f d i s t i l l a t e ta k e - o f f to main­

t a i n c o n s ta n t a re fe re n c e te m p eratu re below th e feed p l a t e .

L evel c o n tr o lle r s have been i n s t a l l e d i n th e r e f l u x c o ll e c to r s o f

th e p u rif y in g and r e c t i f y i n g column which can be used to r e s e t th e d i f ­

f e r e n t i a l p re s s u re c o n tr o lle r s i n o rd e r to m a in ta in c o n s ta n t b o il-u p r a t e s .

A fte r more than two y e a rs u t i l i s i n g Com position C o n tro l System IV, i t has

been found th a t th e re q u ire d v a r i a ti o n s i n fe e d r a t e do n o t produce any

n o tic e a b le in c r e a s e i n th e p re s s u re drop a c ro s s th e column f o r a given

b o il- u p r a t e .
 133

The use o f t h i s c o n tro l system i s by no means lim ite d to th e con­

tin u o u s a lc o h o lic d i s t i l l a t i o n . I t co u ld be used ad v an tag eo u sly i n any

p ro c e ss r e q u ir in g th e removal from th e r e c t i f y i n g s e c tio n o f in te rm e d ia te

sid e -stre a m s o f uniform com positio n . I t s use f a c i l i t a t e s th e c o n tr o l of

th e o p e ra tio n and a t th e same tim e r e s u l t s in more uniform p ro d u c tiv e

c a p a c ity and p ro d u ct q u a lity . In te rm e d ia te re c e iv in g ta n k s between columns

a re re q u ire d f o r i t s a p p lic a tio n . In th e p ro d u c tio n o f a lc o h o lic beverages

and i n d u s t r i a l a lc o h o l, i t i s sometimes found t h a t the p ro d u c t o f one

column, c ith e r in the liq u id o r th e vapor phase, i s fed d i r e c t l y to a

subsequent column. In th a t p a r t i c u l a r c a s e , Composition C o n tro l System

IV i s n o t a p p lic a b le . The use o f Composition C o n tro l System I I I i s

recommended.
 CHAPTER V II

EXPERIMENTAL DATA ON FUSEL OIL DISTRIDUTION IN THE RECTIFYING

COLUMN UNDER DIFFERENT OPERATIONG CONDITIONS

The p o s s ib le a p p lic a tio n o f f u s e l o i l d i s t r i b u t i o n d a ta i n th e de­

sig n and o p e ra tio n o f a lc o h o l d i s t i l l a t i o n u n its was d is c u s s e d in C hapter

V. I t was p o in te d o u t t h a t th e re i s a v i r t u a l absence o f t h i s k in d o f

d a ta in th e l i t e r a t u r e . U n c e rta in tie s re g a rd in g th e n a tu r e and r e l a t i v e

c o n c e n tra tio n s o f th e v a rio u s c o n s titu e n ts o f fu s e l o i l in any p a r t i c u l a r

c a se p re c lu d e th e a p p lic a tio n o f t h e o r e t i c a l methods fo r i t s p r e d ic tio n .

In o rd e r to f i l l t h i s need, a s e r ie s o f experim ents were conducted under

d i f f e r e n t o p e ra tin g c o n d itio n s . The r e s u l t s o f t h i s work a re p re s e n te d

in th e fo llo w in g p a ra g ra p h s.

The e f f e c t o f u t i l i z i n g d i f f e r e n t r e f lu x r a t i o s and a lc o h o lic con­

t e n t s i n th e fe e d was s tu d ie d . Feed com positions o f 20, 30, 40 and 50 p e r

c e n t a lc o h o l by volume a t 60UF were u sed . These v a lu e s cover th e ran g e o f

com positions u s u a lly found in commercial p r a c t i c e . Each feed com position

was s tu d ie d under r e f lu x r a t i o s o f 5 :1 , 4 :1 , 3 :1 and 2 :1 , e x p ressed a s th e

r a t i o -between the v o lu m e tric r a t e o f flow' o f th e r e f lu x and th e main p ro ­

d u c t stre a m s. These r e f lu x r a t i o s cover th e range u s u a lly u t i l i z e d in

commercial p r a c t i c e . The minimum r e f l u x r a t i o re q u ire d to c o n c e n tra te

a 40# a lc o h o l feed in to a 95# a lc o h o l p ro d u c t i s 0 .9 3 .

S in ce th e main p ro d u c t i s withdrawn a s a s id e -s tre a m , th e r a t i o

between th e amount o f l i q u i d flow ing down th e column from th e p ro d u ct

ta k e - o f f p l a t e and th e amount o f main p ro d u c t bein g withdrawn becomes

one u n it l e s s than th e nom inal r e f l u x r a t i o based on th e e x te r n a l r e f lu x

134
 135

stream added to th e to p o f th e column. A ccordingly* when th e r a t i o be­

tween th e e x te r n a l r e f lu x stream and th e main pro d u ct stream i s 5 :1 , th e

r a t i o between th e i n t e r n a l r e f lu x from th e p ro d u ct p l a t e down and th e

main pro d u ct stream i s c o rre sp o n d in g ly 4 :1 .

In a d d itio n to th e above m entioned ex p erim en ts, r e f lu x r a t i o s o f

15:1 and 10:1 were u t i l i z e d w ith a 30$ a lc o h o l fe e d . In two o th e r e x p e ri­

m ents, feeds o f 60$ a lc o h o l were d i s t i l l e d a t r e f lu x r a t i o s o f 5:1 and

2 :1 . In o rd e r to stu d y th e e f f e c t o f f u s e l o i l c o n te n t in th e feed on

th e lo c a tio n o f th e f u s e l o i l band in th e column, two a d d itio n a l e x p e ri­

m ents were run a t a 3 :1 r e f lu x r a t i o and 40$ a lc o h o l in th e fe e d . In one

c a s e , th e feed was p rep ared by d i l u t i n g h ig h c la s s s p i r i t s to th e d e s ire d

p ro o f w hile adding c a lc u la te d amounts o f c o n c e n tra te d f u s e l o i l to produce

an o i l c o n c e n tra tio n a p p ro x im ately o n e -lia lf o f t h a t o b ta in e d in th e 40$

a lc o h o l fe e d . In an o th er c a se , th e r e g u la r raw p ro d u ct from th e b eer

column was d ilu te d to 40$ a lc o h o l w h ile ,a d d in g enough f u s e l o i l to p ro ­

duce an o i l c o n c e n tra tio n ap p ro x im ately tw ice as la r g e as t h a t found

n o rm a lly . The r e s u l t s o f th e s e two a d d itio n a l experim ents were compared

w ith t h a t in which r e g u la r 40$ a lc o h o l feed was d i s t i l l e d u t i l i s i n g a 3 :1

r e f lu x r a t i o .

The o p e ra tio n a l procedure u t i l i s e d in a l l experim ents was a s f o l ­

low s. Fermented m olasses mash was fed in to th e b eer column a t a r a t e o f

about 100 g a llo n s p e r h o u r. The e x h au stin g s e c tio n o f th is column c o n ta in s

25 s ie v e p l a t e s , 12 in c h es nom inal d iam eter a t a p l a te sp acin g o f IS in c h e s .

The r e c t i f y i n g s e c tio n c o n s is ts o f 4 bubble cap p la te s a ls o a t a sp acin g

o f IS in c h e s . An impingement p l a t e s e p a ra te s th e two s e c tio n s w ith th e

 136

purpose o f p re v e n tin g s o lid s from e n te rin g th e to p o f th e column. A r e f lu x

r a t i o o f a b o u t 2:1 was u t i l i z e d i n a l l c a s e s . The overhead p ro d u c t stream

was a d ju s te d to y i e l d a p ro d u c t o f about 60$ a lc o h o l by volume a t 60°F.

The raw d i s t i l l a t e was c o lle c te d i n 500 g a llo n r e c e iv in g ta n k s and d ilu te d

to th e d e s ir e d a lc o h o lic s tr e n g th . This m ix tu re was su b se q u e n tly fed in to

p l a t e 16 o f the p u rif y in g column, d e sc rib e d in C hapter V. T his column, as

m entioned b e fo re , c o n ta in s 40 bubble cap p l a t e s , 8 in c h es nom inal d iam eter

a t 10 in ch p la te s p a c in g . The r a t e o f feed to th e p u rif y in g column was

e s ta b lis h e d a cco rd in g to th e nom inal r a t e o f feed to th e r e c t i f y i n g column

re q u ire d in each p a r t i c u l a r experim ent. A 190°P nh e a d s n stream was removed

in a l l c ase s from th e overhead d i s t i l l a t e o f th e p u rify in g column. The

s i z e o f t h i s stream was such th a t i t c o n ta in e d about 3% o f th e a lc o h o l

e n te r in g w ith the fe e d . A r e f lu x r a t i o o f 25:1 was u t i l i s e d in a l l c a s e s .

The bottom pro d u ct from th e p u rify in g column was c o lle c te d in a 500 g a llo n

re c e iv in g ta n k from where i t was fed in to p l a t e 18 o f th e r e c t i f y i n g column.

The o p e ra tio n was tim ed in such a fa sh io n t h a t t h i s re c e iv in g ta n k always

ra n about h a l f f u l l . As m entioned in C hapter V, th e r e c t i f y i n g column

c o n ta in s 50 bubble cap p l a t e s , 15 in c h e s nom inal d iam eter a t a 1 2 n p la te

sp a c in g .

In th e s t a r t i n g o f o p e ra tio n s o f a l l colvmns, th e bottom p ro d u ct

d is c h a rg e v a lv e was clo sed and enough hot w ater charged in to th e column

to c o v er th e tubes o f th e r e b o i l e r . Steam was ad m itted to th e r e b o i l e r

and e v a p o ra tio n s t a r t e d . W ater a t .its b o ilin g p o in t was i n t e r m i t t e n t l y

added to m a in ta in a c o n sta n t le v e l in th e r e b o i l e r . When a c e r t a in b o i l -

up r a t e was o b ta in e d th e bottom p ro d u c t d is c h a rg e v a lv e was s e t to work

 137

a u to m a tic a lly and th e continuous a d d itio n o f th e a lc o h o l feed s t a r t e d

under t o t a l r e f lu x c o n d itio n s . A d d itio n o f feed under t o t a l r e f l u x was

continued u n t i l a d e s ir e d re fe re n c e te m p eratu re was o b ta in e d a t a given

p o in t o f th e column. Meanwhile, th e c o n tro l p o in t o f th e d i f f e r e n t i a l

p re s s u re c o n tr o lle r was a d ju s te d to produce th e b o il-u p r a te re q u ire d

i n each p a r t i c u l a r c a s e . W ithdrawal o f p ro d u c ts was th en s t a r t e d .

For th e o p e ra tio n o f the r e c t i f y i n g column, a p re lim in a ry run was

made th e day p re v io u s to each experim ent to determ ine under a c tu a l o p e ra t­

in g c o n d itio n s th e tem p eratu re v alu e which should be used to produce a

liq u id com position i n th e p la te j u s t above th e feed p l a t e , ap p ro x im ately

eq u al to th e com position o f th e feed i t s e l f . T h is tem p eratu re v a lu e would

account f o r th e b o ilin g p o in t e le v a tio n produced by th e p re s su re p r e v a il­

in g in th e column w ith th e re q u ire d b o il- u p r a t e . Com position C o n tro l

System IV, d e sc rib e d in C hapter IV, was u t i l i s e d in a l l c a s e s . Drawing

9 shows th e flow diagram and th e arrangem ent o f th e in s tru m e n ta tio n i n

th e r e c t i f y i n g column.

In T able 8 th e v a lu e s o f th e o p e ra tin g v a r ia b le s f o r th e r e c t i ­

fy in g column in each experim ent a r e shown. B esides th e a lc o h o l c o n te n t

in th e feed and th e r e f lu x r a t i o u t i l i s e d , v a lu e s a re given f o r th e r a t e s

o f flow o f th e fe e d , h ead s, r e f l u x , main pro d u ct and f u s e l o i l stre a m s.

C o n tro l re fe re n c e te m p e ra tu re , p l a t e o f main p ro d u c t ta k e - o f f , feed p la te

and th e numbers o f th e ta b le s i n th e Appendix p re s e n tin g th e d a ta o b ta in e d

in each experim ent a r e a ls o in d ic a te d .

The * h ead sn stream o f th e r e c t i f y i n g column c o n ta in e d in a l l c ase s

ab o u t 3$ o f th e a lc o h o l fe d to th e column. P la te 18 was th e feed p l a t e in

 l Vent

Water* _ n
D r a w i n g No. 3 4>
-IL Water
RECTIFYING COLUMN Condenser o
*=
Flow Diagram and Instrumentation
TR.
Receiver-
g lL .C .

u Reflux
F.R.C
ffl} ur Heads

« -► Rum or industrial
z
FR.C f e z A lcoh ol
F eed
Q
Q Q rFuseI OH FR.C
T.C d 0
T.R.
oH eater
- t

-:
•Q - —

11

Q
TC.
o
D.RC FR.C:
O
X
Steam LC. .Steam
£
CODE
Reboiler
F.R.C Flow Rate Controller
S lo p s
- £ is-H L.C Level Controller
T. C. Temperature Controller
T. R. Thermometer
D.RC. Dtffererrtjal Pressure
 TABLE 8

OPERATING CONDITIONS IN THE RECTIFYING COLUMN IN THE VARIOUS EXPERIMENTS CONDUCTED AT

DIFFERENT REFLUX RATIOS AND FEED COMPOSITION'S

Feed Main F u se l O il P la te o f T ables

Nominal R eflux Heads S id e -stre a m R ef.
Compo s i t i o n R eflux P roduct Main Feed Showing
Feed R ate R ate R ate Temp. P ro d u ct
% A lcohol R atio R ate R ate P la te Experimen­
G al/H r.. G al/H r. G al/H r. G al/H r. G al/H r. °F T a k e -o ff t a l D ata
by Volume

20 5:1 70 75 15 0 .5 0 .5 194.5 42 18 XVI, XVII

20 4 :1 75 64 16 0 .5 0 .5 194.5 42 IS X V III, XIX
20 3 :1 75 48 16 0 .5 0. 5 193.0 42 18 XX, XXI
20 2:1 85 40 20 0 .6 0 .5 190.0 46 IS XXII, XXIII

30 15:1 22 .90 6 0 .2 0 .3 191.0 42 18 XXIV, XXV

30 10:1 35 100 10 0 .4 0. 5 191.0 42 18 XXVI, XXVII
30 5:1 50 75 15 0 .5 0 .5 192.0 42 18 XXVIII, XXIX
30 4:1 65 80 20 0 .6 0 .5 191.0 42 IS XXX, XXXI
30 3 :1 65 60 20 0 .6 0 .5 192.0 42 IS XXXII, XXXIII
30 2:1 65 40 20 0 .6 0 .5 1SS.0 46 18 XXXIV, xxxv

40 5:1 38 75 15 0 .5 0 .5 190.0 42 18 XXXVI, XXXVII

40 4 :1 50 80 20 0 .6 0. 5 190.0 42 18 XXXVIII, XXXI
40 3 :1 50 60 20 0 .6 0 .5 190.0 42 18 XL, XLI
40 3 :1 50 60 20 0 .6 0 .5 190.0 42 IS X LII, XLIII
40 3 :1 50 60 20 0 .6 0 .5 190.0 42 IS XLIV, XLV
40 2:1 50 40 20 0 .6 0 .5 1S9.0 46 IS XLVI, XLVII

50 5:1 30 75 15 0 .5 0 .5 ISo.O 42 18 XLVIII, XLIX

50 4 :1 40 80 20 0 .6 0 .5 1S8.0 42 • IS L, LI
50 3 :1 40 ‘ 60 20 0 .6 0 .5 188.0 42 18 L II, L III
50 2:1 40 40 20 0 .6 0 .5 139.0 4b 18 LIV, LV
60 5:1 30 100 20 0 .6 0 .5 187.‘5 42 18 LVI, LVII
60 2:1 30 40 20 0 .6 0 .5 182.0 46 18 L Y III, LIX, i

139
 140

a l l ex p erim en ts. The main p ro d u c t was removed from p la te 42 in a l l cases

except when r e f lu x r a t i o s o f 2:1 wore u t i l i s e d . Under thii l a t t e r co n d i­

tio n s p la te 46 \cas th e ta k e - o f f p la te in o rd e r to g e t a p ro d u ct o f a t

l e a s t about 180°P. In a l l experim ents th e column was run fo r 24 hours

a f t e r w ithdraw al o f p ro d u c t commenced. Samples were taken from p la te s

50, 42, 33, 34, 30, 26, 24, 23, 21, 20, 19, 18, 17, 16, 15, 14, 12, 8

and 4 a t 0 , 3 , 6, 9 , 12, 15, 18, 21, and 24 hours a f t e r w ithdraw al o f

main p ro d u ct commenced. P la te s a re number'cd from bottom up. Numerous

c o n se c u tiv e p la te s around th e feed p la te were s e le c te d s in c e th e i n f o r ­

m ation a v a ila b le in th e l i t e r a t u r e and th e r e s u l t s o f our p re lim in a ry

experim ents in d ic a te d th a t th e f u s e l o i l band lo c a te s i t s e l f in t h i s

re g io n except fo r th e cases when r e f lu x r a t i o s o f 2:1 a re u t i l i z e d . With

r e f lu x r a t i o s o f 2:1 no a p p a re n t sh arp accum ulation occurs and, acco rd ­

in g ly , th e sam pling p la te s were chosen evenly alo n g th e column. In tliis

c a s e , samples were taken from p l a t e s 50, 46, 42, 40, 38, 36, 34, 32, 30,

23, 26, 24, 22, 18, 16, 14, 10, 6 and 2, a t th e same time i n t e r v a l s men­

tio n e d above.

In th e few in s ta n c e s in which m echanical d i f f i c u l t i e s produced some

momentary i n s t a b i l i t i e s s h o r tly b e fo re sam pling tim e s, th e s e t o f samples

co rresp o n d in g to tlia t p a r t i c u l a r p e rio d was d is c a rd e d . A ll sam ples were

a n aly se d fo r a p p a re n t a lc o h o l c o n te n t u t i l i s i n g th e hydrom eter m ethod.

F u se l o i l was determ ined by the Rum P i l o t P la n t m o d ific a tio n o f Komarowsky*s

c o lo r im e tr ic method given in C hapter I I I . P re tre a tm e n t o f th e sam ples was

found n o t to be n e c e s sa ry f o r our p u rp o ses.

Tem perature re a d in g s were taken every hour from p la te s 50, 48, 46,

44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 23, 22, 21, 20, 19, 16, 14,

12 and 6.
 141

No fu s e l o i l sid e stream was removed d u rin g th e f i r s t 12 hours o f

o p e ra tio n in order to a llo w a c o n tin u o u sly in c re a s in g accum ulation o f

f u s e l o i l in the co lu n n . Hence, sam pling a t d i f f e r e n t tim e i n t e r v a l s

d u rin g t h i s p erio d gave f u s e l o i l d i s t r i b u t i o n d ata a t d i f f e r e n t v a lu e s

o f maxiittiun c o n c e n tra tio n in the p la te o f peak accu m u latio n . A fte r ta k in g

th e 12th hour sam ples, w ithdraw al o f f u s e l o i l was commenced from th e

p l a t e where, a cco rd in g to th e a n a ly se s o f th e 9 th hour sam ples, th e maxi­

mum c o n c e n tra tio n was found. A f u s e l o i l ta k e - o f f o f 0 .5 g a llo n s p er

hour was used in a l l cases s in c e , as has been m entioned in p re c ed in g

s e c tio n s , th e re i s no method a v a ila b le which would a llo w an in s ta n ta n e o u s

d e te rm in a tio n o f f u s e l o i l c o n te n t in th e ta k e - o f f p la te j u s t b e fo re be­

g in n in g the removal o f th e o i l stream w ith th e purpose o f e s ta b lis h in g

th e r a t e o f flow o f the l a t t e r bjr m a te i'ia l b a la n c e . The only e x cep tio n

to t h i s was th e experim ent in which a r e f l a x r a t i o o f 15:1 was used.

In t h i s case th e r a t e of fe e d , and co n seq u en tly th e amount o f f u s e l o i l

e n te r in g th e column, was to o low. A s id e -s tre a m o f 0 .3 g a llo n s p er hour

was u t i l i z e d .

The s iz e o f th e f u s e l o i l s id e -s tre a m , r e l a t i v e to i t s f u s e l o i l

c o n te n t and th a t o f th e fe e d , d eterm in es i f th e o i l accum ulation in the

column w ill e ith e r in c r e a s e o r d e c re a se a f t e r w ithdraw al o f th e s id e -

stream has commenced in o rd e r to e s ta b lis h an o i l b a la n c e . Sudden

v a r ia tio n s in the c o n c e n tra tio n o f f u s e l o i l in th e feed w ill produce

c o rresp o n d in g changes in th e accum ulation o f th e o i l in the column. In

our c ase , v a r ia tio n s in th e f u s e l o i l c o n te n t o f th e feed from tim e to

tim e were m ost l i k e l y sin c e v e ry f r e q u e n tly th e ferm ented mash e n te r in g

th e d i s t i l l a t i o n p ro c e ss f o r a given experim ent pro v ein ed from a number

 142

o f fe rm e n te rs w here, in tu r n , fe rm e n ta tio n experim ents were b ein g con­

ducted under d i f f e r e n t c o n d itio n s . For our p u rp o se s, however, v a lu a tio n s

in th e f u s e l o i l accum ulation in th e column a f t e r w ithdraw al o f th e o i l

stream commenced was r a th e r advantageous s in c e i t p e rm itte d th e g a th e rin g

o f d i s t r i b u t i o n d a ta a t a g r e a te r v a r ie ty o f peak c o n c e n tra tio n v a lu e s

f o r each p a r t i c u l a r s e t o f o p e ra tin g c o n d itio n s .

RESULTS

T ables XVI tlirough X X III, i n th e Appendix, p re s e n t th e r e s u l t s ob­

ta in e d in th e group o f experim ents conducted w ith a 20'S a lc o h o l fe e d . For

each experim ent two ta b le s a rc g iv e n . The f i r s t ta b le shows th e f u s e l o i l

d i s t r i b u t i o n by p la te s o f th e column a t d i f f e r e n t time i n t e r v a l s w hile th e

second shows the a p p a re n t a lc o h o l c o n te n t in the same sam ples. The d a ta o f

a lc o h o l d i s t r i b u t i o n s e rv e s to confirm th e e x c e lle n t s t a b i l i t y p r e v a ilin g in

th e column d u rin g th e course o f th e d i f f e r e n t ex p erim en ts. These d ata do n o t

g iv e th e tr u e a lc o h o l c o n te n t fo r th e in te rm e d ia te p la t e s o f th e column where

c o n sid e ra b le c o n c e n tra tio n s o f f u s e l o i l a re p r e s e n t, w ith th e consequent in ­

tro d u c tio n o f d e v ia tio n s . Toward th e ends of th e column, where f u s e l o i l

c o n c e n tra tio n s a r e v ery lowr, th e e r r o r in tro d u ce d would be n e g l ig ib le . True

v a lu e s can be e a s ily o b ta in e d , when re q u ire d , from th e graphs p re s e n te d in

C hapter IV. The ta b le s i n th e A ppendix, however, g iv e th e a p p a re n t v a lu e s

because i t i s f e l t tlia t th e y w ill be more u s e fu l in th e c o n tro l o f a c tu a l

o p e ra tio n s i n a d i s t i l l e r y . The ta b l e s p re s e n te d in c lu d e th e a lc o h o l and

f u s e l o i l c o n te n t o f com posite sam ples o f the fe e d , " h e a d s 1'a n d main p ro d u c t.

From th e d a ta o b ta in e d i t can be observed tlia t th e p la te o f maximum

c o n c e n tra tio n o f f u s e l o i l c o rresp o n d s to p la te s 21, 22 and 24 when u t i l i s ­

in g r e f lu x r a t i o s o f 5 :1 , 4 :1 and 3 :1 , r e s p e c tiv e ly . No d e f i n i t e
 143

accum ulation o f fu s e l o i l o ccu rs when u t i l i s i n g a r e f lu x r a t i o o f 2 :1 .

Only one peak o f c o n c e n tra tio n was found to ccour and t h i s ap p ears

on th e r e c tif y in g s e c tio n a few p la te s over th e feed p la te , th e ex act l o ­

c a tio n depending on th e r e f lu x r a t i o u t i l i s e d . The p la te o f maximum

c o n c e n tra tio n rem ains the same throughout th e d u ra tio n of th e o p e ra tio n .

P la te s a d ja c e n t to t h a t o f peak accum ulation liave f u s e l o il c o n ce n tra ­

tio n s s im ila r to th e l a t t e r becoming in some in s ta n c e s equal w ith in th e

l i m i t s o f accuracy o f th e a n a ly tic a l method. The w idth o f th e fu s e l o i l

band a s w ell a s th e f u s e l o il c o n te n t in th e upper tra y s o f th e column

a t s im ila r maximum c o n c e n tra tio n s on th e f u s e l o i l tu k c -o ff p l a t e , de­

pends on the r e f l a x r a t i o u t i l i s e d .

The c o n c e n tra tio n o f f u s e l o i l a t p la te s o f s im ila r a lc o h o l c o n te n t

i s n o t s im ila r , b u t depends on th e r e f lu x r a t i o b ein g u t i l i s e d . T his w i l l

bo d iscu ssed in d e t a i l in l a t e r p arag rap h s.

Very sm all c o n c e n tra tio n s o f fu s e l o i l were found in th e low er

p la te s o f th e column in a l l c a s e s . In one p a r t i c u l a r experim ent no

f u s e l o i l a t a l l was found in th e low er p la te sam ples, i . e . , p la te 4 from

bottom up, a t any p e rio d o f tim e .

Much g r e a te r accum ulations were o b ta in e d w ith a r e f lu x r a t i o o f

5:1 than w ith 4 :1 , even though about th e same amount o f fu s e l o i l was

le a v in g w ith th e main p ro d u ct and th e heads in both c a s e s, due to th e

f a c t tlia t th e feed in the f i r s t case c o n tain ed about 1 .5 tim es as much

f u s e l o i l as th e second. In th e experim ent in which a 3:1 r e f lu x r a t i o

w'as used the feed co n tain ed about th e same c o n c e n tra tio n o f f u s e l o i l a s

in th e 5:1 c a s e . The main p ro d u c t in th e 3 :1 case, however, c o n tain ed

much more f u s e l o i l than in th e 5:1 experim ent and, th e r e f o r e , sm aller

 144

accum ulations were produced in th e form er s in c e g r e a te r amounts o f the

o i l were le a v in g th e column w ith th e main p ro d u c t.

