IMPROVEMENTS IN THE MANUFACTURE OF SODA, SULPHUROUS AND SULPHURIC ACIDS, CARBONIC ACID, CHLORINE AND MURIATIC ACID, AND APPARATUS USED THEREIN
Year: 1856

page_text: LETTERS PATENT to John Barrow, junior, of the City of Manchester, in
the County of Lancaster, Manufacturing Chemist, for the Invention of
"IMPROVEMENTS IN THE MANUFACTURE OF SODA, SULPHUROUS AND SULPHURIC
ACIDS, CARBONIC ACID, CHLORINE AND MURIATIC ACID, AND APPARATUS USED
THEREIN."
Sealed the 8th August 1856, and dated the 26th February 1856.
PROVISIONAL SPECIFICATION left by the said John Barrow, junior, at
the Office of the Commissioners of Patents, with his Petition, on the
26th February 1856.
I, JOHN BARROW, junior, of the City of Manchester, in the County of
Lancaster, Manufacturing Chemist, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE MANUFACTURE OF SODA, SULPHUROUS AND
SULPHURIC ACIDS, CARBONIC ACID, CHLORINE AND MURIATIC ACID, AND APPARATUS
USED THEREIN," to be as follows:-
My improvements consist in, firstly, the use of manganese or any of its
several oxides, or the oxide of manganese in combination with carbonic acid, as
carbonate of manganese, along with coal or any other carbonaceous matter, for
the purpose of decomposing sulphate of soda, thus obtaining carbonic acid,
and carbonic oxide gases, soda, and sulphuret of manganese.
Secondly, the conversion of the carbonic oxide into carbonic acid, and its
application to the conversion of soda. into carbonate of soda, or for other
purposes.
Thirdly, the use of sulphuret of manganese for the purpose of obtaining
sulphur, sulphurous acid, sulphuric acid, or sulphate of manganese.

page_text: Fourthly, the decomposition of chloride of sodium by means of sulphate o
manganese, with production of sulphate of soda and chloride of manganese.
Fifthly, the decomposition of chloride of manganese into free chlorine, o1
otherwise into muriatic acid, and oxide of manganese.
Sixthly, the arrangement of retorts so as to collect and render useful by
conversion into carbonic acid, the carbonic oxide formed during the decom-
position of sulphate of soda.
Having thus stated generally in what my improvements consist, I shall go
on to state generally the means by which I obtain these results, reserving to
myself the right of describing more fully the details of each operation in my
more complete Specification.
Firstly, the decomposition of the sulphate of soda, I accomplish by mixing
intimately sulphate of soda, coal, or any other convenient form of carbon, and
oxide or carbonate of manganese in certain definite proportions, and then
submitting the mixture to the heat of a common furnace known as a "black
ash" furnace; or I introduce the same mixture into heated retorts arranged
in a peculiar manner; or I first decompose sulphate of soda by means of carbon,
into sulphuret of sodium, and to this body, either dissolved in water or otherwise,
I add a certain proportion of carbonate of manganese, obtaining by this last
method, carbonate of soda and sulphuret of manganese. From this mixture,
namely, sulphate of soda, carbon, and oxide or carbonate of manganese,
supposing the furnace to be used, I obtain a compound consisting princi-
pally of soda and sulphuret of manganese, which I separate by lixiviation in
the ordinary manner. The liquors thus obtained, consists principally of
soda and some sulphuret of sodium and carbonate of soda, which I evaporate
to dryness, and mix with sawdust or other carbonaceous matters, and roast in
an ordinary "finishing furnace," thus obtaining carbonate of soda, which I
dissolve and crystallize for sale as soda crystals, or again evaporate to dryness
for sale as soda ash of commerce.
