AU458317B2 - Compositions useful for eliminating water surface pollution caused by organic substances - Google Patents

Description

21. 9 65 This invention relates to a composition suitable for concentrating pollution on the surface of water, the pollution being caused by organic substances, for example, petroleum products or similar organic substances of either synthetic or natural origin. Water pollution, for example that of the sea, rivers, lakes and big basins, which are often essential to important schemes like irrigation, is becoming an increasingly serious problem. Increases in industry generally cause increases in the water requirement with consequential increases in the quantities of the waste water. Into these waste waters are introduced pollutants generally in the form of detergents, soluble salts and liquid products imuiscible with water constituted generally by oily substances based on petroleum. Another main source of surface Pollution, both of fresh water and of sea water, is caused by losses of crude oil or its fractions.! This problem occurs mainly at sea but also in those rivers and lakes wehere vessels, used for the transportation both of crude oil and its derivatives, operate but also occurs in those watercourses and sheets of water wherein pipelines are placed on the surface or underground. With continuous losses coming from the joints of pipelines or with a pipeline breakage, there is the possibility that on the surface of the water there will appear zones polluted by petroleum, both as a thin film of molecular thickness and as large spots few millimetres thick. Also, in ports generally, on the water surface there is found a diffused laminar layer due to a large number of causes,

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21,965/70 for example losses of shipment and cooling water. The present and future damage of pollutions of this nature is incalculable, part icularly when it is remembered that the pollution can be carried very far from-the place where it first came into contact with the water, owing to the winds and the streams. In this

way the waters and the costs of great tourist centres are permanently threatened, even if far from the originally polluted zones.* Moreover, the presence of pullutants of oil origin damages the normal development of flora and fauna- and, even in mild cases, can make fish and edible mussels, which Live In polluted zones, unpalatable. The problem of water pollution has become more critical in the last ten years with the increase in tran portation. of petroleum and its derivatives by means of -tankers and pipelines. As regards remedies, in the case of water surfaces which are enclosed or delimited, where possible the pollution must be eliminated by actually removing the pollutants, and special vessels which suck the polluting liquid from the water surface have been tried with a certain degree of success. However, in the case of serious'pollution, mainly in the sea, where the vast expanse allows uncontrolled spreading of the pollutant, with the formation of very thin laminar layers, recovering with these special vessels is very difficult and expensive. It is known that on such occasions anti-

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.21.9 65-M7 officially pollution means are used, some of which are and of the prescribed as standard equipment in ports tankers. These anti-pollution means are divided into the action they the following three groups according to employ. Substances acting like solvents and

dispersants consisting of liquids which, when distributed make the oil in the polluted zones, at least partially and products emulsifiable with water. The streams of the wave-motion thereafter cause the dispersion and pollution by diluting it over a large surface values. reducing the concentration to negligible Sinkcing absorbing substances with an form of high specific gravity, which may be in the directly on powder or granules. which are distributed the pollutant the polluted surface, and which absorb to the bottom thereby forming agglomerates which fall of the sea. In this way, at least the surface is looking clean. Floating absorbing substances with a,

low specific gravity, which may be in the form of powder the large spots or gran-ales, which are distributed over of of pollutant with which they farm agglomerates agglomer-ates absorption having a great volume, which may be recovered by a mechanical means. the There is no doubt that the use of either types of the above- recovering vessel or one of the three as mentioned substances has improved the situation regards polluted zones. Of these means, the use of recovery crafts

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21,9 65 nO or of the floating absorbing substances gives the better results because each effectively removes the pollutant from the polluted zone. However, the solvent-dispereant type and the sinking absorbing type, which takes the pollutant to the bottom, cause only a transfer of the pollution; in the first case there occurs a dispersion of it in a greater volume of water, and in the second case, there is only a sinking of the pollutant. Below are listed some of the main defects and considerations on the use of these systems. Sweeper recovery vessels: They must run many times over the whole polluted zone, by sucking in much water particularly when the pollution is constituted by very thin films. On the other hand for pollutions of bigger thickness the sweeper vessel moust be accompanied by a tanker. Solvent dispersant liquids:.' These solvents can somnetimes themselves be considered as pollutants, and at any rate may be damaging as regards the flora and fauna. Thus in the long run, with recurring pollution the amounts of general water pollution is increased by this scheme.. Also, although the cost of these compounds is generally not exorbitant, It-becomes excessive when these compounds are employed in large quantities. Absorbing substances having a high specific gravity: They can be formed of inert material, but there are some products activated by means of substances not completely innocuous. The more dis- advantage of this type of compound is'.that, in the long

