Title: Reactions of butylamines over alumina catalysts
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Title: Reactions of butylamines over alumina catalysts
Physical Description: vi, 100 l. : ; 28 cm.
Language: English
Creator: Cobbledick, David Stanley, 1929-
Publication Date: 1957
Copyright Date: 1957
 Subjects
Subject: Chemical kinetics   ( lcsh )
Catalysis   ( lcsh )
Amines   ( lcsh )
Aluminum oxide   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis - University of Florida, 1957.
Bibliography: Bibliography: l. 97-98.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Bibliographic ID: UF00098021
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000423968
oclc - 11045975
notis - ACH2373

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REACTIONS OF BUTYLAMINES

OVER ALUMINA CATALYSTS










By
DAVID S. COBBLEDICK
jc (.


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY










UNIVERSITY OF FLORIDA
January, 1957














ACKNOWLEDGMENT


The author wishes to express his sincere appreoia-

tion to Dr. W. S. Brey, Jr., Co-Chairman of the author's

Supervisory Committee, ,under whose guidance and direction

this research was oonduoted. His knowledge of the field of

catalysis and his creative ideas were essential factors to

the suooess of this work. The author wishes to thank Mr.

0. A. Workinger for his advice on building the salt bath,

Mr. H. E. Wise for making the drawing of the apparatus,

and Mrs. Mary Joy Breton for typing the manuscript.

The author is indebted to the Researoh Corporation

for the support of this work.














TABLE OF CONTENTS


ACKNOWLEDGMENT . . . . . . . . .

LIST OF TABLES . . . . . . . . .

LIST OF FIGURES. . . . . . . . .

Section

I. INTRODUCTION . . . . . . . .

II. REVIEW OF PREVIOUS WORK .* . . . .

A. The Catalyst--Surface Area, Structure,
Activity, and Activation of Alumina .

B. The Reaction-Deamination of Butylamine
over Alumina. . . . . .

III. EXPERIMENTAL METHODS . . . . . .

A. Catalytic Reaction Runs. . .

B. Activation and Measurement of X-ray
Diffraction of the Catalyst .. .


IV. RESULTS. . . . . . . .

A. Presentation of Data .....

B. Discussion of Results. . .

V. SUI4MARY. . . . . .

APPENDIX . . . . . . . .

Part I. Per Cent Weight Determinations.

Part II. Material Balances. . ...

BIBLIOGRAPHY . . .. . . . .
BIOGRAPHICAL SKETCH. . . . . ..


* a .
* .


.

.

.





iii


Page

ii

iv

v



1

5


5


8

13

13


33

34

34

74

84

86

87

88

97
99

















LIST OF TABLES


Table Page
1. Wavelengths and Optical Densities. . .. 25

2. Reaction Runs with But7lamine, ........ 35

3. Reaction Runs with Dibutylamine. .. * o0
I. Ratios of Partial Pressures for Reaction (f) . 78













LIST OF FIGURES


Figure Page

1. Apparatus . . . . . . 14

2. Salt Bath . . . . . . . . 16

3. Conversion of butylamine to products as a
function of temperature over catalyst
A-2 activated at 5000 in a vacuum.
1/GSSV 11,2. . . * .* * * * 54

4. Conversion of butylamine to products as a
function of space velocity over catalyst
A-2 activated at 500* in a vacuum. Tem-
perature 4150. .* * * * a * * 55

5, Partial pressures of butylamine and products
as a function of space velocity over
catalyst A-2 activated at 5000 in a
vacuum. Temperature 415 . . .. 56

6. Partial pressures of dibutylamine and products
as a function of space velocity over cata-
lyst A-3 activated at 500* in a vacuum.
Temperature 425* . . . 57

7. Conversion of butylamine to products as a
function of space velocity over catalyst
A-2 activated at 5000 in a vacuum. Tem-
perature 400. 9 . . . . . 58
8. Partial pressures of butylamine and products
as a function of space velocity over cata-
lyst A-2 activated at 500* in a vacuum.
Temperature 4000 59
9, Partial pressures of dibutylamine and products
as a function of space velocity over cata-
lyst A-3 activated at 5000 in a vacuum,
Temperature 4100 9 a * 0 0 0 . 0 60













LIST OF FIGURES (Continued)


Figure Page
10. Conversion of butylamine to products as a
function of temperature over catalyst
B-2 activated at 800* in a vacuum.
1/GSSV 10.0. *. . . . . . .. 61

11. Conversion of butylamine to products as a
function of temperature over catalyst
B-2 activated at 800* in a vacuum.
1/GSSV 12.1. . . . . . . . . 62

12. Conversion of butylamine to products as a
function of space velocity over catalyst
B-2 activated at 800* in a vacuum. Tem-
perature 415*0. . * . . . 63

13. Partial pressures of butylamine and products
as a function of space velocity over
catalyst B-2 activated at 800 in a vacuum.
Temperature 415* * * * * 64

14. Conversion of butylamine to products as a
function of space velocity over catalyst
B-2 activated at 800* in a vacuum. Tem-
perature 4020. . . . . . . . 65

15. Partial pressures of butylamine and products
as a function of space velocity over cata-
lyst B-2 activated at 8000 in a vacuum.
Temperature 402o .. 66
16. Conversion of butylamine to products as a
function of space velocity over catalyst
B-3 activated at 800 in the presence of
water vapor. Temperature 415 . . 9 67

17. Partial pressures of butylamine and products
as a function of space velocity over cata-
lyst B-3 activated at 8000 in the presence
of water vapor. Temperature 415. e * 68














SECTION I


INTRODUCTION

The rates of a great many chemical reactions have

been found to be influenced by solid surfaces, which are

said to catalyze the reaction. This investigation is con-

cerned with the course of a particular group of related

reactions--those in the transformation of primary and

secondary amines--at the surface of aluminum oxide cata-

lysts, and with the manner in which the course and rate

of reaction are related to the structure of the solid.

The general picture of the function of a solid

catalyst is that only by virtue of the formation of a

chemisorbed layer are one or more reactants brought into

a more highly reactive state than that possible in the gas

phase under the same conditions of temperature and pressure.

The effective catalyst unit may be thought of as a small

group of neighbor or near neighbor atoms, whose configura-

tion or properties are such that they exert the requisite

forces on the reactant, assisting the breaking of some bonds,

and--by orienting the reactants on the surface so that the

atoms required for the reaction products are in close

proximity--the formation of other bonds.












The surface of the solid is obviously a very im-

portant factor in the effectiveness of the catalyst since

the reaction takes place at the solid-gas interface. Several

features of the surface nature of a solid catalyst which are

important are the surface area, pore structure, lattice

spacing on the surface, and unsatisfied valence forces*

The area of surface exposed to reactant molecules and the

quantity of reactant molecules converted to products show

a direct relationship. The influence of the surface area

is, however, often masked by other factors such as pore

size and lattice spacing on the surface. Small pores ap-

pear to have different catalytic properties, due to their

control of the partial pressure of the reactant molecules

in the inner pore recesses. Reactant molecules partially

trapped in the small pores may pass through a series of

reactions while reactant molecules on the surface pass

through only one or two reactions. The lattice spacing

or the geometry of the surface of a solid and the unsatis-

fied valence forces determine the forces of attraction of

different catalyst atoms for the various parts of the re-

actant molecules. As such forces only operate over short

distances, the interaction is largely deteznined by the

relative spacing of surface and reactant atomse The sur-

face may also show so large a variation in properties from











point to point that only a small fraction of the total

surface is catalytically active.

This study was undertaken with the purpose of

determining the products of the reaction of n-butylamine

over alumina at elevated temperatures, of finding how

changes in the structure and surface area of the alumina

influence the activity of the alumina as a catalyst, and

of studying the kinetics of the reaction of n-butylamine

over alumina. Because of the absence of water in the

reaction, it was thought to be a suitable reaction for

studying the effects of the amount of water in the sur-

face of the alumina on the activity of the alumina as a

catalyst.

The catalytic reaction of n-butylamine over alumina

has not previously been extensively studied. The first step

in the investigation was the study of the path of the reac-

tion in order to establish what significance the observed

quantities of the various products obtained in the reaction

have as a measure of catalytic activity.

The properties of the alumina were varied by thermal

treatment at 500 and 8000 both in a vacuum and in the

presence of water vapor. The form of the solid used was


aAll temperatures in this and the following sections
are given on the Centigrade scale, unless otherwise desig-
nated.








4
identified by mean of X-ray diffraction measurements,










SECTION II


REVIEW OF PREVIOUS WORK

A. The Catalyst--Surface Area, Structure,
Activity, and Activation of Alumina

The variation in surface area of alumina with in-

creasing temperatures of activation has been studied by

Krieger (13), Boreskov, Dzis'ko, and Borisova (1), Boreskov,

Dzis'ko, Borisova, and Krasnopol'skaya (2), and Brey and
Krieger (4). It was found that for temperatures of acti-

vation not exceeding 6000 the surface area is essentially

constant. Further increase of the temperature of activa-

tion to 7500 decreases the area by nearly 15 per cent while
heating to 950* further decreases the area by nearly 40 per

cent. Boreskov, Dzis'ko, Borisova, and Krasnopol'skaya at-
tributed the decrease in area for temperatures of activation

above 6000 to the disappearance of narrow pores.

Changes in the crystal structure of alumina with

increasing temperatures of activation have been studied by

means of X-ray diffraction measurements by Brey and Krieger

(4), and Boreskov, Dzis'ko, Borisova, and Krasnopol'skaya
(2). It was found that samples activated between 5000 and
9000 consist of gamma alumina. Samples activated at 10000











are partially converted to the alpha form while higher tem-
peratures of activation result in larger conversions to the

alpha form.
The variation of the activity of alumina with changes

in surface area and with increasing temperatures of active.

tion has been studied. One of these studies was that by

Brey and Krieger (4), who measured the activity of samples

of alumina activated by heating in a vacuum and in the
presence of water vapor at temperatures between 500 and

10000 for the dehydration of ethanol at reaction tempera-

tures of 350 and 500. The surface area of the samples
of alumina was determined by absorption of nitrogen at

liquid nitrogen temperatures. They found that both total

activity and specific activity decrease as the temperature

increases above 600. Heating in the presence of water

vapor induces an additional loss of area and activity as

compared with heating in a vacuum, but specific activity

of the surface is nearly independent of water vapor.
Another investigation of the variation of activity

with activation conditions is that of Boreskov, Dzis'ko,

Borisova, and Krasnopol'skaya (2), who compared the activ-

ity and surface area of samples of alumina activated at

450, 6000, 800, 1000, and 1200 for the dehydration of
ethanol. They found that activation at higher temperatures

decreases the total activity; however, the specific activity











increases even after heat treatment at 1000.0 After heat

treatment at 12000, the specific activity decreases markedly

and the catalyst becomes mainly dehydrogenating. These re-

sults indicate that the specific activity of gamma alumina

does not depend on heat treatment up to 10000. The apparent

rise is due to the disappearance of small pores which were

inaccessible to reactant molecules but which were accessible

to the molecules used for determining the surface area.

The variation of activity with crystallite size and

with surface area has been studied by Rubinshtein, Vasseberg,

and Pribytova (16), Three forms of alumina of different

grain size were prepared and their activity for the dehy-

dration of ethanol measured. The linear dimensions of

the crystallites were less than 35, 35, and 51.4 A and the

coarsest form was found to be the most active. The surface

areas determined by the B. E. T. method by adsorption of

methanol vapor at 250 were the same for all three forms.

The surface areas determined by the adsorption of CHIa

were quite different and were found to be directly pro-

portional to the crystallite size. It was concluded from

these results that portions of the surface, especially in

fine pores, which are easily accessible to methanol, are

not accessible to the larger CHIs molecules. This shows

that the surface area of a catalyst is a function of the

size of the molecules with which that surface area is










8
measured, and that the lower activity of the finer forms of
the alumina is due to the presence of finer aicropores

which are useless for the dehydration of ethanol.

B, The Reaction-Deamination of
Butylamine over Alumina

The only literature reference to the reaction of

butylamine over alumina is a Dutch patent (15) on the pro-
duction of secondary aliphatic or eyoloaliphatic amines from
primary aliphatic or cycloaliphatio amines. According to
the abstract of this patent, liquid butylamine was mixed
with ammonia in the mole ratio 2:1 and passed over alumina

at 3500 and a total pressure of 20 kg./sq. m,. at a rate
of 100 cc. liquid butylamine/liter of catalyst/hour. It

was found that for each 100 moles of butylamine, 34 moles

were converted into 2-aminobutane, three moles into butene
and ammonia, three moles into other products of dissociation,

and 60 moles remained unchanged. The alumina used for this
reaction was activated at 500 for three hours.

The decomposition of ethylamine over kaolin at 500,

7000, and 10000, and the decomposition of propylamine over
kaolin at 700 have been studied by Upson and Sands (18)
but only in a qualitative manner. It was found that the
chief products formed by the decomposition of ethylamine
at 500* are ammonia, hydrogen cyanide, ethylene, and a











substance which is probably acetonitrile, together with

smaller quantities of hydrogen and nitrogen. At 7000 more

ethylene is formed and no hydrogen cyanide. At 10000 the

chief products were the elements, although traces of ethylene

and probably aoetonitrile are formed. Propylamine at 7000

gives chiefly a nitrile, ammonia, carbon and hydrocarbons,

together with small quantities of hydrogen cyanide and the

elements.

The reactions in the systems methanol-ammonia,

ethanol-amonia, butanol-ammonia, and 2-amino-2-methyl-

1-propanol over alumina have been studied. The reactions

in the systems alcohol-ammonia result in the formation of

mono-, di-, and trialkylamines and are of interest due to

this fact.

The first work done on the reactions in the systems

alcohol-ammonia was that by Sabatier and Mailhe (17). It

was found that a mixture of mono-, di-, and trialkylamines

is formed by passing the vapor of an alcohol with ammonia

over a variety of catalysts, including alumina, at elevated

temperatures.

Brown and Reid (6) studied the alkylation of ammonia

by methyl, ethyl, n-propyl, and n-butyl alcohols by passing

their vapors with ammonia over a variety of catalysts, one

of which was alumina, between 3000 and 5000. It was found

that a mixture of mono-, di-, and trialkylamines is formed.











