Patented July 28, 1936 - 2,049.

358

UNITED STATES PATENT 2,049,358

OFFICE
PRODUCTION of CUPRoUs CYANIDE
Charles Dangelmajer, Niagara Falls, N. Y., as
signor to E. I. duPont de Nemours & Company,
Incorporated, Wilmington, Del, a corporation
of Delaware
No Drawing. Application August 26, 1933,
- Serial No. 687,017
6 Claims. (CI, 23-79)
This invention, relates to the production of pounds; if it is precipitated from an alkaline me
cuprous cyanide and more particularly to an im dium it is contaminated with basic iron com
proved method for producing cuprous cyanide of pounds.
a high degree of purity from relatively impure One method of preparing cuprous cyanide has
raw materials. . . . .- .. .. been proposed which partially overcomes the
Cuprous cyanide has been prepared heretofore above-mentioned difficulties. According to this
by the reaction of a cuprous salt such as cuprous method, an impure alkali cyanide solution con
chloride, with an alkali metal cyanide, or by the taining ferrocyanide is reacted with one-half its
reaction of a cupric salt, such as cupric sulfate equivalent of cuprous salt to form a solution of
10 With an alkali cyanide in the presence of a reduc the double cyanide of copper and the alkali metal. 10
ing agent. The chief disadvantage of these pro The ferrocyanide is precipitated from this solu
cesses as practiced prior to my invention has been tion by the addition of a zinc salt and the pre
that very pure and relatively expensive raw ma cipitate removed by filtration. The purified dou
terials have been required in order to produce ble cyanide solution is then reacted with a fur
cuprous cyanide of sufficiently high purity and ther portion of cuprous salt to precipitate cuprous 15
light color to meet present trade specifications. cyanide. This procedure eliminates the ferrocya
Iron compounds in particular have been found to nide present in the cyanide solution, but obvious
be especially objectionable impurities, as they ly requires that the copper solution used in the
form highly colored complex cyanogen Com last step of the process be free from iron if a pure
20 pounds of which even extremely small amounts product is to be obtained. Furthermore, this 20
are sufficient to cause pronounced discoloration of process involves an additional precipitation and
the product. filtration step which increases the cost of produc
Many commercial grades of cyanide contain tion.
ferrocyanide as an impurity; furthermore, even An object of this invention is to provide an im
25 the purest grades of cyanide when solutions proved method of producing cuprous cyanide of a 25
thereof are handled in iron equipment become high degree of purity and of a light color. A
somewhat contaminated with ferrocyanide. It is further object is to utilize relatively impure raw
practically impossible to remove ferrocyanide materials in the production of cuprous cyanide.
from cyanide solutions because none of the known Other objects will appear hereinafter.
30 precipitants for ferrocyanide will function in the These objects are accomplished according to my 30
presence of free cyanide. Iron is also a common invention by controlling the Condition of pre
impurity in copper salts, particularly those which cipitation of cuprous cyanide So that all iron
have been made from Scrap copper, which usually compounds in the reacting materials remain in
contains appreciable amounts of iron.: The re solution. I have discovered that the presence of 35
35 moval of iron from solutions such as cuprous cuprous chloride in acid solution tends to decom
chloride is not commercially practicable, as the pose or prevent the formation of water-insoluble
cost of carrying out any of the known purifica iron cyanogen compounds. I have found that
tion methods would more than offset the saving Substantially iron free cuprous cyanide can be
effected by the use of cheaper grades of copper in precipitated from solutions containing iron as
long as said solutions are substantially acid in re 40
40 the preparation of the cuprous chloride solution.
