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Патент USA US3025148

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March 13, 1962
Filed June 20. 1958
MOTOZO HlRAO ETAL
3,025,136
METHOD FOR CONTINUOUS PRODUCTION OF
A BASIC CUPRIC SULFATE
4 Sheets-Sheet 1
MKY.E5 WMU I AUEMWTBKAOUmNTM“AO
.KMI
I ‘ WM,
March 13, 1962
MOTOZO
METHOD FOR c
A BA
Filed June 20. 1958
T
RAO ETA
oUs PRODUCT
CUPRIC SULFATE
3,025,136
N OF
4 Sheets-Sheet 2
M. HIRAO
K. HARUTA
Y. KUWATS‘UKA
E. MUNEKATA
S. IMAMOTO
INVENTORS
March 13, 1962
MOTOZO HIRAO ETAL
3,025,136
METHOD FOR CONTINUOUS PRODUCTION OF
A BASIC CUPRIC SULFATE
Filed June 20. 1958
4 Sheets—Sheet 3
M. HIRAO
K. HARUTA
Y- KUWATSUKA
E. MUNEKATA
S. IMAMOTO
INVENTORS
\N
fL/S
March 13, 1962
MOTOZO HIRAO ETAL
METHOD FOR CONTINUOUS PRODUCTION OF
A BASIC CUPRIC SULFATE
Filed June 20. 1958
3,025,136
4 Sheets-Sheet 4
FIG.6
M. HIRAO
K. HARUTA
°
Y. KUWATSUKA
g
E. MUNEKATA
& IMAMOTO
INVENTOR-S
£25,136
Patented Mar. 13, 1962
2
3,025,135
METHOD FOR CUNTINUOUS PRUDUCTIGN UF A
BASlC CUPRIC SULFATE
Motozo Hirao, Kazuo Haruta, and Yasuhiko Kuwatsulra,
Noheoka, and Eiji Munelrata and Sadasuke lmarnoto,
Tokyo, Japan, assignors to Asahi Kasei Kogyo Kahu
shiki Kaisha, Osaka, Llapan, a corporation of .lapan
Filed June 20, 1958, Ser. No. 743,430
5 Claims. (Cl. 23-125)
This invention relates to a continuous method for the
ratio of (Du/S04 of 7 or so may be obtained, but the
particle size of the sediment is so small and the distribu
tion is so wide (05-511, average 2.5/1. or so) that it is
quite inferior to the commonly used basic copper by the
hot process as described before in various points such as
sedimentabi'lity and ?ltrability, etc.
Moreover, a great
amount of ammonium sulfate is adsorbed in the sediment
to the extent that it is di?icult to wash and remove, which
result in a poor actual mol ratio of 4.5 or so including
10 the adsorbed ammonium sulfate with much ?uctuation.
Consequently, it is not too much to say that when such
basic cupric salt is used in the manufacture of the spin
ning solution for cuprammonium- rayon the results which
rayon and to an apparatus thereof.
could be expected from the used of the described basic
Generally speaking, the basic cupric salt which has 15 cupric salt having a high mol ratio can not be substan
manufacture of basic cupric salt of high cupric hydroxide
content suitable for the production of a cuprammonium
heretofore been known for use in the production of a
cuprammonium rayon, i.e., a cupric salt obtained, for ex
ample, by a reaction at about 90° C. of a cupric sulfate
tially obtained.
It is an object of this invention to provide a method
for continuously and commercially manufacturing a basic
solution with a sodium carbonate solution or aqueous
cupric salt at ordinary temperatures which has a high mol
ammonia has a large particle size and it is readily sub 20 ratio i.e. about 7, with little ?uctuation, has few impuri
jected to treatments such as ?ltration, sedimentation,
ties, and is easily subjected to treatments, continuously
washing and the like. On the other hand, a great deal of
washing said basic cupric sulfate with water, subjecting
heat is required for the hot reaction thereof and yet the
it to the reaction with aqueous ammonia and continuously
product obtained has a mol ratio of (Eu/S04 as low as 3.5
supplying it as a cuprammonium solution for use in the
or so. Thus, when it is used to produce a spinning solu 25 production of the spinning solution for cuprammonium
tion, a great amount of caustic soda is necessary in the
rayon, wherein the difficulties encountered in the conven
process of dissolving cellulose to activate or convert into
tional methods can be overcome. It is another object of
cupric hydroxide an inactive copper which has been com
this invention to provide an apparatus thereof.
