Dec. 12, 1950 G. E.

HARIKE 2,533,245
METHOD OF PRODUCING COPPER ~SULFTE
Filed Feb. 24, 1948 2 Sheets-Sheet 1

N/

INVEN TORJ
Patented Bec.. l2, 1950
2,533,2i5

UNiED E `ENT OFFCE

2,533,245
METHD 0F PRODUCENG CPFER SiULlFAl-TIE
George E. llarilre, College Park, Ga., assigner to
Tennessee Copper Company, New York, N. Y.,
a corporation of New L.iersey
Application February 24, 1948, Serial No. 10,287
4 Claims. (Cl. 23-l25)
i
The present invention relates to improvements not desirable since the product is generally used
in the production of copper sulphate from metal as a starting material in manufacturing processes
in which the reaction may be made continuous in which a large metallic surface and high po
and more rapid, and in which the production will rosity are desired. The temperature within the
be free from loss oi copper in the usual side re tower is usually maintained at 150 F.-210 F. by
actions. This application is a continuation in externally heating the solution or by introduc
part of my prior applicationv Serial No. 608,141, ing steam with the air by combinations of these
iiled August 1, 1945. with externally heated air.
The reaction between metallic copper and sul The above described practice of producing cop
phuric acid is slow at atmospheric temperature 10 per sulphate from crude metallic copper follows
even in the presence of oxygen. At higher tem the reactions indicated below:
peratures the reaction becomes practical and is
usually applied at temperatures between 150 F.
and 200 F. However, at these higher tempera
tures the presence of oxygen is not only needed The solubility of cuprous sulphate in the sul
for the formation of copper sulphate but also for phuric acid-copper sulphate solution is slight and
the prevention of the formation of copper sul chemical equilibrium is established quickly be
phide. he oxygen is usually obtained from air. tween the metallic copper and the solution. Thus
Copper sulphate is a product of economic im the reaction between the copper and the solution
portance and much work has been done in the ' is arrested unless and until the cuprous sulphate
past to improve the method by which it is man is oxidized in the second reaction to cupric sul
ufactured. The use of foreign catalysts such as phate. Ordinarily the oxygen is obtained from
ozone with air, the use of increased oxygen con air.
centration by enrichment of air with oxygen or As the relatively insoluble cuprous sulphate ime
by carrying out the reaction 'at super atmospheric pedes the further reaction of solution on the cop
pressures, the use of methods that alternately per, it is necessary to expedite the conversion into
oxidize the copper and then dissolve the oxide, cupric sulphate. Hence the efficiency of this
are some of the improvements heretofore pro process is found to depend upon the readiness
posed. However, these methods involve an in with which the cuprous sulphate can be con
crease in the means and material necessary for verted into the cupric form.
carrying out the reaction. My invention avoids It was the purpose of my invention described
the use of these complicated and expensive meth in application Serial No. 608,14'1 to improve the
ods. f eiiiciency of this reaction and greatly increase the
The submergence of copper in an acid solution production of copper sulphate. The present in
with the introduction of air to the bottom of vention further increases the production of cop
the containing vessel has been disclosed. How per sulphate while maintaining the higher er
ever, this broad procedure does not give improve ciency and utilizing the materially greater pro
ment, due to the lack of uniform establishment portion of the oxygen from the air being applied
of the proper phase relation between the gas, as in the case of my previous process.
liquid and solid reactants. As stated in my pre 40 As pointed out in my previous application,
vicus application, there has been no such prior these results economize the heat required to ef
use that has been successful as far as I am aware. fect the reaction. Where the consumption of
Use of a towel` containing shot copper with oxygen is only partial a greater volume of air
the introduction of solution sprayed on the top must be used. This has several definite objec
of the mass of copper and withdrawn from the tions. First, more heat must be applied to bring
bottom while air is introduced into the bottom the greater volume of air up to the requisite
and withdrawn from the top has heretofore been temperature and second the greater amount of
the most widely applied process. The shot oop air will produce a greater quantity of water vapor
per commonly used in such processes is made by which will be lost in the depleted air which is be
the well known practice of sho'tting the metal by ing vented. Third, larger reaction vessels and
pouring a small stream of molten metal into a accessory equipment are needed and larger
mass of water, producing irregularly shaped par amounts of metallic copper are tied up in the
ticles the size of which can be controlled by process.
