IMPROVEMENTS IN GALVANIC BATTERIES, AND IN THE TREATMENT OF SOLUTIONS THEREFROM FOR THE RECOVERY OF Useful PRODUCTS." PROVISIONAL SPECIFICATION
Year: 1882

page_text: LETTERS PATENT to James Higgin and Alfred James Higgin, both of
Manchester, in the County of Lancaster, Manufacturing Chemists, for an
Invention of "IMPROVEMENTS IN GALVANIC BATTERIES, AND IN THE
TREATMENT OF SOLUTIONS THEREFROM FOR THE RECOVERY OF Useful
PRODUCTS."
PROVISIONAL SPECIFICATION left by the said James Higgin and Alfred
James Higgin at the Office of the Commissioners of Patents on the 20th
January 1882.
"
JAMES HIGGIN and ALFRED JAMES HIGGIN, both of Manchester in the County
of Lancaster, Manufacturing Chemists. IMPROVEMENTS IN GALVANIC BATTERIES
AND IN THE TREATMENT OF SOLUTIONS THEREFROM FOR THE RECOVERY OF USEFUL
PRODUCTS."
Our Invention has for its principal object to lessen the cost of the production of
galvanic currents by means of batteries and to this end we employ elements and
materials which will furnish useful and valuable chemical products. In the
description of battery which we consider to be most suitable to our purpose we
employ tin for one element and carbon for the other and we use dilute sulphuric
acid for the exciting medium. In one form of a battery cell, we use a receptacle
such as a stone-ware jar in which is a hollow cylinder of tin with an inner porous
cell containing a carbon rod or plate which is surrounded with granular pyrolusite
or manganese peroxide which we use to absorb developed hydrogen. During the
action of such a battery the action of the dilute sulphuric acid produces proto-
sulphates of tin and of manganese which remain in solution. When it is desirable
to renew the exciting liquid we treat the solution obtained from the battery in
order to obtain such preparations of tin as are required in the dyeing and printing
of textile fabrics and in other industrial processes. We prefer to heat the solution
with an added quantity of oxide of manganese whereby we convert the proto-
sulphate of tin into a per-sulphate. It is then only necessary to dilute the resultant
with water in order to precipitate stannic acid or oxide from which other preparations
of tin may be obtained by the employment of suitable or ordinary processes. We
may vary the nature of the battery by substituting a perforated or porous copper
cell filled with pyrolusite for the carbon element and a solution of caustic soda for
the dilute sulphuric acid in which case the spent liquid obtained from the cell will
contain stannite or stannate of soda which may be readily recovered. In another
Daina B71

page_text: modification, a compound solution of nitrate of soda and of caustic soda is used
as the exciting liquid for a battery having tin and carbon elements. We do not
confine ourselves to the cylindrical forms of the elements. When a strong current
is required as for example when reqnired for the production of the electric light
we combine together a number of cells as is usual. In another modification we
also employ a stoneware jar or a suitable receptacle with a hollow cylinder of tin
and a porous cell. In the outside vessel we put dilute sulphuric acid, and in the
porous cell a solution of persulphocyanide of iron, either pure or made by mixing a
solution of a persalt of iron such as perchloride or persulphate with an alkaline
sulphocyanide. In the porous cell we place a rod or plate of carbon. In proportion
as the outside cell becomes charged with sulphate of tin, the liquid in the porous
cell becomes changed from persulphocyanide into protosulphocyanide of iron. This
change may be very much retarded by introducing a current of air by means of a
small tube extending about to the bottom of the porous cell and connected with a
blower. A continuous stream of air being passed through, the protosulphocyanide
of iron is continually re-changed into persulphocyanide. When the exciting liquid
is becoming weak in action from saturation with tin it is withdrawn and the liquid
is treated as herein before stated to recover stannic oxide. When in course of time
the liquid in the porous cell has by diffusion become highly charged with a salt of
tin we remove the liquid and after blowing air into it for a sufficient time we
dilute with water, when stannic oxide falls and is removed by subsidence or
filtration. The red liquid remaining is mixed with a solution of a copper salt such
as sulphate or chloride, and then is added a reducing agent such as sulphurous acid
or a sulphite of alkali or alkaline earth or hyposulphate of soda or protosulphate of
iron. A white powder falls which is the disulphocyanide of copper which after
being purified by means of hot dilute sulphuric or hydrochloric acid is suitable for
ordinary uses or it may be decomposed by means of an alkaline or earthy sulphide
in solution whereby sulphide of copper and an alkaline or earthy sulphocyanide
are formed. The former by well known processes may be re-converted into a
soluble salt of copper and the latter may be used to reconstitute the porous cell
absorbent. We can also use as an absorbent in the porous cell other per-salts of
iron such as per-acetate, per-chloride, per-sulphate or per-nitrate of iron in which
