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6/01 c:/CIRC/DateQue.p65-p. 15
THE

DEVELOPMENT OF 4 COMMER CIAL
PROCESS
FOR THE MANUFACTURE oF
DIMETHYLANILINE.

A THESIS
Submitted to the Faculty of the

MICHIGAN AGRICULTURAL COLLEGE

BY

RAYMOND LEROY BAX?ER

Candidate for the Degree
Of Chemical Engineer.

1920.
wN

reer
CONTENTS

Chapter
I Introduction.
II Dimethylaniline: Its importance and use.
Iftl Literature.
IV Experimental Work.

V Design of plant: Operation, and costs.

93879
CHAPTER I.

INTRODUCTION.

Prior to the Great War the production of
dyes in the United States was negligible. Of the
total consumption only about one fifth was produced
in this country, or about 3,000 short tons, and
practically all of the intermediates or basis of

these colors were imported from Germany.

In the year 1914 about seven companies were
engaged in producing dyes employing about 600 men,
and having a total capital of $3,000 (000. The
quanity produced was as Said before, about 6,000,000
pounds with a value of $3,500,000.

In 1918 the United States produced approximately
76,802,959 pounds of different dyes with a total
Valuation of $63,815,746.
Nowe

CHAPTER II.

DIMETHYLANALINE: ITS IMPORTANCE AND USE.

From the ten substances or “crudes" as they
are commonly designated, obtained from coal tar
suitable for making dyes, three hundred intermediates
are manufactured. These three hundred intermediates
from the bases of about nine hundred dyes of commercial

importance at the present time.

The intermediates are divided into about ten
different classes according to the characteristic
groups which they contain. Dimethyl-aniline is a
member of the Secondary Amines and their derivatives
group. It is superceded only by déphenylamine in
quantity used and which amounts to 4,263,458 pounds
with a value of $2,412,820.

At the present time the demand far exceeds

the amount produced.

It finds its main use in the manufacture of
two very important dye stuffs, namely, Malachete
Green and Mekhyl Violet. The quanity of these dyes
used amounts to 290,416 pounds with e valuation of
$1,626,466 for Malachete Green and 632,196 pounds
with a valuation of $1,756,775 for Methyl Violet.
Prom the above figures it can be readily
seen that this compound is of considerable commercial
importance. To develop a process for its manufacture

commercially was a problem thought worthy of under-
taking.
CHAPTER III.

LITERATURE.

The first steps in the work of developing
a commercial process for the manufacture of dimethyl-
aniline was to examine the literature, and to
discover if possible what work had been done on the

manufacture of this intermediate.

A thoro examination revealed that while it
was being manufactured in Germany in considerable
quantity very little had been written regarding the

type of apparatus used and the control of the process.
It was found that there were four processes
of commercial value which are as follows:

ANILINE HYDROCHLORIDE PROCESS

A mixture of aniline seventy-five parts,
aniline hydrochloride twenty-five parts, and methyl
alcohol (free from acetone) seventy-five parts is

heated in a cast iron auto clave at 230° to 270°.
METHYL CHLORIDE PROCESS. |

Aniline (50 kilos) is well agitated in an : |
|
auto-clave with milk of lime made from 40 kilos of
5.

quick line and 75 litres of water. The whole is
heated to 100° C. and methyl chloride pumped in at
5-6 atmospheres pressure. About 62 kilos of methyl
chloride are required and the time taken about three
hours. The dimethyl aniline is then distilled with

stean.
THE IODINE PROCESS.

This process consists in heating aniline with
methyl alcohol and iodine at 230° C for seven hours.
Distilling off the dimethyl aniline with stean.

THE SULPHURIC ACID PROCESS.

Bighty kilograms of aniline, seventy-eight
kilograms of methyl alcohol and eight kilograms of
sulphuric acid 66° Be, ate heated together in an
autoclave at 230° to 235°. The pressure rises to
twenty-eight to thirty-two atmospheres. This pressure
remains constant for three hours after whioh it falls
off as the reaction slows up. The proémct is then
neutralised with caustic soda and the dimethyl aniline
distilled with steam. |

From these four processes the "Sulphuric Acid

Process" was chosen as having the likeliest commroial
possibilities.

The aniline hydrochloride process was
rejected because of the cost of aniline hydro-
chloride and because of the extremely high wear
and tear On apparatus caused by the volatile acid.

