Aug. 2, 1932. , P. J. F.

SQUVHRON
MANUFACTURE op COPPER SULPHATE
Filed Dec. 5, 1929

6 55

. 1. 1 .,
.

55.2

/7 ////// // / / /
 Patented ug. 2, 1932 1,869,521

arrete* sr ras PATENT OFFICE

PIT-RRE JOSEPH FRANQOIS SOUVRON, OF TARBES, FRANCE
MANUFCTURE OF COPPER S'LPI-IATE
Application led December 5, 1929, Serial No. 411,945, and in France December 15, 1928.

The present invention relates to improve ondary metals, that is to say, enabling consid
ments in or relating to the manufacture of era-.ble reduction in costs. y
copper sulphate and provides a method and The method consists essentially in separat
means whereby this substance can be manu ing into two parts, both as regards time and
5 factured more er'liciently and cheaply than place, the action on the copper and the solu
hitherto. tion of the product obtained, the first opera-
It is known that copper sulphate can be tion taking place in the cold in a liquid medi
urn> and the second one taking place without
obtained commercially by the simultaneous necessarily
action on copper of air, water vapour and applying heat from outside. The
10 sulphuric acid, all of which are contained in effect is obtaned by transforming the copper
a closed vessel. in practice the operation is into a salt which can readily be acted upon
by sulphuric acid, for example by transform
carried out by acting on granulated metallic ing the copper into copper oxychloride, which
copper by sulphuric aci-d ina large leaden is insoluble
` tower through which is passed a current of in water but which dissolves in
l5 steam, air and acid, the agents being heated. sulphuric
a- mixture
acid with evolution of heat giving
of solutions of copper sulphate
This process, however, suifers from the fol
lowing disadvantages: l and copper chloride.
l. The operation is extremely slow and The formation of copper oxychloride from
copper is effected by the action thereon in the
necessitates introducing` a considerable quan O
21 tity of copper into the reacting towers, since presence of air of copper chloride, which
it is estimated that one hundredth of the cop simply serves as an intermediate product and
per supplied is acted upon daily. It is the is continuously regenerated, so that the pro
opinion of the applicants that the slowness ductionmore
of the copper sulphate takes place
readily than hitherto and requires only
, of the reaction is due to the fact that this takes
F place in a medium which is mainly gaseous. the theoretical quantities of copper and sul 75
2. rlhe process is costly, either by reason of phuric acid.
the kcost of obtaining pure copper or, if pure ' The reactions which occur in the process
copper- is not used as a starting material, by are as follows:
_ reason of the necessity for the metallurgical
'f operations for obtaining pure copper from the
impure copper containing material. and l
3. It necessitates a considerable expendi
ture of heat for the production of the steam
employed. `
4r. The reaction product has to be removed It is pointed out that, owing to the ease
from the tower and transported to a crystal with which copper oXychloride dissolves in
sulphuric acid, the formation of copper sul
lizer. phate can be effected in the crystallizers
5. Finally the apparatus is relatively com themselves. i
plicated and cumbersome. Vith this process can be prepared either
The present invention has for its object crystallized copper sulphate CuSOiHQO
to provide a method and a means for the in which case the respective quantities ofthe
preparation of copper sulphate from rvery saltsemployed in the/reaction are so meas
varying kinds of copper-containing mate ured that the copper sulphate shall have the 5
as. en rials, such as pure or impure copper, oXi-des', desired concentration for crystallizing out on
>and the like, by means of a simple and eco cooling, or a solution of copper sulphate 'at
nomical plant into which the starting mate any desired concentration if this is desired,
rals can be fed 5 to l0 times faster than in the as might be the case for example if the cop
old methods, and which give theoretical per sulphate were required for the electroly
yields and facilitate the recovery of the sec tic production of copper. " l
 2 1,869,521'
As has been hereinbefore stated, copper It may be rendered continuous by the fol
sulphate can be obtained by this process with lowing improved method carried out in one
out necessarily employing any external of the two types of apparatuses shown on
CTL
source of heat. If, however, it is desired to accompanying drawing:
obtain copper sulphate of the usual commer Figs. l and 2 are a Vertical and a horizontal
cial quality, and to obtain a greater yield at
cross-section of an apparatus of the first type
each crystallization, the temperature of therespectively and Figs. 3, 4 and 5 are a longi
liquid mixture which is normally at about tudinal, horizontal and transversal cross-sec