cases we do not seek to recover the salt of iron, when the liquid in the porous cell
is changed, but oxidise the protosulphate of tin into per-sulphate by means of per-
oxide of manganese as herein before stated and dilute largely with water to
precipitate the stannic oxide. We prefer however to use the persulphocyanide of
iron. In place of the dilute sulphuric acid as an exciting liquid we can use dilute
hydrochloric acid and one or other of the ferruginous absorbents. The separation
of tin from the saturated or partly saturated excitant may then be done by
evaporation and crystallization of the proto-chloride of tin or the solution may be
oxidised by means of peroxide of manganese and sulphuric acid or a sulphate of
an alkali may be added and the liquid be largely diluted with water to precipitate
the stannic oxide. The tin in solution in the porous cell may be treated with
peroxide of manganese and a sulphate or sulphuric acid be added and the liquid
diluted with water as before. In another modification of our battery we employ
the form of cell called the bichromate cell wherein a plate of zinc is fixed between
two plates of carbon and the whole immersed in a solution of chromic acid or in a
mixture of bichromate of potash and sulphuric acid. In one modification the plate
of zinc is replaced by a plate of tin and the exciting fluid is a mixture of persulpho-
cyanide of iron or persulphate, per-chloride, per-acetate or per-nitrate of iron, and
sulphuric or hydrochloric acid. Various modifications of this single fluid battery
may be employed corresponding to the various forms of the bichromatic battery
in ordinary use. We recover stannic oxide by means of oxidation and precipitation
in the presence of sulphuric acid or a sulphate and also recover a sulphocyanide of
alkali or copper as hereinbefore described.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said James Higgin and Alfred James Higgin in the Great Seal Patent
Office on the 20th July 1882.
JAMES HIGGIN and ALFRED JAMES HIGGIN both of Manchester in the County
of Lancaster, Manufacturing Chemists. "IMPROVEMENTS IN GALVANIC BATTERIES
AND IN THE TREATMENT OF SOLUTIONS THEREFROM FOR THE RECOVERY OF
USEFUL PRODUCTS."
Our Invention has for its principal object to lessen the cost of the production of
galvanic currents, by means of improved batteries, and to this end we employ
elements and materials, which will in addition to causing the necessary electrical
currents furnish useful and valuable chemical products. We effect this by
substituting tin for the zinc usually employed as a positive element and by simple
means we recover the tin in a form suitable for certain chemical manufactures
into which that metal enters as a principal ingredient. We are aware that tin
excited by nitric and nitro-muriatic acids has been before proposed as a positive
element in galvanic batteries, but such attempts have not resulted in its successful
employment. In carrying out our Invention we employ two descriptions of
galvanic cells. In one form we have two fluids separated generally by a porous
cell, and in the other we have only one fluid. In the double fluid cell we generally
use a receptacle such as a stoneware jar, in which we place a hollow cylinder of tin
or a plate of tin rolled into a cylindrical form. The edges of the plate need not
touch, as a narrow aperture left to establish a communication between the fluid
inside the cylinder and that outside of it, will be benefical. Inside the cylinder
we place a porous cell, after the manner of the well known" Bunsen" cell. In the
outside cell we place a dilute acid, and in the porous cell a liquid or substance
capable of absorbing developed hydrogen. In one form of our double fluid cell we
employ sulphuric acid diluted with from 5 to 10 times it's volume of water as an
excitant; and as an absorbent in the porous cell, we put a carbon rod or plate,
surrounded by pyrolusite or native peroxide of manganese, broken into small pieces
which may be about the size of peas. We fill up the porous cell with dilute
sulphuric acid, as in the case of the outer cell. A copper wire is connected with
the tin plate and another with the carbon rod or plate. During the action of this
battery the dilute sulphuric acid produces proto-sulphates of tin and manganese,
which remain in solution. When it is desirable to renew the liquids in this cell,
we treat the saturated or partly saturated solution in the following manner to
separate the tin therein contained. We add to the solution which may beneficially
be heated, sufficient peroxide of manganese in fine powder to cause the proto-
sulphate of tin to become persulphate. No fixed quantity of peroxide of manganese
can herein be given, for the reason that the quantity of tin in solution may vary,
but the point at which the peroxidation of the salt of tin is complete can easily be
determined by suitable chemical tests. When the re-action is complete, we dilute
the liquid largely with hot or cold water, when a precipitation of stannic acid or
stannic oxide takes place. When this has been washed with water until free from
soluble salts of iron and manganese, it is thrown on a filter, and drained to a paste,
and may then be treated in various ways to produce valuable chemical products.
