Improvements relating to the Utilization of Liquors from r Chlorination-roasted 'Ores or Tailings.
Year: 1895

page_text: Date of Application, 19th Jan., 1895
Complete Specification Left, 4th Oct:, 1895-Accepted, 9th Nov., 1895
.
PROVISIONAL SPECIFICATION.
Improvements relating to the Utilization of Liquors from
r Chlorination-roasted 'Ores or Tailings.
I, HUGO BREWER, of 5 Grünstrasse, Duisburg, in the Empire of Germany, do
hereby declare the nature of this invention to be as follows :
1
"My invention relates to the utilization of liquors from chlorination-roasted ores
or tailings.
1
In the chlorination-roasting of ores and tailings use is made of sodium chloride
which has heretofore been lost in-the liquors produced from the roasted material.
Moreover the treatment of these liquors as heretofore practiced gives rise to
troublesome waste liquors, so that under these circumstances the treatment of
liquors containing zinc from chlorination-roasted ores does not appear practicable.
To obriate inconveniences of this kind is the object of the aforesaid invention,
according to which the liquors from chlorination-roasted ores are to be treated
without the production of troublesome waste liquors, and with extraction of all the
useful metals contained therein, and with recovery of all the chlorine and sodium
of the sodium chloride used, or with regeneration of the sodium chloride necessary
for the roasting, in such a manner that the additional cost as compared with the
process heretofore used may be obviated, and that the improved process may show
an increased economic advantage, the treatment of such liquors being thus rendered
possible in practice:
.
This object is achieved according to the said invention by transforming the
sulphates of the liquors from chlorination-roasted ore. by--the addition of an
equivalent quantity of calcium chloride into the corresponding chlorides. In the
deposit of calcium sulphate formed, which may be utilized in any desired manner,
for instance as anilines or in the form of burnt gypsum, is to be found the sulphuric
acid of the sulphates formed in the roasting process and the calcium of the calcium
chloride used; for which latter the ammonia-soda process constitutes a cheap source,
thereby enabling also the utilization of the chlorine to be effected which has
heretofore been lost in this soda process:
The liquor separated from the deposit of calcium sulphate now contains the
sodium, zine and the other metals in the form of chlorides instead of as sulphates,
and is then treated for the metals and salts contained therein, that is to say sodium
chloride and calcium chloride, which may be used again in the process.
will proceed to explain my invention by the following example:-
Zinc blende, or ores containing blende, or burnt ores containing zinc, by
themselves, or with addition of pyrites or iron oxide, purple ore, are chlorination-
roasted and then lixiviated.
The liquor obtained, which consists substantially of sodium sulphate, zinc
chloride, sodium chloride, ferric sulphate, besides other metallic salts such as salts
of manganese, cobalt, nickel, silver, is mixed with a quantity of calcium chloride
equivalent to the proportion of sulphuric acid contained in the liquor, which
calcium chloride may be derived from the ammonia-soda process as a by-product.
The sodium sulphate and the. metallic sulphates which may be present are trans-
formed into the corresponding chlorides while calcium sulphate is separated.
the metals and also the sodium are now present in the solution as chlorides and
only a little calcium sulphate is dissolved at the same time, this sulphate being
completely separated in the subsequent course of the process.
All

page_text: Any silver which may be present can be precipitated in the well-known manner,
and the iron is then separated in the form of hydrated ferric oxide by the aid of
calcium carbonate, for which the calcium carbonate slime derived from the caustic
alkali manufacture is very suitable, and as far as the iron was in solution as an iron
salt with ample contact of the liquor with air, which reaction may be represented
for ferrous chloride by the following equation :-
:-
2 FeCl2 + 2 CaCO3 + 3 H₂O + 0 = Fe(OH), +2 CaCl2 + 2 CO₂.
The clear liquor separated from the deposit now contains the chlorine of the
iron salt in the form of calcium chloride and may be freed in the well-known
manner, for instance by means of chlorine, but preferably by means of chloride of
lime from cobalt, manganese and nickel, these metals being separated as oxides and
an equivalent quantity of calcium chloride which dissolves being formed.
The liquor thus treated still contains substantially zinc chloride, sodium chloride
and calcium chloride. It is concentrated by the aid of the exhaust steam from the
engine for the electrolytic apparatus subsequently used, the still dissolved traces of
calcium sulphate being first separated and then all the sodium chloride being
obtained in the solid form. That some zinc chloride has passed over into the latter
is immaterial, this sodium chloride being used again for the roasting, so that the
zinc will not be lost.
The concentrated mother liquor contains zinc chloride and calcium chloride and
also some sodium chloride, and is appropriately submitted to electrolysis, use being
made of zinc cathodes and carbon anodes. The metallic zinc is separated at the
cathodes, and the chlorine at the anodes, the former may be put on the market
either directly or remelted, and the latter in the liquid form or as chloride of lime,
or may at least partly be used in the process.
The calcium chloride remaining behind in the liquor and the undecomposed
zinc chloride is again used in the process, while the calcium chloride which is
necessary in addition may be obtained from the waste liquors of the ammonia-soda
process.
>
In case the roasted masses of ore or the liquors to be treated contain besides
zinc also copper in such quantities that the utilization of the same may be
advantageous or the separation necessary, I proceed in the manner described for
zinc, with the difference that the separation of the silver and copper is effected
either before or after the addition of the calcium chloride. The silver is
precipitated in the well-known manner, and the copper can be separated by the aid
of metallic iron, the chief portion of the copper if desired being separated by
electrolytical means particularly in the case of large quantities of copper, with
obtention of chlorine, whereupon the remainder of the copper may be precipitated
by the aid of metallic iron. I then continue the described process by separating
the iron with calcium carbonate and by means of air as an hydroxide and then
effecting the further separation as described.
When employing my invention for the utilization or treatment of the liquors
containing copper (such as for instance the ultimate liquors from the chlorination-
roasting of burnt ores containing copper) with separation of copper by means of
metallic iron, there would be very much iron and consequently after the separation
of the iron much calcium chloride in solution so that the calcium chloride liquor
obtained may be sufficient for transforming the sulphates in the liquor to be utilized
according to the present invention.
Dated this 19th day of January 1895
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.

