Table Of ContentPIUaiLSIJARY STUDIES FOR THE
TRcOISLAi'IOIJ OF C^IIOIJIC £XCIiAiJGL
TO illl'ffili.L PROCESSING
ROBERT R. K.UPFER
22002
' . • ' A.Thesis
Submitted to the Department of Mineral Dressing
in Partial"Fulfillment of the
Requirements for the Degree of
Master of Science in Llineral Dressing Engineering
tftwwf • %mmm mm
BUTTE, MONTANA
::c:ii';.:iii S:HOOL OF IXLAEH
ButteJ Montana
June 5, 1950
UMI Number: EP33455
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X --3LE OF CONTENTS
P^GE
i. INANCDNCTION 1
ii. IIIJTUR; OF IO:I I^XCINANGE 2
III. INLQRY OF IO:; EXCHANGE 6
Siliceous Exchangers 7
Jenny's Adsorption Isotherm 7
Vageler's Empirical Equation 10
Jenny and Niegner Empirical Equation 10
Freunulich Adsorption Isotherm 11
Resinous Exchangers ..... 13
General Considerations of Resinous Exchangers . 13
Lav/ of Mfss Action 18
Carbonaceous Exchangers*. . 25
The Influence of Exchanging Cations 26
IV. CLASSIFICATION nil) PRE PARETIC!* OF ION EXCHANGERS . 28
Classification of Ion Exchangers 28
Processing of Exchanger Materials 30
V. ION EXCHANGE OFi-R^TIOU 31
Exhaustion 32
glution . . . .. 33
Regeneration 34
Rinsir.0, 35
u, iVVi. _>rixi -ZJ-.J-JT^JU i AV.^JII-'LI AJI •-••->
lie the. of Investigation 36
37
.t;
* J. i."
LV.BLE OF CO_?lLi7Z3
P:.GE
Calibration of Coluan 39
Exchangers 39
Re^ener^nts 40
Flow RatPS 41
Influents 42
Sur^e/ of I^in^ °"^ Hill ,7?ters 43
3'Jiik^T Hill Mill and Fine Jeter ^4
Butte "ine '.Vaters 46
Influents 46
Results and Discussion 47
L-d *7
Silver ." , 49
Zinc 5£
Lcac* or>d Zinc 54
Adsorption Tests of Butte Iline r/cter 59
So.ramar;' 76
VII. conclusions 78
Ion Exchange in Recovering Valuable Metal Cations . 79
Ion Exchange and 3trean Contamination 79
III. PROPOSED ADDITIONAL REOELRCH ol
IX. BIBLIOGRAPHY . 35
.:. --.c._ic.;ii]DG.2;iiT3 as
XI. tiFILIIDIX ' 39
Tn tTu .>•>
Table I. Types of Resinous Exchangers 13
Taole II. Classification of Excnangers <39
lanle III. Analysis of 3unl:er Hill nine and I.Iill .luitrs 45
Table IV. Analrsis of Anaconua Precipitation
Plant Tailings 46
FIC^REo
Fig. 1. Cleavage otractjre of Muscovite o
Fig. ^. Conaensaticn Reaction of m-pnenolsulfonic ucia 16
Fig. 3. Cross-linl:ed Etractare of in-pnenolsulfonic
acid resin 16
Fig. 4. Structure of Resin Particle 17
Fig. 5. Donnan Equilibrium ^2
Fig. 6. extraction vs. Capacity of Lead 43
Fi_. 7. Extraction-vs. Capacity of oilv^r 5w
Fig. 3. Extraction vs. Capacity of Line 53
Fig. 9. Extraction vs. Capacity of Le-d and ^inc . .. 56
Fi ^. 1C. Extr ction vs. Capacity of Iron and ^iiic . . . 6C
Fig. 11. Effluent Analysis of Test lo 61
Fi_. lc. Extr_ction vs. Capacity of Iron and ^inc . . . u3
Fig. 13. ^ffloent analysis of Test 14 o4
Fig. 1-. Extraction vs. Cc p<ucit„ of Iroj- ana ^inc . .. 65
Fig. 15. affluent analysis of T^st 15 57
Fi^. 1C. Extr c.icn vs. Cpaci^ oi' Iron o.na z,inc . .. 59
Flu. i\ti3
Fig. 17. Effluent Analysis of 'I^st IC 7C
Fi^. 1-. £::-C:L\-e-ion vs. C^p-ci-y of Iron, ^inc ,
and Go peer 73
Fig. 19. Effluent Analysis of fest 17 74
Plate I. DiLgran of Ion Exchange apparatus o3
;
;
I
*
imiODUCTio;:
The development of ion excnangers possessing ^.roper-
tie- : at eai be utilize! in the extraction of metallic ions
from solutions le: d.s TO the possibility of applying ion ex-
caange to mineral oeneficiation. The reversible interchange
bet" een metallic ions in solution ana ions on a solid with
the ultimate elation and recovery of the metal certainly
nerits an evaluation of ion exchange in terms of its mineral
processing potentialities.
Identified with water softening for many years,
ion exchange involves the reversible exchange between ions
in solation and an insoluble solid or oase with no percep
tible change in the ^structure of the solid. Upon saturation
ox the exchanger ".vith adsorbed ion, or after a predetermined
eiiMuinu, the exchanging solid is regenerated to its former
condition by treatment with a solution containing ion ori-
0
gi"ollv on. txie exchanger. The base excaanger can tnen oe
used in another adsorption cycle, ^ven from this brief dis
cussion of ion exchange, the possibilities of using this
process for th^ recovery of metallic ions in various phtses
of mineral processing are most attractive.
