Method for herding and/or recovering spilled oil

Oil spills on natural bodies of water are treated with amine-substituted water swelling clays. The organoclays are added to oil spills in an amount which herds oil into islands of oil separated by surfaces of water containing no oil. The clays can also be added to oil spills in an amount which produces quasisolid, buoyant organoclay/oil flocculate clumps which float in the water and which are amenable to collection from the surface of the water.

BACKGROUND OF THE INVENTION 
1. Field Of the Invention 
This invention generally relates to methods of cleaning up oil spills from 
natural bodies of water such as oceans, seas, lakes, harbors and rivers. 
More specifically, this invention relates to methods for flocculating 
and/or agglomerating spilled oil associated with a natural body of water, 
such as a floating layer or film of oil and/or dispersed oil droplets, 
emulsions, etc., in order to facilitate subsequent physical recovery, 
containment, or further treatment of such oil. 
2. Prior Art 
Oil pollution of natural bodies of water, and especially of the ocean, has 
caused extensive environmental problems and ever mounting public concern. 
Such pollution has been caused by illegal dumping, accidents, warfare and 
leakage from oil drilling operations in continental shelf regions. 
Regardless of their cause, however, oil spills invariably produce 
extensive ecological and/or economic damage by destroying or tainting many 
forms of aquatic life and by fouling water intakes, recreational beaches, 
boats, fishing gear, harbor installations and the like. 
Unfortunately, oil cleanup operations are both physically and technically 
difficult; they normally involve one or more of the following measures: 
(1) physical removal of the oil from the water, with or without the use of 
adsorbents, (2) dispersion of the oil through the use of detergents, (3) 
"sinking" the spilled oil and (4) burning floating oil slicks. Each of 
these measures has its own set of special environmental and technical 
considerations. 
Physical removal (e.g., by "skimming" or pumping operations) is of course 
the most ecologically desirable remedy but, using existing technologies, 
it is feasible only under nearly ideal weather, water turbulence and 
response time conditions. Generally speaking, seas higher than about 1-2 
feet, currents in excess of 2-3 knots and/or the passage of a few day's 
time usually makes physical removal operations largely ineffective and 
extremely costly. 
Dispersion of spilled oil through the use of detergents can be accomplished 
much more quickly, but this technology has several detrimental side 
effects. For example, the detergents normally employed to disperse spilled 
oil are very often toxic to aquatic life in their own right. Moreover, 
their use also tends to bring the spilled oil into more intimate contact 
with living organisms than it might otherwise attain. 
Sinking has its own set of detrimental side effects, e.g., sinking strongly 
retards the ultimate degradation of the oil by incorporating it into 
underwater sediments where anaerobic conditions may prevail. However, not 
all water body bottoms are anaerobic or biologically inert. For example, 
nearshore areas often have high levels of biological activity as evidenced 
by the presence of kelps, shellfish, worms, etc. in such areas. 
Consequently, these forms of life may be completely wiped out by "sinking" 
an oil spill into their delicate habitats. 
Burning is of course greatly restricted by: the difficulties associated 
with getting "oil-on-water" fires started, ecological concerns regarding 
any incomplete burning of the oil and any attendant air pollution problems 
produced by such burning. Obviously, such burning also will be restricted 
by any local fire hazard considerations. Burning also represents a total 
economic waste of the oil. 
Certain physical removal methods are accompanied by the use of adsorbents 
such as finely divided or porous solid materials (e.g., straw, clays, 
sawdust, etc.) in order to help agglomerate oil films and/or oil/water 
emulsions. Such agglomeration is desirable because it ultimately aids in 
the physical gathering of the spilled oil. In effect, agglomeration of 
this kind produces relatively large, thick, distinct, patches or globs of 
more viscous, but still "liquid", oil from those relatively thin slicks or 
films of oil which reside on the water's surface and/or from those finely 
dispersed, droplets which comprise oil/water emulsions. This agglomeration 
action is brought about by surface and capillary actions of these 
materials upon spilled oil. Various clays have been used or at least 
suggested for use as such oil agglomeration agents, e.g., attapulgite, 
bentonite, kaoln and montmorillonite are most frequently suggested. 
However, cleanup operations using such clays have not been widely employed, 
largely because--in spite of their ability to sorb oil--such clays also 
tend to allow the oil to desorb in relatively short periods of time. That 
is to say that these clays, in the context of an oil spill on water, tend 
to allow the oil to desorb before the oil patches produced by them can be 
physically collected or otherwise treated, e.g., by chemical treatment, 
microorganism digestion, etc. The use of such clays, in absence of other 
floatable materials such as sawdust, wood chips, etc., also tends to 
produce agglomerated materials which may well sink. Moreover, even if a 
floating oil film and/or a finely dispersed oil/water emulsion can be 
successfully converted to relatively large droplets of oil by the use of 
such clays, and even if those large droplets, once formed, form distinct 
patches which can exist on the surface of the water for periods of time 
long enough to be successfully collected, the inherent problems generally 
associated with separating one liquid from another liquid still remain as 
a distinctly troublesome part of the overall cleanup problem. 