The r e s u l t s p re s e n te d in d ic a te t h a t th e w ithdraw al o f a f u s e l o i l

s id e -stre a m does n o t cause any d isp lacem en t in th e d i s t r ib u tio n o f fu s e l

o il.

With a r e f lu x r a t i o o f 2:1 v ery i n t e r e s t i n g r e s u l t s were o b ta in e d .

Under th e s e c o n d itio n s th e f u s e l o i l band i s v ery wide and no d e f i n i t e

peak o c c u rs. The o i l c o n te n t in th e upper tra y s o f th e co lu n n , and con­

seq u e n tly in the main p ro d u c t, i s v ery h ig h . In th e low er p la te s o f th e

column, however, th e p resen ce o f f u s e l o i l i s as low as when h ig h e r r e f lu x

r a t i o s a rc used. T his su g g ests t h a t th e steam d i s t i l l a t i o n e f f e c t i s

p ro b a b ly th e only f a c to r d e term in in g the c o n c e n tra tio n o f f u s e l o i l in

th e a lc o h o l-e x h a u s te d p l a t e s . I t can be observed fi'om th e d a ta tli a t,

even in th e 0 hour sam ples, th e re i s no evidence o f fu s e l o i l accumula­

tio n . T his in d ic a te s tlia t the accum ulation th a t i s undoubtedly produced

d u rin g th e t o t a l r e f lu x p e rio d i s prom ptly d e stro y ed when w ithdraw al o f

p ro d u c t and "h ea d s" commences. A c tu a lly , th e re i s an in e v ita b le tim e la g

between th e moment when rem oval o f p ro d u c t and "h ea d s" commences and th e

moment when sam ples a re ta k e n . The l a t t e r were c o lle c te d only when th e

u n s t a b i l i t i e s produced by th e t r a n s i t i o n from t o t a l r e f lu x o p e ra tio n to

s te a d y s t a t e o p e ra tio n w ith th e removal o f p ro d u c ts , w ere‘overcome. The

tim e la g i s u s u a lly o f th e oi'der o f 30 m in u te s.

T ables XXIV through XXXV i n th e Appendix p re s e n t th e r e s u l t s ob­

ta in e d in th e group o f experim ents conducted w ith a 30^ a lc o h o l fe e d .

A gain, th e d is t r i b u t i o n o f f u s e l o i l and a lc o h o l by p la te s o f th e column

 145

a re given fo r each experim en t. With t h i s p a r t i c u l a r feed com position,

r e f lu x r a t i o s o f 15:1 and 10:1 were s tu d ie d in a d d itio n to th e 5 :1 , 4 :1 ,

3 :1 and 2:1 r u n s .

The r e s u l t s o b ta in e d fo llo w th e same l i n e s o f th o se o b ta in e d w ith

a 20/j a lc o h o l fe e d . The o b s e rv a tio n s made in th e f i r s t group o f e x p e ri­

m ents were t o t a l l y con fin n ed .

Only one c o n c e n tra tio n peak was form ed. As b e fo re , i t o ccu rs i n

th e lower p la te s o f the r e c t if y i n g s e c tio n above the feed p la te and i t s

e x a c t lo c a tio n v a r ie s w ith th e r e f lu x r a t i o u t i l i z e d . The p la te o f maxi­

mum c o n c e n tra tio n docs n o t change d u rin g th e co u rse o f th e o p e ra tio n .

The removal o f th e f u s e l o i l s id e -s tre a m does n o t produce any s h i f t in

th e l'u scl o i l band. Changes in th e w idth o f th e fu s e l o i l band w ith d i f ­

f e r e n t r e f lu x r a t i o s become e v id e n t in t h i s group o f experim ents in which

a r a th e r wide range o f r e f lu x r a t i o s was s tu d ie d . As an example o f t h i s ,

th e fo llo w in g l i s t g iv es approxim ate v a lu e s to which th e f u s e l o i l con­

c e n tr a tio n s liad dropped a t p la te 30 u sin g d i f f e r e n t r e f lu x r a t i o s and

when th e f u s e l o i l c o n c e n tra tio n in th e p la te o f maximum accum ulation was

o f th e o rd e r o f 11,000 mg. p e r 100 m l. I t should be remembered tlia t

p l a t e 18 was th e feed p la te in a l l c a s e s .

R eflux R atio Approximate C o n cen tratio n o f

F u sel O il a t P la te 30, mg. p er
100 m l.

15:1 200

10:1 500

5:1 1,200

4:1 2,500

3 :1 5,000
 146

A ccordingly, th e c o n c e n tra tio n o f f u s e l o i l in th e upper p la t e s

o f th e column v a rie d markedly w ith r e f l u x r a t i o s . The fo llo w in g con­

c e n tr a tio n s were o b ta in e d in com posite samples of th e " h e a d s ” stream and

th e main pro d u ct a t d i f f e r e n t r e f lu x r a t i o s .

R eflux R atio F u sel O il C ontent, rag. p e r 100 m l.,

Heads Main P roduct

15:1 5 5

10:1 5 10

5:1 10 20

4:1 20 35

3:1 20 135

2:1 •10 370

The r e s u l t s o b ta in e d show t li a t, as in th e p re v io u s group o f ex­

p e rim e n ts, th e c o n te n t o f f u s e l o i l by p la te s i s no t o n ly a fu n c tio n o f

th e a lc o h o l c o n te n t o f the p l a te , b u t a ls o g r e a tly dependent on th e r e f lu x

ra tio u tilis e d .

The absence o f f u s e l o i l from a lc o h o l-e x h a u ste d p la te s was even

more marked in t h i s group o f ex p erim en ts.

Maximum c o n c e n tra tio n s from ab o u t 10,000 to 13,000 mg. p er 100 m l.

were produced in the p la te s o f peak accu m u latio n . These v a lu es v a r ie d ,

a g a in , a cco rd in g to th e r e l a t i v e s iz e s and f u s e l o i l c o n te n t o f th e fe e d ,

•’h e a d s '1, main p ro d u ct and o i l s id e -s tre a m . The r e s u l t s in d ic a te tlia t w ith

th e h ig h e r r e f lu x r a t i o s g r e a te r d if f e r e n c e s in f u s e l o i l c o n te n t a rc ob­

ta in e d between th e p la te s o f peak accu m u latio n and th o se a d ja c e n t to i t .

With low er r e f lu x r a t i o s th e fu s e l o i l band i s f l a t t e r .

As in th e case o f th e 20% a lc o h o l fe e d , no d e f i n i t e accum ulation

 147

i s produced u t i l i z i n g a r e f lu x r a t i o o f 2 :1 . The o i l d is tx 'ib u te s more

o r l e s s ev en ly a lo n g th e la i’ge c e n tr a l p o rtio n in th e column and v ery

liigh c o n te n ts a re produced in th e main p ro d u c t. Even w ith th e wide and

f l a t f u s e l o i l band o b ta in e d , f u s e l o i l was co m p letely a b se n t from th e

a lc o h o l-e x h a u s te d p la te s in th e bottom o f th e column.

T ables XXXVI through XLVII p re s e n t th e r e s u l t s o f th e group o f

experim ents conducted w ith a 40% a lc o h o l fe e d . The r e s u l t s confirm the

o b s e rv a tio n s o f th e two p re v io u s g ro u p s. The p l a t e o f maximum accum ula­

tio n was p la te 20, 21 and 22 fo r r e f lu x r a t i o s o f 5 :1 , 4 :1 and 3 :1 ,

r e s p e c tiv e ly . No d e f i n i t e accum ulation was produced w ith a r e f lu x r a t i o

o f 2 :1 . In one p a r t i c u l a r experim ent v ary low c o n c e n tra tio n s o f f u s e l

o i l were p re s e n t in th e a lc o h o l-e x h a u ste d low er p l a t e s o f th e column. In

a l l o th e r c a se s f u s e l o i l was a b s e n t from th e bottom end o f the column.

Two s p e c ia l experim ents were conducted a t r e f Iilx r a t i o s o f 3 :1 and

40% a lc o h o l fe e d . In one case th e f u s e l o i l c o n te n t was a d ju s te d to ab o u t

one h a lf th e v a lu e found i n th e r e g u la r experim ent a t 3 :1 re f lu x r a t i o .

In th e second s p e c ia l experim en t, c o n c e n tra te d f u s e l o i l was added to th e

raw d i s t i l l a t e from th e b e er column to produce a f u s e l o i l c o n c e n tra tio n

a p p ro x im a te ly tw ice tlia t n a t u r a l l y o b ta in e d in th e r e g u la r ex p erim en t.

The purpose o f th e s e two s p e c ia l runs was to d eterm in e e x p e rim e n ta lly th e

e f f e c t o f d iffe i'e n c e s in th e f u s e l o i l c o n te n t o f th e feed on th e f u s e l

o i l band. The r e s u l t s in d ic a te th a t in th e th re e experim ents run a t a

r e f lu x r a t i o o f 3 :1 and a 40^ a lc o h o l feed , th e p l a t e o f maximum f u s e l o i l

accum ulation wras p l a t e 22 in a l l c a s e s . Maximum accu m u latio n s o f ab o u t

4000 mg. p er 100 m l. were produced i n th e case i n which th e f u s e l o i l

 148

c o n te n t o f the feed was 30 mg. p e r 100 nil. Wien th e feed co ntained 70

mg. o f f u s e l o i l per 100 m l., th e maximum accum ulation produced was o f

th e o rd e r o f 9,000 mg. per 100 mi.. In th e case in which th e feed was

stre n g th e n e d in i t s f u s e l o i l c o n te n t to 140 mg. p e r 100 m l., maximum

c o n c e n tra tio n s o f th e o rd e r o f 15,000 mg. p er 100 m l. were produced in

th e p la te o f peak accum ulation. The c o n c e n tra tio n o f fu s e l o i l in th e

v a rio u s p la te s o f the column i s d e f i n i t e l y a f f e c te d by tlia t o f th e p l a t e

o f peak c o n c e n tra tio n , but no sim ple l i n e a r r e l a t i o n e x i s t s . The e f f e c t

i s la r g e ly n o tic e d in th e c e n tr a l p o rtio n o f th e column. The lower 16

p la te s o f th e column wore v i r t u a l l y u n a ffe c te d . Sm all v a r ia tio n s can be

n o tic e d in the to p 8 tra y s o f th e column.

T ables XLVTII through LV p re s e n t th e r e s u l t s o f th e group of ex­

p erim en ts conducted w ith a 50',j a lc o h o l fe e d . A lthough—as i s a ls o th e

case w ith a l l p rev io u s ru n s— each experim ent p ro v id e s a lc o h o l and fu s e l

o i l d i s t r i b u t i o n d a ta which i s c h a r a c t e r i s t i c o f th e p a r t i c u l a r s e t o f

o p e ra tin g c o n d itio n s used, th e g e n e ra l o b s e rv a tio n s p o in te d ou t p re ­

v io u s ly re g a rd in g th e b eh av io r o f f u s e l o i l , were t o t a l l y confirm ed. Peak

accum ulations o ccu rred a t p la te 20 when u t i l i s i n g r e f lu x r a t i o s o f 5:1

and 4 :1 , w hile i t was found to occur a t p la te 21 when o p e ra tin g a t a 3 :1

r e f lu x r a t i o . A lthough pea!; accum ulations o ccu rred a t th e same p la te

when 5:1 and 4:1 r e f lu x r a t i o s were u t i l i s e d , sm a lle r c o n c e n tra tio n s o f

f u s e l o i l were produced in th e to p reg io n o f th e column when o p e ra tin g

w ith th e 5:1 r a t i o . A somewhat bro ad er band was produced when using a

4 :1 r a t i o . No accum ulation was produced when u t i l i s i n g a 2:1 re flu x

ra tio . A bsolute absence o f f u s e l o i l in th e a lc o h o l-e x h a u ste d p la te s

was observed in a l l c a s e s.
 149

The r e s u l t s o b ta in e d in two experim ents conducted w ith -60$ a lc o h o l

feed s a re p re se n te d i n ta b le s LVI through LX. One experim ent was con­

d u c ted a t a r e f lu x r a t i o o f 5:1 w ith th e o b je c tiv e o f d e term in in g i f w ith

th e u t i l i z a t i o n o f th e se o p e ra tin g c o n d itio n s th e peak accum ulation o f

f u s e l o i l would occur below th e feed p l a t e . The second experim ent was

run a t a 2:1 r e f lu x r a t i o w ith th e o b je c tiv e o f d eterm in in g i f th e g r e a te r

a lc o h o l c o n te n t o f th e feed would produce a s ig n if ic a n t accum ulation o f

f u s e l o i l in a p o rtio n o f th e column.

The r e s u l t s o b ta in e d in d ic a te t h a t a t a r e f lu x r a t i o o f 5:1 peak

a c c u n u la tio n s occur a t p la te 19, i . e . , one p la te above th e feed p l a t e .

C o n ce n tra tio n s in th e feed p la te and below a re n o tic e a b ly low er p ro b ab ly

due to th e d ilu tin g e f f e c t o f th e feed i t s e l f . With a r e f lu x o f 2:1

' d e f i n i t e accum ulation o f f u s e l o i l was found to o ccu r, which shows once

more t h a t th e b eh av io r o f f u s e l o i l in the column would n o t be o n ly a

fu n c tio n o f th e r e f lu x r a t i o used b u t a ls o o f th e a lc o h o l c o n te n t o f th e

fe e d . The f u s e l o i l band produced is , however, v e ry broad r e s u l t i n g in

re la tiv e ly high f u s e l o i l c o n te n ts in th e upper tr a y s o f th e column and

co n se q u e n tly in th e main p ro d u ct and in th e *heads*. Peak accu m u latio n s

o ccu r around p la te s 22 to 24. The r e l a t i v e d i s t r i b u t i o n o f com positions

o b ta in e d i s , in g e n e r a l, l e s s d e fin e d and ste a d y th an when r a t i o s o f 3 :1

o r h ig h e r were u t i l i s e d w ith any feed co m p o sitio n . In b o th experim ents

f u s e l o i l was n o t found in th e a lc o h o l-e x h a u s te d p l a te s o f th e column.

T able LX, in th e Appendix, p re s e n ts a ta b u la tio n o f te m p e ratu re v a lu e s

p r e v a ilin g in s e v e ra l p la te s alo n g th e r e c t i f y i n g column d u rin g th e course

o f th e experim ent conducted w ith a 60$ a lc o h o l feed and a r e f l u x r a t i o o f

 .150

2 :1 . I t can be observed from th e d a ta tlia t tem p eratu re v a lu e s were p ra c ­

t i c a l l y c o n s ta n t a t each p l a t e d u rin g th e c o u rse o f th e ru n . The e x c e lle n t

s t a b i l i t y shown by T able LX i s ty p ic a l o f t h a t o b ta in e d in a l l c a s e s .

T ables 9, 10 and 11 summarize some o f th e r e s u l t s o b ta in e d in th e

c o u rse o f our ex p erim en ts. In T able 9 , the lo c a tio n o f peale accumula­

t io n s under d i f f e r e n t o p e ra tin g c o n d itio n s i s given in term s o f number

o f tr a y s above th e feed p l a t e . The combined e f f e c t o f feed com position

and r e f lu x r a t i o can be r e a d ily o b serv ed . T able 10 g iv e s th e c o n ce n tra ­

tio n o f f u s e l o i l in th e p ro d u c t under d i f f e r e n t o p e ra tin g c o n d itio n s

w h ile Table 11 giv es co rresp o n d in g v a lu e s fo r th e top p l a t e o f th e column.

TABLE 9

LOCATION OF PLATE OF MAXIMUM FUSEL OIL CONCENTRATION UNDER DIFFERENT

OPERATING CONDITIONS, PLATES ABOVE THE FEED PLATE

% A lcohol by R eflu x R atio

Volume in Feed
a t 606F : 2:1 3 :1 4 :1 5:1 10:1 15:1

20 No a c c . 6 4 3 - -

30 No a c c . 5 3 3 2 2

40 No a c c . 4 3 2 mm -

50 No a c c . 3 2 2 - -

60 4-6 1
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TABLE 10

FUSEL OIL CONTEST IN MAIN PRODUCT UNDER DIFFERENT OPERATION CONDITIONS

KG. OF FUSEL OIL PER 100 ML. OF SAMPLE

aja A lcohol by R eflux R atio

V ol. in Feed
a t 60°F 2:1 3 :1 4:1 5:1 10:1 15:1

20 450 120 45 45 — —

30 370 135 35 20 10 5

40 350 85 25 15 — —

50 260 60 25 15 -- —

60 200 — 15 — —

TABLE 11

FUSEL OIL CONTENT IN TOP PLATE OF THE RECTIFYING COLUMN

UNDER DIFFERENT OPERATING CONDITIONS,
MG. OF FUSEL OIL PER 100 ML. OF SAMPLE

% A lcohol by R eflux R atio

V ol. in Feed
a t 60°F 2:1 3 :1 4:1 5:1 10:1 15:1

20 150 20 20 20 — tm mm

30 55 20 20 15 5 5

40 65 10 10 5 — —

50 55 10 15 10 — —

60 35 — 5 — —

CONCLUSIONS

From the r e s u l t s o f t h i s work th e fo llo w in g c o n c lu sio n s may be

drawn:

1. The p o in t in th e column where maximum a c c u u u la tio n s o f f u s e l

 152

o i l occur i s a fu n c tio n o f th e r e f l u x r a t i o u t i l i z e d and th e a lc o h o lic

s tr e n g th o f th e fe e d . At any giv en a lc o h o lic c o n te n t in th e fe e d , th e

h ig h e r th e r e f lu x r a t i o u t i l i s e d th e low er th e lo c a tio n o f the p l a t e o f

maximum f u s e l o i l c o n c e n tra tio n . The d a ta p re s e n te d covers th e most

common range o f o p e ra tin g c o n d itio n s in commercial p r a c tic e and can be

used to determ ine th e p l a t e o f f u s e l o i l ta k e - o f f r e l a t i v e to th e feed

p la te . The 50 p l a t e column u t i l i z e d in th e s e s tu d ie s i s ty p ic a l o f

th o se u t i l i s e d in i n d u s t r i a l p r a c tic e .

2. Under th e o p e ra tin g c o n d itio n s s tu d ie d , a s in g le peak o f fu s e l

o i l c o n c e n tra tio n o ccu rred in a l l c a s e s . The l a t t e r was alw ays found to

o ccu r above th e feed p l a t e . T h is fin d in g co n firm s th e t h e o r e t i c a l con­

s id e r a tio n s p re s e n te d in C hapter V when d is c u s s in g th e d i s t r i b u t i o n curve

given b}r Kobinson and G illila n d and c r e d ite d to U ai'bct, which in d ic a te s

th e o ccu rren ce o f two peaks o f maximum c o n c e n tra tio n , one above and one

below th e feed p la te (3 1 4 ). I t was in d ic a te d t h a t in th e o p e ra tio n r e p re ­

se n te d by B ax'bet's d a ta , feed c o n ta in in g 40$ a lc o h o l by volume was in tro d u c e d

i n t o th e column in th e p l a t e where th e a lc o h o l c o n te n t o f th e l i q u i d was

S0$ by volume. Should th e feed have been added a t th e p la te c o n ta in in g

40$ a lc o h o l, i t seems t h a t th e maximum accu m u latio n would have been p ro ­

duced above th e feed p l a t e . The re g io n o f low f u s e l o i l c o n te n t between

th e two peaks may be a t t r i b u t e d to th e d i l u t i n g e f f e c t o f th e fe e d .

3. Peak c o n c e n tra tio n s o f f u s e l o i l o ccu r where th e a p p a re n t a l ­

c o h o lic c o n te n t o f th e l i q u i d phase o f th e p l a t e i s g e n e r a lly from about

130° to 140°P. T able 12 shows ty p ic a l v a lu e s o f a p p a re n t a lc o h o l c o n te n t

in th e p l a t e o f peak accum ulation .under v a rio u s o p e ra tin g c o n d itio n s when

th e c o n c e n tra tio n o f f u s e l o i l i n th e l a t t e r i s o f th e o rd e r o f 10,000 mg.

p e r 100 m l.
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TABLE 12

APPARENT ALCOHOL CONTENT LN THE PLATE OF MAXIMUM

FUSEL OIL CONCENTRATION

A lcohol by R eflu x R atio

V ol. in Feed
a t 60°F 3:1 4:1 5:1 10:1 15:1

20 138-145 139-141 135-137 — —

30 131-332 13L-135 133-135 130-131 130-134

40 134-137 132-136 ‘ 130-132 — —

50 136-137 135-137 139-142 — —

60 — — 135-137 — —

4. The r e s u l t s p re se n te d in d ic a te t lia t th e w idth o f the fu s e l o i l

band i s a fu n c tio n o f th e o p e ra tin g c o n d itio n s u t i l i s e d . At any a lc o h o lic

c o n te n t in th e fe e d , h ig h e r r e f lu x r a t i o s produced narrow er f u s e l o i l

b an d s. These r e s u lte d in g r e a te r d if f e r e n c e s in f u s e l o i l c o n te n t between

th e p l a t e o f maximum accum ulation and th o se a d ja c e n t to i t . In a d d itio n ,

low er f u s e l o i l c o n te n ts were produced in th e upper tr a y s o f th e column

and c o n se q u e n tly in th e p ro d u ct and ■ heads" stre am s. I t should be p o in te d

o u t h ere t h a t th e n a tu re o f th e c o n s titu e n ts o f th e f u s e l o i l p re s e n t in

any p a r t i c u l a r c a s e , would p la y an im p o rta n t p a r t in t h i s r e s p e c t. A raw

d i s t i l l a t e c o n ta in in g is o p ro p y l a lc o h o l, whose v o l a t i l i t y i s v e ry c lo se to

t h a t o f e th a n o l, a s a s ig n if ic a n t c o n s titu e n t o f th e f u s e l o i l p re s e n t,

would y ie ld h ig h e r c o n c e n tra tio n s o f f u s e l o i l in th e to p o f th e column

than a raw d i s t i l l a t e in which is o p ro p y l a lc o h o l i s p re s e n t in v e ry sm all

am ounts, even i f i n th e l a t t e r case a somewhat low er r e f lu x r a t i o i s

u tiliz e d . In our c a se , we had much g r e a te r v a r ia tio n s in th e com position

 154

and c o n c e n tra tio n of th e f u s e l o i l p re s e n t in th e raw d i s t i l l a t e s than i t

would be expected in i n d u s t r i a l p r a c t ic e . The reaso n fo r t h i s s it u a t io n

i s th a t o u r ferm ented mash was th e p ro d u c t o f fe rm e n ta tio n experim ents in

which a wide v a r ia tio n o f ferm enting c o n d itio n s were employed. I t was

p o in te d o u t in C hapter I th a t th e com position and c o n c e n tra tio n o f f u s e l

o i l in a n y p a r t i c u l a r case would depend on th e c o n d itio n s u t i l i s e d in th e

fe rm e n ta tio n p ro c e s s . In s p ite o f t h i s f a c t , th e d a ta shown in T ab les 10

and 11, a s w ell a s th a t on th e in d iv id u a l experim ents p re s e n te d in th e

Appendix, in d ic a te s d e f i n i t e tre n d s re g a rd in g th e e f f e c t o f r e f lu x r a t i o s

on the c o n te n t o f f u s e l o i l in th e upper re g io n o f th e coluiin. The few

d e v ia tio n s found in T ables 10 and .12 a r e o f th e o rd e r o f 5 to 10 m i l l i ­

grams o f fu s e l o i l per 100 m i l l i l i t e r s o f sam ple. These may be p a r t l y

a t t r i b u t e d to d if f e r e n c e s in th e com position o f th e o i l being handled and

to the in h e re n t l i m it a ti o n s o f th e a n a l y t ic a l method.

5. A v e ry i n t e r e s t i n g o b s e rv a tio n , confirm ed th ro u g h o u t th e course

o f a l l o u r ex perim ental work, i s tlia t th e f u s e l o i l c o n te n t a t p la te s o f

s im ila r a lc o h o l c o n te n t i s n o t n e c e s s a r ily s im ila r , even when s im ila r f u s e l

o i l c o n c e n tra tio n s a re p re s e n t in th e p la t e o f maximum a c c u n u la tio n and

feeds o f th e same a lc o h o l c o n te n t a re used, b u t depends l a r g e l y on th e r e ­

flu x r a t i o being u t i l i z e d . T h is f a c t i s o f g r e a t im portance in th e

p ro d u c tio n o f a lc o h o lic beverages where, v ery o fte n , th e a lc o h o l c o n te n t

o f the l i q u i d i s used as c r i t e r i a fo r e s ta b lis h in g th e main p ro d u ct ta k e ­

o ff p la te . These p o in ts can be i l l u s t r a t e d by th e fo llo w in g d a ta which

in d ic a te th e f u s e l o i l c o n te n t in liq u id s having ab o u t 175°P. The d a ta

i s taken from th e group o f experim ents in which feed c o n ta in in g 40$

alco h o l b y volume was u se d . The f u s e l o i l c o n te n t in th e p l a t e o f peak

 155

c o n c e n tra tio n was about 10,000 mg. p er 100 m l. in a l l c a s e s .

R eflux R atio F u sel O il C ontent in P la te Number

P la te C ontaining L iq u id
a t 175°P

5:1 2,350 26

4 :1 1,350 30

3:1 500 34

The e x p la n a tio n f o r t h i s b eh av io r fo llo w s from th e fig u r e s given

in th e column showing th e p la te number where th e d e s ire d c o n c e n tra tio n

o c c u rre d . At lo v e r r e f lu x r a t i o s th e d e s ir e d a lc o h o lic s tr e n g th i s a t ­

ta in e d a t a h ig h e r p la te i n th e column where th e f u s e l o i l c o n c e n tra tio n

has dropped to a g r e a te r e x te n t. This i n d ic a te s t h a t th e s e p a ra tio n o f

f u s e l o i l does n o t depend s o le ly on th e a lc o h o l enrichm ent o f th e l i q u i d .