page_text: improvements relating to the Utilization of Liquors from
Chlorination-roasted Ores or Tailings.
I, HUGO BREWER, of 5 Grünstrasse, Duisburg, in the Empire of Germany, 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 utilization of liquors from chlorination-roasted ores
or tailings.
In the chlorination-roasting of ores and tailings use is made of sodium chloride
which has heretofore been lost in the liquors produced from the roasted material.
Moreover the treatment of these liquors as heretofore practiced gives rise to
troublesome waste liquors, so that under these circumstances the treatment of
liquors containing zinc from chlorination-roasted ores does not appear practicable.
To obviate inconveniences of this kind is the object of the aforesaid invention,
according to which the liquors from chlorination-roasted ores are to be treated
without the production of troublesome waste liquors, and with extraction of all
the useful metals contained therein, and with recovery of all the chlorine and
sodium of the sodium chloride used, or with regeneration of the sodium chloride
necessary for the roasting, in such a manner that the additional cost as compared
with the process heretofore used may be obviated, and that the improved process
may show an increased economic advantage, the treatment of such liquors being
thus rendered possible in practice.
This object is achieved according to the said invention by transforming the
sulphates of the liquors from chlorination-roasted ore by the addition of au
equivalent quantity of calcium chloride into the corresponding chlorides. In the
deposit of calcium sulphate formed, which may be utilized in any desired manner,
for instance as anilines or in the form of burnt gypsum, is to be found the
sulphuric acid of the sulphates formed in the roasting process and the calcium of
the calcium chloride used, for which latter the ammonia-soda process constitutes a
cheap source, thereby enabling also the utilization of the chlorine to be effected
which has heretofore been lost in this soda process.
The liquor separated from the deposit of calcium sulphate now contains the
sodium, zinc and the other metals in the form of chlorides instead of as sulphates,
and is then treated for the metals and salts contained therein, that is to say sodium
chloride and calcium chloride, which may be used again in the process.
I will proceed to explain my invention by the following example:-
Zine blende, or ores containing blende, or burnt ores containing zinc, by
themselves, or with addition of pyrites or iron oxide, purple ore, are chlorination-
roasted and then lixiviated.
The liquor obtained, which consists substantially of sodium sulphate, zinc
chloride, sodium chloride, sulphate of iron, besides other metallic salts such as
salts of manganese, cobalt, nickel, silver, is mixed with a quantity of calcium
chloride equivalent to the proportion of sulphuric acid contained in the liquor,
which calcium chloride may be derived from the ammonia-soda process as a by-
product. The sodium sulphate and the metallic sulphates which may be present
are transformed into the corresponding chlorides while calcium sulphate is
separated. All the metals and also the sodium are now present in the solution as
chlorides and only a little calcium sulphate is dissolved at the same time, this
sulphate being completely separated in the subsequent course of the process.
Any silver which may be present can be precipitated in the well-known manner,
and the iron is then separated in the form of hydrated ferric oxide by the aid of
.