Butyl alcohol and ammonia in the ratio of 1:1.5 moles re-
spectively were passed over alumina at 3600 at a rate of
one mole of the alcohol per 5.6 hours and it was found
that 6.55 moles of amines were produced for every 100 moles
of butyl alcohol passed over the catalyst.
Dorrell (9) studied the reaction in the system
ethanol-ammonia over alumina, varying such factors as
temperature, time of contact, and the ratio of alcohol to
ammonia. Change of these variables was compared to the
per cent conversion to ethylamine. It was found that in-
creasing the temperature of the catalyst bed from 239* to

2930 results in an increase in per cent conversion to

ethylamine while increasing the temperature from 2930 to

344* results in a decrease. Increasing the time of con-
tact does not, under all conditions, increase the per cent
conversion to ethylamine as expected, and Dorrell concluded
that the most probable cause of this is the decomposition of
the ethylamine. Increasing the ratio of alcohol to ammonia
results in an increase in the quantities of di- and tri-
ethylamines formed.
Breiner and Gandillon (3) studied the reaction in
the system methanol-ammonia over alumina in order to obtain
mines in a simple and more direct manner and to learn more
about contact catalysis in dehydration. A mixture of mono-,
di-, and trimethylamines was obtained under all experimental









11

conditions, and, where the total yield of amines was small,

monomethylamine was the main product. A stepwise path was

indicated due to the rapid conversion of dimethylamine to

trimethylamine when the ammonia was replaced by monomethyl-

amine or dimethylamine. The optimum temperature was about

460. Increasing the ratio of alcohol to ammonia and de-

oreasing the time of contact resulted in decreased yields

of amines.

Egly and Smith (10) made an extensive study of the

effects of operating variables on the reaction in the system

methanol-ammonia over alumina to form a mixture of mono-,

di-, and trimethylamines. The effects of changing pressure,

temperature, and space velocity upon the per cent conver-

sion of methanol and ammonia to mono-, di-, and trimethyl-

amines were determined.

Egly and Smith found that as the temperature is in-

creased at a constant space velocity the per cent conversion

to monomethylamine increases, passes through a maximum, and

then decreases. As the per cent conversion to monomethyl-

amine decreases, the per cent conversion to trimethylamine

increases. Further increase of the temperature at constant

space velocity causes the per cent conversion to trimethyl-

amine to pass through a maximum and then decrease. This

result was attributed to cracking of the trimethylamine

molecules. Decreasing the space velocity or increasing









12
the contact time at a constant temperature was found to give

similar results. As the apace velocity is decreased, the

per cent conversion to monomethylamine either reaches a

maximum or passes through a maximum and then decreases, de-

pending on the temperature. At temperatures where the per

cent conversion to monomethylamine passes through a maximum

and then decreases, the per cent conversion to trimethyl-

amine increases.

Clarke, O'Leary, and Karabinos (8) studied the re-

action of 2-amino-2-methyl-l-propanol over alumina at 3000.

The chief products formed were ammonia, isobutylene, iso-

butylidene mine, isobutylamine, diisobutylamine, and

2,2,5,5-tetramethyl-3,6-dihydroxypiperazine, the diner of
2-amino-2-methyl-l-propanol. A mechanism for the reaction

was proposed which indicated that deamination, amination,

dehydrogenation, and hydrogenation ooour as well as de-

hydration.













SECTION III


EXPERIMENTAL METHODS

A. Catalytic Reaction Runs


1. Apparatus

The arrangement of the apparatus used in the

butylamine and dibutylanine decomposition runs is shown

in Figure 1. The feed material was contained in a 500 ml.

separatory funnel, A, from which the liquid was fed by

means of a finely grooved stopcock, B, through a section

of the feed system, C, which was maintained at a tempera-

ture of 30,00 by means of a water Jacket. The liquid from

the feed system passed through the flowmeter, D, which was

maintained at 30.00 by means of a water Jacket, and into

the delivery tube, from which the liquid was fed into the

first arm of the reaction tube.

The reaction tube, E, was made from 17 mm. heavy-

walled Pyrex glass tubing and was immersed in the salt bath,

G. The reaction tube was bent into the shape of a double

"U" in order to fit into the salt bath. The first "U" por-

tion was packed with glass helices to preheat the amine to
reaction temperature. The first arm of the second "U" por-

tion served as the reaction chamber. This arm was 16.5 cm.











FIGURE I- APPARATUS









15

in length and was equipped with a thermocouple well, F, and

a porous porcelain plug which supported the catalyst bed.

The salt bath, G, was made from a section of quarter-

inch wall iron tubing 13 in, in length and 5 in. in diameter.

The salt bath was supported by an iron panel box the dimen-

sions of which are given in Figure 2. A flat cover plate

was welded to the bottom of the iron tube and a large square

plate with a 5 in, circular hole was welded to the top of the

tube. This flange had a rim attached to its edge so that it

rested snugly on top of the box. The salt mixture was com-

posed of 53 per cent potassium nitrate, 17 per cent sodium

nitrate, and 30 per cent lithium nitrate.

The temperature of the salt bath was controlled by

connecting a chromel-alumel thermocouple immersed in the

bath with a model 234 Wheelco Proportioning Capacitrol.

This instrument, connected in series with the heater,

automatically controlled the temperature of the salt bath

to any desired temperature setting of the instrument within

a range of 20. The thermocouple and lead wires were enclosed

in a Pyrex protecting sheath in order to prevent deteriora-

tion of the couple.

The temperature in the reaction chamber was read by

connecting a chromel-alumel thermocouple inserted in the

thermocouple well, F, with the model 234 Vheelco Propor-

tioning Capaoitrol. The thermocouple terminals of this













FIGURE 2 SALT BATH


S*- 11.


To Temperature Controller










17

instrument were provided with a throw switch which made it

possible to connect the leads from either the couple in the

bath or that in the well.

The delivery tube fed the liquid into the first

"U" portion of the reaction tube where it was vaporized,

brought to temperature, and passed through the reaction

chamber. The vapor issuing from the second "U" portion of

the reaction tube passed over the condenser, H, which was

maintained at a temperature of 0, where the condensible

products were separated and collected in the receiver, I.

The gaseous products passed through the side arm, J, and

were led to a two-way stopcock, K, which could be adjusted

to divert the gas stream to receiver L or L' from which it

passed through a wet-test meter, M, into a sampling bulb.

The sampling bulb was connected to a Fisher Gas Analyzer,

No. 10-600-4.

2. Calibration of Flowmeter

The flowmeter used for the runs was an Emil Greiner

flowmeter, Cat. No. G-91i2. It was calibrated for butyl-

amine and dibutylamine at 30.00 by passing the amines

through the flow system at various flowmeter readings and

collecting the samples in volumetric flasks. Because of

the volatility of the butylamine, the samples were collected

at 00 and the volume was then corrected to 30.0 by applying










18
the correction for cubical expansion. The volumes at 30.0
were divided by the time of flow in minutes to give the

flowrate in milliliters per minute of the liquid. The

range of feed rates obtainable, using both sapphire and

steel rotors, was from about 0.434 to 1.97 ml. of liquid

per minute. Reproducible results were obtained as long as

the flow system was filled with liquid but the reproduci-

bility of feed rates after emptying the flow system and

cleaning it was not good. In order to avoid uncertainty

in the feed rate, the flowmeter was recalibrated before

every run or set of runs.

3. Materials
The butylamine and dibutylamine were Eastman Or-

ganic Chemicals, White Label Grade. These materials were
found to contain small quantities of water and were dried

over potassium hydroxide and distilled before being used.

The catalyst material used was taken from one large

quantity of Alcoa Activated Alumina, grade F-10, obtained

in the form of granules of 8 to 14 mesh size. The catalyst

batches were treated before use by heating in vacuum or in

the presence of water vapor. The alumina was placed in a

quartz tube and heated in a furnace with heat control and

temperature measurement like that used for the salt bath.













4. Reaction Run Procedure
Twenty-five grams of activated alumina was placed

in the reaction chamber of the reaction tube. The salt in

the bath was melted, the reaction tube placed in the molten

salt bath, and the bath heated 100 above the temperature at

which it was desired to make a run. The delivery tube and

condenser, H, were connected to the reaction tube, and the

three-way stopcock, N, in the delivery tube was adjusted so

that the flow system was shut off from the reaction tube.

A mechanical vacuum pump was attached to the side arm of

the condenser and the reaction tube evacuated and filled

with argon by means of the three-way stopcock, N, The

salt bath was then allowed to cool to the desired tempera-

ture, the feed system filled with the amine, and the side

arm of the condenser attached to receiver L. The stopcock,

N, was opened to the reaction tube, and the amine passed

through the reaction tube over the activated catalyst.

The first portion of the products was passed

through receiver L until the system had come to thermal

equilibrium. This was done in order that liquid hold-up

in the reaction chamber might come to a constant value,

and to permit the water in the wet-test meter to come to

equilibrium with the exit gas. Stopcock H was then adjusted

to pass the gaseous products through receiver L', and












receiver I was replaced by a graduated receiver. The

products were collected for a timed period, and simul-
taneously the volume of gas was measured by the vet-test

meter and a sample was withdrawn for analysis. The products

in receivers I and L' were then analyzed by the procedures

described in Section 6 below. At the conclusion of each

run the volume of condensible products and the volume of

gas measured by the wet-test meter were recorded, and the

reaction tube evacuated and filled with argon by a proce-

dure similar to that used before starting the initial run.

In many eases several runs were made without dis.

connecting the system. During such a series, either the

feed rate or the temperature was changed between runs.

After the last run of the set, the reaction tube was

evacuated and filled with argon as described above. The

delivery tube and condenser were then disconnected from
the reaction tube and the latter removed from the salt

bath and flushed out with argon while cooling.

5. Separation and Identification of Products

Seven preliminary runs were made with butylamine

over a sample of alumina, which had been activated at 5000
in a vacuum, in order to find out what products were formed
in the reaction. These runs were made between 4150 and 4L8











at a reciprocal space velocity of 11.2. In these runs

the receivers, L and L', were traps cooled in a Dry Ice-

acetone mixture, rather than containers for sulfuric acid

solutions as in the standard procedure adopted in later

works

An infrared spectrum was obtained for the condemn.

sible products collected in the receiver, I, and then these

products were separated as well as possible by fractional

distillation. The infrared spectrum of the first fraction

between 770 and 780 was identical with that of the feed

material. After removal of the unreacted butylamine, the

distillate was collected in 50 fractions up to 180. The

infrared spectrum of the fraction between 1150 and 120

indicated that this fraction contained butyronitrile. The

infrared spectrum of the fraction between 155 and 1600

indicated that this fraction contained dibutylamine and
N-butylidenebutylamine. Infrared spectra were run on the

pure compounds for comparison. Butyronitrile was prepared

according to the procedure of Jeffery and Vogel (12). N-

butylidenebutylamine was prepared according to the procedure

of Campbell, Sommers, and Campbell (7). In addition to the


The reciprocal space velocity was computed by
dividing the total volume of the catalyst bed by the volume
of gas at standard conditions equivalent to the amount of
amine fed per second.









22

unreacted butylamine, dibutylamine, N-butylidenebutylamine,

and butyronitrile were identified. The absorptions of these

compounds, together with the absorption of butylamine, ao-

counted for the spectrum of the products before separation.

The spectrum of the residue from the distillation

showed, in addition to traces of dibutylamine and N-butyl-

idenebutylamine, another compound or compounds which did

not appear in the spectrum of the condensible products

before distillation. According to Emerson, Hess, and

Uhle (11) pure N-butylidenebutylamine dimerizes when

refluxed between 140 and 150. The infrared spectrum

of N-butylidenebutylanine which had been refluxed for

two hours was almost identical with the spectrum of the

residue. This accounts for the presence of the additional

compound or compounds not found in the spectrum of the con-

densible products before distillation.

The products collected in the Dry Ice traps sepa-

rated into two distinct layers. The infrared spectrum of

the products collected during the first run indicated the

presence of ammonia and unsaturated hydrocarbons. The

volatile products obtained from the third run were passed,

in turn, through a saturated solution of sodium chloride,

a drying tower, and Dry lee traps. An infrared spectrum of

the products collected in the Dry Ice traps indicated that

the unsaturated hydrocarbons were probably 1-butene and









23

ethylene. The ethylene appeared to be present only in trace
quantities. The mixture in the traps was brominated and

1,2-dibromobutane was separated and identified by its boiling

point and refractive index. The dibromo- derivative of

ethylene could not be separated.

The saturated solution of sodium chloride was made

acidic by the addition of 6M HC1, evaporated almost to dry-

ness, and cooled down to room temperature, and a saturated

solution of sodium hydroxide added until the solution was

basic. This solution was heated to 95e with constant stir-

ring and the gas evolved passed, in turn, through an ice

trap, a drying tower, and Dry Ice traps. The infrared

spectrum of the products collected in the Dry Ice traps

was identical with that of ammonia.

The gaseous products obtained from the seventh

run were passed first through concentrated sulfuric acid

and then into the Dry Ice traps. No liquid condensed in

the Dry Ice but, after warming the traps and forcing the

gas into an infrared gas cell, a spectrum was obtained

which was identical with the spectrum of ethylene.

In addition to ammonia, 1-butene, and ethylene,

which accounted for the spectrum of the gaseous products

from the traps before separation, hydrogen and methane

were also identified by Orsat analysis of the gases col-

lected in the sample bulb. The separation and identification











of methane is described in Section 6 below,

Three preliminary runs were made with dibutylamine

over a sample of alumina which had been activated at 5000

in a vacuum. These runs were made between 4150 and 438 at

a reciprocal space velocity of 11.2. The procedure and ap.

paratus used for these runs were the same as those described

for the preliminary runs with butylamine.

The products from these runs were separated and

identified by procedures similar to those used for separating

and identifying the products from the butylamine runs. The

same compounds were identified and no additional compounds

were found,

6, Analytical Methods

(a) Analysis of condensed products.*-Two infrared

cells were cleaned and calibrated by measurement of their

interference patterns. The cell lengths were found to be

0.0270 and 0.0512 mm., and the former will be referred to

as the "standard" cell.

The infrared spectra of butylamine, dibutylamine,
N-butylidenebutylamine, and butyronitrile were run and the

wavelengths suitable for use in quantitative analysis were

chosen. These wavelengths were chosen such that the opti-

cal density of only one of the components of the reaction

mixture was large and those of the other components were









25

small. The wavelengths and optical density of each compound
with the standard cell filled with the pure liquid are re-
corded in Table 1.