The investigation reported herein is a preliminary stu
dy uf t^e translation 'of cationic exchange to mineral pro-
cesoirj. Initially, it ya.-. ^ecessary to appraise and to
become familiar -;ith the principles and operational techni-
ae - presently used in ion exchange. .nfter accomplishing
t ese initial studies, an experimental procedure v.'ut, level-
- 1 -
ope 1 for ap;Iyin^ ion eiicii-n-e to the actual recovery ^rd
co"&e'iUeni removal ol metallic ions contained ir several
ui-e liscn-.rje latere xeaov-il and recovery ul metallic
ions iron mine discharge \m_tero is onl^ one application amon^
several-J/ wmch ion e:;chc.n;e may prove to je useiui anl
economically valuable to iae mineral industries. In a sense,
tne tr^ 'Slstion of cationie excn&nje for txie recovery of
metallic ionb from mine discharge v.aters offers a-1 uruoually
interesting possible application because stream contamina
tion and pollution are ^eccmin^ increasingly critical from
tne standpoint of water conservation. In the mine \*ater
sti died , zinc, copper, and to some extent, lead ^ere found
to :e tne most valuable metallic ions contained therein.
Initial studies involve'"1 tlie extraction of zinc, lead, and
silver from solutions under idealized'conditions. Subse
quent te^t- of actual ai"e discnarje utters \ ere . ade , a"d.
ti.e lat<_ obtained were interpreted on tne oasis oz ion ex-
c..^n,-'e i" tne recovery -01 metallic ions, and ion excxr^e
as c n«r•& jf alieviati- stream contamination. additionally,
0
the ^ouoiuilities of ".pplyinj ion excu^rije tu otner onases
of mineral processing were considered from the standpoint
ox t e experience acquired in tuis preliminary investija-
iX
u J. O "^ .
EISfVHY '_? KIT JZGILJT'iJ
Credit for tne discovery of ion exenan^e is riven to
ifo.ps)^O ^ j_r, - period 1845-1852 found thai certain
j no nc
soils exhibited ion exc^arje. Tnompsor -"^ted t..at a" e^rtn
- 2 -
filter completely extracted the ammonia from solutions of
ai.imonia salts and gave up lime to the solution. \7ay°5, dur-
in i the sane period, showed that the exchange was due to
the presence of complex silicates in the soil. Unable to
identify'the active constituents, "..ay prepared a synthetic
sodium aluminosilicate that exhibited properties of ion ex-
"J r7
enange. In 1858, Hichhorn found that contrary to the opin
ion of 7,'ay, ion exchange was reversible. An addition of a
solution containing the ion initially on the exchanger re
sulted in the regeneration of the exchanger to its original
condition. The reaction appeared to be one of mass action,
since considerably more regenerant was required than neces
sary on the basis of chemical equivalents. The first appli-
cation of ion exchange is attributed to Gans , who in 1906,
was able to produce a granular exchanger and suggested wa
ter softening as an application.
Before 1950, the field of ion exchangers was restricted
to the so-called zeolites—natural or synthetic siliceous
exchangers. Examples are the'greensands or modified glau-
co.nites, clays, and natural or synthetic aluminosilicates.
In 1931, the patent of Borrowman disclosed the use of coal
as a material for exchange adsorption. In 1940, Vaughn00
treated humic material with acid and produced an ion ex
changer. Subsequent developments in the use of modified,
natural-occurring organic materials resulted in the prep-
aration of base exchangers from tannins-1-, peat and v:ooiioi-J
)
a>xi coal and lignite27.
In 1935, .-.dans and holmes1 found that polyhydric phenols,
- 'o -
yiier condensed v;ith formaldehyde, produced a resin with pro
nounced cationic exchange properties. Continued research
led to che development of resinous exchangers possessing a
diversity of chemical properties.
Sarluiii carbonate^, zinc oxide^O, dolomite^, iron ox-
ides , and aluminum oxide , have been suggested for the re
moval of -acids from solution. In a strict sense, the re
actions involved are not anionic exchange, but a chemical
neutralization of the acid with the formation of an insol
uble metal double salt. Chlorinated coal , activated char
coal , alkali-treated asphalt4 , horn, wool, silk, and
leather^ have been mentioned in patents as anion exchangers.
IXirrell-^ has suggested the use of cane sugar, pine sawdust,
a~d wood extracts as ion exchangers.
The literature contains no direct reference to the use
of ion exchange in the mineral industry. Hussey^ reported
considerable success in the use of an anion exchanger in
conjunction v;ith cyanidation in the recovery of gold and
silver from, a- ore containing a large amount of slimes. The
ore, Uiich assayed 0.12 ounces per ton of gold and 1.6 ounces
i;er ton of silver, contained approximately two-thirds slimes
when ground to minus 100-mesh and was very difficult to thick
en. Cyanide leach extraction showed a recovery of 78„4 per-
cer- of the gold and 51.5 percent of the silver. A counter-
current system of a cyanide leach followed by four adsorp-
tio- cycles with an anion exchanger yielded a total recovery
of 95.4 percent of the gold and 79.0 percent of tne silver.