variation in shotting practice but is usually about A still further object of the present invention
1" in maximum dimension. Spherical shot are is to avoid the undesirable production of copper
 2,533,245
3 4
sulphide which has been found to occur when latter condition can be maintained up to the in
ever the solution is allowed to remain quiescent troduction of about 10 cubic feet per minute per
in contact with the copper metal. This reaction square foot when the liquor is moving down
is very undesirable and is quite apt to occur at wardly through the copper mass countercur
the operating temperature of 15G-210 F. The m rently to the ow of air as described in my pre
copper sulphite forms a coating on the copper vious application. At this point the velocity of
metal and practically stops further reaction. the air begins to interfere with the ow of the
Some of the copper sulphide is suspended in the solution over the surface of the metal and pro
solution while some of it settles in the mass of duction is lowered due to the lack of sulphuric
copper plugging the voids in the metal. This acid. With certain types of prepared secondary
condition necessitates the frequent removal of metal such as copper scrap, up to 20 cubic feet
the copper sulphide from the copper surface as per minute per square >foot of area can be in
wall as the sludge from the voids before further troduced without interfering with the uniform
reaction can be carried out. movement of the liquid over the surface of the
As in the case of my previous process, the copper. However, with this higher rate good
present invention maintains a condition in which eiiciencies are obtainable only in higher towers.
the copper shot, scrap copper or clippings of ir The present invention differs from the inven
regular shape and up to two inches in maximum tion of my previous application in that the so
dimension, are covered with a moving layer of lution is supplied to the bottom of the copper
liquor containing sulphuric acid and copper sul- _ mass and moves upwardly through the mass con~
phate while being subjected to a current of air. currently with the air. In my previous process
This condition is established and maintained where the solution moves downwardly counter
throughout a mass of closely packed copper shot currently to the air, the downward flow of the
er the like so that the oxygen 0f the air may be solution is opposed by the upwardly flowing air
brought into contact with the entire liquor-cov 25 and, at rates of air flow greater than the max
ered surface and remain so until its passage out ima stated above, is so reduced in amount that
of the reaction chamber is permitted after it has the desired phase relation described above is not
been depleted of the greater amount of the oxy~ uniformly established and the rate of solution
gen present. Practically, the process can eiec~ of copper is lowered to such an extent that oper
tually consume from 90 to 95% of the oxygen in 30 ation at air ilows above these maxima is not
the air. An incident of this condition is that the practical. In the present process the solution
air the greater portion of the voids be and the air are supplied to the bottom of the
tween the copper particles. This prevents local copper mass and travel upwardly through the
action by which the metal and liquor without mass together. Hence the ow of solution is as
air would react to form copper sulphide. Such sisted by the upward movement of the air and
sulphide is an inert sludge which will cover the the desired air-solution-copper phase relation is
metal surface preventing further reaction and uniformly established at rates of air ow
requiring cleaning from time to time. This can higher than the maxima which limit the opera
be avoided and the process made continuous by tion of the process described in application Se
maintaining the condition characteristic of my 40 rial No. 608,141.
process. The establishment of the desired phase rela
In carrying out the reaction it is most desira tion at such higher rates of air flow by means
ble that the air permeate the voids, substan of concurrent flow of solution and air increases
tially lling them and establishing maximum the productive capacity of the tower. The pro~
contact with the solution covering the surface 45 ductive capacity is directly dependent on the
of the metal. This prevents the liquor from amount of oxygen consumed per unit volume of
filling the voids or allowing the .production of the tower. My previous process more than dou
the sulphide. The particular condition to be bled the productive capacity per square foot of
avoided is the possibility of the solution and the cross-section of the tower as compared with
air following separate channels through the 50 prior commercial practice, but productive ca
chamber, and this possibility is avoided by even pacity was limited by the fact that the tower
distribution of the air over the bottom of the height could not be increased above the point at
tower. Brieiiy stated, the condition most de which substantially all the oxygen was con-
sirable for carrying out the process is a phase sumed at the maximum air rates mentioned
relation of solid copper in contact with the liq 55 above. The present invention maintains all of
uid which liquid is in immediate contact with the desirable features of my previous process by
the air, both the liquid and the air being in mo increasing the tower height with higher rates of
tion. This phase relation is automatically es air flow and this results in increased capacity
tablished by the equipment described later, per square foot of cross section. Thus the de
when operated as described and within the sirable results of decreased equipment cost,
proper limits of air introduced. The proper maintenance, amount of accessory equipment
amount of air introduced per square foot of and lower operational cost are obtained.