The r e f lu x r a t i o u t i l i s e d has a d e f i n i t e e f f e c t . There a rc two opposing

e f f e c t s involved which a re as fo llo w s: By in c r e a s in g th e r e f lu x r a t i o th e

f u s e l o i l band i s narrow ed, should o th e r c o n d itio n s remain th e same. On

th e o th e r hand, in so d o in g , any given a lc o h o lic s tr e n g th would be ob­

ta in e d a t a low er p l a t e in th e colimn c lo s e r to th e g r e a te s t accu m u latio n s

o f fu se l o il. At th e upper s e c tio n o f th e column a sm a lle r v a r i a t i o n in .

th e a lc o h o l c o n te n t by p l a t e w i l l be produced w ith a given change in r e ­

f lu x r a t i o . A ccordingly, in any p a r t i c u l a r case th e s e le c te d a lc o h o lic

s tr e n g th v alu e would determ ine th e e f f e c t o f u sin g d i f f e r e n t r e f l u x r a t i o s

on th e f u s e l o i l c o n te n t o f th e p ro d u c t. The fo llo w in g d a ta , tak en from

th e group o f experim ents run w ith a 30# a lc o h o l fe e d , i l l u s t r a t e s th e s e

p o in ts . The v a lu e s given below corresp o n d to f u s e l o i l c o n c e n tra tio n s

found i n p la te s whose l i q u i d c o n tain ed about 188®P when th e f u s e l o i l

 156

c o n te n t was about 10,000 mg. p e r 100 m l.

R eflux R atio F u sel O il C ontent in P la te Number

P la te C ontaining L iq u id
a t 188°P

15:1 35 34

10:1 60 34

5:1 80 38

5:1 90 42

The ta b le s o f d a ta p re se n te d in th e Appendix under d i f f e r e n t

o p e ra tin g c o n d itio n s may be used ad v an tag eo u sly in the s e le c tio n o f

th e se o p e ra tin g c o n d itio n s .

6. The r e s l u t s o f our expei'im ents proved t h a t v a r ia tio n s in th e

c o n c e n tra tio n o f f u s e l o i l in th e feed w ith a d e f i n i t e s ia e o f fu s e l o i l

stream , would v a ry th e m agnitude o f f u s e l o i l accum ulation in th e column,

b u t w ill n o t produce a d isplacem en t in th e lo c a tio n o f th e p l a t e o f

maximum c o n c e n tra tio n s .

7. I t may be observed from th e d a ta p re s e n te d in th e Appendix,

t h a t in many in s ta n c e s a given in c re a s e in th e c o n c e n tra tio n o f fu s e l

o i l in th e p l a t e o f maximum accum ulation does n o t produce, th e r e f lu x

r a t i o and th e com position o f th e feed rem aining unchanged, a p ro p o rtio n a l

in c re a s e i n th e f u s e l o i l c o n te n t o f th e p la te s i n th e to p and bottom r e ­

gio n s o f th e column. A fte r c e r ta i n v a lu e s a re reach ed a t th e p la te o f

peak c o n c e n tra tio n , an in c re a s e in th e l a t t e r u s u a lly r e s u l t s in a p ro ­

p o r ti o n a lly s m a lle r in c re a s e in th e upper and bottom t r a y s . T h is i s

e x p lain ed by th e f a c t th a t th e f u s e l o i l accum ulated in th e d i f f e r e n t

re g io n s o f th e column v a r ie s in com p o sitio n . Tliat accum ulating in th e

 157

upper tr a y s c o n s is ts m o stly o f th e more v o l a t i l e h ig h e r a lc o h o ls , p r in ­

c i p a l l y iso p ro p a n o l, i f p r e s e n t. During th e co u rse o f con tin u o u s

o p e ra tio n s w ith o u t th e rem oval o f a f u s e l o i l s id e -s tre a m , a r e l a t i v e l y

sm a lle r p o rtio n o f th e most v o l a t i l e c o n s titu e n ts e n te rin g w ith th e feed

id-11 accum ulate in th e column sin c e th e y w ill account fo r th e g r e a te r

p a r t o f th e fu s e l o i l le a v in g w ith th e main p ro d u c t and w ith th e 0 h ead s1*

stre am . A ccordingly, th e o i l c o n tin u o u sly accum ulating in th e column

w hile o p e ra tin g w ith o u t removing a f u s e l o i l s id e -s tre a m , o r when th e

s iz e o f th e l a t t e r i s too sm a ll, c o n s is ts to a g r e a te r e x te n t o f th e

h ig h e r b o ilin g c o n s titu e n t a lc o h o ls which a re fo rc e d down by th e r e c t i ­

fy in g a c tio n ta k in g p la c e i n th e column and which ten d to accum ulate a t

a low er re g io n o f th e l a t t e r . G re a te r accu m u latio n s in the m iddle p la te s

o f th e column c e r t a i n l y a f f e c t tlia t o f th e upper s e c tio n , b u t t h i s e f f e c t

would be g r e a te r should a l l th e most v o l a t i l e c o n s titu e n ts o f f u s e l o i l

remain in th e column in s te a d o f le a v in g w ith th e to p p ro d u c ts in much

g r e a te r p ro p o rtio n s than th e l e s s v o l a t i l e . As should be ex p ected , th e

e f f e c t d isc u sse d above i s more n o tic e a b le w ith h ig h e r r e f lu x r a t i o s sin c e

th e l a t t e r d e c re a se s th e c o n te n t o f h ig h e r b o ilin g c o n s titu e n ts in th e

fu se l o il p re s e n t in th e upper tr a y s o f th e column.

8. R eflux r a t i o s o f 2:1 o r below do n o t produce predom inant a c ­

cum ulations in any re g io n o f th e column w ith fe e d s o f a lc o h o lic s tr e n g th s

up to 50# a lc o h o l by volum e. P ro d u cts v ery h ig h in f u s e l o i l c o n te n t a re

o b ta in e d . When feed c o n ta in in g 60# a lc o h o l by volume was p ro c e ssed under

a 2 :1 r e f lu x r a t i o , a broad band o f f u s e l o i l c o n c e n tra tio n s was produced

which r e s u lte d in a p ro d u ct v e ry h ig h in f u s e l o i l c o n te n t.
 15S

9. F u se l o i l was n o t p r e s e n t in any case in th e a lco h o l-e x h a u ste d

p l a t e s in th e low er re g io n o f th e column. When no d e f i n i t e accum ulation

o f f u s e l o i l o c cu rred w ith th e low er r e f lu x r a t i o s s tu d ie d , th e o i l s d is ­

t i l l e d over w ith th e " h e a d s 11 and main p ro d u ct stream g iv in g bottom s f r e e

from h ig h e r a lc o h o ls . In a l l c a s e s , fu s e l o i l - f r e e samples from th e

bottom and from few tra y s above th e r e b o i l e r , p o ssessed th e c h a r a c te r­

i s t i c “t a i l s 6 odor fr e q u e n tly a t t r i b u t e d to f u s e l o i l and which i s

e v id e n tly due to u n id e n tif ie d im p u r itie s .

10. The e x p erim en tal d a ta o b ta in e d in th e co u rse o f t h i s work can

be ad v an tag eo u sly u t i l i s e d in th e d e sig n o f cquipnent and in th e s e le c tio n

o f o p e ra tin g c o n d itio n s f o r any g iv en pro d u ct s p e c i f ic a ti o n s .

 CHAPTER V I I I

COMPILATION OF EQUILIBRIUM DATA FOR THE SYSTEM ETHANOL-WATER

AT ATMOSPHERIC PRESSURE

111 th e course o f experim en tal in v e s tig a tio n s on s e v e ra l phases o f

a lc o h o lic d i s t i l l a t i o n , th e need was f e l t fo r ta b le s which would p r e s e n t,

in a s in g le c o m p ila tio n , liq u id -v a p o r e q u ilib riu m d a ta f o r th e system

e th an o l-w ate r e x p ressed i n mole f r a c t i o n , p er c e n t by w eig h t and p e r

c e n t by volume, a llo w in g d ir e c t c o n v ersio n between th e se term s. The

term p er c e n t by volume in the v ap o r phase r e f e r s to th e condensate

o b tain ed a f t e r the v ap o r i s t o t a l l y condensed.

E q u ilib riu m d a ta fo r th e system e th a n o l-w a te r a t atm ospheric

p re s su re have been determ ined by Evans (3 6 2 ), R ayleigh (3 6 9 ), S o re l a s

given hy E l l i o t (361), Bergstrom a s given by Hausbrand (3 6 3 ), B lachcr

a s given by Hausbrand (3 6 4 ), C arey and Lewis (3 5 9 ), and C o rn ell and

Montonna (3 6 0 ).

The d a ta of C o rn e ll and Montonna and th a t o f Carey and Lewis a re

th e most re c e n t and a r e g e n e r a lly acc e p ted as th e m ost a c c u r a te . The

agreem ent between the two s e ts o f d ata i s e x c e lle n t and b o th a re ex­

te n s iv e ly used in works on the s u b je c t (358, 370, 3 6 8 ). C o rn e ll and

Montonna u t i l i s e d in t h e i r experim en tal work th e method o f R osanoff,

Bacon and White which c o n s is ts o f d eterm in in g th e com position o f s e v e ra l

f r a c tio n s o f d i s t i l l a t e from a l i q u i d o f known o r i g i n a l com position (3 7 1 ).

The p ercen tag e com positions fo r d i f f e r e n t t o t a l w eights o f d i s t i l l a t e a re

then c a lc u la te d assuming tlia t th e f r a c tio n s were combined s u c c e s s iv e ly .

F in a lly , e x tra p o la tin g back to a e ro w eight o f d i s t i l l a t e th e com position

159
 160

o f th e f i r s t i n f i n ite s im a l f r a c tio n o f vapor evolved from th e l i q u i d ,

which g iv e s th e d e s ir e d vapor com p o sitio n , i s o b ta in e d .

Carey and Lewis u t i l i s e d th e method o f Othmcr which in v o lv e s con­

tin u o u s re c y c lin g o f d i s t i l l a t e to th e e q u ilib riu m s t i l l u n t i l ste a d y

c o n d itio n s have been e s ta b lis h e d (2 6 7 ). From t h a t moment on th e composi­

tio n o f th e d i s t i l l a t e re tu rn in g to th e s t i l l i s th e same a s th e com position

o f th e vapors le a v in g th e s t i l l . Samples a re withdrawn sim u lta n e o u sly from

th e s t i l l and from th e condensate chamber and t h e i r com position determ in ed ,

th u s y ie ld in g th e d e s ir e d liq u id - v a p o r e q u ilib riu m c o m p o sitio n s.

The f a c t tlia t such an e x c e lle n t agreem ent was o b ta in e d between th e

d a ta o f C o rn e ll and tlia t o f Carey w h ile u t i l i z i n g d i f f e r e n t te ch n iq u es

seems to in d ic a te t h a t th e s e r e s u l t s a rc h ig h ly a c c u r a te . The d a ta o f

C o rn e ll was s e le c te d as the b a s is f o r th e p re p a ra tio n o f th e ta b le s p r e ­

s en te d in t h i s workf o r th e reaso n tlia t i t com prises 45 ex p erim en tal

p o in ts co v erin g th e whole range o f com positions w liile t h a t o f C arey com­

p ris e s only 14, and docs n o t go beyond th e a z e o tro p ic p o in t.

The com positions o f th e l i q u i d in term s o f p e r c e n t by w eight were

co n v erted in to mole f r a c tio n s by c a lc u la tio n and in to com positions by

volume a t 60°F and 20°C making use o f th e ta b le s o f th e U, S . Bureau o f

S ta n d a rd s (372, 37 4 ).

E q u ilib riu m com positions i n th e v ap o r, ex p ressed i n mole f r a c ti o n s ,

w ere o b ta in e d from an e q u ilib riu m curve p lo tte d u sin g th e c o o rd in a te s

given by C o rn e ll and Montonna o f a curve drawn by th e s e a u th o rs through

t h e i r own ex p erim en tal p o in ts (3 6 0 ). These com positions in mole f r a c tio n

were c o n v erted in to p e r c e n t by w eight by c a lc u la tio n and were checked

 161

a g a in s t re a d in g s from a second e q u ilib riu m curve p lo tte d u sin g c o o rd in a te s

given by the same a u th o rs and based on th e same ex p erim en tal p o in ts b u t

ex p re ssin g com position in p e r c e n t by w eig h t. Com positions in th e vapor

in p e r c e n t by w eight were conv erted in to p er c e n t by volume in th e

t o t a l l y condensed vapor a t 60°F and 20°C u t i l i z i n g a g ain th e ta b le s o f

th e Bureau o f S ta n d a rd s.

The a z e o tro p ic com position given i s th e g e n e ra lly a cc e p ted v a lu e

o f 0.8943 mole f r a c tio n (359, 370, 36 5 ), wldch i s an average o f th e v a lu e s

found by Young and F o rte y (375) and Wade and Mcrriam (3 7 3 ).

The b o ilin g te m p e ratu res o f the e th a n o l-w a te r m ix tu res were o b ta in e d

by g ra p h ic a l in te r p o la tio n from th e d a ta o f Noyes and W arfel (3 6 6 ). These

d a ta , g e n e r a lly acc e p ted a s v ery a c c u r a te , a re w idely used in jo u rn a ls and

t e x t books (358, 359, 365, 368, 3 7 0 ). The ex p erim en tal r e s u l t s , w ith few

e x c e p tio n s, f a l l on a v e ry smooth curve from which g ra p h ic a l in t e r p o la ­

tio n s can be r e a d ily made. The ex p erim en tal v a lu es around the a z e o ti’opic

p o in t, from 90 to 100 p e r c e n t a lc o h o l by w eig h t, were p lo tte d on a s c a le

o f 1 mm. e q u iv a le n t to 0.001°C . The range between 63.0 and 90 .0 p e r c e n t

by w eight was p lo tte d on a s c a le o f 1 mm. e q u iv a le n t to 0 .0 0 5 “C. The ran g e

from 0 .0 to 63.0 p e r c e n t a lc o h o l by w eight was p lo tte d on a s c a le o f 1 mm.

e q u iv a le n t to 0.02°C . The in te r p o la te d te m p e ratu res a re re p o rte d to th e

same decim al p la c e a s th e e x p erim en tal d a ta .

The ta b u la tio n p rep ared i s p re s e n te d a s T able LXI which w i ll be

found in th e Appendix.
BIBLIOGRAPHY
 BIBLIOGRAPHY

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3 6. , P ro c e ss o f M anufacturing F u se l O il and Components o f I t ,

B r. P a te n t 664,020 (March 20, 1 9 0 6 )J ' ' '

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4 2. __________ , "The P ro d u ctio n o f S u c c in ic A cid D uring F e rm e n ta tio n ", B ied.

Z e n t r ., 37 197 (1 9 0 8 ).

4 3. __________ , "About th e C onversion o f T y ro sin e in to T y ro so l" , B er. , 44,

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44. . "U ber d ie B ildung d es P lasm aeiw eisses b e i Hefen and .

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4 8. . a n d ___________, "R e so lu tio n o f Racemic Amino A cids by Y e a sts",

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49. B nm erling, D ., "P resen ce o f n -B u ty l A lcohol in F u se l O il From G rain*,

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52. E id e rs , C ., and K. Karnbach, "Com position o f F u sel O il O btained by

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, and , "Com position o f F u se l O il O btained by

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114. , "A ctio n o f B a c te ria i n F u s e l O il F orm ation1', Biochem. Z .,

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369. R ay leig h . L ., “ D i s t i l l a t i o n o f B in ary M ix tu re s ”, P h i l . M ae., 4 , 521-37

(1 9 0 2 ).

370. R obinson, C. S . , and E. R. G i l l i l a n d , Elem ents o f F r a c tio n a l D i s t i l ­

l a t i o n , F o u rth E d itio n . New York: McGraw-Hill Book C o ., I n c . ,
1950. Pp. 52.

371. R osanoff, M. A ., C. W. Bacon, and R. M. W hite, ”A Rapid L a b o ra to ry

Method o f M easuring th e P a r t i a l Vapor P re s s u re s o f L iq u id M ix tu res* ,
J . Am. Chem. Soc. , 36, 1803-25 (1 9 1 4 ).

372. U .S. Bureau o f S ta n d a rd s , C irc u la r No. 19, 1924. Pp. 1 6 -7 .

373. Wade, J . , and R. W. M erriam, ” In flu e n c e o f W ater on th e B o ilin g P o in t

o f E th y l A lcohol a t P re s s u re s Above and Below th e A tm ospheric
P re s s u re " , J . Chem. Soc. , 99, 997-1011 (1 9 1 1 ).

374. Woodman, A. G ., Food A n a ly s is , T h ird E d itio n . New York: McGraw-Hill

Book C o., I n c ., 1931. Pp. 454-67.

375. Young, S . , and E. C. F o rte y , "The P r o p e r tie s o f M ixtures o f th e Lower

A lcohols w ith W ater", J . Chem. S oc. , 81, 719-23 (1 9 0 2 ).
APPENDIX
 TABLE I

EFFECT OF FUSEL OIL ON THE DETERMINATION OF ALCOHOL BY PICNOMETER,

IMMERSION REFRACTOMETER AND HYDROMETER

A n a ly tic a l R e s u lts in D egrees P ro o f a t 60aF

F u s e l O il, : : A c tu al A lco h o l C ontent a t tfhich Samples were P rep a re d ,

Mg p e r 100 : A n a ly tic a l : D egrees P ro o f a t 60°F
ml : Method :
20*P 40°P 60*P 80*P 100 *P 120°P 140-P 160“P 180°P
sample •• ••

200 Picnom eter 2 0 .4 4 0 .1 59 .8 79.9 100.1 119.9 140.0 160.1 1 8 0 .2

Hydrometer 2 0 .2 4 0 .0 5 9 .2 8 0 .0 99 .9 1 20.0 140.1 160.4 180.4
R efracto m eter 20.4 4 0 .2 5 9 .4 7 9.6 - - - mm
-

500 Picnom eter 20.7 4 0.6 60.8 80.8 100.8 120.9 140.8 160.4 180.8
Hydrometer 20.6 4 0 .4 6 0 .2 80 .6 100.4 120.8 140.8 160.9 1 8 0 .4
R efracto m eter 21.3 4 1 .2 6 0 .5 8 0 .4 - mm - - -

1000 Picnom eter 21.5 41 .7 62 .0 8 2 .2 1 02.2 122.1 142.1 1 6 2 .2 182.1

Hydrometer 21.8 4 1.6 61.8 8 2 .4 102.4 122.3 142.4 162.6 182.6
R efracto m eter 2 3 .1 4 2.8 6 2 .1 8 2 .1 - - - - -

2000 Picnom eter 23.3 43.8 6 4 .4 8 4 .5 104.6 124.4 144.4 164.1 1 8 4 .0

Hydrometer 2 3 .6 43 .8 64.9 8 4 .1 104.8 124.6 144.3 164.4 1 84.2
R efracto m eter 26.7 4 5.9 65 .0 8 4 .4 — - - - -

4000 Picnom eter i1 4 8 .4 89 .8 109.6 128.9 148.7 168.5 1 8 8 .0

Hydrometer i 47 .8 - 8 9 .2 109.4 129.1 149.0 168.7 1 88.4
R efracto m eter i 51.4 mm
9 2 .0 - - - - —

^ Two l i q u i d la y e r s form ed.

(C ontinued on n e x t page)
 TABLE I (C o n tin u ed )

F u se l O il, : : A c tu al A lcohol C ontent a t Which Samples were P re p a re d ,

Mg p e r 100 : A n a ly tic a l : D egrees P ro o f a t 60°F
ml : Method :
o f sample : : 20°P 40°P 60 °P 80°P 100°P 120 °P 140°P 160#P 180°P

7000 P icnom eter i i 77 .4 9 7 .2 116.2 135.7 1 5 5 .2 174.6

Hydrometer i i 77 .2 97 .0 115.9 135.3 155.7 174.4 -
R efra cto m e te r i i 78.9 - *■» - - - -
10,000 Picnom eter i i 8 5 .4 104.5 123.3 142.4 161.5 181.0 m,
Hydrometer i i 84.8 104.1 1 2 3 .1 142.4 161.7 181.5 mm

R efracto m eter i i 8 8 .4 - mm - - - -

15,000 Picnom eter i i 97.7 115.9 134.3 153.3 172.1 1 9 0 .6 mm

Hydrometer i i 9 7 .2 115.3 134.3 153.8 1 72.2 190.8 -

R efracto m eter i i - - - - - - -

20,000 P icnom eter i i 109.0 1 26.5 144.8 163.1 181.7

Hydrometer i i 108.6 126.4 144.8 163.2 182.0 — •
R efra cto m e te r i i - - «» - mm - -
30,000 Picnom eter i i 129.7 146.7 164.3 182.6 mm

Hydrometer i i 129.6 146.9 1 64.6 182.7 — — «

R efra cto m e te r i i — - - mm mm
 190

TABLE I I

ALCOHOLIC CONTENT OF LIQUID PHASE BY PLATES

OF THE RECTIFYING COLUMN UTILIZING QUANTITY CONTROL
SYSTEM I I

E xperim ental C o n d itio n s: Feed - 60°P a t P la te 16;

R eflux R atio - 5 :1 ; P roduct - P la te 42

A pparent A lcohol C ontent in D egrees P ro o f a t 60°F

Time o f Sam pling A fte r W ithdrawal o f P roduct Commenced

0 hrs. 1 h r. 2 h rs. 3 h rs. 4 h rs. 5 h rs. 6 h rs. 7 h rs

189.6 191.7 191.7 191.4 191.2 190.7 190.0 190,5

46 184.3 189.7 190.5 190.5 189.3 189.2 188.7 188.2
42 187.9 188.4 187.7 187.9 185.2 184.5 183.0 182.1
40 186.2 187.2 186.4 186.3 183.4 182.0 180.1 177.9
38 184.9 185.7 183.8 184.4 180.0 176.5 173.6 171.1

36 183.6 183.7 181.0 180.8 174.1 170.4 162.0 157.4

34 181.7 180.3 176.9 172.6 164.8 158.8 139.2 131.1
32 178.3 175.8 170.3 165.2 148.2 131.1 57.4 53.6
30 171.9 168.5 156.0 146.8 103.9 50.0 20.3 19.7
28 162.0 154.3 118.2 99.0 33.8 18 .0 13.5 13.3

26 129.0 110.0 43.4 30.4 16 .5 1 2 .2 12.1 1 1 .2

24 35.3 35.9 15.8 14.3 11 .0 10 .8 11.3 U .O
22 15 .0 16.7 13.2 12.6 10.6 1 1 .0 11.8 10 .6
20 10.8 12.7 12.1 11.9 1 0 .6 11.3 1 1 .4 10.6
18 1 0 .0 11.4 11.6 12.1 9 .9 1 1 .3 U .3 10 .6

14 4 .9 5.3 5 .5 4.9 4 .6 4 .7 6 .0 5 .4
12 0 .3 5.1 0 .7 0.5 0 .4 0 .2 0 .5 0 .7
10 0 .3 0 .2 0 .0 0 .0 0 .2 0 .0 0 .0 0 .0
8 0 .4 0 .0 0 .0 0 .1 0 .0 0 .0 0 .0 0 .0
6 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
 191

TABLE I I I

FUSEL OIL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING QUANTITY CONTROL SYSTEM I I

E xperim ental C o n d itio n s: Feed - 60°P a t P la te 16;

R eflux R a tio - 5 :1 ; P ro d u ct - P la te 42

Mgs. o f F u sel O il a s Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdrawal o f P ro d u ct Commenced

P la te
0 h rs. 1 h r. 2 h rs. 3 h rs. 4 h rs . 5 h rs . 6 h rs. 7 h rs.

50 15 35 10 20 25 25 30 30
46 20 5 25 20 35 50 60 70
42 20 70 50 120 210 240 380 460
40 . 50 90 no 140 360 480 700 500
38 80 100 220 260 800 900 1700 1600

36 120 230 460 600 1400 1800 3500 3000

34 180 360 1100 1500 2800 2800 3600 3600
32 290 800 1400 2400 3600 3600 1300 500
30 600 650 2600 3200 3600 550 210 250
28 1100 1700 2000 2800 600 200 80 80

26 1500 1400 700 400 100 70 30 50

24 280 320 100 60 40 20 15 25
22 35 70 30 25 15 10 10 15
20 20 25 10 15 5 5 10 10
18 10 15 5 10 10 15 15 10

14 5 5 5 5 5 5 10 5
12 5 5 5 5 5 5 5 5
10 10 5 5 5 5 5 5 5
8 10 5 5 5 5 5 5 20
6 10 5 5 5 10 5 5 5
 192

TABLE IV

ALCOHOL CONTENT OF LIQUID PHASE BY PLATES OF

THE RECTIFYING COLUMN UTILIZING COMPOSITION CONTROL-
SYSTEM I I 1

E xperim ental C o n d itio n s: Feed - 60*P a t P la te 16;

R eflu x R atio - 5 :1 ; P ro d u ct - Overhead D i s t i l l a t e

A pparent A lcohol C ontent i n Degrees P ro o f a t 60°F

Time o f Sam pling A fte r W ithdraw al o f P roduct Comnenced

P la te :
0 h r. 1 h r. 2 h rs. 3 h rs. 4 h rs. 5 h rs.

50 191.2 191.7 191.6 191.4 191.7 1 9 1 .1

42 188.0 187.4 185.1 186.8 185.3 1 8 7 .5

36 182.6 181.0 171.8 182.0 176.3 1 8 1 .8

30 150.6 148.3 135.8 147.2 140.0 1 4 8 .3

24 35 .9 38.0 28.6 36.2 3 4 .1 3 5 .0

20 1 4 .2 12.1 10 .9 10.9 1 4 .5 1 6 .3

18 1 2 .0 10.8 10 .6 8 .9 13.3 1 0 .2

14 7 .3 6 .5 4 .0 5 .0 4 .5 4 .1

10 0 .3 0 .2 0 .0 0 .3 0 .2 0 .2

6 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

Based on v a r y in g th e r e f l u x r a t i o t o m a in ta in c o n s ta n t a r e f e r e n c e
te m p e ra tu re i n th e colum n.
 193

TABLE V

TEMPERATURE OF VAPOR PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM I I 1

E xperim ental C o n d itio n s: Feed - 60°P a t P la te 16;

R eflux R atio - 5 :1 ; P ro d u ct - Overhead D i s t i l l a t e

T em perature, Degrees F a re n h e it

Time o f Reading A f te r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h r. 1 h r. 2 h rs. 3 h rs. 4 h rs. 5 h rs.

