Improvements in the Manufacture of Hydrates of Barium and Strontium.
Year: 1884

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Hydrates of Barium
and Strontium.
I HUGH LEE PATTINSON Junior of Heworth Lodge, Felling on Tyne, in the
County of Durham, Chemical Works Manager do hereby declare the nature of
my invention for IMPROVEMENTS IN THE MANUFACTURE OF HYDRATES OF BARIUM
AND STRONTIUM to be as follows:-
My invention relates to the manufacture of hydrates of barium and of strontium.
In the following specification I will refer only to barium it being understood that
the invention is precisely the same when strontium is in question.
I mix
I take sulphide of barium Ba S (which may be procured either by furnacing the
sulphate with coal or by other known method) and I dissolve it in water.
with this solution either finely ground black oxide (peroxide) of manganese (Mn O₂)
or that compound of manganese known as "Weldon Manganese Mud" washed clear
of calcium-chloride (Ca Cl₂), or manganese hydrate (Mn H, O₂) washed clear of
calcium-chloride, and I pass air into the mixture to produce (if necessary) the
active oxide of manganese or to regenerate the active oxide in proportion as the
manganese imparts oxygen to the barium. It is important to wash the Weldon
mud or manganese-hydrate clear of the calcium-chloride which is associated with it
because I have found that calcium-chloride reacts with barium-hydrate and
produces barium-chloride. The temperature at which the solution of sulphide of
barium should be mixed with the black oxide of manganese, or Weldon mud, or
manganese hydrate, should be about 100° Fahrenheit. I have found by experiment
that this temperature is the best for the purpose, firstly because less air is required
in the process of oxidation if the liquor is hot than if it is cold, while if the
temperature exceeds 100° Fahrenheit there is a tendency to convert the barium
into byposulphite (Ba S, O,) instead of into hydrate (Ba H₂O₂); secondly the
higher the temperature the more barium there is in the liquor and therefore there
is less necessity to concentrate the final solution of hydrate of barium in order to
get crystals. Thus the stronger the liquor the better, provided the temperature
required to keep it strong be not so high that hyposulphite of barium is formed,
D

page_text: Where the operation above described is properly performed about 66 per cent of
the sulphide of barium in the solution is converted into hydrate of barium while
about 33 per cent of it remains insoluble in the form of hyposulphite; also about
33 per cent of the sulphur which was associated with the barium and which is not
in the form of hyposulphite is mixed with the manganese-hydrate and hyposulphite
of barium as a precipitate. The hydrate of barium in the clear solution is separated
I use the manganese
by crystallization after concentration when necessary.
hydrate of the precipitate to oxidise a fresh batch of sulphide of barium but if the
sulphur which is associated with it be not removed the hydrate will not convert so
much as 66 per cent of the sulphide of barium into hydrate of barium-I therefore
remove the sulphur by treating the precipitate with a solvent of sulphur. My
invention is not confined to the use of any particular solvent but I prefer coal tar
naphtha I find that if the precipitate be washed in this solvent after every
operation of converting sulphide of barium into hydrate of barium the manganese
hydrate will continue indefinitely to give the same results as at first. I find further
that if the solvent employed be naphtha the manganese hydrate impregnated there-
with or having a small quantity of naphtha mixed with it will convert as much as
about 80 per cent of the sulphide of barium into hydrate of barium because the
naphtha checks the formation of hyposulphite of barium.
In order to meet the difficulty of keeping a quantity of sulphide of barium liquor
at 100° Fahrenheit during the process of the oxidizing action which naturally
produces heat I adopt one of the three methods which I will proceed to describe :-
(1) If I carry out the operation in one process with the same manganese and
without removing the liquor from contact with it I find it convenient to begin at
a temperature of about 80° Fahrenheit and I pass air into the liquor until the
temperature reaches about 110°; then I stop, let the liquor cool down, then do
another stage and so on step by step until the whole operation is complete, never
exceeding 110° Fahrenheit. (2) According to my second method I compress the
air which I intend to use very strongly into a high pressure receiver-I allow the
receiver to cool so as to dissipate the heat due to compression. Then when I wish
to use the air I discharge it into the liquor and it becomes chilled by the cold due
to the absorption of heat by its own expansion. (3) According to my third
⚫method, which is the one I prefer, I divide the process into 2 stages and introduce
a crystallization of the liquor between the 2 stages-I have found that when about
two thirds of the air which would suffice to clear a batch or given quantity of
sulphide of barium have been injected into the liquor there is no formation of
hyposulphite of barium but this reaction has taken place
2 Ba S+0 Ba O + Ba S.
=
This can be done at almost any temperature and it is practicable to obtain from
such a solution hydrate of barium Ba H, O, as crystals, and get a mother liquor
containing Ba S, (bisulphide of barium) which has much inore barium in a given
bulk at a low temperature than is possible with sulphide of barium and this Ba S₂
can also be treated with air and manganese-hydrate as before. Therefore in
carrying out my third method I take the liquor hot and strong and pass air into it
with a little manganese-hydrate present to act as a carrier-When I have arrived
at the point where all the sulphide of barium is changed into Ba O and Ba S, I stop,
allow the liquor to settle, draw off the clear liquor, add an equal bulk of fresh
The clear liquor
liquor and proceed again with the first stage of the process.
which has been drawn off is allowed to crystallize and cool. The crystals are
pure Ba H, O, impregnated with Ba S, solution. I clear out the Ba S, as much
as is practicable and by redissolving the crystals and recrystallizing I obtain
commercially-pure hydrate of barium. The mother liquor from which the Ba H, O
has crystallized out is then mixed with manganese which has preferably been
washed with naphtha and I blow air into it; as only about one third of the
amount of air which would have been required for a similar quantity of Ba S is
L.