For certain reasons I prefer using retorts of any suitable material, so arranged
as to allow the gases evolved during the decomposition of the materials in one
retort (after passing over the oxides of either copper, iron, or manganese, or any
body capable of yielding oxygen to the carbonic oxide in heated tubes) to pass
over the materials already decomposed in the other. Thus, for instance, I charge
the first retort, which for convenience I shall call No. 1, with the mixed
sulphate of soda, carbon, and oxide or carbonate of manganese, and I obtain
as gases, carbonic acid, and carbonic oxide, the latter of which by passing over
oxide of copper, oxide of iron, or oxide of manganese in heated tubes, becomes
converted into carbonic acid; as soon as the decomposition is complete in No. 1

page_text: retort, I fill No. 2 with a similar charge of mixed materials to that put into
No. 1, and then by simple mechanical arrangements I compel the gases from
No. 2, after passing over the oxides of copper, iron, or manganese, (thus
becoming converted into carbonic acid,) to pass over the already decomposed
materials in No. 1 retort; the soda which it contains thus becoming surrounded
by an atmosphere of carbonic acid, is speedily converted into carbonate of soda.
As soon as the decomposition in No. 2 retort is complete, I take out the
materials from No. 1, which consist principally of carbonate of soda, and
sulphuret of manganese, and replace them with a second charge of mixed
materials; the gases are then compelled to flow back through No. 2 over the
now decomposed charge in that retort, occasioning the same conversion of soda
into carbonate of soda as previously occurred in No. 1, and so on repeating the
process continually. The excess of carbonic acid produced can be collected and
used for other purposes. The mixed compound of carbonate of soda and sul-
phuret of manganese, I separate by lixiviation in the ordinary manner; the
liquor thus obtained being sufficiently pure for immediate crystallization.
Thirdly, the residue from the washers, whether the furnace or retort be used,
consists essentially of sulphuret of manganese, which by heating in a current
of atmospheric air or oxygen in any suitable apparatus, is resolved into sulphate
of oxide of manganese, oxide of manganese, and sulphurous acid, which is
given off as gas, and which I convey by any suitable means, either into the well-
known sulphuric acid chambers or through other suitable apparatus, to be
convertod into sulphuric acid, or I bring into contact the sulphurous acid given
off and oxide of manganese, in such manner as to cause the production of a
further quantity of sulphate of manganese. The sulphate of manganese 1 wash
from the insoluble oxide of manganese, and add to it a certain proportion of
chloride of sodium or common salt, occasioning mutual decomposition, and
obtaining sulphate of soda and chloride of manganese; the sulphate of soda
being transferred for decomposition as herein-before described to the furnace
or retort. The chloride of manganese either alone or mixed with sulphate of
soda, I decompose in the following manner:-I pass over it, heated in any
suitable apparatus, a current of dry atmospheric air or oxygen gas, and I obtain
the chlorine of the chloride of manganese in its free uncombined state, and
ready for any application to which chlorine may be required; the residue, if
chloride of manganese alone has been used, consisting of oxide of manganese in
a fit state for use, in the usual method of manufacturing chlorine. If I wish
to produce chlorine in combination with hydrogen or the muriatic acid of
commerce, I pass over the chloride of manganese, in addition to atmospheric
air, hydrogen gas, or the vapour of water; the residue, if chloride of manganese

page_text: alone 'has been used, consisting of oxide of manganese in a suitable state for
being again used in the manufacture of chlorine. If the mixed materials of
sulphate of soda and chloride of 'manganese have been used in either of the
above operations, tlie residue will consist of sulphate of soda and oxide of
manganese, to which I add the requisite 'quantity of carbon, and transfer it to
the furnace or retort for decomposition, as herein-before stated.
t.
'
Having thus stated generally the nature of my several improvements, I beg
to .state, that without confining myself to the details, as herein mentioned, 'I
distinctly claim as my discoveries and Invention,
Firstly, the manufacture of soda, and the carbónátes of soda, by the 'decom-
position of sulphate of soda, by means of carbon and manganese or any of the
several oxides of manganese, or the carbonate of manganese, and by the decom-
position of the sulphuret of sodium, by means of of the carbonate of manganese.
Secondly, the conversion of carbonic oxide gas into carbonic acid, by means
of the oxides of copper, iron, or manganese, or by any other body capable of
yielding oxygen, and its application to the conversion of soda into carbonate of
soda or bicarbonate of soda, or for any other application to which carbonic acid-
may be required.
Thirdly, the use of sulphuret of manganese for the purpose of obtaining
sulphur, sulphurous acid, sulphuric acid, and sulphate of manganese, and the
use and application of sulphur, sulphurous or sulphuric acids, or sulphate of
manganese so obtained, and the use of the residual oxide of manganese for any
purpose to which oxide of manganese can be applied.
