of Sodium or Potassium from their Sulphates.
Year: 1886

page_text: of Sodium or Potassium from their Sulphates.
I WILLIAM BRAMLEY of 18 Clarence Street Middlesboro on Tees, Analytical
Chemist, do hereby declare the nature of my invention to be as follows:-
Sulphate of barium or such as that produced by a subsequent operation
(preferred) is mixed with carbon such as coal, coke, or other suitable form and
heated (out of contact with air) to redness in a suitable furnace or retort, when
the carbon withdraws the oxygen from the sulphate and barium sulphide is
produced with evolution of carbonic oxide.
The quantities are represented by the formula
Ba So + 4 C = Ba S + 4 Co.
The barium sulphide is then brought to a state of solution with water and then
run through a series of closed vessels so placed that the liquid entering the highest
vessel will flow by gravity to the vessel placed next it on a lower level and so on
till the lowermost vessel is reached. At the same time a current of carbonic acid
gas such for instance as is obtained from lime kilns, is injected into the lowest
vessel and travels in a contrary direction to the liquid.
The gas is introduced at the bottom of the vessel and is distributed by perforated
pipes or other suitable means and passes through the liquid and then through a pipe
communicating with the next vessel above, where it is distributed in a similar
manner and so on until the highest vessel is reached; or it may be liberated after
passing one or more of the vessels and a fresh supply introduced for the other
vessels.
The carbonic acid (which should be as pure as can be conveniently obtained)
combines with the barium in the solution pricipitating barium carbonate and
liberating the sulphur in combination with hydrogen (as sulphuretted hydrogen).
The sulphuretted hydrogen passes out (by a pipe) at the highest vessel, and may be
burnt to manufacture sulphuric acid, or treated for obtaining sulphur by known
means.
The barium sulphide (solution or solid) instead of being treated directly by
carbonic acid gas may be treated with solution of magnesium chloride or hydro-
chloric acid. If treated with the former barium chloride is produced, magnesia at
the same time being precipitated and sulphuretted hydrogen disengaged. The liquid
D

page_text: is then heated until the sulphuretted hydrogen is given off and the latter is then
collected (or treated as above stated); carbonic acid gas is then injected into the
liquid (or mixture) under pressure when magnesium chloride is reproduced for use
again, and barium carbonate precipitated, the latter is separated and washed and
treated with sodium sulphate (or potassium sulphate) and carbonic acid gas (as
stated below).
If the barium sulphide be treated with hydrochloric acid, barium chloride is
formed and sulphuretted hydrogen evolved. After the sulphuretted hydrogen
is given off magnesia is added and carbonic acid gas injected into the mixture
(under pressure) carbonate of barium is precipitated, and magnesium chloride
formed which latter is treated for hydrochloric acid, free chlorine and magnesia.
When the liquid (sulphide of barium) which runs in at the highest vessel (pre-
viously referred to) reaches the lowest vessel of the series it has by the action of
the carbonic acid gas become decomposed, the liquid in the lowest vessel consisting
of a solution of barium bi-carbonate in which is suspended barium carbonate.
When the lowest vessel of the series before mentioned has become sufficiently full,
the liquid (barium carbonate suspended in solution of barium bicarbonate) or part
of the liquid is run into another vessel or vessels placed beneath the lowest of the
series just mentioned.
Sulphate of soda (sufficient for the decomposition of the barium carbonate and
bicarbonate) is then run into this vessel (or it may be run in previously to running
the solution of barium carbonate and bicarbonate) and carbonic acid gas injected
until the sodium sulphate has become decomposed. The liquid will now consist
of a solution of sodium bicarbonate and barium sulphate in suspension which is
run off and the barium sulphate separated from the liquid by known means.
liquid sodium bicarbonate is treated also by known means for carbonate of sodium
and carbonic acid gas or solid bicarbonate of sodium.
The
The sulphate of barium may be washed by suitable means with water and the
washing used to dissolve sulphate of sodium for another operation. The small
quantity of bicarbonate of sodium in the washings assists to neutralize any free
sulphuric acid or to precipitate any iron which may be present in the sulphate
of sodium.
'
If bicarbonate and carbonate of potassium is required to be made then sulphate
of potassium is substituted for the sulphate of sodium.
As pure carbonic acid is not easily obtained an inferior kind may be used for
injecting into the second series (viz; the vessel or vessels for mixing the bicarbonate
of barium and carbonate of barium with sodium sulphate) and using the purest
carbonic acid gas for the first series of vessels. By using gas rich in carbonic acid,
the sulphuretted bydrogen given off at the top vessel will be of a corresponding
degree of richness and consequently will be better adapted for subsequent treatment.
The carbonic oxide evolved during the first operation by treating sulphate of barium
with carbon at a red heat may be used as fuel and the resulting carbonic acid gas
utilised.
Dated thin now do of Tanum 198A

