Sulfonylhydrazines, metal complexes thereof, and solutions containing such compounds for use in extraction of metal values

Certain sulfonylhydrazines, metal complexes thereof and solutions of said compounds in essentially water-immiscible, liquid hydrocarbon solvents are disclosed. The sulfonylhydrazines have the general structural formula: EQU R--SO.sub.2 NHNH--R.sub.1 wherein R and R.sub.1 are as defined in the specification and claims hereof. Particular metal values are recovered from their aqueous solutions by using sulfonylhydrazines dissolved in essentially water-immiscible, liquid hydrocarbon solvents. The extraction process involves contacting the metal value containing aqueous solution with the solution of the sulfonylhydrazines in essentially water-immiscible, liquid hydrocarbon solvent and stripping the metal from the loaded organic phase.

The present invention is directed to novel sulfonylhydrazines, organic 
solvent solutions thereof, metal complexes of such sulfonylhydrazines, 
organic solvent solutions of such complexes and the method of using said 
sulfonylhydrazines to extract metal values from aqueous solution. 
Liquid ion exchange recovery of metal values from aqueous solutions thereof 
has in the past ten years or so become a mature commercial operation. 
Briefly, liquid ion exchange processes function by transfering a metal 
value from Phase A (aqueous) to Phase B (organic) and thence from Phase B 
to Phase C (aqueous). However, complexities of liquid ion exchange arise 
in a number of areas including (1) synthesis and manufacture of the 
reagent system, (2) evaluation of the system's capabilities and (3) 
engineering application leading to large scale metal recovery. 
The key to a successful application of liquid ion exchange is the reagent. 
In this respect, the reagent should desirably meet a number of criteria. 
In the first instance, the reagent should complex with or react with a 
metal or group of metals and such complexing or reaction should be 
relatively fast in order to avoid having to use large holding tanks or 
reaction vessels. It is also desirable that the reagent exhibits 
preference for a single metal where the aqueous starting solutions contain 
a number of metal values. Such selectivity can often be optimized at 
designated pH ranges. The reagent should also desirably complex or react 
quantitatively with the metal under the extraction conditions. 
Additionally, the reagent, as well as the resulting metal complex, must 
exhibit satisfactory solubility in the essentially water-immiscible 
organic solvent being used. Further, the reagent-metal reaction or 
complexing should be reversible so that the metal can be stripped from the 
organic phase. For economic reasons, the reagent should be relatively 
stable so that it can be recycled repeatedly. Also, it should be 
essentially water insoluble to prevent significant loss into the aqueous 
phase or phases. Furthermore, the reagent should not cause or stabilize 
emulsions. Again and principally for economic reasons, the reagent should 
not react with or load significant quantities of acid, for example, from 
aqueous acidic stripping solutions. And, of course, the cost of the 
reagent should be such that the liquid ion exchange process can be 
operated at a profit. 
Of significant, but lesser, importance, is the selection of the essentially 
water-immiscible solvent to be used in the liquid ion exchange process. 
Such selection is important principally from a cost standpoint, especially 
in the recovery of the more common metals. Existing commercial operations 
for copper recovery, for example, generally employ aliphatic kerosenes 
because of the low cost thereof. Thus, the cost of the reagent and the 
solvent is intertwined in providing the desired overall economics of the 
process being commercialized. 
One of the most extensively used systems in commercial operation in the 
last decade for copper recovery has employed benzophenoximes or 
combination reagents including a benzophenoxime component. While being 
economic, improvements can be made since the said benzophenoximes do not 
have total selectivity for copper over iron, for example. Other types of 
reagents have been proposed for use in copper recovery including the 
alkenyl substituted 8-hydroxyquinolines. 
