Patented Jan.

16, 1940 2,187,108

UNITED STATES PATENT OFFICE

2,187,108
PROCESS OFPURIFYING LEAD NTRATE
SOLUTIONS
Bodine Brinton Barrett, Newark, N.J., assignor to
E. I. du Pont de Nemours & Company, Wil
mington, Del, a corporation of Delaware
No Drawing. Application May 27, 1938,
Serial No. 210,429
- 5 Claims. (C. 23-102)
This invention relates to the purification of provide a novel and efficient method for purify
Solutions of lead nitrate, and more particularly ing solutions of lead nitrate in order to render
to the removal of metallic impurities from said them useful in the production of lead chromate
Solutions. pigments. A further and specific object includes
s The presence of metallic impurities, such as the provision of a proceSS adapted to effectively
copper, bismuth and antimony, in metallic lead remove objectionable quantities of soluble copper
is well known and numerous metallurgical meth Salts present in Such solutions. A still further
ods of purification have been proposed. Several object is to effect removal of other metallic im
Such methods are in common commercial use, but purities therefrom, as for instance traces of solu
16the best purified pig lead still contains minute ble Salts of iron, bismuth and antimony. 10:
traces of Such impurities. These and other objects are accomplished in
In the manufacture of lead chromate pigments, my invention which broadly comprises adding
such as chrome yellow, chrome orange, and a soluble ferro-cyanide to a solution of lead ni
chrome greens, it is customary to use a soluble trate containing metallic impurities as soluble
15 salt, such as lead nitrate, as a starting material. Salts, thereby precipitating such impurities out 15.
This is usually prepared by corroding metallic of said solution, and then removing the resultant
lead in the presence of aqueous Solutions of nitric precipitate and recovering the lead nitrate in
acid. Such process carries into solution metallic purified condition.
In a more specific embodiment, the invention
impurities, Such as copper, bismuth, antimony
20 and occasionally iron, which are harmful to the comprises treating at elevated temperatures a 20
relatively impure lead nitrate solution with an
production of satisfactory lead chromate pig exceSS proportion of a soluble ferro-cyanide such
ments. Copper is especially deleterious and ob
jectionable since it exerts an extremely harmful as sodium ferro-cyanide to precipitate the metal
effect on the resulting lead chromate pigments, lic impurities present in said solution, removing.
25 when present in amounts to as low as about the resultant precipitate and recovering the lead 25
0.01% by weight, on the basis of the lead present. nitrate solution in a purified state.
- Warious manufacturing operations exist from In order that the invention may be more
which impure lead residues, as by-products, are clearly understood, the following specific example
obtained, and which offer attractive economies for is given, Said example to be taken as in no wise
30, pigment production. However, these residual lead. in limitation of the scope or underlying principles 30
sludges usually contain a relatively high impurity of my invention:
content, the copper portion thereof ranging to as Eacample. I
high as about 3% or higher by Weight on a 100 gallons of lead nitrate solution (specific
lead basis. Heretofore, no practical method of gravity 1.215) containing approximately 21%
35, using these low cost lead residues in the manu Pb(NO3)2 by weight is determined by analysis 35.
facture of lead chromates has been available and to contain 0.045% copper by weight in solution
consequently it has been very difficult, if not im (0.34% by weight on the basis of metallic lead),
possible, to employ them in such manufactures. or slightly less than 0.5 pound copper. To this
Processes proposed for effecting impurity removal, solution is added 4.3 pounds of sodium ferro 40... .
40 particularly copper, from such residual lead ni cyanide (yellow prussiate of soda or
trate solutions include the introduction of metal
lic lead into the vats. This method, although Na4Fe(CN)6.10H2O)
theoretically attractive, suffers from Serious defi
ciencies when an attempt is made to adopt the The addition is carried out over a period of about
45: same on a commercial scale. Principally, it is 30 minutes at a temperature of about 150°F. 45,
very difficult in such processes to obtain the When a suitable control test shows the substan
proper contact of the impure Solution with the tial absence of copper from Solution, the precipi
free metal in an economically feasible period of tate is removed by filtration and the clear lead
time. Furthermore, as a layer of impurity builds nitrate is run to storage for use as desired.
