Improvements in the Manufacture or Production of Zinc and other Sulphides, in the Utilization of Residual or Waste Products therein, and in Apparatus therefor.
Year: 1887

page_text: Date of Application, 7th May, 1887
Complete Left, 7th Feb., 1888
Complete Accepted, 16th Mar., 1888
Improvements in the Manufacture or Production of Zinc and other
Sulphides, in the Utilization of Residual or Waste Products
therein, and in Apparatus therefor.
We, HARRY GRIMSHAW of the Canal Chemical Works Clayton near Manchester
Chemical Manufacturer and HARTLEY KENYON of 70 Barrett Street Stretford Road
Manchester, Chemist, do hereby declare the nature of this invention to be as
follows:-
This Invention relates to the manufacture and production of Sulphides of all the
metals which combine chemically with sulphur and of sulphides of the earths and
alkalis; to the utilization in the said manufacture of residuals or waste products, and
in the construction and employment therein of apparatus designed adapted and arranged
to facilitate and carry out the processes involved in the manufacture.
In describing the nature of our invention we will do so for greater clearness in
reference to the manufacture or production of Zinc Sulphide, this being the sulphide
most in request and which will more generally be manufactured according to our
Improvements, but we desire it to be understood that the processes and apparatus may
with obvious modifications be employed in the production of other insoluble and of
soluble sulphides.
The residuals or waste products which we employ are:-Le Blanc Soda waste and
the yellow liquors therefrom; gas lime; spent oxide of iron from gas purifiers;
sulphur compounds of like nature; secondary residuals or bye products obtained in
carrying out our Invention; ammoniacal liquors obtained in the distillation of coal,
or in the distillation of animal matters or other nitrogenous materials, or other wastes
or residuals containing ammonia or the elements of ammonia; and the waste gases
from lime kilns and the like or from burning fuel or other source of carbon di-oxide.
The special apparatus we employ are generally of known construction and are:-
Coffy's stills, or obstructed towers connected with stills or series of stills as in the well
known apparatus employed in the distillation of gas liquor; Decomposers, consisting
of towers each containing a series of inclined planes or obstructions down which the
material passes by gravitation; and Agitators consisting of paddles dashers or stirrers

page_text: capable of being rotated or otherwise operated within a closed or partly closed
vessel. In addition, apparatus of obvious and known construction is employed in the
preliminary intermediate and final stages of the manufacture.
In the manufacture or production of sulphide of zinc to which as hereinbefore
indicated, we limit our description for the sake of greater clearness, we employ
any suitable and convenient ores minerals and substances containing the metal in
sufficient quantity, and more particularly we employ flux skimmings or waste from the
zinc baths in galvanizing works as well as waste galvanized iron from similar works.
The zine is brought into solution by means of hydrochloric acid, sulphuric acid or by
other suitable acid, or by ammonia or other alkali as is well understood. Iron or
other substances which would render the solution too impure for the purposes of our
Invention are removed by any of the known oxidising processes, but in solutions of
chloride or sulphate of zinc we prefer to oxidise the iron or other impurity by means
of hot air passed through or in contact with the solution is an obstructed tower or
other suitable vessel; simultaneously or subsequently adding oxide or carbonate of
zinc or oxide or carbonate of an earth or of an alkali. If the solution has been
effected by ammonia we oxidise and precipitate iron or other like impurity by means
of alkaline manganates and permanganates.
The sulphide of zinc is separated or produced from the purified solution by means
of vapours of ammonium sulphide or of sulphuretted hydrogen or a mixture of them
or by means of a solution of a soluble sulphide.
The sulphide of hydrogen or soluble sulphide required in carrying out our Invention
we produce by the hereinafter described or similar operations.
A solution containing ammonia is forced into the top of a Coffy's still, milk of lime
being if necessary injected into the stills in the usual manner. The ammoniacal
solution may be the ammoniacal liquors obtained in the distillation of coal, of animal
matter or of other nitrogenous materials, preferably the former, or it may be the
solution of chloride of ammonia obtained in carrying out this Invention, or other
convenient solution or source of ammonia.