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21,9 6 57 ruii, a part of the absorbed product is released by the absorbent and returns to the surface. The amount of substance required for completely eliminating the pollutant is enormous and consequently the cost for eliminating large pollutions is extremely high. Absorbing substances having a low spe cific gravity. These are more efficient because, when they have absorbed the petroleum products, the resulting spongy agglomerate may be recovered ad removed. Again, however, for a good systematic cleaning of. a polluted zone a large amount of substance is needed and the colstsare then high. According to the present invention, there is provided a composition suitable for concentrating an organic pollutant on the surface of water, which composition is in granular or powder form and comprises a carrier having an apparent density of less than 1 g/cc., a wetting agent consisting of a mono- or polybydric alcohol, and a surface active agent in which the hydrophilic group is one other than a hydroxy group, wherein in each 100 parts by weight of components and there are from 10 to parts of component from 1 to 10 parts of component and from 9 to 80 parts of component The composition of the present invention can be distributed over those zones adjacent to the polluted zones, and should produce the following effects: The contraction of the polluting large spots or their transfer to a single accumulated zone of increased thickness so as to make more economical

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.21, 965/70 and easier the recovery of pollutant by means of one of the systems already known. A particular advantage of the use 'of the new composition is that the recovery may be made with mechanical means so that the pollutant may be reutilized without further treatment; and By suitably choosing the constituents it is possible to obtain compositions which are not damaging with respect to the flora and fauna. The new composition tends to shift the polluting liquids on the water surfaces and if its distribution is effected suitably over the polluted zone, the contraction of polluted surfaces causes the concentration of the pollutant, whereby its recovery by mean of special vessels or absorbents may be made more rapid, more complete and economically advantageous. An experiment was carried out inm our laboratory and has recently been repeated on a realistic scale, both In sea water surfaces ad on the lake surfaces. The polluted surfaces of a basin were measured before and after the use of a new anti-pollutant composition. according to the present invention, and it was observed that laminar pollutions about 0.03 Mm. thick becam concentrated so as to be 3 mm. thick. Thus, in this case, the polluted surface area was reduced about 100 times. Examples of suitable carriers include sawdust, cork, light silicates, for example vermiculite, talc, certain bentonites, diatomite, finely divided vegetable

m~t rinds, vegetable oil. production residues, nd aimalglo~v lsal-Xlor) by-products

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of cereal working, e.g. residues of ground cereals and

the flours derived therefromr, expanded resins in the

form of granules and powder, silica-gel, coal powder, e.go

wood coal, and animal charcoal. The apparent density

of the carrier is less than Ig/cc and should be chosen

so that the composition, which is to act on the water

surface, can float thereon.

Preferably the monohydric or polyhydric alcohol

functioning as the wetting agent has from 1 to 10 carbon

atoms. Examples of suitable polyhydric alcohols are

glycol or polyglycol.

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Examples of the surface active agents include conventional soaps of the alkali metals, e.g. oleatee, palmitates and stearates of sodium and potassium, ricinoleates, sllphoriclnoleates, sulphonates, sulphocyanates and sulphonaphthenates. The efficiency, in use, of the composition depends on the selection and quantity of the different components. A particularly light carrier, if it is finely divided, may be more active but it .needs a stronger wetting agent to obtain immediately the necessary contact with water whereby the spreading of the surfactant is achieved.

If there is employed a surfactant which is suitable from the economic point of view but which is deficient with respect to its functionality, it may be mixed with another surfactant and thereby senzitized with respect to this functionality. The mechanism of action of the new composition is rather complex. The mechanism has not been fully analyzed but it is thought that the mechanism involves the lowering of the surface tension with a consequential motion of the surface layers of the water itself. The surface motion derived therefrom is transmitted to 9, 458317

.21 9 65 no the floating layers of any type of substance whether solid or liquid. At the same time, the low specific gravity carrier migration is noted. Tests carried out in absence of the carrier did not give a satis- factory result and this has made it appear that there is an interaction between the carrier and the other components. As mentioned above, variations in the quality and quantity of the ingredients utilized in the novel compositions depend on the type of water to be cleaned, its temperature, the external temperature and on the pollution type. It is obvious that in the selection of these ingredients the economical factor is very important, particularly in the cases of vast polluted surfaces. The f ollowing Examples illustrates the present invention.

Example 1 The following composition was preparedl. Fenolite (registered Trade Mark) (a phenol resin having an apparent density lower than Igloo). Sodium stearate Isoamyl alcohol The composition was obtained by mixing the Fenolite and sodium stearate in a stirrer with revolving counter- blades. After obtaining complete homogenization, isoamyl alcohol was added separately to one tenth of the homogenized mixture and well mixed in. Then the 4583.17

21.9 65 remainder was added and thoroughly homogenized. The resulting composition was used for cleaning fresh

water surfaces polluted with mineral oils, and was

found to give good results.

Example 2 Following the procedure described in Example

1, there was prepared a product having the following

composition. Polyurethane resin (powder)

Sodium stearate

Sodium alkylsulphon~t Glycerol The product was employed in cleaning sea water polluted with fuel oil of high specifio gravity, and

was found to give satisfactory results. Example 3 Following the procedure described in Example 1, a product having the following composition was prepared: Foam glass Potassium stearate -27% Ethylene glycol 3% The product was used to clean fresh water having an abundant pollution of light petroleum products, and was found to give good results.