For example, the "liquid from liquid" (i.e., oil from water) separation 
problem which must be overcome in order to clean up an oil spill generally 
entails picking up large volumes of water along with an agglomerated 
oil/clay material which has an essentially "liquid" character. In fact, a 
very large proportion of the total material picked up in such cleanup 
operations is in fact water. That is to say that oil cleanup operations 
which use the previously noted clays in order to agglomerate oil films 
and/or oil/water emulsions into larger oil droplets and/or into larger oil 
patches do not avoid the problem of mechanically taking up (e.g., by 
suction and/or pumping operations) those large volumes of water with which 
relatively the smaller volumes of liquid oil are associated. Consequently, 
various additional "oil from water" separation processes are needed to 
complete the overall cleanup operation. They are normally performed in 
tanks on board ships, barges, tenders, etc. under those relatively 
controlled, quiescent, conditions needed to effect the physical and/or 
chemical separation of these two liquids as well as any clays, straws, 
sawdust, etc. with which these fluids are associated. Thus, large volumes 
of oil-contaminated water must be physically handled and chemically 
treated, in closed vessels, in order to successfully capture those 
relatively small volumes of oil associated with the oil-contaminated 
water. The expense of handling and treating such large volumes of water is 
enormous. Worse yet, the time needed to take up and treat such large 
volumes of water and its associated oil is painfully long when viewed from 
the standpoint that the spilled oil is relentlessly damaging the 
environment while simultaneously becoming more and more difficult to 
recover as it becomes more and more dispersed with the passage of time. 
Some representative methods for using clays to convert oil films and/or 
oil/water emulsions into larger oil droplets and patches in order to 
facilitate subsequent oil/water separation operations are taught in the 
following patent references which are each incorporated by reference into 
this patent disclosure. 
U.S. Pat. No. 3,634,227 generally teaches use of various clays such as 
attapulgite, bentonite, and kaolin to agglomerate spilled oil in order to 
facilitate its collection from the surface of the water. 
U.S. Pat No. 2,531,427 teaches that clays of the same type employed by 
applicants can be substituted with amine groups to produce "organoclays" 
which are generally capable of forming stable gels and colloidal 
dispersions in various industrial processes. In general, the amine-treated 
clays taught by this reference constitute the same kinds of "organoclays" 
employed by applicants in their processes. 
U.S. Pat. No. 4,778,627 teaches a process for disposing of radioactive 
liquid hydrocarbons by adding an organic ammonium montmorillonite clay to 
such liquids in quantities sufficient to produce a solid waste product. 
U.S. Pat. No. 3,948,770 teaches that mixtures of finely dispersed oil 
droplets and sea water, and especially those present in oil tanker 
compartments, can be separated through the use of a flocculating agent 
comprised of a dry powered mixture of an anionic polyelectrolyte, such as 
an anionic copolymer of acrylamide, and a montmorillonite clay. This 
reference also notes that when small quantities of oil are finely 
dispersed within a relatively large body of water--a situation typically 
found in the slop tanks of large oil tankers--separation of those fine 
droplets of oil is normally extremely slow and that a much more rapid 
agglomeration into a distinct oil phase may be obtained by use of the 
therein disclosed anionic polyelectrolyte/clay mixture. 
U.S. Pat. No. 4,473,477 ("the 477 patent") teaches that certain organoclays 
of the same type employed in applicants' patent disclosure can be used to 
solidify fluid waste materials in retention ponds or lagoons designed to 
hold such fluid waste materials. Typically the fluid wastes are contained 
by an impermeable liner which forms the bottom and sides of the waste 
pond. This reference also teaches that an adjunct bed of such organoclays 
can be employed in order to capture certain organic contaminants before 
they enter local ground waters. Thus, a contaminated fluid flowing through 
these beds will have its associated organic materials removed by the bed 
so that the resulting leachate (e.g., water) can be safely released into 
the environment. 
In another embodiment of the invention described in the 477 patent (which 
embodiment is discussed from column 7, line 56 to column 8, line 3 of this 
reference), an organoclay is sprayed on an artificial lagoon containing an 
oil-contaminated fluid such as water. In this particular embodiment, the 
organoclays are added in quantities such that the organoclay sorbs the oil 
and forms agglomerate clumps which sink to the bottom and/or sides of the 
lagoon in order to produce an impermeable layer or liner "plug" which 
serves to stop the flow of oil-contaminated water into local ground 
waters. 
SUMMARY OF THE INVENTION 
Applicants have discovered a process for flocculating and/or agglomerating 
spilled oil (for the purposes of this patent disclosure, the terms 
"flocculation" and "agglomeration" may be taken to mean substantially the 
same thing) associated with a natural body of water, e.g., spilled oil 
associated with such water as a floating oil film and/or as dispersed oil 
droplets, emulsions, etc. Such flocculation can be used to facilitate 
recovery, containment or further treatment of the spilled oil. For 
example, such further treatment may be by additional chemical and/or 
biological degradation or digestion of the oil. For example, in some 
special oil spill situations, e.g., spills in relatively shallow bodies of 
water, applicants' process may serve to cause a more or less continuous 
surface film of oil (which shuts off light and oxygen passage through the 
water) to be broken up and "herded" into relatively small "islands" of 
agglomerated oil and thereby leaving large openings of clear water which 
will pass sunlight and, hence, which will aid in the survival of many 
flora and fauna which otherwise would perish under a film of oil on their 
water habitat. In such usage the flocculation agent may also be called a 
"herding agent." In most cases, however, the spilled oil will not only be 
"herded", it also will be further flocculated into floating, solid clumps. 