bined with a sulfate radical. Accordingly the spinning
In order that the invention may be fully understood it
solution obtained contains a great amount of sodium sul~ 30 will now be described with reference to the accompanying
fate, which has been found to be detrimental to the qual
ity of the product yarns (US. Pat. No. 2,758,013; Japa
nese Pat. Nos. 134,172. and 149,821, etc). Accordingly,
drawings, in which
FIG. 1 is a longitudinal sectional view along line B—B
of FIG. 2 of the apparatus of the present invention.
various technical researches have been developed and
FIG. 2 is a cross sectional view of the apparatus of
practical methods have been proposed to overcome the 35 FIG. 1. '
abovementioned di?iculties by the use of basic cupric sul~
FIG. 3 is a longitudinal sectional view of the washing
‘fate having as high cupric hydroxide content or mol ratio
device for the products obtained by the use of the appa
of Cu/SO, as possible for the production of the spinning
ratus of FIG. 1.
solution, such as referred to in the above US. Pat. No.
FIG. 4 is a cross sectional view of the device of FIG. 3.
40
2,758,013 and Japanese Pat. Nos. 113,262, 181,338,
FIG. 5 is the washing device of which a part of wall
198,735 and the like. However, these methods have also
is cut o?f.
encountered many difficulties because they are too com
FIG. 6 is a schematic view of the apparatus for carry
plicated to be practiced on a commercial scale; the na
ing the present process.
ture of the resulting precipitates is not always suitable
According to the present invention, a cupric solution,
for such treatments as ?ltration, sedimentation, washing 45 such as cupric sulfate, and an alkaline solution, such as
and the like; it is very difficult to obtain a constant com
aqueous ammonia or cupric tetrammine sulfate solution
position; and the like. By way of detailed explanation
are continuously supplied into a reaction apparatus which
as to this point, reference is made to the process of the
has a reaction chamber provided with a stirrer and a
abovementioned Japanese Patent No. 198,735. This is
concentration-separation chamber for the reacting prod
the only process in which a chemically pure cupric hy 50 uct or sediment assembled in one apparatus, and the
droxide can be obtained under commercial conditions.
reaction takes place under predetermined constant tem
As shown in the chemical Equations 1 and 2 described
peratures and pH. A part of the sediment which has
below, this process may ?rst produce the basic cupric
been sedimented and concentrated in the concentration
sulfate of comparatively good sedimentability having a
separation chamber by gravity is made a seeding liquor,
mol ratio of 3 or so, which is, then, separated from the 55 which is caused to circulate without destroying the par
mother liquor and subjected to the action of aqueous
ticles- within the range of the predetermined cycle num
ammonia to produce the cupric hydroxide. This two
bers and at a certain constant value. Thus, the reaction
step process is so complicated and the various factors
can take place under the conditions of high copper con
such as sedimentability, ?lterability, etc. involved therein
centration.
60
are not satisfactory to a commercial production.
The starting materials, i.e. a cupric salt solution and
an alkaline solution, are continuously and simultaneous
ly supplied. A cupric sulfate solution may be used as
the cupric salt solution. The concentration thereof may
be l~5 g./ 100 cc., suitably 2.5 g./ 100 cc. calculated as
Cu.
Another reactant to be used is aqueous ammonia
or a solution of cupric tetrammine sulfate. It is prefer
able that the concentration is 2—10 g./ 100 cc. of NH3
when
the former is used, and 1~5 'g./ 100 cc. as Cu when
‘ammonia are caused to react with stirring at room tem
perature under the controlled conditions of pH is easier in 70 the latter is used. It is most convenient for the starting
materials to use solutions recovered in recovery process
operation and has been commercially eliected. By the
as cupric sulfate solution and cupric tetrammine sulfate
use of this method, the basic cupric sulfate having a mol
solution. Additional cupric sulfate solutions equivalent
The method of US. Patent No. 2,758,013 or Japanese
Patent No. 181,338 wherein a cupric sulfate solution and
3,025,136
35
to the amount lost in the recovery process must be added.
Concentrations of the starting materials depend upon this
copper recovery process. In practice, the above men
tioned concentrations are moderate. On supplying the
two reactants simultaneously and at a constant ratio, the
following reaction takes place.
4
to, su?icient growth of the precipitated particles is in
hibited and particle size becomes small, whereby a precip
itate having the desired settling and being easily ?lterable
and washable, cannot be produced. While if cycle num
ber A is more than the ?gure above referred to, the par
ticles are destroyed in a recycling course, ‘growth of par
ticles is inhibited, and moreover, smooth separation of
settling particle phase from supernatant liquid phase is
prohibited, for contacting surface of both phases is turbu
lated.