The Methyl Chloride Procese was considered
unsuitable because of the excessive cost of Methyl

Chloride.

The Iodine Process was also dropped because
of the price of Iodine.

There is one other process which has not been
meationed before but which seems to have commercial
possibilities. This is the treatment of aniline with
dimethyl sulphate. At the present time nothing has
been done with it, but it is a process worthy of
looking carefully into.

 
CHAPTER IV
EXPERIMENTAL WORK.

It is thought that the reactions in the
"Sulphuric Acid Process" are as follows:

&

CHZ0H + Hp80, > (CHg), 80, + 8H,0

In order to carry on the work in the
laboratory it immediately became necessary to
develop some sort of a simple inexpensive piece of |
apparatus capable of standing the tremendous pressure

involved in the reaction.

A bomb made of a piece of two inch pipe six
inches long and capped at both ends which was to be
heated in an oil bath was first concieved. This bomb
held a charge of eighty grams of aniline, seventy-
eight grams of methyl alcohol, and eight gran of
sulphuric acid 66° Be. This was to give a yield of
ninety six grams of di-methyl aniline.

The bomb was heated in an oil bath at 280° to
BS0° for five hours. It became apparent during this

first run that it was going to be difficult to keep
the bomb tight under the temperature and excessive
pressure conditions, and it may be said right here
that this difficulty was encountered thruout all of
the laboratory work and the semi manufacturing scale

as well. It proved to be the hardest difficulty to surmount

and one which is very important as the success of the
process depends upon there being no leaks of pressure
Since during the time of a run even the very slightest
leak will cause a loss of aloohol in the form of vapor
which will prevent complete oonversion and the produot
will be contaminated with the mono methyl compound.

The yield of di-methyl aniline from this

first run was only fifty two grams and of very poor

quality. <A duplicate run was made with but little better

success a yeild of fifty eight grams being obtained.

It was then decided to use oleum of 20%

excess 80, in place of the 66° Be. acid. This did not

In the next run the quantity of

prove of any benefit.
This caused

sulphuric acid was increased to 80 grams.
a complete decomposition with the formation of a coke

like substance.

On the next run it was decided to increase the

time of heating to eight hours. This seemed to be a

step in the right direction for a yield of seventy
six grams was obtained, altho still contaminated

with mono-methyl aniline.
The next several runs were mde with varying
lengths of time of heating. It was found that twelve

hours gave the most satisfactory results. Longer than

this did not accomplish anything.

The best run obtained was a charge of 80 gram
of aniline, 78 grams of methyl aloohol, and 8 grams of >
sulphuric acid 66° Be. heated at 230° C for twelve
hours. <A yield of 94 grams of dimethyl aniline was
obtained containing only .25% of mono methyl. aniline.

During this laboratory work there were several
runs which were absolute failures due to the impossibility
of getting the bombs tight, so various other designs
were tried but with little mocess,.

The first idea that was tried in developing
a new bomb was to screw the caps on the pipe as far as
possible and then to run solder into the joints. This
was found to be impractical because it was impossible
to entirely fill the space and the gas worked under-
neath the solder and around the pipe until it forced

an opening.

Welding the caps on to the pipe and than
drilling and tapping a small hole in the top which
could be closed by a plug and was used for filling and
emptying was then tried but the welding proved always
to be Prous enough so that if the caps were not tight
wd
n 10

the pressure was lost just the same.

Bombs Of a larger size were then tried but it
was found that as the sise of the caps inoreased they
very often had small pinholes in them which under sum
high pressure allowed the vapor to escape, so had to

be discarded.

It was then decided to use a bomb constructed
of smaller pipe inoreasing the length to maintain
the same capacity. An inch pipe 12 inches long was
tried but it wes found that these bombs were just as

difficult to mke tight as those constructed of two
inch.

The next idea tried was to construct a
bomb of heavy steel tubing brasing a top and bottom
into it. The top had a emall nipple welded in it and
this was closed with a cap. One of these was tried out
but the brazing proved to be too weak to stand the

pressure and the bottom was blown out almost resulting

in a serious accident.