TABLE 1
WAVELENGTHS AND OPTICAL DENSITIES

Butyro- N-butylidene- Butyl- Dibutyl-
nitrlle butylamine amine amine

4.4A 0.571a 0.017 0.010 0.018
5.96"< 0.027 2.000a 0.120 0.016

6.23~ 0.023 0.050 0.4101 0.025
8.8y7 0.025 0.235 0.235 1.160a

Characteristic band


Eight synthetic mixtures of known weights, four con-
taining butylamine, dibutylamine, and N-butylidenebutylamine,
and four containing all four compounds, were prepared and
analyzed. The results are tabulated in the appendix.
The fraction of the total volume of each of the
above compounds in the synthetic mixtures was calculated
by means of a series of successive approximations from
values in the table above by the following procedure. It
was found that, because of a shift in the base line, 0.011
and 0.014 had to be added to the optical densities at 4.40
and 6.23/ respectively. The optical densities at these









26
wavelengths after adding the correction will be referred to
as the "corrected" optical densities.
The corrected optical density at 4,40 was divided
by the optical density of pure butyronitrile at 4.404 and
an approximate value of the fraction of the total volume
which was butyronitrile was obtained. This value was then
multiplied by the optical density of pure butyronitrile at

5.96, 6.23, and 8,87/ and these values subtracted from
the optical density at these wavelengths. The optical
density at .596, minus the value due to butyronitrile,
was divided by the optical density of pure N-butylidene-
butylamine at 5.96/ and an approximate value of the
fraction of the total volume which was N-butylidenebutyl-
amine obtained. This value was then multiplied by the
optical densities of pure N-butylidenebutylamine at 4. 0,
6.23, and 8.87P and these values subtracted from the
optical density at these wavelengths. The corrected op-
tical density at 6.23# minus the values due to butyro-
nitrile and N-butylidenebutylamine, was divided by the
optical density of pure butylamine at 6.23j1 and an approxi-
mate value of the total volume which was butylamine obtained.
This value was then multiplied by optical densities of pure
butylamine at 4.40, 5.96, and 8.87w and these values sub-
tracted from the optical densities at these wavelengths.
The optical density at 8.87/, minus the values due to









27
butyronitrile, N-butylidenebutylamine, and butylamine, was
divided by the optical density of pure dibutylamine at
8.87< and an approximate value of the total volume which
was dibutylamine obtained. This value was then multiplied
by the optical densities of pure dibutylamine at 4.4o0

5.96, and 6.234, and these values subtracted from the op-
tical densities at these wavelengths.
The second approximation was calculated as follows.
The corrected optical density at 4.40< minus the values
due to N-butylidenebutylamine, butylamine, and dibutylamine,

was divided by the optical density of pure butyronitrile at

4.404 and a new approximation of the fraction of the total
volume which was butyronitrile obtained. This value was then
multiplied by the optical density of pure butyronitrile at

5.96, 6.23, and 8.87/- and these values subtracted from the
optical density at these wavelengths. The optical density

at 5.96- minus the new value due to butyronitrile and
the values due to butylamine and dibutylamine, was divided
by the optical density of pure N-butylidenebutylamine at

5.96/ and the same procedure followed as used previously.
These successive approximations were repeated until dupli-
cate results were obtained. Three successive approxima-
tions were usually found to be sufficient.
In the absence of butyronitrile, the fraction of
the total volume of each of the compounds in the synthetic











mixtures was calculated by the same procedure as used
previously except the successive approximations began with

the optical density at 5.96r characteristic of N-butyl-

idenebutylamine.
The number of milliliters of each of these com-

pounds was calculated from the total volume and the frac-
tion of the total volume of the compound. The weights and

numbers of moles of the compounds were calculated from the

numbers of milliliters, densities, and molecular weights

of the compounds.

(b) Analysis of gaseous products.--The gaseous

products were analysed by first removing the ammonia and

any condensible products swept over during a run from the

gases by absorption in a known volume of a sulfuric acid

solution of known strength contained in receiver L'. The
sulfuric acid solution was then back titrated with sodium

hydroxide and the moles of base collected during a run in
receiver L' calculated. The gaseous products, after the

removal of ammonia and any condensible products, consisted

of 1wbutene, ethylene, and hydrogen, and were analyzed by

the following procedure.

The per cent by volume of each of the gaseous

products was determined by analyzing a 100 ml. sample of

the gases in an Orsat type gas analyzer. 1-Butene and

ethylene were determined by absorption in an 87 per cent











solution of sulfuric acid and a 22 per cent solution of

sulfuric acid containing 57 ns,. of mercuric sulfate per

200 gas. of 22 per cent sulfuric acid, respectively (5 and

14). Hydrogen was then determined by passing the gases
over copper oxide at 300* and noting the decrease in volume

due to formation of water. The difference between the

initial volume and the volume remaining after the removal

of hydrogen was found to be the per cent by volume of

methane. Methane was identified by oxidizing the saturated

hydrocarbon left, after the removal of hydrogen, by passing

a mixture of the hydrocarbon and oxygen over a hot platinum

wire, From the decrease in volume because of the formation

of water and the volume of carbon dioxide produced, the

saturated hydrocarbon was identified.

The individual volumes of 1-butene, ethylene, hydro-

gen, and methane were calculated from their per cent by

volume and the volume of the gaseous products which passed

through the wet-test meter. The numbers of moles of 1-

butene, ethylene, hydrogen, and methane were calculated,

assuming ideality, from their volumes, temperature, and

pressure.

(c) Calculations based on extended analysis.-.Eight

runs were made with butylamine over a sample of alumina

which had been activated at 5000 in a vacuum and the products

analyzed and material balances obtained. These runs were











made between r 15* and 430o at several flow rates.

The procedures used for analyzing the condensible

products collected in receiver I and the gaseous products,

after removal of amonia and any condensible products,

were those previously described in parts (a) and (b) re-

spectively. The base collected in receiver L' consisted

of ammonia and any condensible products which were swept

over during a run. Butylamine is the only condensible

product which has an appreciable vapor pressure at 0%,

the temperature at which the condenser, H, was maintained,

and as a result it was assumed that butylamine was the only

condensible product swept over. The number of moles of

butylamine swept over was calculated, assuming ideality,

by the following procedure. The number of moles of gaseous

products which passed through the wet-test meter was cal-

culated from the volume, temperature, and pressure. The

number of moles of base collected in receiver L' plus the

number of moles of gaseous products passed through the wet-

test meter was taken as the number of moles of gas passing

through condenser H. This figure was multiplied by the

vapor pressure of butylamine at 00 and then divided by the

barometric pressure to obtain the number of moles of butyl-

amine swept over. The number of moles of ammonia collected

in the trap, L', was calculated by subtracting the moles of

butylamine swept over from the moles of base collected.









31
The total number of moles of butylamlne unreacted

during the butylamine runs or the total number of moles of

butylamine produced during the dibutylamine runs consists

of the sum of the number of moles collected in receivers

I and L'.
The number of moles of ammonia dissolved in the

condensible products during a run was calculated by the

following procedure. The total moles of butylamine, di-

butylamine, N-butylidenebutylamine, and butyronitrile and

the moles of ammonia collected in receiver L' were added

together and subtracted from the moles of butylamine

passed over the catalyst during a run. This difference

was assumed to be ammonia dissolved in the condensible

products since no nitrogen was found in the gaseous

products. The weight of ammonia in the condensible

products was calculated from the number of moles dis-

solved and its molecular weight.

The amount of 1-butene dissolved in the conden-

sible products during a run was calculated by the following

procedure. The number of milliliters of condensible products

collected in receiver I was multiplied by the density of the

condensible products and the total weight obtained. The

weights of the butylamine, dibutylamine, N-butylidenebutyl-
amine, butyronitrile, and ammonia present in the condensible

products were subtracted from the total weight and the









32
difference assumed to be 1-butene dissolved in the conden-

sible products.

The material balances obtained for these eight runs

were found to be very satisfactory and the results are tabu-

lated in the appendix.

(d) Analysis based on material balanoes.--Using the
data from these same eight runs, it was found that satis-

factory material balances substantially equivalent could be

obtained without carrying out the gas analysis. The calcu-

lations of the amounts of products were then modified as

follows.

The condensible products collected in receiver I

were analyzed by the procedure previously described in

part (a). The total number of moles of butylamine un-

reacted or produced during a run was calculated by the

procedure previously described in part (c). The total

number of moles of anmonia produced during a run was cal-

culated by a nitrogen balance by the following procedure.

The numbers of moles of butylamine, dibutylazine, N-butyl-
idenebutylamine, and butyronitrile were added together and

subtracted from the moles of butylamine passed over the

catalyst during a run; the difference is the number of

moles of ammonia produced.

The total number of moles of 1-butene produced

during a run was calculated by a "butyl radical" balance










33
by the following procedure. The total moles of butylamine,
the moles of dibutylamine and N-butylidene multiplied by

two, and the moles of butyronitrile were added together

and subtracted from the moles of butylamine passed over

the catalyst during a run; the difference is the number

of moles of 1-butene produced.

The number of moles of hydrogen produced during a

run was calculated by multiplying the moles of butyronitrile

by two and adding to this the moles of N-butylidenebutyl-

amine.

B. Activation and Measurement of X-ray
Diffraction of the Catalyst

The samples of alumina were activated by heat

treatment at 500* and 8000 for about 48 hours either in

a vacuum or in the presence of water vapor. The alumina

was placed in a quartz tube, heated the prescribed length

of time in a pot furnace, and then bottled.

The form of the activated alumina was investigated

by means of a North American X-ray diffraction recording

spectrophotometer. The radiation used was produced by a

copper target with the X-ray tube operating at 35 kilovolts
with a current of 15 milliamperes. The samples, ground to

pass through a 200 mesh screen, were mounted in a thin film

on a plastic holder.














SECTION IV


RESULTS

A. Presentation of Data
The operating conditions and results of the reaction

runs of butylamine and dibutylamine are presented in Tables

2 and 3 respectively. Catalyst A and B are the oatalysts

activated at 5000 and 8000, respectively. Some of the

figures in the tables require explanation. Column (9) is

a reoiprooal space velocity, computed by dividing the total

volume of the catalyst bed by the volume of gas at standard

conditions equivalent to the amount of amine fed per second.
Column (14) gives the weight of the oondensible

products collected in receiver I during a run; this weight

was oaloulated by multiplying the volume of the oondensible

products by the density. Column (20) gives the number of
moles of gaseous products which passed through the wet-test

meter during a run. Column (21) gives the total number of

moles of gaseous products, which is the sum of the moles of

base collected in receiver L' and the moles of gaseous

products which passed through the wet-test meter during a

run. The other figures in the tables are explained in the
section on analytical methods and reference to this section











can be made for an explanation.


TABLE 2

REACTION RUNS WITH BUTYLAMINE


(1) (2) (3) (4) (5) (6) (7) (8) (9)
Run Catalyst Temp. Temp. Time Feed Feed Feed, 1
No. in in of Vol. Wt., Moles qSSV
Salt React. Run, Ml. Grams Amine
Bath Chain. Min.


A-l
A-1
A-i
A-i
A-i
A-I
A-i
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
A-2
B-1
B-I
B-1
B-1
B-1


425
418
417
430
422
422
418
430
430
425
420
415
429
410
400
405
391
415
415
396
380
415
415
400
400
400
400
430
425
420
416
429


418

423
417
418
414

424
420
417
412
42
408
399
o03
392
412
412
397

412
412
399
399
399
399
424
421
417
413
423


30.0
30.0
30.0
30.0
30.0
25.0
30.0
20.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
24.0
20.0
30.0
30.0
18.0
14.0
12.0
24.0
21.0
18,0
12.0
30.0
30.0
30.0
30.0
30.0


22.5
22,.5
22.5
22.5
22.5
22.5
22.5
15.0
22,5
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.8
23.0
22.5
22.5
26.1
25.4
27.1
22.8
24.2
26.1
25.0
22.5
22.5
22.5
22.5
22.5


16.5
16.5
16,5
16.5
16.5
16.5
16.5
11.0
16,5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.7
16,9
16.5
16.5
19.2
18.6
19.9
16.7
17.7
19.2
18.3
16.5
16.5
16.5
16.5
16.5


0.226
0.226
0.226
0.226
0.226
0.226
0.226
0.151
0.226
0.226
0.226
0.226
0.226
0,226
0,226
0.226
0.226
0.229
0.231
0.226
0.226
0.263
0.256
0.273
0.229
0.243
0*263
0.263
0.251
0.226
0.226
0,226
0.226
0,226


11.2
11.2
11.2
11.2
11.2
9.3
11,2
11.2
11.2
11.2
11.2
11.2
11,2
11,2
11,2
11.2
11.2
8.8
7.3
11.2
11.2
5.6
4.6
3.7
8.8
7.3
5.6
4.0

11.2
11,2
11.2
11.2
11.2
311.2










TABLE 2 (Continued)


(1) (2) (3) (4) (5) (6) (7) (8) (9)
Run Catalyst Temp. Temp. Time Feed Feed Feed, 1
No. in in of Vol. Wt., Moles Egg
Salt React. Run, M1. Grams Amine
Bath Cham. Min.


41
413
407
401


418
413
409
398


B-2
B-2
B-2
B-2
B-2

(10)


30.0
25.0
25.0
25.0
25.0
(12)


25.8
21.5
21.5
21.5
21.5


18.9
15.8
15.8
15.8
15.8


0.259
0.216
0.216
0.216
0.216


(13)


Products--Weight in Grams
N-Butylidene- Buty7ro-
butylamine nitrile
0.94 3.02
1.12 2.42
1.31 1.29
0.96 23
1.20 1
1.35 1.42
1.18 1.58
0,00 0,00
0.82 2.34
1.01 1i98
1,14 1.60
1.21 1.26
0.91 2.22
1.23 1.09
1.27 0.61
1.25 0.84
1.22 0.42
1.30 1.31
1.5 1.10
1.28 0.58
0.78 0.00
1.85 0.88
1.82 0.65
1.76 0,50
1.30 0.48
1.3 o01
1.34 0.42
1.34 0.39
0.94 0.32


10e0
10.0
10.0
10.0
10,0


(14)


Total
Liquid'
11.72
12.50
12.38
10.50
11.38
11.o80
11.55
11.00
10.53
11.23.
11.87
12.48
10.60
12.70
13.14
12.96
14.15
13.00
14. 03
13.80
15.32
15.80
15.76
16.84
14.0o
15.40
17.50
16.58


(11)
Condensible
DibutJyl-
amine
3.18
4.19
4.79
2.65
3.75
4.40
4.20
0.00
2.28
3.23
4.10
4.77
2.43
5.31
5.82
5.58
5.45
5.26
.54
3.70
6.07
5.57
5.03
5.15
4.79
4.hh
2.:6


Run
No.