By selecting the above conditions, the sedimented cop
10
per salt crystal nuclei can grow very compactly with uni
The pH should be maintained between 6.5 and 7.5.
form particle size and excellent sedimentability, which
If the pH is below 6.5, there is obtained only a precipi
becomes easy of access to the treatments such as ?ltra
tate having mol ratio of as low as about 4. If the pH is
tion and washing. Moreover, this has a high mol ratio
more than 7.6, an amount of dissolved copper in super
(about 7) of less ?uctuation and contains lms impurities,
natant liquid increases, thereby yield of a precipitate con
such as A1, Fe, SiO2, etc., therein.
siderably decreases.
The reaction should be conducted at the determined
temperature or 10°-30° C. If the temperature is below
Since the supernatant liquid involved in the production
of basic cupric salt or the supernatant liquid which has
?own out from the ei?uent device of the concentration
10° 0., particle size of precipitate becomes small, and
separation chamber of FIG. 1 hereinafter explained con
such properties as sedimentation and ?ltration are broken
tains 1000-1500 mtg/l. of copper, this can be separated
down, thereby the product cannot be used for practical
and recovered as basic cupric sulfate by neutralizing it
use. For example, rate of sedimentation of particle rel
with sulfuric acid or waste copper-containing acid result
ative to temperature is as follows:
ing from the spinning process. The reaction in this case
M./h. 25 may
be indicated in the following chemical equation,
15° C
1.8
the basic cupric sulfate having a mol ratio of Cu/SO4
10° C
1.3
of about 4 being produced.
5° C-
__
0.5
On the other hand, if the temperature is more than
30° C., a precipitate having mol ratio of as low as 4 is 30
apt to form, and the produced precipitate has so poor
The mol ratio of the basic cupric sulfate recovered
stability that it is readily converted to a basic salt having
from the supernatant liquid is 4 as described before, but
lower mol ratio.
has few impurities so that the sulfate can be used for
the production of the spinning solution by mixing there
Temp., °C.
M01 ratio of
(Du/S04 in precipitate on
M01 ratio of
(Jo/S04 after
12 hrs.
formation
6. 85
6. 50
5. 50
35 with the above basic cupric sulfate of high mol ratio.
In this case, the amount of the recovered copper is less
than 1,50 of that of the basic cupric sulfate of high mol
6. 55
6.05
4. 95
ratio, so that the substantial reduction of the actual mol
ratio does not occur by the use of the mixture. When
40 the countercurrent continuous water-washing device as
explained below is used, it is convenient to conduct this
mixing in a hopper in admixture with the slurry of the
The rate of stirring is not critical.
basic cupric sulfate of high mol ratio because washing
Some of the sediment resulted from the above reaction
is caused to circulate as a seeding liquor. The other 45 with water may concurrently be effected.
It is of course possible in the neutralization of the above
sediment is withdrawn and passed to the washing device
supernatant liquid to use the above apparatus for con
as shown in FIGS. 3, 4 and 5 described in detail below.
In the above circulation, care must be taken as to the
tinuously manufacturing the basic cupric salt. In such
a case, similar advantages may also result wherein the
The reason why some of a sediment should 50 sediment which is readily washable and has uniform
cycle number so that the seeding liquor should not be
destroyed.
be circulated is that it is essential in the present inven
tion to effect the reaction at the high concentration of
copper.
particle size, excellent sedimentability, few impurities
and a mol ratio of less ?uctuation can be obtained.
The waste supernatant liquid which has been stripped
of copper may be passed to an ion-exchange vessel where
cording to the following equation, the suitable value be 55 in the remaining copper in amount of 100-300 mg./l.
can be adsorbed and removed. Thereafter, the ammonium
ing between 10 and 50 depending upon the particle size
sulfate contained therein can be recovered either as such
of the sediment.
by concentration as described in US. Patent No. 2,758,
013 or as aqueous ammonia by distillation after addition
Cycle number A:
60 of alkali such as lime and the like.
x: The copper concentration newly introduced into the
Similarly the waste washing water resulting from the
reaction chamber, i.e. copper freshly fed to the reaction
counter-current continuous water-Washing device may be
chamber (g.) per 100 cc. of liquid volume freshly fed
stripped of the copper contained therein in an ion-ex
The cycle number is a numerical value calculated ac
to the same chamber.
change vessel and can be used as a source of ammonium
: The copper concentration of the circulating liquid
(forward), that is, copper concentration in a circulat
sulfate or ammonia as described just above if the ammoni
um sulfate content thereof is suitably high, e.g., more
ing liquid which is withdrawn from the reaction cham
ber and fed to a concentration-separation chamber
than 1%.