Example 4 Following the procedure described in Example

1, a product having the following composition was

prepared: Polyvinylchloride in granular form 11. 4583.17

21.965 Polystyrol (powder)

Potassium stearate

Hexylene glycol

The product was employed in the treatment of sea water polluted with gasoil and other light

fractions of petroleum, and was found to give

satisfactory results.

Example Following the procedure described in Example 1, a product having the following composition

was prepared: Wood dust

Sodium stearate Potassium dodecylbenzene sulphonate

Cyclohexanol 2% Decalin (decahydronaphthalene) 3% The composition was employed for removing crude oil from fresh water with good results. Example 6 Following the procedure described in Example 1, a product having the following composition was prepared: Degreasing cake obtained from peanuts seeds working Sodium stearate =18% Hexylene glycol 2% The composition which was very cheap, was satisfactorily

employed for removing large areas of pollution com-

prising petroleum products and the like.

Example 7

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21.965 0 Following the procedure described in Example

1, a product having the following composition was prepared:

Aerosil (Trade Mark for pyrogenic silica) (not-compressed)

Sodium stearate

Sodium dodecylbenzensulphonate 3% Octyl alcohol 2%

The composition was satisfactorily employed

in the removal of a very thin film of petroleum products and the like, on water. Example 8

Following the procedure described in Example

1, a product having the following composition was prepared: Residues from the sieving of powdered vegetable matter

Potassium palmitate

Octyl alcohol The product was employed in the cleaning of

polluted brackish water so as to collect and remove very

thin layers of heavy and light petroleum products from

the surface. Example 9

Following the procedure described in Example 1,

a product having the following composition was prepared:

Charcoal powder Sodium sulphoricinoleate

Nonylphenol/ethylene oxide (1:7

ratio) (Surfactant) 3% Butyl alcohol 2%

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21.9 65 rm The product was employed for cleaning fresh and

brackish waters having a high pollution percentage, and

found to give satisfactory results. Example

3 Following the procedure described in Example 1,

a product having the following composition was prepared: By-products (as powder) of rice

working Sodium stearate

Sodium dodecyl benezenesulphonate 4%

Ethylene glycol 1%

The product was employed successfully both in

fresh water and in brackish water for concentrating pollu-

tion in the form of petroleum products. Example 11

Following tha procedure described in Example 1,

a product having the following composition was prepared:

Finely divided talc powder

Fish powder

Sodium oleate .Glycerol The product was pasted, dried and milled, and was

employed successfully in the treatment of fresh and

brackish water polluted with petroleum products. Example 12

Following the procedure described in Example 1,

a product having the following composition was prepared:

Milled and sieved vermiculite Triethanolamine oleate Sodium dodecylbenzenesulphonate 4% I A 4583,17

21.9 65/70 Amyl alcohol 1% The product was successfully employed in cleaning fresh water polluted with petroleum products.

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Claims (1)

1. 21.965n0

   The claims defining the invention are as follows:

   1. A composition suitable for concentrating/en-

   organic pollutant on the surface of water, which is in a granular or powder form and comprises a carrier

   having an apparent density of less than 1 g/cc, a

   wetting agent consisting of ameao2-or polyhydrio

   alcohol havig from I to 10 carbon atoms, and a

   surface active agent in which the hydrophilic group is

   one other than a hydroxyl group, wherein in each 100

   parts by eight of components and there are

   from 10 to 90 parts of component from 1 to 10 parts

   of component and from 9 to 80 parts of component

   2. A composition as claimed in Claim 1, wherein the

   carrier is formed of sawdust, cork, finely divided

   vegetable matter, a silicate, talc, bentonite, foaQi f lor, vegtable oamni A, a by-product of cereal

   working or a flour derived therefrom, expanded resin,

   silica gel or an animal er vegetabl co

   3. A composition as claimed in claim 1 or 2, wherein

   the surface active agent is an alkali metal soap, a

   sulphoricinoleate, sulphonate, ricinoleate, sulphpcyanate

   or sulphonaphthenate.

   4. A composition as claimed in Claim 3, wherein the

   alkali metal soap is sodium or potassium oleate, palmitate

   or stearate.

   A composition as claimed in any preceding claim, wherein the wetting agent is a monohydric alcohol, a

   glycol or polyglycol.

   6. A composition as claimed in Claim 1, substantially as described in any one of the foregoing Examples. 16. 4583.17

   21,9

   7. A method of concentrating on the surface 'of a polluted zone of water an organic pollutant, which method comprises applying a composition as claimed in any preceding claim adjacent to the polluted zone. 8. A method according to Claim 7, I which further comprises removing from the surface of the water the concentrated pollutant. 9. A method according to Claim 7 or 8, substantially as hereinbefore described with reference to any one of the Examples.

   DATED: 25th November, 1974. SNAM PROGETTI S.p.A. By its Patent Attorneys: PHILLIPS ORMONDE FITZPATRICK

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