Generally speaking, the process of this patent disclosure comprises adding 
an amine-substituted clay to an oil-contaminated body of water. Again, 
this is done in order to flocculate and/or agglomerate the oil contained 
in a continuous "film" on the surface of the water and/or contained in an 
oil/water emulsions into: (a) small (relative to the size of an oil film) 
distinct oil patches or "islands" separated by spaces of unpolluted water 
or (b) distinct buoyant, quasisolid, clumps which are particularly 
characterized by their possession of mechanical strength sufficient to 
enable said clumps to be gathered as if they were "solids." For the 
purposes of this patent disclosure, clumps having levels of mechanical 
strength sufficient to enable the clumps to be picked up out of the water, 
without appreciable breakage of said clumps, will be referred to as 
"quasi-solid" clumps. Regardless of technology, clumps having these 
characteristics can be much more efficiently gathered than those more 
"liquid" forms of clay/oil agglomerates which are produced by those 
"natural", i.e., "untreated", clays which do not contain the herein 
disclosed amine and/or amine/organic substituents. 
The amine-substituted clays used in our process are generally produced by 
reacting a water swelling clay, e.g., a smectite clay, with an amine 
compound selected from the group consisting of a primary amine salt, a 
secondary amine salt, a tertiary amine salt or a quaternary ammonium salt. 
Each of these salts is, most preferably, further characterized by its 
possession of an organosubstituent in order to produce a material which 
might be characterized as an "organoclay" flocculation agent. Thus, less 
preferred, but still very useful, amine substituted clays for the practice 
of this invention may have no organo group substituent; but our more 
preferred flocculation agents also will have certain hereinafter described 
organo groups as part of their overall chemical structures. 
In either case however, because the amine substitution of the clay molecule 
is such an extremely important aspect of this invention, those clays which 
are capable of undergoing reactions with amine compounds, e.g., those 
having substantial ion exchange capacities, generally will constitute the 
more preferred starting materials for the clays used in making the 
flocculation agents employed by this particular process. The more 
preferred amine-substituted clays and/or organo organoamine-substituted 
clays for the practice of this invention, as well as certain preferred 
methods for producing them, are generally described in U.S. Pat. Nos. 
4,473,477 and 2,531,427 and these two references are specifically 
incorporated by reference, in their entireties, into this patent 
disclosure. 
Applicants' amine-substituted clay flocculation agents may be added to the 
oil-polluted water in widely varying proportions depending upon the end 
result desired in a given embodiment of applicants' process. As a minimum 
requirement however, applicants' clays should be added to the 
oil-contaminated water in amounts sufficient to at least promote a 
"herding effect" upon an oil film. For the purposes of this patent 
application the expression "herding effect" can be taken to indicate the 
phenomenon wherein a continuous oil layer, slick or film is (even before 
any solidification or "clumping" action takes place) broken up into 
distinct, discrete "islands" of oil on the surface of the water and 
thereby leaving larger surface areas of clear water having no oil film 
and/or emulsion which would otherwise hinder passage of sunlight through 
the water. 
Next, it should be noted that relatively low "dosage" or loading rates of 
the herein described flocculation agents generally will produce this 
herding effect while relatively higher loading rates generally will 
promote formation of buoyant, (i.e., floating, as opposed to sinking) 
quasi-solid, amine-substituted clay/oil flocculate "clumps."Incidentally, 
for the purpose of this patent disclosure the terms "loading rates", 
"usage rates", "dosage rates,", "concentrations", etc. should be regarded 
as synonymous and they usually will be expressed in pounds of clay per 
U.S. gallon of oil or in some cases, as indicated, as a percentage, by 
weight, of the clay to the oil. In any event, in general, the herding 
effect takes place at loading rates far less than what is usually needed 
to form the semi-solid clumps. Thus such differences in loading rates 
represents a means of controlling our process. 
For example, applicants have produced herding effects at loading rates as 
low as about one-tenth of a pound of amine-substituted clay per gallon of 
oil. Again, in some cases this "herding" action may be all that is 
required and/or desired, but in most cases the formation of applicants' 
semi-solid clumps or clots is the more desired end result. Applicants have 
also found that loading rates higher than about three-tenths of a pound of 
clay per gallon of oil tend to produce semi-solid clumps rather than the 
"herding" effect. The most preferred loading rates for producing such 
clumps generally will be from about five-tenths of a pound of clay per 
gallon of oil to about one and one-half pounds of clay per gallon of oil. 
Again, loading rates much greater than those needed to form the desired 
semi-solid clumps can be employed, but such higher load rates are not 
preferred because they may produce "sinkable" clumps. However, it also 
should be specifically noted that loading rates high enough in theory to 
sink the resulting clumps can be employed before any sinking of the 
resulting clumps takes place--a result which applicants' process is 
designed to avoid. 
Indeed, in seeking an upper limit to the loading rate (with the expression 
"upper limit" being defined as the loading rate which causes the resulting 
oil/clay clumps to sink), applicants found that loading rates up to about 
3.5 pounds of organoclay per gallon oil produced clumps which still 
floated even though they theoretically had densities greater than that of 
sea water. This seemingly paradoxical phenomenon is probably caused by 
surface forces and/or surface chemistry phenomena between our flocculation 
agents and water as well as by the entrapment of air in said clumps. 
