COMPOUNDS
FROM
Standard Solutions (lower left) Are Used by the Operator in
Control of Amyl Acetate Column at the Sharples Wyandotte Plant
A Staff-latdustruCdlabos tive Renort
T HE production of synthetic organic chemicals derived from
petroleum sources is one of the largest fields in the chemical
industry today. The mid-continent gas fields are the source of
several raw materials used in the production of many useful prod-
ucts. The pentanes, which are removed from natural gas by
fractionation, are the raw materials from which a large group of
amyl compounds are synthesized by Sharples Chemicals at its
Wyandotte, Mich., plant. The production statistics for amyl
acetate and amyl alcohol from all sources are shown in Table I.
Development of the present industrial process for synthesis of
amyl compounds was stimulated by two related findings in the
early 1920’s. Ayres found that when the hydrolysis of amyl chlo-
ride was carried out in the presence of a dispersing agent, such as
sodium oleate, there was a marked reduction in the percentage of
the chloride which was dehydrochlorinated to amylenes ( 4 ) .
There was a corresponding increase in the yield of amyl alcohols.
I n addition, there was developed a vapor-phase method for the
chlorination of hydrocarbons which was more satisfactory with
respect to yield of the desired products and also reduced the
explosion hazard. Several patents were later granted to Ayres
(2,s)for this type chlorination.
PENTANE
RICHARD L. KENYON AND
GORDON c. INSKEEP
Associate Editors
in collaboration with
LESLIE GILLETTE AND
J. FRANK PRICE
Sharples Chemicals, Inc., Wyandotte, Mich.
(. (. (.
SHARPLES HISTORY
The Ayres features were incorporated into. the process by the
Sharples Company and a pilot plant was built in Texas. This
plant was operated only long enough to prove the superiority of
the newly developed techniques. The rising demand for high
boiling lacquer solvents to supply the expanding automobile
industry indicated a need for a full scale industrial plant. Fusel
oil and fusel oil acetates were being demanded by the lacquer in-
dustry but could not be obtained in sufficient quantities. Fusel
oil was obtained as a by-product in the ethyl alcohol fermentation.
Kirkpatrick has pointed out the economic aspects considered
in selection of a site for this new plant (9). A survey by the
Sharples Company in 1925 and later an independent but con-
firmatory investigation by E. B. Badger and Sons recommended
location a t Belle, W. Va. This was near a casing-head gas source
and was near enough to eastern and central United States dis-
tribution centers to balance the problems of raw materials and
distribution satisfactorily. Caustic and chlorine were readily
available from the Belle Alkali Company. Ground was broken
for this plant in March 1926 and amyl alcohol was being pro-
duced there by December of that year.
December 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 2389

rides the 2-me-2-chlorobutane or the 3-me-2-chlorobutane may

TABLEI. AMYLACETATEAND AMYLAr.coHoL PRODUCTION"
decompose t o form 2-me-2-butene or 3-me-1-butene. These
Am 1 Acetate, Amyl Alcohol, olefins can be recycled t o the chlorination step and under the
Year Founds Pounds
conditions used, in the vapor phase at high temperature and
under pressure, will chlorinate rather than add chlorine to t h e
double bond
CHa--CH=C(CHs)CHa + Cla---t
CH&I-CH=C(CHa)CHa + HCI
Thus the mixed chlorides will contain all the possible isomers of
normal and isopentane as well as some unsaturated amyl chlo-
0 U.8. Tariff Commission reports. rides.
b Reliable data unavailable. The hydrolysis of the amyl chlorides is carried out in the pres-
ence of sodium oleate using aqueous sodium hydroxide. The
sodium oleate may act either to emulsify the amyl chloride in the
aqueous sodium hydroxide solution, or it may react with the amyl
The hydrolysis was run batchwise at the beginning. The chloride forming amyl oleate which in turn is hydrolyzed by the
sodium oleate remained in the reactors; the raw materials were aqueous sodium hydroxide. Since amyl oleate has been isolated
pumped in, agitated, and distilled off, The operation was con- from the reaction, it is evident that the hydrolysis proceeds, a t
verted t o a continuous process in March 1928 with the result least partially, in this manner
that the yield from the chloride to alcohol rose t o 60% and even-
Na Oleate
tually t o 67%; this was with continuous hydrolysis but batch-
wise distillation. +
CSHI~CI NaOH -+ CbHllOH + NaCl
The conventional method of esterification was not found satis- C6HllC1 + Na Oleate -+- C& Oleate + NaCl
factory for the production of amyl acetate. Accordingly,
Sharples set about studying the acetylation of amyl alcohol. By C&l Oleate + NaOH +CsHllOH + Na Oleate
March 1927 the present method for introduction of the catalyst
During this hydrolysis, the amyl chlorides are also dehydro-
and flashing of the alcohol had been developed and was incorpo-
chlorinated by the sodium hydroxide solution yielding the various
rated into a process for the manufacture of the ester.
isomeric pentenes
. The copstruction and operation of the Belle plant has been
discussed previously in the literature (1, 6-7).
A favorable arrangement with the Pennsylvania Salt Company
+
C ~ H ~ I C I NaOH --+ C6H10 + NaCl + HzO
made a move to Wyandotte, Mich., attractive for the Sharples The unsaturated amyl chlorides hydrolyze either rapidly or
organization. Land was available adjacent t o the Penn Salt with difficulty, depending on the position of the chlorine atom
plant and contracts for chlorine, caustic, and some utilities were relative to the double bond. The allylic-type amyl chloride
worked out. hydrolyzes quite rapidly whereas the vinyl type goes through the
I n the fall of 1932, dismantling of the Belle plant was begun. hydrolysis step largely unreacted
Actually, this was a meticulous project. By scheduled shutdown
of t,he various units i t was accomplished with little interruption CHa(CHa)C=CH-CH2CI + NaOH+
of customer's supplies. Each piece of equipment, from large CH3(CH3)C=CH-CH20H + NaCl
columns to small sample valves, was oarefully marked and cata-
loged t o simplify the job of reassembly. The equipment, Table I1 gives a typical composition of crude amyl alcohol,
housed in pew quarters a t Wyandotte, was back in operation by as determined by infrared analysis.
March 1933.
Although refinements have been made in the
field of instrumentation and some changes in
materials of construction, the present operation
of the chlorination, hydrolysis, and acetylation
units at Wyandotte is basically the same as at the
original Belle plant.
Additional amyl derivatives of the chloride and
alcohol are now being made at the Wyandotte
plant (8) and are described in this article.