50 172.5 172.5 172.5 172.5 172.5 172.5

42 175.0 175.5 175.5 173.0 176.0 175.0

34 176.5 177.0 177.5 177.0 178.0 177.0

30 180.0 181.0 183.5 181.0 184.0 181.5

26 191.0 192.0 192.5 192.0 193.5 193.0

22 199.0 203.0 205.0 202.0 203.0 202.5

18 203.0 203.5 203.0 203.0 204.5 203.5

16 205.0 205.5 205.0 205.5 206.0 205.0

12 215.0 215.5 215.5 215.5 217.0 216.0

6 219.0 219.5 219.0 219.0 219.5 219.0

^ Based on v a r y in g th e r e f l u x r a t e t o m a in ta in c o n s ta n t a r e f e r e n c e
te m p e ra tu re in th e colum n.
 194

TABLE VI

ALCOHOL CONTENT OF LIQUID PHASE BY PLATES OF

THE RECTIFYING COLUMN UTILIZING COMPOSITION CON1ROL
SYSTEM IIA 1

E xperim ental C o n d itio n s: Feed - 60®P a t P la te 16}

R eflu x R a tio - 5:1} P ro d u ct - Overhead D i s t i l l a t e

A ppatent A lcohol C ontent in Degrees P ro o f a t 60*F

Time o f Sam pling A fte r W ithdrawal o f P roduct Coamenced

P la te :
0 h r. 1 h r. 2 h rs. 3 h rs. 4 h rs. 5 h rs.

50 191.7 191.5 191.8 191.6 191.7 191.6

42 189.2 188.8 189.6 188.6 188.2 188.8

36 183.9 183.6 184.4 184.1 183.6 183.5

30 153.2 152.2 154.0 153.7 153.8 152.5

24 4 0 .2 38.7 41.6 40.9 39.6 39 .0

20 17.3 16.1 1 7 .0 17 .4 1 6.1 16 .6

18 1 4 .0 13.1 1 4 .5 14.9 13.6 13.9

14 8 .3 7 .0 8 .6 7 .6 8 .3 7 .2

10 0 .4 0 .3 0 .2 0 .3 0 .0 0 .4

6 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

^ B ased on v a r y in g th e o v erh ea d p ro d u c t r a t e to m a in ta in c o n s ta n t a
r e f e r e n c e te m p e ra tu re i n th e colum n.
 195

TABLE V II

TEMPERATURE OF VAPOR PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM IIA 1

E xperim ental C o n d itio n s: Feed - 60°P a t P la te 16;

R eflux R atio - 5 :1 ; P ro d u ct - Overhead D i s t i l l a t e

T em perature, D egrees F a re n h e it

Time o f Reading A f te r W ithdrawal o f P ro d u ct Commenced

P la te :
0 h r. 1 h r. 2 h rs. 3 h rs. 4 h rs. 5 h rs

50 172.5 172.5 172.5 172.5 172.5 172.5

42 174.5 173.0 175.0 173.5 175.0 175.0

34 176.5 176.5 177.0 177.0 176.5 176.5

30 179.5 180.0 180.0 180.0 180.0 180.0

26 190.5 191.0 191.5 191.5 191.0 191.0

22 198.0 198.0 1 98.5 1 98.5 198.5 198.5

18 200.5 200.5 201.0 200.5 200.5 200.5

16 203.0 203.5 203.0 203.0 203.5 203.0

12 215.0 215.5 215.5 215.5 215.5 215.5

6 219.0 219.0 219.0 219.5 219.0 219.0

1 Based on v a r y in g th e o v erh ead p ro d u c t r a t e to m a in ta in c o n s ta n t a

r e f e r e n c e te m p e ra tu re in th e colum n.
 196

TABLE V III

ALCOHOL CONTENT OF LIQUID PHASE BY PLATES OF

THE RECTIFYING COLUMN UTILIZING COMPOSITION CONTROL
SYSTEM I I l l

E xperim ental C o n d itio n s: Feed - 60#P a t P la te 17 }

R eflux R a tio - 5 : l j P ro d u ct - P l a te 42

A pparent A lcohol C on ten t in D egrees P ro o f a t 60®F

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s .

50 191.8 192.6 191.9 192.2 191.7

42 189.6 190.7 190.6 190.3 1 90.1
38 188.3 189.0 188.5 188.6 . 188.5
34 185.7 186.7 185.8 186.1 1 85.9

30 182.8 183.4 182.0 182.1 1 81.5

26 175.4 177.1 174.4 174.9 1 74.0
24 168.8 171.1 163.3 169.6 169.3
23 164.5 166.6 168.5 165.9 164.1

22 158.7 161.2 159.8 161.7 160.4

21 151.4 154.8 151.4 155.8 152.8
20 143.3 145.9 141.1 149.8 145.8
19 121.3 121.3 118.1 136.6 131.1

17 4 4 .0 45.3 4 7 .1 67.6 65.8

16 24.4 22.0 24.0 4 3 .6 37.8
15 10.3 9 .2 9 .4 19 .6 12.6
14 7 .2 4 .6 5 .8 1 1 .1 8 .1

12 0 .5 0 .7 4 .2 3 .0
10 •ew m
0 .4 0 .5 0 .5 0 .7
8 — 0 .2 0 .0 0 .7 0 .3
4 0 .5 0 .2 0 .0 0 .2 0 .3

Based on v a ry in g th e r a t e o f w ith d raw al o f th e p ro d u c t a s a s id e

s tre a m to m a in ta in c o n s ta n t a r e f e r e n c e te m p e ra tu re in th e
colum n.
 197

TABLE IX

FUSEL OIL CONTENT OF LIQUID PHASE BY PLATES OF

THE RECTIFYING COLUMN UTILIZING COMPOSITION CONTROL
SYSTEM I I l l

E xperim ental C o n d itio n s: Feed - 60*P a t P la te 17;

R eflux R atio - 5 :1 ; P ro d u ct - P la te 42

Mgs. o f F u se l O il a s Amyl A lcohol p er 100 m l. o f Sample

Time o f Sampling A fte r W ithdrawal o f Product Commenced

P la te :
0 h rs. 3 h rs. 6 h rs . 9 h rs . 12 h r s .

50 15 10 15 20 25
42 15 15 25 30 25
38 25 35 55 65 65
34 65 95 165 350 300

30 200 320 700 650 850

26 620 1,050 1,850 3,000 4,500
24 1,150 1,800 1,500 3,500 5,000
23 1,450 2,400 4,500 4,000 6,500

22 1,700 4,000 5,000 8,000

21 1,950 5,000 7,500 6,500 9,500
20 2,050 5,500 7,500 8,000 11,000
19 2,150 5,500 6,500 10,000 11,000

17 400 600 950 4,000 4,500

16 250 240 240 2,500 3,150
15 100 70 110 400 90
14 100 45 65 250 220

12 40 15 20 100 55
10 20 10 15 50 25
8 10 5 10 15 15
4 5 5 • 10 10 10

1 Based on v a ry in g th e r a t e o f w ith d ra w a l o f th e main p ro d u c t a s a s id e

s tre a m to m a in ta in c o n s ta n t a r e f e r e n c e te m p e ra tu re in th e colum n.
 198

TABLE X

ALCOHOL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM I I I 1

E xperim ental C o n d itio n s: Feed - 60°P a t P la te 17j

R eflux R atio - 5 : l j P ro d u ct - P la te 42

A pparent A lcohol C ontent in D egrees P ro o f a t 60°F

Time o f Sam pling A fte r W ithdraw al o f P roduct Commenced

P la te
4 h rs. 6 lu 's. 9 h rs. 12 h r s . 15 h rs . 18 h r s . 24 h rs .

50 191.7 192.9 192.6 192.6 192.4 192.9 192.9

42 190.7 190.7 190.7 190.5 190.5 191.0 190.7

38 189.0 189.0 188.9 188.7 188.8 188.8 188.9

34 187.0 187.0 186.4 186.2 186.1 186.1 186.2

30 183.9 183.9 1S3.2 183.1 181.9 182.5 182.5

26 177.1 178.5 177.4 177.1 176.5 176.3 176.4

24 172.5 173.5 172.9 173.5 173.3 171.4 171.8

23 169.4 171.5 170.3 170.1 169.8 167.5 168.6

22 165.0 169.4 166.9 167.0 166.8 164.3 165.2

21 159.2 161.7 161.0 161.3 161.2 158.6 160.4

20 152.9 157.9 156.9 156.1 156.9 154.6 156.5

19 137.3 145.8 146,3 147.0 148.4 144.9 148.5

17 67.2 79.5 83.8 8 7.1 89.4 82.3 88 .1

16 43.7 63.5 73.5 79.5 87.6 77.0 88.2

14 9 .2 20.7 27.9 1 3 .2 55.3 47.3 62.2

12 1 .5 4 .8 7 .8 10 .1 1 9 .1 18 .2 16.1

8 0 .5 0 .2 0 .2 0 .0 0 .2 0 .4 0 .6

Based on v a ry in g th e r a t e o f w ithdraw al o f th e Main P ro d u ct a s a s id e

stream to m a in ta in c o n sta n t a re fe re n c e te m p e ratu re in th e column.
 199

TABLE XI

FUSEL OIL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM I I I 1

E xperim ental C o n d itio n s: Feed - 60*P a t P la te 17j

R eflux R atio - 5 :1 ; P ro d u ct - P la te 42

Mgs. o f F usel O il a s Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sampling A fte r Withdrawal, o f Product Commenced

P la te
4 h rs . b h rs. 9 h rs. 12 h rs . 15 h r s . 18 h r s . 24 h r s .

50 20 20 25 25 25 25 10

42 25 25 35 30 35 35 40

38 40 45 65 60 60 70 85

34 160 160 200 240 240 280 220

30 360 360 4S0 600 600 740 700

26 1,200 1,100 1,450 1,650 1,800 2,200 2,000

24 2,000 2,000 2,350 2,550 2,650 3,100 3,000

23 2,550 2,350 2,650 ------------ 2,250 4,500 3,750

22 2,950 2,650 3,200 3,000 3,500 6,750 6,250

21 3,750 3,300 4,750 4,750 4,500 8,250 8,500

20 4,500 4,000 5,750 5,050 5,500 9,350 9,000

*

19 4,750 5,250 6,250 6,500 7,000 9,500 10,500

17 1,600 2,200 2,650 3,200 3,200 4,750 5,250

16 800 1,700 2,500 2,950 3,750 4,750 5,750

14 110 380 640 980 2,650 2,300 4,000

12 30 95 160 280 660 700 750

8 15 20 30 30 50 60 55

Based on v a ry in g th e r a t e o f w ithdraw al o f th e main p ro d u ct a s a sid e

stream to m a in ta in c o n sta n t a re fe re n c e tem p eratu re in th e column.
 200

TABLE X II

ALCOHOL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM IV1

E xperim ental C o n d itio n s: Feed - S0°P a t P la te 18$

R eflax R atio - 4:1$ P ro d u ct - P la te 42

A pparent A lcohol C ontent in Degrees P ro o f a t 60°F

Time o f Sampling A f te r W ithdraw al o f P ro d u ct Commenced

P la te
! 3 h rs. 6 h rs . 9 h rs. 12 h r s . 15 h r s . 18 h r s . 24 h r s .

50 192.2 192.1 191.9 191.9 192.1 191.9 191.6

42 189.6 189.0 189.0 189.5 189.3 189.5 189.6
38. 187.0 186.8 186.5 186.8 1S6.7 186.3 186.0
34 184.2 183.2 183.0 183.8 183.3 183.1 183.0

30 179.7 178.3 178.0 177.9 177.2 177.6 178.4

26 171.1 169.1 168.6 168.5 167.3 167.2 168.7
24 160.9 160.4 160.1 160.9 159.8 158.7 160.3
23 155.7 154.4 153.5 154.1 153.1 153.6 153.9

22 150.8 147.0 147.0 147.8 147.0 146.9 146.6

21 133.1 132.8 133.8 133. S 135.2 134.6 135.5
20 118.5 114.8 115. S 119.7 119.5 123.2 122.5
19 75.6 74.5 77.2 83.7 82.5 87.5 83.8

18 44.6 44.1 44.4 50.8 52.6 44.7 51.9

17 20.7 24.5 16 .4 29.8 24.1 28.1 25.7
16 9 .2 9 .5 7 .1 7 .4 9 .2 10.7 8 .1
15 3.7 4 .9 3 .3 4 .2 3 .0 3 •5 2.6

14 0 .8 2 .1 0 .9 0 .7 1 .0 2 .5 1 .8
12 0 .6 0 .8 0 .0 0 .4 0 .0 0 .1 0 .9
8 0 .4 0 .0 0 .0 0 .2 0 .0 0 .0 0 .0
4 0 .2 0 .0 0 .5 0 .0 0 .0 0 .0 0 .0

Based on v a r y in g th e fe e d r a t e t o m a in ta in c o n s ta n t a r e fe r e n c e tem­
p e r a tu r e in th e colum n.
 201

TABLE X III

FUSEL OIL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM IV1

E xperim cntal C o n d itio n s: Feed - SO°P a t P la te 1.8j

R eflux R atio - 4 : l j P roduct - P la te 42

Mgs. F usel O il a s Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sampling A fte r W ithdrawal o f P ro d u ct Commenced

P la te
3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 24 h r s .

50 10 5 0 10 10 10
42 15 25 30 25 40 40 30
38 65 100 125 HO 130 135 125
34 185 325 200 395 260 215 160

30 580 1,200 1,200 1,150 1,350 1,400 1,400

26 2,000 3,100 3,400 3,700 3,750 4,650 4,450
24 3,650 4,800 6,100 6,400 6,550 5,850 6,600
2.3 ' 3,950 6 ,9 50 7,550 8,250 S, 900 8,800 8,450
0'> 5,350 7,100 9,000 9,500 9,350 8,850 S,800
21 5,800 8,100 9,100 9,650 10,400 11,500 10,600
20 5,500 6,750 8,300 9,800 10,300 10,400
19 1,950 2,950 2,950 4,850 4,250 5,550 4,800

IS 630 600 750 SOO 1,050 1,250 900

17 290 ' 405 605 625 760 760 550
16 70 105 130 120 170 170 140 ’
15 30 50 75 75 65 70 70

14 15 50 30 45 25 60 45
12 15 25 5 40 5 10 25
8 35 25 20 35 0 30 45
4 25 30 40 45 0 40 45

^ Based on v a r y in g th e fe e d r a t e to m a in ta in c o n s ta n t a r e fe r e n c e tem ­
p e r a tu r e in th e colum n.
 202

TABLE XIV

ALCOHOL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM IV l

E xperim ental C o n d itio n s: Feed - 80°P a t P la te 18;

R eflux R atio - 3 :1 ; P roduct - P la te 42

A pparent A lcohol C ontent in Degrees P ro o f a t 60°F

Time o f Sampl in g A fte r W ithdrawal o f P ro d u ct Commenced

P la te
3 h rs . 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 24 h r s .

50 191.3 191.4 191.1 190.7 191.3 191.1 191.3

42 187.7 187.7 167.7 187.7 187.9 187.7 18S.0
38 183.8 183.3 162.7 163.0 183.3 .183.6 183.5
.34 178. S 177 .5 177.8 177. <1 177.8 176.4 178.4

30 171.0 168.9 169 .5 169.5 169.5 169.5 170.0

26 157.4 156.9 156.3 156.3 156.0 156.3 157.4
24 148.1 146.0 147.5 145.0 146.5 146.9 148.3
23 142.9 139.7 141.3 139.7 140.4 140.7 141.8
o«>
M M 136.0 135.1 •136.0 135'. 7 136.0 136.3 135.6
21 122.5 121.9 125.0 • 125.1 12-1.8 125.1 125.3
20 106. S 10S.5 113.5 115.1 114.9 115.1 114.9
19 83.8 84.7 88.7 88.5 89.3 89.5 88.5

18 56.9 60.2 60.1 60.8 o0.3 60.1 59.0

17 27.4 30,0 30.6 30.4 30.0 31.0 31.0
16 12.7 15.6 14.0 15.1 1 5.4 16.0 16.0
15 5.8 4 .5 5.7 4 .1 5.0 5.8 5.5

14 1 .8 2.5 2.7 2.o 2.5 2.6 2.5

12 0 .4 0 .3 0 .4 0 .4 0 .4 0 .4 0 .4
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0.0

^ B ased on v a r y in g th e fe e d r a t e to m a in ta in c o n s ta n t a r e fe r e n c e tem­
p e r a tu r e in th e colum n.
 203

TABLE XV

FUSEL OIL CONTENT OF LIQUID PHASE BY PLATES OF THE RECTIFYING

COLUMN UTILIZING COMPOSITION CONTROL SYSTEM IV l

E xperim ental C o n d itio n s: Feed - SO°P a t P la te I8 j

R eflux R a tio - 3 : l j Product - P la te 42

Mgs. F u se l O il a s Amyl A lcohol p er 100 m l. o f Sample

Time o f Sam pling A fte r W ithdrawal o f P roduct Commenced

rj.ii to
3 h rs. 6 h rs . 9 h rs. 12 h r s . 15 h rs . 16 h rs . 24 h r

50 15 15 10 10 10 10 15
42 50 95 80 85 85 80 80
38 400 600 550 600 500 450 500
34 800 1,250 1,300 1,550 1,400 1,100 1,350

30 2,000 3,500 3,600 5,550 3,800 3,800 3,650

26 5,500 S,500 S,600 9,800 9,000 8,500 8,100
24 8,500 10,500 12,300 13,600 13,500 12,100 11,400
23 8,500 11,300 13,500 15,500 14,800 13,300 12,900

22 S,500 12,000 14,200 16,100 15,000 14,900 14,500

21 8,500 11,200 13,800 15,500 14,600 14,300
20 7,500 9,000 13,100 14,100 13,200 13,500 13,100
19 2,000 3,500 5,900 5,400 6,300 5,700 5,250

18 950 1,000 1 , 600 2,350 2,350 1,800 1,650

17 200 600 800 1,000 1,000 1,000 1,100
16 120 180 330 370 460 440 380
15 50 75 50 100 100 100 100

14 20 40 50 55 90 75 70
12 5 5 15 15 20 15 15
8 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0

B ased on v a r y in g th e f e e d r a t e t o m a in ta in c o n s ta n t a r e fe r e n c e tem­
p e r a tu r e in th e colum n.
 TABLE XVI

FUSEL OIL DISTRIBUTION IX RECTIFYING COLUMN

E xp erim en tal C o n d itio n s : Feed - 2Q% A lc o h o l a t P la t e 18; R ei'lnx R a tio - 5 :1 ; P roduct - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P l a te s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A f te r vvitndrav/al o f Produc t Commenced

P la te
0 h rs. 3 h rs. 6 h rs 9 h rs. 12 h r s . 15 h r s . IS h r s . 21 h r s . 24 h r s .

50 15 20 15 10 15 20 20 20 25
42 20 25 25 30 40 40 50 50 55
38 35 55 65 115 250 150 250 250 250
34 90 170 250 450 550 500 SCO 700 750
30 500 700 800 1,600 2, SCO 2,000 3,000 3,000 3,500
2b 2,000 3,000 4.0CG 5, 500 6,000 0,000 7,500 9,000 7,500
24 3,000 5,000 6,500 10,000 11,000 11,500 14,000 13,000 12,500
23 4,000 6,000 8,000 11,000 13,500 14,000 14,000 16,500 14,000
22 4,500 7,000 10,000 13,500 14,500 16,000 17,000 17,500 17,000
21 5,500 8,500 11,500 13,500 16,000 17,000 15,500 15,500 17,500
20 5,000 6,000 11,000 13,500 lo ,0 0 0 l o , 500 15,000 l b , 000 16,000
19 1,200 3,000 4,000 5,000 7,500 ----- 5,000 6,000 5,500
18 500 600 950 1,100 1,500 2,500 1,500 2,000 1,500
17 350 350 550 650 800 1,300 700 750 600
16 b5 110 200 250 350 500 500 350 300
15 40 55 95 120 200 300 150 200 150
14 25 40 65 £5 100 .LTD 100 no 90
12 15 20 30 50 50 70 50 60 50
8 5 10 15 20 20 25 15 20 15
4 0 10 5 5 5 10 5 10 5

Feed t o R e c t i f 3rin g Column - 75

P rod u ct from R e c t if y in g Column - 45
Heads fx'om R e c t if y in g Column - 20
 TABLE XVII

ALCOHOL DISTRIBUTION IN RECTIITINC COLUMN

E x p erim en ta l C o n d itio n s : Feed - 2G;-J A lc o h o l a t P l a t e 15; R e f i l l R n tio - 5 :1 ; Pi-oduct - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P la te s , Degrees P ro o f a t o0°F

Time o f Sampling A fte r Withdrawal o f Product Commenced

: 0 lir s . 3 h rs. 6 h rs . 9 h rs. 12 h r s . 15 h r s . IS h r s . 21 h r s . 24 h r s .

50 190.9 192.5 192.4 192.0 191.1 192.1 192.0 191.8 192.5

42 190.2 190.3 190.1 192.0 189.2 190.0 189.5 1S9.6 1=9.9
38 188.5 185.2 1SS.1 158.0 137.0 187 .7 136.7 187.2 157.0
34 1S5.S 185.5 1S5.4 184.2 153.0 1A5. o 182.9 183.4 153.4
30 181.7 181.6 181.0 176.1 177.2 178.7 176.3 .! 77.6 176.6
26 174.3 172.9 172.2 167.0 166.1 167.7 163.6 164.4 164. 5
24 166.6 164.3 163.8 1 56.7 156.0 157.4 152.6 154.2 154.0
23 159.7 157.9 157.6 145.5 145.5 1.50.1 144 • 6 14 5.6 146.8
22 150.9 150.6 144.5 139.0 3 39.5 143 . 5 137.2 138.9 138.9
21 131.5 135.1 lo i . 1 126.5 132.0 135.1 124.6 124.1 125.2
20 108.4 114.7 119.3 110.7 116.7 125.5 105.0 105.9 103 .S
19 52. S 57.4 61.8 56.9 62.0 61.5 53.2 56.5 54.7
18 28.5 31.7 34 .4 30.6 34.1 32.0 30.2 29.4 25.1
17 17.1 19.3 21.1 18.5 •>-J • oJ 21.6 20.5 17.1 16 .5
16 7.8 9 .4 10.4 9 .4 1 2 .3 10.2 10.3 S .7 3 .0
15 3 .9 4 .5 4 .5 4.7 5.7 5 .1 3 .o 4 .2 3.9
14 1 .6 2 .2 ' 2 .6 2.0 3 .2 1.7 2.1 2 .2
12 0 .2 0 .4 0 .5 2 .2 0 .9 1 .3 0 .4 0 .5 0 .5
8 0 .0 0 .0 0 .1 0 .1 0.0 6 0 .0 0 .0 0.0 6 0 .0
4 0 .0 0 .0 0 .1 0 .0 0.06 0 .0 0 .0 0.1 0 .0

Feed to R e c t if y in g Column - 3 9 .4
P rod u ct from R e c t if y in g Column- 1 S 9 .9
Heads from R e c t if y in g Column - 1 9 2 .6
 TABLE XVIII

FUSEL OIL DISTRIBUTION1 IN RECTIFYING COLUMN

E xp erim en tal C o n d itio n s: Feed - 20% A lc o h o l a t P la t e I S ; R e flu x R a tio - 4 :1 ; P roduct - P la t e 42

F u sel O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r m l. o f Sample

Time o f Sampling A fte r W ithdrawal o f P roduct Commenced

-L a"
: 0 h rs. 3 h rs. 6 h rs . 9 h rs. 12 h rs . 15 Iirs. 19 h r s . 21 h r s . 24 h r s .

