Year: 1887

page_text: Date of Application, 31st May, 1887
Complete Left, 23rd Feb., 1888
Complete Accepted, 13th Apr., 1888
hereby declare the nature of this invention to be as follows:-
The object of my invention is to produce hydrate of baryta from sulphate of barium,
or heavy spar, without having recourse to the intermediate production of carbonate
of barium.
For this purpose I employ as main agent hydrogen, which is an element that
possesses greater affinity to sulphur and
than barium.
oxygen
The sulphate of barium is mixed in comminuted state with carbonaceous materials,
such as saw-dust, coal, cokes, tar, hydrocarbons, &c.; the mixture is heated to a high
temperature, and hydrogen gas, water-gas, or other gas containing hydrogen, is
caused to act upon the same.
Under these conditions a portion of the hydrogen
combines with the sulphur of the sulphuric acid to form sulphuretted hydrogen,
another portion of the same combines with a portion of the oxygen of the said acid
to form water, the rest of the oxygen unites with the carbon and forms therewith
carbonic acid, while the water obtained as stated, passes over to the barium oxide,
whereby hydrate of baryta is produced. The hydrogen or hydrogen-containing gas
requires to be employed in excess in order to ensure the complete conversion of the
sulphur into sulphuretted hydrogen and the production of a sufficient quantity of
steam, necessary to prevent the formation of carbonate of barium. At the end of the
process the mass is exposed to the action of saturated (non-superheated) steam, in
view of completing the conversion of the baryta into bydrate of baryta. The product
thus obtained is slaked in water. In some cases it is advantageous to add fluxes, such
as soda, potash, lime, &c., to the mass to be treated, in order to cause the same
to melt.
The process may be carried out in a furnace heated by hydrogen or a gas containing
the same, and the gas may be blown into the mass either in the furnace itself, or in
a vessel alike to a Bessemer converter, the mass being run into the latter after having
been melted (with the addition of fluxes) and partly reduced.

page_text: In case it should be desired to lessen the amount of hydrogen consumed by the
process, this may be attained by means of oxyde of zinc; of copper, of manganese or
of iron, or the hydrates thereof. The oxide may be added at the beginning of the
operation to the mixture of sulphate of barium and carbon, which is thereupon first
exposed to the action of a reducing flame, or it is added after the mass has been partly
desulphurated, the metal of the oxide combining with a portion, or the remaining
portion (as the case may be) of the sulphur contained in the barium sulphate. The
sulphides thus obtained, may be regenerated, subsequent to their separation from the
hydrate of baryta, by means of hydrogen.
Dated the Twenty-sixth day of Max 1907
COMPLETE SPECIFICATION.
Improved Process of Producing Hydrate of Baryta from Sulphate
of Barium.
I, RICHARD SCHNEIDER, Engineer residing in Dresden, kingdom of Saxony,
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 :-
The object of my invention is to produce hydrate of baryta from sulphate of
barium, or heavy spar, without having recourse to the intermediate production of
carbonate of barium.
و.
F
For this purpose I employ as main agent hydrogen, which is an element that (
possesses greater affinity to sulphur than either barium or oxygen.
The sulphate of barium is mixed in comminuted state with carbonaceous materials, 2
the mixture is heated to a high temperature and hydrogen gas is caused to act upon
the same.
Under these conditions a portion of the hydrogen combines with the
sulphur of the sulphuric acid to form therewith sulphuretted hydrogen, another..
portion of the same combines with a portion of the oxygen of the said acid to form
water (in the state of steam), the rest of the oxygen of the acid unites with the carbon a
and forms therewith carbonic acid, while by means of the steam obtained as stated,
the barium oxide is converted, to a greater or less extent into hydrate of baryta, and
the formation of carbonate of barium is prevented. At the end of the process the
mass is exposed to the action of non-superheated steam in view of the farther
conversion of the baryta into hydrate of baryta. The product thus obtained is slaked
in water, whereby the said conversion is completed.