FUNDAMENTAL CHEMISTRY

The fundamental chemistry related t o these

processes is relatively simple. The chlorination
of pentane is carried out in the vapor phase be-
cause higher yields t o the primary chlorides are
obtained. Also, the vapor-phase chlorination af-
fords more control over the formation of dichlo-
rides, The principal reaction i s this chlorination
of pentane proceeds with the formation of amyl
chloride and hydrogen chloride

CdH,z + Clr CsHnCl + HCI

Coal Fired Pipe Still Reactor
During the rectification of the amyl chlo- Surrounding barricade can be blanketed by ateam in emergency
2390 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No: 12

Amyl alcohols are esterified with acetic acid in the presence o& formaldehyde resins. It has been used successfully as the vola-
sulfuric acid catalyst to yield amy1 acetate and also some by- tile portion of hydraulic fluids, and recently in antibiotic recovery
product pentenes as an extractant.
CsHiiOH + HOAC +CsHii0-4~+ HzO Primary n-amyl alcohol, isobutylcarbinol, sec-butylcarbinol,
diethylcarbinol, and tert-amyl alcohol are separated by the frac-
CbHiiOH +CjHio + Hi0 tional distillation of the crude amyl alcohols. All the isomers are
used in various organic syntheses. Diethylcarbinol is used in
the manufacture of flotation agents for nonferrous ores.
By esterification of amyl alcohol with acetic acid, Sharples pro-
duces a mixture of the isomeric amyl acetates (11). Large vol-
umes of acetate are used as a penicillin extractant. It is also used
in nitrocellulose lacquer formulations, and small quantities are
CALCIUM CHLORIDE used in the food industry as a flavoring agent.
DEHYDRATOR The amyl chlorides are reacted with sodium hydrosulfide to
give a mixture of amyl mercaptans (13) which is used as a fuel
gas warning agent; one pound per million cubic feet of gas is the
CH LO R I N E usual concentration.
TO VAPORIZER Amyl meieaptan is a mixture of the various amyl isomers and
r----eA can be used as a starting material in the synthesis of organic sul-
fur compounds.
Amyl sulfide is a yellow liquid having the amyl group present in
its isomeric forms. I t is used in the preparation of sulfones, sulf-
oxides, and other organic sulfur compounds through addition
TRACK "SCALE reactions.
LINKED TO WEIGHING BEAM Although Sharples has been producing amylphenols since the
WHICH ACTUATES ALARM HORN.
early 1930's, until just recently the amyl group present was
Figtin. I . ( liloiiii(. t iilo.i<lirig *I~II;O~I either wholly or predominantly the tertiary isomer. The com-
mercial scale production of the secondary amylphenols by reac-
tion of the normal pentenes has been initiated by Sharples in the
The pentenes are used in alkylating phenol and naphthalene past 5 years
to form the corresponding amyl derivatives p-tert-Amylphenol (fd) is used in the preparation of pale-
colored, light-stable, oil-soluble resins and also as a n intermediate
for pharmaceuticals.

Amyl mercaptans are formed through the reaction of sodium

hydrosulfide with amyl chloride in the presence of a mutual sol-
TABLE
11. COMPOSITION O F CRUDEAMYL ALCOHOL
vent
Roiling
C5HllCl + NaSH +CsHllSH + S a C l Component Formula
Point,
C. Percentage
Amyl sulfide and amyl disulfide are also formed in this reaction 2-Me-2-butanol (CH3)zCOHCHzCHa 101.8 6.0
2-Pentanol CHa(CHz)%CHOHCHs 119.3 25.1
as by-products 1-Pentanol CHalCHz)aCHzOH 138.0 25.5
3-Me-1-butanol (CHa)&HCHzCHzOH 132.0 11.9
2CsHiiSH + HzS
+(CbHii)2S 2-Me-1-butanol
3-Pentanol
CHaCH&H(CIla)CH2OH
(CHsCH2)zCHOH
129.5
115.6
16.8
9.4
2CsHiiSH + [OI +(CjHii)2S2 + HzO
3-Me-2-butanol (CRs)&HCHOHCHz 112.0 2.2
9-Butanol CHGHzCHOHCHa 99.5 1.2
2-Me-1-butene-3-01 CHz: C(CHa)CHOH-CHs 116.6 1.3
Products and Their Uses. The mixture of most of the theo- 2-Me-2-butene-1-01 CHICH:C(CHJ)CH?OH 139.4 0.7
retically possible isomeric chloropentanes of n-pentane and iso-
pentane obtained from the vapor-phase reaction is marketed as
mixed amyl chlorides. It is used in the synthesis of other amyl
compounds and as a solvent in the formulation of synthetic rub- Two isomeric o-amylphenols are produced; in one the amyl
ber cements. I n some alkylation reactions the primary isomers group is predominantly tertiary and in the other predominantly
are more desirable; for these reactions a fractional distillation is secondary. Both products can be used as intermediates for the
used to produce mixed primaries which are available at a slightly synthesis of other compounds where specific properties are re-
higher price. quired. Both are effective antiskinning agents for paints and
Dichloropentanes produced are a mixture of about 40% true varnishes. Diamylphenol is also used for this puipose; the
amylene dichloride and 60% a mixture of most of the other di- choice of agent depends on the nature of the other components.
chloro derivatives of both normal and isopentane. This product Mono-, di-, and polyamylnaphthalenes also are marketed b v
has found use as a solvent, insecticide, soil fumigant, and oil Sharples (14). These are somewhat viscous liquids resembling
additive. It is also used in the formulation of dipping cements lubricating oil in appearance and are used as plasticizers, heat
for synthetic rubbers of the Buna N type. Dichloropentanes transfer media, solvents, and as starting materials in the manu-
are one of the lowest priced chlorinated solvents now commercially facture of surface-active agents.
available.
Hydrolysis of the chloride yields the alcohol. Sharples pro- PRODUCTION OF AMYL COMPOUNDS AT SHARPLES
WYANDOTTE PLANT
duces commercially only the alcohols containing five carbon
atoms in the molecule. One commercial product is a mixture of Raw Materials. Pentane is received from West Virginia, Okla-
the isomers (IO); i t contains six of the possible seven isomeric homa, and Texas. I t s composition varies, according to specifi-
amyl alcohols b u t is predominantly composed of the three pri- cation, from a high n-pentane to a high isopentane content.
mary alcohols. This product is used as a latent solvent in the Most of the product contains approximately equal proportions of
formulation of nitrocellulose lacquers and as a solvent for urea- the straightr and branched-chain isomers.
December 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY
2392 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 12

