Table Of Contentm rnm m tAM Zc cqjspow©
m i OH fUE VAPO&
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of the Graduate School
fulfillment of the requirements
fo r th e of Doctor of Philosophy
In€l ana llnlwr s 1 ty,
*
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work was carried out at the suggestion
and- with tha assistance o f Fr-o.fassor G* ¥*>. Brown*
without whose anoow^g-eisafit this work cotald not
haw been done*. B# has wp grateful appreciation*
11
tm iM of
mmwmm **. ' ***■*» * * * .* * * * * » * .* * * * ti
Iniro&u€tion* * * *. *. .* * * ,«. =*. * * * * • • * « « * 1
Foealble V ariable Factor* * „. * * . * * .* . * * * * 3
Measurement of tli# tempera tore*. * .* * * * » « * •*. * 3
SSeaswement of the Hate of Flow of B'ttrohenscm© •*. * 4
Measurement of the Hat® of Flow of the Hydrogen .* * 4
Preparation of the C atalyst ♦ * # * * * * • * * * * 5
Determin&tion of the Yield of Aniline *- * * * * -* * 6
Material* Used* «. * * * * * * * .. * * +. * * *. * + « 6
PrGoe&ure ;»• k»- * * m m ■»' <*> « * ■#• •• * >#- •* •*• <► ***. T
If foot of Variation of Temperature on the Yield of
Aniline-i* * *• •« *• * * * ♦• # * * *• * * #• .♦ * * ?
Ha tore of the r ochse t * #- #. « «. <* *: # « *- m- * * .# «■ 12
Sffeot of Varying the Hate of Flow of Hydrogen* * * 12
Kffeot of Varying the Rate of Flow of Hltrobenaene* 13
SonolyeioB® * * * « » * » *. ^ •*. .* .-#. * *• ♦ * * * * .» 14
BXBLXO^iA^Hf* * *■ * * <# •* * * * * * * * *: *r ■«■ * * * lb
ill
UBt of T m m s
■* . 10, 11
tv
1
m m tftfm activity m m znm nm m 'iM m oom m m n ow
OADOTUM GOFFER CM THE VAPOR Pil* 3E
Rsmjcfioif or h o tg m w i
Introduction
When a mixture o f ca ta ly sts is used* the resu lt
wmj be additive* to some cases* howror., a foreign sub
stance may pro-mote the a c tiv ity of a catalyst* I f a co
b a lt ca ta ly st contains .some nicies!* the speed is greatly
enhanced* When the net e ffe c t 1® greater than the sum
o f the independent e ffe c t# * It %& ca lled promoter action*
In other instances* the presence of a foreign substance
may poison a catalyst* toad and platinum f a ll into th is
category * mutually poisoning each other*
While .mixtures of catalysts have been studied*
an investigation of the literature rewaled that there
was no published data on the ua© of definite intermetal-
lie compounds as reduction catalysts in the vapor phase
with th© exception of the work reported by Brown* Bor-
1
land* Johnson, and G rills, who used the Inte metallic
compounds of thallium and lead* $XgPb* am thallium and
bismuth, fl^Bi* which they found to- possess in general
the same ca ta ly tic power as that of the components*
This paper deals with an invwstigation of the
use of an in te m eta l Ho compound of cadmium and copper,
^Brown, 0* W*., Borland* J* 3. * Job no on* 3* ,hj
and drills, R* C« J* Bars- Chem- 42 (1939).
2
In iba- vapor* phase reduction of nitrobenzene to
art! line * th e interm® i si 11 o compound ha© a maxi mzm free z*~
ins point of 3$5°®-** ithloh is much feller than that of
cadmium alone* The use of copper alone ms Investigated
by Brow tod Henke^ and th® most e ffic ie n t opera tin g
temperatur© was .found to be 260°,0,* -The us® of cadmium
alone was investigated by Brown and Hartman^ and the most
e ffe c tiv e o p eratin g tem perature was. found to be 319°G*
j t is th e object of th is in v estig atio n to de
term ine th® most e ffe c tiv e operating conditions fo r the
vapor phase reduction of nitrobenzene to a n ilin e w ith
the use of Cd^Ou^ as a catalyst* tod to compare th© re -
J> .<£
suit® obtained w ith those obtained when the individual
metals were used alone in order to ascertain whether the
compound acts in an additive manner, or w e th e r the m etals
promote or poison the a c tiv ity of each other*
Th® m aterial used and the general procedure were
essentially th® earn® as those used by Brown and Henke* Zi
S o w e r , a short vertical furnace used by Borland was
used instead of the horizontal furnace* 111 .Is fumaae
was constructed In a manner similar to tha h o rizo n tal
^Brown, 0. W», and Henke, 0. 0, jr. ffhyg* _CMa.
gj, (1928).*
3
Brown* 0.* W*, and Hartman, fl* 1* J* Pixy s.* Chcma
34 (1950).