The results of the laboratory work are given

in tabulated form as follows:

 
ll

 

TABLE 1
No. Length % Mono
Run Charge of %@ Yield % Aniline Methyl
. : Run Hr. aniline
80 gms. CoH NH,
1 78 gms. CH,0H 5 50% wenn —
8 gms. H»80, 66°
z " 5 55% wane wenn
3 78 gms. CHg0H 5 48% ---- ~---
4 78 gms. CHz0H 5 -e-- ete ee
60 gms. HpS0466°
60 gms. CoHpWH,
& 60 gm. C.H,NH, Leak in Bomb
8 gms. Hp80,4
6 " 8 13% Some 11%
7 " Leak in Bomb
8 " 10 86% None 10%

9 " 12 90% None 2.5%
12

 

PARLE 1
No. ‘Length % Mono
Run Charge of % Yield % aniline Methyl
Run Hrs. Aniline
80 gms. CoH NH,
10 78 gms. CHs0H 15 90% Hone 3%
8 gms. H,80, 66°
11 " 12 91% None © 25%
160 gms. CeHeWH »
12 156 gms. CH,0H Leaky Bomb
13 " 12 88% None 4.5%
14 " Leaky Bomb
60 gms. Op HeNHo
15 78 gms. CH OH 12 89% None 1.5%

8 gis. H,80,-66°
 

 

13

noted,

3x
13

The process was now tried out on a seni-
manufacturing scale. An eight gallon antoclave
manufactured by the Buffalo Foundry md Manhine
Company was used for this work.

This autoclave held a charge of 6 kilogms.
of aniline, 5.85 kilogms. of mthyl aloohol and .6
of a kilogram of H,80,- 66°. This charge yielded
about 15 pounds of dimethyl aniline.

Considerable trouble was encountered in
keeping this autoclave tight as it was designed
with an agitator, and it was found impossible to
keep the stuffing box from leaking under this high

pre seaure.

It may be stated here that a discrepancg was noted,
whether the literature was wrong or whether the pressure

gauge on the antoclave recorded high is not known
but the maximum pressure was found to be 700 pounds
per square inch or approximately 45 atmospheres, where

as it was given in the literature to be from 30 to 32

atmos pheres.

To overcome the leaking of the stuffing box
an Oil bath was built and the agitator not used. after
cOnsiderable difficulty in which several runs were
spoiled, the packing of the stuffing box so that it

 
14

did not leak was accomplished. However, the auto-
clave was never gotten absolutely tight as the open-
ing for the blow off valve was in rather poor shape
and there was a slight leak around the threads of

the nipple which fitted in there.

Various means of stopping this were tried.
Filling the joint with glycerine and red lead was
one thing tried. Another was calking with lead.
A lead washer with a locknut was also tried, but
the most successful one of all was using an

asbestoes copper covered gasket with a locknut.

Gas was used for heating the oil bath

which surrounded the autoclave.

The results of the work on a senmi-

manufacturing basis are given in tabulated form in

Table &.
15

 

TABLE &
No. Length % Mono
Run Charge of %@Yielé %# aniline Methyl
Run Hr. Aniline
6 Kgn. CoH NH,
1 5.58 Kgm. CH,0H Leaky stuffing box.
2 " 11 80% None 3.5%
3 " Leaky stuffing box.
4 " 12 - 13 88% None 2.5%
5 n 12 - 13 88% None 3%
6 " 12 - 13 90% None 8%

It was tried to recover Run No. 3 by adding mre
aloohol and sulphuric acid and heating again but it was

not very successful.

Various experiments were run to see if when
dimethyleniline was contaminated with mono-methylaniline
whether it could be purified. Fraoctionating was tried
first but proved unsuccessful due to the nearness of

the boiling points of the two compounds.

Agitating with dilute sulphuric was tried but
16

this did not accomplish anything. It was found that

acetic anhydride would take out the mono-methylaniline

but as a commercial proposition would be too
expensive.

It is believed, however, that with a properly

built autoclave and a well designed plant that the
product could be prepared with less than 1/2% of

Mono-methylaniline.
In the following chapter is submitted a design

for a plant to manufacture 1,000 pounds of dimethyl-
adiline per day and a detailed outline of operation

and material costs.

 
17

CHAPTER V.-
DESIGN OF PLANT: OPERATION AND COSTS.

The equipment necessary for the manufacture
of 1,000 pounds of dimethylaniline per day consists
of (Plate 1) seven 75 gallon autoolaves (A) tO Ay)

@ measuring tank for aniline (1), a measuring tank
for alcohol and sulphuric acid (1), two large steam
stills (B and B)), a steam trap (C,), two condensers
(C and D), a separating tank (E) and a sponge

filter (F).