At the same time we force into the top of the still suitable sulphur compounds in
solution or suspension such as vat waste, the yellow liquors therefrom, gas lime and
other sulphides or analogous sulphur compounds. By this means the ammonia is
driven off at the top of the still or tower wholly or chiefly in combination with sulphur
as ammonium sulphide. To ensure the dryness or comparative freedom from moisture
of the ammonium sulphide we may and prefer to reduce the temperature of the vapour
at its exit from the tower below 160° F.
In order to secure the complete conversion of the Ammonia into sulphide of
ammonium we prefer to pass the ammoniacal vapours from the tower or Coffy's still
into the lower part of the decomposer down which is passed by gravitation Le Blanc
Soda waste, gas oxide or other similar sulphur compounds, which if too dry may be
moistened with yellow liquors, or with soluble sulphur compounds in solution, or
water.
If necessary we also superheat the ammoniacal vapours before they enter the
decomposer in order to facilitate the chemical re-action and to prevent loss of ammonia
by condensation.
If we require an excess of sulphuretted hydrogen beyond that which is needed to
convert the ammonia or carbonate of ammonia into sulphide, we work the stills more
quickly in order to obtain a larger proportion of moisture in the ammoniacal vapours
which enter the decomposer and at the same time pass into the decomposer at a lower
level carbon dioxide which is preferably superheated and which decomposes a further
portion of soda waste or its equivalent material liberating Sulphuretted hydrogen
from the top of the decomposer together with the sulphide of ammonium.
The carbon dioxide we obtain by any of the well known means such as from lime
kilns or from burning fuel, or we may obtain it by burning the residual lime carbonate
from the decomposer and stills.
When we require Sulphuretted hydrogen alone we: pass carbon dioxide and steam
into the decomposer and by preference we superheat the gas and steam.

page_text: If the ammoniacal liquors used in the stills do not contain too large a quantity of
fixed ammonia compounds such as the chloride we may remove the carbon dioxide
from them previously to distillation by agitation with soda waste, gas lime, yellow
liquors or similar sulphur compounds.
When spent oxide of iron from gas purifiers is used in the decomposer we prefer to
conduct the operation at a higher temperature as thereby the ammonia, nitrogen, and
a portion of the sulphur are driven off as gaseous compounds and the residual spent
oxide is rendered much better adapted for use in the manufacture of sulphuric acid.
As hereinbefore set forth, the vapours of ammonium sulphide, sulphuretted hydrogen
or a mixture of them obtained from the decomposer or from the Coffy's still are passed
into the purified solution of zinc in hydrochloric acid, sulphuric acid, ammonia or
other alkali when, by well understood re-actions sulphide of zinc and chloride or
sulphate of ammonia or caustic ammonia or other caustic alkali is formed according
to the solvent which has been used.
This re-action is conducted in the agitator by means of which the solution and the
vapours are brought into intimate contact and complete absorption of the latter is
ensured.
We prefer to bring the solution of zinc to a high state of concentration before
placing it in the agitator, by which means we obtain a pasty mass of precipitated
sulphide of zinc and ammonia and ammonium chloride in solution. The pasty mass
is thereafter dried and heated to such a temperature as to volatilize the ammonium
chloride without decomposing the zinc sulphide.
When a solution of sulphate of zinc or of zinc in a fixed alkali is used, or in any
case, we may employ the ordinary or any suitable methods of subsidence, filtration,
washing and the like operations for the separation of the zinc sulphide from the
matters in solution.
The hereinbefore described methods processes and apparatus may be employed with
suitable and obvious modifications in the production or separation of the sulphides of
the well known metals which combine chemically with sulphur and of the sulphides
of the earths and the fixed alkalis.
D
WILLIAM E. HEYS,
70, Market Street, Manchester,
Agent for the Applicants.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture or Production of Zinc and other
Sulphides, in the Utilization of Residual or Waste Products.
therein, and in Apparatus therefor.
We, HARRY GRIMSHAW of the Canal Chemical Works Clayton near Manchester,
Chemical Manufacturer and HARTLEY KENYON of 70 Barret Street Stretford Road
Manchester Chemist, 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 :-
This Invention relates to the Manufacture and production of sulphides of all the
metals which combine chemically with sulphur and of sulphides of the earths and
alkalis to the utilization in the said Manufacture of residuals or waste products
and in the construction and employment therein of apparatus designed adapted and
arranged to facilitate and carry out the processes involved in the manufacture.