One of the principal obstacles which prevent action and contain appreciable amount of cu
the precipitation of substantially iron-free cup prous chloride.
rous cyanide from solutions containing iron is the In one method of preparing cuprous cyanide
fact that the iron compounds usually present in according to my invention a solution of an alkali
45 metal cyanide is added to an acidic Solution of 45
such solutions are of two different types, i.e., sim
ple iron salts such as ferrous chloride, and iron cuprous chloride, which may also contain other
cyanogen compounds such as ferrocyanide The salts such as ammonium chloride or an alkali
iron cyanogen compounds are generally soluble in metal chloride in Order to increase the Solubility
alkaline solutions, but in an acid medium insol of the cuprous chloride. The amount of alkali 50
50 uble highly colored compounds are formed . On metal cyanide solution used is slightly less than
the other hand, the simple iron salts are soluble the theoretical equivalent of the copper so that at
in acid solutions but form basic precipitates such the end of the precipitation the solution is acidic
and contains an excess of cuprous chloride. The
a hydroxides in alkaline solutions. Thus, if the precipitated cuprous cyanide is then filtered from
cuprous cyanide is precipitated from an acid me
55. dium-it is contaminated with iron cyanogen com the Solution, washed, and dried. 55
 2 2,049,358
The following example provides a specific illus somewhat according to the amount of iron pres
tration of a preferred modification of my inven ent. I have found that as little as 0.5 gram of
tion. copper per liter of solution is effective when rela
A solution of cuprous chloride is prepared by tively small amounts of iron are present. When
5 passing chlorine gas into a sodium chloride brine larger amounts of iron are present the exceSS
solution containing a small amount of cupric cuprous chloride concentration may be increased
chloride in contact with scrap copper; then allow to any desired extent, although there appears to:
ing the solution to remain in contact with excess be no advantage in using concentrations higher
copper until substantially all of the cupric chlo than 5 grams of copper per liter at the completion
10 ride is converted to cuprous chloride. A. Small of the precipitation. - . .. . . . 10
amount of sodium bisulfite is added to the solu
tion to insure complete reduction of the copper
During the precipitation of the cuprous cya
-
nide, it is generally desirable to add additional
and to provide free acid in the form of SO2 liber acid or acid salt to the reaction mixture from
ated from the sodium bisulfite. The composi time to time in order to neutralize the alkaline
tion of the resultant cuprous chloride solution constituents such as carbonate which are gener- 15
may be as follows: ally present in the cyanide. If the solution be
Grams/liter -comes alkaline during the precipitation, basic iron
Copper--------------------------------- 100. compounds may be precipitated. Such com
Tron------------------------------------ 0:1 pounds may be redissolved by subsequent acidifi
20. NaCl-----------------------------------260 cation but the solution thereof often is somewhat 20
NaHSO3-------------------------------- 3 to 5 slow and uncertain; I therefore prefer to keep
A300solution of sodium cyanide containing 250 to the solution in an acid condition at all times. . .
grams of NaCN per liter is gradually added to Although Ihayeidescribed my process with pare
the above solution with constant agitation until aticular
raw
reference to the use of cuprous chloride as 25
material, I may also use other cuprous
the concentration of copper remaining in solution salts or cupric salts in conjunction with suitable
is approximately 1 gram per liter. During the reducing agents. It is necessary only that cur
addition of the sodium cyanide small amounts of prous ions and chloride ions also be present dur
sodium bisulfite are added to the reaction mixture ing the addition of cyanide in order to provide 30
from time to-time as required in order to have a the necessary cuprous choride in the motheriquor
certain amount of SO2 present at all times. Dur to prevent precipitation of iron cyanogen com:
ing the precipitation, the heat of reaction is suffi pounds. . . . . . . . . . . . . . . . .
cient to raise the temperature of the reacting The process of my invention makes it possi
mixture to 60 to 80°C. The precipitated cuprous ble to utilize the cheapest sources of copper for
cyanide is filtered off and washed, first with hot the production of a highly pure cuprous cyanide. 35
water containing approximately 4% HCl, then The process involves only...a single precipitation.
With hot water until the filtrate is substantially step and may be carried out with a minimum of
free from chlorides. The washed product is labor and equipment. For these reasons it af
dried at 110° C. : . . .. . .. . . . ..
Cuprous cyanide prepared in the above manner of fords a more convenient and economical method
preparing
is pure white to light cream in color and contains posed cuprous cyanide than has been pro-
heretofore. . . . . . . . . . . . . .
40
over 99.3% cuprous cyanide.