Again, however, as a practical matter, use of loading rates greater than 
those needed to produce clumps (e.g., loading rates preferably ranging 
from about 0.5 to 1.5 pounds of clay per gallon of oil) having sufficient 
mechanical strength to be picked up without unacceptable amounts of 
breakage of said clumps represents an unnecessary economic expense and 
introduces the possibility of producing clumps which may sink. Applicants 
have found that, in general, clumps having sufficient mechanical strength 
to be effectively collected by a wide variety of mechanical means without 
breaking said clumps into unacceptably small pieces (e.g., those having 
average diameters of less than one tenth of an inch) can be produced at 
loading rates less than about 2.0 pounds of clay per U.S. gallon of 
virtually any kind of oil product. 
That is to say that, in theory, "floatability" implies that the resulting 
clumps have densities less than about 1.025 in the case of sea water 
spills and densities less than 1.00 in the case of spills in fresh water. 
Such clumps will have an oil component generally having a density from 
about 0.85 to 0.98 and a clay components generally having a density 
greater than 2.0 and less than 3.0 (for example, most of applicants' 
preferred organoclays will have densities between about 2.5 and about 
2.8). Consequently, agglomeration of these two kinds of material will 
produce clumps having densities greater than that of the oil component 
alone. In general, it is preferred that the density of the clumps 
resulting from this process have densities less than that of the water 
with which the oil is associated. That is to say that in general, the 
resulting clumps preferably, but not necessarily, will have specific 
gravities less than 1.0 (i.e., the specific gravity of "fresh" water) or, 
in the case of oil spills in sea water, such clumps preferably should have 
specific gravities less than 1.025 (i.e., the specific gravity of sea 
water). In other words, since the organoclays themselves generally will 
have specific gravities from about 1.5 to about 2.0 and a bulk density of 
32 lbs. to 45 lbs. per cubic foot (specific gravity bulk 0.5 to 0.7), care 
should be taken not to add so much of the amine-treated clay to a given 
area that the resulting clumps will have specific gravities greater than 
that of the water in which the oil spill has occurred. Again, however, 
clumps having theoretically calculated densities which would cause them to 
sink will, in fact, float owing to air entrapment, surface chemistry, etc. 
At this point, it also should be reiterated that applicants' process seeks 
to form organoclay/ oil clumps which have the opposite character with 
respect to "sinkability" from those agglomerates produced by the process 
of the 477 patent; i.e., the clumps produced by applicants' process are 
specifically designed to "float" while those produced by the process of 
the 477 are specifically designed to "sink" so that they will serve to 
plug up leaks in an artificial liner of an artificially constructed toxic 
waste pond. With respect to the 477 patent reference, it also should be 
noted in passing that petroleum is a nonpolar material and thus can be 
distinguished from the majority of contaminant materials mentioned in the 
477 patent which are associated with polar solvents. 
The organoclay herding and/or agglomeration agents used in applicants' 
process are preferably sprayed on the spilled oil in substantially dry, 
finely divided, particle forms. However, in some cases they might be mixed 
with a liquid carrier such as water or other ingredients such as alcohols 
and the like. Ship mounted spray guns can be employed for these purposes 
or the amine-substituted clays can be dispensed from aircraft by various 
"cropdusting" spray techniques known to the art. For example, one 
particularly preferred method of dispersing the herein disclosed 
flocculation agent(s) onto an oil slick is through the use of bags carried 
under a helicopter by means of a sling. When the helicopter arrives over 
the oil spill a dump spout on the bag can be opened by a line controlled 
from the helicopter. The down-draft from the rotors will disperse the 
powder over the spill. The proper dump altitude will be determined from 
experience, observation, and will no doubt be dependent upon those local 
wind conditions which exist during the dispensing operation. 
The organoclay particles dispensed by such methods can vary in size, but 
generally speaking smaller particles are preferred. For example, at least 
a major portion or, in some cases, substantially all of the organoclay 
particles will preferably be sized at about 200 mesh or smaller. Multiple 
applications of these organoclay agents are also contemplated. Other 
active or inactive ingredients can also be simultaneously dispensed in 
particle forms as homogenous mixtures or as separately applied materials. 
Most preferably, the quasi-solid organoclay/oil clumps resulting from the 
use of appropriate loading rates will have average diameters greater than 
about one tenth of inch. In most cases, however, the resultant clumps will 
have even larger average diameters--e.g., greater than about one inch. 
Indeed, clumps having average diameters greater than three inches will 
often result from applicants' process. In general, larger clump sizes are 
produced by the use of relatively larger loading rates of the organoclay 
(e.g., those between about one and about two pounds of clay per gallon of 
oil). Again, care should be taken when using such relatively higher 
loading rates, not to add so much of the organoclay to a given spill that 
sinkable clumps are in fact formed. Regardless of their size, however, the 
quasi-solid state of such organoclay/ oil clumps--in conjunction with the 
fact that they are rendered in the form of floating units having average 
diameters greater than one tenth of an inch--makes them highly susceptible 
to being mechanically collected without having to simultaneously collect 
and treat huge quantities of water as part of the overall cleanup process. 