It has now been discovered that certain novel sulfonylhydrazines, as more 
fully defined hereinafter, are useful in liquid ion exchange recovery 
processes. The new compounds of the present invention are represented by 
the following general structural formula: 
EQU R--SO.sub.2 NHNH--R.sub.1 
wherein R is a radical selected from the group consisting of alkyl, aryl, 
alkarayl and aralkyl, in which the alkyl groups are linear or branched 
chain and wherein R.sub.1 is a heterocyclic radical selected from the 
group consisting of pyridine, quinoline and benzothiazole. The linear or 
branched chain alkyl groups will generally contain from 1 to 20 carbon 
atoms. Moreover, it is generally preferred that the compounds of the 
invention possess at least one alkyl group containing at least eight 
carbon atoms. Dodecylbenzene is typical of the preferred groups 
represented by R in the general structural formula. 
The compounds of the present invention are also characterized as having 
solubilities in essentially water-immiscible liquid hydrocarbon solvents 
of at least 2% by weight. Correspondingly, they are further characterized 
in that the copper (Cu++) complexes of the compound have solubilities of 
at least 2% by weight in the said water-immiscible, liquid hydrocarbon 
solvents. Especially preferred compounds of the invention are those which 
exhibit solubilities of at least 2% by weight in both pure and complexed 
form, in aliphatic or aromatic hydrocarbons, or mixtures thereof, having 
flash points of at least 150.degree. F. Thus, the compounds of the 
invention may preferably be further characterized as having substituents 
containing a sufficient number of carbon atoms and/or branching in the 
alkyl chains to provide at least the minimum 2% solubility in the 
aforementioned solvents. 
The aforementioned preference for alkyl substituents containing at least 8 
carbon atoms and/or possessing a branched chain structure is due to their 
contribution to the solubilities of the compounds in the above-described 
solvents. The beneficial effect provided by the number of carbon atoms is 
obtained by having an alkyl substituent of at least 8 carbon atoms or more 
than one alkyl substituent in which the sum of the carbon atoms is at 
least 8. Accordingly, the most preferred compounds of the present 
invention are those possessing one or more branched chain alkyl 
substituents having at least 8 carbon atoms or those possessing branched 
chain alkyl substituents in which the sum of the carbon atoms is at least 
8. 
Thus, according to preferred embodiments, the sulfonylhydrazines of the 
invention have the general structural formula: 
##STR1## 
wherein R.sub.1 is as previously defined and R.sub.2 is a linear or 
branched chain alkyl containing at least 8 carbon atoms. Of these 
compounds those in which R.sub.2 is dodecyl have been found to be 
particularly effective in extracting metal values from aqueous solutions. 
Typical of these compounds are 
2-(dodecylbenzenesulfonylhydrazino)-pyridine having the structure: 
##STR2## 
2-(dodecylbenzenesulfonylhydrazino)quinoline having the structure: 
##STR3## 
8-(dodecylbenzenesulfonylhydrazino)quinoline having the structure: 
##STR4## 
and 2-(dodecylbenzenesulfonylhydrazino)benzothiazole having the structure: 
##STR5## 
However, it should be understood that as the utility of the compounds of 
the invention resides in their ability to extract metal values from 
aqueous solutions, various substituents which do not interfere with 
chelation may be appended without departing from the scope of the 
invention. Illustrative of such substituents are electron withdrawing 
groups, e.g., halogen nitrile, nitro, trifluoromethyl, ester and the like. 
Additionally, certain other radicals may be substituted for those 
described above as R.sub.1 notably 2-hydroxyethyl, --CH.sub.2 CH.sub.2 OH. 
However, for purposes of this application, the heterocyclic species is 
preferred. 
The sulfonylhydrazines of the invention are prepared by reaction of the 
appropriate hydrazines with a substituted sulfonyl chloride according to 
the reaction: 
EQU R.sub.1 --NHNH.sub.2 +R--SO.sub.2 Cl.sub.pyridine R--SO.sub.2 
--NHN--R.sub.1 
The substituted sulfonyl chloride may be prepared from substituted sulfonic 
acids by reaction with thionyl chloride. In the Examples which follow the 
dodecylbenzenesulfonylchloride was prepared as in Example I-A of U.S. Pat. 
No. 4,100,163, the disclosure of which is incorporated herein by 
reference. 
Further details of the synthesis of the compounds of the invention are 
found in the Examples which follow the description of the invention. 
