DE2212605A1 - Process for removing oil pollution from water - Google Patents

Description

dr. ing. H. NEGENDANK · dipl.-ing. H. HAUCK ■ Dipl.-Phys. W. SCHMITZ dipl.-ing. E. GRAALFS · dipl-ing. W. WEHNERT

HAMBURG-MUNICH ADDRESS FOR SERVICE: HAMBTTRG 36 NEWER WAH 41

TBI ,. 36 74 28 AND 30 41 15 TELEGH. NEGEDAPiTENI HAMBUnG

MUNICH 15 MOZARTSTR. 33

INTERNATIONAL PAPExH COMPANY te _{L. s 38} ο »so '

220 East 42nd Street temoh. negedapatent Munich

New York, NY / USA "Hamburg, March 14, 1972

Procedure for removing oil spills of waters

The invention relates generally to an improved method of removing oily soils, such as oil stains Waters, using special hydrophobized materials. More particularly, the invention relates to a method of removing oil stains from bodies of water by treatment the oil stain surface with particularly hydrophobized, finely divided Wood pulp.

So far, oil-absorbing substances have been natural for removing oil stains from ports, rivers and other bodies of water Origin, such as perlite, sand, straw, sawdust or peat has been used by adding the absorbent material to the surface of the oil stain was distributed. Natural latex granules with good oil absorption properties are also useful for removing

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Oil stains have been used on bodies of water. However, these materials have disadvantages, so that their use is not satisfactory Result leads. The naturally occurring materials listed above will generally be inadequate hydrophobic and preferably insufficiently oil-wetted to allow maximum oil absorption before submerging in water the oil stains sink. And the highly absorbent latex granules tend to float into the center of the oil stain and so make the delimitation of the spot difficult, and the subsequent separation of the oil from the latex is actually impossible.

Since finely divided substances with a hydrophobic surface are preferably wetted by oil, tests have been carried out have been to use absorbent powdery materials of volcanic origin which have been rendered hydrophobic, to remove oil spills from bodies of water to facilitate. The powders were used on their own as well as in conjunction with other common materials. These Another class of absorbents has various disadvantages such as insufficient spreading due to their tendency to atomize, the tendency of the dust to sink below the surface of the water after it has absorbed oil, and the

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allowing the agglomerated material to seep through during disposal.

From US-PS 3,484,371 is carted, oil spills from to eliminate water surfaces by placing hydrophobized, spray-dried hollow water glass particles on them to be spread out. The thin-walled hollow spherical particles become more organic by treatment with vapors Halosilanes made hydrophobic. This process is due to the special process used to produce hollow water glass particles limited, and special handling is required, to avoid breakage. In addition, these tempered hollow particles are difficult to control and easily float, if not with a latex emulsion to grinder grains are agglomerated. According to US Pat. No. 3,464,920, oil stains are removed from bodies of water by treating a stain with organic substances Materials such as sawdust, wood chips, coffee grounds and the like, which are treated with an organic halosilane have been eliminated. In this process, the sinking to the bottom of the treated with the halosilane is treated organic material after it has absorbed the oil is avoided, but treatment with organic halosilane is recommended very expensive and, more importantly, that

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Amount of oil per kilogram of silane-treated organic Material can be absorbed is uneconomical. In US-PS 3,536,615 a product for the treatment of oil silt is described, which by treating Sawdust, wood chips, shavings, bark, cork and the like with an adhesive to hold carbon together and others for oil absorption. capable materials. This product is in the process of being manufactured expensive and offers no advantages over other known methods.

The invention is based on the object of providing a method for removing oil pollution from bodies of water create that does not have the disadvantages of the previously known methods. The task is done through a process solved, which is characterized in that distributed on the water polluted with oil hydrophobized wood pulp is removed, and then the wood pulp with the oil it has absorbed from the surface of the water is, the hydrophobization of the wood pulp with a synthetic or natural sizing agent, such as a Resin glue, a wax emulsion, an emulsion of a dimeric alkyl ketene, a stearic acid-an-r-hydride emulsion, a natural or synthetic glue, and if resin glue is

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is used, in addition with alum, aluminum chloride, sodium aluminate, a water-soluble aluminum salt, a chromium-alkaline earth metal, iron or manganese salt will.