9
10
11
12
15
14
16
17
18
19
20
21
22
24
25
26
27
28
29
30
31
32

36
36
37


Butyl
amine
3.05
3.41
3*54


11.00
3.39
3.62
3.86
420
3.36
4.26
5.04
4.50
7.17
4.22
4.60
5.76
10.70
6.92
7.72
9.66
6.82
8.82
11.3.7
12.84


*










TABLE 2 (Continued)


(10) (11) (12) (13) (14)
Run Condensible Products--Weight in Grams
No. Buty7 Dibutylo N-Butylidene- Butyro- Total
amine amine butylamine nitrile Liquid


3.59
3 .98



.98
4.35
4.63
5.50
(15)


Run C<
No. Butyl-
amine
9 0.0118
10 0.0467
11 0.0593
12 0.0485
1 0. 0575
14 0.0572
15 0.0542
16 0.151
17 0.0465
18 0.0495
19 0.0528
20 o0.075
21 0.0460
22 0.0582
24 0.0690
25 0.0617
26 0.0982
27 0.0577
28 00628
29 0.0789
30 0.1464
31 0.0947
32 0.1057
33 0.1322


3.64
3. 64
1449
4.496
3.18
3.92
4.04
4.70
5.29
5.62
(16)


1.01
1.11
1.25
1.31
1.05
1,11
1.02
1.09
1,16
1.20
(17)


ondensible Products--Moles


Dioul;ty- L-BuLtylliene-
amine butylamine


0.0246
0.0324
0.0371
0.0205
0.0290
o. 0340
0.0325
0.0000
0.0177
0.0250
0.0318
0.0369
0.0188
0.0411
0o.0450
0.0447
0.0422
0.0407
o.o0445
o.o447
0.0287
0,0469
0.0431
0.0390


0,0074
0.0089
0.0103
0.0076
0.0095
0.0106
0.0093
0,0000
0.0065
0.0080
0.0090
0,0096
0.0072
0.0097
0.0100
0,0098
0.0096
0,0102
0.0121
0.0101
0.0061
0.0146
0.0143
0.0138


2.76
2.24
1.82
1.53
2.67
2.32
1.12
0.75
0.49
(18)


Butyro-
nitrile
0.0437
0o.0351
0.0187
0.03 1
0.0244
0. 0206
0.0228
0.0000
0. 0340
0.0296
0.0232
0.0182
0.0321
0.0158
0,0089
0.0122
0.0061
0.0190
0,0160
0.0084
0.0000
0.0128
0.0094
0.0072


11.68
11.94
12.65
12.84
11.77
13.80
11.77
12.46
12.84
13.26
(19)
Total
Base
in L'
0.0980
0.0936
0.0989
0.1124
0.1042
0.1008
0.0996
0.0000
0,1130
0.1090
0.1052
0.1020
0.1147
0.0959
0.0800
0.0892
0.0604
0.0954
0.0951
0.0790
0.0380
0.0904
0.0776
0.0700












TABLE 2 (Continued)


(15) (16) (17) (18) (19)
Run Condensible Produets--Moles Total
No. Butyl- Dibutyl- N-Butylldene- Btyro-- Base
amine amine butylamine nitrile in L'


0.0933
0.1205
0.1557
0.1760
0.0492
0.o544
0.0552
0,0088
0.o 98
o.o0608
0.0545
.o0580
0.0633
0.0753


(20)
Moles of
Gaseous
Prods.

0.157
0.122
0.089
0o.154
0.115
0.097
0,102
0.000
0.156
0.129
0.105
0.089
0.151
0.071
0.043
0.058


0.0399
0.0371
0.0344
0.0222
0.0236
0.0282
0.0348
0,0390
0.0246
0.0304
0.0313
0o.o364
0.0410
.o0435

(21)
Total
Moles of
Gaseous
Prods.
0.254
0.216
0.188
0.266
0.219
0.198
0.202
0,000
0.269
0.238
0.210
0.191
0.266
0.167
0.123
0.128


0.0102
0.0105
0.0106
0.0074
0.0079
0.0087
0.0099
0.0103
0.0082
0.0088
.o0081
0.0086
0.0091
0.0094

(22) (23)


Butyl-
amine
in L'

0.0104
0.0089
0.0077
0.0109
0, 0090
o, 0081
0.0082
0. 0000
0.0110
0,0098
0.0086
0.0078
0.0109
0.0068
0.0050
0,0053


Ammonia
in L'


0.0876
0.0847
0.0912
0.1015
0.0952
0.0927
0.0914
0.0000
0.1020
0.0992
0.0966
0.0941
0.1037
0.0891
0.0750
0.0839


0.0071
0.0061
0,0056
0,0046
0.0400
0.0327
0,0264
0.0222
0.0387
0,0336
0.0210
0.0162
0.0109
0,0071

(24)
Total
Butyl-
amine

0.0522
0.0552
0.0670
0.0594
0.0665
0.0653
0.0624
o, 01510
0.0575
0.0593
0.0614
0.0653
0.0569
0.0650
0.0764
0.0670


0.0680
0.0606
0.0527
0.0352
0.1006
0.0982
0.0954
0.0920
0.1006
0.1220
0.0976
0.0927
0.0867
0.0790

(25)


Ammonia
in
Liquid
Prods.
0.010
0.009
0.002
0.002
0.003
0.00
0.000
0.008
0.006
0.003
0 002
0.007
0.005
ooo5
0,013
o.o08


Run
No.


9
10
11
12


16
16

19
20
21
22
2
25


- -











TABLE 2 (Continued)


(20) (21) (22) (23) (24) (25)
Run Moles of Total Butyl- Ammonia Total Ammonia
No. Gaseous Moles of amine in L' Butyl- in
Prods. Gaseous in L' amine Liquid
Prods. Prods.


0.020
0.081
0.070
o.o4o
0.040

0.042
0.035
0.034
0.028
0.025
0.016
0.152
0.127
0.103
0.087
0.146
0.143
-.094
0.075
0.056
0.040


0.080
0.176
0.165
0.083
0.053
0.143
0.120
0.105
0.102
0.089
0.083
0.052
0.253
0.225
0.198
0.179
0.247
0.265
0.192
0.168
0.143
0,119


0,0032
0,0072
0,0068
0.0034
0.0022
0.0059
0.0048
0.0043
0.0042
0.0036
0.0034
0.0021
0.oo104
0.0092
0.0081
0. 0073
0.0101
0.0109
0.0079
0.0069
0.0059
0.0o49


0.0572
0.0883
0.0756
0. 0358
0.0845
0.0728
0.0657
0.0638
0.0570
0.0543
0.0331
0.0902
0.0890
0.0873
0.0847
0.0905
0.1111
0.0897
0.0858
o.o58
0.0808
0.0741


0.1014
0.0649
0.0696
0.0823
0.1486
0.1006
0.,1105
0.1362
0.0975
0.1247
0.1591
0.1781
0.0596
0.0636
0.0633
0.0660
0.0599
0.0717
. 0624
0.0649
0.0692
0.0802


0,009
0.006
0.001
0. 00
0.004
o.004
0.006
0.011
0.010
0.000
0.000
0.006

0.004
0.004
0.*0043
0.003
0.oo0
0,004
0.005
0.002











TABLE 2 (Continued)


(26) (27) (28) (29) (30) (31)
Run Total 1-Buteno 1-Butene Hydro- Conver ion
No. Ammonia in Prod. gen Fraction of Peed
Prod. Liquid Prod. Butyl- Dibutyl-
Prods. amino amine


0.098
0.094
00 0
0.10
0.0
0.096
0.099
0.000
0.110
0.105
0.100
0.096
0..111
0.094
0.088
0.092
0,066
0.094
0.089
0.081

0.079
0.077
0.074
0.065
0.054
0.039
0.095
0.093
0.091
0.089
0.094
0.114
0.093
0.090
0.092
0.076


0.0239
0.0214
0.0112
0.0157
0.0082
0.0073
osoO84
0.000
0.0281
0.0228
0.0197
0.0198
0.0296
0.0126
0.0032
0.0101
0.0096
0.0187
0.0076
0.000
0.000
0,000
0.00014
0.000
0.000
0.0143
0.0087
0.0164
0.0116
0.0205
0.0337
0.0216
0.0202
0.0169
0.0075


0.066
0.003
0,046
, o058
0.051
0.057
0.000
0.086
0.072
0.060
0.050
0.085
0.044
0,033
0.038
0,.015
0.043
0.032
0.026
0.008
0.027
0.021
0.024
0.024
0.017
0o.o008
0.009
0.063
0. 06
0.047
0.039
0,061
0.07

0.0
0,036
0.023


0,095
0.079
0.048
0.078
0.058
0.052
0.055
0.000
0.074
0.065
0.0 5
0.046
0.071
o0o041
0,028
0.034
0.022
0.048
0o044
0.027
0.006
0.033
0,028
0.024
0.023
0.022
0.017
0.088
0.073
0.063
0.054
0.08
0.076
0.050
0.041
0.031
0.024
O:OVI

0:024


0.231
0.244
0.29
0.263
0.294
0.289
0.276
1.000
0.254
0.263
0.272
0.287
0.252
0.288
0.327
0.296
0.449
0.283
0*301
0.364
0.638
0. 71
0. 432
0.426
0.503
0.603
0.710
0.263
0.281

0.265
0.276
0.289
0.300
0.321
0.371


0.218
0.287
0,328
0.182
0.256
0.301
0.288
0.000
0.157
0.221
0.281
0.327
0.166
0.363
0.39
0.395
0.373
0.356
0.385
0*3
0.254
0.357
0.336
0,288
0.349
0.305
0.262
0.177
0.209
0.250
o.304
0.345
0.217
0.235
0.290
0.338
0.380
o.oO3











TABLE 2 (Continued)


(32) (33) (34) (35) (36)
Run Conversion
No. Fraction of Feed Partial Pressure
N-Butylidene- Butyro- 1-Butene Butyl- Dibutyl.
butylamine nitrile amine amine


0.066
0.079
0.091
0.067
0.084
0.094
0.082
0.000
0.058
0.071
0.080
0.085
0.064
0.086
0.088
0.087
0.085
0.089
0.105
0.089
0.054
0.111
0.112
0.101
0.089
0,086
0.080
0.059
0.070
0.077
0.087
0.091
0.073
0.068
0.075
0.080
o.084
0.087


0.193
0.155
0.091
0.155
0.108
0.091
0.101
0.000
0.151
0.221
0.102
0,080
0.142
0.070
0.039
0o.o054
0.027
0.083
0.069
0.037
0.000
0.049
0.037
0.026
0.031
0.025
0.021
0.018
0.177
0.1145
0.117
0.098
0.171
0.130
0.097
0.075
0.051
0.033


0.292
0.234
0.203
0.334
0.257
0.225
0.252
0.000
0.380
0.318
0.265
0,221
0.376
0.194
0.146
0.168
0.066
0.198
0.138
0.115
0.034
0.103
0.086
0.088
0.105
0.070
0.034
0.036
0.279
0.248
0.206
0.174
0.270
0.290
0.250
0.208
0.167
0.106


0.135
0.154
0.209
0.156
0.194
0.196
0.185
1.000
0.149
0.164
0.180
0.203
0.149
0.209
0.258
0.225
0.387
0.203
0.227
0.294
0.622
0.305
0.356
0.419
0.352
0.440
0.542
0.6143
0.158
0.178
0.189
0.206
0.162
0.175
0.195
0.214
0.240
0.305


0.064
0.090
0.116
0.054
0:085
0.102
0.096
0.000
0.046
0.069
0.093
0.114
0.049
0.132
o.157
0.150
0.161
0.127
0.145
0.160
0.120
0.142
0.139
0.120
0.144
0.131
0.117
0.080
0.063
0.079
o.104
0.122
0.066
0.074
0.098
0.120
0.142
0.165











TABLE 2 (Continued)


(37) (38) (39) (40) (41)
Run Partial Preo aure
No. N-Butylldene- BUtyro- Amaonia 1-Butene Hydrogen
butylamine nitrile


0.019
0.025
0.032
0.020
0.028
0.032
0.028
0.000
0.017
0.022
0.026
0.030
0.019
0.031
0.035
0.033
0.037
0.032
0.039
0.036
0.026

o.o4
0.014
0,042
0.037
0.037
0.036
0.027
0.021
0.024
0.030
0.032
0.022
0.021
0.025
0.028
0.032
0.036


o.
0.096
0,058
0.092
0.071
0.062
0.068
0.000
0.088
0,079
0.068
0.056
0.084
0.051
0.031
0.041
0.023
0.059
0.052
,o030
0.000
0.039
0.030
0.022
0.026
0.022
0.019
0.016
0.106
0.092
0.079
0.069
0.105
0,082
0,066
O0 055
0.036
0,0 27


0.235
0.263
0.291
0.274
0.285
0.291
0.293
0.000
0.285
0.289
0.293
0.296
0.291
0.302
0.306
0.308
0.252
0.294
0,290
0.289
0.176
0.267
0.255
0.237
0.267
0.230
0.194
0.141
0.252
0.251
0.272
0,278
0,254
0,278
0.291
0.297
0.318
0,288


0.171
0. 148
0.4)4
0.198
0.169
0.1$K
0.168
0.000
0.223
0.198
0.176
0.1.55
0.223
0.,141
0. 21
0.128
0.0$?
0.134
0.104
0.093
0.033
0.082
0.068
o.07468
0.087
0.060
0.027
0.0oo
0.167
0.157
0.140
0.122
0.165
0.183
0.169
0.152
0.125
0.087


0.245
0.221
0.150
0,205
0.169
0.158
0,163
0.000
0.193
0.180
0.163

0.132

0.102
o.114

oo
o,o84
0,.1$0

0.025
0.121
0,106
0.086
o,o88
00080
0.075
0.060
0.234
0.188
0.171
0,226
0,185
0.156
0.135
0,107
0o090












TABLE 2 (Continued)


(1) (2) (3) (4) (5) (6) (7) (8) (9)
Run Catalyst Temp. Temp. Time Feed Feed Feed, 1
No. in in of Vol., Wt., Moles GSSV
Salt React* Run, Ml* Grams Amine
Bath Chain. Min.