The process of the present invention is a liquid ion exchange process in 
which any one of the sulfonylhydrazine compounds of the invention is 
dissolved in an essentially water-immiscible, liquid hydrocarbon solvent 
and the resulting solution is contacted with a metal containing aqueous 
phase to extract at least a portion of the metal values into the organic 
phase. The phases are then separated and metal values are stripped from 
the loaded organic phase by use of an aqueous stripping medium. 
A wide variety of essentially water-immiscible, liquid hydrocarbon solvents 
can be used in the metal recovery process of the present invention. These 
include: aliphatic and aromatic hydrocarbons such as kerosenes, benzene, 
toluene, xylene and the like. The choice of the said essentially 
water-immiscible liquid hydrocarbon solvent for particular commercial 
operations will depend on a number of factors including the design of the 
solvent extraction plant (i.e., mixer-settlers, Podbielniak extractors, 
etc.), the value of the metal being recovered, disposal of plant effluent 
and the like. The process of the present invention finds particular use in 
the extraction recovery of the major, non-ferrous, transition 
metals--i.e., copper, nickel, zinc, cobalt(II) and cobalt(III), as will be 
described more fully hereinbelow. Essentially, all of the major plants in 
operation currently for the recovery of these metals (particularly Cu++) 
use mixer-settlers, with relatively large organic inventories and some 
loss of solvent invariably occurs by evaporation, entrainment in the 
aqueous and the like. Under these circumstances, preferred solvents for 
use in the metal recovery processes of the present invention are the 
aliphatic and aromatic hydrocarbons having flash points of 150.degree. F. 
and higher and solubilities in water of less than 0.1% by weight. These 
solvents are also essentially non-toxic and chemically inert and the costs 
thereof are currently within practical ranges--i.e., normally less than 
one dollar (U.S.) per gallon to as low as thirty cents (U.S.) or so. 
Representative commercially available solvents are Kermac 470B (an 
aliphatic kerosene available from Kerr-McGee--Flash Point 175.degree. F.), 
Chevron Ion Exchange Solvent (available from Standard Oil of 
California--Flash Point 195.degree. F.), Escaid 100 and 110 (available 
from Exxon-Europe--Flash Point 180.degree. F.), Norpar 12 (available from 
Exxon-U.S.A.--Flash Point 160.degree. F.), Conoco C-1214 (available from 
Conoco--Flash Point 160.degree. F.), Aromatic 150 (an aromatic kerosene 
available from Exxon-U.S.A.--Flash Point 150.degree. F.) and various other 
kerosenes and petroleum fractions available from other oil companies. 
The present invention thus additionally relates to new compositions wherein 
the sulfonylhydrazine compounds of the invention are dissolved in the 
essentially water-immiscible, liquid hydrocarbon solvents described above. 
In this regard, liquid ion exchange reagents are often sold as solutions 
in organic solvents. These new compositions consist essentially of 
solutions of at least 2% by weight of the sulfonylhydrazines in 
essentially water-immiscible, liquid hydrocarbon solvents. When sold as 
concentrates, the solutions will preferably contain from about 25 to 75% 
by weight of the sulfonylhydrazines. 
In the process of the present invention, the organic solvent solutions will 
preferably contain from about 2 to 75% by weight of the sulfonylhydrazine 
compounds and even more preferably from about 5 to 20% by weight thereof. 
Additionally, volume ratios of the organic:aqueous phase vary widely since 
the contacting of any quantity of the reagent solution with the metal 
containing aqueous phase will result in extraction of metal values into 
the organic phase. However, for commercial practicality, the 
organic:aqueous phase ratios are preferably in the range of about 5:1 to 
1:5. For practical purposes, the extracting and stripping are normally 
conducted at ambient temperatures and pressures although higher or lower 
temperatures and/or pressures are entirely operable. Most advantageously, 
the entire process can be carried out continuously with the stripped 
organic solvent solution being recycled for contacting further quantities 
of metal containing solutions. 