In describing the nature of our Invention we will do so for greater clearness in
reference to the manufacture or production of zinc sulphide, this being the sulphide
most in request and which will more generally be manufactured according to our
Improvements, but we desire it to be understood that the processes and apparatus may
with obvious modifications be employed in the production of other insoluble and of
soluble sulphides.
The residuals or waste products which we employ are :-Le Blanc Soda waste and
the yellow liquors therefrom; gas lime; spent oxide of iron from gas purifiers;
sulphur compounds of like nature; secondary residuals or bye products obtained in
carrying out our Invention; ammoniacal liquors obtained in the distillation of coal,
or in the distillation of animal matters or other nitrogenous materials, or other wastes'
or residuals containing ammonia or the elements of ammonia; and the waste gases
from lime kilns and the like or from burning fuel or other source of carbon dioxide.
The special apparatus we employ are generally of known construction and are :-
Coffy's stills, or obstructed towers connected with stills or series of stills as in the well
known apparatus employed in the distillation of gas liquor; Decomposers, consisting of
towers each containing a series of inclined planes or obstructions down which the soda
waste or analogous minerals descends by gravitation and up which a stream of
ammoniacal vapours ascend; and Agitators consisting of paddles dashers or stirrers
capable of being rotated or otherwise operated within a closed or partly closed vessel.
In addition, apparatus of obvious and known construction is or may be employed in
the preliminary intermediate and final stages of the manufacture.
In the manufacture or production of sulphide of zinc to which as herein before
indicated, we limit our description for the sake of greater clearness, we employ any
suitable and convenient ores minerals and substances containing the metal in sufficient a
quantity, and more particularly we employ flux skimmings or waste from the zinc
baths in galvanizing works as well as waste galvanized iron from similar works. The

page_text: zine is brought into solution by means of hydrochloric acid sulphuric acid or by other
suitable acid, or by ammonia or other alkali as is well understood. Iron or other
substances which would render the solution too impure for the purposes of our
Invention are removed by any of the known oxidising processes but in solutions of
chloride or sulphate of zinc we prefer to oxidise the iron or other impurity by means
of hot air passed through or in contact with the solution in an obstructed tower or
other suitable vessel, sinultaneously or subsequently adding oxide or carbonate of
zinc or oxide or carbonate of an earth or of an alkali. If the solution has been
effected by ammonia we may oxidise and precipitate iron or other like impurity by
means of alkaline manganates and permanganates.
The sulphide of zinc is separated or produced from the purified solution by means
of vapours of ammonium sulphide or of sulphuretted hydrogen or a mixture of them
or by means of a solution of a soluble sulphide.
The sulphide of hydrogen or soluble sulphide required in carrying out our Invention
we produce by the hereinafter described or similar operations.
A solution containing ammonia is forced into the top of a Coffy's still, or similar
apparatus, milk of lime being if necessary injected into the stills in the usual manner.
The ammoniacal solution may be the aminoniacal liquors obtained in the distillation
of coal, of animal matter or of other nitrogenous materials, preferably the first named
or it may be the solution of chloride of ammonia obtained in carrying out this Invention,
or other convenient solution or source of ammonia. At the same time we force into
the top of the still suitable sulphur-compounds in solution or suspension such
as vat waste, the yellow liquors therefrom, gas lime and other sulphides or analogous
sulphur compounds. By this means the ammonia is driven off at the top of the still or
tower wholly or chiefly in combination with sulphur as ammonium sulphide. To
ensure the dryness or comparative freedom from moisture of the ammonium sulphide
we may, and prefer to, reduce the temperature of the vapour at its exit from the
tower below 160° F.
In order to secure the complete conversion of the Ammonia into sulphide of
ammonium we prefer to pass the ammoniacal vapours from the tower or Coffy's still
into the lower part of the decomposer up which the vapours ascend and down which
is passed by gravitation, Le Blanc soda waste, gas oxide or other similar sulphur
compounds, which if too dry may be moistened with yellow liquors, or with soluble
sulphur compounds in solution, or water. If necessary we also superheat the
ammoniacal vapours before they enter the decomposer in order to facilitate the chemical
reaction and to prevent loss of ammonia by condensation. If we require an excess of
sulphuretted hydrogen beyond that which is needed to convert the ammonia or
carbonate of ammonia into sulphide, we work the stills more quickly in order to obtain
a larger proportion of moisture in the ammoniacal vapours which enter the decomposer
and at the same time pass into the decomposer at a lower level, carbon dioxide which
is preferably super heated and which decomposes a further portion of soda waste or
its equivalent material, liberating sulphuretted hydrogen from the top of the decomposer
together with the sulphide of ammonium.
