Improvements in and connected with the Production of Alcohols.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
Improvements in and connected with the Production of Alcohols.
We, BASIL JOHN ATTERBURY, of The Rowans, New Maldon, Surrey, Engineer,
THOMAS MACALPINE, of 22, Sutton Court Road, Chiswick, Middlesex, Doctor of
Science, Consulting and Research Chemist, and THE ALCOHOL SYNDICATE LIMITED,
of 42A, Bloomsbury Square, London, do hereby declare the nature of this invention
to be as follows:-
This invention relates (a) to improvements in the production of alcohols from
acetylene and hydrogen gases in conjunction with sulphuric acid, (b) to the employ-
ment of ethylene gas (C2H4) in connection with the production of alcohols with
sulphuric acid, (c) to an improved production of acetylene and hydrogen gases in a
combined form for use with sulphuric acid for the production of the alcohols.
The gas supply is conducted to receivers containing sulphuric acid to be
chemically combined therewith as hereafter stated. To effect this process it is
desirable that the gas should be brought into contact with ever changing particles
of the sulphuric acid, and to effect this in an expeditious manner.
We will now proceed to describe how our invention is carried into effect.
The acetylene gas as generated is conveyed by means of a pipe fitted with cocks
or valves through cooling coils to a gasholder. At the same time as the acetylene
gas is being generated we also produce hydogen gas in any of the known ways, and
this hydrogen gas we also convey to the same gasholder where it may combine
with the acetylene gas, or may merely form a mechanical mixture; or we may keep
the gases separate. We prefer to purify both the gases by the ordinary means,
that is to say, by passing the acetylene over or through sulphuric acid, and the
hydrogen through water. We next convey the gases into a vessel containing
sulphuric acid. The gases should preferably whether introduced to the acid in
combination or as a mechanical mixture, or separately, bear the following proportions
acetylene gas by weight 13, hydrogen gas by weight 1.
It is clear from this that as the chemical formula for acetylene gas is CH, wo
make by the above addition an alteration in the compound or mixture, so that after
the addition of the hydrogen in the above named proportions it becomes C²H² + H²,
if in the form of a mixture, or C2H+, (ethylene gas,) if in the form of a compound.
While the above are theoretically the exact proportions, we have found it preferable
in practice to present the hydrogen in excess. In vessels to which we introduce
the gases we have a suitable supply of concentrated sulphuric acid preferably of the
strength denoted by the formula H2SO4 + H2O. If we have Nordhausen or fuming
acid, we add combining proportions of water to bring it to the above strength. We
prefer to have the acid as free as possible from nitrogenous compounds which are nearly
always present in ordinary commercial sulphuric acid. Our reason for the preference
for concentrated sulphuric acid is, that the absorption of the gas or gases by the acid
is much more rapid and complete when the acid is of the strength named. It follows

page_text: that the acid may be of lower strength but the results are not so satisfactory as
regards the speed of absorption unless we also use pressure to pass the gases into
the acid. We have obtained good results while working at a density of 1.750 sp. gr.
at a pressure of one fifth of an atmosphere, and a less satisfactory result by working
at a slightly lower specific gravity.
If the acetylene and hydrogen gases are brought into contact with the sulphuric
acid in any other form than a chemical combination, that is to say as a mechanical
mixture, then we alter the character of the absorbing acid by previously mixing
with it a quantity of rectified spirits of wine. There are two ways to do this:-
(a) a small quantity of alcohol may be added to the acid in the proportion of one
twentieth, and then the gases either in combination or mixed led into the compound;
or (b) a quantity of alcohol may be mixed with sulphuric acid in chemical pro-
portions and the gases introduced to the compound together with a small quantity
of fresh sulphuric acid. The acid should be presented before the gases, and as the
gases are absorbed, more acid should be allowed to drop in. The acid should
always be slightly in excess until the vessel is filled when the balance of the gases
may be passed in and absorbed. Or before passing the mixed or compound gases
in to the acid, we may pass them through rectified alcohol, the latter being at any
temperature between OC, and the vapourising point.
It is obviously desirable that the gases should be absorbed as rapidly and com-
pletely as possible. We have good results from the agitation of the acid solely
from the passage of the gas or gases through it by putting the gas under pressure,
and when we follow that plan we provide a series of "Woulffe" bottles, or a series
of vessels arranged after the manner of "Woulffe" bottles. We also find it
preferable in addition to passing the gas or gases through the sulphuric acid under
pressure, to heat the acid to between 150 & 200 F. The result of this action is that
if the gases or gas enter the acid in the form of a mechanical mixture, a combina-
tion of the gases takes place with certainty, and the gases or gas thus formed
enters into more perfect combination with the sulphuric acid.
When the acid has absorbed as much gas as possible, it (the acid) is conveyed
into a suitable "still" and diluted with water and subjected to heat when alcohol
distils over.
A further plan to produce the gas or gases to be absorbed into the acid is to produce
the acetylene and hydrogen in a combined form in the following manner. We intro-
duce into the generator already charged with water a mixture in suitable proportions
of zinc, caustic lime and calcic carbide, in as fine a state of division as possible.
It is desirable that the hydrogen should be produced slightly in excess of the actual
combining proportions so that no acetylene may pass out uncombined. The presence
of a slight quantity of uncombined hydrogen is unobjectionable as it will pass
through the sulphuric acid and escape. When the gases are produced and dealt
with in this manner in the generator, we afterwards pass them through the sulphuric
acid as previously described.
The sulphuric acid, or alcohol and sulphuric acid, having become saturated with
the acetylene and hydrogen gases, or the resultant combined gas produced as
described, its chemical characteristics are shown thus C2H6 + SO. To this we add
water and heat the compound in a "still" of suitable construction for the compound
till ethyl alcohol passes over as a distillate but as the alcohol comes over it is
desireable that more water should be added to the contents of the still in the exact
quantity of the alcohol distilled.
Dated thin 15th Jan of Tanuo 1900