The present invention also relates to the metal complexes of the 
sulfonylhydrazine compounds and to the essentially water-immiscible, 
liquid hydrocarbon solvent solutions thereof. The solutions consist 
essentially of the said solvent and at least 2% by weight, and preferably 
less than 75% by weight, of the metal complexes. While not normally 
practiced in the industry, the solutions of the metal complexes can be 
obtained at one location and transported to another for stripping as 
hereinafter described. The term "metal complex" as used herein is meant to 
connote compositions of the sulfonylhydrazines with other than 
insignificant quantities of metal ions. Although the exact structural 
nature of these complexes has not been ascertained, indications are that 
under conditions of maximum loading, particularly with Cu++ and Zn++ metal 
ions, the complexes comprise the metal and sulfonylhydrazine compound 
generally in a molar ratio of 1:2. Maximum loading, however, is not 
required for achieving acceptable performance in liquid ion exchange 
processes and hence the metal complexes are generally defined as including 
the designated metals in more than insignificant quantities up to maximum 
loading. 
The metal recovery process of the present invention is useful for the 
recovery of the following metal values from their aqueous solutions: Cu++, 
Ni++, Zn++, Co++ and Co+++. These metal values are all transition metals 
in Groups Ib, IIb, and VIII. The extraction of these various metals from 
aqueous solutions depends upon a number of factors, including, for 
example, the concentration of the metal ion, the particular anions 
present, and the pH of and/or ammonia concentration in the aqueous 
solutions, as well as the particular sulfonylhydrazine selected and its 
concentration in the organic phase. Generally, it is preferred to extract 
the metal values from ammoniacal solutions in which the preferred 
concentrations of ammonia is from about 10 to 150 g/l. However, it is 
understood that for each aqueous metal solution and reagent solution there 
will be a preferred or optimum set of extraction conditions, and those 
skilled in the art, based on the information given herein, especially in 
the examples to follow, will be able, after a limited number of trial 
runs, to determine such preferred or optimum conditions for the respective 
systems under consideration. This is equally true of the stripping 
operations. By the term "stripping" is meant the transfer of at least a 
portion of the metal values in the loaded organic phase to the aqueous 
stripping medium. The metal values so stripped are desirably recovered 
from the aqueous stripping medium by conventional techniques, preferably 
electrolysis. The volume ratios of loaded organic:aqueous stripping phase 
can also vary widely. However, the overall object of the process is to 
provide a metal containing stripping solution of known composition and 
concentration suitable for conventional recovery techniques such as 
electrolysis. Accordingly, the metal will preferably be present in higher 
concentrations in the aqueous stripping medium than in the strating metal 
containing solution. To accomplish this, the loaded organic:aqueous 
stripping medium phase ratio will normally be in the range of about 1:1 to 
10:1. The stripping medium is preferably an aqueous mineral acid solution 
such as 25 to 250 g/l H.sub.2 SO.sub.4. 
While the process of the present invention has been described as 
particularly effective in extracting Cu++, Ni++, Zn++, Co++ and Co+++, 
metal values from aqueous solutions, it may also be applied to extract 
other chemically similar metal values, such as Cd++, Hg++, Ag+ and Pb++. 
They have also been found to be mildly effective in extracting uranium, 
molybdenum, vanadium and iron. The process of the invention thus provide a 
simple, continuous method of extracting valuable metal values from aqueous 
solutions. Of equal importance is the economic advantages attendant from 
the process which allows the extracting reagent to be stripped of metal 
values and recycled for subsequent loading. 
To further illustrate various aspects of the invention, the following 
Examples are provided. However, it is understood that as their purpose is 
entirely illustrative, they are in no way intended to limit the scope of 
the invention.

EXAMPLE 1 
Preparation of 2-(dodecylbenzenesulfonylhydrazino)-pyridine 
Starting Materials: 2.4 g (0.022 mol) 2-hydrazinopyridine 6.9 g (0.02 mol) 
dodecylbenzenesulfonylchloride 2.5 g (0.025 mol) triethylamine 20 ml 
tetrahydrofuran 
To a solution of the dodecylbenzenesulfonylchloride in 10 tetrahydrofuran 
was added a solution of the hydrazinopyridine and triethylamine in 10 ml 
tetrahydrofuran. The reaction mixture was maintained below 10.degree. C. 
in an ice bath until the addition of the second solution was complete and 
thence for 30 minutes longer while the mixture was continuously stirred. 