Dissolved in an aqueous solution of caustic potash or soda, it forms the stannate of
soda or potash, well known in the arts of calico-printing and dyeing. Dissolved
in hydrochloric acid, it forms bichloride of tin also used in calico printing and
dyeing, and by the addition of metallic tin to this latter, the bichloride of tin by
assimilating more tin, becomes protochloride of tin, which may be at once used in
the arts or the solution may be evaporated and crystals of protochloride of tin be
obtained. In a modification of our battery cell we exchange the dilute sulphuric
acid in the porous cell containing pyrolusite and a carbon rod or plate, for a
solution of persulphocyanide of iron, and in this case we omit the pyrolusite and
retain the carbon rod or plate only. The solution of persulphocyanide of iron, may be

page_text: 6
conveniently made by dissolving a persalt of iron such as persulphate or perchloride
in water adding thereto an alkaline or earthy sulphocyanide, in chemical proportion
to the iron salt employed. A convenient strength for the persulphocyanide of iron
solution may be 50 grains of the compound Fе (CNS) in each ounce measure
of water, but we do not confine ourselves to this strength. In proportion
as the outside cell becomes charged with sulphate of tin, the liquid in the
porous cell becomes changed from persulphocyanide into protosulphocyanide of
iron and free free hydrosulphocyanic acid. By introducing a current of air
by means of a small tube going down to the bottom of the porous cell, and
connected with a blower, we can provide for the continual reconstitution of
the persulphocyanide by the oxidising action of air. When it is desirable to
renew the liquid in the porous cell, when using persulphocyanide of iron, we
remove the liquid and treat it in the following manner. We first ascertain if there
is any protosulphate of tin in solution, and if there is we either blow air into the
liquid for a sufficient length of time or we add peroxide of manganese, or other
convenient oxidiser, and when the tin is all in the state of persulphate we dilute
largely with hot or cold water, when the tin is precipitated as stannic acid or stannic
oxide. If the tin in the liquid from the porous cell, be already in the state of
persulphate, the preliminary oxidisation is unnecessary and the solution may be
at once diluted with water. After removing the precipitate by subsidence or
filtration, we add to the solution a salt of copper preferring to use the sulphate.
The subsequent addition of a reducing agent such as sulphurous acid, or an alkaline.