page_text: It is clear from this that the chemical formula for acetylene gas is C2H2, we'
make by the above addition an alteration in the compound, so that after the addition
of the hydrogen in the above named proportions, it becomes C2H2 + H2², if in the
form of a mixture, or C2H, if in the form of a compound. While the above are
theoretically the exact proportions we have found it preferable in practice to
introduce the hydrogen in excess. It is preferred to use ethylene gas instead of
using the acetylene and hydrogen as above explained. We may obtain our supply.
of ethylene gas from any convenient source, but preferably by the means described
for the production of this gas in the Specification of our later Application
No. 2961/1898. In the vessels to which we introduce the ethylene or mixture of
acetylene and hydrogen, we have a suitable supply of concentrated sulphuric acid
preferably of the strength denoted by the formula H2SO4 + H2O. Our reason for
preferring concentrated sulphuric acid is that the absorption of the gas or gases by
such acid is much more rapid and complete than when the acid is less concentrated.
The acid used may be of lower strength but the results are not so satisfactory as
regards the speed of absorption. We may alter the character of the absorbing acid
by previously mixing with the sulphuric acid a quantity of absolute alcohol. There
are two ways in which this can be done, viz. (a) a small quantity of alcohol may be
added to the acid and then the gas or gases either separately or together let into
the compound, or, (b) a quantity of alcohol may be mixed with the gas or gases by
passing it or them through rectified spirits of wine before it or they are introduced
into the sulphuric acid. It is obviously desirable that the gas or gases should be
absorbed as rapidly and as completely as possible. In order to induce this absorption
we break up and divide the gas or gases
and so cause it or them to

page_text: be presented to the acid in minute particles. This can be done by mechanical
means, or by shaking of the vessel holding the acid. We have had good results
from the agitation of the acid solely from the passage of the gas or gases through
it by putting the gas under pressure, and when wo follow that plan we provide
a series of "Woulfe" bottles to hold the acid, and put the gas under sufficient
pressure to force it through all the bottles. When passing the gas or gases through
or into the sulphuric acid under pressure, we prefer to raise the temperature of the
acid to about 150 degrees F. A further plan to obtain the gas to be absorbed into
the acid is to produce the acetylene and hydrogeu in a combined form in the
following manner. We introduce into the generator already charged with water a
mixture in suitable proportions of zinc, caustic lime, and calcic carbide, in as fine
a state of division as possible. It is desirable that the hydrogen should be produced
slightly in excess of the actual combining proportion so that no acetylene may pass
out uncombined. The presence of a slight quantity of uncombined hydrogen is
unobjectionable as it will pass through the sulphuric acid and escape.
gases are produced in this manner in the generator, we afterwards pass them
through the sulphuric acid as previously described. The sulphuric acid having
become thoroughly saturated with the acetylene and hydrogen gases, or the ethylene
gas, the compound is conveyed into a suitable "still," to this we add sufficient water
to prevent the formation of ether, and then distil over the alcohol. As the alcohol.
comes over it, it is desirable that more water should be added to the contents
of the "still" so as to keep the dilution of the sulphuric acid approximately
constant.
When the
In the production of vinyl alcohol, we use the acetylene gas alone but in all
other respects the process is substantially as above described for the production of
ethyl alcohol.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, we would observe that we are
aware that chemical works state that ethyl alcohol can be produced from acetyleno
and hydrogen gases or ethylene gas, in conjunction with sulphuric acid, and that
vinyl alcohol can also be produced from acetylene gas and sulphuric acid, but
hitherto such productions have only been a chemical curiosity or matter of laboratory
experiment, the alcohol so obtained costing several times more than its market
value, and so far as we know no complete process has been known or described
before our invention by which these alcohols could be produced from acetylene and
hydrogen gases and sulphuric acid that is capable of being worked successfully on
a commercial manufacturing scale, but what we claim is:
1. The production of ethyl alcohol from a mixture of acetylene and hydrogen
gases in conjunction with sulphuric acid, herein before described.
2. The production of ethyl alcohol from ethylene gas in conjunction with sulphuric
acid herein before described.
3. The production of vinyl alcohol from acetylene gas in conjunction with
sulphuric acid, hereinbefore described.
FREDERIC PRINCE,
37, Cursitor Street, Chancery Lane, Agent for Applicant.