The r:hloriniLtioii w r l hydn,l,isis opmatiom are aliowri in

Figure 2.
I'rom the storage tanka, i x n b n o for the: imxx:as is pumped by
positivc pressure p u m p to the dehydrstion tsnk, R 45Wgallon.
uiwight, rertmn skel, <wnc.httrmed tank with a %inch gas iii-
duct,ion pipe entering the top ;rod rrrtrliing to within 18 i w h w of
1.hebottom. TI,? iriduition pipe ir blinded on ihe cud and drillwl
with numerous holes. Thv dehydraldon tank is connected :L
grltVity N o x line and RISU I,y it pressure cqut\iirstioo line to a 300.1-
gdlon horizontal mnkc-up t m k .
About 3300 gallons u f p w t a i a ~:m punipd to thc daliydn~tii,n
t m k arid hydrogen &lorid* gas, ii by-product of chlorination, is
consturrtly bubbled in through t,hc induction pipi. A s it rism it
absorbs m y moisture premnt iii the pentane and a dilute solut,ion
ui hydrochloric acid colltiats in ttw Irjttom oi tlic tlrnk from which
it is driiint.d to the EWPT >it.rsgular intervals. Tlrc excess hydro-

Tertiary Arnylphenol Unit Shewing Alkylation and

Digestion Autoclaves

Tibe p i t a n t : i8 sliip~wdiri SLiiiidiLid ~ t e e lkink O:LE having 2%

trc,t,tuni v d w . The h y d r u ~ : d m ii s puiriped from this bottom
~ mc:~risuf erplofiion-pruof carrtrifugnl pumps, tlirough a
y i i l v ~by
HcLxilAr muclni how, to &ort~gct m k P to which the kink cars are
d 8 0 r:umected hy intliiris of pwsmm wjudizw linos. Thu tanks
m e 27,000-g:tllon Irorisontttl units of wt:lric,ri construction.
Chlorine is rcaeived from Pc:orisylvmia Salt Msnuiacturing
Company, l o u a t d j u s t itcross the highway, in %ton b n k CBIB.
:I full car, in addition to tlut hcing unloaded, is rnuirittLiued R t
the unloadiug statim. F i g u r ~1 nhow tho stutioii schematically.
The liquid chlorine i s forced out of the CKP by compressed sir and
is transferrod to a st;indb,v, or aiicliov car. In order to minkin
anhydrous eonditiuns, this sir is previously dried by passing it
through calcium chloride traps. The ~ I K ; / I O Pcar i s a lGton tank
which sits on iixlf-track scales (2.4).
A small mercury switch is trLtaehnd to the weighing beam
After the supply car has gone empty and the weight of the anchor
car stnrts to decrease, the bezm drorrs act,uating an electric horn.
Thr operator then knows it is t,ime to change o v v supply cars.
He t.hrows H mtrnuiil swiiah which turns off the born and sels
tire circuit to ~:ont,acl, again whco tho weight oi the tank starts to
increme. When Ire bears tlie alarm again, he knows that the
anchor ear hxu started t,o fill. Tuniirrg off t,he itlmn automati-
cslly sets tho circuit for contwting when the weight. sI.iwt?l,o fall;
the cycle is then repeated. In this system t,hc anrbor (I% serves
bs a surge tank between tlie iirromirig chlorine CN.I'Sand the
pmress itself; there arcl no other chlorinc storage iia.ilitiea.
Caustic is also reeeivcd from I'con Salt. It is pumped under-
ground from their plant, as li35y0 solution of sodium hydroxide,
to storage tanka when, i t is diluted wit,b w:itor to s 12% concen-
tration
OtIlL'I important raw ,ni,terinls rccei"c<!by Sharpies nrt: HhOW,,
in Table 111.
December 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY
Deasters in Continuous Alcohol Fractionation
2393
1STEAM ~ U D Ean
.sm€
m NEUTRALIZATION
AHD BITCH
MSTILLATION
Figure 3. Flow Sheet for f'roclvetinn of Amyl
Acetate
Ilydmgtw diloriric errtws tlre tmtturrr u i the series of 8ini:h
cella m d is pollcrl upward by the va~uunito be met hy a down-
ward R o n o i water which ubsorlx most a i it. Tho unabmrbod
gas p:uscs to the hottom o i the Ginch cell bank where the process
is rqw:~trd. Tho Rinah d l yields 22" BO. lrvdrocbloric acid,
n h t w w thc Binrh cell giwa i t iiolotion of 18" BB. strength. The
neid str~iiiiw.pafie through il~anot*'rawhich itre of Imrtiruler value
i n t,l,<. r b a r t ~ p wbiw
, sonw ixmti~rici:ond<mscs in the cold system.
The p n t x w i s held io the &ranter irrrd is fllmhrd off by the hot
acid solul,ion which iu ioormtd. Iluring the absorption p~oct:ssin
118, residual pcntmr in thr: hydrogen chloride stream is
vaporii;t:d by the heat of solution in tht: ~ ~ 4 1und 6 p~sscsout the
top ni i.lrc cells through a brim seruhher and a condenser to a
reeeivcr. Any uneondc!nrrd jxmtstnt?g w s through the compresmr
o n tilt! intiikr aide and is dixh:uged, uodor 60 pounds per square
i i i c h prwsure, through n coodcnwr into u reccivcr. tincondonsit-
Iilw are veut,od off through R VWIYC, and bhe pntnne is diseharged
to thc mrrkc-up tank by the pransure.
Ttic :icid irom the Ginrh-diamrtm a:ll b m k is fed t ~ storiige
) by
gravity :LS thr take-off is 8cwral Feet sbovc, thc ground. The
arid imm the longer Bind-diameter (.ell bank discharges to B
blow <:ax*from which it is trmsierred by air prem~ret n ator-
"be. Ahout 98% of the hydrogcn chloride formed is reclaimed
in this system. A very pun, grade hydrochloric acid is produced
arid ia used ~:aelusivt~ly in tho food industry.
T h e lxine untxi in t.he pentane serubbw i s a 20% salt solution,
eontiioing a.bout 0.5% sotlimn hydroxide, which is R by-product
of the subsequent hydrolysis o i amyl chloride. From the
srrubber it is discharged to the 8ewcr. The scrubbers are roain
impregnated asbestas ( 6 A ) tanks packed with carbon Kusahig
hgs.
Vents from all aoid tanks, blow cases, snd cars are connected
to B water scrubber. The resultant scrubber solution, which is
mildly acid, is run to the sen'er, the eontents of which are alkaline.
 2394 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 12