50 15 15 15 20 25 15 15 25 20
42 30 45 50 55 55 40 45 40 40
38 70 150 250 250 300 200 200 200 200
34 250 550 soo 750 750 500 500 250 450
30 650 1,900 3,000 '3 ,0 0 0 3. COO 2,000 2,500 1,500 2,000
26 2,900 5,500 7 , 500 7,500 7,000 5,000 4,500 3 , 500 4,500
24 5,500 8,000 10,000 11,000 10,000 7, 500 6 , 500 o,500 6,500
23 6, 500 10,000 12,000 13,000 12,000 9,000 8,500 7,500 7,500
22 7,00-0 10,500 13,500 13,500 13,500 10,000 9,000 8 , 500 8,000
21 6,000 9,500 12,500 13,000 12,000 9,000 9,000 8,000 7,500
20 4,500 8,000 9,500 11,500 9,000 7,000 7,000 b,000 6,000
19 1.500 2,500 3,500 4,000 3,500 2,500 2,500 2,500 2,000
IS 300 500 550 700 500 400 450 400 300
17 200 300 400 450 400 250 300 300 200
16 55 90 105 145 90 75 75 75 70
15 35 55 45 75 60 45 50 50 50
14 20 35 45 50 40' 30 25 35 30
12 15 25 25 25 20 15 15 20 20
8 10 10 25 15 10 10 10 15 10
4 5 5 15 10 10 10 10 10 5

Feed t o R e c t if y in g Column - 50
P roduct frtm R e c t if y in g Column - 45 to
Heads from R e c t if y in g Column - 20 a-.
 TABLE XIX

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 20 % A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 4 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60aF

Time o f Sampling A fte r W ithdraw al o f P ro d u ct Commenced

P la te
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .
50 192.0 190.5 191.8 191.7 192.0 191.9 191.7 191.5 191.7
42 189.5 188.3 189.4 189.5 189.5 189.5 189.5 189.5 189.1
38 187.1 185.8 186.5 186.6 186.6 187.0 187.0 186.8 186.4
34 1 84.2 182.9 182.6 183.1 183.0 183.6 183.9 183.6 183.5
30 179.4 176.6 176.2 176.1 176.4 178.0 178.2 177.9 178.3
26 1 70.1 166.6 165.5 164.6 1 65.2 167.8 168.8 168.6 168.8
24 160.2 156.9 154.6 154.5 155.6 158.1 159.0 159.4 159.1
23 151.3 148.7 147.1 147.0 147.4 150.1 151.3 152.2 151.9
22 141.0 139.3 138.6 138.6 138.7 140.3 141.4 1 42.0 142.4
21 115.8 118.9 1 2 1 .0 1 20.2 119.1 120.4 122.8 120.3 1 20.1
20 92.6 98.4 9 8 .0 98.3 9 6 .1 9 6 .1 99.8 95.9 9 7 .2
19 45.9 47.5 49.9 43 .7 4 8 .2 4 7.9 49.7 41 .7 4 9 .7
18 29.5 3 0 .3 29.3 30.1 30.8 3 1 .2 32.7 31.3 3 0.0
17 1 9 .2 1 9 .4 1 8.9 1 9 .2 19.3 20.4 20.7 2 1 .2 1 9 .2
16 9 .8 9 .6 9 .6 9 .7 9 .2 .1 0 .8 9 .6 10 .9 9 .6
15 5.7 6 .0 1 .5 4 .7 5 .1 6 .0 5 .6 6 .4 ^.5
14 2 .4 2 .8 2 .6 2 .4 2 .2 3 .0 2 .1 2 .6 2 .6
12 0 .5 0 .5 0 .7 0 .5 0 .5 0 .5 0 .3 0 .5 0 .5
8 0 .3 0 .2 0 .1 0 .2 0 .1 0 .3 0 .1 0 .1 0 .1
4 0 .2 0 .0 0 .0 0 .1 0 .1 0 .1 0 .1 0 .1 0 .0

F eed t o R e c t if y in g Colunn - 3 8 .7
P ro d u c t from R e c t if y in g Column - 1 8 9 .5

207
Heads from R e c tif y in g Column - 1 9 1 .3
 TABLE XX

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 20# A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 3 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r m l. o f Sample

•
Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced
P la te •

: 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 15 20 20 20 20 20- 25 15 25
42 40 70 115 100 120 140 150 110 120
38 200 300 550 550 500 650 500 500 500
34 400 700 1,500 2,000 2,000 2,000 2,000 1,500 2,000
30 1,500 3,500 3,000 4,000 4,000 4,000 3,500 4,000 3 ,500
26 3,000 4,500 5,500 6,500 7,000 7,000 7,000 6,000 7,000
24 3,500 5,500 6,500 8,500 9,500 9,000 8,500 7,500 8,000
23 3,500 5,000 6,500 7,500 9,500 8,000 8,000 7,000 7,500
22 2,500 4,500 5,500 6,000 9,000 7,500 6,500 7,000 7,000
21 1,500 2,500 3,500 4,000 6,500 5,000 5,000 4,500 5,000
20 900 1,100 1 ,800 3,000 4,500 3,500 3,500 3,000 3 ,0 0 0
19 250 450 500 750 1,000 700 700 650 750
18 70 250 130 200 300 250 200 200 250
17 55 85 105 200 250 250 170 150 150
16 30 45 55 80 95 80 80 80 75
15 20 30 35 50 55 55 45 50 60
14 5 20 25 35 40 35 25 40 35
12 5 15 15 20 35 25 15 25
8 0 10 10 15 20 15 10 15 30
4 0 0 5 5 10 10 5 5 5

F eed t o R e c tif y in g Column - 70

P ro d u c t from R e c tif y in g Colunn - 120 Av.
Heads from R e c t if y in g Colunn - 20
 TABLE XXI

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 20/6 A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 3 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60*F

Time o f Sampling A fte r W ithdraw al o f P ro d u ct Conmenced

P la te
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 189.8 191.0 190.8 191.2 191.0 191.0 190.7 189.8 1 91.2

42 187.5 187.5 187.2 188.7 187.4- - 187.1 186.9 186.9 186.9
38 183.9 183.4 182.5 182.5 182.5 182.7 182.8 183.0 1 8 2 .2
34 179.5 178.0 176.5 176.0 177.5 176.7 176.2 176.8 1 76.2
30 172.8 170.8 1 6 8 .5 167.5 169.1 167.3 167.6 168.2 167.9
26 160.2 157.7 154.3 153.2 156.1 154.1 143.4 1 53.6 153.2
24 145.5 141.6 138.1 138.9 143.4 145.3 138.6 139.8 138.6
23 130.5 126.0 121.4 125.2 133.4 128.7 125.6 127.4 125.1
22 114.2 111.2 107.5 111.4 121.0 115.1 111.6 113.0 112.0
21 84.1 8 5 .2 7 9 .5 85.3 9 6 .5 87 .6 8 9.6 8 7 .6 8 6 .4
20 65.5 6 8 .4 65.6 67 .0 75.8 70.8 7 2.8 68 .7 6 9 .6
19 4 3 .0 43.3 4 2 .2 43.7 4 5 .1 4 4 .1 4 3 .8 42 .9 43 .8
18 34.4 34.9 3 2 .4 33.9 33.9 35 .4 34.3 33.9 34.7
17 26.6 26.3 26.0 26.7 25.9 26.9 27.7 26.8 27.1
16 17.8 22.2 16 .4 1 7 .7 1 5 .9 17 .7 1 9 .1 1 7 .7 20 .4
15 11.7 1 1 .5 1 0 .1 1 0 .6 9 .3 11 .0 1 1 .5 10.9 1 1 .0
14 6 .9 6 .5 6 .0 7 .2 5 .5 6 .2 6 .9 7 .6 7 .8
12 1 .8 2 .2 1 .8 2 .2 2 .0 2 .3 2 .6 2 .5 3 .3
8 0 .1 0 .1 0 .1 0 .1 0 .1 0 .0 0 .1 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 3 8 .6

P ro d u c t from R e c t if y in g Column - 1 8 6 .6

209
Heads from R e c t if y in g Colunn - 1 9 1 .3
 TABLE XXII

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 20/S A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r m l. o f Sample

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

P la te
: 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 110 200 200 100 200 200 150 65 70

46 500 450 450 500 400 450 400 350 300
42 1,350 1,500 1,100 1,500 1,300 2,000 1,500 1,100 950
40 2,000 2,000 2,500 2,000 2,000 2,000 2,000 2,000 2,000
38 3,500 2,500 2,500 2,000 2,500 2,000 2,000 2,000 2,500
36 3,000 2,000 2,500 2,000 2,000 2,000 1,500 2,000 2,500
34 2,500 2,000 2,500 2,000 2,000 2,000 1,500 1,500 2,000
32 2,500 2,000 2,000 2,000 2,000 2,000 1,500 1,500 1,500
30 2,000 2,000 2,000 2,000 2,000 2,000 1,000 950 1,200
28 2,000 2,000 1,500 2,000 1,500 2,000 1,000 800 1,150
26 1,650 1,500 1,050 900 1 ,500 1 ,050 350 600 1,050
24 1,450 1,500 850 850 1 ,5 0 0 850 200 450 900
22 1,250 700 750 850 1,500 850 150 300 650
20 900 400 550 550 1,000 550 100 135 500
18 95 80 200 200 90 85 70 70 80
16 55 50 100 100 55 50 40 40 45
14 30 30 25 30 30 30 20 20 20
10 15 15 15 20 15 15 5 10 10
6 10 10 15 15 15 10 5 5 10
2 5 10 10 5 10 5 5 5 5

F eed t o R e c tif y in g Column - 85

P ro d u c t from R e c t if y in g Colunn - 450
Heads from R e c t if y in g Colunn - 45
 TABLE X XIII

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 2056 A lc o h o l in P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , Degrees P ro o f a t 60°F

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

P la te
: 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 185.8 183.7 184.4 183.8 184.9 185.4 1 8 4 .2 184.3 1 85.6

46 180.0 178.1 177.8 1 78.4 179.3 178.7 177.9 179.9 1 8 1 .2
42 168.3 167.1 1 66.2 1 66.0 165.5 167.3 164.6 166.0 169.0
40 159.1 1 58.2 157.3 156.4 156.1 157.3 153.9 155.8 161.9
38 150.2 150.7 148.1 1 48.5 143.6 146.6 144.5 141.4 152.6
36 132.9 134.0 130.5 130.5 122.7 128.6 126.1 119.4 136.4
34 1 28.0 131.0 127.1 1 27.1 119.0 125.7 122.4 114.0 121.6
32 116.9 113.8 110.3 111.3 9 9 .6 108.6 1 02.5 95.3 103.7
30 110.3 107.8 104.8 1 0 4 .1 9 6 .6 102.5 1 00.2 95.7 104.1
28 106.6 102.3 98 .4 9 8.4 91.0 9 5 .2 89 .6 8 8 .2 9 9 .0
26 101.9 93.7 9 3 .5 94.3 8 7.1 91 .9 - — 7 6 .2 92.2
24 9 3 .2 8 4 .2 8 4.6 8 6.0 80 .6 82 .1 ____ 69.7 8 3 .3
22 88.7- 77.4 81 .5 81 .5 77.6 79.8 ------ 58.0 71.8
20 7 1 .2 61.1 65.9 66.8 66.8 6 2 .2 ------ 4 7.8 56.3
18 3 9 .5 4 0 .2 38.7 39.9 45.1 39.6 4 0 .0 39.7 39 .4
16 30.8 3 3 .2 3 2 .0 32.5 31.9 30.9 3 3 .4 33 .5 32.7
14 21.8 21.4 1 9 .5 20.8 1 9 .b 1 9 .4 21.3 24.9 20.4
10 2 .3 3 .6 4 .4 4 .3 3 .4 3 .0 3 .9 6 .9 4 .0
6 0.06 0 .0 8 1 .3 1 .0 0 .5 0 .2 0 .4 0 .7 0 .4
2 . 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed to R e c t if y in g Column - 3 6 .6
P ro d u c t from R e c t if y in g Column - 1 7 8 .8
Heads fro m R e c t if y in g Colunn - 1 8 5 .8
 TABLE XXIV

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed 30/6 A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 1 5 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f sample

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s .
50 5 5 5 5 5 5 5 5
42 5 5 5 5 5 5 5 5
38 10 10 10 10 15 10 10 10
34 20 30 35 30 45 35 40 50
30 85 115 165 150 235 150 190 260
26 525 740 930 650 950 750 800 1,050
24 1,100 1,550 1,850 1,900 2,600 2,450 2,650 2,850
23 2,150 2,650 2,950 3,300 5,000 3,650 4,000 4,100
22 3,400 3,550 4,400 4,900 7,100 5,650 5,550 5,800
21 4,600 5,750 6,900 7,800 8,500 8,200 9,000 8 ,500
20 5,500 6,450 7,900 9,300 10,750 10,400 10,700 10,500
19 4,400 5,300 6,650 6,750 7,100 — 7,500 7,700
18 1,750 550 700 1 ,4 0 0 1,150 2,900 2,950 2,000
17 255 180 345 460 510 570 605 655
16 40 20 20 95 95 95 165 150
15 15 10 55 35 30 25 45 40
14 5 5 5 15 10 5 15 15
12 0 0 0 0 0 0 0 0
8 0 0 0 0 0 0 0 0
4 0 } 0 0 0 0 0 0 0

F eed t o R e c t if y in g Column - 85
P ro d u c t from R e c t if y in g Column - 5
Heads from R e c tif y in g Column - 5
 TABLE XXV

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s :. Feed - 3055 A lco h o l a t P l a t e 1 8 ; R e flu x R a tio * 1 5 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P la t e s , Degrees P ro o f a t 60°F

Time o f Sam pling A f te r W ithdrawal o f P roduct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h rs. 15 h r s . 18 h r s . 21 h r s .

50 192.6 192.4 192.2 192.9 192.8 192.9 1 9 2 .S 192.8

42 191.3 190.6 190.8 191.0 190.9 191.0 191.1 191.0
38 190.4 190.2 190.4 190.0 190.1 190.2 190.0 190.1
34 188.9 188.9 188.9 188.7 168.8 188.7 188.9 188.8
30 187.0 165.9 186.2 186.4 186.2 186.4 186.5 186.6
26 . 182.3 180.8 180.6 181.2 181.6 181.1 161.0 181.6
24 176.4 174.8 174.8 175.0 175.6 175.1 175.2 175.8
23 170.9 170.3 170.1 170.8 170.9 170.7 170.7 170.6
22 163.0 163.3 163.0 163.3 164.2 163.6 163.3 163.0
21 147.8 145.8 147.9 148.4 149.5 148.5 147.4 147.8
20 129.7 132.8 133.0 133.5 134.2 134.0 133.6 133.0
19 85.1 88.0 8 8.6 89 .2 89.6 8 8.5 87.9 88 .2
18 — 40.9 36.6 3 5 .2 35.4 39.5 42 .3 39.7
17 17.4 13.7 14.7 13 .2 16.3 lb .3 1 4 .S 15.9
16 3 .0 2 .0 2 .2 2 .8 2.8 4 .4 3 .4 3 .8
15 0 .7 0 .2 0 .7 0 .8 0 .5 0 .4 0.9 0 .7
14 0 .0 0 .0 0 .3 0 .2 0 .4 0 .3 0 .5 0 .6
12 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

Feed to R e c tif y in g Column - 5 8 .8

P ro d u c t from R e c tif y in g Column - 1 9 1 .7
Heads from R e c tif y in g Column - 1 9 2 .9
 TABLE XXVI

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed 30£ A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio 1 0 :1 ; P ro d u c t - P l a t e 42

F u sel O il C ontent o f L iq u id Phase by P l a t e s , rags, o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 18 h r s . 21 h r s . 24 h r s .
__
50 5 5 5 5 5 15 10
42 5 5 5 10 10 10 10 10
38 20 15 20 20 20 30 20 20
34 30 40 55 60 100 60 70 60
30 ’ 100 180 310 330 480 260 280 300
26 590 700 1,100 1,400 2,200 1,150 1,100 1 ,6 0 0
24 1,150 1,600 2,500 3,100 3,950 2,550 3,050 3,100
23 1,680 2,500 3,600 4,500 6,000 3,900 4,300 3,900
22 2,400 3,800 4,800 5,700 7,400 5,300 5,100 4 ,900
21 3,100 4,200 6,300 7,900 9,700 6,900 6,400 6,800
20 3,500 5,000 7,300 9,000 10,300 7,400 7,100 7,100
19 1,600 1,700 4,500 6,000 7,400 6,000 4,050 4,050
18 520 410 900 1,100 1,250 1,200 600 600
17 97 290 420 300 640 200 220 190
16 15 25 50 65 100 55 70 55
15 10 10 20 25 35 25 20 20
14 5 0 5 10 10 5 5 5
12 0 0 0 0 0 0 0 0
8 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0

Feed t o R e c tif y in g Colunn - 60

P ro d u c t from R e c tif y in g Column - 10
Heads from R e c tif y in g Column - 5
 TABLE XXVII

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 30$ A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 1 0 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60°F

P la te Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

0 hrs . 3 hrs. 6 hrs. 9 hrs. 12 h rs . 18 h r s . 21 h r s . 24 h r s .

50 192.2 192.0 192.2 192.1 192.1 192.3 192.2 192.2

42 191.1 191.2 191.2 191.1 191.0 191.3 191.1 1 91.1
38 190.0 190.3 190.0 190.0 189.9 190.1 189.9 1 9 0 .2
34 187.9 188.1 187.6 187.7 187.9 188.0 188.0 187.9
30 185.3 185.8 185.4 185.4 185.3 185.6 185.6 185.6
26 179.5 179.6 179.4 179.4 179.1 179.7 179.3 179.3
24 174.2 174.2 173.9 173.6 173.6 174.0 176.3 173.6
23 168.9 169.3 168.9 168.8 169.4 168.7 168.2 169.0
22 161.4 161.6 161.8 161.8 161.9 161.7 161.7 162.0
21 149.1 149.3 148.5 149.1 148.5 149.4 149.6 149.2
20 125.7 127.4 1 27.0 130.4 131.0 130.9 1 2 7 .3 128.3
19 71.4 6 9 .2 91.5 7 6.9 79 .0 76 .4 75.7 74.1
18 34.6 37.1 3 5 .8 3 9.7 35.6 39 .1 34.9 3 4 .5
17 17 .0 16 .2 1 5 .2 14. 6 17.7 15 .1 1 4 .6 1 4 .5
16 2 .8 3 .2 3 .7 2 .6 5.3 3 .3 4 .3 3 .4
15 0 .7 0 .3 0 .7 0 .9 0 .9 0 .9 0 .7 0 .8
14 0 .2 0 .1 0 .2 0 .1 0 .2 ' 0 .1 0 .1 0 .2
12 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 5 9 .5

P ro d u c t from R e c tif y in g Column - 1 9 0 .7
Heads from R e c tif y in g Column - 1 9 2 .4
 TABLE XXVIII

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed 30$ A lco h o l a t P l a t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

F u sel O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f sample

Time o f Sam pling A fte r W ithdrawal o f P roduct Commenced

P la te
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . IS h r s . 21 h r s . 24 h r s .

50 5 5 15 10 15 15 10 5 20
42 10 10 20 20 10 25 20 20 25
38 20 30 50 80 85 85 100 90 65
34 80 134 195 230 260 270 260 255 270
30 365 400 850 700 1,350 1,100 1,100 1,300 1,250
26 1,100 1,900 2,950 3,750 5,250 3,850 4,300 4,500 4,150
24 2,300 3,900 6,050 7,550 8,100 8,300 8,250 7,500 7,700
23 2,950 5,350 8,000 10,000 10,420 9,000 10,700 10,760 11,190
22 3,950 7,300 10,500 10,900 11,600 11,300 11,400 11,050 12,600
21 4,700 7,900 11,400 11,500 13,150 12,800 12,000 13,000 14,000
20 4,450 7,850 10,500 10,000 13,050 11,400 10,500 11,150 12,450
19 850 2,000 2,450 4,150 5,450 3,700 3,450 3,750 2,700
18 335 840 800 750 750 650 700 1,000 650
17 205 325 470 655 655 770 610 600 565
16 71 123 160 210 240 270 180 200 200
15 30 50 . 70 80 100 90 80 80 90
14 20 25 45 60 60 50 50 55 45
12 5 10 15 20 20 25 15 20 15
8 0 5 10 0 5 10 0 5 • 5
4 0 0 5 ‘ 5 10 10 0 0 0

Feed to R e c tif y in g Column - 80

216
P ro d u c t f r a n R e c tif y in g Colunn - 20
Heads from R e c tif y in g Column - 10
 TABLE XXIX

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 30# A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60aF

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 191.2 1 92.4 192.0 192.0 192.0 192.0 192.2 192.2 191.4

42 189.8 190.2 1 90.0 189.6 189.8 189.8 190.0 190.1 189.9
38 188.1 188.0 187.5 188.0 187.6 187.6 187.6 187.6 187.3
34 — 185.3 184.7 184.8 184.6 184.8 184.8 184.6 184.5
30 181.6 181.2 179.7 179.9 179.4 179.6 179.4 179.8 179.7
26 174.3 173.7 171.1 1 7 0 .5 169.5 170.1 169.3 170.5 170.5
24 167.3 165.6 162.7 162.0 160.7 160.2 159.9 161.4 160.6
23 160.0 159.8 156.5 155.8 154.3 154.1 - 153.8 154.7 154.7
22 153.5 151.6 148.5 148.3 146.6 146.9 145.6 147.2 147.5
21 136.7 137.8 132.6 132.6 133.0 135.6 132.7 132.4 133.6
20 117.1 118.5 110.3 116.4 118.3 118.9 114.4 114.3 115.9
19 54.3 56.5 6 0.1 70.7 69.6 63.6 65.5 64.6 6 0 .2
18 37.4 42.3 4 0.0 3 5.5 36.5 38.3 37 .4 4 1 .6 37 .3
17 22.3 20.6 21 .4 24.8 19.8 25.0 21.4 22 .0 1 9 .1
16 9 .6 8 .3 10.9 1 1.7 8 .3 1 1 .5 8 .3 9 .4 7 .4
15 0 .9 2 .4 8 .3 3 .6 2 .2 3 .0 2 .4 3 .3 0 .9
14 0 .4 — — 1 .8 1 .1 1 .3 1 .2 1 .6 0 .7
12 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 .0.0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

Feed to R e c tif y in g Column - 58.7

P ro d u c t from R e c tif y in g Column - 1 8 9 .9
Heads from R e c tif y in g Colunn - 192.7
 TABLE XXX

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed 30% A lco h o l a t P l a t e 1 8 ; R e flu x R a tio - 4 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iquid Phase by P la te s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A f te r W ithdrawal o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 10 15 30 20 20 25 30 25 25
42 20 25 45 45 50 50 50 — 40
38 55 70 110 200 250 200 200 200
34 150 250 400 600 750 500 550 550 500
30 500 850 1,400 2,500 2,500 4,000 2,500 2,500 2,000
26 1,400 2,500 4,000 5,000 5,000 4,500 . 5,000 5,000 4 ,500
24 2,500 4,000 6,500 8,000 8,500 7,000 7,500 7,500 7,000
23 4,000 5,000 8,000 9,000 10,500 9,000 9,500 9,000 7 ,000
22 4,000 7,000 9,000 9,500 11,500 10,500 10,000 10,000 8,000
21 4,000 7,500 9,000 10,000 12,500 13,000 12,000 10,500 9,000
20 3,500 6,500 8,000 10,000 11,500 13,000 11,500 10,000 9,000
19 1,000 3,500 3,500 4,500 6,000 6,000 11,500 5,000 3,500
18 300 600 1,400 1,200 1,300 1,400 2,000 2,000 1,500
17 200 450 700 650 900 1,050 1,050 800 600
16 100 160 300 350 400 400 450 500 300
15 40 85 - 100 115 165 200 250 200 150
14 25 55 80 85 110 150 150 150 80
12 10 25 35 35 50 60 55 55 35
8 5 10 15 10 15 15 20 15 10
4 0 5 10 5 5 10 10 5

Feed to R e c tif y in g Column - 65

P ro d u c t from R e c tif y in g Column - 35
Heads from R e c tif y in g Column - 20
 TABLE XXXI

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 30 % A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 4 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P la t e s , D egrees P ro o f a t 60°F

Time o f Sam pling A i'te r W ithdraw al o f P roduct Comaenced

P la te
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 192.1 192.0 192.0 192.0 191.7 191.8 192.1 191.7 192.0

42 189.6 189.6 189.3 189.2 169.1 189.1 189.3 188.9 189.3
38 187.2 187.1 186.7 186.7 186.4 186.5 186.0 186.0 186.9
34 184.4 184.0 182.6 182.9 182.7 183.1 182.6 182.3 183.4
30 179.4 179.0 178.2 177.3 176.6 177.7 177.7 176.6 178.0
26 172.0 169.8 16S.9 166.6 166.5 167.9 168.0 166.7 168.8
24 164.2 161.5 160.4 157.9 156.7 160.1 159.7 157.8 159.3
23 156.6 156.2 153.4 151.5 151.2 151.2 153.4 152.2 152.1
22 148.2 149.1 1 46.2 144.2 141.9 144.8 146.9 144.8 145.5
21 128.3 133.4 1 35.1 131.9 131.4 133.3 133.6 131.6 134.9
20 113.3 114.2 115.8 116.9 114.8 118.1 119.2 114.0 119.1
19 64.2 72.9 73.7 7 3 .5 76 .8 7 7 .2 77.9 71 .4 72 .1
18 42.8 4 2 .2 4 4 .0 4 5 .4 44.9 45.5 49 .0 46.9 45 .8
17 2 3 .5 25.5 27.4 28.6 27.9 28.3 2S.5 2S.9 28.5
16 1 3 .5 13.3 1 4 .4 1 4 .2 13.3 13.1 14.9 14.7 14.6
15 6 .2 6 .4 5 .3 5 .9 5.5 5 .7 6 .3 6 .6 7 .0
14 3 .4 3 .6 3 .0 4 .0 2 .6 3 .0 4 .0 4 .0 3 .8
12 0 .7 0 .9 0 .7 0 .5 0 .7 0 .5 0 .9 0 .5 0 .5
8 0 .2 0 .1 0 .0 0 .0 0 .0 0 .1 0 .1 0 .1 0 .1
4 0 .1 0 .1 0 .2 0 .0 0 .1 0 .0 0 .1 0 .1 0 .1

F eed t o R e c tif y in g Column - 5 8 .2

P ro d u c t from R e c tif y in g Column - 1 8 9 .1
Heads from R e c t if y in g Column - 1 9 2 .0
 TABLE XXXII

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

I
E xperim ental C o n d itio n s: Feed 30$ A lcohol a t P la te 18; R eflux R atio - 3 :1 ; P ro d u ct - P la te 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f sample

Time o f Sam pling A fte r W ithdrawal o f P ro d u ct Commenced

P la te :
0 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .
__
50 5 15 30 20 20 20 25
42 25 100 90 120 150 220 150 150
38 90 550 350 400 1,000 1 ,5 0 0 1,000 500
34 300 1,200 3,000 4,000 2,500 2,500 2,000 2,000
30 700 5,000 4,500 5,000 5,000 5,500 6,000 4,000
26 2,000 7,500 8,500 9,000 8,000 10,500 8,500 7,500
24 4,000 9,500 9,500 11,500 9,500 11,500 10,500 9,500
23 4,500 10,000 10,000 12,000 11,500 12,500 11,500 9,500
22 4,500 8,500 9,000 12,000 8,500 11,000 10,500 9,000
21 4,000 5,500 6,000 9,000 9,000 7,500 9,500 •7,000
20 3,000 3,500 — 6,500 5,200 o,000 5,500 5,000
19 1,000 500 1,100 2,000 3,000 2,500 2,500 2,500
18 300 250 350 400 600 480 500 400
17 200 180 200 300 450 350 400 300
16 50 140 110 125 230 200 200 150
15 50 70 70 80 130 90 80 70
14 30 50 60 45 80 70 60 50
12 45 25 25 25 45 50 25 25
8 5 10 10 0 10 15 15 10
4 0 10 15 0 10 5 5 5

Feed t o R e c tif y in g Column - 120

220
P ro d u c t from R e c tif y in g Column - 135
Heads from R e c tif y in g Column - 20
 TABLE XXXIII

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 30^ A lc o h o l a t P la t e 1 8 ; R e flu x R a tio - 3 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P la t e s , Degrees P ro o f a t 60°F

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h rs 18 h r s . 21 h r s . 24 h r s .