*SBwww
4
Brown and.He-hk®. op* cit •
3
tmsmmtm and wm heated wlte chrome1 resistance wire* Tim
fmmm® mm 3® OS* tn height and had a volume- capacity of
#1 e&* In a fwiiaa# of this- type the ilsa of contact of
tee ftaMnis with the catalyst la shorter than that In
tee horizontal tmmmm*.
Feasible Variable Factors
Th® apparatus permitted the following variables
to be son trolled and altered independently of each other t
the temperature of the ga&eon® mixture in contact with the
catalyst! the rate of flow of the nitrobenzene; the rate
of flow of tee hydrogen! and tee compositions, amount* and
mode of preparation of the catalyst* In additions it
provided for a qimntIte ttv© reoept&em for the product so
that th© yield of -aniline in per cent of theory sou Id be
determined*
■Measurement of tee Temperature
The temperature was measured by mans of a copper-
00 net an tan couple* t be voltage being read by means of a
high resistance wlXlt*rol teeter* Th® thermo couple was
made by wrapping copper and ©onet&nten (advance) wire sep
arately wite tebes.te* eerd* after which they were wrapped
together with tee ©asbestos cord* The ends were then twisted
tin-* timM and stae* The temperature within the oats**
Iy#& chamber m mlabitei within a range of plus or
m$mm- 5°&* -of the €«irsd
Sfe&etireiBetrt of tee Hate of Flow of nitrobenzene
By mrnmrn of & c&liferated 111 liter pipette
tte nitteben mn® mm introduced into a tube sealed to a
aapiXI&ry tube* the pipette delivered under the eon&i**
ll<m# of the experiments &*-3908 grams of nitrobenzene *
The rate of flow was controlled by varying the height
of tee column of mercury which ms- inquired to f&ree- the
nitrobenzene through tee capillary tube at a sufficiently
rapid .rate*. When tee time Interval of 55 minutes was &m~
•ployed in the initial experiments ? for the comple tm dl&*
charge of tee Meters of nitrobenm oe into the
t umaee* the rate of flow- was 4*® grama per hour*
of tee Hate of Flow of tee Hydrogen
& flowmeter was u»d for the purpose of measuring
tee rate at- white tee hydrogen wan passed into tee fur*
naoe* This was calibrated e Imply h$ noting tee time re~.
qulred for tee displacement -of s3js liters of water from
a elae^Hter calibrated flaalc under conditio**© approximately
5
fee mmm mm fees© under white tto experiments were eon*-
tooted* Th» time ,,respired w&© w w W for four differ
ent tote© of flow and a graph mi aon-a true tod plotting
tea rate of flow in 11 tars par tour against the flow-meter
difference©*
Itopio*atism of tea Catalyst
-O-feemieally pwtm hydrated sulfates, of copper and
eadsslM awe dlasolwd together In fee ratio of feto# gram
atoms of cadmium for eaoh too grw atom of copper* the
tifdroxitos were preolplt&tea. by fe© addition of the ite-
onet leal quantity of a ■solution of sodium hydros Ida solu
tion* fhe praoipltete was iton was bed wife distilled water
fire timm& fay toe&ntetion and ftw Mme® throng m -3t*eto*p
funnel* It- was than dried-at H0°0* in an cnnm* Fifty-six
grams of tee dried hy&r oxides were placed In fee fiimaos
on a floor of copper, gaums* ffels was then lilted to
tee oxides at S50°-&*.-r after which It was reduced at 50O0G*.
to tee in term etallic ea^otmd Od^Ou.^* flile me thod of pre
paration is similar to feat found to to the most suitable
for fee preparation of the cadmium catalyst alone*