The inventive method has the advantage that it abundant naturally occurring oleophilic materials are used that be hydrophobized according to the invention in an economical manner. In addition, the hydrophobized material can over the oil stain layer is distributed without sinking through, and the oil stain can be confined to a limited area without sinking to the bottom. Since the invention Process used treated wood pulp is highly hydrophobic and preferentially absorbs oil, this can Material to be used in cases where there is no continuous layer of dirt, or in cases where either Oil-in-water or water-in-oil emulsions are present. Another advantage to which the invention leads is that the treated wood pulp with that of their absorbed oil can be easily removed from the body of water can. The oil it absorbs can be easily separated and the wood pulp can be used again as an absorbent can be used. But you can also use the wood pulp

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with the oil it has absorbed as fuel when the oil pollution is cleaned up (when the oil spill is cleaned up).

After separating the oil from the treated wood pulp the oil can be used for the purpose for which it was originally intended. If the oil is not from the treated If wood pulp is separated, the entire product can be used in road construction. A particular advantage of the process according to the invention, the high oil absorption that is possible per unit of treated wood pulp is possible is. In fact, it can absorb as high as 28 times its weight in crude oil. Other advantages of the The method according to the invention will emerge from the detailed description below.

According to the invention, leaked oil can be removed, by the specially treated, hydrophobized and olephile, finely divided wood pulp according to the invention over the surface of the oil stain is distributed. Spreading the treated wood pulp on the surface of the oil stain can by blowing or sprinkling the treated wood pulp over the whole area. After the treated wood pulp Having absorbed oil, it does not sink to the bottom and can

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recovered by any suitable means e.g. by removing them from the surface of the water by means of scrapers, sieves or other devices will. If pumps are used to remove from the surface of the water, the pulp has absorbed with that of it Oil has the advantage that it does not clog the pump like other materials. The pulp laden with oil can squeezed out and reused as an oil absorbent, or it can be pressed into briquettes, which can then be sold as fuel. The reuse of the pulp brings another economical one The advantage of this is that much smaller amounts of absorbent are used, which also reduces its disposal. Since essentially all of the material removed from the surface of the water is also easily combustible the overall cost and the problems of elimination are reduced.

The specially treated or hydrophobized finely divided Wood pulp can be made from any conventional paper-making pulp, i.e. from a Wood pulp which has been prepared by any method known for this purpose, such as the wood pulp method, the neutral or acidic Sulphite digestion, the Asplund steam defibration process, the

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cold soda ash, etc., bleached or unbleached. After the wood pulp, which has an oleophilic character, has been rendered water-repellent, it is expedient to loosen it, either by drying the pulp in a stream of hot air at high speed or by breaking up the pulp, which has been dried in the usual way, to increase the surface area. The treated wood pulp used for the process according to the invention expediently has a density of less than 24.027 kg / m 2. The density is preferably below 20.022 kg / m ⁵ , and it is even more favorable if it has a density below 12.013 kg / m, for example 3.2 kg / m. The density is determined by the TAPPI test method T21-Sm59, except that the sample is not compressed, but must be filled carefully to fill all cavities in containers before the density measurement. It has been found that the use of bark and sawdust in the process of the invention is not as suitable as wood pulp.

The rapid drying or pulverization of the conventionally dried pulp results in an exceptional one high capacity for oil removal. These treatments can often improve the oil absorption capacity of the hydrophobic wood pulp by about 10 times. Fast Drying means drying the pulp in an air

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high speed current at elevated temperature. Suitable conditions for rapid drying are temperatures between about 121 and 640 ° C., preferably between 121 and 343 ° C, and flow velocities over about 140 nr / sec '., e.g. between 252 and 840 nr / sec, preferably between 280 and 560 nr / sec. The reason for this unusual increase in oil absorption capacity pulverizing or flash drying is seen to increase the fiber surface area and increase capillarity produced by these treatments.