page_text: For carrying out the process, I prefer to employ water-gas or other gases containing
hydrogen instead of the pure hydrogen gas, which is too expensive. The sulphate of
baryta, after having been ground or otherwise reduced to powder, is mixed with
from 10 to 30 per cent., or thereabouts, of the carbonaceous material. As such may
be used saw-dust, rasped wood, ground charcoal, brown-coal, mineral coal or cokeš,
tar or other substances containing light or heavy hydro-carbons and two or more of
these materials may be employed together. The mixture of the sulphate of barium
with the carbonaceous material is brought into a furnace, heated by the said gas as
fuel, and, after having been gradually warmed therein, it is carried to a temperature
above red heat, so that the mass, which is at first pulverulent, will become sintered
and subsequently melted. In order that all the sulphur may with certainty be
converted into sulphuretted hydrogen, and that a sufficient quantity of steam be
produced for preventing the carbonic acid, generated during the process, from
combining with the barium oxide and forming therewith carbonate of barium,
hydrogen requires to be present in excess. Besides, it is advantageous, and may be
necessary, for the complete elimination of the sulphur, to force hydrogen or hydrogen-
containing gas into the molten material in addition to causing it to act thereon from
the surface. This may be done by blowing the gas from the bottom of the bearth on
which the material is melted through the latter, or the material, after having been
melted and partly reduced, is run into an apparatus similar to a Bessemer converter
and is treated therein alike to the iron in the Bessemer-process except that hydrogen-
containing gas is introduced instead of air. When the evolution of gases containing
sulphuretted hydrogen ceases, the main part of the operation is finished.
If the described process is carried out wholly in a furnace, the product obtained is
run into a chamber adjacent to the former and maintained at a lower temperature,
and non-superheated steam is blown into the chamber, whereby the conversion, into
hydrate, of the portion of the said product having remained in anhydrous state, is
commenced, while simultaneously, as in the main part of the process, the action of
the carbonic acid on the molten baryta and hydrate of baryta is prevented. If the
process is performed in a converter, the latter is turned down subsequent to the
reduction of the mass, and non-superheated steam is blown in above the surface
thereof. When, during this operation, the mass has cooled down sufficiently to
become thick or viscous, it is run into water in view of its complete conversion into
hydrate.
A furnace adapted for the performance of the described process is shown on the
annexed sheet of drawings, the figures 1 and 2 being vertical sections thereof on
the respective lines A B and C D, while fig. 3 is a sectional plan on the lines E F,
figs. 1 and 2. The gas serving to heat the hearth 0 of this furnace is introduced
alternately by either of the channels G₁ and G³, and the air serving to support
combustion by either of the channels L' and L', the said channels being in
communication with regenerators not shown in the drawing. When gas and air pass
in through the channels G' and L', the products of combustion issue through the
channels G and L, and vice-versa, as usual in furnaces provided with regenerators.
Below the bottom of the hearth are arranged air-channels for preventing the same
from being beated to an injurious extent, the said channels being in communication
with the chimneys S1 and S2. The raw material is introduced at the top of the
inclined shaft N, and is warmed therein by a portion of the combustion-gases passing
through the said shaft and the channels p₁ and p² to the chimneys S' and S. From
the shaft N the material slides, or is pushed down on the hearth O, and aftor having
undergone the melting and converting process, it is drawn off into the chamber P,
which is heated from the hearth through the apertures Q, o, o³, os, provided with the
regulating-slides q, t¹, t, t³, the temperature of the said chamber being kept
considerably below that of the hearth. rare pipes for the introduction of steain
into the chamber P, and F is the discharge-aperture of the same. The furnace does
not, however, form any part of the invention which I claim herein.
In the described process a large amount of hydrogen or hydrogen-containing gas
is required, especially in the latter stage of the same. In case it should be desired

page_text: to lessen the said amount, this may be attained by means of oxides or hydrated oxides
of zinc, of copper, of manganese, or of iron. The oxide or hydrated oxide may be
added at the beginning of the operation to the mixture of sulphate of barium and
carbon, which is thereupon first exposed to the action of the reducing flame, or it is
added after the mass has been partly desulphurated, the metal of the oxide combining
with a portion, or the remaining portion (as the case may be) of the sulphur contained
in the barium sulphate. After the mixture of hydrate of baryta and metallic sulphide
has been cooled by means of steam and slaked in water, the said hydrate may be
lifted off the sulphide, which forms a slimy mass. The sulphides thus obtained inay
be reconverted by means of hydrogen or hydrogen-containing gases into the oxides
or hydrated oxides required in the described process.
For promoting the melting-process, fluxes, such as soda, potash, lime and the like
may be added to the mass to be treated.
Having now particularly described and ascertained the nature of my inven-
tion and in what manner the same is to be performed, I declare that what I
claim is:
1. The process of converting sulphate of barium into hydrate of baryta, which
consists in mixing the sulphate of barium with carbonaceous materials, exposing the
same to the simultaneous action of heat and of hydrogen, water-gas or other hydrogen-
containing gas passing non-superheated steam to the desulphurated mass and finally
slaking it in water, substantially as hereinbefore described.
2. The modification of the process claimed above, which consists in adding an oxide
or hydrated oxide of zinc, of copper, of manganese or of iron to the non-desulphurated
or incompletely desulphurated mass, substantially as specified.
Dated the Twentieth day of February 1888.
CARL PIEPER,
Agent for Applicant..