or earthy sulphite, or of protosulphate of iron, causes the precipitation of white
powder which is the disulphocyanide of copper, which may be further purified by
treatment with hot dilute sulphuric or hydrochloric acid and is then capable of
being used in certain processes of calico-printing, or may be reconverted into an
alkaline or earthy sulphocyanide by treatment with an aqueous solution of an
alkaline or earthy sulphide, whereby sulphide of copper and an alkaline or earthy
sulphocyanide are produced, which latter may be used to reconstitute the persulpho-
cyanide of iron for the porous cell. The sulphide of copper can by well known
processes be readily reconverted into a soluble salt of copper: Or, after dilution of
the porous cell liquid to eliminate the tin, we can add an alkaline such as potash
or soda, or an alkaline earth such as lime or baryta, when the iron will be thrown
down as oxide and the filtered liquid can then be evaporated to concentrate it. The
resulting sulphocyanide can be used to reconstitute the persulphocyanide of iron
liquid for the porous cell. We can also use in this form of our galvanic cell other
persalts of iron in solution in the porous cell, as absorbents of hydrogen such for
example as persulphate, perchloride or pernitrate of iron, either with or without
the presence of pyrolusite. A convenient strength at which to use these solutions
is such as that the solution shall contain iron equal to 20 grains of peroxide of iron
in every ounce by measure. When by diffusion through the wall of the porous
cell, the liquid has become charged with sulphate of tin, we oxidise the proto-
sulphate of tin into persulphate by means of peroxide of manganese as herein before
stated, and dilute largely with water to precipitate stannic acid or oxide. In most
cases however the tin will be already in the state of a persalt and the liquid will
only need dilution with water. In the case of employing perchloride or pernitrate
of iron we can after separation of any stannic acid or oxide, treat the liquid with
lime whereby an oxide of iron falls capable of being redissolved in acid to recon-
stitute the ferruginous absorbent, and where pernitrate of iron has been used, we
can evaporate the solution to obtain a concentrated solution of nitrate of lime or
the same salt in a dry state, which salt is valuable for several purposes, and notably
for agricultural dressings or manures. We can also in this form of our galvanic cell
use as an excitant diluted hydrochloric acid of a strength equal to one volume of
hydrochloric acid of specific gravity 1. 16 to four volumes of water. In the porous
cell we place one or other of the ferruginous absorbents above described, dispensing
with the use of pyrolusite. The action of this excitant produces protochloride of
tin, which may be evaporated and crystals of protochloride of tin be obtained, or

page_text: the solution may be treated with lime to throw down protoxide of tin, which after
washing free from lime salts, can be made into stannate of soda by well known
processes or the solution of protochloride of tin may be treated with peroxide of
manganese or any other convenient oxidiser and sulphuric acid or an alkaline
sulphate be added and the solution then be largely diluted with water to obtain
stannic acid or oxide as above described. When using hydrochloric acid as an
excitant and it becomes necessary to separate any tin-chloride which may have
diffused into the porous cell, if the liquid in the porous cell is yellow shewing
the presence of a persalt of iron, the tin compound will not require
an oxidising treatment but an addition of sulphuric acid or a sulphate
only, followed by dilution with water, when stannic acid or oxide will
precipitate. If however the liquid in the porous cell is colourless, protochloride of
tin may be present, and in that case its conversion into a persulphate by an
oxidiser and the addition of sulphuric acid or a sulphate will be necessary, before
dilution with water will precipitate the tin as stannic acid. We can further
modify our galvanic cell by using caustic soda or potash in solution in water as an
excitant, in which case we form our negative pole by usingja cylinder of copper or
iron wire gauze or of perforated copper or iron about the same size as the porous
cell employed by us in the acid cells. Into this cage we put pyrolusite in small
pieces and we attach a copper wire to the top of the cage. During the action of
this cell stannate or stannite of potash or soda is formed and may be at once used
in calico printing and dyeing, or may be evaporated to form the dry stannates
used in commerce. In another modification of our alkaline galvanic cell, we make
a mixture of a solution of caustic potash or soda and nitrate of soda or potash
and we employ a carbon plate or rod as a negative pole. The strength of the
caustic alkaline solution may conveniently be of specific gravity 1.10 and when
nitrate of potash or soda is dissolved in this we add about 22 grains of nitrate to
each fluid ounce of the alkaline solution. To prevent the action of the carbonic
acid of the air upon the caustic alkali we pour on the top of it a little paraffin or
similar oil, which has no tendency to oxidation. We are aware that it has been
proposed to use caustic alkaline solutions as excitants for a tin positive, but such
arrangements as have hitherto been proposed have been defective owing to the
absence of any means for absorbing hydrogen. In our arrangements the hydrogen
is absorbed by means of the pyrolusite in one case and in the other the alkaline
nitrate produces ammonia from the nascent hydrogen. In carrying out our
Invention we sometimes prefer to use what is generally termed a single-fluid cell.