tower cross-section is dependent on the apparent Using shot copper, and at the same rate of
porosity of the charge of copper in the tower. air flow below l0 cubic feet per minute and the
As described in my previous application, when 65 same tower height, the results obtained with
using shot copper as ordinarily produced by the present process are substantially equivalent
smelters for use in manufacturing copper sul~ to those obtained with my previous process. The
phate, and when the air is less than one cubic following table indicates the conditions and pro
foot per minute per square foot of tower cross portions normally prevailing in the reaction
section, the phase relation is not established sought for a tower approximately 30 square feet
uniformly. There is an excess amount of con in cross-section and containing approximately 9
tact between the liquor and the solid with no air feet of copper. By way of explanation of this
in the voids. As the amount of air is increased, table, it is noted that in the usual commercial
the number of voids containing no air is dimin operation prior to my inventions, some unused
ished until all of the voids contain air. This 75 free acid remained in the solution so that the
 5 6
copper sulphate was crystallized from the acid
solution by cooling. Processes embodying the
present invention can be operated in the same
manner, as indicated in. column A, but their
great eniciency makesl it economical. to produce
also neutral copper sulphate solutions for direct
consumption in the production of other copper
salts as indicated by column B;
Table
ad
Cgsgb for Direct
Solution composition-Initial:
Cu, gms. per liter ___________________ __
H2SO4, gms. per liter ..... __
Fiual~Cu, gms. per liter___.
H2804, gms. per liter ____ __
Temperature, 0 _____________ __
Circulating Rate, Gels. per Minn c_ _
Air to Tower (Calc. to 760 n ru., 0 C. Dry
Basis): c, f. n1. per square foot of tower
cross-section ___________________________ _.
Inlet air-percent Oxygen ___-
Exit air-percent Oxygen (Avg.
Oxygen consumed:
Percent oi Entering OxY gen......... __
Pounds per square foot per mnute____
Production Rates (Copper Sulphate from
Metal):
Pounds l persquare footof tower cross
section per day .................... __
Pounds 1 per tower (31.17 sq. ft.) per
day_ ______________________________ _ _
1 NOTE: Pounds of copper sulphate as CuSO4 (HgO).
As the rate of air dow- is increased, the height
oi the tower must also be increased in order
to maintain good eiciencies. Thus at a rate
of air flow of 8-10 cubic feet per minute, the
tower height must be increased to about 18 feet
in order to maintain theA efficiency in the range 40 rying out the process consists of a tower which
of 90-100% (with regard to acid solution). In
the process of my previous application', the rate
of air flow can not be further increased with
out excessive interference with the downward
now of the solution. In the present process,
however, the rate of air flow can be much greater
with good eiciency andy increased productive
capacity per squarel foot of cross-section. The
following data indicates the results obtainable
at such higher rates of air flow, the eniciencies
being stated with regardV to acid solution. The
operating conditions may be the same as in the
table, except for the increased rate of air flow
and for a corresponding increase in the rate of
circulation of the solution to maintain the re 55 continuous concurrent operation and Figs. 2, 3
action temperature.
Assuming for example a rateV of air flow of 35
cubic feet per minute per square foot of tower
cross-section, the efficiency at the column height
of 18 feet mentioned above will be about 40%. ce
However, if'the column height is- increased to 2e circulated upwardly through the mass of copper
feet, the eciency will increase to about 50%,
and if the column height is further increased
to about 45 feet, the efficiency will further in~
crease to about 80%. l-liciencies of 90-100%
will be obtained at column heights of about 50
feet.