page_text: solution from the barium carbonate produced; adding to the solution the remainder
of the magnesia; again injecting carbonic acid gas; and again separating: or the
second portion of magnesia may be added to the mixture in the form of of
bicarbonate. Then heat and separate the solution from the precipitate. Any
small quantity of barium chloride still remaining in the solution of magnesium.
chloride may be decomposed by means of a solution of bicarbonate of magnesia,
and the barium carbonate will separate out during the treatment of the magnesium
chloride solution, and may be recovered-The presence of a small quantity of
barium chloride in the magnesium chloride solution will not however interfere with
the regeneration of the magnesia, as described below.
The solution of magnesium chloride, having been separated from the precipitated
barium carbonate, can be treated by known means for the recovery of the magnesia
for further use and the production of hydrochloric acid, or free chlorine and hydro-
chloric acid.
The barium carbonate having been washed to free it from any magnesium
chloride (in a solution of which it was suspended), is treated with a solution of
sodium sulphate, or potassium sulphate, and carbonic acid gas is injected. Bi-car-
bonate of sodium or potassium is formed in solution, and sulphate of barium.
The solution can be treated by known methods for the production of carbonate
of sodium or carbonate of potassium, and carbonic acid gas, or bi-carbonate of
sodium or bi-carbonate of potassium. For the decomposition of the bi-carbonate,
and formation of carbonate of sodium or potassium I add magnesia to the solution
of alkaline bicarbonate, apply heat in a closed vessel, agitate, and separate the
solution from the precipitate-By this method the bicarbonate is rapidly decom-
posed, and the magnesia recovered in the form of hydrated carbonate of magnesia,
or a mixture of hydrated carbonate of magnesia and hydrate of magnesia, which
should be employed for the decomposition of the barium chloride, as previously
described In order to ensure the complete decomposition of the bi-carbonate, an
excess of magnesia should be employed over and above the theoretical quantity
required, or the solution should be treated with magnesia a second time after the
separation of the precipitate-By heating in a closed vessel the escape of carbonic
acid gas is prevented and more perfect decomposition of the bi-carbonate is effected.
The sulphate of barium is washed for use again; the washings which are too
dilute to be worth treatment for the alkali they contain may be used for dissolving
a fresh quantity of the alkaline sulphate, the alkali assisting to neutralise any free
acid, or precipitate any iron, contained in the sulphate.
As potassium sulphate is not a very soluble salt, part should be added in a solid
state when treating with barium carbonate, so as to obviate the resulting solution
of potassium bi-carbonate being as dilute as it would be if water had been added
to the potassium sulphate in sufficient quantity to completely dissolve it.
For the treatment of the solution of sodium sulphate with barium carbonate
I prefer one of the following methods:-
(a.) To a solution of two equivalents of sodium sulphate add one equivalent of
barium carbonate, and inject carbonic acid gas-Separate the resulting barium
sulphate from the solution, and add to the latter two equivalents of barium car-
bonate, and again inject carbonic acid gas-The solution will contain sodium
bi-carbonate, and the precipitate consist of one equivalent of barium sulphate and
one equivalent of barium carbonate. This precipitate is again treated with two
equivalents of sodium sulphate in solution, and carbonic acid gas injected, and so
forth. This method is also applicable for the treatment of potassium sulphate, as
before-mentioned-for the manufacture of potassium bi-carbonate or carbonate.
(b.) Treat the barium carbonate in a series of vessels similar to those used for
the lixiviation of black ash-the solution of sulphate being run from one to the
other, (each being charged with barium carbonate to commence with) and gradually
decomposed, and converted into solution of bicarbonate of sodium or potassium-
By arranging the vessels in a continuous series, each vessel can in turn be recharged
with barium carbonate, as the previous charge becomes converted into barium

page_text: ulphate. Carbonic acid gas should be injected into the liquor whilst passing
brough the vessels-As in (a), part of the potassium sulphate may be added in a
olid form.
Having now particularly described and ascertained the nature of my said
nvention and in what manner the same is to be performed, I declare that what
claim is :-
1. The complete process of manufacturing carbonates or bicarbonates of sodium
r potassium substantially as herein described and consisting essentially in:-
(a.) Heating sulphate of barium mixed with carbon to redness for the production
of sulphide of barium.
(b.) Treating the sulphide of barium with hydrochloric acid, adding magnesia
in the various forms specified to the solution, and injecting carbonic acid
gas as specified, for the production of barium carbonate and magnesium
chloride.
(c.) Treating a solution of sodium sulphate, or potassium sulphate, or potassium
sulphate partly in solution and partly in solid form, with barium carbonate
and carbonic acid gas for the production of bicarbonate of sodium or bicar-
bonate of potassium and barium sulphate.
2. Treating sulphide of barium with hydrochloric acid, adding magnesia in the
various forms specified to the solution, and injecting carbonic acid gas as specified,
for the production of barium carbonate and magnesium chloride, substantially as
specified.
3. In the manufacture of carbonates or bicarbonates of sodium or potassium the
method of obtaining the sulphur in the form of sulphuretted hydrogen gas sub-
stantially as specified.
•
4. Obtaining from the alkaline bicarbonates produced in the manner specified
alkaline carbonates and hydrated carbonate of magnesia or a mixture of hydrated
carbonate of magnesia and hydrate of magnesia, by adding magnesia to the solution
of alkaline bicarbonates, and heating the mixture as specified; the precipitate so
obtained being employed for the purpose of converting barium chloride into barium
carbonate, substantially as and for the purposes set forth.
5. The process for the manufacture of carbonates and bicarbonates of sodium
and potassium substantially as specified whereby the use of carbonate of lime is
dispensed with.
Dated this 15th day of October 1886