In the well-known bichromate cell a plate of zinc is suspended between two plates
of carbon, and the whole is immersed in a solution of chromic acid or a mixture
of bichromate of potash and sulphuric acid. In our modification we substitute a
plate of tin for the zinc and use as an excitant a mixture of either dilute sulphuric
or hydrochloric acid and one or other of the salts of iron herein before described.
The strengths of these acids may be as hereinbefore described and the quantity of
iron dissolved therein in the persalt employed may be equal to 20 grains of
peroxide of iron in each fluid ounce. Copper wires are attached to the tin plate
and the carbons for leading away the electrical currents produced. The separation of
valuable tin preparations as well as other valuable products from these single fluid
cells is conducted according to the processes herein before given. In another form
of our single cell battery we employ a solution of caustic soda or potash mixed
with nitrate of soda as an exciting fluid and a tin plate suspended between two
carbon plates. The resulting liquid when the action is stopped or has ceased is
stannate of soda or potash. Other forms of our single fluid cell corresponding to
the various forms of bichromate batteries in present use can be employed using a
tin positive element and carbon negative element, with any of the above mentioned
exciting liquids.
In order that the manner in which our Invention may be carried into effect may
be readily understood we have attached hereunto a sheet of drawings made to a
scale of about eight inches to the foot. The precise way in which we find it

page_text: .
convenient to make our single fluid cell is illustrated by Figs 1 to 4. Fig: 1 is a
vertical section of the cell and Fig: 2 a plan of the same. In the said Figs a is a
rectangular cell made of stoneware, glass or wood lined with gutta-percha. A bar
of iron b rests by its ends on the rectangular cell and is secured to a plate of tin c.
In the example pieces of wire are inserted in holes in the tin plate and are secured
by running in melted tin. The projecting ends of these wires are screwed and
binding screws d are screwed on the said ends and the plate of tin is thus
attached to the iron bar. Two plates of gas carbon e, e are placed one on
each side of the plate of tin, but are separated from it by means of two
bars ff of insulating material such as vulcanite. A binding clamp of brass g
provided with tightening and binding screws clamps together the carbons,
the vulcanite bars and the tin plate. At one end of the rectangular cell
and close to the bottom thereof is placed a curved glass pipe h made
of what is known as "quill tubing" which is cemented into the rectangular
cell midway from the sides and curled over at the top, the outlet h¹ being a little
below the top of the rectangular cell. The tin and carbon plates being now placed
in the rectangular cell as shewn in Fig. 2, they will be supported by the iron bar
which rests on the ends of the cell and when the cell is filled with the exciting
fluid until drops begin to flow from the overflow pipe at h¹ and copper wires are
connected to the binding screw of the clamp g and one of the binding screws d
the cell will be in action. A mode of providing for a continuous current passing.