Thus in the countercurrent process of my
previous application, using the maximum rate
or air ow for copper> shot or 10 cubic feet per 70 maintained. i charging. hopper ii mounted in
minute and a column height; of about 18' feet to
obtain 100%- eliciency, the amount of oxygen
consumed per square foot of column cross-sec
tion will be about two cubic feet per minute,
which is a direct measure of the numberv of
pounds of copper sulphate produced. WithA a
column height of 45 feet and a rate of air flow
of 35 cubic feet per minute, the present process
will consume; about 5.9 cubic feet of oxygen per
minute per square foot, so that the production
per square foot is approximately tripled. How
ever, there is a drop in eiiiciency to about 80%
which is reflected principally in increased heat
loss'. This increased loss can be avoided by in
10 creasing the column height to about 60 feet at>
which the efficiency will. be nearly 100% and
A B
production will be multiplied about 31/2 times.
The above examples apply to shot copper and
l dus it is well known that shot copper varies in size,
distribution and specific surface (surface per unit
ing Consump volume). Also these variations with respect to
tion
size, distributionk and specific surface are much
wider in the case of copper scrap than in the
100
160
100
80
case of copper shot. It will be apparent that
l60 160 20 the data given in the above examples will vary
S0 0 with the variations in the shot copper or> copper
185 185
l50~200 15G-200 scrap.
In the case of either shot copper or copper
2. 5 2. 'i scrap, an air flow rate of approximately 50 cubic
20. 9 20. 9 25 feet per minute per square foot of column cross
2.6 7. 3
section is about the maximum that can be prac
90 70
. 04l9 . 0326
tically and economically used. With this rate
of air flow, the efficiency at a column height of
about 35 feet will be approximately 50%. How
941 732 ever, to obtain eiciencies approaching 100%, a
29, 35() 22, 837 column height of about 100 feet would be needed.
Such a height is undesirable for reasons of
economy and ease of operation. Air ow rates
higher than 50 cubic feet per minute, when used
with practicable column heights, result in ef
ficiencies that are too low for practical applica
tion.
The principal feature of the equipment for car
may be made of masonry or other suitable mate
rial. It is important that this tower shall have
a height of at least five feet and it may be much
higher as indicated above. While the tower is
usually lined with acid-proof material such as
lead, any other means of protecting its inner sur-
face may be used.
The process can be operated continuously by
supplying fresh` solution and air to the botton of
the tower so that they move up through' the cop
per concurrently and by withdrawing reacted
solution from the top of the tower.
My invention has been illustrated by way of
example on the attached drawings. Fig. 1 shows
a diagram of a reaction chamber arranged- for
and 4 show details of the structure and' location
of the air jets. Figs. 5 and 6 show two other
arrangements suitable for continuous concurrent
operation.
In the form shown in Figs. l-e, the solution is
shot in the tower i. suitably spaced> above the
bottom 2 of the tower is a false bottom or grate
3. This will permit the solution to pass through
but will support the copper particles down to the
ines. The bottom 2 has an inlet pipe :il through
which the solution is supplied. A cover extends
the top of the tower. Tl'irough> this cover
the top is'v charged andY the circulation of gases
the cover 5 permits the periodic' introduction of
shot copper or the like. This hopper' is closed
when not charging.
The shot copper' or scrap copper is built upV to
form a column of at least ve feet in height, or.`
 2,533,245
L
to greater heights as indicated above. The size an extension 35 0f the pipe 34. This extension
of the copper particles is such that they form a pipe passes down through the hot mixture of
mass through which liquid may percolate or gases solution and air in the tower to a point below the
may rise evenly and without forming large pas grate 2l where the solution escapes from the pipe
sageways or channels. through an outlet opening 35, the pipe preferably
The liquor inlet pipe d is connected to a tank 'E having a baiile 31 at the outlet opening. The
from which the liquor is delivered to the tower solution rises and fills the tower to the level of
by a pump 8. In the circulating tank a coil or the outlet 38 above the top o the mass of copper,
other heating means -I" is provided to maintain the overflowing solution returning to the tank 32
the desired temperature. |This restores the heat lO through the return pipe 39.
lost in the tower I to maintain the temperature Movement of air and solution thus take place
of the reactants in the tower in the range stated concurrently in an upward direction, but the mass
above. Any desired number of inlets l may be of copper is maintained submerged in the aerated
provided. The liquor moves upwardly through solution and the desired phase relation is estab
the mass of copper, being assisted by the upward 15 lished and maintained under the conditions speci
flow of air as described below, and overows ed above.
