IMPROVEMENTS IN THE MANUFACTURE OF SODA ASH AND SULPHURIC ACID
Year: 1855

page_text: LETTERS PATENT to William Blythe, of Oswaldtwistle, in the County of
Lancaster, Manufacturing Chemist, and Emile Kopp, of Accrington, in
the County of Lancaster, Chemist, for the Invention of "IMPROVEMENTS
IN THE MANUFACTURE OF SODA ASH AND SULPHURIC ACID."
Sealed the 20th April 1855, and dated the 15th February 1855.
PROVISIONAL SPECIFICATION left by the said William Blythe and
Emile Kopp at the Office of the Commissioners of Patents, with their
Petition, on the 15th February 1855.
We, WILLIAM BLYTHE, of Oswaldtwistle, in the County of Lancaster,
Manufacturing Chymist, and EMILE KOPP, of Accrington, in the County of
Lancaster, Chymist, do hereby declare the nature of the said Invention for
"IMPROVEMENTS IN THE MANUFACTURE OF SODA ASH AND SULPHURIC ACID" to be
as follows:-
Our Invention consists in the use of the oxides or carbonates of manganese,
zinc, copper, and lead, instead of lime or carbonate of lime, in the manufacture
of black ash, or crude soda. In fluxing sulphate of soda with coal slack and
lime, the ordinary black asb, or crude soda, is obtained. Now we, in using the
oxides or carbonate of manganese instead of lime, obtain a peculiar manga-
niferous crude soda. In using instead of lime the oxide or carbonate of zinc,
we obtain a peculiar zinciferous crude soda. In using instead of lime the
oxide or carbonate of copper, we obtain a peculiar cupriferous crude soda. In
using instead of lime the oxide or carbonate of lead, we obtain a peculiar

page_text: plumbiferous crude soda. In using a mixture of these different metallic
oxides, we obtain a mixture of the above-mentioned metalliferous crude sodas.
These metalliferous crude sodas are afterwards decomposed into, firstly, a
watery solution of carbonate of soda, which by evaporation yields soda ash.
Secondly, a residue of the sulphurets of these different metals. These
sulphurets being subjected to an oxydising and roasting process, yield sul-
phurous acid, (which is converted by the ordinary process into sulphuric acid)
and oxides of the different metals, which oxides are again used for the
preparation of a new quantity of metalliferous crude soda.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said William Blythe and Emile Kopp in the Great Seal
Patent Office on the 14th August 1855.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, WILLIAM
BLYTHE, of Oswaldtwistle, in the County of Lancaster, Manufacturing
Chymist, and EMILE KOPP, of Accrington, in the County of Lancaster,
Chymist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Fifteenth day of February in the year of our
Lord One thousand eight hundred and fifty-five, in the eighteenth year of
Her reign, did, for Herself, Her heirs and successors, give and grant unto
us, the said William Blythe and Emile Kopp, Her special license that we,
the said William Blythe and Emile Kopp, our executors, administrators,
and assigns, or such others as we, the said William Blythe and Emile
Kopp, our 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
MANUFACTURE OF SODA ASH AND SULPHURIC ACID," upon the condition (amongst
others) that we, the said William Blythe and Emile Kopp, by an instrument
in writing under our hands and seals, or under the hand and seal of either of
us, 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 we, the said William Blythe and Emile Kopp,
do hereby declare the nature of our said Invention, and in what manner the
same is to be performed, to be particularly described and ascertained in and
by the following statement, that is to say:-
Our said Invention of improvements in the manufacture of soda ash and
sulphuric acid consists in the use of the oxides and carbonates of manganese,
zinc, copper, and lead, instead of lime or carbonate of lime, in the manufacture
of black ash or crude soda, from which soda ash is obtained in manner
herein-after mentioned and the sulphurets of the different metals produced by
the process we use for the purpose of forming or reproducing sulphuric acid,
as herein-after mentioned.
In performing our Invention by the use of manganese, we proceed as
follows:-We flux together in a furnace sulphate of soda, oxide or carbonate
of manganese (either natural or artificial) and coal slack, by which we obtain
a manganiferous barilla or crude soda.
And
We charge a furnace with these materials, when of the ordinary quality,
in about the following proportions, namely, two and a half hundredweight of
sulphate of soda, from one and a half to two hundredweight of black
oxide of manganese, and from one hundred and twenty to one hundred
and forty pounds of coal slack, varying these proportions, however, when
necessary, by a different strength or purity of any of the materials used; and
for producing a good result, we deem it expedient to use the materials in
such proportions that there shall not be less than five parts of pure dry sesqui-
oxide of manganese for every nine parts of pure dry sulphate of soda.
we may also observe that we prefer to use the manganese a little in excess, in
order to prevent as much as possible the presence of sulphuret of sodium
in the carbonate of soda obtained by the process. The coal slack being used
as a deoxydising agent, any other carbonaceous fuel may be used, the propor-
tion or quantity depending on the quantity of carbonaceous matter which the
fuel may contain, but we avoid as much as possible any excess of the car-
bonaceous matter used, because we consider it injurious in the subsequent parts
of the process. We reduce the materials into a state of powder and mix
them, after which they are fluxed and worked together in a furnace in the
same way as in producing ordinary barilla. When the materials have been
sufficiently fluxed (which will require about the same time for that purpose as
the ordinary materials for making black ash), they are to be drawn into an
iron waggon or other convenient receptacle in the usual manner and allowed
to cool. A lump of manganiferous barilla thus obtained is next made to
undergo a crumbling process before lixiviation, for- the purpose of facilitating

