IMPROVEMENTS IN THE MANUFACTURE OF BARYTES AND STRONTIAN AND THEIR SALTS. AND IN THEIR APPLICATION TO VARIOUS PURPOSES
Year: 1856

page_text: LETTERS PATENT to William Clark, of 53, Chancery Lane, in the County
of Middlesex, Engineer, for the Invention of IMPROVEMENTS IN THE
MANUFACTURE OF BARYTES AND STRONTIAN AND THEIR SALTS. AND IN THEIR
APPLICATION TO VARIOUS PURPOSES
A communication
Sealed the 31st March 1857, and dated the 11th November 1856.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the
11th November 1856.
I, WILLIAM CLARK, of 53, Chancery Lane, in the County of Middlesex,
Engineer, do hereby declare the nature of the said Invention for "IMPROVE-
MENTS IN THE MANUFACTURE OF BARYTES AND STRONTIAN AND THEIR SALTS,
AND IN THEIR APPLICATION TO VARIOUS PURPOSES," to be as follows:-
This Invention consists in utilizing theliquid residuum from themanufacture
of chlorine and of chloride of lime,so as to serve for the conversion of natural
sulphate of baryta into chloride of barium. This transformation takes place
by heating in a reverberatory furnace a mixture of the residuum in question
(which is formed principally of chloride of manganese) with sulphate of barytes
and ecal The chloride of barium is then obtained by the lixiviation of the
Price 811

page_text: mass. The chloride is thus obtained at a rate comparatively ixexpensive,and
will be found useful for many industrial purposes. For instance, it serves for
purifying water charged with plaster or other carthy substances for feeding
steam boilers; I make use of it particularly for the reproduction of muriatic
acid. By adding sulphuric acid to the rectified solution, it regenerates the
sulphate of baryta, and produces it in a state in which it may be used for
ummorous purposes. I recover the muriatic acid in the liquid. By reason of
its low price, I use chloride of barium to form nitrate of baryta, which I effect
by mixing it in a state of solution with nitrate of soda. The nitrate of baryta
obtained, mixed with sulphuric acid, is suitable for the preparation of ni!:ic
acid by the wet process. I also calcine the nitrate of baryta in muffle furnaces,
or in cylinders, to generate nitrens vapours in the preparation of sulphuric
acid; and the residuum left in such muffles or cylinders I apply in particular to
harden plaster, and to, prepare organic acids, tartaric, nitric, and fatty acids.
The processes of operation and nentralization, described with reference to
the natural sulphate of baryta, applies equally to the sulphate of strontian.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said William Clark in the Great Seal Patent Office on the
11th May 1857.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, WILLIAM
CLARK, of 53, Chancery Lane, in the County of Middlesex, Engineer, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Eleventh day of November, in the year of our Lord
One thousand eight hundred and fifty-six,in the twentieth year of Her reign,
did, for herself, Eler heirs and successors, give and grant unto me, the
said William Clark, Her special licence that I, the said William Clark, my
executors, administrators, and assigns, or such others ns 1, the said William
Clark, 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 BARYTES AND STRONTIAN AND THEIR SALTS, AND IN THEIR APPLICATION TO VARIGUN
PURPOSES," a communication, upon the condition (amongst others) that I, the