Plate number (II) shows the type of auto-

Glave to be used. ‘This autoclave is constructed of

acid resisting iron so that an extra liner is done

away with. It is set in a metal bath (K) consist-

ing of 70% lead and 30% tin. fhe bath is set in a
fire brick setting as show in Plate II, and is heated

by means of an oil burner.

The eutoclaves are loaded from the mesuring
tanks I and I' situated near the ceiling. The
aniline measuring tank is constructed of sheet iron
and is show in Plate III. The alcohol and acid
measuring tank is mde of wood lined with sheet lead.
18

From the autoolaves the product is blown
into the steam stills (B and B)). These stills, the
drawing of which is shown on Plate IV, are made
of boiler plate, and are eight feet long and five
feet in diameter. At the bottom in the front is a
2° drain. On the top at the front and back are
located two 4 inch flanged opmings and between them
is situated a 24" manhole for cleaning purposes.

On the front end an opening for putting steam into the
interior is provided. The still itself is made of
9/16" boiler plate and the jaoket of 1/2" boiler
Plate. The steam jacket has one inlet;this is
thought to be sufficient. The entire still is
covered with insulating material for effieiency.

The vapours from the still are conducted
first to the steam separator C, ; here any overflow-
ing liquid is separated and returned to the still.
This is just an ordinary type steam separator. The
vapours then go into condenser C Plate V, which
consists of 20° of 1" lead pipe, and from here inte
condenser D Plate VI, which consists of 60' of 1"
lead pipe. From C the comensate flows thru s
siphon tube back into the still. Condenser C can
be entirely out off by means of valves as it is only
used at the beginning for the reoovery of methyl

alcohol. It is necessary to use quite an excess of

 
19

alcohol in the autoclaves and costs make it desirable
to recover this. It amounts to about 2,000 pounds

a month.

The condensed steam and dimethyl aniline
now flow into the separator E, Plate VII. This
separator is constructed of 1/4" wrought iron plate
end is so designed as to be continuous in its

operation. Phe mixture flows into the perforated
tube in the center. At the end of every operation
water ie drawn off from Z until dimethyl-aniline
flows from P. Then at the beginning of the next
run valves p, P> and s are closed, the mixture
collecting separates the water flowing off at s)

and the dimethyl-aniline at Pp into the sponge
filter, Plate VIII.

The sponge filter consists of a tank which
is partly filled with a bag of sponges. The sponges
take up what little water is left in the dimethyl
aniline and it is ready for shipping.

After steam distillation dimethyl-aniline
should not come in contact with copper, bronze or
brass as it is discolored by these metals. This

same will occur in glass bottles when exposed to
Ss

light and especially with simultaneous addition of
air.

Cast or sheet iron drums are to be used as

containors when shipping.
21

DETAILS OF OPERATION.

Work is started at six in the morning. The
autoclaves are charged from the masuring tanks wi th
80 kilograms of aniline, 78 kilograms of methyl
alcohol and 8 kilograms of sulphurié acid in each.
It is thot desirable to prepare the aloohol and
sulphuric acid a head of time as this tends to speed
up the reaction. Half of the aniline is run in and
then the alcohol and sulphuric acid and then the
rest of the aniline. It is figured that the loading
ought to be completed by 10 o'clock at whioh time
heating is begun and the temperature held at 230° to
235° C. as shown by a thermometer placed in the metal
bath. At about 2 o'clock in the afternoon the maximum
pressure ought to be reached. This pressure remains
constant for about three hours and recedes slightly
there after. At 11 o'clock at night the heating is
completed and the autoclaves allowed to cool until
the next morning.

In the moming the blowing off is started:
the blow off valves in the autoclaves are slowly opened,
these are connected to a system of pipes which oonvey
the issuing gases and steam to a condenser in which
the methyl alcohol condenses. The gases which pases
thru the oondenser consisting mainly of methyl ether
22

are passed thru a water scrubber before being
released into the air. This sorubber will alse
keep back any methyl alcohol that passes thru the

condenser.

After all the pressure is released, the
blowing off of the product into the steam still is
commenced. This is accomplished by means of con-

pressed air.