Such mechanical collection of the floating, quasi-solid flocculate clumps 
from the surface of the water will be most efficient when the mechanical 
collection means employed allows most of the water collected and/or taken 
up with the quasi-solid clumps to be drained away from said clumps before 
they are actually taken on board a cleanup vessel, hauled ashore or 
otherwise collected. By way of example, the mechanical collection means 
could include, but not be limited to, paddle collectors, water "porous" 
conveyor belts, screens, "raking" devices, floating fences and/or 
nets--and especially seine nets having mesh sizes less than the average 
diameter of the clay/oil flocculate clumps being collected. It also should 
be noted in passing that local conditions and available mechanical 
equipment may dictate certain clump "size" preferences. For example, 
larger clumps may be easier to pick up with certain kinds of mechanical 
equipment (e.g., "paddle" pick up devices) while smaller clumps generally 
will be more effective in attracting and further agglomerating oil as such 
smaller clumps are being collected for pickup, e.g., through the use of 
seine nets. Again, in some instances multiple applications of applicants' 
treated clays may aid in the production of larger clump sizes tailored to 
being collectible by different mechanical operations. 
It also should be noted that, for the purpose of this patent disclosure, 
the expression "quasi-solid" also can be taken to mean that the 
organoclay/oil clumps resulting from applicants' process, even in a wet 
state (such as that existing just after such clumps are taken from the 
water by mechanical means and allowed to "drain" before being taken on 
board ship), will have an angle of repose ("angle of repose"--as that term 
is employed in tests commonly used to measure a material's tendency to 
"flow") of at least 20 degrees. That is to say that the clumps produced by 
the herein disclosed process can be piled up at this angle without flowing 
"downhill". In most cases, however, a mass of the clumps formed by 
applicants' process will be characterized by having an angle of repose far 
greater than 20 degrees. Indeed, in many cases, the clumps resulting from 
the herein disclosed process may even have an angle of repose greater than 
90 degrees, i.e., the clump units may well be so cohesive that they will 
even support an "overhang" of such organoclay/oil clump units if they were 
subjected to such "angle of repose" test measurements. As previously 
noted, applicants also have found that the individual clumps formed by 
their process have more than enough mechanical strength to readily resist 
breakage into smaller units as a result of the rough mechanical handling 
operations they would experience in being collected in the water, picked 
from the surface of the water, drained and placed in a cleanup container. 
In effect, this embodiment of applicants' overall process converts the 
inherently more difficult problem of gathering and separating a liquid 
from a liquid to the inherently less difficult problem of gathering and 
separating a floating, immiscible solid from its associated liquid. In 
those embodiments of the herein disclosed process employing higher loading 
rates, the oil from water separation problem is solved by applying those 
amounts of organoclay flocculation agents to an oil spill so as to produce 
organoclay/oil clumps having a proper state (quasi-solid), a proper 
density (e.g., the clumps will be "floatable" and preferably have 
densities between about 0.85 and about 0.98) and a proper physical size 
(greater than one tenth of an inch on the average) in order to render 
those clumps susceptible to being retrieved without having simultaneously 
to take up large volumes of water. Thus, applicants' process stands in 
sharp contrast to those prior art processes using untreated clays which do 
not "solidify" the agglomerated oil, but rather merely agglomerate it into 
larger drops of "liquid" oil. 
Applicants' process has other virtues as well. For example, the clumps 
produced by this process will form quickly, e.g., in less than about an 
hour and, once formed, persist in their quasi-solid state for very long 
periods of time, e.g., days and even weeks. That is to say they will 
persist in "solid" forms for periods of time long enough for cleanup 
vessels to get to the spill site and begin operations. Moreover, its use 
tends to prevent migration of the oil spill since floating quasi-solids 
are less mobile in water than oil droplets which are broken down into 
finer and finer--and hence more "mobile"--dispersions by the action of 
waves and/or currents. Moreover, even if these quasi-solid clumps do land 
on beaches, they will not soak, wet or drain into a sand substrate in the 
manner of a "liquid" oil which has been agglomerated to a more viscous, 
but not solidified, form through the use of "untreated" (i.e., not having 
the herein described amine compounds) clays. The clumps resulting from 
applicants' process also will not commence to flow in the presence of 
sunlight in the event they do land on a beach. Hence, applicants' clumps 
have the added advantage of being able to be cleaned from the beach by 
mechanical means, e.g., sifting or screening devices, capable of 
separating one solid from another. 
Expressed in patent process terminology, applicants' method for 
flocculating oil dispersed in an oil-contaminated portion of a natural 
body of water will generally comprise: (1) adding to said oil-contaminated 
portion of water, a flocculant comprised of an amine-substituted clay 
formed by reacting a water swelling clay with an amine compound selected 
from the group consisting of a primary amine salt, a secondary amine salt, 
a tertiary amine salt or a quaternary ammonium salt (and preferably 
comprising amine salts of the type just noted and further comprising 
organosubstituents having from 1 to 24 carbon atoms), (2) adding said 
flocculant to said oil-contaminated portion of the body of water in 
amounts sufficient to promote formation of: (1) islands of agglomerated 
oil/clay materials from oil films or oil/water emulsions and/or (2) 
buoyant, quasi-solid organoclay oil flocculate clumps having average 
diameters greater than about one tenth of inch and, where applicable 
(e.g., in the case of formation of applicants' oil/clay clumps), (3) 
mechanically collecting said buoyant, quasi-solid flocculate clumps from 
the surface of the water or beachfront area if retrieval of said clumps is 
a desired object of the process. Again the herein disclosed processes also 
may be employed in situations where the agglomerated islands of oil clay 
material and/or quasi-solid clumps are not mechanically removed from the 
surface of the water, but rather are further treated. Such further 
treatment might include further chemical treatment of the oil contained in 
the islands and/or clumps and/or digestion of said oil by microorganisms. 