page_text: said William Clark, my executors oradministrators, byan instrument in writing
under my, or their, or one of their hands and seals, 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 Lettors Patent.
NOW KNOW YE, that I, the said William Clark, do
the nature of my said Invention, and in what manner the
performed, to be particularly described and ascertained in and
statement (that is to say) :-
-
hereby declare
same is to be
the following
This Invention relates to the manufacture of baryta, of strontian, and of
the salts of these bases, and of various applications of the same, especially to
the preparation of mineral and organic acids.
First, with reference to the preparation of the chloride of barium or of
strontian.
The principal object of this Invention consists in using, for the manufacture
of salts or baryta or of stroutian, the chloride of manganese which results from
the production of chlorine and of chlorides.
This manufacture is based upon the transformation of the chloride of
manganese into chloride of barium by means of sulphuret of barium; but this
chemicalaction obtained by the combination of the two solutions necessitates a
previous manuf: cture of sulphuret of barium, and produces gelatinous precipi-
tates difficult to wash. After numerousand costly experiments, I havesucceeded
in reducing to practice the production of two chemicalactionsinoneoperation by
a dry process, and thereby to obtain sulphuret of manganese easy to be washed.
I proceed in the following manner :-First, I saturate with natural carbonate
of baryta or stronian the excess of acid of the liquid residuum resulting from
the manufacture of chlorine, I then pour it into a reverberatory furnace at a
red heat, and into which has been previously introduced a mixture of natural
sulphate of baryta or stronian, with carbon in powder. The liquid part
absorbed bythe above said mixture is quickly dried, and the whole heated to a
red heat, when it soon resolves itself into a pasty inass like raw soda, and
emitting flames of carbonic oxide after three or four hours of heating; the
pasty matter so obtained is withdrawn,and another operation proceeded with.
When the manufacture of chlorine is not conducted on the same premises
used for this new manufacture, the impure chloride of manganese is dried and
calcined in ovens, and the mass obtained by the calcination is pulverized and
mixed with the mixture of sulphate of baryta and carbon. The hearth of
the reverberatory furnace used for this operation is divided by a small raised

page_text: ridge dividing it into two compartments; the part farthest from the fire serves
for the concentration and desiccation, whilst that compartment nearest to the
furnace serves for the calcination and for the completion of the operation.
The saturation by the carbonate of natural baryta or of strontian may be
rendered more complete by heating the mixture by means of an injection of
stean. In this latter case, a great part of the chloride of iron, which is a part
of the residuum of the manufacture of chlorine,is decomposed. By this mode
of treatment there is not any sensible escape of vapours of muriatic acid
during the calcination.
For establishing the proportions of the material, I at first, had recourse to
the well-known chemical formula. This formula is as follows:-
Cl. MSO, Ba. O + 4C SM + CL. Ba. + 4 CO.
The proportion indicated by theory would thus be
Chloride of manganese, dry
Sulphate of baryta
Carbon
and the results would be,-
Sulphurate of manganeso
Chloride of barium
:-
-
54 parts,
- 100 parts,
20 parts;
37 parts,
.
89 parts;
but in practice these proportions may be modified, according to the mixture
of various chlorides or chloride of manganese; it is also convenient to add a
greater quantity of carbon. The proportions which have given excellent
results are as follows:--Eighty to ninety parts of chloride of manganese dry.
or from three hundred and twenty to four hundred parts of liquid chloride
after its saturation with the carbonate of natural baryta, one hundred parts of
sulphate of baryta, and from thirty to thirty-five parts of pulverised conls.
Some modifications may be necessary in these proportions, according to the
richness or strength of the peroxide of manganese which produced the liquid
residuum used.
Secondly, in some circumstances it will be advisable to decompose by
means of lime the chloride of manganese liquid. Such is the case in regen-
eration, in order to make it serve again. In all cases in which chloride of
calcium may be cheaply obtained, instead of transforming the chloride
of manganese into chloride of barium, 1 produce, by an analogous chemical
action, the transformation of the chloride of calcium into chloride of barium
or of strontian. The theoretical formula of this chemical action is as follows,
as to what relates to the salts of baryta :-