page_text: now needed I avoid heat in the final stage of the process and at the same time
get a liquor which is readily crystallizable.-This liquor may be heated and used
to dissolve the crystals obtained by the first part of the process.
I find it very desirable to use in the second stage of the process if I adopt two
stages, or in the whole process if I have only one stage, a particular proportion of
manganese to the sulphide of barium; this proportion I obtain when I adopt the
formula Mn O, + Ba S. A given quantity of Mn O, will answer for an indefinite
quantity of Ba S if the above proportion be observed in each operation and
the Mn O, be washed clear of sulphur by a suitable solvent.as already described
after each operation.

page_text: Improvements in the Manufacture of Hyḍrates of Barium
and Strontium.
I HUGH LEE PATTINSON, Junior, of Heworth Lodge, Felling-on-Tyne, in the
County of Durham, Chemical Works Manager 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 :—
My invention relates to the manufacture of hydrates of barium and of strontium.
In the following Specification I will refer only to barium it being understood that
the invention is precisely the same when strontium is in question.
I take sulphide of barium-Ba S-(which may be procured either by furnacing
the sulphate with coal or by other known method) and I dissolve it in water.
I mix with this solution either finely ground black oxide (peroxide) of manganese-
(Mn O₂) or that compound of manganese known as "Weldon Manganese Mud"
washed clear of calcium-chloride (Ca Cl₂), or manganese-hydrate (Mn H, O₂)
washed clear of calcium-chloride and I pass air into the mixture to produce (if
necessary) the active oxide of manganese or to regenerate the active oxide in
proportion as the manganese imparts oxygen to the barium. It is important to
wash the Weldon mud or manganese-hydrate clear of the calcium-chloride which
is associated with it because I have found that calcium-chloride reacts with barium
hydrate and produces barium chloride. The temperature at which the solution of
sulphide of barium should be mixed with the black oxide of manganese, or Weldon
mud, or manganese hydrate should be about 100° Fahrenheit. I have found by
experiment that this temperature is the best for the purpose, Firstly, because less
air is required in the process of oxidation if the liquor is hot than if it is cold,
while if the temperature exceeds 100° Fahrenheit there is a tendency to convert
the barium into hyposulphite (Ba S₂ O₂) instead of into hydrate (Ba H, O₂);
Secondly, the higher the temperature the more barium there is in the liquor and
therefore there is less necessity to concentrate the final solution of hydrate of
barium in order to get crystals. Thus the stronger the liquor the better, provided
the temperature required to keep it strong be not so high that hyposulphite of
barium is formed.
Where the operation above described is properly performed about 66 per cent of
the sulphide of barium in the solution is converted into hydrate of barium while
about 33 per cent of it remains insoluble in the form of hyposulphite; also, about
33 per cent of the sulphur which was associated with the barium and which is not
in the form of hyposulphite is mixed with the manganese hydrate and hyposulphite
of barium as a precipitate. The hydrate of barium in the clear solution is
separated by crystallization after concentration when necessary. I use the man-
ganese hydrate of the precipitate to oxidise a fresh batch or quantity of sulphide
of barium but if the sulphur which is associated with it be not removed the
hydrate will not convert so much as 66 per cent of the sulphide of barium into
hydrate of barium. I therefore remove the sulphur by treating the precipitate
with a solvent of sulphur. My invention is not confined to the use of any
particular solvent but prefer coal tar naphtha. I find that if the precipitate be
washed in this solvent after every operation of converting sulphide of barium into
hydrate of barium the manganese hydrate will continue indefinitely to give the