tubc. Feed enters the bottom header and the effluent mixture
MIXED comes from the top header. The temperature in the digesters is
PENTENE
CONDENSER regulated by automatic control of the steam pressure in thr
heaters within a range of j=1O C.
Once this start-up has been effected, constant chaiging of amyl
PHENOL chloride is begun. The chloride enters digester 1 through a
1-inch-diameter pipe, 8 feet long, which is closed a t the end and
perforated with ‘/*-inch holes to fecd a spray of the chloride into
the reaction mixture. There are sufficient holes to be equivalent
YQRMA!.
to one and a half times the cross-sectional area of the inlet pipe.
WEIGH PENTENES Addition of caustic, a t the suction side of the circulatory pump,
TANKS is begun at a rate which n-ill maintain a c*oncentrationof sodium
hydroxide of not less than 0.570 in digester 2. The caustic
passes through concentric tube preheaters which are heated b y
the condensate from steam traps.
The feed of both amyl chloride and caustic is regulated by
means of pneumatic controllers ( 4 A ) which control the steam
pressure operating the positive displacement pumps on both feed
lines. The pumps operate with a steam pressure of about 150
pounds per square inch. Pressure in the digesters is limited by
COLUMN a pressure relief valve which blows into a condenser a t the pres-
ALKYL AT I ON sure limit. An alternate valve is maintained for checking pui-
AUTOCLAVE
poses.
Product distills from a take-off line leading from the top of
I I
c CONDENSER
digester 2 to a shell-and-tube condenser in which cold water
-m

I3-6-
DECANTER

WATER
DIAMYLENE
passes through the tubes. The alcohol mixture which contains
amyl alcohol, amyl chloride, amylene, and water flows from the
Londenser through a decanter, where a major portion of the water
is removed and sent to a stripper to recover the alcohol. At t h i s
point the organic portion of the reaction product mixture is only
about 3Oj, soluble in water and separation is relatively easy.

I IDiGESTER
CRUDE
AMYL PHENOLS
TO BATCH
DISTILLATION
Figure 4. Flow Sheet for Production of
Amylphenols
Hydrolysis. Amyl chloride (a mixture of primary, secondary,
and tertiary chlorides) is transferred by positive displacement
”pumpsfrom storage to weighing tanks. These are steel tanks of
1000-gallon capacity, set on scales. As the chloride still contains
some traces of hydrogen chloride it is passed through a caustic,
scrubber before entering the digester. The scrubber is an un-
packed tank. It is partially filled with 12y0 caustic from the
regular supply, and the chloride is pumped into the bottom to
rise through the caustic. The scrubbing solution is checked a t
intervals of approximately 3 hours. When its strength is reduced
to 4% sodium hydroxide, i t is drained-and the solution replen-
ished.
The hydrolysis of amyl chloride i s carried out in a pair of di-
gesters, which are steel reaction vessels without packing or agita-
tion, insulated with 2-inch magnesia blocks. Digester 1 is filled,
a t start-up, with oleic acid, amyl chloride, and enough preheated
12y0 caustjc solution to bring the entire reaction mixture to a
sodium hydroxide concentration of 3%. The mixture flows froin
No. I through a n outlet near the bottom which is controlled by a
gate valve, through a heater, and into the top of digester 2. A
stream is pumped by centrifugal pump from the bottom of KO.
2, through another heater, and enters the top of digester 1.
The digester heaters are made of 2-inch pipe inside 3-inch
pipe and are designed as parallel hairpin turns feeding into com-
mon headers. Because of its consistmcy, the reaction mixture is
referred to as the “paste.” The paste flows through the innci
The residue, or bottoms, in the digester consists of a brine
d m o s t saturated &ith sodium chloride and containing about
0.5% sodium hydroxide. This is continuously drawn off thc
bottom of digester 2 through an automatic control valve ( S A )
which is regulated by the specific gravity differential between tho
cffluent brine and the reaction mixture in the digesters. A
check sample is constantly drained near the bottom of digester 2
within sight of the operator. The brine is milky, and the reaction
mixture is dark. Visual indication is thus given if the brine level
falls below the safe point. The brine sample is analyzed regu-
larly by the operator to determine its alkalinity. The rate of
caustic feed is based on the alkalinity of the brine. A very small
make-up of oleic acid is added occasionally.
If all the chloride and alcohol were depleted during the hy-
drolysis there would remain a sticky mass which could not be
pumped. As a safeguard, a sample is taken from the pump oncr
every 2 hours; i t is acidified and steam distilled to determine the
amount of volatile material present. Another safeguard is a red
light for which electrical contact is maintained by the brine under
pressure. If the paste gets into the pressure tap, the small line
plugs up; this reduces the pressure on the electrical contact :tnd
turns off the light.
The brine, which is drawn from digester 1, is discharged by
digester pressure t o a flash tank on the second floor, wherc thc
small amount of low boiling organic material contained is flash-
distilled through a water-cooled condenser to a decanter and
thence to a column. The brine then goes to storage tanks. Some
of it is used to neutralize hydrogen chloride which comes off with
pentane vapors from the hydrochloric acid unit.
The product which distills from the top of digester 2 is pumped
from a receiver to a 26-plate bubble-cap column which is sparged
with steam. This column operates under preksure of 26 pounds
per square inch. The low boiling organic material which is
flashed from the brine also goes to this column. The stream is
introduced just below the middle of the column. Amylene is
taken from the t o p of this column and passes through a shell-and-
tube condensei. A portion is returned to the column as refluy,
 December 1950 INDUSTR,IAL A N D E N G I N E E R I N G C H E M I S T R Y 2395