45 CL55" may be raised to about 80G-90 quite
tion of an apparatus of the second type re
simply by injecting steam directly into the spectively. The former apparatus is more
crystallizer itself. especially of advantage in the case where
The operation can be carried out for eX lump copper (wires, particles of refuse cop
ample as follows: per and the like) is used whereas the latter
In a large flat cement vat, which need not apparatus is better adapted for use with pul
be lined with lead since theoretically it should verulent copp-er (cement copper, filings and 80
not contain at any moment any free acid, are the like). The reaction vat preferably oVC
placed a number of perforated lead tubes concrete is divided in two parts by means of
connected to a fan and adapted to supply a partition l the top of which is a few centi
powerful currents of air through the con meters lower than the normal level of the
20
tents of the vat at points distributed as much chloride solution 2, the larger of the two com
as possible throughout the vat. Copper for partments 3 thus provided is arranged as de
example, in the form of scrap metal, is in scribed hereinabove i. e. it contains a wooden
troduced into the vat and the desired quan- grating 8 carrying the copper-containing ma
25
tity of copper chloride solution containing teri al 4L and the perforated lead blast pipes 5
150 grammes of CuCl2 per litre is added. fed through the air pipe 5 whereas the second DC
This solution is further to contain at the end smaller compartment 6 is empty at the outset
of the operation copper sulphate in such and serves, vas will be explained hereinafter,
amount that is near to the point of satura' as a reservoir for receiving the oirychloride
tion, formed 7. Owing to the stirring action pr -
30
If it is desired to treat waste copper in vided by the incoming air in the liquid of the
powdered form (such as inillings, filings, ce reaction vat, the copper oxychloride which
ment copper etc), a number of frames of per forms as a suspension is brought to the sur
forated wood are disposed in tiers in the face and the greater part thereof passes into
vat and the material is placed on these the smaller compartment with the li uid flow~
frames. ing into it under the action of the Cdifference 100
Also the bottom of the vat may be so between the levels in the two compartments
formed that a transverse section shows a produced by the blowing of air into the larger
series of saw-toothed grooves, the air tubes one. Suitable means are provided for ex
being deposited each at the bottom of a groove tracting in a continuous or discontinuous
and along the length of the edge thereof. manner the fluid oxychloride paste contained
This arrangement has the advantage inter in the smaller compartment; but the process
alia of causing the tubes to be covered with in the larger compartment is a continuous one.
the material to be treated and of reducing In the cases where it is to be feared that
the volume of the deposits between the tubes. a very light pulverulent material, such as cer
The mass is then traversed by a current of tain precipitates may be carried out of the 110
air when the copper is converted gradually reaction vat proper into the reservoir com
into copper oxychloride in suspension in the partment before the reaction is completely at
liquid to which it gives a milky appearance. an end, it is advantageous to provide between
The aeration is arrested as soon as the liq the two compartments i. e. the reaction vat
50
uid has the desired content of oXychloride, and the reservoir, a third compartment form
which is then allowed to settle. After about ing a secondary reaction vat; air blowing
l2 hours the precipitate of oXychloride is pipes are then adapted to keep the material in
sufliciently settled to allow half of the total suspension therein so as to allow the reaction
volume to be decanted as a clear liquid, This to be brought to completion before the said
clear liquid which maybe drawn ofi' by means material is allowed to pass into the reservoir
of a siphon for example is conducted to an where it deposes. Obviously no further raw
other reaction vat or into a reserve container. material is fed into this intermediary com
The product remaining` in the reaction vat partment.
is then again agitated by air currents and The second type of apparatus differs from
drawn olf in turn by means of a siphon or that disclosed hereinabove solely by the fol
pump to be conducted directly into a lead lowing features. \ The wooden grating 8 car
crystallizer provided if desired with plates rying the raw material is disposed in tiers and
of lead or copper suspended in the mass. the openings of each tier thereof is idisposed
The just described method of operation is a over the solid parts of the tier just underneath
discontinuous one. it. Moreover the walls of the compartment 3
 1,869,521 3