The mixture was then treated with Skelly B solvent. The Skelly B solution 
was washed three times with an aqueous solution of sodium chloride, dried 
over magnesium sulfate, filtered and evaporated to give 8.2 g of a dark 
orange syrup. Nuclear magnetic resonance (NMR) and infra-red (IR) analysis 
confirmed the product to be 2-(dodecylbenzenesulfonylhydrazino)pyridine. 
EXAMPLE 2 
Preparation of 2-(dodecylbenzenesulfonylhydrazino)-quinoline 
Starting Materials: 3.1 g (0.02 mol) of 2-hydrazinoquinoline 6.9 g (0.02 
mol) dodecylbenzenesulfonylchloride 40 ml tetrahydrofuran 4 ml 
dimethylformamide 2.5 g (0.025 mol) triethylamine 
To a solution of the sulfonyl chloride in 10 ml tetrahydrofuran was added a 
solution of the hydrazinoquinoline and triethylamine in 30 ml 
tetrahydrofuran (4 ml dimethylformamide was included to aid solubility). 
The temperature of the reaction mixture was maintained below 10.degree. C. 
during the addition and for 30 minutes thereafter while the mixture was 
continuously stirred. The product was recovered as in Example 1 yielding 
8.4 g of a tan solid. NMR and IR analysis confirmed the product to be 
2-(dodecylbenzenesulfonylhydrazino)quinoline. 
EXAMPLE 3 
Preparation of 8-(dodecylbenzenesulfonylhydrazino)-quinoline 
Starting Materials: 3.2 g (0.02 mol) 8-hydrazinoquinoline 6.9 g (0.02 mol) 
dodecylbenzenesulfonylchloride 2.5 g (0.025 mol) triethylamine 30 ml 
tetrahydrofuran 
The starting materials were combined as in the previous Examples and the 
resulting reaction mixture was stirred for one hour while being maintained 
at a temperature below 10.degree. C. Diethyl ether and water were added, 
the layers were separated and the aqueous layer was extracted with diethyl 
ether. The organic solutions were then combined, washed twice with a 6% 
ammonia solution, three times with an aqueous sodium chloride solution, 
dried over magnesium sulfate, filtered and evaporated to give 8.2 g of a 
dark red syrup. NMR and IR analysis confirmed the product to be 
8-(dodecylbenzenesulfonylhydrazino)quinoline. 
The 8-hydrazinoquinoline was prepared by the method of A. Krasavin, et al., 
Metody Polucheniya Khim. Reaktivov i Preparatov, Gos. Kom. Sov. Min. SSSR 
po Khim., No. 7, 5(1963) as described in Chem. Abstr., 61, 3070 (1964). 
Preparation of 8-Hydrazinoquinoline 
Starting Materials: 72.6 g (0.5 mole) 8-hydroxyquinoline 165.0 g (5.0 mole) 
hydrazine, 97% 85.0 g (4.7 mole) water 
A solution of hydrazine in water (equivalent to 250 ml of 100% hydrazine 
hydrate) was added to the 8-hydroxyquinoline and the mixture was refluxed 
under nitrogen for 68 hours. After cooling to about 40.degree. C., brine 
was added and the mixture was extracted with benzene. The benzene solution 
was washed once with brine, three times with Claisen's alkali (prepared by 
dissolving 35 g of potassium hydroxide in 25 ml of water, cooling, and 
adding 100 ml of methanol), twice again with brine, dried over magnesium 
sulfate, filtered and evaporated to give 60.0 g of an orange oil which 
crystallized on standing. IR and NMR analysis confirmed the product to be 
8-hydrazinoquinoline. 
