376 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 26, No.

against discoloration by water that temporarily finds its way
behind bevel siding and then seeps out between the over-
lapping boards to run down over the paint.
ACKNOWLEDGMENT
Acknowledgment is made of assistance of C. E. Hrubesky
in supervision of the tests on western larch, of Don Brouse
in supervision of the tests on Douglas fir and in the making of
inspections, and of the following organizations in providing
test fences for some of the experiments: Bureau of Standards,
North Dakota Agricultural College, National Lead Company,
W. P. Fuller Company, and Southern Pacific Railroad.
LITERATURE
CITED
(1) Am. SOC.Testing Materials, Proceedings, 191, 384 (1919).
(1A) Browne, F. L., Am. Paint Varnish Mfrs.’ Assoc., Sei. See.,
Circ. 317, 480 (1927).
(2) Browne, F. L., Federation Paint Varnish Production Clubs,
OfiCial Dkest 95, 106 (1930).
Browne, F. L., IND.ENQ.CHEM.,22, 847 (1930).
Ihid., 23, 290 (1931).
Ihid., 25, 836 (1933).
Browne, F. L., J. Chem. Education, 10, 529 (1933).
Browne, F. L., PTOC. Am. SOC.Testing Materials, 30, Pt. 11, 852
(1930).
Edwards, J. D., Paint, Oil Chem. Rev., 88, No. 13, 10 (1929).
Edwards, J. D. and Wray, R. I., Federation Paint Varnish
Production Clubs, Oficial Digest,122, 15 (1933).
Edwards, J. D., and Wray, R. I., IND.ENQ.CHEM.,17, 639
(1925); 19, 975 (1927).
Gardner, H. A., Am. Paint Varnish Mfrs.’ Assoc., Proc. Sci. Sec..
Circ. 412, 181 (1932).
Gardner, H. A., Ibid., 428, 107 (1933).
Gardner, H. A., and Hart, L. P., Ihid., 374 (1931). 406 (1932),
422 (1932).
Hartwig, 0. R., Ibid., 355, 742 (1930).
(15) Nelson, H. -4.. Am. Paint J.,15, N o . 28, 20 (1931).
(16) Schmuta, F. C., Palmer, F. C., and Kittleberger, W. W., IND.
ENQ.CHEM.,22, 855 (1930).
(17) Walker, P. H., Ihid., 16, 528 (1924).
RECEIVED
October 2 4 , 1933.