page_text: same results as at first. I find further that if the solvent employed be naphtha
the manganese hydrate impregnated therewith or having a small quantity of naphtha
mixed with it will convert as much as about 80 per cent of the sulphide of barium
into hydrate of barium, because the naphtha checks the formation of hyposulphite
of barium.
1
In order to meet the difficulty of keeping a quantity of sulphide of barium liquor
at 100° Fahrenheit during the process of the oxidising action which naturally
produces heat I adopt one of the three methods which I will proceed to describe :-
(1.) If I carry out the operation in one process with the same manganese and
without removing the liquor from contact with it, I find it convenient to begin at
a temperature of about 80° Fahrenheit and I pass air into the liquor until the tem-
perature reaches about 110°; then I stop, let the liquor cool down, then do another
stage and so on step by step until the whole operation is complete, never
exceeding 110° Fahrenheit. (2.) According to my second method I compress the
air which I intend to use very strongly into a high pressure receiver. I allow the
receiver to cool so as to dissipate the heat due to compression. Then when I wish
to use the air I discharge it into the liquor and it becomes chilled by the cold due
to the absorption of heat by its own expansion. (3.) According to my third
method which is the one I prefer I divide the process into two stages and introduce
a crystallization of the liquor between the two stages. I have found that when
air has been passed into a liquid containing sulphide of barium up to the point
when barium begins to precipitate as an oxidized sulphur compound a change of
this character has taken place:
x Ba S + 0 (x
-
-
1) = (x 1) Ba O + Ba S
Of the value of a I am uncertain as it may vary with different heats and strengths
of solution but the most probable value is 3 and the sulphide which in that case
would be formed is of course a tersulphide. Therefore although a tersulphide is
produced, as I believe, I cannot say a higher sulphide is not or cannot be produced
and the higher the sulphide the better since a greater proportion of barium must
therefore appear as hydrate. This treatment can be effected at almost any tem-
perature and it is practicable to obtain from such a solution hydrate of barium
Ba H, O, as crystals and get a mother liquor containing Ba S, (or a higher
sulphide) which has much more barium in a given bulk at a low temperature than
is possible with sulphide of barium, and this Ba S, (or higher sulphide) can also be
treated with air and manganese hydrate as before. Therefore in carrying out my
third method I take the liquor hot and strong and pass air into it with a little
manganese hydrate present to act as a carrier. When I have arrived at the point
where all the sulphide of barium is changed into 2 Ba O + Ba S, (or higher
sulphide) I stop, allow the liquor to settle, draw off the clear liquor, add an equal
bulk of fresh liquor and proceed again with the first stage of the process.
clear liquor which has been drawn off is allowed to crystallize and cool. The
crystals are pure Ba H, O, impregnated with Ba S, (or higher sulphide) solution.
I clear out this Ba S, as much as is practicable and by redissolving the crystals
and recrystallizing I obtain commercially pure hydrate of barium. The mother
liquor from which the Ba H, O, has crystallized out is then mixed with manganese
which has been preferably washed with naphtha and I blow air into it. As only
about one-third of the amount of air which would have been required for a similar
quantity of Ba S is now needed I avoid heat in the final stage of the process and
at the same time get a liquor which is readily crystallizable. This liquor may
be heated and used to dissolve the crystals obtained by the first part of the
process.
The
I find it is very desirable to use in the second stage of the process if I adopt two
stages, or in the whole process if I have only one stage, a particular proportion of
manganese to the sulphide of barium, this proportion I obtain when I adopt the
formula Mn O, + Ba S.-A given quantity of Mn O, will answer for an indefinite
of Ba S if the above proportion be observed in each operation and the Mn O, be

