Year: 1886

page_text: Date of Application, 16th Aug., 1886.
Complete Left, 14th May, 1887.
Complete Accepted, 24th June, 1887.
I, JOHN BARROW, of Dalton Chemical Works, Clayton, near Manchester, in the
county of Lancaster, Manufacturing Chemist, do hereby declare the nature of this
invention to be as follows:-
This invention relates to the manufacture of soda or potash, or the carbonates,
bicarbonates, or hydrates thereof, in such a manner as to obviate the loss of chlorine
usually resulting in the ammonia soda process, and also the loss of sulphur and the
production of vat waste resulting in the Le Blanc process.
According to my invention soda or potash, or the carbonate, bicarbonate, or hydrato
thereof are produced by a succession or cycle of operations in such manner that some
of the re-agents or substances employed for producing the required alkali are
continually regenerated for further use.
The succession or cycle of operations for producing carbonate or bicarbonate of
soda are as follows:
:-
First. A sodium salt, such for example as chloride of sodium, is converted into
sulphate of soda with the production when such chloride of sodium is used, of
hydrochloric acid, suitable for the purpose of manufacturing chlorine, or other uses.
Second. The sodium sulphate thus obtained is decomposed by barium sulphide, or
by a mixture of barium sulphide and barium oxide, with the production of sodium
sulphide and barium sulphate, or a mixture of sodium sulphide and sodium oxide and
barium sulphate respectively.
Third. The sodiuin sulphide obtained in the second operation with or without
soda, according as barium oxide was used or not, is converted into carbonate or
bicarbonate of soda by means of carbonic acid gas, with the production of sulphuretted
hydrogen.
Fourth. The conversion of the sulphuretted hydrogen obtained from the preceding
operation into sulphuric acid for re-use according to the first operation.

page_text: Fifth. The reduction by means of carbonaceous matter of the barium sulphate
obtained in the second operation, to barium sulphide or to a mixture of barium
sulphide and barium oxide for re-use in the said oporation.
As will be obvious, carbonate or bicarbonate of potash may be obtained by a similar
succession or cycle of operations, chloride or other salt of potassium being substituted
for the sodium salt; also where the alkaline sulphate can be obtained ready formed,
the first operation may be omitted.
It will also be obvious that sulphide of strontia may be substituted for sulphide of
barium.
Dated this 16th dose of And AD 1000

page_text: Improvements in the Manufacture of Alkali.
I, JOHN BARROW, of Dalton Chemical Works, Clayton, near Manchester, in the
County of Lancaster, Manufacturing Chemist, do hereby declare the nature of this
invention and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
This invention relates to the manufacture of soda or potash, or the carbonates,
bi-carbonates, or hydrates thereof, in such a manner as to obviate the loss of chlorine
usually resulting in the ammonia soda process, and also the loss of sulphur and the
production of vat waste resulting in the Le Blanc process.
According to my invention seda or potash or the carbonate, bicarbonate, or hydrate
thereof is produced by a succession or cycle of operations in such manner that some
of the re-agents or substances employed for producing the required alkali are
continually regenerated for further use.
The succession or cycle of operations for producing carbonate or bicarbonate of
soda are as follows:-
First. A sodium salt, such for example as chloride of sodium, is converted into
sulphate of soda with the production when chloride of sodium is used, of hydrochloric
acid which may be used for manufacturing chlorine, or for other uses. The operation
may be effected in the manner and with the apparatus heretofore usually employed
for the manufacture of sulphate of soda or salt cake.
Secondly. The sodium sulphate thus obtained is decomposed by barium sulphide, or
by a mixture of barium sulphide and barium oxide, with the production of sodium
sulphide and barium sulphate, or a mixture of sodium sulphide and sodium oxide and
barium sulphate respectively. The sodium sulphate is mixed in equivalent proportions
with the barium sulphide, or with the barium sulphide and barium oxide, the mixture
is placed in any convenient vessel, and a suitable quantity of hot or cold water
is added.
The quantity of barium sulphide or barium sulphide and barium oxide employed
should be sufficient to precipitate the whole of the sulphuric acid contained in the
sulphato of soda. Or instead of adding water, the solution of soda salts obtained in
the third oporation (hereinafter described) after separation of the bicarbonate of soda,
may be added. The mixture is stirred or boiled and when the decomposition is
complete, the barium sulphate is allowed to settle and the supernatant liquid or
solution containing sodium sulphide or sodium sulphide and oxide is run off
for use according to the third operation. The barium sulphate is collected for
reconversion into barium sulphide or barium sulphide and barium oxide in the manner
hereinafter described as the fifth operation.
Thirdly. The sodium sulphide obtained in the preceeding operation with or without
seda, according as barium oxide was used or not, is converted into carbonate or
bicarbonate of soda by means of carbonic acid gas, with the simultaneous production
of sulphuretted hydrogen.
The Carbonic acid gas may be obtained by any suitable process but I prefer to
adopt the process in which it is produced by forcing air through an incandescent mass