The general process will readily be understood from
(g./100 cc.).
FIG. 6.
z: The copper concentration of the circulating liquid 70 This invention can be carried out in the apparatus as
shown in FIG. 1 and FIG. 2. This apparatus is similar
(backward), that is, copper concentration in a circulat
ing liquid which is concentrated in a concentration
in construction to an accelerator, and a settler which has
separation chamber and returned to the reaction cham
been known as water clari?cation apparatus but is func
' ber (g./l00 cc.).
tionally different therefrom in that the agitation in the
If cycle number A is less than the ?gure above referred 75 reaction chamber can be controlled depending upon the
5
3,025,136
particular conditions of reaction and the optimum stirring
conditions can be set so as to obtain the predetermined
sediment of basic cupric salt and that the sedimentation
and concentration in the sedimentation~separation cham
ber can be conducted as satisfactorily as possible depend
ing upon the sedimentability of the sediment.
In the
case of water clari?cation, the sediment ?ock tends to be
destroyed by a slight power so that it can not stand vig
orous agitation, whereas in the sedimentation of basic
6
The concentration-separation chamber B is so con
structed that the cone-shaped bottom wall 7 inclines at
an angle more than 40° and the ratio of heights or L1/L2
of the cylindrical section and the conical section is
less than 1 so as to respond to the sedimentability of the
basic cupric salt having large particle size. Because of
such special design, it is possible that the sediment of
the basic cupric salt which has large particle size and is
very easy to sediment does not accumulate on the bottom
cupric salt, the sediment is strong enough to stand such 10 part of the reaction chamber or other parts, resulting in
vigorous agitation because it is necessary to circulate the
a smooth circulation and highly e?icient concentration.
sediment’as a concentrated seeding liquor (for example,
In FIG. 1 and FIG. 2, 16 is a stirring shaft for rotating
10-25 g./100 cc. as Cu) at the cycle number of 10 to 50;
the stirrer 4 and the adjustable wing means 5 fastened
the particle size is so large that the sedimentation rate
thereto. Wing means 5 draw liquid from the central
is greater and the local accumulation tends to occur, 15 space 17 in the interior of funnel-shaped wall 3, which
which necessitates a vigorous agitation in the reaction
central space 17 forms the upper portion of chamber A
chamber (for example, 200 rpm. in the apparatus hav
upwardly through and past the hollow stirrer 4 into the
ing a capacity of 25 kg./hr. of Cu); and the sediment is
space about stirrer shaft 16, inside inner tube wall 1; 19
quite dense. Also in the case of water clari?cation, the
is a partioning plate for making the ?ow in the draft
product is a supernatant liquid, while in the apparatus for 20 tube uniform; and 20 are baiile plates. Units shown in
the manufacture of basic cupric salt, the product must be
FIGS. 1 and 2 must be made of a material which is not
the sediment itself. Accordingly, the sedimentation-con
corroded by either reactants or products; for instance,
centration should be in conjunction with the subsequent
they can be made of stainless steel.
water~washing device, such that the capacity of concen
In the ‘operation of the above described apparatus, the
tration is very high. Thus, the apparatus of the present 25 reactant liquids or an alkali and a cupric salt solution,
invention has such a special design as described before
in the structure of the reaction chamber and the concen
tration-separation chamber, which distinguishes itself from
for example, aqueous ammonia such as 5 g./ 100 cc. NH;.;
and a ‘cupric sulfate solution such as Cu 2.5 g./ 100 cc. so
lution, or a solution of cupric tetrammine sulfate such as
Cu 2.5 g./1100 cc. solution and a cupric sulfate solution
the conventional water-clari?cation apparatus.
The reaction chamber A and the concentration-separa 30 such as Cu. 2.5 g./100\ cc. solution, are continuously fed
tion chamber B are concentrically established in one
through the pipes 8 and 9 into the reaction chamber A at
apparatus, both of which are separated from each other
the predetermined rate shown in the chemical Equations 3
by an outer tube 2 and an inner tube 1 of a draft tube,
and 4. In the chamber A, the reaction is e?ected with the
and a compartment wall 3 having a shape similar to an
action of the stirrer 4 lwhile adjusting the pH in the cham
inverted funnel. The reaction chamber A is provided with
ber at a constant value (6.5-7.5).