through the cell or cells is shewn in Fig: 5 wherein I is a cistern which may be
made of stoneware or of wood lined with gutta percha and is provided with a
tap k made of stoneware or by preference of gutta percha or vulcanite. This tap
is fitted with a ball governor floating in the feeding trough which is provided
with a curved pipe m similar to the one described in Fig: 1. The cistern I being
filled with the exciting fluid, the ball tap is so regulated as that the liquid in the
feeding trough remains always at one height and a slender stream of the fluid is
continuously discharged from the pipe m thereby keeping the liquid in the battery
cell a at an, uniform level which is regulated by the overflow pipe h. This pipe
delivers the partly spent liquid into a pipe connected with a reservoir under the
cistern I from whence the said cistern is occasionally replenished. For some
purposes and when a very strong electrical current is required, several cells are
placed side by side and the feeding trough is may long enough to supply all the
cells simultaneously a feeding pipe being fitted to each of the cells. The cells are
then connected together by wires as is well understood. The fluid is passed several
times through the cells until it becomes exhausted or until the galvanic action is
becoming too weak to be servicable. For battery cells of moderate power, but
required to furnish a constant and long continued current we prefer to employ the
cell illustrated by Figs 6 to 8. In Fig 6 n is a rectangular vessel of stoneware or
glass say about 6 inches long, 4 inches wide and 6 inches deep. Inside this vessel
is a ledge or projection o. A thin slab of porous earthenware p is inserted in the
smallest division of the vessel and rests against the said projection. A plate of
gas carbon r is placed in the smaller division about half inch from the end and not
quite touching the bottom, the remainder of the small chamber being packed with
a mixture of pyrolusite and gas carbon in small pieces about the size of peas. To
the top of the carbon plate is fastened a copper or other wire sufficiently long to
pass through a hole in the cover of the cell which cover is a glass plate drilled
with three holes as shewn in Fig: 8. In the large division is mounted a plate of
tin s to one end of which are soldered two screwed copper wires which are passed
through the holes t, t in the cover shewn in Fig: 8. Sulphuric acid diluted in the
proportion of one volume of sulphuric acid to 10 volumes of water is put into both
chambers of the cell so as to fill them nearly to the top. The glass covering plate
Fig: 8 is then put on and is secured to the cell with any suitable cement which
can be softened by heat. On the projecting ends of the three wires are now
screwed binding screws, and the two plates are thus suspended in the cell, the
plate of tin being about half an inch from the porous slab. When conducting

page_text: wires are attached to the binding screws, the battery cell will be ready for use for
any purpose in cases wherein a moderate current is required, such as telegraphy
or for working telephones. This arrangement gives a constant and long continued
When requisite the cover is loosened and the spent or partly spent
liquid is withdrawn and is utilised as previously described, fresh dilute sulphuric
acid being put in the cell.
current.
The tin plates in our various forms of battery cells are improved in efficiency by
being amalgamated although this is not essential to their action.
We do not confine ourselves to the strengths of the solutions nor to the pro-
portions of materials herein given by way of example nor to the exact dispositions
of the agents employed as in some cases we can reverse the dispositions as for
example in place of putting the dilute acid in the outer cell and the hydrogen
absorbents in the inner cell we may put the said absorbents in the outer cell and
the dilute acid in the inner cell.
Having now described our said Invention and indicated modes of carrying the
same into practical effect we would observe in conclusion that we claim :-
First, batteries having tin for the positive element and cells charged with dilute
acid and pyrolusite and producing protosulphate of tin which can be treated to
obtain useful salts of tin substantially as set forth.
Secondly, batteries having tin for the positive element and cells charged with
solutions of persulphocyanide of iron alone or in conjunction with pyrolusite
substantially as set forth.
Thirdly, batteries having tin for the positive element and cells charged with
certain solutions which will absorb hydrogen such as solutions of persulphate,
perchloride, or per-nitrate of iron alone or in conjunction with pyrolusite substan-
stantially as set forth.
Fourthly, treating the spent solutions of such batteries in order to obtain useful
salts of tin such as stannic acid or oxide, bichloride of tin, protochloride of tin,
stannate of soda, and stannate of potash.
Fifthly, treating the spent solutions of such batteries in the various ways herein
set forth in order to obtain a copper salt which may be used in dyeing and calico
printing and for other purposes.
Sixthly, batteries having tin and copper elements excited by solutions of caustic
soda or potash and having pyrolusite in the cell or cage forming the copper
element and producing stannate or stannite of soda or potash substantially as set
forth.
Seventhly, batteries having tin and carbon clements excited by combined
solutions of caustic soda or potash and nitrate of soda or potash and producing
stannate or stannite of soda or potash substantially as set forth.
Eightly the use of persulphocyanide of iron as an absorbent of hydrogen in
galvanic batteries.
In witness whereof we the said James Higgin and Alfred James Higgin
have hereunto set our hands and seals this Eighteenth day of July in
the year of our Lord One thousand eight hundred and eighty-two.
JAMES HIGGIN.
(L.S.)
ALFRED JAMES HIGGIN. (L.S.)
Signed, sealed and delivered
in the presence of
EDWARD K. DUTTON,
41, John Dalton St.,
Manchester,
(Agent for the Patentees).