50, up on the lead, the rate of reaction, which at Analysis shows the amount of copper remaining 50
best is slow, decreases very rapidly. Other meth to be about 0.0001% by weight on a". solution basis
ods such as electrolytic purification have likewise (0.000.7% on a lead basis). .
proved slow, expensive and inefficient. . . The precipitate is found to contain a Substan
It is, accordingly, among the objects of this tial amount of lead, equivalent roughly to ten
as invention to overcome these difficulties and to pounds of lead nitrate lost for every pound of. 55
 2 2,187,108
Copper removed from Solution and corresponding used herein, is to be construed in its broadest
to a yield OSS of about 2.5%. Sense and to include other types of ferrocyanides,
The ferocyanideS of time various netals inen Such as those of potassium or calcium, as well
tioned, Viz., lead, copper, bismuth, antimony and as those which are ordinarily considered insolu
iron are known to be relatively insoluble in water. ble. In the use of Such ferrocyanides, the effect
Data, as to actual Solubilities are not clear cut of contaminating ion introduction into the lead
and are CCnfused by the tendency of ferocyanides nitrate must also be considered and in the light
to forI) gelatitious precipitates of uncertain con Of the Subsequent use of the purified material.
stitution. Theoretically, a precipitate obtained For instance, if it is desired to completely elimi
10 by adding a Soluble ferrocyanide to a lead nitrate. . nate the effect of the contanninating ion, such O
Solution containing one or more of the above as the Sodium ion, it is possible to effect the re
contaminating metals should be a mixture of the InOVal of the copper or otheir metallic impurity by
Various in Soluble ferocyanides in proportions adding a freshly prepared and washed slurry of
determined by the relative conceintrations of the lead fel'rocyanide to the lead nitrate Solution.
5 Sats in the original Solution and by the Solt Although this method eifects an efficient renoval 5
bilities of the severai ferrocyanides. of the copper, it involves an extra operation and
The following reactions are typical of those is, therefore, not ny preferred procedure.
which may be pi'esumed to take place: The conditions of temperature, time of addition
Of the ferrocyanide, rate of agitation and the
20 like" are also non-critical and are largely deter 20
mined by the condition of the precipitate and its
Pb2Fe(CN)6-4. NaNO3 ease of filtration. At best, it is a Slimy material
However, it is highly probable that the insolubie and somewhat difficult to filter and the conditions
25, precipitate is not composed of a mixture of the described are those which have been found to
pure Cheninical compounds which the formulaS be most conducive to the formation of a readily
would indicate. I am Linable to determine its filterable precipitate.
exact composition beyond the fact that it con Although throughout the description of the
tains a relatively large proportion of lead to the invention, the removal of copper from lead ni
other metals. Nevertheless this loSs - of lead is trate Solutions has been StreSSed, removal of
30, relatively Small compared with the importance other metallic impurities therefrom, notably iron, 30,
of the removal of the copper and other contami bismuthnitrate
and antimony, frequently present in lead
froin impure Sources of lead, is contem
nating metals from tie Solution.
Therefore, I have found it, preferable to employ plated. I have found that my purification step
35
a relatively small excess of Soluble ferrocyanide removes bismuth and antimony equally as well
Over the theoretical amount indicated by reac as it removes copper and, furthermore, that it 35
tion (i) above, and that Such Small excess will removes a large part of the iron. A slight modi
Suffice to remove the copper and other contam fication. Such as the adjustment of the hydro
inating metals from the solution. Generally, gen ion concentration to a value lower than that
represented by a pH of 4.0 will effect complete
from about 1.25 to about 2.5 times the theoretical
40. amount of ferrocyanide appears to be the op renoval of the iron.
timum for effecting removal of Substantially all It will be apparent from the foregoing that
the copper without an excessive loss of lead. the present invention affords a novel method
Thus, although the Sodium ferocyanide used in for preparing lead nitrate from contaminated,
the above example corresponds to 2.5 times the impure residues whereby. Said nitrate is rendered
45 theoretical amount necessary to remove the cop fit for use in the production of lead chromate
per present, this may ce further reduced to as pigmentS. The product recovered Will be in rela
low as 1.25 times the theoretical with a very good tively pure condition and free from objectionable
purification and a somewhat lower loss of lead quantities of contaminating metallic impurities,
nitrate. Although the degree of purification is particularly copper, which WOuld otherwise in
50 slightly less than . With the larger amount of hibit the use of Such residues in pigment pro
ferrocyanide, it is frequently Sufficient and ques duction.