a stirrer 4, to which feed pipes 8 and 9 are open for re
The resulting product is guided by the tubes 1 and 2
spectively introducing the reactant liquids, a cupric salt
into the chamber B wherein the sedimentation and con
solution and an alkaline solution. The pipes may pref
centration take place by virtue of gravity. A major
erably be closely located against the stirrer 4 so that, on
part of the resulting sedimentation liquid is caused to
introduction of the reactants, they are intimately mixed 40 circulate from the bottom of the chamber B through 15
with each other to produce a homogeneous solution. The
into {the chamber A. Thus, the reaction chamber may
ends of the pipes form cycles on which a plurality of holes
be maintained under such high copper concentration
are perforated. The concentration-separation chamber B
as 10-25 g./ 100 cc. (as Cu). As the interface between
is made of an outer wall 6 or the cylindrical section and
the supernatant liquid and the sediment in the chamber
a bottom wall 7 or the cone section and the outer tube 2 45 B is not disturbed by the circulating liquid coming from
of the draft tube.
When both reactant liquids are con
tinuously and simultaneously fed from the feed pipes 8
and 9 to the chamber A and caused to react with a vig
the chamber A due to the action of the tubes 1 and 2, it
is possible not only to completely separate the supernatant
liquid from the upper part of the chamber B and cause
orous agitation by the stirrer 4, a sediment of basic cupric
it to over?ow therefrom, but also to continuously with
salt is produced, which is then carried upwards by the 50 draw the sediment from the bottom of the chamber, part
action of the stirrer 4 and passed through the inner and
outer tubes 1 and 2 into the chamber 13 where the sedi
mentation-concentration takes place. Some of the sedi
of which is under quite concentrated conditions such as
a slurry density of 20-50‘ g./ 100 cc. or a Cu concentration
of 10-25 g./100 cc. In the withdrawal of the sedi
ment is withdrawn by a suitable slurry pump such as a
mentation liquid, it is effected in such a manner that the
diaphragm pump through a sediment-withdrawing pipe 55 amount thereof will be balanced with that of the fresh
10 while the supernatant liquid is caused to flow out from
cupric salt introduced into the chamber A. Also the
an e?luent device 11 and is continuously withdrawn from
temperatures of the reactant liquids should be adjusted
a supernatant liquid exit pipe 12. A lower end of pipe
prior to the introduction into the reaction chamber so
10 opens near the bottom of the chamber A so that it
that the temperature of the chamber may be ‘kept at con
takes up concentrated precipitate which is concentrated 60 stant (l0\°-30° C.).
in chamber B and circulated in chamber A, without clog
ging. A major part of the sediment is caused to circulate
When the above apparatus for the manufacture of
basic cupric salt is used and the reaction takes place
into the chamber A as a concentrated seeding liquor
under the above conditions, the circulating liquid be
through a passageway 15 which is established in the bot
comes a concentrated seeding liquor of Cu 10-25 g./ 100
tom part of the chamber B. The stirrer 4 in the reaction 65 cc. so that the particles of the sediment grow densely in
chamber is provided with a movable wing means 5 which
a ‘uniform and large size (15-40”, average 25p.) and
can be set at any angle and favors circulation of liquid
the sedimentation rate of slurry reaches 1-3 m./hr. at
in a de?nite direction from downwards to upwards. Also
the above copper concentration which is comparable with
the inner tube 1 of the draft tube is provided with an
that of the hot process basic cupric salt. Subsequent
adjustment window 13 which opens to any degree by the 70 treatments such as washing and sedimentation will be
up and down movement of an adjustment rod 14. By
very easy. Thus, when a continuous water-washing de
setting the wing means 5 of the stirrer 4 at a suitable
vice -as shown in FIGS. 3, 4 and 5 as a slurry water-wash
angle and adjusting the degree of opening the window
ing device is used, a small amount of water (2-5 times
13 of the inner tube 1, it is possible to adjust the cycle
as much to the amount of slurry) is su?icient to wash it
number A of the sediment to suitable values of 10 to 50‘. 75 easily and continuously, whereby the basic cupric salt
3,025,136
8
ratio, i.e. about 7, can be obtained. For example, it is
possible to continuously obtain a basic cupric salt in a
In the apparatus similar to that shown in FIG. 1 and
FIG. 2, 5 g./100 cc. of aqueous ammonia and 2.5 g./
100 cc. (as Cu) of cupric sulfate solution are caused
concentrated form which has 1a mol ratio of 7 or so
to react with each other in a continuous manner while
having excellent qualities and high purity with high mol
(about 6.5 even when the adsorbed ammonium sulfate is
included) in a less ?uctuation and contains very little
impurities such as SiO2, Ca, Mg, Al, Fe, organic sub
stance ‘and others which are detrimental to the dissolving
or the spinning processes.