page_text: The proportions to be adopted are the following:-
Natural sulphate of baryta
Coals in powder
Chloride of calcium dry, or calculated dry
Quick lime
233 parts,
4S parts,
111 parts,
28 parts, or chalk 50 parts.
The chloride of manganese(residuum of chlorine; maybe easilytransformed
into chloride of calcium by heating in an oven, some residuum of raw soda
in excess in a state of paste mixed with the residuum of the chlorine. The
mass which results from the calcination consists of sulphuret of manganese
and of iron insoluble, which can be made use of as pyrites, or be mixed with
pyrites for the manufactureof sulphuric acidand of chloride of calcium, which
is thereby obtained in a very pure state.
Thirdly, I have said that by the calcination of a mixture of sulphate of
natural baryta, of carbon, and of residuumsresulting from the manufacture of
chlorine, without the previous saturation of the liquid with the chalk or lime,
there may be a loss of muriatic acid by escape to the chimney. To avoid this
inconvenience, and also to avoid the use of the carbonate of baryta, which is
more costly than the sulphate, I have recourse to a mixed process, or to the
combination of the two processes which I have just described. I add to
the liquid residuum some chalk, then a little lime, or it may be simply
the oxysulphuret of calcium, the residuum of a ley of raw soda, until there
is no manifestation of acidity on the test paper, thus indicating that the whole
of the iron has been precipitated.. This liquid so saturated is then mixed with
the deposit of oxide of iron precipitated, marking twenty-eight to twenty-
nine degrees Beaumé, and then conducted into the oven upon a mixture of
sulphate of baryta, coals and chalk, thewhole being well mixed soon dries,aud
becomes, when heated to redness, of a thin pasty consistency, from which,
when a disengagement takes place of oxide of carbou, it announces the termi-
nation of the operation. In this operation an excess of chalk is used,
sufficient to form the oxysulphuret of calcium with the sulphate of calcium,.
which results from the chemical action herein-before indicated.
The proportions which I have found to succeed best are,-
100 parts sulphate of baryta pulverised,
40 parts carbon,
170 parts saturated liquid chloride of manganese,
15 parts of line or chalk.
In either of these three modes of operating for manufacturing the chloride
of barium, the product of the calcination in the reverberatory furnace is
bruised, then washed in the same manner as raw soda in a methodic or

page_text: systematic manner; the chloride of barium isso obtainedat twenty-five degrees
Beaumé. It is submitted to crystallization by cooling, or it is concentrated or
dried in ovens to produce the chloride of barium dry. It is almost needless to
say that the chloride of strontian is similarly produced, by modifying the
proportions so as to produce an equivalent of sulphate of strontian instead of
the sulphate of baryia. I will add, that the heating of the reverberatory
furunce may bo increased or obtained more rapidly by means of a blast instead
of a free or open draught. The time occupied by the operations may be
reduced to one-half by this means.
Fourthly, I also obtain the chloride of barium byeffecting the condensation
of the vapours of muriatic acid arising from the decomposition of salt; this is
done by putting these vapours (before leading them into the chimney) in con-
tact with native carbonate of baryta slightly moistened, or by agitating this
pulverized salt with some water in the presenceof the vapours of muriaticacid.
The chloride of barium obtained by either of these four methods may be
used for various purposes, which I will now enumerate.
SECOND PART.
The application of tho chlorideof barium.-Thischlorideservestoregenerate
hydrochloric acid, and for producing artificial sulphate of baryta by mixing
with a solution of this sulphate, marking twenty-five degrees Beaumé, taw
sulphuric neid in chambers of lead until precipitation ceases. The artificial
sulphate of baryta precipitates to the bottom, when the supernatant liquid
(muriatic acid marking about six degrees or seven degrees Beaumé) may
be decanted. By operating with more concentrated and hot solutions, a more
concentrated acid may be obtained, unless it is preferred to concentrate it by
introducing it in apparata with a solution of acid gas.
Instead of sulphuric acid from the lead climbers, in certain circumstances
residuums containing this acid may be used, such as the acid residuum from
the manufacture ofstearic acid,or sulphates of littlevalue. The motherwaters
of the saline solutions, which contain sulphate of soda and even plaster, may
be turned to account when the only question is to produce artificial sulphate
of baryta.
I have also made an important application of the chloride of barium, that is
to say, I substitute it for chloride of calcium in the manufacture of tartaric
acid to make citric acid.
Isaturate the lemon juice with the sulphate of
barium, and then decompose the citrate or the tartrate by means of sulphuric
acid, for obtaining by crystallization citric or tartaric acid and artificial
sulphate of baryta.