page_text: calcium carbonate, for which the calcium carbonate slime derived from the caustic
alkali manufacture is very suitable, and as far as the iron was in solution as a
ferrous salt with ample contact of the liquor with air, which reaction may be
represented for ferrous chloride by the following equation :-
2. FeCl2CaCO3 + 3 H₂O. +0 = Fе₂(OH) + 2 Ca€ + 2CO₂.
The clear liquor separated from the deposit now contains the chlorine of the
iron salt in the form of calcium chloride and may be freed in, the well-known
manner, for instance by means of chlorine, but preferably. by means of chloride
of lime from cobalt, manganese and nickel, these, metals being separated as oxides
and an equivalent quantity of calcium chloride which dissolves being formed..
The liquor thus treated still contains substantially zine chloride, sodium chloride
and calcium chloride. It is concentrated by the aid of the exhaust steam from
the engine for the electrolytic apparatus subsequently used, the still dissolved
traces of calcium sulphate being first separated and then all the sodium chloride
being obtained in the solid form. That some zinc chloride has passed over into the
latter is immaterial, this sodium chloride being used again for the roasting, so
that the zinc will not be lost.
The concentrated mother liquor contains zinc, chloride and calcium chloride and
also some sodium chloride, and is appropriately submitted to electrolysis use
being made of zinc cathodes and carbon anodes. The metallic zinc is separated
at the cathodes, and, the chlorine at the anodes; the former may be put on the
market either directly or remelted, and the latter in the liquid form or as chloride
of lime, or may at least partly be used in the process.
The calcium chloride remaining behind in the liquor and the undecomposed zinc
chloride is again used in the process, while the calcium chloride which is necessary
in addition may be obtained from the waste liquors of the ammonia-soda process.
In case the roasted masses of ore or the liquors to be treated contain besides
zinc also copper in such quantities that the utilization of the same may be
advantageous or the separation necessary, I proceed in the manner described for
zinc, with the difference that. the separation of the silver and copper is effected
either before or after the addition of the calcium chloride. The silver is
precipitated in the well-known manner, and the copper can be separated by the
aid of metallic iron, the chief portion of the copper if desired being separated by
electrolytical means, particularly in the case of large quantities of copper, with
obtention of chlorine, whereupon the remainder.of the copper may be precipitated
by the aid of metallic iron. I then continue the described process by separating
the iron with calcium carbonate and by means of air as an hydroxide and then
effecting the further separation as described.
When employing my invention for the utilization or treatment of the liquors
containing copper (such as for instance the ultimate liquors from the chlorination-
roasting of burnt ores containing copper) with separation of copper by means of
metallic iron, there would be very much iron and consequently after the separation
of the iron much calcium chloride in solution so that the calcium chloride liquor
obtained may be sufficient for transforming the sulphates in the liquor, to be
utilized according to the present invention..
Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what. I
claim is
1. The process of utilizing liquors from chlorination-roasted, ores or tailings,
the characteristic feature of which is that the sulphates contained in such liquors
are transformed by means of calcium chloride, in order that the regeneration of
the sodium chloride, necessary for the chlorination-roasting, may be rendered
possible and in order to prepare the liquors for the extraction of the metals
contained in the same partly by electrical and partly by chemical means..

page_text: 2. The process, described in the first claim for the utilization of liquors,
containing zine from chlorination-roasted ores or tailings, carried out in such a
manner, that the sulphates of these liquors are transformed into the corresponding
chlorides by the addition of calcium chloride while serviceable or useful sulphate
of calcium is precipitated and obtained; the metals and especially the iron being
subsequently precipitated by means of carbonate of calcium and, if necessary air
and manganese, cobalt and nickel by means of chlorine or chloride of lime, while
calcium chloride is generated; that subsequently from the liquor thus obtained-
and which liquor is by evaporation freed from chloride of sodium which latter S
again applicable for the roasting process-the chloride of zinc is, by electrolytical
means separated into extractable chlorine and metallic zinc, so that ultimately a
calcium chloride liquor is generated, which again serves for the process of
transforming the sulphates and which still contains non-decomposed chloride of
zinc and slight quantities of sodium chloride.
3. A method of carrying out the process, described in the second claim, for
liquors which also contain silver, or manganese, cobalt or nickel, the characteristic
feature being that, according to the process described in the said second claim the
precipitation of the silver is effected before the iron is precipitated, the separation
of the manganese, cobalt or nickel by the aid of chlorine or chloride of line is
effected after the precipitation of iron and before the separation of sodium
chloride.
4. A method of carrying out the process, described in the second and third
claims respectively, for liquors which also contain copper, the characteristic
feature being that, in the said processes the precipitation of the copper is effected
before the precipitation of iron by means of metallic iron.
5. A method of carrying out the process described in the 2nd and 3rd claims
respectively, for liquors which also contain copper, the characteristic feature being
that in the said process before the precipitation of the iron, the main bulk of the
copper is precipitated by electrolytical means under simultaneous extraction of
the chlorine, while the remainder of the copper is extracted by means of metallic
iron.
6. The utilization of the sodium chloride which has not been decomposed during
the chlorination-roasting and which has been lixiviated, simultaneously with the
sodium chloride obtained according to the second claim by evaporation.
7. A method of carrying out the process, according to the fifth claim, the
characteristic feature being that the copper is electrically and under simultaneous
extraction of the chlorine, precipitated from the sodium sulphated liquor without
the preceding treatment with sodium chloride liquor, whereas the rest of the copper
is precipitated by means of metallic iron; the remaining liquor being treated in
conformity with the process described in the 1st, 2nd and 3rd claims, according to
which any silver that may be contained in the liquor, is to be precipitated in the
known manner and before the electrolytic extraction of the copper.
8. The utilization of the chlorine from the ammonia soda process, the
characteristic feature being, that the chlorine combined with the calcium by the
ammonia soda process is according to the first, 2nd, 4th and 5th claims-obtained
as sodium chloride (for any desired suitable use) or as free chlorine (suitable for
chloride of lime or liquid chlorine).
Dated this 4th dor of Oatuhan 100%
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.