50 191.4 191.1 191.1 191.1 191.3 191.1 191.3 191.3

42 188.1 186.9 187.4 186.7 185.6 186.7 187.4 186.7
38 185.0 182.2 183.3 181.3 180.8 181.1 182.7 182.3
34 181.0 175.1 1 75.1 173.4 173.1 172.9 175.4 173.1
30 174.6 165.3 162.6 162.6 163.5 161.0 164.6 163.6
26 163.7 151.1 145.9 147.8 149.3 146.6 149.4 145.9
24 153.9 140.4 133.2 138.5 1 38.2 138.0 138.7 138.5
23 144.6 132.2 124.4 132.4 1 31.2 131.2 132.2 131.0
22 134.8 122.3 112.7 126.0 1 22.2 124.2 124.4 121.9
21 110.5 8 4 .4 9 8 .6 106.4 103.3 103.1 103.1 1 0 2 .1
20 9 1 .0 — 86.7 84.8 — 8 4 .2 84.7 85 .9
19 56.6 57.5 53.1 5 5 .1 62.4 52.4 56.0 52.3
18 4 2 .1 4 1 .4 41.7 4 2 .6 46 .7 4 6 .0 ' 4 4 .5 4 1.9
17 26.8 25.4 23.7 2 5.4 3 2 .5 2 6 .5 2 8 .0 26 .1
16 14.9 16.3 16 .1 1 4.7 1 9 .6 16.1 1 7 .1 1 6 .0
15 6 .8 8 .1 8 .1 7 .7 1 0 .6 8 .1 8.7 7 .6
14 9 .2 5 .3 5 .7 4 .3 5 .9 5 .5 5 .7 5 .3
12 2 .6 2 .0 1 .2 1 .3 1 .5 1 .4 1 .2 1 .0
8 0 .2 0 .0 0 .1 0 .0 0 .1 0 .2 0 .1 , 0 .1
4 0 .1 0 .0 0 .1 0 .1 0 .0 0 .2 0 .0 0 .1

F eed to R e c tif y in g Column - 5 8 .7

P ro d u c t from R e c tif y in g Column - 1 8 6 .3
Heads from R e c tif y in g Column - 1 9 1 .6
 TABLE XXXIV

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed 30$6 A lc o h o l a t P la t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

F u se l O il C ontent o f L iq u id Phase by P l a t e s , rags, o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sampling A fte r W ithdraw al o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 15 65 65 50 50 45 60 50 50
46 35 355 405 245 270 210 330 370 315
42 70 1,050 1,350 900 950 850 1,400 1,300 1,150
40 240 1,600 1,800 1,300 1,500 1,500 1,850 1,950 1,450
38 335 2,050 1 ,8 0 0 1,550 1,700 1,750 2,250 2,100 l,3CO
36 455 2,750 1,700 1,550 1,800 2,100 2,000 1,750 1,200
34 400 2,900 1,550 1,400 1,550 2,100 1,800 1,450 1,300
32 750 2,700 1,200 1,300 1,100 1,450 1,200 1,050 950
30 1,100 2,750 1,300 950 1,150 1,400 1,350 1,050 1,000
28 1,550 2,700 1,050 1,050 1,050 1,150 1,300 1,100 1,000
26 1 ,950 2,600 1,200 1,000 1,100 1,250 1,200 900 950
24 1,800 2,300 1,100 900 850 1,000 1,250 850 850
22 1,150 2,450 1,150 990 850 1,000 1,200 900 750
20 795 2,300 900 910 750 1,000 900 700 600
18 135 260 145 110 125 155 140 135 135
16 95 190 89 95 70 105 105 90 70
14 35 50 25 30 20 45 45 35 35
10 0 0 0 0 0 5 5 5 5
6 0 0 0 0 0 0 0 0 0
2 0 0 0 0 0 0 0 0 0

Feed t o R e c tif y in g Column - 75

ts3
P ro d u c t from R e c tif y in g Column - 370 to
Heads from R e c tif y in g Col tram - 40 to
 TABLE XXXV

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 30# A lco h o l a t P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

A pparent A lcohol C ontent o f L iq u id Phase by P la te s , Degrees P ro o f a t 60“F

Time o f Sampling A fte r W ithdrawal o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 188.3 185.9 1 85.4 185.8 186.0 186.1 186.0 185.9 186.0

46 186.0 178.3 178.3 177.3 179.4 178.5 179.9 1 79.1 177.7
42 175.5 168.3 167.7 167.1 167.0 166.6 165.9 1 67.0 165.0
40 167.5 158.9 158.9 159.9 158.0 158.3 159.1 159.4 158.6
38 159.6 144.8 145.7 145.1 146.7 144.2 145.7 146.8 143.7
' 36 139.9 132.2 130.6 131.9 1 31.1 130.6 131.6 130.9 128.2
34 135.5 126.1 128.5 125.5 124.0 126.1 124.5 124.0 125.2
32 128.7 122.0 121.3 120.1 117.2 119.8 116.0 119.3 118.8
30 120.6 113.4 113.4 111.1 109.3 110.3 109.3 111.0 109.8
28 116.3 311.9 111.3 109.3 106.2 109.1 107.2 109.9 107.7
26 114.1 108.3 107.7 106.6 104.1 105.8 105.2 105.3 104.6
24 111.8 101.1 100.8 103.1 102.2 101.1 101.1 101.9 100.0
22 100.6 98.9 9 9 .4 96.3 94.9 95.3 9 6 .4 95 .8 96.3
20 89.7 9 0 .1 9 2 .3 9 1 .0 89.7 90.9 92.8 9 0 .0 9 1 .8
18 57.1 59.0 58 .0 58.5 59.5 56.8 57.1 5 9 .1 58.5
16 47.3 46.3 5 0 .4 45.1 47.7 43.8 4 5 .9 4 9 .1 4 1 .0
14 29.6 28.0 29.6 27.7 25.1 27.3 26.8 26.9 25 .1
10 2 .8 2 .9 3 .7 2 .6 2.7 3 .9 4 .0 3 .9 3 .2
6 0 .4 0 .8 1 .0 1 .0 0 .8 1 .0 0 .6 0 .6 0 .8
2 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 5 9 .6

P ro d u c t from R e c tif y in g Column - 1 7 8 .8
Heads from R e c tif y in g Column - 1 8 7 .0
 TABLE XXXVI

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E xperim ental C o n d itio n s: Feed - 40% A lcohol a t P la te 18; R eflu x R a tio - 5 :1 ; P ro d u ct - P l a te 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 0 5 5 5 10 5 5 0
42 5 10 10 15 20 20 15 20
38 20 30 40 50 55 75 45 40 40
34 65 90 165 170 190 170 160 135 150
30 280 380 500 800 1,050 900 450 500 400
26 800 1,300 1,750 2,200 2,800 2,350 2,150 1,950 2,100
24 1,500 2,250 3,400 4,750 5,850 4,900 4,050 3,850 3,850
23 2,300 3,150 4,500 6,850 7,850 6,750 5,500 4,750 5,400
22 2,850 4,300 6,300 8,400 8,500 8,000 8,500 6,300 6,750
21 3,000 4,950 7,150 9,250 9,700 9,300 8,850 7,000 7 ,3 0 0
20 3,850 6,150 7,450 9,600 31,000 9,500 9,150 7,800 8 ,250
19 1,200 2,400 2,800 6,350 7,000 5,400 3,750 3,100 3,900
18 485 850 950 1,200 2,150 1,350 900 900 800
17 200 370 370 685 890 660 510 510 505
16 55 110 140 165 210 160 140 125 140
15 25 35 40 60 70 70 65 50 55
14 10 15 25 55 60 40 30 30 40
12 0 5 5 30 30 5 5 20 35
8 0 0 0 30 30 0 0 __ 0
4 0 0 0 30 35 0 0 —
— 0

F eed t o R e c tif y in g Colvmn - 65

P ro d u c t from R e c t if y in g Column - 15

224
Heads from R e c t if y in g Column- - 5
 TABLE XXXVII

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 40J5 A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , Degrees P ro o f a t 60°F

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Conmenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 192.3 192.4 192.3 1 9 1 .2 192.1 192.2 192.4 192.4 192.4

42 190.5 190.5 190.3 189.8 190.5 190.2 190.2 190.5 1 9 0 .2
38 1 89.2 188.7 188.7 187.3 188.5 188.4 188.8 188.4 1 8 8 .:
34 183.1 186.7 185.9 1 8 5 .2 186.0 186.2 185.7 186.4 186.7
30 176.5 183.1 1 8 2 .1 181.7 181.6 182.3 182.1 182.3 182.5
26 173.9 1 77.0 175.1 173.6 174.1 174.8 174.7 175.1 175.3
24 170.0 170.7 168.1 1 6 6 .2 166.1 167.9 1 6 7 .2 168.3 168.3
23 164.6 164.7 163.1 1 6 0 .5 160.5 162.3 162.0 163.0 163.9
22 157.4 1 59.4 157.0 154.1 155.0 156.0 155.0 157.1 156.7
21 1 42.4 147.0 141.6 143.0 143.6 144.3 144.5 142.8 145.9
20 124.6 1 31.4 125.5 129.5 131.0 130.6 129.1 125.6 131.4
19 84.5 84.4 7 9.8 89.8 9 2 .1 8 2 .1 8 6 .0 8 1.9 85 .3
18 48 .5 5 4 .2 4 7 .0 47.3 4 7 .0 4 6 .1 4 5 .0 43 .6 45.5
17 1 9 .1 2 3 .6 1 7 .5 20.3 1 9 .4 16 .9 20.3 22.3 14 .9
16 7 .5 1 0 .0 8 .0 8 .1 8 .0 6 .5 8 .2 8 .6 6 .0
15 2 .7 2 .5 1 .6 2 .3 2 .3 2 .3 2 .4 3 .3 2 .7
14 0 .0 0 .7 0 .0 2 .1 1 .7 1 .3 0 .5 1 .6 1 .6
12 0 .0 0 .0 0 .0 0 .7 0 .2 0 .0 0 .0 0 .0 0 .9
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 7 7 .2

P ro d u c t from R e c tif y in g Column 1 9 0 .3

225
Heads from R e c tif y in g Column - 1 9 0 .7
 TABLE XXXVIII

FUSEL OIL DISTRIBtrriON IK RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 40 % A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 4 : 1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

•
«
P i at.ff • Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Conmenced
•
• 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 5 10 5 0 10 10 10 5
42 10 15 25 30 25 — 35 30
38 40 65 100 125 110 130 135 125 125
34 160 185 325 200 395 260 215 310 160
30 500 580 1,200 1,200 1,150 1 ,3 5 0 1,400 1,300 1 ,4 0 0
26 1,200 2,000 3,100 3 ,400 3,700 3,750 4,650 4,250 4,450
24 2,350 3,650 4,800 6,100 6,400 6,550 5,850 5,850 6,600
23 3,050 3,950 6,950 7,550 8,250 8,900 8,800 8,200 8,450
22 3,850 5,350 7,100 9,000 9,500 9,350 8,850 8,900 8,800
21 4,150 5,800 8,100 9 ,1 0 0 9,850 10,400 11,500 11,600 10,600
20 3,650 5,500 6,750 8,300 9,800 10,300 11,400 10,400
19 1,000 1,950 2,950 2,950 4,850 4,250 5,550 4,700 4,800
18 295 630 600 750 800 1,050 1,250 950 900
17 180 290 405 605 625 760 760 740 550
16 40 70 105 130 120 170 170 175 140
15 20 30 50 75 75 65 70 70 70
14 10 15 50 30 45 25 60 55 45
12 0 15 25 5 40 5 10 35 25
8 15 35 25 20 35 0 30 0 45
4 10 25 30 40 45 0 40 65 45

Feed to R e c tify in g Column - 60

226
P ro d u ct from R e c tify in g Column - 25
Heads from R e c tify in g Column - 5
 TABLE XXXIX

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 40/S A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 4 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60°F

P la te : Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 . 192.4 1 92.2 1 92.1 191.9 191.9 192.1 191.9 192.6 1 91.6

42 190.0 189.6 1 89.0 1 8 9 .0 1 89.5 188.3 189.5 189.8 189.6
38 187.9 1 87.0 186.8 186.5 186.8 185.7 186.3 186.7 1 8 6 .0
34 181.4 1 8 4 .2 1 8 3 .2 1 8 3 .2 183.8 182.3 183.1 1 8 3 .6 1 8 3 .0
30 180.9 179.7 178.3 178.0 177.9 1 7 7 .2 177.6 1 7 8 .1 1 7 8 .4
26 173.6 171.1 1 6 9 .1 168.6 168.5 167.3 1 67.2 167.5 168.7
24 160.9 160.9 160.4 1 60.1 164.9 159.8 158.7 159.8 160.3
23 — 155.7 154.4 153.5 154.1 1 5 3 .1 153.6 1 53.4 153.9
22 152.7 150.8 147.0 1 47.0 147.8 147.0 146.9 147.3 146.6
21 135.8 135.1 132.8 133.8 133.8 1 3 5 .2 134.6 135.5 135.5
20 117.6 118.5 114.8 115.8 119.7 119.5 1 3 3 .2 123.0 122.5
19 7 8 .4 75.6 7 4.5 77.2 83.7 82 .5 8 7 .5 8 4 .2 8 3 .8
18 4 2 .1 4 4 .6 4 4.1 4 4 .4 50.8 52.6 44.7 45 .3 51 .9
17 20.9 20.7 24.5 16 .4 29.8 24 .1 28.1 32.7 25.7
16 7 .1 9 .2 9 .5 7 .1 7 .4 9 .2 10 .7 10 .7 8 .1
15 3 .1 3 .7 4 .9 3 .3 4 .2 3 .0 3 .5 3 .1 2 .6
14 0 .7 0 .8 2 .1 0 .9 0 .7 1 .0 2 .5 1 .8 1 .8
12 0 .0 0 .6 0 .8 0 .0 0 .4 0 .0 0 .1 0 .3 0 .9
8 0 .4 0 .4 0 .0 0 .0 0 .2 ' 0 .0 0 .0 0 .0 0 .0
4 0 .4 . 0 .2 0 .0 0 .5 0 .0 0 .0 0 .0 0 .0 0 .0

Feed t o R e c tify in g Column - 78 .5

P ro d u ct from R e c tify in g Column - 189.6

227
Heads from R e c tify in g Column - 1 92.4
 TABLE XL

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 40 % A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 3 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 mL. o f sample

•
•
Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Connenced
•
« 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h rs . 18 h r s . 21 h r s . 24 h r s .

50 10 15 15 15 15 10 10 0 0
42 20 35 65 70 75 65 70 65 70
38 75 200 300 350 400 400 350 300 350
34 300 600 800 950 1 ,000 500 650 1 ,0 0 0 1,200
30 700 1 ,000 2,000 2,000 2,000 2,500 2,400 2,500 2,400
26 2,000 3,000 4,000 4,500 5,000 5,500 5,800 5,700 5,500
24 2,500 4,500 5,500 6,000 7,000 7,500 7,600 8,100 7,500
23 2,650 5,200 6,000 6,500 7,500 8,500 8,500 8 ,7 0 0 7,900
22 2,900 5,500 6,500 6,500 7,500 9 ,0 0 0 8,900 8,700 8,100
21 2,850 5,100 6,500 5,500 6,000 7,000 7,500 8,100 6 ,600
20 2,000 2,500 5,000 5,000 5,500 5,500 6,400 6 ,9 0 0 4,900
19 1,000 1,000 2,000 1,500 1 ,000 2,250 2,100 2,200 1,550
18 350 550 700 550 800 770 650 730 580
17 150 250 400 300 450 550 500 350 300
16 40 50 100 100 150 200 200 150 200
15 15 40 50 50 65 80 80 65 55
14 5 20 30 30 40 40 35 40 35
12 0 5 5 10 10 10 5 10 5
8 0 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0 0

Feed t o R e c tif y in g Column - 70 to

to
P ro d u c t from R e c tif y in g Column - 65 03
Heads from R e c tif y in g Column - 20
 TABLE XLI

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 40% A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio ~ 3 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , Degrees P ro o f a t 60“F

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

P la te : ■
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 191.2 191.2 191.1 191.2 191.2 191.1 191.1 1 9 1 .2 1 9 1 .2

42 187.6 187.5 1 8 7 .4 187.0 187.0 187.1 187.0 187.1 1 8 7 .0
38 183.8 183.2 1 8 3 .0 1 8 2 .4 182.4 182.4 182.6 182.6 182.4
34 177.3 177.3 177.4 176.9 176.5 176.9 176.7 176.5 176.5
30 1 7 2 .2 172.0 171.4 169.5 169.1 168.9 169.1 168.7 1 6 9 .1
26 162.8 162.2 160.3 1 58.1 157.4 157.4 157.4 157.2 157.0
24 152.5 152.5 151.6 149.3 148.8 148.9 147.7 147.7 147.7
23 144.6 144.6 143.6 143.0 141.5 142.4 141.3 140.5 140.8
22 137.6 137.4 137.7 135.9 134.3 137.1 1 35.5 134.3 134.0
21 1 25.1 124.3 125.0 123.2 122.0 117.0 117.0 117.5 117.4
20 112.4 112.8 111.3 110.8 110.6 110.3 109.5 108.8 1 09.0
19 8 2 .0 82.8 82.7 82 .6 82.9 82.7 82 .6 8 3 .0 8 2 .8
18 61.6 61.8 62 .2 6 0 .0 59.0 6 3.2 60.5 59.9 6 1 .5 ‘
17 3 5 .2 35.6 3 6 .5 3 6 .2 35.5 36.8 36 .6 3 6 .0 3 5 .4
16 15.3 15 .8 1 7 .8 15 .8 1 7 .4 18.8 1 8 .5 1 7.4 18.3
15 6 .1 7 .2 6 .6 7 .2 7 .4 8 .1 7 .5 6 .6 6 .8
14 2 .6 2 .6 3 .4 3 .4 3 .8 • 3 .6 3 .5 3 .3 3 .3
12 0 .1 0 .2 0 .5 0 .6 0 .4 0 .4 0 .2 0 .1 0 .4
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

Feed to R e c tify in g Coliann - 78 .4

P ro d u ct from R e c tif y in g Column - 187.0
Heads from R e c tify in g Column - 191.2
 TABLE XLII

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E xperim ental C o n d itio n s: S y n th e tic Feed Low in F u sel O il - 40% A lcohol a t P la te 18;
R eflu x R a tio - 3 :1 ; P roduct - P la te 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r ICO m l. o f sample

Time o f Sam pling A f te r W ithdrawal o f P ro d u ct Conmenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 5 5 5 5 5 10 - 5 5 15
42 20 35 30 40 50 40. 45 40 40
38 75 90 120 155 185 155 165 155 . 155
34 180 250 350 450 600 450 500 480 500
30 450 500 600 800 1,070 960 880 770 800
26 650 1,000 1,400 1,800 2,300 2,000 1,950 1,800 1,800
24 900 1,800 2,200 1,600 3,300 2,950 3,050 2,750 2,550
23 1,050 2,100 2,400 3,080 3,600 3,500 3,270 3,225 2,650
22 .1,100 2,250 2,900 3,400 3,600 3,750 3,450 4,180 3,150
21 1,000 2,050 2,860 3,350 3,090 3,450 3,050 3,050 2,790
20 850 — 2,150 3,250 2,300 3,250 3,250 2,750 2,200
19 380 600 450 550 950 850 600 550 670
18 75 350 450 575 350 420 330 625 325
17 90 225 250 450 200 250 200 250 225
16 30 80 90 175 65 90 65 100 110
15 10 30 40 60 30 40 35 35 45
14 0 10 15 30 15 25 20 25 30
12 0 0 0 5 10 5 0 0 10
8 0 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0 0

Feed to R e c tif y in g Column - 30

230
P ro d u c t from R e c tif y in g Column - 30
Heads from R e c tif y in g Column - 10
 TABLE X L III

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E xperim ental C o n d itio n s: S y n th e tic Feed Low in F u se l O il - 4 0 % A lcohol a t P la te 18;

R eflu x R a tio - 3:1} P ro d u ct - P la te 42

A pparent A lcohol C ontent o f L iq u id Phase by P la t e s , Degrees P ro o f a t 60°F

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 hrs

50 191.2 191.4 191.2 191.3 191.1 191.4 191.3 191.2 191.3

42 187.6 188.3 187.7 187.6 187.5 187.6 187.4 187.6 187.5
38 183.5 184.3 183.9 183.4 182.5 183.6 183.0 182.8 183.2
34 178.8 179.7 179.7 178.6 178.1 179.1 178.6 178.8 178.1
30 172.3 173.4 173.6 172.5 171.2 172.1 171.9 172.3 171.6
26 164.0 166.3 165.3 163.4 162.6 162.6 163.0 162.1 1 6 3 .2
24 154.8 155.3 155.8 154.9 152.2 152.8 1 53.2 153.4 153.7
23 149.7 152.5 150.1 1 5 1 .4 147.0 147.6 147.0 147.6 147.2
22 141.8 145.8 143.5 143.9 140.6 . 140.8 140.3 140.8 ' 140.2
21 130.3 132.8 131.5 132.4 129.1 128.2 128.0 129.1 128.4
20 114.8 111.4 113.5 112.0 110.7 111.3 110.5 113.6 113.2
19 83.2 84.8 84.1 84 .0 8 3 .5 83.0 8 3 .2 84.7 83.9
18 70.7 69.3 7 0 .5 71.7 68.0 66.8 67 .b 67.0 67.8
17 47.3 45.7 44.8 49.1 4 5 .5 44.6 46 .0 47.8 4 7 .1
16 24.0 22.3 22.0 26 .5 25 .5 24.6 23.8 25.7 26.5
15 1 2 .4 11.0 10.6 11.7 10 .1 9 .7 10.3 9 .7 12 .4
14 4 .3 4 .5 4 .0 5.8 5 .0 5 .2 5 .6 5.6 6.3
12 0 .2 0 .2 0 .2 0 .5 0 .2 0 .5 0 .5 0 .5 0 .5
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

231
Feed to R e c tif y in g Column - 7 8 .5
P ro d u c t from R e c tif y in g Column - 1 8 7 .6
Heads from R e c tif y in g Column - 1 9 1 .3
 TABLE XLIV

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E xperim ental C o n d itio n s: Feed E nriched w ith F u se l O il - 40^ A lcohol a t P la te 18;

R eflu x R a tio - 3 : 1 ; P ro d u ct - P la te 42

F u se l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdrawal o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 '20 15 15 10 10 10 10 10 15
42 15 50 95 80 85 85 80 70 80
38 100 400 600 550 600 500 450 500 500
34 400 800 1,250 1,300 1,550 1,400 1,100 1,200 1,350
30 500 2,000 3,500 3,600 5,550 3,800 3,800 3,500 3,650
26 3,000 5,500 8,500 8,600 9,800 9,000 8,500 7,900 8,100
24 4,500 8,500 10,500 12,300 13,600 13,500 12,100 11,500 11,400
23 5,500 8,500 11,300 13,500 15,500 14,800 13,300 13,000 12,900
22 6,000 8,500 12,000 14,200 16,100 15,000 14,900 14,4CG 14,500
21 5,500 8,500 11,200 13,800 15,500 — 14,600 14,100 14,300
20 -4,500 7,500 9,000 13,100 14,100 13 , 200 13,500 - 13,900 13,100
19 1,500 2,000 3,500 5,900 5,400 6,300 5,700 5,400 5,250
18 450 950 1,000 1,600 2,350 2,350 1,800 2,150 1,650
17 250 200 600 800 1,000 1,000 1,000 900 1,100
16 60 120 180 330 370 460 440 400 380
15 25 50 75 50 100 100 100 100 100
14 10 20 40 50 55 90 75 80 70
12 0 5 5 15 15 20 15 15 15
8 0 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0 0

232
F eed t o R e c tif y in g Column - 140
P ro d u c t from R e c tif y in g Column - 70
Heads from R e c tif y in g Column - 20
 TABLE XLV

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E xperim ental C o n d itio n s: Feed E nriched w ith F u se l O il - 4 0 % A lcohol a t P la te 18;

R eflu x R a tio - 3 :1 ; P ro d u ct - P la te 42'

Fuse] O il C ontent o f L iq u id Phase by P la t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 hr;

50 191.1 191.3 191.4 191.1 190.7 191.3 191.1 191.3 191.3

42 188.3 187.7 187.7 187.7 187.7 187.9 187.7 188.2 188.0
38 ~ 183.8 183.8 183.3 182.7 183.0 183.3 183.6 183.5 183.0
34 178.2 178.8 177.5 177.8 177.4 177.8 178.4 178.4 178.4
30 171.2 171.0 168.9 169.5 169.5 169.5 169.5 170.1 - 170.0
26 158.2 157.4 156.9 156.3 156.3 156.0 156.3 157.4 157.4
24 148.9 148.1 146.0 147.5 145.0 146.5 146.9 148.1 148.3
23 143.5 142.9 139.7 141.3 139.7 140.4 140.7 141.8 141.8
22 137.7 136.0 135.1 13b. 0 135.7 136.0 136.3 135.2 135.6
21 121.9 122.5 121.9 125.0 125.1 124.8 125.1 124.9 125.3
20 102.5 106.8 108.5 113.6 115.1 114.9 115.1 115.5 114.9
19 82.9 83.8 84.7 88 .7 88 .6 69.3 8 9.5 87.6 8 8 .5
18 56.6 5t>.9 60 .2 60 .1 60.8 60.3 6 0.1 60.5 5 9.0
17 27.9 27.4 3 0 .0 30.6 30.4 30 .0 31.0 28.5 31 .0
16 13.7 12.7 l 5 .o 1 4.0 15.1 1 5 .4 16.0 1 5 .4 16 .0
15 4 .9 5 .8 4 .5 5 .7 4 .1 5 .0 5 .8 5.S 5 .5
14 1 .9 1 .8 2 .5 2.7 2 .5 2 .5 2 .6 2.7 2 .5
12 0 .3 0 .4 0 .3 0 .4 0 .4 0 .4 0 .4 0 .4 0 .4
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 ' 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

t-
Feed t o R e c tif y in g Column - 7 8 .7
P ro d u c t from R e c tif y in g Column - 1 8 7 .7
Heads from R e c tif y in g Column - 1 9 1 .3
 TABLE XLVI

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed 4 0^ A lco h o l a t P l a t e I S ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 40

F u se l O il C ontent o f L iq u id Phase by P la te s , mgs. o f Amyl A lcohol p e r 100 m l. o f sample

Time o f Sam pling A fte r W ithdraw al o f P roduct Commenced

P la t? *
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 45 55 70 70 70 70 65 60
46 150 350 350 350 350 350 300 300 250
42 650 1,200 800 500 500 500 400 400 400
40 1,000 1,300 800 500 500 550 450 450 400
38 1,200 1,100 800 550 500 550 500 400 400
36 1,750 950 700 550 500 600 500 450 450
34 1,900 950 650 500 550 550 500 450 450
32 2,000 650 500 500 500 550 450 400 400
30 2,000 650 500 550 500 550 450 400 400
28 2,000 650 500 500 500 550 450 400 400
26 2,000 650 500 500 500 550 400 400 400
24 2,000 550 450 500 500 450 350 325 350
22 2,0C0 500 450 500 450 400 300 320 350
20 1,800 450 400 450 400 350 250 250 300
18 250 150 150 100 150 150 100 100 100
16 35 40 40 40 35 30 30 30 25
14 10 10 10 5 5 10 5 5 5
10 0 0 0 0 0 0 0 0 0
6 0 0 0 0 0 0 0 0 0
2 0 0 0 0 0 0 0 0 0

Feed t o R e c tif y in g Column - 100

P ro d u c t from R e c tif y in g Column - 350

234
Heads from R e c tif y in g Column - 55
 TABLE XLVII

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 40/S A lc o h o l a t P l a t e 18; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60°F

Time o f Sam pling A f te r W ithdrawal o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 188.5 188.0 188.0 167.9 166.4 186.7 187.0 186.3 186.6

46 183.2 183.0 182.4 181.3 180.0 180.6 180.3 180.0 180.7
42 170.7 170.6 169.1 168.7 168.3 168.5 168.1 168.7 168.3
40 163.7 162.0 161.2 160.3 159.8 159.9 160.4 159.3 160.0
38- 156.4 155.1 154.3 153.7 153.1 152.7 153.2 153.6 152.8
36 150.0 149.2 148.0 146.9 146.0 146.3 147.0 146.0 146.4
34 142.6 142.1 141.1 139.0 139.1 138.9 139.3 139.7 139.0
32 134.4 134.1 133.6 132.1 132.4 131.9 131.9 139.2 139.9
30 128.2 128.0 127.5 126.9 126.3 126.0 126.6 126.9 126.4
28 124.6 124.0 123.6 122.8 123.0 122.8 122.4 122.8 122.5
26 120.3 120.0 119.3 118.3 118.0 118.6 118.1 118.8 118.0
24 109.5 109.0 108.5 107.9 107.6 108.0 103.2 107.7 107.8
22 100.0 99.6 99.7 98.6 9 8 .2 98.9 98 .4 9 8.3 98 .8
20 88.6 88.0 8 7 .5 86.3 86.0 86.6 86 .4 8 6.0 86 .4
18 67.2 66.8 6 6.1 65.0 65.7 65.3 65.9 65.1 65.5
lb 3 8 .2 37.7 3 7 .0 36.8 36 .1 36.8 37.0 36.3 36.7
14 18.2 17.3 1 7.0 1 6.6 16.6 17 .1 16 .3 16 .8 16.8
10 7 .3 7 .0 7 .0 6 .4 6 .8 6 .2 6 .5 b .7 6 .0
6 1 .7 1 .4 1 .1 1 .0 0 .9 1 .0 0 .8 1 .2 1 .1
2 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .6

Feed to R e c tif y in g Colunn - 7 9 .0

235
P ro d u c t from R e c t if y in g Column - 1 8 0 .0
Heads from R e c tif y in g Column - 1 8 6 .8
 TABLE XLVIII

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 50% A lco h o l a t P la t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P la te s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct

P la te
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 10 10 10 10 10 10 10 10 10
42 10 15 15 15 15 15 10 10 10
38 25 35 40 45 40 35 30 30 30
34 85 150 165 180 180 165 150 120 115
30 275 525 580 710 690 600 520 450 410
26 750 1,600 2,100 2,200 2,350 1,950 1,800 1,400 1 ,400
24 1,650 3,100 3,450 3,900 3,900 3,550 3,100 2,700 2,600
23 2,500 3,900 4,400 5,000 5,200 4,900 4,150 3,450 3,450
22 3,150 4,800 5,500 5,700 6,700 5,650 4,750 4,300 4,200
21 3.850 6,000 7,250 7,700 8,900 6,900 5,900 5,450 5,300
20 4,300 6,100 7,900 8,800 9,770 7,400 7,150 6,100 5,900
19 3,900 5,600 7,200 8,600 9,240 7,100 6,500 5,850 5,350
18 1,250 1,600 2,200 3,900 4,300 2,850 2,650 2,100 2,050
17 290 450 600 1,500 1,650 1,000 900 600 ‘ 550
16 100 185 245 295 410 240 250 145 160
15 20 45 55 70 100 70 60 40 35
14 10 15 25 35 30 20 25 10 20
12 0 0 0 0 0 0 0 0 0
8 0 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0 0

F eed t o R e c tif y in g Colunn - 70

236
P ro d u c t from R e c tif y in g Column - 15
Heads from R e c t if y in g Column - 15
 TABLE XLIX

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 50^ A lco h o l a t P l a t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , Degrees P ro o f a t 6Q°F

Time o f Sam pling A f te r W ithdrawal o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h rs . 21 h r s . 24 h r s .