55
61
68
69
67
68
69
70
71
72
73
75
76
77
78
79

95
96

99
100
101
102
103
104
106
107
109
110


B-2
B-1
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
A-2
A-2
A-4
A-4
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-2
B-3
8-3
B-3
B-3
B-3


429
410
430
423
417
411
429
405
399
393
383
429
429
429
425
425
415
415
415
402
402
402
415
415
402
402
402
415
415
415
415
415
415


422
408
423
417

413
40o


422

423
423

423
421
412
412
412
400
400
400
412
1123
412
400
400
400
413
413
413
413
413
413


25.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
25.0
20.0
30.0
25.0
20.0
18.0
14.0
9.0
18.0
14.0
9.0
30.0
26.0
21.0
18.0
14.0
9.0


21.5
22.5
20.7
20.7
20.7
20.7
20.7
20.9
20.9
20.9
20.9
20.8
22.9
22.9
22.5
22.5
20.3
20,9
22.3
20.3
20.9
22,3
25.8
27.1
25.5
25.8
27.1
25.5
21.2
21.7
22.4
25.8
27.7
26.6


15.8
16.5
15.2
15.2
15.2
15.2
15.2
15.3
15.3
15.3
15.3
15.3
16.8
16.8
16.5
16.5
14.9
15.3
16.4
14.9
15.3
16.4
18.9
19.9
18.7
18.9
19.9
18.7
15.6
15.9
16.4
18.9
20.3
19.5


0.216
0.226
0.208
0.208
0.208
0.208
0.208
0.210
0.210
0.210
0.210
0.209
0,230
0.230
0.226
0.226
0.204
0.210
0.224
0.204
0.210
0.224L
0.259
0.272
0.256
0.259
0.272
0.256
O,213
0.213
0.225
0.259
0.278
0.267


10.0
11.2
12.1
12.1
12.1
12.1
12.1
12.1
12.1
12.1
12.1
12.1
11.0
11.0
11.2
11.2
12.4
10.0
7:
12.4
10.0
7.5

3.0
.38

3.0

7.9
5.8
4.3
3.0


--










TABLE 2 (Continued)


(10) (11) (12) (13) (14)
Run Condensible Products--Weight in Grama
No. Butyl- Dibutyl- NButlidene- Butyro- Total
amine amine butylamine nitrile Liquid


55
61
65
66
67
69
69
70





ioi
71
72
73
75
76
7
79





99



104
1095




106
107
106
109
110


3.42
4.12
2.87
2.99
3.25
3.67
2.82
4.55
5.28
6.59
1039
2.81
3.09
3.08
3.35
3.60
3.90
4.00
4.90
5.08
6.05
7.58
8.18
10.65
12*73
11.92
15.44
16.22
5.08
5.42
6.57
9.23
12.54
14.42


2.81
5.92
2.20
3.14
4.10
4.88
2.35
5.74
5.32
3.38
2.20
2.42
2.56
2.90
*.35
4.20

4.95
5.27

i.24
2.89
3.47
2.59
1.19
4.87
4.94
5.17
4.93
4.08
2.68


0.86
1.47
0.80
0.94
1.10
1.20
0.78
1.32
1.36
1.29
0.84
1.06
0.8;
0.89
0.95
1.06
1.21
1.29
1.52
1.28
1.35
1. 38
1.88
1,81
1.37
1.23
1.00
0.61
1.50
1.56
1.71

1.24


2.29
1.59
3.53
2.55
1.89
1.37
3.28
0.94
0.5
0.41
0.00
2.79
2.841
2.86
2.16
2.27
1.40
1.18
0.98
0.72
0.47
0.73
0.65
0.00
0.54
0.00
0,00
0.75
0.57
0.48
0.43
0.00
0.00


10.84
13.50
10.54
10.94
11.50
12.02
10.62
12.75
13.20
1 O 13
10.1
10.54
11.30
11.63
11.50
11.78
12.70
12.68
13.12
13.94
15.88
17.56
17.14
17.18
18.60
17.90
12.78
13.o05
13.95
16.67
18.60
18.25











TABLE 2 (Continued)


(15) (16) (17) (18) (19)
Run Condensible Products--Moles Total
No. Butyl- Dibutyl- N-butylidene- Butyro- Base
amine amine butylamine nitrile in L'


55
61
65
66
67
69
70
71
72
73
75
76
77
78
79

96
94



99
100
101
102
103
104
105;
106
107
108
109
110


0.0468
0.0563
0.0392
0.0409
0.o445
0.0503
0.0385
0.0625
0.0724
0.0903
0.1422
0.0385
0.0413
0.0421
0.0461
0.0492
0.0533
0.0547
0.0672
0.0697
0.0828
0o1035
0.1120
0.1458
0.1740
0.1633
0.2115
0.2220
0.0695
0.0742
0.0900
0.1262
0.1718
0.1972


0.0218
0.0458
0.0170
0.0243
0.0317
0.0378
0.0182
0.0432
0.0445
0.0412
0.0262
0.0170
0.0187
0.0198
0.0225
0.0259
0. 0325
0.0347
0.0376
0.038
o.0367
0.0409
0.0328
0.0224
0.0269
0.0201
0.0092
0.0377
0.0383
0.0399
0.0382
0.0316
0.0208


0.0068
0.0116
0.0063
0.0074
0.0086
0.0095
0.0062
0.0104
0.0107
0.0101
0.0064
o.0084
0.0067
0.0070
0.0074
0.0083
0.0096
0,0101
0.0119
0.0101
0.0106
0.0108
0.0143
0.0108
0.0097
0.0078
o.oo48
0.0048
0.0118
0.0123
0.0134
0.0142
o.0134
0.oo0098


0.0332
0.0231
0.0512
0.0369
0.0273
0 0198
0.0475
0.0135
0,0084
0.0059
0.000
0.0404
0.0411
o.0414
0.0313
0.0329
0.0203
0.0172
0.0142
0.0104
0.0080
0.o0068
0.0106
0.0094
0.000
0.0079
0.000
0.000
0.0108
0.0083
0.0070
0.0063
0.000
0.000


0.1030
0.0868
0.0932
0.0904
0.0880
0.0863
0.0940
0.0837
0.0745
0.0610
0.0344
0.0948
0.1093
0.1058
0.1201
0.1121
0.0882
o. 0841
0.0812
0.0735
0.0672
0.0596
0.0804
0.0680
0.0455
0.0476
0.0340
0.0202
0.0798
0.0826
0.0763
0.0713
0.0576
0.0347


- --












TABLE 2 (Continued)


(20) (21) (22) (23) (24) (25)
Run Moles of Total Butyl- Ammonia Total Ammonia
No. Gaseous Moles of amine in L' Butyl- in
Prods. Gaseous in L' amine Liquid
Prods. Prods.


55
61
65
66

69
61
69
70
71
72
73
75
76
79
78
79



99
96o
98
99
100
101
102
103
104
105
106
107
108
109
110


0.139
01 0
0.172
0.135
0.106
0.080
0.164
0.057
0.047
o.oo7
0.003
0.002
0.150
0.163
0.162
o.148
0.10
0.088
0.076
0.062
0.o044
0.037
0,030
0.048
0.038
0.023
0.023
0.017
0.011
0.054
o.o049
o0.040 o
0.035
0.025
0.018


0.242
0.167
0.265
0.225
0.194
0.166
0.258
0.122
o.064
0.036
0.2o5
0.272
0.268
0.268
0.262
0.176
0.160
0.143
0.118
0, 104
0.090
0.128
0.106
0.069
0.071
0.051
0.031
0.134
0.132
0.116
0.106
0.083
0.053


0.0099
0.0068
0.0109
. 0092
0.0079
0.0068
0.0106
0.0058
0.0050
0.0026
0.0015
0.0101
0.0112
0. 0o10
0.0110
0.0107
0.0072
0.0066
0.0059
0.0048
ooo43
0.0037
0.0052

O, 0029
0.0021
0.0013
0.0055
0.004
0.0048
0.004

0.0022


0.0930
0.0800
0.0823
0.0812
0.0800
0.0795
0.07o0
0.0695
0.0584
0.0329
0.08647
0.0980
0.0948
0.1090
0. 1014
0.0810
0.0775
0,0753
0.0687
0.0630
0. 0560
0.0752
0.0636
0.0427
0.0447
0,0319
0.0198
0.0743
0.0772
0 0715
0.0669
0.0542
0.0325


0.0567
0.0631
o.oSol
0.0501
0.0524
o.0571
0.0492
0.0683
0.0774
0.0929
0.1437
0.0486
0.0525
0.0531
0.0571
0.0599
0. 0605
0.0613
0.0731
0.0745
0.0871
0.1072
0.1172
0.1502
0.1768
0.1662
0.2136
0.2233
0,0750
0.0796
0,0948
0.1306
0.1752
0.1994


.oo005
0.003
0,001
0.008
o0.008oo
0.004
0,004
0.000
0.000
0.002
0.000
0.010
0.013
0.000
0.000
0.000
0.009
0.012
0.002
0.000
o~oo6
0.006

0,001
o. ool
0.000
0.003
0.003
0.000
0.0000
0.002
0.000
0.000
0.004
0:02













TABLE 2 (Continued)


(26) (27) (28) (29) (30) (31)
Run Total 1-Butene 1-Butene Hydro- Conversion
No. Ammonia in Prod. gen Fraction of Feed
Prod. Liquid Prod. Butyl- Dibutyl.
Prods. amine amine


55
61
65
66
67
69
69
70
71
72
73
75
76
77
78
79


96
96
97
98
99
100
101
102
106
104
10o5
106
107
108
109
110


0.098
0.083
0.083
0.089
0.088
0.084
0.087
0.078
0.074
0.060
0.033
0.095
0.111
0, 109
0.108

0.086
0.087
0.071
0.063
0.062
0.076
0.065
o. 046
0.048
0.032
0,019
0.077
0.079
0.072
0.067
0.057
0.036


0.0244
0.0070
0.0200
0.0210
0.0184
0.01.50
0.0128
0.0066
o,oo4$
0.0037
0.000
0.0100
0.0239
0.0205
0,0346
0.0068
0.0014
0.0091
0.0025
0.0110
0.000
0.000
0.000
0.0034
o. oo16
0.0016
0.000
0.000
0.000
0.0094
0.0094
0.000
.00o48
0.0039
0.000


0.069
0.025
0.060
0.058
0.048
0.036
0.062
0.021
0.014
0.009
0.000
0.069
0.085
0.082
0.078
0.065
0.039
0.042
0.0386
0.022
0.012
0.015
0.020
0.018
0.013
0.012
0.003
0.005
0.028
0.029
0.018
0.016
0.013
0.006


0.073
0.058
0.109
0.081
0.063
0.049
0.101
0.037
0.028
0.022
0.007
0.089
0.089
0.090
0.070
0.074
0.050
0,044.
0.040
0.031
0.027
0.024
0.036
0.033
0.011
0.026
0.008
0.005
0O033
0,029
0.027
0.027
0.013
0.010


0.262
0.279
0.241
0.241
0.252
0.274
0.237
0.325
0.369
0.442
0.685
0.232
0.228
0.230
0.252
0.265
0.296
0.292
0.326
0.365
0.1$
0,479
0.452
0.552
0,692
0,6142
0.785
0O873
0.352
0.365
0. 421
0.505
o.630
0,747


0.202
0.405
0.163
0.234
0.305
0,363
0.175
0.411
0,423
0.392
0.249
0,163
0,163
0.172
0.199
0.229
0.318
0.330
0.332
0.375
0.389
0,328
0.316
0.241
0.175
0.208
0.148
0.072
0.354
0,351
0.355
0.295
0.227
0.155












TABLE 2 (Continued)


(32) (33) (34) (35) (36)
Run Conversion
No. Fraction of Feed Partial Pressure
N-Butylidene- Butyro- 1-Butene Butyl- Dibutyl-
butylamine nitrile amine amine


55
61
65
66

69
70
71
72
73
75
76
79
78
79
96
%

995

99
100
101
102
103
104
105
106
107
108
109
110


0.063
0.107
0.061
0.071
0.082
0.091
0.060
0.099
0.102
0.096
0.061
0.080
0.058
0.061
0.066
0.073
0.094
0.096
0.105
0.099
0.101
0.097
0.114
o.ii4
0.105
0.084
0.075
o.058
0.038
0.111
0.113
0.119
0.110
0,096
0.074


0.154
0.102
0.245
0.171
0.131
0.095
0.226
0.064
0.040
0.028
0.000
0.193
0.178
0.180

0.145
0.099
0.084
o.o64
0.051
0.038
0.030

0.035
0.000
0.030
0.000
0,000
0.051
0.038
0.032
0.024
0.000
0.000


0.319
0.116
0.288
0.275
0.231
0.173
0.298
0.100
0.067
0.043
0.330
0.37C
0.357
0.345
0.287
0.191
0.200
0.169
0.108
0.057
0.066
0.077
0.066
0.051
0.046
0.011
0.020
0.131
0.133
0.080
0.069
0.047
0.024


0.158
0.204
0.133
0 164
0.195
0.133
0.251
0.301
0,386
0.665
0.132
0.130
0.132
0o153
0.162
0.206
0.208
0.242
0.290
0.351
0.407
0.373
o. 65
0,632
0.562
0.752
0.839
0.275
0.288
0.349
0.434
0.577
0.707


0.061
0.148
o.o45
0.014
0.070
0.099
0.129
0.049
0.159
0.173
0,171
0.121
0.046
0.046
0.049
0.060
0.070
0. 111
0.117
0.125
0.149
0.164
0.140
0.130
0.102
0.080
0.091
0.071
0.035
0.138
0.139
0.147
0.127
0.104
0.074.
O.O227













TABLE 2 (Continued)


(37) (38) (39) (40) (41)
Run Partial Pressure
No. N-BButylidene Butyro- Ammonia 1-Butene Hydrogen
butylamine nitrile


55
61
65
66
67
68
69
70
71
72
73
75
76
77
78
79

94
97
97
98
99
100
101
102
103
104
105
106
107
108
109
110


o.061
0,038
0.017
0,021
0.027
0.032
0.017


0.030
0.023
0.017
0.017
0.020
0.022
0.031
0.034
0,039
0.039
0.043
0.041
0.047
0.0141
0,044
0.039
0.033
0.027
0.018
0.043
0.049
0.047
0.0o44
0.035


0.093
0.075
0.136
0.106
0.086
0.068
0.128
0.050
0.033
0.024
0.00
0.110
0.102
0.103
0.084
0.089
0.069
0.058
0.040
0.032
0.026
0.034
0.029
0.000
0.027
0.000
0.000
0.o 040
0.030
0.026
0.021
0.000
0.000


0.274
0.268
0.221
0.256
0.276
0.287
0.235
0.287
0.288
0.249
0.153
0.259
0.275
0.271
0.289
0.281
0.276
0.291
0.282
0.276
0.254
0.236
0.24
0.201
0.164
0.162
0.113
0.071
0.282
0.286
0.265
0.223
0.188
0.128


0.193
0.081
0.160
0.167
0.150
0.123
0.167
0.077
0.054
0.037
0.000
0.188
0.210
0.204
0.209
0.176
0.133
0.142
0.126
0.086
0.048
o.0 57
0.064
o0.056
0.046
0. 040
0.011
0.019
0.103
0.105
0.066
0.060
0. 043
0.021


0.204
0.187
0.289
0.234
0.198
0.167
0.272
0.136
0.107
0.091
0.030
0.243
0.220
0.224
0.187
0.200
0.171
0.149
0.132
0.121
0.109
0.093
0.111
0.102
0. 039
0.086
0.027
0.018
0.121
0.105
0.100
0.090
0.044
0.035










TABLE 3


REACTION RUNS WITH DIBUTYLAMINE


(1) (2) (3) (4) (5) (6) (7) (8) (9)
Run Catalyst Temp. Temp. Time Feed Feed Feed, 1
No, in in of Vol., Wt., Moles 5STV
Salt React. Run, Ml. Grams Amine
Bath Cham. Min.