page_text: of lime-stone and carbonaceous matter as is well understood. The carbonic acid gas
is passed into the solution of sodium sulphide or of sodium sulphide and sodium oxide,
as the case may be, contained in a suitable vessel, and kept cold the sodium salt or
salts being thereby converted into carbonate of sodium with the simultaneous
production of sulphuretted hydrogen. The carbonate of sodium may be obtained
from the solution by crystallization or otherwise as is well understood. If excess of
carbonic acid gas be used the carbonate of sodium first formed will be converted
into bicarbonate of sodium which will precipitate; carbonate of sodium or carbonate
and oxide of sodium will remain in solution if the process be not completed and such
a solution may be used in the second operation as hereinbefore mentioned.
Fourthly. The sulphuretted hydrogen obtained from the preceeding operation is
converted into sulphuric acid for re-use according to the first operation as follows:-
The sulphuretted hydrogen is mixed with air and passed through or over heated
substances such for example as burning sulphur or burning pyrites or other heated
substance that will cause the combustion of the sulphuretted hydrogen and its
conversion into sulphurous anhydride and water, which are then passed into sulphuric
acid chambers and converted into sulphuric acid by the aid of nitric or nitrous acid in
the ordinary manner as well understood.
Fifthly. This operation consists in the reduction by means of carbonaceous matter
of the barium sulphate obtained in the second operation, to, barium sulphide or to a
mixture of barium sulphide and barium oxide for reuse in the manner hereinbefore
described under the second operation. The reduction may be effected by heating a
mixture of the barium sulphate with carbonaceous matter in any suitable apparatus
such for example as in retorts or on the bed of a reverberatory furnace in a manner
that will be readily understood without further description. The addition of sulphate
of soda in the proportion for example of about 5 to 10% of the mixture assists
the operation, the result of which is the formation of barium sulphide with or
without barium oxide. For some purposes as for instance in the manufacture of
caustic alkali I separate the oxide or Hydrated oxide of Barium from the sulphide by
crystallization and use the oxide or Hydrated oxide of Barium alone in the second
operation to decompose sulphate of soda thereby producing caustic alkali and
throwing down the sulphuric acid as Barium sulphate for re-use. Thus the sulphur
contained in the barium sulphato originally used for preparing the barium sulphide
for use when commencing the manufacture of alkali according to this invention, is
continually recovered and re-used. As will be obvious carbonate or bicarbonate of
potash may be obtained by a similar succession or cycle of operations, chloride or
other salt of potassium being substituted for the sodium salt; also where the alkaline
sulphate can be obtained ready formed, the first operation may be omitted.
It will also be obvious that sulphide of strontia may be substituted for sulphide of
barium. As will be evident the several operations above respectively described may
be more or less modified in detail.
Having now particularly described and ascertained the nature of my said invention
and in what manner the same is to be performed I declare that what I claim in the
manufacture of alkali is :-
1. The production of carbonate or bicarbonate or hydrate of soda or of potash
substantially in the manner and by the succession or cycle of operations hereinabove
described.
2. The recovery and reuse substantially as described of sulphur obtained originally
from the sulphate of barium as hereinabove set forth.
W. LLOYD WISE.