The concentration of acid required in the reac I claim: . . .. . . .
tion medium in order to carry out my invention 1. A method of producing cuprous cyanide
45 may vary considerably. As little as 0.05% free which comprises providing an impure acidic so
lution of cuprous: chloride containing an iron
HCl is generally sufficient to give a good product compound
from raw materials containing the usual amounts alkali metaland adding thereto a solution of an
of iron as impurity. In general I prefer not to cipitate cuprous cyanidesuch
cyanide-in quantity as to pre
and leave in solution a
exceed an acidity equivalent to about 1%.HCl, as concentration of unreacted cuprous chloride
50 with higher acidities the cuprous cyanide is ap equivalent to 0.5 to 5 grams of copper per liter, 50 - -

preciably soluble and some HCN may be evolved while maintaining an acidity equivalent to 0.05
in the course of the reaction. I have found it
advantageous to keep the reaction medium in an to 1% by weight of hydrogen chloride in said so
lution and removing precipitated cuprous cyanide
acid condition, preferably by the use of an acid
salt which exerts a buffer action on the solution from said solution. - . . .. .
55 - - . -
2. Method of producing cuprous cyanide which 55
and thereby facilitates keeping the solution in ancomprises providing an impure acidic solution of
acid condition without exceeding the limits of cuprous chloride containing an iron compound
acidity which result in HCN evolution. I prefer and adding thereto a solution of an alkali metal
to use for this purpose an alkali metal bisulfite cyanide in such quantity as to precipitate cuprous
60 which has the additional advantages that the cyanide and leave in solution a concentration of
odor of SO2 provides a convenient method of de cuprous chloride equivalent to 0.5 to 5 grams of
tecting the acid condition of the solution and copper per liter while maintaining said solution
furthermore, the presence of SO2 in the solution in an acidic condition by the addition of suitable
:
prevents or counteracts atmospheric oxidation of quantities of an acidic reducing agent and re
65. the cuprous salt. In place of or in addition to the moving precipitated cuprous cyanide from said
bisulfite, gaseous SO2 may be passed into the solu
tion or other known buffering agents may be used. solution. .. .. . . . . . . . .
3. Method of producing cuprous cyanide which
The use of a reducing agent such as sulfur di comprises providing an impure acidic solution of
oxide or a bisulfite may be dispensed with. How cuprous chloride containing an iron compound
ever, if reducing agents are not used, I prefer to and adding thereto a solution of sodium cyanide'
keep the reacting solution out of contact with air in such quantity as to precipitate cuprous cyanide
to prevent the formation of cupric compounds by and leave in solution a concentration of cuprous
atmospheric oxidation.
The amount of excess cuprous chloride required chloride equivalent to 0.5 to 5 grams of copper
75. to prevent precipitation of iron compounds varies per liter, while maintaining said solution in an
acidic condition by the addition of suitable quan
 2,049,858 3
tities of sulfur dioxide and removing precipitated by the addition of an alkali metal cyanide to a
CuproS Cyanide from Said Solution, cuprous chloride Solution, the method compris
4. Method of producing cuprous cyanide which ing maintaining said solution in a state of acid
comprises providing an impure acidic solution ity and maintaining an excess of cuprous chlo
Containing cuprous chloride containing an iron ride equivalent to at least 0.5 gram of copper per
Compound and alkali metal chloride and adding liter in Said solution during the entire course of
thereto a Solution of Sodium cyanide in such Said addition of cyanide.
quantity, as to precipitate cuprous cyanide and 6. In a process for preparing cuprous cyanide
leave in solution a concentration of cuprous by the addition of an alkali metal cyanide to a
O chloride equivalent to at least 0.5 gram of copper Solution of a cuprous salt, the method comprising O
per liter While maintaining the Solution in a con maintaining Said solution in a state of acidity and
dition of acidity and preventing substantial oxi maintaining an excess of dissolved cuprous salt
dation of cuprous compounds by suitable additions equivalent to at least 0.5 gram of copper per liter
of a reducing agent and removing precipitated in Said solution during the entire course of Said
5 cuprous cyanide from said solution. addition of cyanide. 5
5. In a proceSS for preparing cuprous cyanide CHARIES DANGEL.MAJER,