page_text: The application of the artificial sulphate of baryta.-The artificial sulphate
of baryta which I produce by this cheap process I apply to new purposes; I
use it'in painting, by applying it in two or three coats of distemper, that is,
mixed with paste, starch, or other adhesive matter, and further fix the color
by means of a solution of silicate of potassium or of soda; I also produce the
fixing with limewhite or water of baryta when I apply the artificial sulphate
of baryta in distemper.
This chloride has also other uses, and may becoine of considerable use for
decomposing the plaster contained in selenitical waters, and for preventing the
incrustation of steam boilers, &c. I have also found another important.appli-
cation of the chloride of barium; this application consists in the reciprocal
decomposition of nitrate of soda of Peru by this chloride. The two bodies are
combined in a state of saturated solution (when hot), in the proportions of the
weight of their chemical equivalents. By cooling, nearly the whole of the
nitrate of baryta is obtained in a crystallized form.
The mother water, after concentration, has still left a few crystals of the
nitrate, but retains only a small part of the salt, which is decomposed by adding
to the liquid, until the cessation of precipitation, some sulphate of soda or
sulphuric acid. The salt obtained may afterwards enter into the composition
of the soda; an addition of a little carbon will destroy the effect of nitric acid
which is held in but small proportion.

page_text: so easily obtained by the double decomposition as the nitrate of baryta, the
nitrate of strontian being much more soluble.
FIFTH PART
The application of caustic baryta aud of the natural carbonate.-The caustic
nuhydrous baryta, obtained bythecalcinationof nitratesorihe hydrated baryta,
which I propare by separating, by means of hydrated oxide of manganese, the
sulphur from the sulphuret of barium, or the oxysulphuret may be used with
effect, first, to transform fatty bodies into fatty acids by substituting the baryta
for the lime now used; the precipitation bysulphuric acid still further produces
a useful material (artificial sulphate of baryta), which does not take place
when employing line; 2nd,in soaking in a solution of baryta inwater,objects
moulded in plaster, the surface of which acquire, after several days'exposure
to the atmosphere, a great degree of hardness; third, when the natural car-
bonate of bariumor sulphuret of barium is used for saturating pyrolignous
acid, a solution of acetate of baryta is obtained. This salt, being purified from
tar by a slight torrefaction, is then decomposed by sulphuric acid, and produces
acetic acid, which is concentrated in vessels of copper; if the solution of
acetate is too much concentrated, the artificial sulphateof barytais precipitated
with difficulty.
Having described the nature of this Invention, and the manner of perform-
ing the same, I hereby declare that what I claim as of the Invention intended
to be secured by the Letters Patent is,―
First, the production of chloride of barium or strontian from the liquid
residuums of the manufactures of chlorine, or chloride of calcium,and natural
sulphates of baryta or strontian.
Secondly, the preparation of the nitrate of baryta from the nitrate of soda
and the chloride of barium.
Thirdly, the use of chloride of barium for preparing hydrochloric acid,
turtaric acid, and artificial sulphate of baryta, and the application of the
sulphate, and also of the sulphate of strontian, to distemper, coloring, or
painting.
Fourthly, the preparation of nitric acid bythewet process, and the prepara-
tion of caustic baryta with the nitrate, obtained as herein-before explained.

page_text: Fifthly, the use of the sulphuret or oxysulphuret of barium for obtaining,
by their combination with hydrated oxide of manganese, hydrated baryta free
from sulphur, and in the application of the hydrate to the hardening of plaster
objects, or to the fixing of colours applied with size or fecula.
Lastly, the use of the oxide or of the sulphuret of barium forthepreparation
of stearic and acetic acids.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Eleventh day of May, in the year of our Lord One
thousand eight hundred and fifty-seven.
WILLIAM CLARK. (L.S.)
Witness,
WILLIAM G. E. SWINNOCK.