and the remainder goes to a decanter from which watrr is X C ~ I L -

rated and the amylene is sent to a receiver tank.
Amyl alcohol, amyl chloride, and water are taken from the
bottom of the first column, wher? the liquid level is maintained
hy liquid-level ( S A ) control traps. The mixture is discharged by
pressure to column 2, a 26-plate column, the stream enaring
about the middle. A sparge ot steam is used to maintain thr
dexired heat. Amyl chloride is taken from the top of the column
through a condenser and partly returned to the column as reflux.
The remaining poition of the stream flows to a decanter whew
water is separated and the amyl chloride flows to receivers; from
here it id returned directly to the digester feed weighing tanks.
The alcohol and water are collected from the bo,ttom of column
2 and passed through a coil-in-shell cooler, thence pumped cen-
trifugally to a decanter. Water goes to the collection tank which
receives all decanter water from this operation, and the amyl
alcohol goes to column 3, which is called the dehydration column.
This c o h m n has a steam heated coil reboiler. All water and a
small amount of alcohol are taken off through the top of tthe
column, through a condenser, and to a decanter. The alcohol
collected from the decanter is returned to the'colunin as reflux.
From the reboiler, a stream of alcohol is taken through a coil
cooler and is centrifugally pumped into 500-gallon receivers.-
After analysis it is sent to storage.
Alcohol Distillation. After thc crude alcohol is collected in a
storage tank it is rectified. The rectification still consistrj of ti
G000-gallon steel kettle with a 26-plate bubble-cap colhmrt,
There are two of these columns.
. Pentane Dehydration Tank, Product Storage Tanks in
About 5500 gallons of alcohol are charged into tho kettle, Foreground
which is heated by means of a steam scroll. The distillatr stream
is passed through a decanter until it has become nearly dry. A begun and is continued a t a rate to maintain the liquid volume
distillation rate of about 1200 gallons per hour is then established. of the still. Acetic acid is added to maintain the 40% concen-
A small stream of alcohol is taken off and the remainder R i re- t,ration.
turned as reflux until the stream is thoroughly dry. The take-off The water resulting from the esterification reaction must be
is then increased and the collection of distillate fractions i R begun. taken off. The distillate from the still passes through a tube-
Alcohol specifications are shown in Table IV. and-shell condenser and into a decanter. One side stream is
taken from the decanter as crude acetate and another as water.
/ A portion of both the water and the acetate is refluxed to the
TABLE
IV. AMYLALCOHOL
SPECIFICATIONS column.
The crude acetate is collected in receivers where it is held until
Normal
PentaEol tert-Amyl Amyl Alro- nn analysis has been made. It then flows to the neutralizing
No. 27 Alcohol hol tank where sodium carbonate solution is added to produce neu-
Color Water white Water white Water white trality. From the neutralization tank, the product is pumped to
Specific gravit 20/20° C. 0.81-0.82 0 81-0.82 0.82
Acidity, mg. K%H/g. maxiroilill 0.06 0.06 0.06 a storage tank which feeds the rectification still. After analytical
Water content None None None
Distillation, C. checking, the batch is fed to a 6000-gallon carbon steel batch still
Initial, min. 112.0 with bubble-cap column. The f i s t product from the still is the
Not more than 5 % below 118.0
Not more than 5 0 7 belaw ia5.o .. amylene produced by decomposition during the process. The
Not more than 8 5 2 below
Final, max.
13o.o
140.0
... nest product is water which goes to a decanter for separation of
95% bdtween 0 8 . S-'io3.8
the crude acetate. A cut is then taken which consists of about
23% acetate and the remainder alcohql. This is recycled back'
to acetylation. Anintermediate cut follows. This is about 60%
The residue, amounting to about 201, of thc total charge, is acetate with alcohol which is returned to the crude neutralizing
redistilled to obtain amyl ether, which is collected over a dis- tank. The relative volumes of these heads cuts depend on the
tillatFn of 165" to 199' c. The remaining residue, which is ester content of the crude ester charged. The remainder of the
principally oleic acid, is discharged as waste products. lmtch comes off as amyl acetate product containing about 87 to
Amyl Acetate. A flow shect for the acetylation reaction is SSyoamyl acetate in amyl alcohol. All cuts are collected through
")
shoivn in Figure 3. Amyl a9etate is prepared in a 4 ~ - g a l I o n a copper shell-and-tube condenser. There is no residue in the
copper reaction kettle to which is attached a bubble-cap copper still. The final product is blended with amyl alcohol to produce a
column, 4 feet in diameter. Amyl alcohol and glacial acetic acid consistent 86% concentration of acetate.
(approximately 99%) are added with enough water to give an Water fractions from this distillation are sent to a storage tank.
acetic acid concentration of approximately 4Q% in the total When a sufficient quantity has accumulated, i t is distilled through
mixture. Two per cent, by weight, of concentrated sulfuric n pot still t o recover the acetate, which then goes to the acetate
acid is added. rectification still.
Steam, at 40 to 60 pounds pressure is passed through the heat- Tertiary Amylphenols. The pentenes produced as a by-prod-
ing coil to begin distillation. About 5% acetic acid is initially uct in the hydrolysis 6f the amyl chlorides contain all the isomeric
carried over in the stream. The entire product is fed back as 1 pentenes. The two tertiai y pentenes, %methyl-Zbutene and
reflux until the acetic acid content is 0.5yo or less. The take-off Zmethyl-1-butene, are preferentially reacted with phenol to
is then opened to the receivers to give a 3: 1 reflux ratio and the form the tertiary amyl phenols. This process is shown in Figure
product is collected in reveivers. The nddition of alcohol is then 4. Phenol is alkylated with the tertiary pentenes in the presence
2396 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 12
December 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 2397