EXAMPLE 4 
Preparation of 2-(dodecylbenzenesulfonylhydrazino)-benzothiazole 
Starting Materials: 3.3 g (0.02 mol) 2-hydrazinobenzothiazole 6.9 g (0.02 
mol) dodecylbenzenesulfonylchloride 2.5 g (0.025 mol) triethylamine 35 ml 
dimethylformamide 
To a solution of the sulfonylchloride in 10 ml dimethylformamide was added 
a solution of the hydrazinobenzothiazole and triethylamine in 25 ml 
dimethylformamide. The temperature of the reaction mixture was maintained 
below 10.degree. C. during the addition and for 30 minutes thereafter 
during which time it was continuously stirred. The product was recovered 
in the manner described previously in Examples 1 and 2. Nmr and IR 
analysis confirmed the product to be 
2-(dodecylbenzenesulfonylhydrazino)-benzothiazole. 
EXAMPLE 5 
Extraction of Metal Values 
To determine the ability of the various sulfonylhydrazine compounds of the 
present invention to extract metal values from aqueous solutions, tests 
were conducted in accordance with the following procedures. 
A 0.1 molar solution of a sulfonylhydrazine compound in an identified 
essentially water-immiscible liquid hydrocarbon solvent and five aqueous 
solutions of the following compositions were used: 
______________________________________ 
Metal Composition 
______________________________________ 
Cu.sup.++ 0.05 M CuSO.sub.4 (3.2 g/l Cu.sup.++), 
0.4 M NH.sub.3, and 0.1 M (NH.sub.4).sub.2 SO.sub.4 
Ni.sup.++ 0.05 M NiSO.sub.4 (2.0 g/l Ni.sup.++), 
0.4 M NH.sub.3, and 0.1 M (NH.sub.4).sub.2 SO.sub.4 
Zn.sup.++ 0.05 M ZnSO.sub.4 (3.2 g/l Zn.sup.++), 
0.4 M NH.sub.3, and 0.1 M (NH.sub.4).sub.2 SO.sub.4 
Co.sup.++ 0.025 M CoSO.sub.4 (1.5 g/l Co.sup.++) 
1.7 M NH.sub.3, and 0.1 M (NH.sub.4).sub.2 SO.sub.4 
prepared as needed under an 
atmosphere of nitrogen 
Co.sup.+++ 0.25 M CoSO.sub.4 (1.5 g/l Co.sup.++), 
1.7 M NH.sub.3, and 0.1 M (NH.sub.4).sub.2 CO.sub.3 
(air oxidized to Co.sup.+++) 
______________________________________ 
Portions of the organic solution were shaken with the five aqueous 
solutions at an organic:aqueous phase volume ratio of 1:1 for one hour at 
ambient temperature. The organic phases were then analyzed for metal 
content. If a third phase was present, both the organic and aqueous phases 
were clarified and analyzed. Table A summarizes the data obtained from the 
extraction tests for various sulfonylhydrazine reagents of the present 
invention. In the table all concentrations are given in g/l. 
TABLE A** 
__________________________________________________________________________ 
REAGENT SOLVENT* 
[Cu++] 
[Ni++] 
[Zn++] 
[Co++] 
[Co+++] 
__________________________________________________________________________ 
2-(dodecylbenzene- 
sulfonylhydrazino)- 
Solvesso 150 
1.50 2.22 1.05 1.01 0.855 
pyridine 
2-(dodecylbenzene- 
sulfonylhydrazino)- 
Solvesso 150 
1.53 Aq. 0.900 
1.38 Aq. 0.013 
0.395 
quinoline 
(ppt'd after 1 week) 
8-(dodecylbenzene- 
sulfonylhydrazino)- 
Solvesso 150 
1.39 1.71 0.85 1.15 1.2 
quinoline 
2-(dodecylbenzene- 
sulfonylhydrazino)- 
Solvesso 150 
0.515 
1.09 2.28 0.97 0.596 
benzothiazole 
__________________________________________________________________________ 
*Solvesso 150 is an aromatic kerosene having a flash point of 150.degree. 
F. 
