IMPROVEMENTS IN THE PRO- DUCTION OF IODINE AND BROMINE, AND IN APPARATUS THEREFOR.
Year: 1871

page_text: LETTERS PATENT to Alfred Morris, of the Royal Exchange, in the
"
-
- A
City of London, for the Invention of "IMPROVEMENTS IN THE PRO-
DUCTION OF IODINE AND BROMINE, AND IN APPARATUS THEREFOR.'
communication from abroad by Joseph Pellieux and Albert Mazé.
Launay, of Kerhuon, Finisterre, France.
Sealed the 11th June 1872, and dated the 20th December 1871.
PROVISIONAL SPECIFICATION left by the said Alfred Morris at the
Office of the Commissioners of Patents, with his Petition, on the
20th December 1871.
I, ALFRED MORRIS, of the Royal Exchange, in the City of London,
do hereby declare the nature of the said Invention for "IMPROVEMENTS IN
THE PRODUCTION OF IODINE AND BROMINE, AND IN APPARATUS THEREPOR," (a com-
munication to me from abroad by Joseph Pellieux and Albert Mazé-
Launay, of Kerhuon, Finisterre, France," to be as follows:-
Heretofore iodine and bromine have usually been precipitated from
the so-called factory waters remaining after all the salts of soda and

page_text: potash have been removed from the kelp, heating the same by means
of fire with sulphuric acid and oxide of manganese.
It is well known that the bromine in suspension in such factory
waters does not begin to precipitate until the whole of the iodine is
thrown down, but in the ordinary process as heretofore practised the
iodine is first deposited on the inner surface of the tubes leading from
the precipitating vessel, and if the process be not then stopped at once
the bromine is next deposited on the top of the iodine, and these two
substances neutralize or decompose one another, causing thereby a
considerable waste.
It is well known that the gas denoted by NO 4 is the best agent for
the separation of iodine from the iodides. The excess of this reactive
being without effect on the iodine precipitated as well as on the bromides,
avoids the well-known inconvenience of the reactives employed in the
ordinary processes. A great variety of experiments conducted with
most minute care as well as practical manufacture on a large scale,
demonstrate however that even where the reactive is not in excess, all
the processes of oxydisation of hydroiodic acid by means of peroxide of
manganese or of chlorine are the cause of very considerable waste,
amounting to an average of 6 per cent. on the production.
Hitherto the employment of NO 4 has also been limited or prohibited
by the cost of obtaining it and by the complications, which, if no remedy
could be found, its presence gives rise to in the liquors of the iodine
factory especially when regenerated in the presence of chlorides, and of
the matrix waters strongly acidulated, as well as the difficulty expe-
rienced by the operatives by the noxious vapours of nitrous products.
Now by the new process of economical generation of NO, and the
regeneration of the same by the oxygen of the air, these difficulties have
been solved in such a manner that not only the maximum relative pro-
duction is obtained, but the work is carried on at so trifling a cost as
barely to reach one-fourth of the cost of production by the processes
heretofore used.

page_text: same with reference to the apparatus, which has been found to answer
the purpose when manufacturing on a large scale. It consists, firstly,
of a vessel or reservoir for holding the non-saturated waters; next of a
vessel which is the recipient of the nitric and sulphuric acids, and which
is placed at a lower level than the first-named vessel. It is fitted with
a bell-mouth pipe passing down from the top (where it is open to the
atmosphere) to within a short distance of the bottom. A small pipe
conveys the non-saturated water from the first-named vessel to the bell-
mouth pipe of the latter in carefully regulated quantities.
The next part of the apparatus consists in a series of closed vessels
of gradually decreasing size and connected together by elbow pipes as
hereafter described. They contain the matrix or factory waters from
which the iodine and subsequently the bromine are to be extracted.
The NO 2 vapours evolved in the before-named acid recipient mix with
atmospheric air forming NO 4, and are forced or drawn down through
a pipe to the bottom of the first in the series of the vessels containing
factory waters, where they escape into and pass up through the same,
causing thereby precipitation of iodine and being reduced into NO 2.
After having passed up through the factory waters these vapours are
reconverted into NO 4, and go off through a pipe leading to the next
vessel of the series, escaping at the bottom and passing up through the
waters while causing precipitation of iodine; the gas then escapes to
the next vessel of the series, and so on, the number of vessels being only
limited by the exhaustion of the air by being deprived of its oxygen.
Any suitable and well-known forcing or exhausting apparatus, such
as a fan or pump, may be used. Immediately the precipitation of the
iodine is completed the exhauster is stopped in its action or thrown
out of connection with the apparatus, and the waste above alluded to
caused by the untimely precipitation of bromine is thus avoided.
After the removal of the iodine the bromine may be precipitated in
the same manner, or if desired the precipitation of the bromine may be
effected in a separate apparatus, the saturated waters under treatment
being run off to the same.
To prevent the formation of nitrates sulphuric acid is added to the
factory water in the vessels, thereby transforming all the iodides into
hydroiodic acid.