through a pipe 9 which returns it to the tank '1. In addition to the advantages mentioned above,
A vent provided in the cover 5 is connected with the concurrent operation as shown in Figs. 1 and
the exhaust blower l0. By this means the de 5 also prevents fine copper particles from getting
Ipleted air is drawn oi from the tower at a regu 20 into the feed lines and circulating tank, while
lated rate. the upward movement of the solution tends to
A blower I I is provided and connected through prevent clogging of the grate 2l. The arrange
the top to the inlet air pipe I2. The pipe I2 ment shown in Fig. 5 has the further advantage
extends to approximately the level of the grate 3. that if the circulation of solution should be
At that point it is branched as shown at I3 and stopped temporarily, the solution remaining in
provided with a plurality of downwardly extend the extension pipe S5 is kept hot by the sur
ing nozzles Iii. The air discharged at these noz rounding hot solution in the tower and thereby
zles will be only under the hydrostatic pressure prevented from crystallizing in the pipe.
of the column of mixed liquid and air in the tower The concurrent upward flow of solution and air
and rises throughout the mass of copper to estab 30 also makes possible the use of the air lift principle
lish the phase relation above described. The for circulating the solution, thus eliminating the
blower I I is an air compressor which delivers air need for circulating pumps such as 8 and 33.
through the nozzles at the required pressure. Fig. 6 shows such a system diagrammatically.
The heating of the solution in the tank 'I may The tower 4G, bottom or grate LEI, air inlet l2 and
be supplemented by heating the air introduced 35 nozzles 43 may be the same as in Figs. l-5. The
into the tower through the pipe I2, or if desired tank 44 corresponds to the tanks 'I and 32, but
the total heat required may be supplied by intro is elevated to a point adjacent the top of the
ducing steam with the air. column of copper indicated at 45. Solution ows
The aqueous solution of copper sulphate con by gravity from the bottom of the tank through
taining the initial proportion of sulphuric acid is 40 a pipe 46 to the bottom of the tower. If desired,
fed from the circulating tank 'I through the pipe this pipe can be located inside the tower as in
Il. The solution also includes liquor from the the case of the extension pipe 35 of Fig. 5.
final crystallization operation and wash water. The solution entering the bottom of the tower
The solution has a temperature of 15G-210 F., rises through the copper concurrently with the
preferably 185 F. This is maintained by means air from the nozzles 43. The specific gravity of
of steam coils I in the circulating tank '!. The the mixture of solution and air is less than that
solution is fed to the tower at whatever rate is of the solution alone, and the hydrostatic head
necessary to maintain the temperature of the re of the column of solution in the tank lll and
action at 180-185 F. pipe 46 maintains the level of the lighter aerated
The concentration of the circulating solution solution in the tower above the top of the copper
is analyzed periodically and adjustment made column, the solution returning to the tank
when necessary by adding sulphuric acid. Wash through the pipe 41. Thus continuous circula
water containing some copper sulphate is used tion of solution through the tower is maintained
to replace the water evaporated in the tower. without the use of circulating pumps,
When the copper content of the Solution is about By adhering to the process above described the
160 gms. per liter, the solution in the circulating reaction can be made substantially continuous
tank is pumped out and another batch started. as it has been found no interruption is required
Circulation over the tower and introduction of either for recharging, cleaning, or changing the
air into the bottom of the tower is continuous solution.
however. At the same time the scrap copper or shot is
Fig. 5 shows a tower 25 similar to the tower I completely consumed and no particular care need
but arranged for upward circulation of solution be exercised either in grading the initial charge
through the tower concurrently with the air. As or removing under-sized particles after the reac
in Figure l, the copper particles are charged tion has progressed. ' '
through a hopper 26 and are supported on a grate The eliicient use of the oxygen has several ad
21. Air is introduced into the bottom of the vantages among which are the marked economy
tower by means of a blower 28, pipe 29, and noz in the quantity of heat required and the reduced
zles 3D, while the top of the tower is vented amount of water vapor lost through the exhaust.
through an xhaust blower 3I. The solution is The fact that the reaction vessel is under no
stored and heated in a tank 32 from which it is 70 pressure above atmospheric, except that due to
withdrawn by a pump 33 and delivered through the mass of the reactants, simplifies the opera
a pipe 34 to the top of the tower. tion to a large degree. Conspicuous absence of
Instead of being delivered to the top of the copper sulphide as an objectionable byproduct
mass of copper in the tower, however, the solution is noted.