page_text: washed clear of sulphur by a suitable solvent as already described after each
operation.
According to a modification of my invention, after mixing the sulphide of barium
solution with manganese-hydrate or other oxide of manganese higher than Mn O,
I blow in air until the barium begins to precipitate in the form of a sulphite or
byposulphite of barium or some other oxidized-sulphur-compound of barium. At
this time the state of the liquor is as follows:-A certain proportion of the barium
presumably about two-thirds but it might be more or less exists in the form of
hydrate and the remainder is in the form of polysulphide (I believe tersulphide) of
barium (Ba Ss). I allow this liquor to cool in suitable pans after separating it by
filtration or settling from the manganese which can then be used for treating
another batch or quantity of sulphide of barium. I remove the crystals which
are mainly hydrate of barium and I wash them with water until the tersulphide
(or polysulphide) which adheres to them is carried away in the water. This may
be done either by allowing the crystals to drain or by washing them in a hydro-
extractor which I prefer. I redissolve the washed crystals in hot water and then
either simply crystallize or if I wish to obtain a special pure product I blow in air
until the last traces of sulphur are removed by oxidation. I then allow the liquor
to settle and run it into crystallizing pans where I obtain crystals of practically
pure hydrate of barium, Ba H₁ О, and 8 H, O, which I may dry as before either
by draining or by hydro-extractors. The residual liquor from the first operation,
if the original liquor was strong enough, will be a saturated solution of tersulphide
(or polysulphide) of barium at normal temperatures with a little hydrate of barium
dissolved also. I evaporate this liquor in pans or otherwise and use the tersulphide
(or polysulphide) again to produce mono-sulphide; this can be done by furnacing the
tersulphide (or polysulphide) in a reducing atmosphere with or without more or
less coal. The washings from the hydro-extractor in the first instance being a
mixture of tersulphide (or polysulphide) and hydrate of barium, I use them to
dissolve more sulphide of barium and of course the hydrate of the washings is
thus recovered after the new sulphide has been converted by air and allowed to
crystallize, as before.
If it is found undesirable to use as the original liquor so strong a solution of the
sulphide as to give a saturated solution of the tersulphide (or polysulphide), as
above stated, when the liquor has been cooled to ordinary temperatures, I use the
mother liquid from the first process again and again until it does yield a saturated
solution of the tersulphide (or polysulphide).
As regards the quantity of manganese to be employed, good results are obtained
when the formula 2 Ba S + Mn O is realized but more or less can be used. If
the oxide or compound of manganese be used in sufficient quantity to yield the
necessary amount of oxygen to effect the conversion the addition of air is not
essential. I can also dispense with the manganese and depend upon the air alone
for the necessary supply of oxygen. I blow the air into the solution until I obtain
approximately that state of the liquor already described in which about two-thirds
of the barium exists in the form of hydrate and the other third mainly in the form of
tersulphide (or polysulphide), the process being then continued as already explained.
More air however will generally be necessary than when an oxide or compound of
manganese is used while there will be a certain formation of insoluble compounds
of barium before the tersulphide (or polysulphide) is produced; this formation is
due partly to the oxidation of some of the sulphur in the liquor and partly to the
action of the carbonic acid in the air. The carbonic acid can be readily
eliminated from the air by blowing it through milk of lime as is well understood.
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 is
1. The manufacture of bydrate of barium or hydrate of strontium by converting
a solution of sulphide of barium or of strontium into hydrate and byposulphite by

page_text: means of an oxide or compound of manganese (free from calcium chloride) and air
substantially in the manner set forth the hydrate of barium or of strontium in the
resulting clear solution being then separated by crystallization.
2. I claim specially the mixing of the sulphide of barium or of strontium with
the oxide or compound of manganese for the purpose referred to in claim 1 at a
temperature of 100° Fahrenheit or approximately so for the purposes set forth.
3. I claim specially in carrying out the process referred to in claim 1 the
particular proportions of manganese and sulphide of barium represented by the
formula Mn O₂ + Ba S.
4. I claim as part of a continued series of such processes the removal of the
sulphur from the hydrate of manganese of the precipitate by means of a solvent as
described so that the hydrate of manganese can be used efficiently in the treatment
of a fresh quantity of sulphide of barium or of strontium.
5. I claim specially the employment of coal tar naphtha for the purpose of
removing the sulphur as referred to in claim 4.
6. I claim the employment of a small quantity of coal tar naphtha with the
oxide or compound of manganese used to obtain hydrate of barium or of strontium
from the sulphide, as set forth.
7. I claim in the process of obtaining hydrate of barium or of strontium from the
sulphide in the manner described, conducting the process step by step without
removing the manganese from the liquor-the liquor being always allowed to cool
down when it reaches a temperature of about 110° Fahrenheit for the purpose
explained.
8. I claim in the process of obtaining hydrate of barium or of strontium from
the sulphide in the manner described, the employment of air which has been
previously compressed in a high pressure receiver and then allowed to cool therein,
for the purpose explained.
9. I claim in the process of obtaining hydrate of barium or of strontium from
the sulphide in the manner described, dividing the process into two stages as
explained, crystallizing the clear liquor drawn off after the first stage and thereby
obtaining crystals of somewhat impure hydrate of barium or of strontium which
can, if required be redissolved in the clear liquor resulting from the second stage
of the operation and made to yield a commercially pure hydrate of barium or of
stroutium:
10. The manufacture of hydrate of barium or hydrate of strontium by converting
a solution of sulphide of barium or strontium into hydrate and tersulphide (or
polysulphide) by means of an oxide or compound of manganese (free from calcium
chloride) with or without air, or by means of air without manganese substantially
in the manner set forth, the hydrate of barium or strontium being subsequently
separated from the solution.