This serves, after continuous
addition thereto of concentrated aqueous ammonia (for
example, 25 g./ 100 cc.) in a ratio of NH3/Cu=2-2.5
for example, as Schweizer’s reagent which may be con
the pH and the temperature in the reaction chamber are
respectively adjusted to 6.8—7.0 and 28° C., and the
cycle number A is maintained at 15. As a result, the
sediment withdrawn at a value of Cu 20 g./ 100 cc. is
continuously obtained, which has the composition as
indicated (a) in the following table. In the table, the
composition (b) is that subsequently washed by two steps
of the counter-current continuous water-washing device
As compared with the
analysis (0) of the basic cupric salt which has been
is made of anti-corrosive material such as stainless steel 15 commercially obtained by the conventional method
(Japanese Patent No. 181,338), it is obvious that this
or has lead-lining. It is provided with a simple rotary
tinuously fed to the production of a spinning solution.
The water-washing device shown in FIGS. 3, 4 and 5
as shown in FIGS. 3, 4 and 5.
has a very high purity as well as a high mol ratio.
type distribution pipes 25 which serve concurrently as
an upper agitation wing for the cylindrical tank 34 and
Table
from which the sedimented copper salt slurry is allowed
to be ejected into the tank 34. The water for washing 20
is sprayed out from the distribution pipes 27 having col
lecting wings ‘and ?xed in the bottom part in a co-axial
relation with the pipes 25. By bringing the sedimented
Cu _________________ _
copper salt into counter-‘current contact with the water,
the distribution of the sedimented copper in the tank 25 S10
34 is made uniform so that a very high washing efficiency
and uniform washing effect may be realized with a mini
mum amount of water.
In the water-washing device, the sedimented copper
slurry withdrawn from units of FIGS. 1 and 2 and pumped 30
In the above table, the bottom parentheses show the
out by slurry pump is continuously introduced from an
mol ratios exclusive of adsorbed ammonium sulfate.
upper feed tube 21 into a hopper 22, from which it
In this example, the analysis of the supernatant e?luent
?ows down through a double pipe 24 concentrically ?xed
is as follows.
with a rotary agitation shaft 23 into 2 to 5 radial slurry
distribution pipes 25 which have a plurality of small 35 Cu _________________________________ __ 1350 mg./l.
(NH4)2SO4 _______________________ _._ 3.51 g./100 cc.
openings 41 ‘directed downwards. The slurry is dis
charged from these openings into the tank 34. The
This copper salt may be subjected to the reaction with
washing water is passed through the lower tube 26 into
the waste copper-containing liquid (Cu 0.98 g./ 100 cc.;
the pipes 27 and sprayed into the tank 34 through a plu
H2804 4.95 g./ 100 cc.) in the above described apparatus.
rality of Openings in the above pipes which are directed
The reaction conditions are adjusted to pH 6.3, tempera
downwards. The pipes 27 are ‘also provided with wings
ture 28° C. and cycle number (A) 20. The withdrawn
33 for collecting the sediment. If desired, other agita
sediment has a copper concentration of 25 g./ 100 cc.
tion wings 28 may be attached to the shaft 23. The
(as Cu). This sediment may be mixed in the hopper of
shaft 23 can be driven by a motor 29‘. The sediment
the counter-current continuous water-washing device with
in the slurry which has been discharged from the open 45 the above-described sediment of the basic cupric sulfate
ings 41 of the pipes 25 ?ows down under the effect of
of high mol ratio and washed so that both may be well
gravity through the tank 34, coming into counter-cur
mixed.
rent contact with the water passing upwards from the
The supernatant effluent of the basic cupric sulfate of
bottom for uniform washing, reaching the inclined bot
high mol ratio, which has been stripped of its copper as
tom 42 and being introduced into the sediment storage 50 far as the same was present in the form of basic cupric
space 30 by means of the collecting wings 33 in which
sulfate by the above mentioned means, may still contain
storage space 30 it is sedimented and concentrated to a
residual copper. When it is removed in the ion-exchange
predetermined slurry density and discharged out through
vessel 4.10 g./ 100 cc. of aqueous ammonium sulfate may
be obtained in this case, which can be mixed with the
pump. The liquid in the slurry is passed upwards under 55 washing water of the counter-current continuous water
dilution by the washing water into the uppermost over
washing device and concentrated for use in the recovery
flowing zone 32, from which it flows out and is removed
of ammonium sulfate or added with lime and distilled
through an exit tube 43.
to produce aqueous ammonia.