The preferred clay starting materials for producing the amine-substituted 
(and/or organoamine-substituted) clays which are employed in our processes 
are smectite-type clays, particularly those having a cation exchange 
capacity of at least 75 milliequivalents per 100 grams of clay. Such ion 
exchange capacities may exist in certain natural clays. However, those 
natural clays having lower ion exchange capacities may be chemically 
treated in order to give them higher ion exchange capacities. For example, 
such clays can be converted to more suitable metallic ion containing 
forms, e.g., sodium forms, if they are not already in such forms in their 
natural state. This can be effected by well known cation exchange 
reactions with, say, soluble sodium compounds. For example, such exchanges 
may be readily accomplished by mixing such clays with an aqueous solution 
of a sodium salt such as sodium carbonate or sodium chloride and then 
recovering a high sodium content clay product. In either case, the object 
is to obtain and/or prepare clays suitable for reaction with the amine 
(and/or organoamine) compounds which create the compounds which are used 
in the herein disclosed oil spill cleanup process. 
Montmorillonite, bentonite, beidelite, hectorite, saponite, sepiolite and 
stevensite clays are especially well suited for producing our particular 
flocculation or agglomeration agents. Mixtures of such clays can be used 
as well. Among the clays noted above, montmorillonite clays selected from 
the group consisting of sodium montmorillonite, calcium montmorillonite or 
magnesium montmorillonite are especially well suited for creation of the 
amine-substituted (and/or organoamine-substituted) clays which are 
subsequently used to carry out the herein disclosed oil spill cleanup 
processes. One preferred montmorillonite type clay for use in such 
clay/amine compound reactions is a sodium montmorillonite clay having at 
least a 50% milliequivalent exchangeable cation concentration (meq/%). 
Even more preferred are those sodium montmorillonite clays having between 
about 60 and about 75% sodium meq/%. Perhaps the most preferred 
montmorillonite clays for the production of the flocculation agents of our 
process are those which constitute the principal constituents of bentonite 
rock. Generally they have the chemical compositions and characteristics 
described in Berry and Mason, "Mineralogy", 1959, pp. 508-509. Still other 
organoclays which may be used for the practice of this invention might 
comprise the higher dialkyl dimethyl ammonium organoclays such as dimethyl 
di(hydrogenated tallow) ammonium bentonite; the benzyl ammonium 
organoclays, such as dimethyl benzyl (hydrogenated tallow) ammonium 
bentonite; and ethylhydroxy ammonium organoclays such as methylbis 
(2-hydroxyethyl) octodecyl ammonium bentonite. 
The natural or ion-exchanged enhanced clay starting materials can be 
reacted with the hereinafter described amine compounds in various ways. By 
way of example, such reactions may be accomplished by merely mixing or 
mulling a dry clay material with the selected amine. Alternatively, wet 
processes may be used wherein the clay is slurried in fresh water and an 
amine and/or ammonium salt added to the slurry. In general, the amounts of 
such ammonium salts substituted on the clays can vary between about 0.5% 
to about 50% of the resulting organoclay's weight. The clay/amine reaction 
products are then filtered or centrifuged from the slurry and dried to a 
low moisture content. However, a small percentage of water may sometimes 
be retained to attain maximum product efficiency. For example, the 
retention of a few percent of water, e.g., between about 1 and about 5% 
water based on a final organo ammonium clay product may prove beneficial. 
For the purposes of this patent disclosure, the term "organoclays" has 
been, and will be, used to describe the more preferred flocculation or 
agglomeration agents used in our processes, i.e., water swelling clays 
having certain "organoamine" or "organoammonium" ion substituents thereon. 
Most preferably, the "organo" portion of our organoclays will be provided 
in the form of an organosubstituent which forms a part of an amine group 
(i.e., a part of a primary, secondary and/or tertiary amine salt) which 
is, in turn, substituted on to the clay molecule. Generally speaking, such 
organo groups most preferably will be an organo group selected from the 
group consisting of aliphatic, aromatic, cyclic, heterocyclic, or 
polyamine groups. Such organo groups most preferably will range in size 
from 1 to 24 carbon atoms. The most preferred of these are those organo 
substitutents having at least 10 carbon atoms such as those having 
dodecyl, hexadecyl, octadecyl, dimethyloctadecyl groups. In general, 
however, the most preferred organoammonium ion substituents for our 
purposes are those described in U.S. Pat. Nos. 2,531,427 and 2,966,506 and 
the teachings of both of these patents are incorporated herein by 
reference. 
Speaking from a molecular structure point of view, some of the most highly 
preferred organoclays which can be used in the practice of this invention 
will comprise one or more of the following quaternary ammonium cation 
substituted clays: 
##STR1## 
wherein R.sub.1 is an alkyl group having at least 10 carbon atoms and up 
to 24 carbon atoms, and preferably having a chain length of from 12 to 18 
carbon atoms; R.sub.2 is hydrogen, benzyl or an alkyl group of at least 10 
carbon atoms and up to 24 carbon atoms, and preferably from 12 to 18 
carbon atoms; and R.sub.3 and R.sub.4 are each hydrogen or lower alkyl 
groups, viz., they contain carbon chains of from 1 to 4 atoms, and 
preferably are methyl groups. 