of sulfuric acid. The reaction is carried out at 50' C. in a glass-

lined reactor ( 8 A ) . The unreacted normal pentenes are re- TABLE OF CONSTRUCTION
V. MATERIALS
moved from the reaction mass by distillation after the addition Product. or
Operation Equipment Material Remarks
of water to inactivate the sulfuric acid. The aqueous layer is
Chlorination Pentane de- Monel-clad Aqueous HCl present
decanted from the alkylate and the latter. is transferred to a di- Chlorination Venturi
hydrator
mixer cone
Cast steel Anhydrous conditions
gester. After digestion, the crude containing a preponderance Chlorination Pipe still Carbon steel Anhydrous conditions
of p-terl-amylphenol is neutralized with dilute caustic solution. Chlorination Fractioneting Carbon steel Anhydrous conditions
columns
This neutralized crude is then sent t o a batch vacuum still t h a t HCI recovery Gas absorbers Ceramic Aqueous HC1 present
separates the isomeric monoamylphenols and the diamylphenol. HCI recovery Decanters Haveg Aqueous HCI present
HCI recovery Blow cases Rubher-lined Aqueous HCI present
The still is equipped with a two-stage steam ejector which pro- Pentane recovery Scrubbers Haveg Caustic and brine used
to neutralise HC1
vides 29 inches of mercury vacuum. Hydrolysis Digesters Carbon steel Alkaline material a t
Secondary Amylphenols. The unreacted normal pentenes high temperatures
Alcohol distilla- Kettles arid Steel Neutral conditions
from the terl-amylphenol process are reacted under more drastic tion columns
Esterification Kettle and Copper Acetic acid present
conditioris to form sec-amylphenols. The reaction temperature column
is 100' C. and the pressure above 1.50 pounds per square inch. Eater distillation Kettle and Steel Neutral conditions
column
The normal pentntnes containing only traces of isopentenes are terl-Amylphenol Reactor Glass-lined Phenol present
tert-Amylphenol Still Steel Crude is neutralized
pumped into an autoclave which contains molten phenol and a terl-Amylphenol Condenser Stainless steel Product is discolored
catalyst. The r a t , of the pentcne feed is regulated by the pressure and subse- by iron
quent lines
in the wtocIav(*. After the desired degree of alkylation is sec-.dimylphenol Autoclave Nickel-clad Acidic conditions a t
high tern eratures
reached, the nrutrslised crude is pumped t o intermediate storage Amylnaphthalenes
Amyl mercaptan
HC1 scrubber
Autoclave
Wood
Inconel-clad
A ueous HE^ present
SJfideR and chlorides
and then to a high temperature vacuum still. This still is pro- present
vided with the same type two-stage ejector but is operated a t a
kettle temperature in excess of 200" C. A biphenyl ether heat
transfer medium (Id)is circulated in the heating coils. The
mass is then pumped to a neutralizer where dilute caustic is added
ortho-, para-, di-, and poly-ser-amylphenols are separated in this and the aluminum chloride complex is decomposed. The unre-
still. acted amyl chloride and pentene are then distilled off. The
Amylnaphthalenes. T h r amylnaphthalenes are produced by
aqueous layer is separated from the crude amylnaphthalenes
alkylating naphthalene with the unreackd normal pentenes from
which are dried in an aerator. The dried crude is filtered and
the amylphenol process and with amyl chloride using aluminum
then fractionated in a high temperature vacuum still. The
chloride in the Friedel-Crafts reaction (Figure 5 ) . Mixed amyl mono-, di-, and polyamylnaphthalenes are separated by this
chlorides are mixed with molten naphthalene and the sytem is fractionation.
dehydrated azeotropically by distilling off a portion of the amyl Amyl Mercaptans. The amyl mercaptans are produced by re-
chloride. Aluminum chloride is then added to the dry mixture, acting mixed amyl chlorides with an aqueous solution of sodium
and the temperature is increased. When most of the hydrogen hydrosulfide in a mutual solvent, ethanol (Figure 6). Amyl
chloride is vented off t h o u g h a scrubber, more aluminum chloride chloride, aqueous sodium hydrosulfide, and ethanol are charged t o
is added and then normal pentenes are pumped in a t a rate to an autocalve; the total charge is 650 gallons. Thie mixture is
maintain the reaction mass a t about 180" C . T h e erude reaction reacted at 140' C. and 325 pounds pressure for 5 hours. The

Weigh Tanks for Amyl Chloride and C a u s t i c F e d to Digesters; Acetylation K e t t l e at R i g h t