show longitudinal in-dentations or corruga lizersj Vthe mother liquors, saturated with
tions as shown on Fig. 5 at 9. Water may be copper sulphate, and containing the regener
admitted through the pipe 10 for removing ated copper chloride, are again introduced
the residuary mud from the reaction vat 3 into the reaction vats. The chloride em
into the receiver 12 through the cock 13 con ployed can thus be used indefinitely except
trolling the passage from the said vat into handling and transporting losses which are
the said receiver. , negligible.
A partition such as 14 (Figs. Sand 4C) may The crystals deposited in the crystallizer
be provided with either type of apparatus to are removed, washed, dried and sorted by 75
form the intermediary reaction vat men any known and/ or suitableV means. Experi
tioned hereinabove. Obviously it may be ence shows amongst other things that the
used with the lirst type of apparatus shown presence of chloride of copper in the mother
and it may be omitted in the second. A pump liquors does not in any way influence the
or .similar device 15 is advantageously dis quantity or appearance of the crystals ob
posed in the reservoir compartment 6 of tained. '

either type for forcing the oxychloride The chief advantages of this method of
formed into the lead crystallizers 16. manufacture are as follows :`
It is pointed out that in all cases the pro 1. It is possible to obtain copper sulphate,
portions of copper, copper chloride and air the only materials expended being sulphur-ic 85
must be carefully chosen, so that theI sus acid and metallic `copper which need not be
pended oxychroride may thus be obtained in pure without its Vbeing necessary to carry out
the form of a paste .sufficiently fluid to en any preliminary metallurgical operation on
able it to be readily conducted through the the copper or to apply heat in carrying out
lead pipes by means of a siphon or pump. the reaction.
The product is then again allowed to settle 2. The reaction is very much more rapid
in the crystallizer for several hours, so that a and requires a very much simpler apparatus
further quantity of clear liquid can be drawn thlan is the case with hitherto known meth~
oc s.
off. 3. The reaction is produced by a liquor
This oxychloride is then treated with sul 95
phuric acid at 60o or 66o B., for example, so which doesnot contain free acid, thus per
as to be instantly converted in the crystallizer mitting the reaction to take place in cement
itself into copper sulphate and cupric chlo vessels without a lead lining.
ride which is thus re-formed. 4. The handling is extremely simple since
This addition of acid has the effect of rais the materials are transported by siphons or
pipes right up to the crystallization stage. 100
'\ mg the temperature of the mixture to .lcec
C., this being due as much to the heat evolved 5. It is possible to produce the copper sul
by hydration of the concentrated acid as to phate in the crystallizers themselves.
that evolved by the chemical change of oxide 6. It is possible to obtain crystallized cop
into sulphate. per sulphate without any heating or with a
very much reduced heating produced by di 105
40 In practice sulphuric acid is added in ex
cess of that necessary to obtain exact satura rect injection of steam into the crystallizer.
tion, in amount such as to give an acid re Whilst a preferred method of carrying out
action with methyl orange. this invention has been hereinbefore de
Under these conditions the copper sulphate scribed, it will be understood that various
formed is present in a state of supersatura modifications may be made without depart
tion, and a portion of it is precipitated in the ing from the scope of this invention.
form of sulphate snow, whilst another por lWhat l claim is:
tion is precipitated later on cooling in the 1. A closed circuit process for the prepara
form of large crystals. If desired, the for tion of copper sulphate consisting in treat
50 mation of sulphate snow may be avoided by ing metallic copper with a solution of cupric
reducing the amount of oXychloride so as not chloride, submitting the cuprous chloride
to exceed the point of saturation in the crys formed to the action of air, treating the cop
tallizer. In this case, however, the volumetric per oxychloride formed with sulphuric acid,
yield is diminished, the rise of temperature precipitating the excess of copper sulphate '
55 being less pronounced. formed and treating fresh copper with the
lf it is desired, for reasons hereinbefore mother liquor constituted by a solution of
mentioned to raise the temperature of the cupric chloride and copper sulphate. _
mixture to about 900, it is only necessary to 2. A closed circuit process for the prepara
introduce into the crystallizer a lead tube for tion of copper sulphate consisting in treating
60 injection of steam without necessarily em metallic copper waste with a solution of
ploying a coiled pipe which renders difficult cupric chloride, submitting the cuprous chlo
the removal of the crystals deposited at the ride formed to the action of air, treating the
bottom of the crystallizer and considerably copper oXychloride formed with sulphuric
increases the costs of each crystallization. acid, precipitating the excess of copper sul Lard

After cooling the liquids in the crystal phate formed and treating fresh copper Waste
 4 1,869,521
with the mother liquor constituted by a so
lution of cupric chloride and copper sul
phate.
3. A Closed circuit process for the prepara
tion of copper sulphate consisting in treat
ing metallic copper With a solution of cupric
chloride, submitting the cuprous chloride
formed to the action of air, treating the cop
per oxychloride formed With concentrated
10 sulphuric acid, precipitating the excess of
copper sulphate formed and treating fresh
copper with the mother liquor constituted by
a solution of cupric chloride and copper sul
phatc.
16 4. A closed circuit process for the prepara
tion of copper sulphate consisting in treat
ing metallic copper with a solution of cupric
chloride, submitting the cuprous chloride
formed to the action of air, treating the com
20 paratively Huid copper oxychloride formed
with sulphuric acid, precipitating the excess
of copper sulphate formed and treating
fresh copper with the mother liquor consti
25
tuted by a solution of cupric chloride and
copper sulphate.
5. In the process claimed in claim l the
step consisting` in heating the reacting mix
ture of copper oxychloride and sulphuric
acid.
30
In testimony whereof I have aiiixed my
signature.
PIERRE JOSEPH FRANCOIS SOUVIRON.

35

UZ Cil

65