In FIGS. 3, 4 and 5, 35 is a transmitting means from the
In this case the copper content in the sediment coming
motor 29 to the rotary shaft 23; 36 is an agitation wing
from the counter-current continuous water-washing device
for the sediment storage 30, 38 is a cover for the agi
is 12.07 g./ 100 cc., which can be continuously supplied,
tation shaft; 39 is a support for the washing-water dis
after addition of 24 g./ 100 cc. of aqueous ammonia, as
tribution pipes 27; 40 is a support for the wings 36;
a solution of tetrammine copper hydroxide having the
and ‘44 is an upper bearing for the agitation shaft 23.
following composition for the production of spinning
The continuous washing device as shown in FIGS. 3, 65 solution for cuprammonium rayon.
4 and 5, hereinafter called “counter-current continuous
In FIG. 6, ammonia and copper salt solutions are
water-washing device,” may be used either alone or in
respectively fed from their storage tanks 45 and 46 to
combination of two sets. The advantage of the use
basic copper salt continuous manufacturing apparatus 50
of the connected two sets is that, by decreasing the amount
by pumps 47 and 48. The copper salt solution passes
of washing water in the ?rst set so that the concentration 70
a tube 31 by means of a slurry pump such as a diaphragm
of ammonium sulfate contained in the waste washing
liquor may be made higher, the ‘ammonium sulfate or
heat-exchanger 49 by the way, where the solution is
heated or cooled so as to correspond to reaction tempera
ture in 50. Sedimented copper slurry in 50 is con
tinuously withdrawn by diaphragm pump 51 and fed to
An example of the present invention is indicated as
75 the ?rst washing apparatus 53 where the slurry is washed
follows:
ammonia can be recovered from the waste.
3,025,136
With water, and then to the second washing apparatus 55
through diaphragm pump 54. The washed slurry in 55
is withdrawn by pump 56 and fed to copper-concentration
controller 57 where the slurry is diluted to a de?nite
copper concentration, for example, 12 g./100 cc. of Cu. 01
The slurry is fed to a tetrammine copper hydroxide manu
facturing apparatus 52 where an ammonia aqueous solu
tion containing 24 g./100 cc. NH3 is added so that
NH3/Cu is a de?nite value (for example, 2.25) and a
tetrammine copper hydroxide solution containing for 1O
10
(b) continuously withdrawing part of the resulting
slurry, and permitting the withdrawn part to settle
to obtain a concentrate containing from about 10 to
25 grams Cu per 100 cubic centimeters of the result~
ing slurry in a settling zone,
(0) recirculating the slurry from said settling zone into
fresh mixture obtained by (a) at a substantially
constant recycling rate A of about 10 to 50,.A being
equal to
example,
Cu ______________________________ __ 6.50 g./100 cc.
NHB ______________________________________ .._ 15%
is formed. The solution is fed by pump 60 to a storage 15
tank 62 via a heat-exchanger ‘61 and, if desired, is sub
jected to dissolution step of a cellulosic material via
pump 63.
A supernatant liquid from 50 is fed by pump 52 to a
supernatant neutralization unit 64 where it is neutralized
with sulfuric acid. Sedimented basic copper salt thus
formed having mol ratio of 4 is fed by diaphragm pump
65 to ?rst washing device 53 where the copper salt,
wherein x is the concentration of Cu in the cupric
sulfate solution freshly introduced into (a), y is
the concentration of Cu in the slurry being with
drawn under (b), and z is the concentration of Cu
in the slurry being recirculated under (c), thereby
obtaining a basic cupric sulfate substantially corre
sponding to the formula 6Cu(OH)2.CuSO4 and
consisting of granules of about 15 to 40 microns.
3. A continuous method of producing a basic cupric
sulfate suitable for use in the manufacture of cupram
monium rayon which comprises:
together with sediment having higher mol ratio from 50,
(a) mixing in aqueous solution at a temperature of
is washed with water. Supernatant from 64 is passed 25
from 10° to 30° C. and a pH within the range of from
through ion-exchangers 66 and 67 to split off residual
6.5 to 7.5 cupric sulfate in a concentration corre
copper and then fed to ammonia recovering unit (not
sponding to from about 1 to 5 grams of Cu per
shown).