2398
--
NORMAL PENTEN
INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
CONDENSER
HCI VENT
SCRUBBER
F-
II
TANKS
I I CONDEJNSER
-
c
COLUMN
Figure 5. Flow Sheet for Production of A m y l Naphthalenes
crude mixture in the autoclave is discharged to a batch still
where the hydrogen sulfide and a portion of the pentenes are dis-
tilled off. The hydrogen sulfide is absorbed in two caustic scrub-
bers forming sodium hydrosulfide which is used in subsequent
batches. The crude amyl mercaptans are steam distilled in this
still separating them from the amyl sulfides and disulfides. The
residue in the still is separated into two layers; the lower aqueous
layer is disposed of with no subsequent treatment and the upper
sulfide layer is sent to storage. The crude amyl mercaptans arc
sent to a second still where the last traces of hydrogen sulfide and
pentenes are removed. The charge is then aeeotropicab dried
and the amyl mercaptans are separated from ethanol,. amyl
chloride, amyl alcohol, and amyl sulfides.
Control of odor is the biggest problem in this process. All
vents from the scrubbers and tanks are connected to a header
which leads to a flare. This flare handles all hydrogen sulfide
and amyl mercaptan vapors. Aqueous discharges are chlorin-
ated before dropping t o the sewer. Chlorination converts the
odorous mercaptans and sulfides to sulfoxides and sulfones.
The blending room, where open streams of mercaptans are pres-
ent, is ventilated b y an exhaust blower which discharges through
a n activated charcoal tower. By constant vigilance, escaping
odors from this process are kept to a minimum.
n
CORROSION
Vol.. 42, No. 12'
In a series of rwctions involving the usc
or formation of such materials as chlorine,
hydrochloric acid, caustic, and brine, tre-
mendous problems of corrosion would be
rxperted. Althdugh these problems w e r ~
almost overwhelming during the initial
stages of operation, most of them have been
satisfactorily workcd out.
WA~ER
TO SEWER
Clark (6) pointed out that the dehydration
o f the pentane was originally attempted in
coke-packed touws. Because of the gradual
WATER a
disintegration of the coke and packing of the
RECOVEREO wetted coke, the towers required frrquent
PENTENES cleaning and replacement of packing. Thc
remedy found was the one that is still in usc
today-bubbling anhydrous hydrochloric acid
through the pentane.
By rarefully maintaining anhydrous con-
ditions, it is possihle t o use carbon steel
equipment for the chlorination. A carbon film
forms in the Venturi mixer and undoubtedly
serves a s an effective protective coating.
Where the aqueous hydrochloric acid must
be handled, ceramic , resin-impregnated as-
bestos, and rubber-lined equipment is suc-
cessfully used. More expensive metals such
as tantalum have been considered, but an
economic balance of their high initial cost
against the replacement costs of the present
materials does not indicate that use of such
metals would be advisable.
Corrosion in the KO. 1 digester is negligible
because the unit is always full of liquid. In
the No. 2 digester, which is operated with a
vapor chamber, the corrosion is evident. The
possibility of using a different type material
for construction of the upper section is being
considered.
The scrubber for vented hydrogen chloride
vapors is a barrel-like structure made entirely
of wood and containing several perforatcd
plates.
Corrosive conditions in the preparation of
phenol derivatives arc met by the use of glass-
lined equipment and nickel-clad autoclaves. Stainless steel
equipment is used €or handling distilled amylphenols because
iron would cause discoloration of the product.
Some of the important pieces of cquipment along with the inn-
terials of construction arc listed in Tahlc V.
SAFETY
With' large quantities of flammablc, volatile, and skin-corrosive
materials as well as toxic gases to contend with, attention t o
safety is particularly important. Safety systems and devices
designed specifically for the process are found throughout thc
plant.
Fire prevcntion and fire fighting are planned in great detail.
All persons entering the plant are required to surrender matches
and smoking is not tolerated in any of the danger areas. Non-
sparking shoes are worn by all operators in the fire hazardous
areas; toe or heel plates are expressly prohibited.
Emergency steam hoses are located a t convenient points
throughout the plant. Ininiediatcly on spillage of any flammable
material, the area is blanketed with steam to prevent fire while
the material is being cleaned up. Instructions are issued to all
opwators pointing out the danger of throwing any clcctrical
switch in a n explosive atniospherc.
 1
December 1950 INDUSTRIAL A N D ENGINEERING CHEMISTRY
The pentane dehydration tank and the make-up tank are situ-
ated adjacent to each other in an area surrounded by a Transite
wall. The door to the area is kept closed a t all times, except
when an operator is inside. The entire area can be flooded with
live steam in event of a fire. The shed around the c o a l - h d pipe
still can also be flooded with steam in an emergency. Valves on
the steam lines to these zones are located away from potential fire
areas.
Wherever necessary, all vents carrying flammable vapors are
run to the outside of the buildings and are protected with flame
arrestors.
All motdrs and other electrical equipment are of explosion-
proof design when installed in any area where flammable vapors
might be encountered.
The two-story buildiiig housing the digesters and the alcohol
rectification units is equipped with one indoor and three. outdoor
slide poles for rapid exit. I n addition, the second floor is con-
nected by a walkway to an adjacent building.
A specially engineered 'fie alarm system (6A) is installed
throughout the plant with boxes located a t strategic points.
Employees are instructed to turn in as an alarm any emergency
which could lead to a fire.
Each storage tank for holding pentane received by tank car is
surrounded by a dike about 3 feet high. A fire fighting system,
controlled at a central station, is piped t o each of these dikes.
In the control house there is a mixing chamber which is con-
nected with a feed line from the plant water system; foam gener-
ating chemicals are available and can be added to the water a t
this point.
Operators who would be able to leave their production units in
an emergency are designated as members of the plant fire squad;
squad members participate in special training drills.
'I'
2399
At the first sound of the fire alarm, the plant water pressure is
immediately increbsed by the powerhouse. When the squad
member assigned to the foam generation unit is notified of a fire
in one of the dike areas, he opens the valve which feeds the dike
in t h a t area and dumps into the mixing chamber a 5-gallon can of
foam generating chemical. Several dikes in the adjacent areas
are also flooded with foam. The entire dike system is outlined
in colors on the wall of the fire control house with each dike area
painted a different color and the valve which feeds that dike area
painted the same color.
It is important in the Venturi mixing chamber, where pentane
and chlorine are combined under pressure, t h a t the pressures of
the two components are maintained in the proper relationship.
T o prevent. the entrance of chlorine into the pentane system, an
indicator light device is attached to the pentane feed chamber.
When the pressure is maintained at the proper level a green light
burns, an excessive pressure rise lights an amber light, And a red
light indicates a drop in the pentane pressure.
Respirators with cartridges for chlorine or hydrogen chloride
vapors are provided .at convenient points. Operators are re-
quired to wear a respirator when changing chlorine supply cars,
and gas masks with chlorine canisters are available in case of any
major leaks.
I n the derivatives processes, phenol, caustic, acetic and sulfuric
acids, as well as the various amyl compounds must be handled
safely. Rubber gloves and goggles are required attire when oper-,
ators are exposed to any of these skin-corrosive chemicals.
CONTROL
Two separate control groups are maintained a t the Wyandotte
plant. The regular control laboratory checks all raw materials
as well as some of the materials in process and finished products.
WATER
AMYLENE
AMYL CHLORIDE
AMYL MERCAPTAN
SERIES
 w

2400 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 12

The shipping control group checks all materials prior to shipping.
Although much of the routine process control testing is done by
the plant operators, there are analysts in the laboratory for each
shift.
Raw Materials. The boiling range is checked on samples from
each car of mixed pentanes received. Initial boiling point mu'st
not be below 27' C. and 95% of the sample must boil in the range
of 28" to 39' C.; final boiling point must not be above 40' C.
Infrared absorption analyses are made on every car for company
reference and for billing purposes.
UPPER SPECIFICATION L I M I T : * I I I *C.
by specific gravity measurement each time one is full. If the
specifications are not, met, the product is returned to the column.
At other points in the process a statistical study of the neces-
sary sampIing frequency has been made. I n several cases i t was
found that many more samples were being taken than were
actually necessary to keep the operation running within the con-
trol limits.
Customer Complaints. All complaints from customers are
reported to the control group by any employee who receives or
hears of them. Investigation is made immediately to assign
causes and make corrections. Record cards are kept on each
product showing complaints per lo00 shipments. By means of
control charts whose limits have been determined by statistical
study, the quality of the production and shipping techniques can

IO8 t be determined at a glance.