Some other preferred organoclays for our purposes can be represented by the 
formula: 
##STR2## 
wherein R.sub.1 is CH.sub.3 or C.sub.6 H.sub.5 CH.sub.2 ; R.sub.2 is 
##STR3## 
and R.sub.3 and R.sub.4 are alkyl groups containing long chain alkyl 
radicals having 14 to 22 carbon atoms, and most preferably wherein 20 to 
35% of said long chain alkyl radicals contain 16 carbon atoms and 60% to 
75% of said long chain alkyl radicals contain 18 carbon atoms. One 
particularly preferred organoclay species is alkyl dimethyl benzyl 
ammonium chloride. 
It also should be understood that the organoclay flocculation agents of 
this patent disclosure may further comprise other active ingredients. That 
is to say that applicants' flocculation agents may contain ingredients 
(other than "inert" carrier fluids--if carrier fluids are in fact 
employed) which may, in certain circumstances aid in the overall practice 
of this invention. For example, applicants' flocculation agent composition 
may further comprise one or more polar organic compounds. The use of these 
additional ingredients may be especially efficacious in sea water. That is 
to say that the addition of the polar organic compound may provide for 
substantial reduction in the amount of amine-substituted clay required to 
achieve the same substantial solidification of the oil. Again, this may be 
especially true in the case of oil spills in sea water. If employed, such 
polar organic compound(s), preferably, will constitute from about 0.01 to 
about 10 parts by weight of the polar organic compound(s) per 100 parts by 
weight of the amine-substituted clay. Suitable polar organic compounds for 
the practice of our invention would include alcohols, carbonates, 
acetates, ethers, ketones, benzoates and halogenated hydrocarbons and 
especially those having between about I and about 10 carbon atoms. Within 
these broad groups the most suitable polar organic compounds will include 
diethyl carbonate, propylene carbonate, methylacetate, ethylacetate, 
isoamylacetate, diisopropyl ether, diethyl ether, methylethyl ketone, 
diethyl ketone, diisopropyl ketone, ethyl benzoate, trichloroethane, 
carbon tetrachloride, and chlorobenzene. However, in general, the most 
preferred of these compounds will be the least expensive polar organic 
compounds. The most preferred of these can be taken from the group 
consisting of the lower molecular weight alcohols having between 1 and 
about 8 carbon atoms, particularly: methyl alcohol, ethyl alcohol, 
n-propyl alcohol, isopropyl alcohol, hexyl alcohol and tert-butyl alcohol. 
In general, these polar organic compounds can be added to the 
amine-substituted clay in any of several ways known to this art, e.g., by 
incorporating the polar organic compound into the organoclay to produce an 
organoclay/polar organic compound mixture for later use as a flocculation 
agent or by physically mixing the organic compound with the clay as they 
are dispensed upon the spilled oil.

DESCRIPTION OF PREFERRED EMBODIMENTS 
It should first be noted that in applicants' initial series of experiments, 
which were made in anticipation of a "sinking" of the resulting clumps in 
the manner taught in the 477 patent, applicants used formulations having 
known floatable materials such as UV-resistant polystyrene beads, chopped 
hemp fibers, gas-forming chemicals, etc. as a part of each flocculation 
agent compositions then under consideration. The "controls" against which 
these floatable material--containing formulations were tested, were simply 
the herein disclosed organoclays used without the additional flotation 
materials (beads, hemp fibers, etc.) noted above. Quite surprisingly, the 
"controls" produced agglomerated materials which continued to float at 
unexpectedly high loading rates (e.g., those implying theoretical 
densities significantly greater than 1.0). That is to say that applicants 
found that the additional floatable materials such as sawdust, beads, 
etc., simply were not needed to form either the oil/clay islands or the 
oil/clay "clumps". 
In response to this discovery, and in order to test the effectiveness of 
various clays (both "amine treated" organoclays as well as analogous, 
"untreated" clays), an aquarium test tank was filled with sea water. This 
permitted observation and photography of the top, underside, edges and 
bottom of the test tank. A given loading rate was chosen for a given set 
of experiments. Various loading rates were held constant, e.g., at 2.0 
pounds of clay per U.S. gallon of oil for a given test series. By way of 
example, one such series of experiments involved placement of 300 ml of 
Ventura Crude oil on a simulated sea water composition in a tank which 
formed a sea water surface area having 9".times.18" dimensions. These 
conditions produced a system having an initial oil spill thickness of 
about 2.87 mm. Thus, the loading rate, in effect, was two pounds per 
gallon of the Ventura crude oil. This represented a loading rate of 
approximately 25% by weight. Various visual observations of the system 
were made over time. Various observations were made and recorded. By way 
of example, the observations made with respect to a treated 
montmorillonite clay/ Ventura oil system is shown as Table 3. Analogous 
observations also were made for analogous systems employing "untreated" 
clays. For example the results of such observations for "untreated" sodium 
montmorillonite clay and/or untreated sepiolite clay are shown in Tables 1 
and 2 respectively. Again, the results of these tests are to be contrasted 
with the results shown in Table 3 which indicates the results of using an 
amine-treated clay of the type employed in this process. This particular 
table (Table 3) depicts the results of using a montmorillonite clay 
treated with dimethyl di(hydrogenated tallow) ammonium chloride. 
In comparing these results, note for example the result of using an 
untreated clay such as sodium montmorillonite or sepiolite was the 
formation of an unconsolidated slime which adhered to the sides and bottom 
of the tank. It also should be noted that, in both cases, these untreated 
clays sank at least a part of the oil. The sunken oil formed on the bottom 
of the tank and had no form other than that produced by surface tension. 