tions of economy make the lower excess prefer I Clain as my invention:
able in Sone cases. AS already indicated, llow l. A method for purifying lead nitrate through
ever, as the amount of impurities increase, it will removal of copper impurities present therein and
55 be found desirable to use larger amounts of While avoiding any substantial loss of lead, com
ferrocyanide. In a given instance, the optimulin prising Subjecting a Solution of lead nitrate, to
ratio of soluble ferrocyanide to the theoretical reaction. With a Soluble ferocyanide from the
can be easily disternined by experiment. Lower group consisting of alkali and alkaline earth
and higher amountS can be employed and With metal ferrocyanides, employing an excess amount
60: Successful results. Generally, lower aii Cunts will Of Such ferrocyanide ranging from about 1.25, to
not effect as complete renova. Of the Soluble about, 2.5 times that Stoichiometically required
copper or other metallic inpurities, while higher to precipitate the copper as cupric ferrocyanide,
amounts tend to effect undesired lead nitrate and separating the purified lead nitrate from the
losses. A useful and preferable upper limit com reaction precipitate.
65 prises that already mentioned, i. e., not to exceed 2. A method for purifying lead nitrate through
about 2.5 times the theoretical required. removal of Copper imprities present therein and
AS Will be apparent, the conditions Specified While avoiding any Substantial loss of lead, com
hereinabove and in the foregoing example are prising Subjecting a Solution of lead, nitrate to
not generally critical and variance therefrom reaction with a Soluble Sodium ferrocyanide, em
70 ploying an excess amount of Such ferrocyanide 70.
may be suitably had. Similarly, the type cf. Solu
ble ferrocyanide employed in the invention is ranging from about 1.25 to about 2.5 times that
relatively unimportant, economic considerations Stoichiometrically required to precipitate the cop
Suggesting Sodium ferrocyanide aS most feasible per aS Cupric ferrocyanide, and separating the
due to its ready availability and inexpensiveness. Efied lead nitrate from the reaction precipi
Accordingly, the term. 'Soluble ferrocyanide', as ate.
 2,187,108 3
3. A method for treating copper-containing of Said ferrocyanide ranging from about 1.25 to
lead nitrate to purify the same by removing about 2.5 times that stoichiometrically required
metallic impurities present therein while avoiding . to precipitate the copper as cupric ferrocyanide,
any Substantial loss of lead, comprising treating heating the resultant mixture to precipitate said
a lead nitrate solution with a soluble ferrocyanide metallic inpurities, and separating the purified
from the group consisting of alkali and alkaline lead nitrate from the reaction precipitate.
earth metal ferrocyanides, employing in such 5. A method for treating copper-containing
treatment an excess amount of said ferrocyanide lead nitrate to reduce the amount of metallic
ranging from Substantially 1.25 to about 2.5 impurities present therein below substantially
O times that stoichiometrically required to pre 0.01%, based on the weight of the lead, while O
cipitate the copper as cupric ferrocyanide, and avoiding any substantial loss of lead, comprising
Separating the purified lead nitrate from the adding to a lead nitrate solution a Solubie Sodium.
reaction precipitate. ferrocyanide in excess proportion ranging from
4. A method for treating copper-containing about 1.25 to about 2.5 times that stoichiomet
5 lead nitrate to purify the same by removing me rically required to precipitate the copper as 15
tallic impurities present therein while avoiding cupric ferrocyanide, heating the resultant mix
any Substantial loss of lead, comprising subject ture to effect precipitation of said metallic im
ing a lead nitrate solution to treatment with a purities, and separating the purified lead nitrate
Soluble ferrocyanide from the group consisting from the reaction precipitate.
of alkali and alkaline earth metal ferrocyanides, 20
employing in Such treatment an excess quantity BOOINE. B. BARRETT.