"Fourthly, the decomposition of chloride of sodium or common salt, by means
of sulphate of manganese, and the use and application of the sulphate of soda,
and chloride of. manganese so 'obtained.
Fifthly, the décomposition of chloride of manganese (whether obtained' by
.the above decomposition, or obtained as the e ordinary waste product from the
usual method of manufacturing chlorine or from any other source), 'by means
of a current of dry. oxygen gas, or a'tinospheric air into 'free chlorine, and oxide
ofmanganese, or by means of a current of oxygen gas and hydrogen gas, or a
current of atmospheric air and vapour of water into muriatic acid," and oxide
of, manganese. And I claim the use and application of chlorine,*"*muriatic
acid, and oxide of manganese so obtained, to any purpose for which chlorine,
muriatic acid, or oxide of manganese may or can be required.
Sixthly, the arrangement of retorts, so as to collect and render useful" (by
conversion into carbonic acid) the "carbonic oxide forined during the decom-
position of sulphate of soda, as herein described.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said John, Barrow, junior, in the Great Seal Patent Office on the
23rd August 1856.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JOHN
BARROW, junior, of the City of Manchester, in the County of Lancaster,
Manufacturing Chemist, send-greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Royal
Letters Patent, bearing date the Twenty-sixth day of February, in the year
of our Lord One thousand eight hundred and fifty-six; in the nineteenth
year of Her reign, did, for Herself, Her heirs and successors, give and grant
unto me, the said John Barrow, junior, Her special licence that I, the
said John Barrow, junior, my executors, administrators, and assigns, or sucli
others as I, the said John Barrow, junior, 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 MANUFACTURE OF SODA, SULPHUROUS AND SULPHURIC
ACIDS, CARBONIC ACID, CHLORINE, AND MURIATIC ACID, AND APPARATUS USED
THEREIN," upon the condition (amongst others) that I, the said John Barrow;
junior, by an instrument in writing under my hand and seal, should par-
ticularly 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 Royal Letters Patent.
NOW KNOW YE, that I, the said John Barrow, junior, do hereby declare
the nature of the said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following:
statement (that is to say)-
My improvements consist, firstly, in the use of manganese, or any of its
several oxides, or the oxide of. manganese in combination with carbonic acid,
as carbonate of manganese, along with coal or other carbonaceous matters, for
the purpose of decomposing sulphate of soda; thus obtaining carbonic acid
and carbonic oxide gases, soda, and sulphuret of manganese.
'
Secondly, in the conversion of the carbonic oxide into carbonic acid, and its
application to the conversion of soda into carbonate of soda, or for other
purposés.
Thirdly, in the use of sulphuret of manganese for the purpose of obtaining
sulphur, sulphurous acid, sulphuric acid, or sulphate of manganese.

page_text: Fourthly, in the decomposition of chloride of sodium by means of sulphate
of manganese, with production of sulphate of soda and chloride of manganese.
Fifthly, in the decomposition of chloride of manganese into free chlorine, or
otherwise into muriatic acid, and oxide of manganese.
And, sixthly, in the arrangement of retorts so as to collect and render useful,
by conversion into carbonic acid, the carbonic oxide formed during the decom-
position of sulphate of soda.