Applicants also noted that many of the liquid oil "clots" produced by the 
untreated clays which formed on the bottom of the tank eventually rose 
again to the surface, apparently as a result of an unknown gas-forming 
reaction. When such rising clot reached the surface, they released a 
bubble of gas and the oil of the clot simply rejoined the unconsolidated 
oil on the surface. It was not possible to discern any evidence of 
solidification of these materials in the regions where such rising "clots" 
had surfaced. Moreover, the entire surface remained uniformly slimy and 
unconsolidated. Such materials also covered the entire top of the sea 
water in the tank. That is to say there were no openings created in the 
resulting oil slick. The "clots" which remained on the bottom could not be 
retrieved, except by pipet, since they had no mechanical strength. In 
effect, materials were simply a liquid only slightly more viscous than the 
original crude oil itself. Agitation of the water in the tank demonstrated 
that no solidification had taken place. 
Such observations were contrasted with results obtained after applying 
amine-substituted clays to the oil under otherwise comparable test 
conditions. Again, the results given in Table 3 are more or less typical 
of those found for various other analogous experiments, e.g., as those 
using loading rates different from 2.0 pounds/gallon. Those loading rates 
falling in applicants' 0.5 to 1.5 pounds/gallon preferred range produced 
clumps generally having as much mechanical strength as those produced at 
higher loading rates, e.g., those produced at loading rates of 3.5 
pounds/gallon. Next, it should be emphasized that there were no "sinking 
clots" created by the use of applicants' amine-treated clays over the 
entire loading range of 0.1 to 3.5 pounds of clay/gallon of oil. All 
clumps created in this manner remained afloat. 
Mild agitation, simulating wave action, immediately opened up large areas 
of open water, as the solidified clumps formed up into balls and chunks of 
varying size, all of which remained afloat and were easily retrieved 
either singly or by netting without any significant breakage. The results 
of the repitition of such tests in many variations of these tests show 
that when amine-substituted clays are added to oil spilled on water in 
quantities of from about 0.3 to about 3.5 pounds of such clay per U.S. 
gallon of oil will produce quasi-solid, floating clumps of oil/clay having 
sufficient mechanical strength to be picked up out of the water without 
appreciable breakage of said clumps. Such clumps have average diameters of 
at least one-tenth of an inch and in most cases will be significantly 
larger diameters on the order of 2-3 inches, or even larger. 
TABLE I 
__________________________________________________________________________ 
Test Results Using Untreated Sodium Montmorillonite 
Observation # 
__________________________________________________________________________ 
0A 
Edge view of slick - no clay added 
1A 
2 min after drop of Sodium Montmorillonite 
2A 
3 min after drop of Sodium Montmorillonite 
3A 
4 min after drop of Sodium Montmorillonite 
4A 
5 min after drop of Sodium Montmorillonite 
5A 
6 min after drop of Sodium Montmorillonite 
shows sunken clots; also some clay 
6A 
8 min after drop of Sodium Montmorillonite 
on top; oil on top is unaffected, 
7A 
10 min after drop of Sodium Montmorillonite 
untreated. Clots on bottom ex- 
9A 
12 min after drop of Sodium Montmorillonite 
tremely fluid; no "forming." 
__________________________________________________________________________ 
Note: Some of the clots that initially dropped to bottom developed 
internal gas and came back up. These rose very rapidly, and broke through 
the untreated oil, "burped" off their gas, and simply disappeared (as 
clots, that is) in the plain oil on top. 
TABLE 2 
______________________________________ 
Test Results Using Untreated Sepiolite 
Observation # 
______________________________________ 
10A Edge view of slick - 
no clay added 
11A 3 min after drop of Sepiolite 
12A 6 min after drop of Sepiolite 
Same "rise" activity 
13A 30 min after drop of Sepiolite 
as with Sodium Mont- 
14A 30+ min after drop of Sepiolite 
morillonite. Clots on 
16A 30+ min after drop of Sepiolite 
bottom slightly more 
17A 30+ min after drop of Sepiolite 
firm. Oil on top 
18A 30+ min after drop of Sepiolite 
remained fluid; no 
19A 30+ min after drop of Sepiolite 
"forming." 
______________________________________ 
TABLE 3 
__________________________________________________________________________ 
Test Results Using Treated Clay 
Observation # 
__________________________________________________________________________ 
1 Edge view before drop 
2 5 min after drop - 
3 10 min after drop - nothing falling 
4 15 min after drop - 
5 15+ min after drop - top view, 
surface not disturbed 
6 15+ min after drop - top view, 
surface not disturbed 
7 15+ min after drop - undersurface, not 
disturbed 
8 15+ min after drop - mild agitation; clots 
shown - all floated back up 
9 15+ min after drop - heavy agitation 
10 
15+ min after drop - heavy agitation 
12 
15+ min after drop - heavy agitation 
shows solidification, 
13 
15+ min after drop - heavy agitation 
flotation, clear water 
14 
15+ min after drop - heavy agitation 
on top 
__________________________________________________________________________ 
Finally, it should be understood that various changes may be made in the 
details and arrangements of this process as well as in the procedures and 
functions carried out by them, without departing from the scope of the 
invention which consists of the matter shown and described herein and set 
forth in the hereinafter appended claims.