A little water and sufficient Caustic soda
to neutralize the excess acid are placed in the still.
As 800n as the dimethyl-aniline is all in,a little
steam is turned into the inside to mix the contents,
then the steam is turned into the jacket. Water and
methyl alcohol distill off first and are condensed.
After most of this alcohol is out, steam is turned
into the inside of the still. ‘fhe steam carries out
the dimethyl-aniline and also a little alcohol which
remains. This passes into the first condenser where
the steam and dimethyl-aniline are condensed and
returned to the still; the methyl alcohol passes on to
the second condenser where it is cond ensed and collected.
The distillation is carried on slowly until drops of
dimethyl-aniline separate rapidly from the mixture in
the still. The vapours are now conducted direotly
into the large condenser. The condensate which is a

mixture of water and dimethyl-aniline is then run

 
uy .
a

25

into the separating tank where the dimethyl-aniline
is drawn off and the water flows away. From the
separating tank the dimethyl-aniline is run into a
sponge filter which removes all of the water. The
dimethyl-aniline is now placed in oontainers for
shipping.

There is little more to say in regard to
details of operation. Three ma@m on each shift ought
to be sufficient to run the entire plant.

STEAM REQUIREMENTS.

During the maximum distillation period the
condensate consists of 1 part dimethyl-aniline and
6 parts water added as steam. However, before and
after this period mre steam is required, further
the jacket of the still is steam heated and steam is
used for the compressing of air. Therefore, six
fold weight is not sufficient and it is figured that
15 parts of steam to 1 part of dimethyl-aniline will
be required. At the present time it is impossible
to figure the cost of this as the price of coal is go

variable.

TESTING OF DIMETHYL-ANILINE.

For the determination of mono-methyl-aniline
YY

24

the acetic anhydride test is used. acetic anhydride
added to pure dimethyl-aniline causes a lowering of
the temperature of almost 1 degree. In the best
commercial grades about 1/2 degree. If the mono-
methyl-aniline content is not too high 1° increase

in temperature corresponds to about 1/2% of mono-
methyl-aniline (exact .815° for 1% mono methyl-
aniline acoording to the Chemiker Zeitung 1889 S387).

The specifications for de-nethyl-aniline at
the present time are that it mst have a boiling
point within 4° of its true boiling point, which
is 192° C. allowing a variation of 2°- or 2°+ and
mest not contain mre than 1/2% of mono-methyl-

aniline, this last is very important.

The mono-methyl aniline test is carried out
as follows 10 c.c.of dimethyl-aniline are pipetted
into a test tube and 3 c.a. of acetic anhydride into
another. <A thermometer graduated to 0.1° is placed
in the first, both test tubes are placed in water
for about a 1/4 of an hour until the temperatures are
the same. The andydride is then added to the dimethyl-
aniline. The mixture is stirred with the thermometer and
the risé in temperature observed. With a smell content
of mono-methyl aniline the temperature at first falls
Slightly and then gradually rises.

 
25

The boiling point determination is carried

out as in the usual manner for aniline.

If it is found necessary to analyse te
analine or aloohol any of the standard methods may be
used. However, it is not likely that this will be
necessary as both of these compounds may be obtained
in pure enough form for this process.

 
26

MATERIAL costs.

Based on a yield of 92% of the theory.

60 Kilogms. - 176# CgHsWHp at 364 = $63.36
76 kilogms. - 171.6# CHgOH at 544 «= $92.66
6 Kilogms. - 17.6# Hy80, at .0105 = .19

65 kilogms. - 14.3¢ NeO0H at .059 » 84
TOTAL $157.05

93:122::176:x
93 X = 21472

X = 231# Dimethylaniline
92% yield = 212.5¢

$157.05 ¢ 212.5 = 73.94 per #
27

BIBLIOGRAPHY.

Department of Commerce Special Agents Series No. 121,

Artificial Lbyestuffs used in the United States.

Oil Paint and Drug Reporter - 1919 year book.

Orgenic Colouring Matters,
By Arthur Ge Green.

Coal Tar Dyes and Intermediates,

By Ss. DeBarry Barnett.

The Manufacture of Organic Dyestuff.
By F. W. atock.

Chemiker Zeitung 1910 - 641,
By T. Walter.

Journal of the Sooiety of Chemical Industry,
1887 - 436.
. 28

To Mr. H. 8S. Reed, Professor of
Industrial Chemistry, I wish to extend my
sincerest thanks for his help and advice and

under whose supervision this work was preformed.
/

The End.
 

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