422
429
432
425
425
425
425
411
411
411
411
425
425
411
411
430


410
414
415
413
41
414
403

405


432


(11)


20.0
20.0
20.0
25.0
20.0
12.0
25.0
20.0
15.0
12.0
18.0
12.0
18.0
12.0
20.0

(12)


25.0
25.0
25.0
26.8
25.9
25.9
27.3
23.4
24.0
25.0
27.3
25.7
27.3
25.7
27.3
24.0


18.8
18.8
18.8
20.0
19.5
19.5
20.5
17.6
18.1
18.8
20.5
19.3
20.5
19.3
20.5
18.1


(13)


0.146
o.l46
0.156
0.151
0.151
0.159
0.136
0.140
0.146
0,159
0.159
0.150
0.190
0 9~
0:90o


11.6
11.6
11.6
13.5
11.2
8.4
6.4
15.5
12.0
8.7
6.4
4.0
2.5
4.0
2.5
12.0


(14)


Condensible Products--Weight in Grama


Butyl- m1Duty71
amine amine


7.37
6.18
4.22

7.8

8,30
9.90
11.99
11.18
13.09
13.18
15.13
17.45


rH- yllaene-
butylamine
1.90
1.86
1.58
2.12
2.21
2.40
2.6
1.78
2.49
2.19
2.34
2.$2
2.38
2.04
1.85
0.49


Bu yro-
nitrile
1.34
1.70
2.58
2.62
2.04
1.9
1.92
1.32
1.20
0.82
0.69
0.678
0*76
0.00
0.00


TOta1
Liquid
15.22
14.40
14.20
16.25
16.03
16.38
1 .20

17.2
1 .60
1 .78
18.i6

17.98
19.34
17.90


A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3
A-3

(10)


Run
No.

62
63
64
80
81
82

8i
89



89
90
91
92


1.65
1.57
2.11
2.38
2.1 7
2.k14
1.90
2.10
1.64
1*64
1.72
1 49
1.49
1.47
0.00











TABLE 3 (Continued)


(15) (16) (17) (18) (19)
Run Condensible Produots--Molea Total
No. Butyl- Dibutyl- N-Butylidene- Butyro- Base
amine amine butylamine nitrile in L'


0.0225
0.0215
0, 0293
0.0326
0.0293
0.0279
0.0275
0.0280
0.0250
0.0258
0.0224
0.0236
0.0214
0.0201
0.0201
0.000


(20)


Moles of
Gaseous
Prods.

0.131
0.158
0.184
0.182
0.154
0.114
0.096
0.098
0.083
, 066
0.055
0.066
0.048
0.o040
0.029
o. 014


0.0570
0.0478
0.0327
0.0453
0.0505
0.0668
0.0728
0.0528
0.0642
0.0768
0.0927
0.0866
0.1013
0.1020
0.1172
0.1345
(21)


Total
Moles of
Gaseous
Prods.
0.163
0.204
0.207
0.206
0.173
0.130
0.110
0.117
0, 098
0,077
0.077
0.065
0.075
0.055
0.o046
0.033
0.016


0.0149
o.0147
0.0132
0.0158
0.0174
0,0189
0.0206
0. 0139
0,0159
0.0172
0.0184
0.0192
0.0195
0.0161
, 0145o
0.oo038


0.0195
0.0257
0.0372
0,0365
0.0296
0.0222
0.0181
0.0192
0.0173
0.0118
0.0100
0.0112
0.0091
0.0068
0.000
0.000


0.0317
0.0360
0.022$
0.0244
0.0194
0.0160
0.0137
0.0147
0.0115
0.0095
0.0089
0.0071
0.0060
0.oo14

(25)
Ammonia
in
Liquid
Prods.
0.001
0.000
0.011
0 002
0.005
0.005
0,006
0.003
0.003
0.o003
0.005
0.001
0.001
0.000
0.003
0.000


Run
No.


62
6z
6?
80
81
82
83
84
85
86
87
88
89
90
91
92


(22)


Butyl-
amine
in L'

0.0067
0.0084
0.0085
0,0084
0.0071
0.00o 3
0. 0045
o.oo48
0.0040
0.0032
0.0026
0.0031
0.0023
0.0020
0.0014
0.0006


(23)
Ammonia
in L'


0.0250
0.0276
0.0140
0.0160
0.0123
0.0107
0.0092
0.0139
0.0107
0.0083
0.0069

000148
o.oo4o8
O. 0040
0.0028
0.0008


(24)
Total
Butyl-
amine

0.0292
0.0299
0.0378
0.0410
0.0364
0.0332
0.0320
0.0328
0.0290
0.0290
0.0250
0.0277
0.0237
0.0224
0.0215
0.0006










TABLE 3 (Continued


(26) (27) (28) (29) (30) (31)
Run Total 1-Butene 1-Butene Hydro- Conversion
No. Ammonia in Prod. gen Fraction of Feed
Prod. Liquid Prod. Butyl- Dibutyl-
Prods. amine amine


0.026
0.028
0.025
0.018
0.017
0.016
o0.015
0.017
0.014
0.011
0.012
0.007
0. 006
0.oo0
0.006
0.001


0.0444
0.0540
0.0620
o,o613
0.0362
0o, 06
0.0369
0.0504
0.0402
0.0346
0.0257
0.0285
0.0246
0.0146
0.0142
0.000


(32)
Conv<
Fraction
N-Butylidene-
butylaaine
0.102
0.100
0.090
0.102
0.115
0.125
0.130
0.102
o.n4
0.118
0.116
0.128
0.123
0.107
0.091
0.027


0.100
0.112
0.125
0.112
0.100
0.087
0.081
0.087
0.073
0.063
0.061
0.054,
0.o044

0.033
0.003


(33)


version
of Feed


BUIyro-
nitrile
0.134
0.176
0.255
0.234
0.196
0.147
0.114
0.141
0.124
0.081
0.063
0.075
0.057
0.o045
0.000
0.000


0.054
0.066
0.088
0.089
0.077
0.063
0.057
0.052
0.050
0. 041


0.030
0.014
o.oo4


(34)


1-Butene

0.174
0.192
0.164
0.105
0.114
0.104
0.096
0.122
0.093
0.075
0.082

0.o44
0.027
0.038
0.006


0.200
0.205
0.258
0.262
0.241
0.220
0.201
0.241
0.207
0,196
0.157
0.184

0.149
0.135
0.004
(35)


Partial
Butyl-
amine
0.097
0.092
0.105
0.115
0.111
0.111
0.108
0.119
0.110
0.116
0.097
0.112
0.094
0.104
0.104
0.00lo4
0.004


0.390
0.327
0.224
0.290
00.35
0.403
0.4 7
0.388
0.458
0.525
0.582
0.577
0.637
0.682
0.737
0.9%2

(36)


Pre sure
Dibu-yl-
amine
0.190
0.148
0.091
0.127
o.154
0.203
0.245
0.192
0.243
0.307
0.361
0.350
0.418
0.472
0.566
0.915


Run
No.


62
63
80
81
82

85
84
86
89
89
90
91
92


II











TABLE 3 (Continued)


(37) (38) (39) (40) (41)
Run Partial Pressure
No. N-Butylldene- Butyro- Ammonia 1-Butene Hydrogen
butylamine nitrile

62 0.050 0.065 0.087 0.333 0.160
63 0.045 0.079 0.086 0.345 0.204
64 0.037 0.104 0.070 0.348 0.245
80 0.044 0.102 0.050 0.313 0.249
81 0.053 0.090 0.053 0.305 0.235
82 0.063 0.074 0.052 0.290 0.210
83 0.069 0.061 0.051 0.273 0.192
84 0.050 0.070 0.062 0.316 0.189
85 0.060 0.066 0.053 0.276 0.193
86 0.068 0.047 0.04 0.252 0.164
87 0.072 0.039 0.047 0.237 0.148
88 0.078 0.045 0.028 0.219 0.169
89 0.080 0.038 0.029 0.186 0.156
90 0.074 0.031 0.018 0.162 0.137
91 0.070 0.000 0.029 0.160 0.070
92 0.026 0.000 0.005 0.020 0.004


The results of the
are presented by Figures 3


butylamine and dibutylamine runs
through 17. Figures 3 through


9 present the results using catalyst A and Figures 10
through 17 present the results using catalyst B.
In Figure 3 is plotted the conversion, as moles of
butylamine converted to each product per mole of butylamine
in the feed, against the temperature of the salt bath for
the catalyst activated at 500 in a vacuum. In Figures 10
and 11 are plotted the conversion, as moles of butylamine
converted to each product per mole of butylamine in the











Figure 3.--Conversion of butylamine to products as
a function of temperature over catalyst A-2 activated at
500 in a vacuum. 1/GSSV 11.2.


O Dibutylamine
Q N-Butylidenebutylamine
a Butyronitrile
1-Butene
4 Unreacted butylamine



0.7



0.6-


0








0.3
0



I 0.2 -
0








380 390 400 410 420 430
Temperature of Salt Bath











Figure 4.--Conversion of butylamine to products as
a function of space, velocity over catalyst A-2 activated at
5000 in a vacuum. Temperature 415.

O Dibutylamine
0 N-Butylidenebutylamine
( Butyronitrile
e 1-Butene
C Unreacted butylamine



0.7



0.6-


0.-








03
0*3

o 0.2

o 0,


0.1
O.)
0 /










0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
1/GSSV











Figure 5.--Partial pressures of butylamine and
products as a function of space velocity over catalyst
A-2 activated at 5000 in a vacuum. Temperature 415


O Dibutylamine
8 N-Butylidenebutylamine
O Butyronitrile
e 1-Butene
D Ammonia
O Hydrogen
0 Unreacted butylamine


0.4



o
S0.3





0.1
q- 0.2




0.1


2.0 4.0 6.0 8.0
1/GSSV


10.0 12.0 14.0 16.0


0.0" -
0.0











Figure 6,--Partial pressures of dibutylamine and
products as a function of space velocity over catalyst
A-3 activated at 5000 in a vacuum. Temperature 1250.

9 N-Butylidenebutylamine
( Butyronitrile
D Butylamine
e 1-Butene
() Ammonia
9 Hydrogen
O Unreacted dibutylamine


0.4




S0.3


C


(d
S0.2


14

0.1


2.0 4.0 6.0 8.0 10.0
1/GSSV


12.0 14.0 16.0


0.0"
0.0











Figure 7.--Conversion of butylamine to products as
a function of space velocity over catalyst A-2 activated at
5000 in a vacuum. Temperature 4000.

O Dibutylamine
N-Butylidenebutylamine
( Butyronitrile
e 1-Butene
0 Unreacted butylamine


0.7



0.6-











0



o .2
S




( /
Bd
mt / ^
a
^ /^


12.0 14.0 16.0


l/GSSV












Figure 8.--Partial pressures of butylamine and
products as a function of space velocity over catalyst
A-2 activated at 5000 in a vacuum. Temperature 400.


Dibutylamine
N-But yl idenebut ylamine
Butyronitrile
1-Butene
Ammonia
Hydrogen
Unreacted butylamine


0.3




0.2
0
p$

0.2
(0


2.0 4.0 6.0 8.0 10.0
1/GSSV


12.0 14.0 16.0


0.0 L
0.0











Figure 9.--Partial pressures of dibutylamine and
products as a function of space velocity over catalyst
A-3 activated at 5000 in a vacuum. Temperature 4100

Q N-Butylidenebutylamine
0 Butyronitrile
0 Butylamine
0 1-Butene
(D Ammonia
O Hydrogen
O Unreacted dibutylamine


0.5





o. 4




0.3


4-'
it-
6


0.1


.0,0 2,0


10.0 12.0 14.0 16.0


1/OSSV


0


3.2









61

Figure 10,--Conversion of butylamine to products as
a function of temperature over catalyst B-2 activated at
8000 in a vacuum. 1/GSSV 10.0.

O Dibutylamine
Q N-Butylidenebutylamine
0 Butyronitrile
1-Butene
0 Unreacted butylamine



0.7



0.6-







o
0 .0*
0.
O








o 0.2
0





>j 0.3
01











0.1o I I I
38o 390 400 410 120 430
Temperature of Salt Bath











Figure l1.--Conversion of butylamine to products as
a function of temperature over catalyst B-2 activated at
800o in a vacuum. 1/GSSV 12.1


O Dibutylamine
Q N-Butylidenebutylamine
0 Butyronitrile
0 1-Butene
C Unreacted butylamine



0.7



0.6

e





o 0. -

r-l

093 -

0

S0 2


z .


Temperature of Salt Bath









63
Figure 12.--Conversion of butylamine to products as
a function of space velocity over catalyst B-2 activated at
8000 in a vacuum. Temperature 4150


O Dibutylamine
9 N-Butylidenebutylamine
0 Butyronitrile
e 1-Butene
4D Unreacted butylamine


0.01 - I I
0.0 2.0 4.0 6.0 8.0 10.0
1/GSSV


12.0 11.0


16.0










Figure 13.--Partial pressures of butylamine and
products as a function of space velocity over catalyst B-
2 activated at 800 in a vacuum. Temperature 415.

O Dibutylamine
Q N-Butylidenebutylamine
P Butyronitrile
5 1-Butene
() Ammonia
0 Hydrogen
SUnreacted butylamine




0.5




0,4







S0.2
o0-3

0


3 0.2




0.1 -




0.o0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
1/GSSV












Figure lh.--Conversion of butylamine to products as
a function of space velocity over catalyst B-2 activated at
8000 in a vacuum. Temperature 4020.

O Dibutylamine
N-butylidenebutylamine
0 Butyronitrile
e 1-Butene
1' Unreacted butylamine



0.7



0.6
rtd


r 0.53



o 0.4








0
o




0.1





0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
l/GSSV











Figure 15.,-Partial pressures of butylamine and
products as a function of spaco velocity over catalyst B-
2 activated at 8000 in a vacuum. Temperature 4020.

O Dibutylamine
N-Butylidenebutylamine
( Butyronitrile
1 1-Butene
(D Ammonia
e Hydrogen
D Unreacted butylamine




0.5




0.4 -




0.3 -

0.







0.1


2.0 4.0 6.0 8.0 10.0 12.0 116.0 16.0
1/GSSV










67

Figure 16.--Conversion of butylamine to products as
a function of space velocity over catalyst B-3 activated at
8000 in the Presence of water vapor. Temperature 4150.