I accomplish my said improvements, firstly, by mixing intimately sulphate
of soda, coal, or any other convenient form of carbon, and oxide or carbonate
of manganese, in certain definite proportions approaching as nearly as I can,
according to the degree of purity of each body, the well-known chemical equi-
valent quantities of each body, using from four to six equivalents of carbon to
one equivalent of sulphate of soda, and one equivalent of oxide or carbonate of
manganese, and then submitting the mixture to the heat of a common furnace
known as a "black-ash" furnace; or I introduce the same mixture into heated
retorts arranged in a peculiar manner; or I first decompose sulphate of soda
by means of carbon in any suitable furnace or retort, or other apparatus, into
sulphuret of sodium, and to this body, either dissolved in water or otherwise, I
add an equivalent proportion of carbonate of manganese, obtaining by this last
method, carbonate of soda and sulphuret of manganese. From this mixture,
namely, sulphate of soda, carbon, and oxide or carbonate of manganese,
supposing the furnace to be used, I obtain a compound consisting principally
of soda and sulphuret of manganese, which I transfer as quickly as possible
from the furnace to air-tight iron boxes or barrows, provided with loose lids,
and having covered the surface of the hot mass with sawdust or other con-
venient form of carbon to protect it from the oxygen of the air. I place on
the lid, and allow the masses to become cold; I then take out the contents of the
barrows, familiarly known as "black balls," and break them up and expose
them as freely as possible to the action of atmospheric air and moisture, or to
the action of carbonic acid and moisture, and as soon as the soda has taken
up sufficient carbonic acid, I separate the carbonate of soda from the sulphuret
of manganese by lixiviation in the ordinary manner. The liquors consisting
principally of carlionate of soda I evaporate to dryness for sale as the soda ash
of commerce, or I evaporate to a certain extent, and then set them aside in
suitable vessels to crystallize for sale as the soda crystals of commerce.
Secondly, I make use, occasionally; of retorts of any suitable material, so
arranged as to allow the gases evolved during the decomposition of the
materials in one retort (after passing over the oxides of either copper, iron, or
manganese, or any other body capable of yielding oxygen to the carbonic

page_text: oxide in heated tubes,) to pass over the materials already decomposed in the
other. Thus, for instance, I charge the first retort, which for convenience I
shall call No. 1, with the mixed sulphate of soda, carbon, and oxide or car-
bonate of manganese; and I obtain as gases carbonic acid, and carbonic
oxide, the latter of which by passing over oxide of copper, oxide of iron, or
oxide of manganese in heated tubes, becomes converted into carbonic acid. As
soon as the decomposition is complete in No. 1 retort, I fill No. 2 retort with
a similar charge of mixed materials to that put into No. 1, and then by a simple
mechanical arrangement I compel the gases from No. 2 retort, after passing
over the oxides of either copper, iron, or manganese (thus becoming converted
into carbonic acid), to pass over the already decomposed materials in No. I
retort; the soda which it contains thus becoming surround by an atmosphere
of carbonic acid, is soon converted into carbonate of soda. As soon as the
decomposition in No. 2 retort is complete, I rake out the materials from No. 1,
(which consist principally of carbonate of soda and sulphurėt of manganese,)
and replace them with a fresh charge of mixed materials; the gases are then
compelled to flow back through No. 2 over the now decomposed charge in that
retort, occasioning the same conversion of soda into carbonate of soda, as pre-
viously occurred in No. 1, and so on repeating the process continuously; the
excess of carbonic acid can be collected and used for other purposes. The
mixed carbonate of soda and sulphuret of manganese obtained I separate by
lixiviation in the ordinary manner.
Thirdly, the residue from the washers, whichever process has been adopted,
consists essentially of sulphuret of manganese, which, by heating in close
vessels, yields sulphur, or by heating in a current of atmospheric air or oxygen,
either in retorts, furnaces, or in any other suitable apparatus, is resolved into
sulphate of oxide of manganese, oxide of manganese, and sulphurous acid given
off as gas, and which I convey by any suitable means, either into the well-
known sulphuric acid chambers or through other suitable apparatus, to be
converted into sulphuric acid; or I bring into contact with the sulphurous acid
given off, an extended surface of oxide of manganese, or I pass the the gas
through vessels of water in which oxide of manganese is mechanically suspended,
so as to produce a further quantity of sulphate of manganèsé, or I use the
sulphurous acid for any purpose for which sulphurous acid may be required.
Fourthly, the sulphate of manganese I wash from the insoluble oxide of
manganese, and add to the solution an equivalent quantity of common salt or
chloride of sodium, occasioning mutual decomposition, and yielding sulphate
of soda and chloride of manganese. I separate these two salts by concen-
trating the liquor, and crystallizing, either by allowing the liquor to cool, when

page_text: sulphate of soda separates in crystals containing a large quantity. of water of
crystallization, or by continued boiling until the sulphate of soda falls down in
small crystals; and which I cause to be raked out as fast as they are formed;
and thrown upon drainers placed over the boiler. The chloride of manganese
remains in the liquid state and ready for drying down, as herein-after described:
The sulphate of soda, if required quite pure, requires.re-crystallization.