We claim:
1. A continuous method of producing a basic cupric
sulfate suitable for use in the manufacture of cupram
monium rayon, comprising,
(a) mixing with stirring at a temperature of about
10° to 30° C. and a pH of about 6.5 to 7.5, an
aqueous cupric sulfate solution and a member selected 35
from the group consisting of aqueous ammonia solu
tion and aqueous alkaline cupric ammine salt solution
in such amounts that the molar ratio of CuzNHs is
about 7:12 and the molar ratio of Cu:SO4 in the
?nal product is about 7:1, thus producing a precip 40
itate of basic cupric sulfate,
100 cc. of solution with ammonia in a concentration
of from about 2 to 10 grams of NH3 per 100 cc. of
solution,
(b) continuously withdrawing part of the resulting
slurry, and permitting the withdrawn part to settle
to obtain a concentrate containing from about 10 to
25 grams Cu per 100 cubic centimeters of the result
ing slurry in a settling zone,
(c) recirculating the slurry from said settling zone
into fresh mixture obtained by (a) at a substantially
constant recycling rate A of about 10 to 50, A being
equal to
(b) continuously withdrawing part of the resulting
slurry, and permitting the withdrawn part to settle
to obtain a concentrate containing from about 10 to
25 grams Cu per 100 cubic centimeters of the result 45
ing slurry in a settling zone,
(0) recirculating the slurry from said settling zone into
fresh mixture obtained by (a) at a substantially
constant recycling rate A of about 10 to 50, A being
equal to
50
wherein x is the concentration of Cu in the cupric
sulfate solution freshly introduced into (a), y is
the concentration of Cu in the slurry being With
drawn under (b), and z is the concentration of Cu
in the slurry being recirculated under (0), thereby
obtaining a basic cupric sulfate substantially corre
sponding to the formula 6Cu(OH)2.CuSO4 and
consisting of granules of about 15 to 40 microns.
4. A continuous method of producing a basic cupric
sulfate suitable for use in the manufacture of cupram
monium rayon which comprises:
wherein x is the concentration of Cu in the cupric
(a) mixing in aqueous solution at a temperature of
sulfate solution freshly introduced into (a), y is 55
from 10° to 30° C. and a pH within the range of from
the concentration of Cu in the slurry being with
6.5 to 7.5 cupric sulfate in a concentration corre
drawn under (b), and z is the concentration of Cu
sponding to from about 1 to 5 grams of Cu per
in the slurry being recirculated under (0), thereby
obtaining a basic cupric sulfate substantially corre
sponding to the formula 6Cu(OH)2.CuSO4 and 60
consisting of granules of about 15 to 40 microns.
2. A continuous method of producing a basic cupric
sulfate suitable for use in the manufacture of cupram
monium rayon, which comprises:
(a) mixing in aqueous solution at a temperature of 65
from 10° to 30° C. and a pH within the range of from
6.5 to 7.5 cupric sulfate having a concentration
corresponding to from about 1 to 5 grams of Cu
er 100 cc. of solution with a member selected from
the group consisting of ammonia in a concentration 70
of from about 2 to 10 grams of NHS per 100 cc. of
solution and complex cupric ammine sulfate in a
concentration corresponding to from about 1 to 5
grams of Cu per 100 cc. of solution, thus producing
a precipitate of basic cupric sulfate,
75
100 cc. of solution with tetrammine cupric sulfate in
a concentration corresponding to from about 1 to 5
grams of Cu per 100 cc. of solution,
(b) continuously withdrawing part of the resulting
slurry, and permitting the withdrawn part to settle
to obtain a concentrate containing from about 10 to
25 grams Cu per 100 cubic centimeters of the result
ing slurry in a settling zone,
(c) recirculating the slurry from said settling zone
into fresh mixture obtained by (a) at a substantially
constant recycling rate A of about 10 to 50, A being
equal to
wherein x is the concentration of Cu in the cupric
sulfate solution freshly introduced into (a), y is
3,025,136:
11
12
the concentration of Cu in the slurry being With
References Cited in the ?le of this patent
drawn under (b), and z is the concentration of Cu
UNITED STATES PATENTS
in the slurry being recirculated under (0), thereby
obtaining a basic cupric sulfate substantially corre
sponding to the formula 6Cu(OH)2.CuSO4 and
consisting of granules of about 15 to 40 microns.
5. The method described in claim 2, wherein said
complex cupric amrnine sulfate is tetrarnmine cupric
sulfate.
2,206,889
2,536,097
2,655,436
2,678,914
2,750,265
2,75 8,013
1940
1951
Bishop et al. _________ __ Oct. 13, 1953
Kalinske ____________ __ May 18, 1954
Gulbrandsen __________ __ July 9,
Rowe ________________ __ Jan. 2,
Hadsel _____________ __ June 12,
Munekata ____________ __ Aug. 7,
1956
1956
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