page_text: the separation of the soda from the sulphuret of manganese. This crumbling
process consists in exposing the barilla in a convenient building to the action
of the atmosphere, moisture, and carbonic acid artificially supplied, and is
exactly the same as that described for the treatment of ferruginous barilla in
the Specification of Letters Patent granted to us, and sealed on the Third day :
of October, One thousand eight hundred and fifty-four. The powdered barilla
thus obtained is then to be lixiviated, for the purpose of obtaining the soda in
a state of solution, for which purpose we put the powder into a suitable iron
cistern with water, and cause it to be well stirred. As much of the powdered
barilla is put into the water as will produce a clear solution of a specific
gravity of from twenty to thirty degrees of Twaddle's hydrometer. The black
residuum of the barilla being allowed to settle, the clear solution is then to
be drawn off into a separate vessel. The residuum is then to be lixiviated
two or three times with fresh water; the solution thus obtained being used
for lixiviating fresh portions of barilla until it forms a solution sufficiently
strong, or of the specific gravity herein-before mentioned.
The concentrated solution of carbonate of soda obtained in this way, after
standing a sufficient time to allow the impurities to subside, may be further
concentrated, so as to produce crystallized carbonate of soda, or dried into
soda ash in the same way as is usually adopted in treating the liquor obtained
from ordinary barilla.
When the powdered manganiferous barilla, above mentioned, has been
lixiviated in water so as to dissolve the soda or carbonate of soda it contains, a
black or dark coloured residuum remains, consisting principally of sulphuret
of manganese. This residuum, after being well washed, we place in a pit
(similar to a plasterer's lime pit) or in any convenient vessel, for the purpose
of the water being drained from it. After being thus drained until it is
sufficiently firm or stiff, we cause it to be dried in the air, or in a stove, or by any
other convenient means, until (when handled) it crumbles to a damp powder
between the fingers. In this condition, the residual sulphuret of manganese is
ready to be applied in the making of sulphuric acid by burning it at a red
heat. The manner of conducting this part of the operation is the same as
that described for burning artificial sulphuret of iron in the Specification of
the Letters Patent herein-before referred to.
By the process of burning, the sulphuret of manganese is re-converted into
oxide of manganese, which may be again used for making a fresh portion of
manganiferous barilla; and the oxide of manganese produced by the repetition
of the above process may be repeatedly employed, in manner herein-before
described, until earthy matters shall accumulate in it, so as to interfere with

page_text: its action or the quality of the products obtained by the process. The
sulphuric acid from time to time produced, in manner above mentioned, may
also be employed in the ordinary manner for decomposing chloride of sodium
and obtain sulphate of soda, in manner above described, for the purpose of
manufacturing soda ash and reproducing sulphuric acid.
When the oxide or carbonate of zinc is employed, we flux together two and
a half hundredweight of sulphate of soda, one and a half to one and three
quarter hundredweight of oxide of zinc, and from one hundred and fourteen
to one hundred and twenty pounds of coal slack. When these materials are
fluxed together in the same manner as herein-before described, a zinciferous
barilla is obtained, which when treated in a manner similar to that used
with the manganiferous barilla yields a solution of carbonate of soda and a
residue of sulphuret of zinc. The sulphuret of zinc may be roasted in the
same manner as the sulphuret of manganese, to liberate the sulphur and
obtain oxide of zinc.
When the oxide and carbonates of copper are employed, we prefer to flux
together two and a half hundredweight of sulphate of soda, one and a half
hundredweight of black oxide of copper, and one hundred and twenty pounds
of coal slack. When the oxides or carbonates of lead are employed, we
prefer to use litharge; for this purpose we flux together two and a half
hundredweight of sulphate of soda, four hundredweight of litharge, and from
one hundred and ten to one hundred and twenty pounds of coal slack.
When the oxides of copper or lead are employed, metalliferous barillas are
obtained, which when treated in the same manner as the manganiferous
barilla yield carbonate of soda and residual sulphurets of the metals. These
sulphurets can be afterwards heated for the purpose of liberating and recover-
ing the sulphur, and for reconverting them into oxides, to be again used in the
same manner as herein-before described.
In witness whereof, I, the said William Blythe, have hereunto set my
hand and seal, this Thirteenth day of August, in the year of our Lord
One thousand eight hundred and fifty-five.
Witness,
H. B. BARLOW,
Manchester.
WILLIAM BLYTHE. (L.S.)