Dibutylamine
N-Butylidenebutylamine
Butyronitrile
1-Butene
Unreacted butylamine


(T. f


0.6


0.5



0.4


0.3


0.2


0.1


r nl


V.
0.0


2.0 h.0 6.0 8.0 10.0
1/GSSV


/-
7-


12.0 1.o 16.o


A












Figure 17.--Partial pressures of butylamine and
products as a function of space velocity over catalyst B-3
activated at 8000 in the presence of water vapor. Tempera-
ture $15.
0 Dibutylamine
Q N-Butylidenebutylamine
0 Butyronitrile
e 1-Butene
(D Ammonia
0 Hydrogen
O Unreacted butylamine


0.4 1





a 0.3
0


0
k 0.2




0.1


2.0 4.0 6.0 8.0 10.0
1/GSSV


12.0 14.0 16.0


0.0 '
0.0
0110











feed, against the temperature of the salt bath for the
catalyst activated at 800 in a vacuum. Figure 10 repre-
sents the results obtained using the catalyst immediately
after activation, while Figure 11 represents the results

obtained using the same catalyst after it had been stored
for several months.
In Figures 4 and 7 are plotted the conversion, as

moles of butylamine converted to each product per mole of

butylamine in the feed, against the reciprocal of the space

velocity for the catalyst activated at 5000 in a vacuum.

In Figures 5 and 8 are plotted the partial pressures of

the products formed by butylamine against the reciprocal
of the space velocity for the catalyst activated at 5000

in a vacuum. In Figures 6 and 9 are plotted the partial
pressures of the products formed by dibutylamine against

the reciprocal of the space velocity for the catalyst

activated at 5000 in a vacuum.

In Figures 12 and 14 are plotted the conversion,
as moles of butylamine converted to each product per mole
butylamine in the feed, against the reciprocal of the space

velocity for the catalyst activated at 8000 in a vacuum*

In Figures 13 and 15 are plotted the partial pressures of

the products formed by butylamine against the reciprocal

of the space velocity for the catalyst activated at 8000

in a vacuum. In Figure 16 is plotted the conversion, as












moles of butylamine converted to each product per mole of

butylazine in the feed against the reciprocal of the space

velocity for the catalyst activated at 8000 in the presence

of water vapor. In Figure 17 are plotted the partial pres-

sures of the products formed by butylamine against the re-

oiprocal of the space velocity for the catalyst activated

at 8000 in the presence of water vapor.

For the catalyst activated at 5000 in a vacuum, the

conversion to dibutylamine and N-butylidenebutylamine passes

through a maximum, and the conversion to butyronitrile and

1-butene increases steadily as the temperature is increased.

For the catalyst activated at 8000 in a vacuum, the oon-

version to dibutylamine and N-butylidenebutylamine passes

through a maximum, the conversion to butyronitrile increases

steadily, and the conversion to 1-butene increases steadily

and appeared to be approaching a maximum as the temperature

was increased.

For the reaction temperatures above 4000, the con-

version to dibutylamine and N-butylidenebutylaaine passes

through a maximum and the conversion to butyronitrile and

1-butene increases steadily as the contact time is increased.

At 4000 the feed rate was not reduced enough to permit the

dibutylamine and N-butylidenebutylamine maxima to be reached

but there seems no doubt that they could have been observed.











There was a consistent trend in activity with use

during the first few runs or sets of runs. Runs 9, 10,

and 15 were made separately and 11 and 12, and 13 and 14

were made in pairs over a sample of alumina, A-1, which

had been activated at 5000 in a vacuum. The results of

these runs indicated that the activity of the catalyst

was decreasing. Runs 17 through 21 were made over a

fresh sample of alumina, A-2, from the same batch as used

for the previous runs. Runs 17 and 21 were made under

equivalent conditions and gave essentially the same re-

sults. The activity of this sample appeared to be the

same as the activity of sample A-1 after it had decreased.

Runs 22 through 37 were made over sample A-2. The results

of runs 17 through 37 were used to plot Figures 3, 4, 5,

7, and 8. Runs 76 and 77 were made under equivalent con-

ditions and with the same sample of alumina as used for

runs 17 through 37 except that the catalyst was steamed for

four hours at 4300 between runs. The results of this pair

of runs were essentially the same. Comparison of runs 76

and 77 with 17 and 21 indicated that the activity of the

catalyst had increased slightly. Runs 78 and 79 were made

under equivalent conditions using a fresh sample of alumina,

A-4, which had been activated at 5000 in a vacuum from a new

batch except that the catalyst was steamed for five hours at

4250 between runs. The results of this pair of runs










indicated that the activity of the catalyst had decreased
slightly after being steamed.
Runs 38 through 42 were made over a sample of
alumina, B-1, which had been activated at 800 in a vacuum
and then stored for seven months. Runs 38 and 42 were made
under equivalent conditions and gave essentially the same
results, Run 61 was also made over sample B-1 after the
catalyst had been stored for an additional two months.
Comparison of run 61 with runs 38 through 42 indicates
that the activity of the catalyst had increased. Runs
49 through 55 were made over a sample of alumina, B-2,
immediately after it had been activated at 800 in a
vacuum. Runs 65 through 73 were made over the same sample
of alumina, B-2, after the catalyst had been stored for two
months. Runs 65 and 69 were made under equivalent condi-
tions and gave essentially the same results. Comparison of
runs 65 through 69 with runs 49 through 55 indicates that
the activity of the catalyst had increased. The results
of runs 49 through 55 were used to plot Figure 10 and the
results of runs 65 through 73 were used to plot Figure 11.
Runs 65, 69, and 75 were made under equivalent conditions
and with the same sample of alumina except that the catalyst
was steamed for two hours at 400 prior to the 75th run.
Comparison of the results of run 75 with the results of
runs 65 and 69 indicates that the activity of the catalyst









73

had changed slightly but had neither increased nor decreased.
The per cent conversion to butyronitrile had decreased, the

per cent conversion to 1-butene had increased, and the per
cent conversion to dibutylamine and N-butylidenebutylamine
and the unreacted butylamine remained the same.
Runs 93 through 104 were made over sample B-2. The

results of runs 93 through 104 were used to plot Figures

12, 13, 1l, and 15. Runs 105 through 110 were made over
a sample of alumina, B-3, immediately after it had been

activated at 8000 in the presence of water vapor. The
results of runs 105 through 110 were used to plot Figures

16 and 17.

Runs 62 and 63, and 64 were made over a sample of

alumina, A-3, which had been activated at 5000 in a vacuum;

these runs were made in order to obtain the products formed

by the reaction of dibutylamine over alumina. Runs 80

through 91 were also made over sample A-3. The results of
runs 80 through 91 were used to plot Figures 6 and 9.
Run 16 was made with butylamine in the absence of

a catalyst in order to determine if any reaction occurs by
thermal decomposition. The butylamine from this run was
recovered unreacted which indicates that no reaction occurs

by thermal decomposition. Run 92 was made with dibutylamine
in the absence of a catalyst in order to determine what
products, if any, are formed by the thermal decomposition









74
of dibutylamine. The dibutylamine from this run decomposed

into N-butylidenebutylamine, 1-butene, butylamine, and
ammonia. However, 96.2 per cent of the dibutylamine was

recovered unreacted which indicates that thermal decomposi-

tion accounts for only a small fraction of the reaction.

B. Discussion of Results

1. Path of Decomposition of Butylanine over Alumina

In order to evaluate the effects of changes in the

catalyst structure upon activity, the path of the reactions
which are taking place must be considered, The results of

this work on the decomposition of butylamine over alumina
have established the following points:

(1) Starting with butylamine, there are produced
ammonia, 1-butene, dibutylamine, N-butylidenebutylamine,

and butyronitrile in varying proportions, depending upon

the temperature, space velocity, and catalyst activity.

(2) Starting with dibutylamine, there are produced
1-butene, butylamine, ammonia, N-butylidenebutylamine, and

butyronitrile, the relative amounts in this case also

depend on the conditions.

(3) Starting with butylamine at sufficiently high
temperatures, the dibutylamine and N-butylidenebutylamine
contents of the products pass through a maximum and then

fall off. As the dibutylamine and N-butylidenebutylam~ln











contents of the products fall off, the butyronitrile con-

tent of the products increases.

(4) Starting with dibutylamine, the 1-butene, N-
butylidenebutylamine, and butyronitrile contents of the

products are larger than when starting with butylamine.

The various possible reactions which may be involved

in the overall process are:

(a) C0He-NHa =% CHy-CH=NH + He

Although no butyl mine was found in the reaction products,

the possibility of this reaction taking place could not be

ruled out. If this material did form, it must have been

lost by subsequent rapid reaction.

(b) CaHy-CH--NH

C4H,-NHg + CaHT-CH= NH ; NH

CaH,-CH3

C3H,-CH--NH CHT7-CH,

NH + H NH + NHO

CSHV-CHS C3H,-CH4

Dibutylamine is produced quite rapidly in the initial

stages of the reaction, indicating that it comes directly

from the butylamine. However, because of the rapid initial

production of dibutylamine and the small partial pressure

of hydrogen at small reaction times, conversion to the

dibutylamino by this particular pathway seems to be a











relatively unimportant reaction.

(c) CaH,-C~=NH Wfi CHT-C=N + HN

This reaction cannot be a major source of butyronitrile

because of the fact that the butyronitrile content of the

products is larger when starting with dibutylamine than

when starting with butylamine.
H
(d) C4He-NHa + C4He-NH4 C4He-N-C4H + NH

Dibutylamine is produced quite rapidly in the initial

stages of the reaction, indicating that it comes directly

from the butylamine as mentioned above. It is not possible

from the results to exclude all contribution from process (b),

but the present reaction seems to be the predominating re-

action.

(e) C4He-NH, : CCHg-CuHCCH + NH,

The occurrence of the forward reaction is indicated by the

fact that some 1-butene production occurs at small times of

reaction.
H
(f) C4HBN-C,4H* CI4H-NHB + CH,-CHUCHS

Starting with dibutylamine, 1-butene and butylamine are

produced quite rapidly in the initial stages of the reaction,

indicating that they come directly from the dibutylamine.

Also, starting with butylamine, the rate of formation of

1-butene rises rapidly as the dibutylazine concentration

approaches a maximum, indicating that 1-butene is produced

by a reaction other than (e).










H
(g) C4H,-N-C.H--' CaH,-CH=N-C4He + Hg
Starting with butylamine, N-butylidenebutylamine concen-

tration reaches a maximum as the dibutylamine concentration

reaches a maximum, and then falls off.
(h) CsHv-CBHN-C4He -- COH,-C-N + CsH,-CH=CH + HO

Butyronitrile production is small at small times of reaction

and increases steadily as the N-butylidenebutylamine concen-
tration passes through a maximum and falls off.
The ratios of partial pressures for reactions (d),

(e), (f), (g), and (h) were calculated from the results of
the butylamine runs at 4150 and 400o for all forms of the

catalyst. The ratios for reactions (d), (e), and (g)
showed no agreement for any set of runs using the same
catalyst, and, as a result, the ratios were of no value for
determining the equilibria involved in these reactions. The
ratios for reaction (h) increased as the reaction times were

increased for all sets of runs using the same catalyst which

indicates that the equilibrium for this reaction was not

attained. The ratios for reaction (f) showed some agreement
for any set of runs using the same catalyst and the averages
for any set of runs at one temperature showed fair agreement
for all forms of the catalyst. The values for the ratios

calculated from the butylamine runs at 415o over catalysts
A-2, B-2, and B-3; and from the butylamine runs at 400o
over catalysts A-2 and B-2 are given in Table 4. The










ratios are tabulated in increasing

TABLE 4
RATIOS OF PARTIAL PRESSURES


78
order of reaction times.



FOR REACTION (f)


415 41 415 400oo 4oo
A-2 B-2 B-3 A-2 B-2

o0258 0.364 0.200 0.261 0.456
0.173 0.225 0.238 0.126 0.116
0.175 o.183 0.205 0.201 o.252
0.163 0.244 0.161 0.212 0.166
0.214 0.253 0.218 o.189 0.103
0.358 0.246 0.208 0.167
0o223a 0.256a 0.205a 0.198* 0.210a

aAverage Values


The initial reactions in the butylamine decomposition
appear to be (d) and (e). The dibutylaaine produced by (d)
appears to react according to either (f) or (g). The final
reaction appears to be the decomposition of the N-butylidene-
butylamine, produced by (g), by (h). The end products are
1-butene and butyronitrile, along with hydrogen and ammonia.

2. Activity and Changes in the Alumina Surface
The surface area of the catalysts used for this
study was not determined. The variations in surface area









79

of alumina with increasing temperatures of activation have

been studied by other workers and the results show that for

temperatures of activation above 6000 the surface area de-

creases. Because of this fact, the total activity of the

catalysts activated at 8000 should be smaller than the total

activity of the catalysts activated at 5000 provided the

specific activity of the catalysts is the same. Before

comparing total activity and specific activity of the

catalysts with activation temperatures, the relationship

between catalyst activity and the temperature of activation

of the catalyst will be considered.

Inspection of Figures 4 and 12, 5 and 13, and 7 and

14 indicates the relationship between the dehydrogenation

activity of the catalysts and the temperature of activation

of the catalysts in a qualitative way. These figures, in

view of the fact that temperatures of activation above 6000

result in a decrease in surface area, show that the catalyst

activated at 8000 in a vacuum is more active for dehydro-

genation reactions than the catalyst activated at 5000 in

a vacuum as indicated by the per cent conversion of butyl-

amine to butyronitrile and the partial pressures of butyro-

nitrile and hydrogen in the reaction products. The more
active dehydrogenation catalyst would be expected to in-

crease the rates of reactions (g) and (h), and, as a result,

the per cent conversion of butylamine to dibutylamine would











be smaller than the per cent conversion of butylamine to
dibutylamine for the less active dehydrogenation catalyst

Inspection of Figures 4 and 12 reveals this fact. The more

active dehydrogenation catalyst would also be expected to

shift reaction (f) to the left in order to maintain equi-
librium, because of the increased conversion of the di-
butylamine to N-butylidenebutylamine, and, as a result,

the per cent conversion of butylaaine to 1-butene would

be smaller than the per cent conversion of butylamine to

l.butene for the less active dehydrogenation catalyst.

Inspection of Figures 4 and 12 confirms this supposition

also.
Inspection of Figures 3 and 11, in which are

plotted the moles of butylamine converted to each product
per moles of amine in feed against the temperature, also
indicates that the catalyst activated at 8000 in a vacuum

is more active for dehydrogenation reactions than the

catalyst activated at 5000 in a vacuum as indicated by

the larger per cent conversion of butylamine to butyro-

nitrile.
The relationship between the total activity of the

catalyst and the temperature of activation of the catalyst

can be obtained by comparing Figures 4 and 12, and 7 and 14.