New American Iodine Industry

G. Ross ROBERTSON,
University of California at Los Angeles

A BOUT seven years ago a

young petroleum chemist
of S i g n a l H i l l , L o n g
Beach, Calif., was s t r u g g l i n g
Oil-well brines in southern California are now
able to furnish the entire iodine requirementsof
the United States at present business levels, with
some possibility for expansion when needed.
marine vegetation yielded first
petroleum as an organic residue
and iodide as an aqueous ex-
tract. Districts lying outside
with the problem of separating the supposed seaweed zone, such
emulsified brine from the native The iodine present in very dilute solution as as a t Santa Fe Springs, of great
crude oil of the local field. The iodide is separated either as the free element, ad- oil fame, do not show such high
great resistance of this mixture to sorbed in or in the form of silver iodide, iodine content; the large oil
c o n v e n t ion a1 demulsification fields t o t h e n o r t h a r e n o t
technic led him to look for dis- f r o m which the desired element m a y readily be ob- Dromisine. both from lack of
turbing substances among the water and” distance from the
ionic components of the aqueous marine location. The bromide
phase, It was soon noted that the addition of an acidic oxi- content is not high, so that no special concentration of a pre-
dizing agent, such as nitrous acid, turned the brine slightly historic sea water is indicated.
yellow, and considerable quantities of iodine were revealed. The iodine industry, always something of an uncertain
Although iodine has been observed in oil-well brines of commercial quantity, is no more of a bonanza here than in
other districts, such as Louisiana, the high content in the Chile, Japan, or other foreign production center. Production
California wells was particularly encouraging. Later sur- costs are always substantial. Since Los Angeles County’s
veys have shown, however, that only a few petroleum zones three iodine producers are now meeting the equivalent of the
of the Far West have enough iodine content to warrant de- entire United States’ demand for iodine, a future potential re-
velopment. These lie in and near Long Beach, Calif., and source is recognized. At the present writing approximately
include not only Signal Hill, of the 1922 boom-time oil fame, one-half ton per day of so-called “crude” iodine, of purity
but the near-by Dominguez and Seal Beach fields which are above 99 per cent, is being manufactured.
not far from the city limits of Los Angeles. I n these districts Even the high figure of 70 parts per million, while favorable,
the day of flush oil production is long past, and the current naturally requires plant processes suited to huge flows of
flow from wells shows a high percentage of saline water. brine. If the raw material were clean, one might hope to pa,y
These facts are to the advantage of the iodine producer. the expenses of concentration by running an adjunct salt
The brines in question, aside from iodine content, approxi- business. The contaniinstion of oil and mud, however, in-
mate sea water in general composition. The usual high per- troduces serious difficulties.
centage of sodium chloride, and substantial calcium and mag- Fortunately there are several characteristic properties of
nesium content, are found. Iodide ion, in amounts ranging iodine which offer aid in reclamation from extremely dilute
from 30 to 70 parts per million, is the unique feature. solution. Chief among these are the ease of oxidation of io-
A reasonable explanation pictures a vast forest of seaweed in dide to volatile iodine, and the readiness and completeness of
some past geological epoch in the southern part of what is precipitation as silver iodide. These two fundamental re-
now Los Angeles County. It is known that the whole actions are the basis of the present California processes and
southern coast, running for many miles on either side of Long are discussed in detail below.
Beach, has had comparatively recent elevation from sub-
marine levels. The entire lowland section adjacent to Los MINORPROCESSES
Angeles was under water during the Tertiary geological The classical experiment of extracting iodine from solution
period. Not only ordinary kelpweed, but possibly deposits with the aid of chloroform or similar oil solvent led to consid-
of diatoms and similar small plants may have accumulated. erable investigation of the application of the cheaper kerosene
Presumably the decomposition of huge quantities of the to a large-scale method. Emulsion difficulties and fire haz-
April, 1934 I N D U S T R I A L -4N D E N G I ?I E E R I IC’ G C H E M I S T R Y
ards, among other factors, have led to the abandonment of the
plan, a t least temporarily.
The blowing-out process, sometimes known as the Turren-
tine process, has been used in Louisiana ( 2 ) but has been
shelved there and in California. By this scheme the iodide is
first oxidized to the free state with any cheap oxidizing agent.
The pH is necessarily adjusted, according to the patent claim,
to a value not greater than 3.5. Air is now blown through the
resulting dilute iodine solution. The efffuent air, laden with
the halogen, passes into bubble towers where iodine is ex-
tracted with aqueous caustic alkali. Final isolation of the
product may then proceed as discussed later.
Precipitation of the native iodide as the cuprous salt seems
feasible and has been tried. Unfortunately the necessary
reduction or splitting of the cuprous iodide is not so readily
accomplished as the like procedure for silver iodide, pre-
sumably because of the higher position of copper in the elec-
tromotive series. Oxidation of the cuprous ion may offer
difficulty as well. Similarly the mercurous iodide process
has not come into favor.
PRACTICAL
METHODS
Before any chemical process is started, a clean-up of the
brines is an obvious necessity. Some of the umtttractive raw
material comes from oil traps, settling tanks, and other
containers where the petroleum was supposed to have been
separated from the water. Other fractions come from rotary
drill operations (during prosperous times when wells are being
drilled) and still others from petroleum dehydration plants.
The combined flow runs to several million gallons daily.
The huge flow means the exclusion of such filter aids as
charcoal or diatomaceous earth as being too expensive. Sand
filters are employed. By a system of ponds, each emptying
into the next through a submerged spillway, much of the gross
accumulation of crude oil is left behind. Where rotary drill
mud has entered, colloidal clay persists even in the presence
of the salts and makes some trouble in later operations.
Peculiarly, the effluent of the iodine plant is more attractive
than its raw material, and hence cannot but be a benefit
rather than a nuisance to the adjacent beaches,
The clurzed brine is now subjected either to the silver io-
dide or the charcoal process, the two plans a t present favored.
377
The latter method accounts for more than half of the recent
Los Angeles output; two operators use the silver process.