**All analyses on organic unless otherwise stated. 
EXAMPLE 6 
pH Isotherms 
To determine the extent of extraction of various metal ions as a function 
of pH, tests were conducted as follows. Portions of a 0.1 molar solution 
of a particular sulfonylhydrazine in an identified essentially 
water-immiscible liquid hydrocarbon solvent were shaken with aqueous 
solutions composed of equivolumes of the following components: 
Component A--0.2 M metal sulfate solution in water 
Component B--water or sulfuric acid or sodium hydroxide solutions ranging 
from 0.01 to 0.1 M 
Component B was selected in such a manner as to insure the desired pH of 
the aqueous raffinate. In each test, the organic solution and aqueous 
solution were shaken at an organic:aqueous phase volume ratio of 1:1 for 
one hour at ambient temperature. Subsequent analysis of the organic phase 
for metal content and the aqueous phase for pH generated the data 
contained in Tables B and C which demonstrates the degree of metal 
extraction as a function of pH for the particular reagent systems under 
study. In the Tables, concentrations are given in grams per liter unless 
otherwise indicated. 
TABLE B 
______________________________________ 
2-(dodecylbenzenesulfonylhydrazino)pyridine in 
Solvesso 150 
AQ AQ 
[Cu] pH [Ni] pH 
______________________________________ 
.018 .66 .009 .68 
.520 1.39 &lt;.005 1.44 
1.20 1.88 .021 3.88 
1.77 2.79 .980 5.77 
2.35 4.77 2.06 7.32 
______________________________________ 
TABLE C 
______________________________________ 
8-(dodecylbenzenesulfonylhydrazino)quinoline 
in Solvesso 150 
AQ 
[Ni] pH 
______________________________________ 
.007 .64 
.007 1.39 
.135 3.98 
1.73 5.55 
3.12 7.16 
______________________________________ 
EXAMPLE 7 
Ammonia Isotherms 
To determine the extent of extraction of various metal ions as a function 
of total ammonia concentration in the aqueous phase, tests were conducted 
in accordance with the following procedure. Portions of a 0.1 molar 
solution of a particular sulfonylhydrazine compound in Solvesso 150 
solvent were shaken at 1:1 organic:aqueous phase volume ratio for 
approximately one hour at ambient temperature with aqueous ammoniacal 
solutions containing a particular metal ion. The organic phase was then 
separated and analyzed for metal concentration, generating the data 
contained in Tables D, E and F which demonstrate the degree of metal 
extraction as a function of ammonia concentration for particular reagent 
systems. In the Tables, all concentrations are given in grams per liter. 
TABLE D 
______________________________________ 
2-(dodecylbenzenesulfonylhydrazino)pyridine 
in Solvesso 150 
[Cu] 
AQ % 
[NH.sub.3 ] 
Feed [Cu] Extraction 
______________________________________ 
15.1 .316 .322 100 
29.9 .311 .324 100 
55.4 .316 .314 99 
85.1 .314 .256 82 
104.0 .320 .168 52 
141.9 .343 .127 37 
______________________________________ 
[Ni] % 
[NH.sub.3 ] 
AQ Feed [Ni] Extraction 
______________________________________ 
15.1 .347 .300 86 
30.0 .357 .295 82 
60.0 .359 .305 85 
89.5 .369 .295 79 
118.0 .378 .262 69 
149.6 .374 .195 52 
______________________________________ 
TABLE E 
______________________________________ 
8-(dodecylbenzenesulfonylhydrazino)quinoline 
in Solvesso 150 
[Cu] 
AQ % 
[NH.sub.3 ] 
Feed [Cu] Extraction 
15.1 .316 .260 82 
29.9 .311 .210 67.5 
55.4 .316 .178 56 
85.1 .314 .148 47 
104.1 .320 .130 41 
141.9 .343 .108 31 
______________________________________ 
[Ni] % 
[NH.sub.3 ] 
AQ Feed [Ni] Extraction 
______________________________________ 
15.1 .347 .296 85 
30.0 .357 .270 75 
60.0 .359 .164 45 
89.5 .369 .092 24 
118.6 .378 .061 16 
149.6 .374 .038 10 
______________________________________ 
TABLE F 
______________________________________ 
2-(dodecylbenzenesulfonylhydrazino)benzothiazole in Solvesso 150 
% % 
[Ni] Ex- [Zn] Ex- 
AQ trac- AQ trac- 
[NH.sub.3 ] 
Feed [Ni] tion [NH.sub.3 ] 
Feed [Zn] tion 
______________________________________ 
15.1 .347 .300 86 14.4 .330 .305 92 
30.0 .357 .283 79 28.9 .332 .260 78 
60.0 .359 .205 57 58.3 .332 .121 36 
89.5 .369 .150 41 87.2 .332 .064 19 
118.6 .378 .086 23 116.2 .331 .044 13 
149.6 .374 .056 15 147.0 .331 0.27 8 
______________________________________ 
EXAMPLE 8 
Acid Stripping, Ammonia Loading and Acid Loading 
In order to determine (1) the extent of metal stripping as a function of 
acid concentration, (2) the extent of ammonia loading during extraction 
and (3) the extent of acid loading during stripping, the following tests 
were conducted. A 0.1 M solution of the particular sulfonylhydrazine 
compound in Solvesso 150 and aqueous solutions having the following 
compositions were prepared. 