50 192.0 192.1 192.2 192.0 192.0 192.1 192.1 192.1 192.1

42 190.1 190.0 190.1 190.0 190.1 190.1 190.1 190.0 1 90.2
38 188.3 188.3 188.4 188.3 188.3 188.5 188.3 188.5 188.5
34 185.7 185.8 185.8 185.9 185.9 186.0 186.0 186.0 186.0
30 182.3 182.0 182.1 182.0 182.0 182.2 182.3 182.3 182.4
26 176.7 176.6 176.9 176.7 176.5 176.9 176.9 176.9 176.9
24 170.0 169.1 170.0 169.4 169.2 170.0 169.8 170.0 169.9
23 166.3 165.7 166.2 . 166.2 165*7 165.7 1 66.2 167.3 167.3
22 160.5 161.0 161.0 161.1 160.4 160. b 160.8 161.4 161.4
21 149.6 149.8 149.6 149.7 150.2 150.4 150.8 150.8 151.5
20 139.6 140.2 142.3 142.3 140.4 140.4 142.5 142.3 139.9
19 1 08.2 109.2 114.5 116.7 118.2 117.5 117.5 117.2 115.5
18 68.1 69.6 76.7 77.4 75 .6 71 .6 70 .4 70.7 7 3 .2
17 23.1 22.6 26.8 4 1 .1 38.7 35.9 37 .0 3 3 .2 31 .7
16 15.3 8 .5 10.4 12 .6 13 .5 12 .1 13 .1 1 0.8 10 .4
15 4 .3 3 .1 2 .2 3 .9 3 .4 3 .6 3 .4 2 .6 2 .4
14 1 .4 1 .2 0 .9 1 .4 1 .1 0 .8 1 .4 1 .3 1 .0
12 0 .1 0 .1 0 .1 0 .0 0 .2 0 .0 0 .0 0 .1 0 .1
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 9 8 .3

237
P ro d u c t from R e c tif y in g Column - 1 8 9 .8
Heads from R e c t if y in g Column - 1 9 1 .6
 TABLE L

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed 50^ A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 4 : 1 ; P ro d u c t - P l a t e 42

F u sel O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdrawal o f P roduct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . IS h r s . 21 h r s . 24 h r s .

50 5 10 10 15 15 15 15 20 15
42 5 15 20 30 25 25 20 25 25
38 15 30 65 65 75 75 70 75 70
34 60 230 250 300 360 320 310 330 320
30 150 360 720 800 1,050 1,000 980 900 890
26 430 . 1,250 2,150 2,450 3,000 2,800 2,600 2,250 2,500
24 700 2,100 3,650 3,800 4,250 4,200 3,500 3,650 3,800
23 1,000 2,900 4,400 5,100 5,600 5,100 4,400 4,850 4,750
22 1,100 3,500 5,050 6,300 6,900 5,950 5,800 5,750 5,900
21 1,200 3,800 6,400 7,650 8,900 7,350 6,800 6,750 6,350
20 1,100 4,200 6,900 8,300 9,040 8,000 7,350 6,850 6,600
19 500 3,650 6,900 8,000 8,470 6,900 6,150 6,100 5,400
18 225 1,000 2,850 3,300 4,100 2,500 1,950 2,200 1,850
17 85 440 1,050 1,650 2,300 1,250 950 1,000 750
16 25 50 340 430 580 350 230 260 140
15 5 35 • 100 140 140 • 95 65 70 40
14 10 10 25 35 50 30 25 25 10
12 0 0 0 5 5 5 5 0 0
8 0 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0 0

Feed t o R e c tif y in g Column 70

238
P ro d u c t from R e c tif y in g Column - 25
Heads from R e c tif y in g Colunn - 25
 TABLE LI

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 50$ A lco h o l a t P l a t e I S ; R e flu x R a tio - 4 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60°F

Time o f Sampling A fte r W ithdrawal o f P roduct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 191.6 191.8 191.7 191.9 191.6 191.6 191.7 191.8 191.6

42 188.4 189.0 188.4 168.9 188.4 188.6 188.6 188.4 188.6
38 186.9 187.0 187.0 187.0 186.9 187.0 186.9 187.0 186.8
34 183.0 183.4 183.4 163.4 183.5 183.3 183.7 183.4 183.4
30 180.0 179.9 180.2 179.9 180.3 179.9 179.8 179.9 1 80.0
26 173.6 172.7 173.0 172.7 173.0 172.9 172.6 172.9 172.9
24 166.9 166.2 166.3 166.5 166.2 166.5 • 165.7 166.0 166.4
23 162.2 162.0 161.7 161.9 162.1 161.9 161.4 161.4 161.7
22 156.3 156.0 156.1 156.9 156.0 155.6 155.1 155.9 156.2
21 145.5 146.3 146.1 145.9 145.4 145.9 146.2 145.6 145.6
20 136.8 136.6 135.2 137.4 136.8 137.8 13o .0 136.8 136.3
19 105.8 108.7 108.7 110.3 1 11.1 110.9 111.2 108 ;1 108.9
18 84.9 87.8 87.8 85.9 84.9 8S.0 85 .2 84J2 86 .6
17 42.0 45.3 4 6 .0 4 9 .2 51.5 4 6.2 40 .9 46.8 4 3 .2
16 14.6 16.9 14.8 18.9 1 5 .5 16.7 14.8 14 .1 1 7 .0
15 7 .6 6 .9 7 .4 6.7 8 .8 7 .4 5 .6 4 .8 6.S
14 1 .7 1 .1 0 .9 1 .0 1 .9 2.0 0 .9 0i8 0 .9
12 0 .5 0 .2 0 .2 0 .3 0 .3 0 .3 0 .3 0 .2 0 .3
S 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 9 9 .8

239
P ro d u c t from R e c tif y in g Column - 1 8 8 .4
Heads from R e c tif y in g Column - 1 9 1 .6
 TABLE L II

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed 50^ A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio 3 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P l a te s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

0 h rs. 3 h rs. 6 h rs. . 12 h r s . 15 h rs 21 h r s . . 24 h r s .

50 5 5 10 10 10 5 5
42 15 20 35 55 65 65 60
38 45 95 180 275 305 340 305
34 125 295 505 700 900 880 875
30 380 765 1,300 1,900 2,000 2,050 1,950
2b 930 1,700 2,650 4,000 4,200 3,700 4,950
24 1,250 2,500 3,950 5,600 6,900 7,600 7,400
23 1,750 2,950 5,050 7,350 S,250 8,950 8,700
22 1,750 3,550 5,900 7,700 8,400 9,350 9,700
21 1,850 3,850 6,100 8,700 9,400 10,000 9,900
20 1,550 3,450 5,900 8,300 8,550 9,900 10,000
19 900 2,250 3,700 6,700 7,650 8,450 7,350
IS 405 715 900 3,000 2,500 2,400 2,450
17 125 375 570 1,950 1,500 1,400 900
16 30 85 110 840 535 550 320
15 10 25 50 185 115 120 90
14 0 10 20 75 45 40 40
12 0 0 0 5 0 5 5
8 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0

Feed t o R e c tif y in g Column - 110

P ro d u c t from R e c tif y in g Column - 60

240
Heads from R e c tif y in g Column - 70
 TABLE L I U

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 50% A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 3 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C o n ten t o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60*F

Time o f Sam pling A fte r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 12 h r s . 15 h r s . 21 h r s . 24 h r s .

50 191.3 191.4 191.6 191.3 191.4 191.3 191.5

42 1 8 8.2 187.8 188.0 187.7 187.8 187.8 187.8
38 184.7 1 84.5 1 8 4 .6 184.1 184.3 1 84.5 184.1
34 181.0 180.0 181.4 180.9 180.3 1 81.0 180.6
30 1 7 6.2 1 7 6 .2 176.7 176.9 177.7 177.1 1 7 6 .4
26 1 6 7 .0 - 166.0 166.7 166.6 167.2 166.7 1 6 7 .2
24 160.8 159.8 160.1 1 59.6 159.6 1 60.1 1 5 9 .6
23 155.0 154.7 154.8 155.8 154.2 154.4 154.7
22 149.0 1 4 8 .4 147.1 1 4 8 .1 148.0 149.3 1 48.1
21 134.6 135.0 1 3 5 .1 137.3 136.6 136.0 1 36.1
20 122.3 123.0 122.3 115.1 114.4 113.7 114.2
19 109.6 109.7 1 1 2 .2 115.1 114.4 113.7 1 1 4 .2
18 75.6 7 6 .1 76.9 73.9 75.3 7 8 .1 7 6.3
17 4 2 .4 40.7 4 3 .3 38.7 4 3 .1 4 0 .2 3 8 .4
16 2 2 .4 2 0 .1 2 4 .2 18.9 21 .1 19 .7 2 2 .0
15 6 .2 6 .5 6 .9 8 .3 6.9 7 .0 5 .1
14 1 .3 3 .2 2 .4 4 .0 4 .6 3 .8 2 .2
12 0 .2 0 .3 0 .2 0 .3 0 .3 0 .5 0 .3
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 9 9 .1

P ro d u c t from R e c tif y in g Column - 1 8 7 .8
Heads from R e c tif y in g Column - 1 9 1 .6
 TABLE LIV

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 50 % A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

F u s e l O il C ontent o f L iq u id Phase by P l a t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A f te r W ithdrawal o f P ro d u ct Commenced

P la te :
3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 55 55 55 55 50 50 55 55
46 280 260 260 240 250 240 240 240
42 350 300 320 310 280 310 340 310
40 370 320 320 320 300 285 320 310
38 380 390 340 350 330 315 330 300
36 440 400 380 400 380 370 390 330
34 440 410 360 380 370 250 400 350
32 270 290 245 340 265 250 360 280
30 230 240 195 320 220 230 380 225
28 190 190 160 285 170 180 330 170
26 140 160 150 220 140 125 290 120
24 140 120 120 180 100 95 230 85
22 150 100 105 140 90 80 175 75
20 120 90 100 120 75 95 140 85
18 100 120 110 140 120 120 130 140
16 30 40 28 35 22 36 31 35
14 0 5 0 0 0 5 0 0
10 0 0 0 0 0 0 0 0
6 0 0 0 0 0 0 0 0
2 0 0 0 0 0 0 0 0

F eed t o R e c tif y in g Column - 140

242
P ro d u c t from R e c tif y in g Column - 260
Heads from R e c tif y in g Column - 58
 TABLE LV

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 50% A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , D egrees P ro o f a t 60°F

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

P la te
3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 187.9 186.9 187.2 187.8 187.0 187.1 187.2 187.2

46 181.7 180.0 181.2 181.8 1 80.7 180.9 181.2 181.4
42 1 7 3.2 170.9 172.9 172.5 173.0 173.3 172.8 1 73.1
40 166.5 165.0 1 6 6 .0 165.7 1 66.2 166.7 165.9 1 6 6 .2
38 161.0 158.7 159.7 159.0 161.6 160.0 157.9 160.8
36 1 5 6.5 154.2 156.7 155.1 157.0 153.8 153.7 156.3
34 151.3 149.2 1 50.1 148.7 151.0 148.0 149.4 151.9
32 146.6 1 4 4 .2 146.1 143.5 145.0 143.6 144.9 146.3
30 142.7 141.0 143.0 140.0 142.5 140.1 141.8 143.0
28 139.2 137.7 139.0 137.1 1 39.5 136.9 139.0 139.9
26 135.6 133.9 135.6 134.0 135.5 133.7 135.1 1 3 5 .4
24 129.6 1 26.0 1 29.1 128.3 129.3 127.0 129.9 130.3
22 122.9 1 1 9.2 123.1 122.0 122.6 120.6 124.0 124.1
20 312.0 108.7 113.7 111.9 112.7 HO. 3 112.9 113.3
18 86.9 8 4 .2 8 9 .0 88.8 8 9 .2 85.3 86.7 8 7 .2
16 4 6 .0 43.3 48.3 4 7.7 4 8 .0 45 .1 4 6 .2 46 .6
14 26.8 23.8 27.9 2 7 .0 28 .2 24.4 26.6 2 6.4
10 9 .5 7 .1 9 .9 1 0 .0 10 .3 8 .3 9 .0 9 .1
6 2 .1 2 .0 2 .3 2 .0 2 .6 1 .8 2 .4 2 .6
2 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed to R e c tif y in g Column - 9 9 .5

P ro d u c t from R e c tif y in g Column - 1 8 1 .2
Heads from R e c tif y in g Column - 1 8 7 .2
 TABLE LVX

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 60% A lco h o l a t P l a t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

F u se l O il C ontent o f L iq u id Phase by P la te s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced *

P la te
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 5 5 5 5 5 5 5 5 5
42 10 10 15 15 15 — — 15 15
38 15 30 40 50 60 60 55 45 50
34 40 95 160 175 225 200 195 180 200
30 95 345 520 590 740 670 670 630 645
26 320 900 1,500 1,600 2,350 2,100 1,900 1,600 1 ,700
24 400 2,050 2,850 3,300 3,950 3,700 3,700 3,300 3 ,000
23 800 2,600 3,550 4,300 5,250 4,900 4,750 4 ,500 3,900
22 1,100 3,250 4,300 5,250 6,400 6,050 5,750 5,450 4 ,900
21 1,400 4,000 5,500 6,800 8,200 7,600 7,250 7,000 6,450
20 1,800 4,750 6,250 8 ,000 9,750 9,200 8,150 8,250 7,050
19 1,850 4,950 6 ,450 9,300 10,650 9 ,4 5 0 8,850 8,700 7,900
18 550 2,550 3,500 5,900 6,700 7 ,0 5 0 6,350 5,950 3,800
17 280 550 1 ,700 4,150 4,850 5,050 4,450 2,850 1,800
16 30 170 275 1,000 1,590 1 ,7 4 5 1,390 670 370
15 5 45 80 165 295 380 295 180 95
14 — 10 20 60 90 145 115 55 35
12 0 0 0 0 5 5 5 0 0
8 0 0 0 0 0 0 0 0 0
4 0 0 0 0 0 0 0 0 0

F eed t o R e c tif y in g Colunai - 95

P ro d u c t from R e c tif y in g Column - 15
Heads from R e c tif y in g Column - 5
 TABLE LVU

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 60^ A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 5 :1 ; P ro d u c t - P l a t e 42

A pparent A lcohol C ontent o f L iq u id Phase by P l a t e s , Degrees P ro o f a t 60°F

Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 192.2 192.2 192.3 1 9 2 .4 1 92.2 192.2 192.2 192.3 1 92.4

42 189.9 189.9 1 9 0 .0 1 9 0 .1 189.9 1 9 0 .0 190.0 190.0 1 9 0 .0
38 1 88.2 188.2 1 8 8 .2 188.2 1 88.1 188.2 188.1 188.3 1 8 8 .2
34 185.5 185.6 185.7 185.7 185.3 185.6 185.5 185.7 185.7
30 183.0 182.6 1 8 2 .1 1 8 2 .4 1 82.1 182.1 182.1 1 8 2 .4 1 82.6
26 177.7 177.6 176.7 1 77.2 176.5 176.4 176.4 177.0 1 7 7 .0
24 172.0 171.5 1 7 1 .4 171.7 171.0 170.8 171.0 1 71.1 1 7 1 .7
23 168.2 167.6 1 67.2 167.8 167.0 167.2 167.2 167.7 167.9
22 164.9 163.6 163.8 164.5 163.4 163.6 163.4 163.6 163.9
21 157.8 156.3 156.4 157.7 156.1 1 5 7 .0 157.0 156.6 1 5 6 .5
20 1 4 7.0 147.7 149.1 150.1 1 4 9 .5 150.6 150.7 149.9 1 4 9 .1
19 126.7 124.8 132.8 135.5 134.7 135.9 134.9 1 3 4 .0 1 3 1 .5
18 97 .2 9 6 .5 1 04.8 104.9 1 0 3 .0 105.9 107.0 104.9 102.3
17 70.9 7 3 .4 74.7 7 9 .4 8 0 .2 75 .8 7 6.7 7 6 .6 79.3
16 37.6 3 6 .4 3 5 .1 30 .7 '3 2 .0 3 3 .2 30.7 3 4 .5 3 4 .0
15 1 5 .0 13.3 1 4 .2 9 .0 10 .9 1 0 .9 8 .4 10 .9 1 1 .8
14 3 .1 2 .7 3 .1 2 .1 2 .5 3 .3 2 .0 3 .2 3 .5
12 0 .2 0 .2 0 .2 0 .2 0 .2 0 .2 0 .4 0 .3 0 .2
8 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
4 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 1 1 9 .3

P ro d u c t from R e c tif y in g Colunn - 1 9 0 .0

245
Heads from R e c tif y in g Column - 1 9 2 .8
 TABLE L V III

FUSEL OIL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : Feed - 60^ A lco h o l a t P l a t e I S ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

F u se l O il C ontent o f L iq u id Phase by P la t e s , mgs. o f Amyl A lcohol p e r 100 m l. o f Sample

Time o f Sam pling A fte r W ithdrawal o f P roduct Commenced

•
• 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 15 25 40 35 20 30 35 40 30
46 25 130 140 230 250 180 155 200 165
42 55 440 625 865 830 570 605 835 710
40 145 625 700 990 700 700 840 1,080 930
38 200 710 840 1,240 1,030 S90 1,240 1,190 1,400
36 270 1,000 1,240 1,400 1,510 1,290 1,860 2,190 2,190
34 365 1,450 1,680 2,050 1,510 1,920 2,390 3 ,090 2,700
32 490 1,400 2,250 2,930 2,760 2,760 3,360 3,860 3,760
30 645 1,800 2,840 3,550 3,000 3,650 3,760 5,200 3,860
28 865 2,690 3,000 3,360 4,290 4,650 5,190 5,850 5,690
26 930 2,590 3,550 4 ,290 4,910 5,850 6,670 6,670 6,460
24 1,400 2,690 4,180 4,910 6,050 7,650 7,110 7,370 7,990
22 1,920 2,760 3,550 4,290 6,670 7,110 8,640 7,370 8,310
20 2,050 2,700 4,180 3,960 5,350 7,650 9,150 7,370 8,310
18 840 1,240 1,740 2,050 2,630 3,650 3,360 2,690 3,450
16 690 990 2,000 1,860 3,760 5,510 6,260 4,540 5,510
14 60 309 365 490 830 690 962 740 890
10 0 5 5 0 0 10 15 10 15
6 0 0 0 0 0 0 0 0 0
2 0 0 0 0 0 0 0 0 .0

F eed to R e c tif y in g Column - 85

P ro d u c t from R e c tif y in g Column - 200

246
Heads from R e c t if y in g Column - 30
 TABLE LIX

ALCOHOL DISTRIBUTION IN RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 60/S A lc o h o l a t P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

A pparent A lcohol C ontent o f L iq u id Phase by P la te s * D egrees P ro o f a t 60°F

•
• Time o f Sam pling A f te r W ithdraw al o f P ro d u ct Conmenced
P la te !■
•• 0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 186.1 1 88.0 187.8 187.6 188.0 188.1 1 88.2 187.8 188.0

46 184.8 184.6 184.4 184.6 184.6 184.6 184.3 183.5 1 83.1
42 179.1 178.4 177.7 176.6 177.9 177.9 177.7 177.7 177.5
40 177.1 175.7 174.6 174.4 175.3 174.8 174.6 1 74.4 174.7
38 173.3 171.1 1 6 9 .5 172.0 171.3 170.9 169.9 169.9 170.6
36 168.8 1 6 8.2 167.9 166.9 167.9 1 6 8 .2 168.1 166.8 166.4
34 166.4 165.8 164.4 166.0 165.6 165.0 166.0 164.5 163.9
32 163.2 162.6 1 6 1 .0 1 60.1 161.0 160.9 161.3 1 59.5 160.0
30 1 5 8.2 157.5 157.4 156.3 158.0 157.9 157.6 155.3 156.0
28 155.8 154.8 154.3 154.5 155.0 155.0 154.3 1 54.5 154.2
26 153.0 152.5 152.5 150.9 152.2 151.3 151.4 1 50.4 150.7
24 148.5 147.0 1 4 7 .2 146.2 147.6 147.6 147.0 145.4 146.8
22 1 4 4.4 142.3 1 42.4 142.0 142.6 143.2 142.8 1 4 1 .8 142.3
20 138.6 135.7 1 3 5 .2 135.2 135.7 136.8 136.6 136.0 136.7
18 109.7 111.1 110.7 110.1 108.9 109.4 109.7 1 09.4 109.9
16 94.8 94.0 9 1 .1 8 8 .1 95 .3 9 8 .0 9 8 .4 95 .6 9 7 .1
14 24.0 3 0 .2 25.7 2 6 .2 28 .1 30.3 26.8 27.5 29.8
10 0 .2 0 .4 0 .4 0 .3 0 .3 0 .3 0 .3 0 .3 0 .3
6 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
2 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0

F eed t o R e c tif y in g Column - 1 1 9 .5

P ro d u c t from R e c t if y in g Colunn - 1 8 4 .5

247
Heads from R e c tif y in g Column - 1 8 9 .2
 TABLE LX

TEMPERATURE OF VAPOR PHASE BY PLATES OF RECTIFYING COLUMN

E x p e rim e n ta l C o n d itio n s : F eed - 60% A lco h o l a t P l a t e 1 8 ; R e flu x R a tio - 2 :1 ; P ro d u c t - P l a t e 46

Tem perature in D egrees F a re n h e it

Time o f Reading A f te r W ithdraw al o f P ro d u ct Commenced

P la te :
0 h rs. 3 h rs. 6 h rs. 9 h rs. 12 h r s . 15 h r s . 18 h r s . 21 h r s . 24 h r s .