The following descriptions are representative of California
technic, subject to interchange of operations and modification
with rapidly changing conditions.
SILVER
IODIDE
PROCESS
To the clarified brine, in a wooden tank, is added the exact
theoretical requirement of silver nitrate in a 1 to 2 per cent
solution. Mechanical stirring facilitates the immediate and
complete precipitation of silver iodide without trouble from
localized formation of silver chloride. A small quantity of
ferric chloride is added, and this hastens the subsidence of the
desired silver precipitate. Within 2 to 4 hours the settlkg is
complete, and most of the supernatant liquid is run out to
waste.
The mixed silver iodideferric hydroxide precipitate, with
some residual brine, is pumped out as a thin sludge. A
second settling and further elimination of brine may take place
in a second tank. Concentrated hydrochloric acid is now
added; this of course dissolves the ferric hydroxide. The
resulting acidic slurry of silver iodide is now mixed with clean
new steel scrap (punchings, wire, etc.). If the brine is clean,
transformation to metallic silver and ferrous iodide is com-
plete in an hour. With oil contamination, several hours may
be required. The material for the container in this reaction
has been something of a problem, neither wood nor iron being
entirely satisfactory.
The reclaimed silver, in a finely divided state, is readily
converted into silver nitrate and sent back for repeated duty.
The ferrous iodide filtrate is now treated with whatever oxi-
dizing agent is favored by the manufacturer or the market.
Chlorine, or sodium dichromate and sulfuric acid, or nitrite
and acid, are employed. Granular iodine is a t once precipi-
tated. This is melted, while still wet and fresh from filtration,
under concentrated sulfuric acid. The resulting slightly di-
luted acid is of such high boiling point that iodine can be di-
rectly melted under its surface. The liquid iodine phase can
be tapped off or otherwise separated in a condition relatively
free from acid. After the materia1 has cooled, the cake of
iodine is cracked up, washed free of acid, and dried over cal-
cium chloride in drying chambers. The product, while
378 I N D U S T R I A L A N D E X G I NE E R I N G C H E M I S T R Y
termed “crude” iodine, is often of 99.8 per cent purity and
has been purer than much of the more beautiful resublimed
iodine known in ordinary commerce. The final product is
shipped in 200-pound kegs. No attempt is made in Cali-
fornia to prepare either the resublimed flake iodine or any of
the salts. Further details of this method are discussed in the
patent literature ( 3 ) .
CARBON PROCESS
The brine, partially cleansed of its oil and mud, is treated
with the amount of sulfuric acid needed for the oxidation re-
action which soon follows. The change in acidity causes some
further clarification, and accordingly this operation is con-
ducted in a pond where deposition of solids offers no complica-
tions.
Just as the acidified water is about to reach the main tank,
the proper quantity of sodium nitrite solution is added. 10-
dide is oxidized to iodine, and presumably the nitrite is re-
duced to nitric oxide. In view of the exposed condition of the
solution, we may also presume that atmospheric oxygen may
cause the formation in turn of nitrogen dioxide, fresh nitrous
acid, and thus start a new cycle in reduced quantity.
The resulting yellow solution, carrying free iodine, is treated
with Nuchar or equivalent activated carbon, and the whole is
thoroughly stirred with a battery of vertical-shaft individually
motored agitators. Iodine and some clay and oil are caught
in the carbon.
After the carbon has settled in the reaction tank, most of the
clear mother liquor is run to waste. Successive batches, up
to twelve or fifteen in number, of new oxidized brine are in-
troduced, aad the charcoal is eventually loaded with iodine
to the limit of efficiency. The mixture is then thickened to
a sludge with appropriate drainage of the worthless mother
liquor.
EXTRACTION
OF IODIXE
The sludge passes t~ a large rectangular vacuum filter,
suggestive of an immense Riichner funnel, with a canvas filter
bed. The residue from filtration is treated with caustic soda
solution until the latter acquires about 3 per cent of sodium
iodide. Apparently the iodate, which should appear in the
familiar ratio of 1 iodate to 5 iodide, is a t least partially re-
duced. Possibly the carbon catalyzes the reduction. This is
of course a disadvantage in view of the oxidizing agent re-
quired soon thereafter.
The iodide solution is now treated in a conical precipitating
vessel with chromic-sulfuric acid mixture. Iodine collects as
Vol. 26, No. 4
a dull granular lumpy m a s I t is either melted under sulfuric
acid, as previously described in the other process, or steam-
sublimed. By the latter procedure the crude iodine is melted
in a large metal vessel. Steam is blown through the material,
and the vapors pass to a long vitrified stoneware pipe line
wrapped in cloth over which water constantly pours. Since
the steam is completely condensed, less loss of iodine is ex-
perienced than would occur in a conventional air-sublimation
process. The latter technic, however, yields a more beautiful
product.
The wet iodine sublimate is dried on trays in the presence
of calcium chloride in a heated room. Fortunately this place
which is thoroughly saturated with iodine can be out of doors.
IODINEMARKET
Thanks both to the California producers and the Japanese
kelp iodine industry, the old pegged price level of $4.68 per
pound seems to have been abandoned indefinitely. This
question has been taken up in detail by Holstein (1) who dis-
cusses in particular the Chilean situation. Roman (4) has
given an elaborate review of the economics of iodine over a
period of several decades, with world-wide consideration. An
extended bibliography is given with his paper.
The old standard price of iodine, maintained without regard
to general business conditions, apparently was based to some
extent on the observation that no one person or company
seems to need a large quantity of the material. Iodine does
not make up a large part of the cost of any major world
product. At the same time a great many customers need
small amounts. In case6 where iodine would seem to be
requisite in quantity, usually its brother bromine, or perhaps
chlorine, can be drafted into service without serious diffi-
culty. Accordingly the traffic in iodine, like that in dia-
monds, has been able to bear a price not directly related to
production costs.
Under present-day competitive conditions, however, the
price of iodine is approaching manufacturing costs, or does SO
in regions of respectable living standards. Unless some new
and important use for iodine is discovered, we may expect
comparatively little expansion of the California industry.
LITERATURE
CITED
(1) Holstein, P. F., Chem. & M e t . Eng., 39, 422 (1932). I
(2) Jones, C. W., U. S. Patent 1,853,621 (1932).
(3) Ibid., 1,837,777 (1931).
(4) Roman, W., Z.angew. Chem., 44, 9 (1931).
RECEIVED
February 12, 1934.