Inspection of these figures shows that the total activity

of the catalyst decreases with increasing temperatures of











activation as expected from the decrease in surface area
with increasing temperatures of activation.
The relationship between specific activity and the

temperature of activation of the catalyst can be obtained

by comparing Figures 4 and 12, 5 and 13, 7 and 14, and 8
and 15, and the results obtained by Brey and Krieger on

the surface area of alumina as a function of temperature.

Brey and Krieger found that the surface area of alumina

is constant after heat treatment up to 5000 and decreases

about 42 per cent after heat treatment at 800o. The total

activity of the catalyst activated at 8000 is slightly

smaller than the total activity of the catalyst activated

at 5000 but the decrease in total activity does not appear
to be nearly as great as would be expected from the dif-

ference in surface areas. This indicates that the specific

activity of the catalyst activated at 8000 is larger than
the specific activity of the catalyst activated at 500.0

This increase in specific activity can be accounted for by

examination of the effects of the more active dehydrogena-
tion catalyst. The shifting of reaction (f) to the left,

as mentioned above, results in a larger conversion of

butylamine to products and, as a result, the specific

activity of the catalyst activated at 800* should be

greater than the specific activity of the catalyst acti-
vated at 5000o











The increased dehydrogenation activity of the

catalyst activated at 800 may be caused by the partial
conversion of the surface of the catalyst to another form.

The X-ray diffraction patterns of the alumina samples

activated at 500* and 800 showed that both samples con-

tained gamma alumina and that the degree of crystallinity

of both samples was about the same. In spite of these re-

sults, there is a possibility that the surface of the

alumina activated at 800 has been partially converted to

the alpha form. Boreskov, Dzsiako, Borisova, and

Krasnopol'ska7a found that alpha alumina was mainly a

dehydrogenation catalyst, and, in view of this fact, the

increased dehydrogenation activity of the catalyst acti-

vated at 800 may be caused by the partial conversion of

the surface of the alumina to the alpha form.

The relationship between the total activity of the

catalysts activated at 800 in a vacuum and in the presence

of water vapor can be obtained by comparing Figures 12 and

16. Inspection of these figures indicates that the total

activity of the catalyst activated in the presence of water

vapor has decreased. The results obtained by Brey and

Krieger on the surface area of alumina activated at 800

in a vacuum and in the presence of water vapor show that
there is about a 50 per cent decrease in surface area after
activation in the presence of water vapor. The decrease in









83
total activity, in view of this fact, appears to be caused
by a decrease in surface area. The specific activity of
the catalysts activated at 8000 in a vacuum and in the

presence of water vapor, in view of the smaller surface

area of the catalyst activated at 8000 in the presence of
water vapor, appear to be about the same.
The change in activity of the catalyst with use

was observed but was not studied. It was found that by

evacuating the reaction tube after each run and filling

the latter with argon that the activity of the catalyst

did not change with use. The increase in activity with

use observed for the catalyst activated at 8000 was

probably a result of steaming the catalyst between the

set of runs represented by Figure 10 and the set of runs
represented by Figure 11.













SECTION V


SUMMARY

(1) The products of the decomposition of n-butyl

amine over alumina at elevated temperatures have been
separated and identified. The products are ammonia, 1-
butene, hydrogen, dibutylamine, N-butylidenebutylamine,
and butyronitrile together with traces of ethylene and
methane.

(2) The catalytic activity of samples of alumina
prepared by heating at 5000 and 800 in a vacuum has been
measured for the decomposition of butylamine as a function
of temperature between 380 and 4300*

(3) The catalytic activity of samples of alumina
prepared by heating at $00o and 8000 in a vacuum and at
8000 in the presence of water vapor has been measured for
the decomposition of butylamine as a function of the re-
ciprocal of the space velocity at 415 and 4000

(4) The catalytic activity of a sample of alumina
prepared by heating at 500o in a vacuum has been measured
for the decomposition of dibutylamine as a function of the
reciprocal of the space velocity at 4159 and 4000,










(5) The probable path of the decomposition of
butylamine over alumina at elevated temperatures has been

established in the light of the results obtained from the

decomposition of butylamine and dibutylamine as a function
of the reciprocal of the space velocity.

(6) The catalyst activated at 800 in a vacuum, in
view of the decrease in surface area with activation tem-

peratures above 600, has been shown to be a more active

catalyst for dehydrogenation reactions than the catalyst

activated at 500, in a vacuum.

(7) It has been shown that the total activity of
the catalyst activated at 8000 in a vacuum is smaller than
the total activity of the catalyst activated at 5000 in a
vacuum, and that the total activity of the catalyst acti-

vated at 800o in the presence of water vapor is smaller than
the total activity of the catalyst activated at 8000 in a

vacuum.































APPENDIX












PART I

Per Cent Weight Determinations


The results of the procedure used to analyze the
condensible products are tabulated in per cent weight since
known weihts of the compounds were used to prepare the
mixtures. The fractions of the total volume were first
determined and, from these and the total volume, the milli-
liters of the compounds were calculated. The weights of
the compounds were calculated from the milliliters and the
densities of the compounds. The per cent weights were cal-
culated from the weights of the separate compounds and the
total weight of the mixture.


Butyl-
amine
Act. Cale

a5.1 45.5
74.5 75.1
53.3 53.0
59.9 59.4
41.9 42.4
58.1 58.8
46.6 46.4
49.9 49.6


Dibutyl.
amine
Act. Cal.

51.7 51.8
19.2 19.6
37.6 38.6
27.1 28.3
48.1 47.4
15.0 14.7
32.8 32.8
22.5 22.8


n-Butylidene- Butyro-
n-butylamine nitrile
Act. Cal Act. Cal.

3.2 2.6
6.3 5.1
9.1 8.4
12.8 12.2
3.0 2.6 7.0 7.6
4.9 4.5 22.1 22.0
7.9 7.8 12.7 12.7
10.7 10.8 16.9 16,9


(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)













PART II

Material Balances

The results of the material balances obtained

for the eight runs are tabulated in moles. Line (18)

gives the difference between the calculated moles of

l-butene produced and the actual moles of 1-butene

found by analysisa-line (11) plus line (14). The re-

sults are low as expected due to the formation of

ethylene and methane. Line (19) gives the difference

between the moles of hydrogen found by analysis and

the calculated moles of hydrogen produced. The results

are low as expected due to decomposition which is evident

by the presence of ethylene and :.3thane. Line (20) gives

the difference between the moles of hydrogen which would

be formed by the decomposition of (18) and the moles

accounted for by ethylene and methane which should give

the same result as (19). The eighth run was made in the

absence of a catalyst in order to determine if any re-

action occurs by thermal decomposition.











Run No. 9 0.226 moles of butylamine passed over

catalyst at 425* at a reciprocal space velocity of 11.2.
(1) Butylamine collected in receiver I. .... 0.0O18
(2) Dibutylamine .. . . . . . . 0.0246

(3) N-Butylidenebutylamine. . . . . . . 00074
(4) Butyronitrlle . . .. .. *. 0.0437
(5) Base collected in receiver L' . . . . 0.0980
(6) Butylamine collected in receiver L' . . . 0.0104

(7) Ammonia collected in receiver L'. .* * .. 0.0876
(8) Total Butylamine Unreacted. . . . . 0.0522
(9) Ammonia dissolved in condensible products . 0.010
(10) Total ammonia produced. . . . . . . 0.098
(11) 1-Butene dissolved in condensible products. . 0.0239
(12) 1-Butene produced . . . . . . .. 0.066

(13) Hydrogen produced . . . . . . 0.095
(14) 1-Butene in gaseous products. . . . . 0.0319
(15) Ethylene in gaseous products. . . . . 0.0016
(16) Hydrogen in gaseous products. . . . . 0.1142
(17) Methane in gaseous products . . . . . 0.0087
(18) 1-Butene difference . . . . . 0.010
(19) Hydrogen difference * . . . . 0.019
(20) Hydrogen produced by decomposition. . . . 0.019













Run No. 10 0*226 moles of butylanine passed over
catalyst at 4180 at a reciprocal space velocity of 11.2.
(1) Butylamine collected in receiver I. . .. 0.0467
(2) Dibutylamine. . . . . . . . . 0*0324

(3) N-Butylidenebutylamine. . . . *. 0.0089
(4) Butyronitrile . . . . . . 0.0351
(5) Base collected in receiver L' .. . . . 0.0936
(6) Butylamine collected in receiver L' . . 0.0089
(7) Ammonia collected in receiver L'. . . . 0.0847
(8) Total Butylamine Unreacted... *. . . 0.0552
(9) Ammonia dissolved in condensible products . 0.009
(10) Total ammonia produced. . . . * * 0.094
(11) 1-Butene dissolved in condensible products. . 0.0214
(12) 1-Butene produced. . . * * * *. 0.053

(13) Hydrogen produced . . . . . . * 0.079
(14) 1-Butene in gaseous products. .. . . .. 0.0244
(15) Ethylene in gaseous products .. . .* . o 0.0015
(16) Hydrogen in gaseous products. * * *. 0.0922
(17) Methane in gaseous products .. . . 0.0078
(18) 1-Butene difference . . . .. . . 0.007
(19) Hydrogen difference . 9 . . . 0.013
(20) Hydrogen produced by decomposition. . . . 0.009












Run No. 11 0*226 moles of butylamine passed over


catalyst at 417 at a reciprocal space velocity of

(1) Butylamine collected in receiver I. . . .

(2) Dibutylamine. .. . * * * *

(3) N-Butylidenebutylamine ...* .. .

(4) Butyronitrile . *. . . * .
(5) Base collected in receiver L' *. * *.
(6) Butylamine collected in receiver L' . . .

(7) Ammonia collected in receiver L'. . ...
(8) Total butylamine unreacted. . . . .

(9) Ammonia dissolved in condensible products .

(10) Total ammonia produced. . . . . .

(11) 1-Butene dissolved in condensible products. .

(12) 1-Butene produced *. . .. . . .

(13) Hydrogen produced . . *. . .

(14) 1-Butene in gaseous products. ........

(15) Ethylene in gaseous products. .......
(16) Hydrogen in gaseous products . . ... .

(17) Methane in gaseous products . . .
(18) 1-Butene difference . . . .

(19) Hydrogen difference . . . . .. .

(20) Hydrogen produced by decomposition. . . .


L1.2.

0.0593

0.0371
0,0103

0.0187
0.0989

0.0077

0.0913
0.0670

0.002

0.093
0.0112

046

0.048

0.0315
0.000

0.0499

0.0048

0.003
0.002

0.002












Run No. 12 0.226 moles of butylamine passed over

catalyst at 4300 at a reciprocal space velocity of 11.2.


(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)


Butylamine collected in receiver I. . .

Dibutylamine * . . . . .0 .

N-Butlidenebutylamine. . . . . .

Butyronitrile . . . . . . . .

Base collected in receiver L' . . . .

Butylaaine collected in receiver L' . . .

Ammonia collected in receiver L'. .. .* .

Total butylamine unreacted. . .. *.

Amuonia dissolved in condensible products .


(10) Total ammonia produced .. . ..

(11) 1-Butene dissolved in condensible pro

(12) 1-Butene produced . . . .

(13) Hydrogen produced . . . .

(14) 1-Butene in gaseous products. ...

(15) Ethylene in gaseous products. .

(16) Hydrogen in gaseous products. . .

(17) Methane in gaseous products . .

(18) 1-Butene difference .. . . .

(19) Hydrogen difference . . . .

(20) Hydrogen produced by decomposition.


* d 0

ducts.


* 0 0

O

O 0

O 0 0

* 0 0

00000

00000

O 0 0 0

* 0 0 0


0

0

S

0

0

0



0


* S

* 0


o.o085

0.0205

0.0076

0.0351

0.1124

0.0109

0.1015

0.0594

0.002

0.104



0.075

0.078

0.0475

0.0015

0.0923

0.0078

0.013

0.014

0.023











Run No. 13 0.226 moles of butylamine passed over
catalyst at 422 at a reciprocal space velocity of 11.2.
(1) Butylamine collected in receiver I. . . . 0.0575
(2) Dibutylamine. . . . . . . 0 ,0290

(3) N-Butylidenebutylamine. . . .. 0.0095
(4) Butyronitrile .. ... . ... . . . 0.0244
(5) Base collected in receiver L' . . . . 0.1042
(6) Butylamine collected in receiver L' . . . 0.0090

(7) Ammonia collected in receiver L'. . 0.0952
(8) Total butylamine unreacted. . . . . 00665
(9) Ammonia dissolved in condensible products . 0.003
(10) Total ammonia produced. . . . . . 0.098
(11) 1-Butene dissolved in condensible products. . 0.0082
(12) 1-Butene produced .. . . . . . 0058
(13) Hydrogen produced . * 0.058
(14) 1-Butene in gaseous products. . . . . 0,0456
(15) Ethylene in gaseous products. . . . . 0.000
(16) Hydrogen in gaseous products. . . . 0.0647
(17) Methane in gaseous products . . . . 00049
(18) 1-Butene difference . . . . . . . 0.004
(19) Hydrogen difference . . . . . . . 0.007
(20) Hydrogen produced by decomposition. . . 0.006













Run No. 14 0.226 moles of butylamine passed over
catalyst at 422* at a reciprocal space velocity of 9.3.
(1) Butylamine collected in receiver I. . . 00572
(2) Dibutylamine. .* . . . .. . 0.0340

(3) N-Butylidenebutylamine. . . . 0.0106
(4) Butyronitrile . . . . . 0.0206
(5) Base collected in receiver L' . . . . 01008
(6) Butylamine collected in receiver L' .* 0.0081

(7) Ammonia collected in receiver L'. . .. 0.0927
(8) Total butylamine unreacted . . . . 0.0653
(9) Ammonia dissolved in condensible products . 0.003
(10) Total amnonia produced. . . . . * 0.096
(11) 1-Butene dissolved in condensible products. 0.0073
(12) 1-Butene produced . . . . . 0.051
(13) Hydrogen produced . . . . 0.052
(14) l-Butene in gaseous products. . . 0.0352
(15) Ethylene in gaseous products. . .. 0.0007
(16) Hydrogen in gaseous products. . . . 0.0557
(17) Methane in gaseous products . .. . 0.0068
(18) 1-Butene difference . .. .. 0.008
(19) Hydrogen difference . .. .. .. . . 0.004
(20) Hydrogen produced by decomposition. . .. 0.018




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