page_text: It is to be observed that the distinctive feature of this Invention is
the mode of or means of extraction of iodine and bromine from the salts
in solution by means of NO 2, constantly regenerated by abstracting
from the atmosphere the oxygen necessary for its conversion into NO 4,
while the primary production of NO 2 may be effected by a variety of
well-known processes.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Alfred Morris in the Great Seal Patent Office on
the 20th June 1872.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, ALFRED
MORRIS, of the Royal Exchange, in the City of London, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twentieth day of December, in the
year of our Lord One thousand eight hundred and seventy-one, in the
thirty-fifth year of Her reign, did, for Herself, Her heirs and succes-
sors, give and grant unto me, the said Alfred Morris, Her special
licence that I, the said Alfred Morris, my executors, dministrators,
and assigns, or such others as I, the said Alfred Morris, my executors,
administrators, and assigns, should at any time agree with, and no
others, from time to time and at all times thereafter during the term
therein expressed, should and lawfully might make, use, exercise, and
vend, within the United Kingdom of Great Britain and Ireland, the
Channel Islands, and Isle of Man, an Invention for "IMPROVEMENTS
IN THE PRODUCTION OF IODINE AND BROMINE, AND IN APPARATUS THEREFOR," (a
communication to me from abroad by Joseph Pellieux and Albert Mazé-
Launay, of Kerhuon, Finisterre, France,) upon the condition (amongst
others) that I, the said Alfred Morris, my executors or administrators,
by an instrument in writing under my, or their, or one of their hands
and seals, should particularly describe and ascertain the nature of the
said Invention, and in what manner the same was to be performed,
and cause the same to be filed in the Great Seal Patent Office within
six calendar months next and immediately after the date of the said
Letters Patent.

page_text: NOW KNOW YE, that I, the said Alfred Morris, do hereby declare
the nature of the said Invention, and in what manner the same is to be
performed, to be particularly described and ascertained in and by the
following statement thereof, reference being had to the accompanying
Drawings and to the letters of reference marked thereon, that is
to say:-
Heretofore iodine and bromine have usually been precipitated from
the so-called factory waters remaining after all the salts of soda and
potash have been removed from the kelp, heating the same by means
of fire with sulphuric acid and oxide of manganese.
It is well known that the bromine in suspension in such factory
waters does not begin to precipitate until the whole of the iodine is
thrown down, but in the ordinary process as heretofore practised the
iodine is first deposited on the inner surface of the tubes leading from
the precipitating vessel, and if when all the iodine in the waters has
been thrown off and deposited the process be not stopped at once, the
bromine is next deposited on the top of the iodine, and these two
substances decompose one another, causing thereby a considerable
waste.
It is well known that the gas denoted by the chemical symbol NO 4
is the best agent for the separation of iodine from the iodides. The
excess of this reactive being without effect on the iodine precipitated
as well as on the bromides, avoids the well-known inconvenience of
the reactives employed in the ordinary processes. A great variety of
experiments conducted with most minute care as well as practical
manufacture on a large scale demonstrate however that even where the
reactive is not in excess all the processes of oxydisation of hydroiodic
acid by means of peroxide of manganese or of chlorine are the cause of
very considerable waste, amounting to an average of 6 per cent. on the
production.
Hitherto the employment of NO 4 has also been limited or pro-
hibited by the cost of obtaining it, and by the complications which, if
no remedy could be found, its presence gives rise to in the liquors of
the iodine factory, especially when regenerated in the presence of
chlorides, and of the matrix waters strongly acidulated, as well as the
difficulty experienced by the operatives by the noxious vapours of nitrous
products.

page_text: Now by the new process of economical generation of NO 4, and the
regeneration of the same by the oxygen of the air, these difficulties have
been solved in such a manner that not only the maximum relative pro-
duction is obtained, but the work is also carried on at so trifling a cost
as barely to reach one-fourth of the cost of production by the processes
heretofore used.
And in order to explain this new process I proceed to describe the
same with reference to the apparatus, which has been found to answer
the purpose when manufacturing on a large scale. This apparatus is
shewn on the accompanying Sheet of Drawings, Fig. 1 being a plan,
and Fig. 2 a side elevation of same.
It consists, firstly, of a vessel or reservoir A for holding the non-
saturated waters; next of a vessel B, which is the recipient of the nitric
and sulphuric acids, and which is placed at a lower level than the first-
named vessel; but I do not limit myself to this particular method of
creating NO 4, or to the particular agents employed, as there are other
equally good and cheap methods of producing this gas. The vessel B
is fitted with a bell-mouth pipe C passing down from the top (where it
is open to the atmosphere) to within a short distance of the bottom.
A small pipe a conveys the non-saturated waters from the first-named
vessel A to the bell-mouth pipe C of the vessel B in carefully regulated
quantities.
The next part of the apparatus consists in a series of closed
vessels E, E¹, E", E", E, and E, of gradually decreasing size, and
connected together by elbow pipes D, D¹, D", D, D, and Dш, us
hereafter described. The first four of these contain the matrix or
factory waters, from which the iodine and subsequently the bromine
are to be extracted. The NO 4 vapours evolved in the before-named
recipient B are forced or drawn down through the pipe D, freely mixed
with common air drawn in simultaneously through C to the bottom of
the first vessel E in the series of the vessels containing factory waters,
where they escape into and pass up through the same, causing thereby
precipitation of iodine and being reduced into NO 2.
After having
passed up through the factory waters these vapors are reconverted into
NO 4 by taking up two parts of oxygen from the atmosphere with
which they are mixed, and go off through a pipe D' leading to the next
vessel E³ of the series, escaping at the bottom and passing up through
the waters while causing precipitation of iodine, and being again re-

page_text: variety of well-known processes, all substantially as and for the purposes
herein set forth.
And, secondly. The employment of the herein-described or equivalent
apparatus, separately and combined, all substantially as and for the
purposes set forth.
In witness whereof, I, the said Alfred Morris, have hereunto set my
hand and seal, this Fifteenth day of June, in the year of our Lord
One thousand eight hundred and seventy-two.
Witness,
T. G. MORRIS,
Winchester.
ALF. MORRIS. (L.S.)