flows down to the bottom of the tower through 75 The process may be carried out as above indi
 10 Y
cated and with a wide range of factors including it moves upwardly through and in contact with
concentration of solution, temperature, speed of the mass by introducing air into the bottom of
air current and the like without departing from the mass at a rate of 1 to 50 C. F. M. per square
the invention as dened in the appended claims. foot of cross sectional area of the mass, thereby
What is claimed is: establishing liquid layers conforming to and
l. The method of producing copper sulphate covering the exposed surfaces of said particles
which comprises forming a mass of copper that and in contact with air substantially filling the
is substantially porous throughout by forming voids between said particles, the pressure of the
said mass of copper particles having a. maxi gas above the solution being substantially atmos
mum dimension not greater than about two pheric, maintaining the aerated solution at a
inches, maintaining said mass submerged in a 10 reaction temperature between 150 F. and 210 F.,
150-2l00 F, aerated solution of copper sulphate and withdrawing reacted solution from a point
and sulphuric acid, air being continuously in near the top of the mass.
troduced into the bottom of the mass at the rate 4. The method of producing copper sulphate
of 1 to 50 C. F. M. per square foot of cross sec which comprises continuously supplying a solu
tional area of the mass, the pressure of the gas tion or" copper sulphate and sulphuric acid to the
above the solution being substantially atmos bottom of a mass of copper that is substantially
pheric, the solution being continuously intro porous throughout, being formed o1 copper par
duced to the bottom of the mass and moving up ticles having a maximum dimension not greater
wardly therethrough with the air and being than about two inches, aerating the solution as
withdrawn from the top, and maintaining the 20 it moves upwardly through and in contact with
reaction temperature. the mass by introducing air into the bo-ttom of
2. The method of producing copper sulphate the mass at a rate of 1 to 50 C. F. M. per square
which comprises forming a mass oi copper that foot of cross sectional area of the mass and
is substantially porous throughout by forming distributing the air ow substantially uniformly
_said mass of copper particles having a maxi over said area, thereby establishing liquid layers
mum dimension not greater than about two conforming to covering the exposed surfaces
inches, maintaining said mass submerged in a. of said particles and in contact with air sub
l50-210 F. aerated solution of copper sulphate stantially filling the voids between said particles,
and sulphuric a'cid, air being continuously introi the pressure of the gas above the solution being
duced into the bottom of the mass at the rate of 30 substantially atmospheric, maintaining the mass
l to 50 C. F, M. per square foot of cross sec for particles as copper is consumed in the reac
tional area of the mass, the pressure of the gas tion by supplying more particles to the top of
above the solution being substantially atmos the mass, maintaining the aerated solution at a`
pheric, the solution being continuously intro reaction temperature between 150 F. and 210 F.,
duced to the bottom of the mass and moving 35 and withdrawing reacted solution from` a point
upwardly therethrough with the air and being near the top of the mass.
withdrawn from the top, maintaining the mass GEORGE E. HARIKE.
of particles as copper is consumed in the reac
tion by supplying more particles to the top of the
mass, and maintaining the reaction temperature. 40 REFERENCES CITED
3. The method of producing copper sulphate The following references are of record in the
which comprises continuously supplying a solu le of this patent:
tion of copper sulphate and sulphuric acid to the
bottom of a mass of copper that is substantially
UNITED STATES PATENTS
45 Number Name Date
porous throughout, being formed of copper par
ticles having a maximum dimension not greater 1,944,444 Marsh et al _______ __ Jan. 23, 1934
than about two inches, aerating the solution as 2,153,908 Bagby ___________ __ Apr. 11, 1939
 Certificate of Correction
Patent No. 2,533,245 f December 12, 1950
GEORGE E. HARIKE '
It is hereby certified that error appears in the printed specification of
the above numbered patent requiring correction as follows: '
l (lolumn 3, line 6, for sulphite read sulphide; line 13, for wall read
we Z;
and that the said Letters Patent should be read as corrected above, so that
the same may conform to the record of the case in the Patent Office.
Signed and sealed this 25th day of December, A. D. 1951.

[Smm]

THOMAS F. MURPHY,
Assis tant Uommz'ssz'o'rzer of Patents.