50 172.0 172.0 172.0 172.0 172.0 172.0 172.0 172.0 172.0

48 173.0 173.0 173.0 173.0 173.0 173.0 173.0 173.0 173.0
46 174.0 1 74.0 174.0 174.0 174.0 174.0 174.0 174.0 1 74.0
44 174.5 174.5 174.5 174.5 174.5 174.5 174.5 174.5 174.5
42 174.0 1 7 4.5 174.5 174.5 174.5 174.5 174.5 174.5 174.5
40 174.0 174.5 174.5 1 7 4 .5 174.5 174.5 174.5 1 74.5 174.5
38 174.0 174.5 175.0 1 7 5 .0 1 75.0 175.0 175.0 175.0 175.0
36 174.5 175.5 1 75.5 1 75.5 176.0 176.0 176.0 176.0 176.0
34 174.5 175.0 176.0 176.0 176.0 176.0 176.0 176.0 176.0
32 175.5 175.5 1 76.0 176.0 1 76.5 176.5 ; 176.5 176.5 1 76.5
30 176.5 176.5 177.0 177.5 177.0 177.5 1 177.5 177.5 177.5
28 176.5 176.5 177.0 177.5 1 77.5 177.5 177.5 177.5 177.5
26 179.0 179.5 179.5 180.0 180.0 180.0 180.0 180.0 180.0
24 179.0 179.5 179.5 1 80.0 180.0 180.0 180.0 180.5 1 8 0 .5
23 179.0 179.5 179.5 180.0 180.0 .180.0 180.0 180.5 180.5
22 179.5 179.5 180.5 1 80.5 180.0 180.0 180.5 180.5 180.5
21 179.5 179.5 180.5 180.5 180.5 180.5 180.5 180.5 180.5
20 180.5 180.5 1 81.5 1 8 1 .5 181.5 181.5 181.5 181.5 181.5
19 182.0 182.0 182.0 182.0 182.0 182.0 182.0 182.5 1 82.5
16 188.5 189.0 189.0 189.0 189.0 189.0 189.0 189.5 189.5
14 205.0 206.0 206.0 206.0 206.0 206.0 206.0 206.0 206.0
12 214.0 214.0 214.0 214.0 214.0 214.0 214.0 213.5 213.5
6 217.0 217.0 217.0 217.0 217.0 217.0 217.0 217.5 217.5

248
 TABLE LXI

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l in th e L iq u id Phase B o ilin g Tem perature E th an o l in th e Vapor Phase

Weight Mole % Volume % Volume Weight Mole % Volume % Volume
F ra c tio n 60°F 20°C °C °F % F ra c tio n 60°F 20°C

0.00 0.000 0.00 0.0 0 100.00 212.0 0 .0 0.000 0.0 0 0 .0 0

0.5 0 0.002 0.63 0 .6 4 99.65 211.4 5.3 0.021 6.61 6.64
1.0 0 0.004 .1.26 1.2 6 98.95 210.1 10.3 0.043 12.76 12.81
1.50 0.006 1.88 1.89 98.55 209.4 1 4 .4 0.062 17.74 17.80
2.00 0.008 2.51 2 .5 2 98.05 208.5 1 9 .2 0.085 23.52 23.59
2.50 0.010 3 .1 4 3 .1 5 97.50 207.5 22.9 0.104 27.91 27.99
3.00 0.012 3.76 3.78 97.11 206.8 26.3 0.122 31.91 31.98
3.50 0.014 4.38 4 .4 0 96.56 205.8 29.9 0.143 36.07 36.14

4.00 0.016 5.00 5.0 2 96.00 204.8 32.5 0.159 39.03 39.09
4.50 0.018 5.62 5.65 95.63 204.1 3 5 .4 0.177 42.28 42.35
5.00 0.020 6.24 6.26 95.22 203.4 37 .5 0.190 44.60 44.67
5.50 0.022 6.86 6.89 94.84 202.7 4 0 .0 0.207 47.33 47.39
6.00 0.024 7.48 7 .5 1 94.56 202.2 41.9 0.220 49.37 49.42
6.50 0.026 8.10 8.13 94.10 201.4 43.7 0.233 51.29 51.35
7.00 0.029 8.71 8.7 5 93.73 200.7 45.3 0.245 52.97 53.04
7.50 0.031 9.33 9.36 93.40 200.1 46.7 0.255 54.43 54.49
8.00 0.033 9.94 9.98 93.10 199.6 4 8 .1 0.266 55.88 55.94
8.50 0.035 10.56 10.60 92.78 199.0 49.3 0.275 57.12 57.17
9.00 0.037 11.17 11.21 92.42 198.4 50.5 0.285 58.34 58.39
9.50 0.039 11.78 11.82 92.10 197.8 51.6 0.294 59.45 59.50
10.00 0.042 12.39 12.44 91.80 197.2 52.7 0.304 60.55 60.61
10.50 0.044 13.00 13.05 91.46 196.6 53.6 0.311 61.45 61.50
11.00 0.046 13.61 13.66 91.12 196.0 54.6 0.320 62.44 62.50
11.50 0.048 14.22 14.28 90.84 195.5 55.6 0.329 63.43 63.48

249
(C ontinued on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l in th e L iq u id Phase B o ilin g Tem perature E th an o l in th e Vapor Phase

W eight Mole % Volume % Volume Weight Mole % Volume % Volume
F ra c tio n 60“F 20° C °C °F F ra c tio n 60"F 20°C
%

12.00 0.051 14.83 14.89 90.54 195.0 56.5 0.337 64.31 64.36
12.50 0.053 15.44 15.50 90.30 194.5 57.3 0.344 65.09 65.14
13.00 0.055 16.05 16.10 90.02 194.0 58.1 0.352 65.86 65.91
13.50 0.058 16.65 16.71 89.79 193.6 58.8 0.358 66.54 66.59
14.00 0.060 17.26 17.32 89.56 193.2 59.5 0.364 67.21 67.26
14.50 0.062 17.86 1 7.92 89.36 192.8 60.1 0.371 57.78 67.83
15.00 0.065 18.47 1 8.54 89.16 192.5 60.7 0.377 . 68.3b 68.40
15.50 0.067 19.07 1 9 .1 4 88.94 192.1 61.3 0.383 68.92 68.97

16.00 0.069 19.68 19.74 88.72 191.7 61.9 0.389 69.49 69.53
16.50 0.072 20.28 20.35 88.52 191.3 62.4 0.394 69.96 70.01
17.00 0.074 20.88 20.95 88.32 191.0 62.9 0.399 70.43 70.48
17.50 0.077 21.48 21.55 88.11 190.6 63.4 0.404 70.90 70.94
18.00 0.079 22.08 22.15 8 7.92 1 9 0 .3 63.9 0.409 71.36 71.41
18.50 0 .0 8 2 22.68 22.75 87.77 190.0 64.3 0.413 71.73 71.78
19.00 0.084 23.28 23.35 87.62 189.7 64.8 0.419 7 2.20 72.23
19.50 0.087 23.88 23.95 87.47 189.4 65.2 0.423 72.56 72.61

20.00 0.089 24.47 24.55 87.32 189.2 65.6 0.427 72.93 72.97
20.50 0 .091 25.07 25.14 87.02 188.6 66 .0 0.432 73.30 73.34
21.00 0.094 25.66 25.74 86.71 188.1 66.4 0.436 73.66 73.71
21.50 0.096 26.26 26.32 86.41 187.5 66.8 0.440 74.03 74.07
22.00 0.099 26.85 26.92 8 6 .U 187.0 67 .2 0.445 74.39 74.44
22.50 0 .1 0 2 27.44 27.51 86.02 186.8 67.5 0.44S 74.66 74.71
23.00 0.105 28.03 28.10 85.94 186.7 67.8 0.432 74.94 7 4 .9 7 .
23.50 0.107 28.62 28.69 85.85 186.5 68.1 0.455 75.21 75.24

(C ontinued on n e x t page)

250
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l in th e L iq u id Phase B o ilin g Tem perature E th an o l in th e Vapor Phase

W eight Mole % Volume % Volume Weight Mole % Volume % Volume
% F ra c tio n 60°F 20°C °C •F % F ra c tio n 60°F 20° C

24.00 0.110 29.21 29.29 85.76 186.4 68.4 0.458 75.48 75.52
24.50 0.113 29.80 29.88 85.67 186.2 68.7 0.462 75.75 75.78
25.00 0.115 30.39 30.46 85.58 186.0 68.9 0.464 75.93 75.96
25.50 0.118 30.97 31.05 85.50 185.9 69.2 0.467 76.20 76.23
26.00 0.121 31.56 31.62 85.41 185.7 69.4 0.470 76.37 76.41
26.50 0.124 32.14 32.21 85.32 185.6 69.7 0.474 76.64 76.68
27.00 0.126 32.72 32.79 .85.22 185.4 70.0 0.477 76.91 76.94
27.50 0.129 33.30 33.38 85.13 185.2 70 .2 0.480 77.09 77.12

28.00 0.132 33.88 33.95 85.04 185.1 70.4 0.482 77.26 77.30
28.50 0.135 34.46 34.52 84.95 184.9 70.7 0.486 77.53 77.56
29.00 0.138 35.03 35.10 84.86 184.7 70.9 0.488 77.71 77.74
29.50 0.141 35.61 35.6S 84.79 184.6 71 .1 0.490 77.88 77.92
30.00 0.144 36.18 36.26 84.70 184.5 71.3 0.493 78.06 78.09 *
30.50 0.147 36.75 36.82 84.62 184.3 71.5 0.495 78.23 78.26
31.00 0.149 37.32 37.39 84.54 134.2 71.7 0.498 78.41 78.44
31.50 0.152 37.89 37.96 84.46 184.0 71.9 0.400 78.58 78.62

32.00 0.155 38.46 38.54 84.37 183.9 72.0 0.502 78.67 78.71
32.50 0.159 39.02 39.09 84.28 183.7 72.2 0.504 78.85 78.88
33.00 0.162 39.59 39.66 84.20 183.6 72.4 0.506 79.02 79.05
33.50 0.165 40.15 40.22 84.12 183.4 72.6 0.509 79.20 79.28
34.00 0.168 40.72 40.78 84.04 183.3 72.8 0.512 79.37 79.40
34.50 0.171 41.28 41.35 83.96 183.1 72.9 0.513 79.46 79.49
35.00 0.174 41.83 41.90 83.87 183.0 73.1 0.515 79.63 79.66
35.50 0.177 42.39 42.46 83.79 182.8 73.2 0.517 79.72 79.75
(C o n tin u e d on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l in th e L iq u id Phase B o ilin g Tem perature E thanol in th e Vapor Phase

W eight Mole % Volume % Volume
«.c Weight Mole % Volume Jo Volume
% F ra c tio n 60eF 20°C % F r a c tio n 60‘ F 20°C
36.00 0.180 42.94 43.01 83.72 182.7 73 .4 0.519 79.89 79.92
36.50 0.184 43.50 43.57 83.65 182.6 73.6 0.522 80.06 80.10
37.00 0.187 44.05 44.11 83.58 182.4 73.7 0.523 80.15 80.18
37.50 0.190 44.60 44.67 83.51 182.3 73.8 0.524 80.24 80.27
38.00 0.193 45.15 45.21 83.44 182.2 7 4 .0 0.527 80.41 80.44
38.50 0.197 45.70 45.76 83.37 182.1 74.2 0.529 80.58 80.62
39.00 0.200 46.24 46.30 83.30 181.9 74.3 0.531 80.67 80.70
39.50 0.203 46.79 46.85 83.24 181.8 74.5 0.533 80.84 80.87
40.00 0.207 47.33 47.39 83.18 181.7 74.6 0.535 80.93 80.96
40.50 0.210 47.87 47.94 83.13 181.6 74.7 0.536 81.01 81.04
41.00 0.214 48.41 48.47 83.07 181.5 74.8 0.537 81.10 81.12
41.50 0.217 48.94 49.01 83.01 181.4 75.0 0.540 81.27 81.30
42.00 0.221 49.48 49.54 82.95 181.3 75.1 0.541 81.36 81.38
42.50 0.224 50.01 50.80 82.89 181.2 75.2 0.543 81.44 81.47
43.00 0.228 50.54 50.61 82.83 181.1 75.4 0.545 81.61 81.64
43.50 0.231 51.08 51.14 82.78 181.0 75.5 0.547 81.70 81.78
44.00 0.235 51.60 51.67 82.72 180.9 75.6 0.548 81.78 81.81
44.50 0.239 52.13 52.19 82.66 180.8 75.7 0.549 81.87 81.89
45.00 0.242 52.66 52.72 82.60 180.7 75.9 0.552 82.04 82.07
45.50 0.246 53.18 53.24 82.54 180.6 76 .0 0.553 82.12 82.15
46.00 0.250 53.70 53.77 82.48 180.5 76.1 0.555 82.21 82.23
46.50 0.254 54.23 54.29 82.42 180.4 7 b .2 0.556 82.29 82.32
47.00 0.258 54.75 54.81 82.37 180.3 76 .4 0.559 82.4b 82.49
47.50 0.261 55.26 55.32 82.30 180.1 76.5 0.560 82.54 82.58
(C o n tin u e d on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l i n th e L iq u id Phase B o ilin g Tem perature E th an o l in th e Vapor Phase

Weight Mole % Volume % Volume oF Weight Mole % Volume % Volume
60 °F 20° C
•c 60*T 20 °C
% F ra c tio n % F ra c tio n

48.00 0.265 55.78 55.84 82.25 180.0 7 6 .6 0 .562 82.63 82.66

48.50 0.269 56.29 56.35 82.19 179.9 76.8 0 .564 82.80 8 2.82
49.00 0.273 56. e i 56.87 82.13 179.8 76.9 0.566 82.88 82.91
49.50 0.277 57.32 57.38 82.07 179.7 77.0 0.567 82.97 82.99
50.00 0.281 57.83 57.89 82.02 179.6 7 7.1 0.568 83.05 83.08
50.50 0.285 58.34 58.39 81.96 179.5 7 7 .2 0.570 83.14 83.16
51.00 0.289 58.84 58.90 81.91 179.4 77.3 0.571 83.22 83.25
51.50 0.293 59.35 59.40 81.86 179.3 77.4 0.573 83.30 83.33

52.00 0.297 59.85 59.91 81.81 179.3 77 .5 0.574 S3.39 83.42

52.50 0.301 60.35 60.41 81.76 179.2 77.7 0.577 83.56 83.58
53.00 0.305 60.65 60.91 81.70 179.1 77.8 0.578 83.64' 83.67
53.50 0.310 61.35 61.41 81.65 179.0 77.9 0.580 83.72 83.75
54.00 0.315 61.85 61.90 81.60 178.9 7 8.0 0.581 83.80 83.83
54.50 0.319 62.34 62.40 81.55 178.8 78 .1 0.583 83.89 83.92
55.00 0.323 62.84 62.89 81.49 178.7 7 8 .2 0.584 83.97 84.00
55.50 0.328 63.33 63.38 81.44 178.6 78.3 0.586 84.06 84.08

56.00 0.332 63.82 63.87 81.38 178.5 78.4' 0.587 84.14 84.17
56.50 0.337 64.31 64.36 81.33 178.4 78.6 0.590 84.30 84.33
57.00 0.341 64.80 64.85 81.28 17S.3 78.7 0.591 84.39 84.42
57.50 0.346 65.28 65.33 81.23 178.2 78.8 0.593 84.47 84.50
58.00 0.351 65.77 65.82 81.18 178.1 7 8.9 0.594 84.55 84.58
58.50 0.355 66.25 66.30 81.13 178.0 79 .1 0.597 84.72 84.74
59.00 0.360 66.73 66.78 81.06 177.9 79 .2 0.589 84.80 84.82
59.50 0.365 67.21 67.26 81.04 177.9 79.3 0.600 84.88 84.91

253
(C ontinued on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E thanol in th e L iquid Phase B o ilin g Tem perature E th an o l in th e Vapor Phase

W eight Mole % Volume % Volume
°C Weight Mole % Volume % Volume
°F
% F ra c tio n 60°F 20° C % F ra c tio n 60°F 20* C

60.00 0.370 67.69 67.73 81.00 177.8 79.4 0.601 84.97 84.99
60.50 0.375 68.17 68.21 80.96 177.7 79.6 0.o04 85.13 85.16
61.00 0.380 68.64 68.69 80.91 177.6 79.7 0.606 85.21 85.24
61.50 0.385 69.11 69.16 80.86 177.5 79.6 0.607 85.30 85.32
62.00 0.390 69.59 69.63 80.80 177.4 79.9 0.609 85.38 85.40
62.50 0.395 70.06 70.10 • 80.74 177.3 80.1 0.612 85.54 85.57
63.00 0.400 70.52 70.57 80.642 177.16 80.3 0.614 85.70 85.72
63.50 0.405 70.99 71.03 60.592 177.06 80.4 0.616 85.79 85.81

64.00 0.410 71.45 71.50 80.541 176.97 80.5 0.618 85.87 85.89
64.50 0.415 71.92 71.96 80.491 176.88 80.6 0.619 85.95 85.98
65.00 0.421 72.38 72.42 80.438 176.79 SO.S 0.622 . 86.11 86.13
65.50 0.426 72.84 72.88 SO.391 176.70 80.9 0.624 86.19 86.22
66.00 0.432 73.30 73.33 80.341 176.61 81.1 0.62b 86.36 86.38
66.50 0.437 73.76 73.80 80.291 176.52 81.2 0.628 86.44 86.46
67.00 0.443 74.21 74.25 80.237 176.43 81.4 0.631 86.60 86.62
67.50 0.448 74.66 74.71 80.191 176.34 81.5 0.633 86.68 86.70

68.00 0.454 75.11 75.15 80.142 176.26 81.7 0.636 86.84 86.87
68.50 0.460 75.57 75.61 80.093 176.17 81.8 0.637 86.92 S6.94
69.00 0.465 76.02 76.05 80.042 176.07 81.9 0.639 87.00 87.02
69.50 0.471 76.46 76.50 80.000 176.00 82.1 0.642 87.16 87.18
70.00 0.477 76.91 76.94 79.952 175.91 82.2 0.644 87.24 87.27
70.50 0.483 77.35 ' 77.39 79.906 175.83 82.4 0.647 87.40 S7.42
71.00 0.489 77.79 77.82 79.862 175.75 82.6 0.650 87.56 87.58
71.50 0.495 78.23 78.27 79.813 175.66 82.7 0.652 87.64 87.67

254
(C o n tin u ed on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l in th e L iq u id Phase B o ilin g Tem perature E thanol in th e Vapor Phase

Weight Mole % Volume % Volume Weight Mole % Volume % Volume
% F ra c tio n 60°F 20°C °C °F ct
f0 F ra c tio n 60°F 20°C

72.00 0.502 78.67 78.71 79.767 175.58 82.9 0.655 87.80 87.82
72.50 0.508 79.11 79.14 79.721 175.50 83 .1 0.658 87.96 87.98
73.00 0.514 79.54 79.57 79.683 175.43 83.3 0.661 88.12 88.14
73.50 0.520 79.98 80.01 79.630 175.33 83.4 0.663 88.20 88.22
74.00 0.527 80.41 80.44 79.585 175.25 S3.6 0.666 88.36 88.38
74.50 0.533 80.84 80.87 79.541 175.17 83.8 0.669 88.52 88.54
75.00 0.540 81.27 81.30 79.505 175.11 84.0 0.672 88.68 88.70
75.50 0.547 81.70 81.72 79.452 175.01 84.1 0.674 8S.76 88.78

76.00 0.553 82.12 82.15 79.404 174.93 84.3 0.676 88.92 88.93
76.50 0.560 82.54 82.57 79.362 174.85 84.5 0.681 89.07 89.09
77.00 0.567 82.97 82.99 79.316 174.77 84.7 0.684 89.23 89.25
77.50 0.574 83.39 83.42 79.271 174.69 84.9 0.687 89.39 89.40
78.00 0.581 63.80 83.83 79.227 174.60 85.1 0.691 89.54 89.56
7 8.50 0.588 84.22 84.25 79.183 174.53 8 5 .2 0.693 89.62 89.64
79.00 0.595 84.64 84.66 79.133 174.44 85.4 0.696 89.78 89.79
79.50 0.603 85.05 85.07 79.094 174.37 85.6 0.699 89.93 89.95

80.00 0.610 85.46 85.48 79.050 174.29 85.8 0.703 90.09 90.10
80.50 0.618 85.87 85.89 79.008 174.21 8 6 il 0.708 90.32 90.33
81.00 0.625 86.27 86.30 78.968 174.14 86.3 0.711 90.47 90.48
81.50 0.633 86.68 86.70 78.925 174.07 86.5 0.715 90.62 90.64
82.00 0.641 87.08 87.11 78.879 173.98 86.8 0.-720 90.86 90.87
82.50 ‘ 0.648 67.48 87.51 78.844 173.92 87 .0 0.724 91.01 91.02
83.00 0.656 67.88 87.91 78.806 173.85 87.2 0.728 91.16 91.17
83.50 0.664 88.28 88.30 78.767 173.76 87.5 0.733 91.39 91.40

255
(C ontinued on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E thanol in th e L iquid Phase B o ilin g Tem perature E thanol in th e Vapor Phase

Weight Mole % Volume % Volume Weight Mole % Volume % Volume
°C •F ci°i
% F ra c tio n 60°F 20°C F ra c tio n 60°F 20°C

84.00 0.673 88.68 88.70 78.723 173.70 87.7 0.737 91.54 91.5b
84.50 0.681 89.07 89.09 78.668 173.64 8 8.0 0.741 91.77 91.78
85.00 0.689 89.46 89.48 78.645 173.56 88.2 0.746 91.92 91.93
85.50 0.698 89.85 89.87 78.613 173.50 88.5 0.751 92.14 92.16
86.00 0.706* 90.24 90.26 78.575 173.44 88.6 0.756 92.37 92.38
86.50 0.715 90.62 90.64 7S.543 173.36 89.1 0.762 92.59 92.60
87.00 0.724 91.01 91.02 78.530 173.35 • 89.4 0.767 92.81 92.82
87.50 0.733 91.39 91.40 78.475 173.26 89.7 0.773 93.04 93.04
88.00 0.741 91.77 91.78 78.445 173.20 90.0 0.779 93.25 93.27
88.50 0.751 92.14 92.16 78.411 173.14 90.3 0.784 93.47 93.48
89.00 0.760 92.52 92.53 78.385 173.09 90.6 0.790 93.69 93.70
89.50 0.769 92.89 92.90 78.350 173.03 90.9 0.796 93.91 93.92
90.00 0.779 93.25 93.26 78.323 172.98 91 .2 0.802 94.13 94.13
90.50 0.788 93.62 93.63 78.295 172.93 91.6 0.809 94.41 94.42
91.00 0.798 93.98 93.99 78.270 172.89 91.9 0.816 94.63 94.63
91.50 0.608 94.34 94.35 78.265 1 7 2 .SS 92.3 0.S24 94.91 94.92
92.00 0.818 94.70 94.71 78.259 172.87 92.6 0.831 95.13 95.13
92.50 0.828 95.05 95.06 78.241 172.83 93.0 0.839 95.41 95.42
93.00 0.839 95.41 95.41 78.227 172.81 93.4 0.847 95.69 95.69
93.50 0.849 95.76 95.76 78.211 172.78 93.8 0.855 95.97 95.97
94.00 0.860 96.10 96.11 78.195 172.75 94.2 0.S64 96.24 96.24
94.50 0.871 96.45 96.45 78.186 172.73 94.7 0.874 9o.58 96.58
9 5 .00 0.881 96.79 96.79 78.177 172.72 95.1 0.883 96.86 96.86
95.50 0.892 97.125 97.129 78.174 172.713 95.55 0.893 97.158 97.164

(C o n tin u ed on n e x t page)
 TABLE LXI (C o n tin u ed )

EQUILIBRIUM COMPOSITIONS FOR THE SYSTEM ETHANOL-WATER AT ONE ATMOSPHERE

E th an o l in th e L iq u id Phase B o ilin g Tem perature E th an o l in th e Vapor Phase

V eight Mole % Volume % Volume W eight Mole % Volume % Volume
F r a c tio n 60°F 20°C °C °F 20 “C
% . % F ra c tio n 60*F

95.58 0.8943 97.179 97.184 78.174 172.713 95.58 0.8943 97.179 97.184
96.00 0.903 97.459 97.464 78.174 172.713 95.88 0.901 97.379 97.381
96.50 0.915 97.79 97.79 78.179 172.72 96.3 0.911 97.66 97.66
97.00 0.927 98.12 98.12 78.181 172.73 9 6.8 0.923 97.99 97.98
97.50 0.938 98.44 98.44 78.191 172.74 97.3 0.934 98.31 9 8 .3 2
98.00 0.950 98.76 98.76 78.205 172.77 97.8 0.946 98.63 98.63
98.50 0.963 99.08 99.07 78.222 172.80 98 .4 0.960 99.01 99.01
99.00 0 .975 99.39 99.39 78.243 172.84 98.9 0 .972 99.32 9 9.32
99.50 0.987 99.70 99.70 78.270 172.89 9 9.4 0.985 99.63 99.63
100.00 1.000 100.00 100.00 78.300 172.94 100.00 1.000 100.00 100.00

257
G ra p h ic a l C o n tro l P a n e l, Rum P i l o t P la n t, A g r ic u ltu r a l E xperim ent S ta tio n
U n iv e rs ity o f P u e rto R ic o .
 AUTOBIOGRAPHY

Herminio M, Brau was bora in Cabo R ojo, P u erto R ico, on August 27,

1922. He a tte n d e d th e Cabo Rojo p u b lic sch o o ls g ra d u a tin g from th e Pedro

F . Colberg Grammar School in 1936 and from th e Cabo Rojo High School in

1940. He e n te re d th e C ollege o f A g ric u ltu re and M echanical A rts o f th e

U n iv e rs ity o f P u e rto R ico, a t Mayagues, P u e rto R ico, in th e f a l l o f 1940,

.where he was awarded th e degree o f B achelor o f S cien ce in Chemical En­

g in e e rin g in May 1944. Im m ediately upon g ra d u a tio n , he e n te re d in to

a c tiv e duty in the U nited S ta te s Armed Foi*ccs a tte n d in g th e O ffic e rs

C andidate School, a t F o rt Benning, G eorgia, where he re c e iv e d h is com­

m ission as a Second L ie u te n a n t in O ctober, 1944. S in ce h is d isc h a rg e

from th e s e r v ic e , in J u ly 1946 to th e p r e s e n t, he lias been a manber o f

th e T ech n ical S t a f f o f th e A g ric u ltu ra l Experim ent S ta tio n o f th e U niver­

s i t y o f P uerto R ico. In th e f a l l o f 1948, h e e n te re d New York U n iv e rs ity ,

a t New York C ity , where he re c e iv e d th e d eg ree of M aster o f Chemical

E ngineering in May 1949. He a tte n d e d th e G raduate School o f L o u isian a

S ta te U n iv e rs ity d u rin g th e academic y e ars o f 1951-52 and 1955-56 and

i s a t p re s e n t a can d id a te fo r th e D octor o f P h ilo so p h y D egree.

259
 EXAMINATION AND THESIS REPORT

Candidate: Herminio M. Brau

Major Field: Chemical E ngin eerin g

Title of Thesis: H igher A lco h o ls i n th e A lc o h o lic D i s t i l l a t i o n from Ferm ented

Cane M olasses
Approved:

Major Professor and Chairman

Dean^ef'the raduatc School

EXAMINING COMMITTEE:

Date of Examination:

J u ly 1 0 , 1956