Complaint causes are also bioken down as to department, or
operation; this breakdown includes such classifications as pro-
cedure, operation, handling, carrier, and vendor. These data
are also subject to careful statistical study and are available to
0 top management in the form of regular reports.
0
3
0
- 0 ECONOMICS
102 0 The operation of the chlorination, hydrolysis, and esterification
units on a 7-day continuous schedule requires a total of 28 men,
rach norking an average of 42 hours pel week. For the produc-
tion of amylphenols, mercaptans, and naphthalenes an additional
28 operators are required.
Four shift superintendents working under an operations
manager provide night and week-end supervision for the plant.
I The entire plant is divided into three areas, each with its own day
1 2 4 8 1 2 4 8 1 2 4 8
AM PM AM supervisor. These area supervisors work only days but are on
-
TIME 24-hour emergency call. The shift superintendents are selected
on the basis of their previous operating and supervisory experi-
Figure 7. Sample Control Chart
ence; all have worked as operators themselves.
The cost distribution in the production of the chloride, alcohol,
and acetate is presented in Table VI. The value of the by-prod-
It is extremely important that the water content of the chlorine ucts is treated as a credit to the cost of raw materials, and starting
be controlled; specifications require this to be less than O . O l ~ o . materials which are produced a t the plant are charged a t factory
Samples from each car are analyzed by a gravimetric absorption cost.
technique.
Freezing point determinations are used to check the purity of
the incoming phenol, naphthalene, and acetic acid. Caustic TABLE
VI. COSTDISTRIBUTION
samples are titrated for sodium hydroxide content and the iodine (Cents per dollar of total cost)
number is run on samples of oleic acid. However, neither speci- Cost
fication is critical. Amyl Amyl Amyl
chloride alcohol acetate
Process Materials. As far &s is practical, all control testing is Raw material cost less
done in the plant at the site of the operation and by the operator. by-product credit 67 7SQ 91a
Laboratory equipment used in the plant has been modified and Direct labor and suudiea 20 12 4
Indirect labor and- Sup-
standard solutions adjusted so that the plant techniques and cal- plies 13 10 5
a Includes starting amyl compound at factory colt.
culations are relatively simple.
Control of the fractionating towers after the chlorination reac-
tion offers a good example of the type process control encountered
in the plant. The final vapor temperature of the first column is The direct labor and supplies include utility costs, operating
maintained at approximately 40 " C. Special control is exercised labor, maintenance labor and materials, and miscellaneous process
in column No. 3 to keep the final boiling point of the distillate lo~v supplies. Charges for indirect labor and supplies cover such
enough to prevent distillation of dichlorides. Control charts things as materials handling, control, shipping, and billing.
have been set u p plotting the fina1,boiling point against time; a Utility requirements for an average day of opelation are sum-
sample chart is shown in Figure 7 . The control limits have been marized in Table VII.
determined by a statistical analysis of data from several years of An indication of the amount of recycled material as well as the
operation. Although the upper specification limit is 111" C., total raw material requirements is given in Table VIII.
the control limit is 105" C. A sample of the distill&te is taken
every 4 hours. When the boiling point goes out of control, sam-
TABLE
VII. UTILITIES IiEQGIREhIEXTS
ples are taken as often as every half hour until changes in feed,
(Per day of operation)
reflux, or take-off correct the situation.
Amyl Amyl 4myl
T o make certain that all monochlorides are being distilled off, Chloride Alcohol Acetate
a sample is also taken from the bottom of the No. 3 column every Steam, thous. lb. 450 440 11s
2 hours. Initial boiling point of this sample must be above Water, thous. gal. 1000 700 540
Electricity, kw.-hr. 700 45 130
135' C. Coal, tons 3.8 , . . ...
The amyl chloride in the receivers from column 4 is analyzed
 L l l t i . H * T l l H E CII'EU

0 )A ~ I C Bii., I<.. I X D .l i x a . CMBM..

21, H!)Y
904 (1929).
(2) Ayrex, IC. E.. 1'. S. Pateiit 1,717,136
(1929).
I:j) ll,i,l,, l,U31,474 and 1,835,202 (1931).
(4) .AYlPS, I<. 13.. and 11aillrata,I. I:. I%..
IBid., 1,691,424 5 6 (1928j.
( 5 ) 130hnll. t i . .k,,Rt$,mr 'val,L7<il( h a o i 7 n r .
M / Y . . 11, 438-43 (1982).
( t i ! ('lark. L. H.. Ciism. and Mcd I l u g . , 38,
206~1 0 (1931).
( 7 ) ('lark. 1.. II., IN". END.(~IM., 22, 43'3
43 (1930).
(kjH,,,it. x.,
1'. Ibid., 35, 1 0 1 R 5 2
(1943).
(5)) Kiikpat,riok. Y. D., Chcm. a d M e t .
En@.,34, 276 9 (1Y2i).
i l o j Sharpies ('hemicais. Inc.. l ~ t i i l ~ d r l p l i i a .
.i,tbetio Ormriic Chemicals,"
1 5 l i i ~ &p.
. i. 1947.
i l l ) rbia., p. 15.
(12) !bid., I). 47.
(13) Zbid., P. 51.
Hatch Still for A lenhol Distillation (14) Zbid.. P. 95.

TABLE
VIII. HAW hIATERIAL ~tEQUrREMEsTs
!Fur 10.000 wunds of nroduot)
(10.2) \Vallaoe and Tierrwi, Newark. N. J.. high-cawaoity chlorine
rHwxssmC: EVuri'miwr
(1Aj Uow Clieniieui Co., Midland, hlich.. heat traaafer inedium,
Donthorn,.
(ZAj Fairbanks. Morse R; C u . , Chiexgo. Ill., reilroad track ecalou.
(3A) Fisher Goveinor <'<>.,hlaralridltown. Iowa. liquid-level contiel-
lers and traps.
(4A) Foxhro &., Y,,x'boro, Mass.. liguid-feed controllera.
(SA) (:anicwcll C"., Newton 1:pper Palls. Muss.. fire alarm aystpnis.
(IiA) Hnvey Corp., IVcst Newwk, Del., wid-resistant chemicd
eqiiipn*ont..
(i.4) Iron I,.iiemsn Mfg. Co.. I'mtland, Ore., w t o m a t i c coal
burlrels.
( S A ) I'fnudler Go.. Koohenter. N. Y., glass-lined equipnrcnt.
(9.4) Thcrmnl Syndioato. Ltd.. Now Yoik.'N. Y., Bull., 4. Vitvcoail
pas absorber..
flowmeter.

i i a c w r r i i Ootobei 23. 1950