(A) a 0.1 M metal sulfate, 0.6 M NH.sub.3 and 0.15 M (NH.sub.4).sub.2 
SO.sub.4 solution in water. 
(B) 0, 25, 50, 100 and 150 gpl H.sub.2 SO.sub.4 solutions in water. 
In the first step, the reagent solution was shaken with aqueous solution A 
at an organic:aqueous phase volume ratio of 1:2 for one hour at ambient 
temperature. The phases were separated and the loaded organic phase was 
contacted a second time as before with fresh aqueous solution A. The 
resulting organic phase was separated and analyzed for metal 
concentration. The loaded organic phase was then shaken with solution B at 
an organic:aqueous phase ratio of 1:1 for one hour at ambient temperature. 
The phases were then separated and the organic phase was analyzed for 
metal content while the aqueous phase was analyzed for ammonia 
concentration. Next, the stripped organic phase was washed with water at 
an organic:aqueous phase ratio of 1:1 for one hour and analyzed for 
H.sub.2 SO.sub.4 concentration. The results of this procedure are 
disclosed in Tables G and H. All concentrations are given in grams per 
liter. 
TABLE G 
______________________________________ 
2-(dodecylbenzenesulfonylhydrazino)pyridine in Solvesso 150 
ACID CONC g/l 
METAL 0 25 50 100 150 
______________________________________ 
[Cu] 2.23 .34 .275 .077 .030 
% Stripping 0 85 88 97 99 
[NH.sub.3 ] Aq Scrub 
-- .051 -- -- .065 
pH Aq Scrub -- 2.18 1.95 -- 1.19 
[Ni] 1.76 .570 .465 .550 .240 
% Stripping 0 68 74 69 86 
[NH.sub.3 ] Aq Scrub 
-- .425 .391 .476 .493 
pH Aq Scrub -- 5.28 4.41 4.66 2.00 
______________________________________ 
TABLE H 
______________________________________ 
8-(dodecylbenzenesulfonylhydrazino)quinoline in Solvesso 150 
ACID CONC g/l 
METAL 0 25 50 100 150 
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[Cu] 2.24 .800 .560 .353 .239 
% Stripping 0 64 75 84 89 
[NH.sub.3 ] Aq Scrub 
-- 2.55 -- -- 1.36 
pH Aq Scrub -- 3.31 3.04 2.12 .92 
[Ni] 1.90 .388 .266 .256 .185 
% Stripping 0 80 86 87 90 
[NH.sub.3 ] Aq Scrub 
-- .85 .82 1.17 1.12 
pH Aq Scrub -- 2.19 1.17 1.12 1.19 
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While the present invention has now been described in terms of certain 
preferred embodiments, and exemplified with respect thereto, the skilled 
artisan will readily appreciate that various modifications, changes, 
omissions, and substitutions may be made without departing from the spirit 
thereof. It is intended, therefore, that the present invention be limited 
solely by the scope of the following claims.