The carbon dioxide we obtain by any of the well-known means such as from lime
kilns or from burning fuel, or we may obtain it by burning the residual lime
carbonate from the decomposer and stills.
When we require sulphuretted hydrogen alone, we pass carbon dioxide and steam
into the decomposer and by preference we superheat the gas and steam.
Cyanide, chloride and carbonate of ammonia when present in the ammoniacal
liquors used in the stills may be converted into sulphides previous to distillation by
agitation with, percolation through, or other means for producing intimate contact
with, soda waste, yellow liquors gas lime, spent oxide or similar sulphur compounds,
the reaction taking place in the cold.
When spent oxide of iron from gas purifiers is used in the decomposer we prefer
to conduct the operation at a higher temperature, as thereby the ammonia, nitrogen
and a portion of the sulphur are driven off as gaseous compounds and the residual spent
oxide is rendered much better adapted for use in the manufacture of sulphuric acid.

page_text: As hereinbefore set forth, the vapours of ammonium sulphide, sulphuretted hydrogen
or a mixture of them obtained from the decomposer or from the Coffy's still are
passed into the purified solution of zinc in hydrochloric acid, sulphuric acid, ammonia
or other alkali, when, by well understood reactions sulphide of zinc and chloride or
sulphate of ammonia or caustic ainmonia or other caustic alkali are formed according
to the solvent which has been used.
This reaction is conducted in the agitator by means of which the solution and the
vapours are brought into intimate contact and complete absorption of the latter is
ensured.
We prefer to bring the solution of zinc to a high state of concentration before
placing it in the agitator, by which means we obtain a pasty mass of precipitated
sulphide of zinc and ammonia or ammonium chloride in solution. The pasty mass is
thereafter dried and heated to such a temperature as to volatilize the ammonium
chloride without decomposing the zinc sulphide as described in the Specification to
Letters Patent No. 16118 of A.D. 1886 granted to Hartley Kenyon.
When a solution of sulphate of zinc or of zinc in a fixed alkali is used, or in any
case we may employ the ordinary or any suitable methods of subsidence filtration
washing and the like operations for the separation of the zinc sulphide from the
matters in solution.
The hereinbefore described methods processes and apparatus may be employed with
suitable and obvious modifications in the production or separation of the sulphides of
the well known metals which combine chemically with sulphur and of the sulphides of
the earths and the fixed alkalis.
Having now particularly described and ascertained the nature of our said
Invention and in what manner the same is to be performed, we declare that what
we claim is :
(1) The manufacture of sulphides of the metals which combine chemically with
sulphur, of the earths and of the alkalis; the processes of manufacture consisting in
the solution of the base by means of an acid or of an alkali ; the removal of impurities
by oxidation with or without the addition of an oxide or of a carbonate; the separation
of the base as a sulphide by the addition of gaseous or liquid sulphur compounds and
the separation of the soluble from the unsoluble salts by sublimation or by subsidence
and decantation or by filtration or by other known and suitable means; substantially
as hereinbefore described.
(2) A decomposer or apparatus for effecting the complete conversion of the ammonia
into ammonium sulphide, constructed and operated substantially as hereinbefore
described.
(3) The production of carbon dioxide from the decomposer residuals and its
utilization in the production of sulphuretted hydrogen employed in the manufacture
of sulphides; substantially as described.
(4) In the manufacture of sulphides, the conversion of cyanide, chloride carbonate
and other salts of ammonium in ammoniacal liquors into sulphide by intimate contact
in the cold with soda waste, yellow liquors, gas lime, spent oxide and analogous
substances, substantially as hereinbefore described.
Dated this 4th day of February A.D. 1888.
WILLIAM E. HEYS,
Agent for the Applicants.