Fifthly, the chloride of manganese, after as much as possible of the sulphate
of soda has been.separated, I evaporate to dryness, and. pass.over it.heated in
retorts,, furnaces, or any other suitable apparatus, a current of dry atmospheric
air or oxygen gas; and I obtain the chlorine of the chloride of manganese in
its free uncombined state, and ready, with proper precautions. for use, for any
purpose for which chlorine may be required. The residue consists of oxide
of manganese in a fit state for further use in the manufacture of chlorine or
for any other purpose to which oxide of manganese may. be required; or if I
wish to procure chlorine in combination with hydrogen or the muriatic acid of
commerce, I pass over the chloride of manganese, heated in retorts, furnaces,
or other suitable apparatus, in addition to atmospheric air, hydrogen gas, or
the vapour of water, thus obtaining muriatic acid, the residue being the
same in both operations:
Sixthly, the arrangement and heating of the retorts and tubes I accom-
plish by placing two retorts, and two tubes in the same position and in
the same kind of ovens as is now used in the manufacture of gas from
coal. I place the tubes a little above the retorts, connecting No. 1 retort
at the back with No. 1 tube at the back, and No. tube with No. 2
tube at the front, and No. 2 tube with. No. 2 retort at the back; the egress
pipe of each retort being placed over the mouth piece, and provided with
a stop-cock, so that by closing the egress pipe over No. 1 retort, the gases
formed must necessarily pass through both tubes and through No. 2 retort,
and escape at the egress pipe of that retort, and to reverse this current I close
the egress pipe of No. 2. retort, and open that of No. 1, by which means the
object desired is effected.
Having thus stated in what my improvements consist, and the means I
adopt for obtaining these results, I wish it to be distinctly understood that I
do not bind myself to the exact details herein described, nor to the exact
quantities of materials named; but I claim,
Firstly, the manufacture of soda and the carbonate of soda by the decom-
position of sulphate of soda by means of carbon and manganese, or any of the
several oxides of manganese or the carbonate of manganese, and by the
decomposition of sulphuret of sodium by means of carbonate of manganese.

page_text: Secondly, the conversion of carbonic oxide gas into carbonic acid by means
of the oxides of copper, iron, or manganese, or by any other body capable of
yielding oxygen, and its application to the conversion of soda into carbonate
or bi-carbonate of soda, or for any other application for which carbonic acid
may be required.
Thirdly, the use of sulphuret of manganese, whether obtained by this or
from any other source, for the purpose of obtaining sulphur, sulphurous acid,
sulphuric acid, sulphate of manganese, and the residual oxide of manganese,
and the use and application of sulphur, sulphurous acid, sulphuric acid,
sulphate of manganese, and oxide of manganese so obtained, to any purpose to
which these several bodies can be applied.
Fourthly, the decomposition of chloride of sodium or common salt, by means
of sulphate of manganese, and the use and application of sulphate of soda and
chloride of manganese so obtained.
Fifthly, the decomposition of chloride of manganese (whether obtained by
the above decomposition or obtained as the ordinary waste product from the
usual method of manufacturing chlorine, or from any other source,) by means
of a current of dry oxygen gas or atmospheric air, with the assistance of heat,
into free chlorine and oxide of manganese, or by means of a current of oxygen
gas or hydrogen gas, or a current of atmospheric air and vapour of water,
with the assistance of heat, into muriatic acid and oxide of manganese, and
the use and application of chlorine, muriatic acid, and oxide of manganese so
obtained, to any purpose for which chlorine, muriatic acid, and oxide of
manganese may or can be required.
Sixthly, the arrangement of retorts, so as to collect and render useful (by
conversion into carbonic acid) the carbonic oxide formed during the decom-
position of sulphate of soda, as all such improvements are herein described.
In witness whereof, I, the said John Barrow, junior, have hereunto set
my hand and seal, this Twenty-second day of August, One thousand
eight hundred and fifty-six.
JOHN BARROW, JUN". (L.S.)
Signed, sealed, and delivered by the within-named
John Barrow, junior, in the presence of
E. J. HUGHES, Patent Agent,
Manchester.