The wood pulp is made water-repellent by the Wood pulp is dispersed in water to form an aqueous slurry, the aqueous slurry a natural or synthetic water repellent or paper sizing agent, such as a resin size (e.g., Paper Products 2409, marketed by Arizona Chemical Co., which is a rosin resin of the abietic acid type) is added. Appropriately, at least about 4.53 kg, preferably

kg
about 11.32 or 18.12 /> the more rosin size per ton of dry wood pulp is added to the wood pulp slurry. A sufficient amount of alum is then added to precipitate the resin glue on the surface of the wood pulp. Preferably the amounts of alum and rosin glue added to

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applied to the pulp, about 1.25 to 1.05 parts by weight of alum per part by weight of rosin size. If less than 1 part by weight Alum is used on one part by weight of resin glue, some of the hydrobicity is lost during the oil treatment process. lost process. The amount of alum required is usually at least about 6.79 kg, preferably about 22.65 kg or above, based on the ton of dry wood pulp.

The water is removed from the pulp and the hydrophobized pulp is dried by any of the usual methods. For example, the pulp can be processed and dried on a conventional paper machine or it can be subjected to rapid drying be subjected.

Although larger amounts of rosin and alum, such as in excess of 18.12 kg and 22.65 kg per ton of dry wood pulp, can be used, these amounts are in fact not required and are of no benefit in the process of the invention.

The resin glue may be any of the known non-reinforced or reinforced rosin, e.g. a rosin made from tall oil, abietic acid, or from the extraction of pine stumps has been received.

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Instead of applying the rosin glue and alum to the wood pulp while it is dispersed in a slurry, it is also convenient to apply these materials to the wood pulp by greening, coating, or impregnating the pulp with aqueous or solvent solutions or dispersions of these materials. Of the

be '
The purpose of adding alum / is to deposit the resin glue on the negatively charged fibers of the finely divided wood pulp. This treatment renders the resin size insoluble and prevents it from being washed off the pulp and thereby eliminating the hydrophobic nature of the hydrophobized wood pulp during the oil removal of the invention. In addition to alum, other water-soluble aluminum salts such as sodium aluminate or aluminum chloride or the acids, acidic salts or other salts of the metals chromium, iron, manganese and alkaline earth can be used.

Other sizes can also be used to make the pulp water-repellent such as Aquapel 360 C (from Hercules Powder Co.), a dimeric alkyl ketene in which the alkyl groups, those of fatty acids, Neuphor 100 (Hercules Powder Co.), a synthetic sizing product of the modified rosin type Cyjiasize 400 (American Cyanamid

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a stearic anhydride emulsion, Alwax 251-H (American Cyanamid Co.), a wax emulsion of a crystalline paraffin wax, other wax emulsions or other sizing agents commonly used to make pulp water repellent will. Sufficient amounts of sizing agent must be used to ensure water resistance, see above that, determined by the test method TAPPI T 491-Su63, not more than 3O? 6 moisture can be absorbed.

In order to better describe the invention, examples are given below. However, these are for illustrative purposes only and do not represent a limitation of the invention. In the examples, as are throughout the description the quantities are parts by weight, unless stated otherwise.

example 1

Unbleached pine kraft pulp was in water at one Liquor ratio (-weight consistency) of about 1% to slurried. 36.24 kg of rosin size (Paper Products 2409) per ton of dry pulp was added to the slurry. The slurry was stirred and then 45-3 kg of alum per ton of dry pulp was added to it. The excess water was removed by centrifugation and the dehydrated

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Pulp broken. Thereafter the pulp was dried 'and its oil absorption capacity is increased by providing them with an air stream at a flow rate of about 672 wP / Hinute and a temperature of 282 ⁰ C in a first drying stage, and with an air stream the same temperature, but a flow rate of only 252 nr / Hinute was treated in a second stage. The finished pulverized hydrophobized pulp had a moisture content of ΛΛ% and a density of 10.571 kg / m ³ .

The treated finely divided pine pulp was then evaluated in a turbulence test for its ability to remove oil from bodies of water. In this test 100 ml of a motor oil (10 W) was poured into 500 ml of water in a bottle and the oil and water were shaken in an International bottle shaker. The bottle was then opened and 2 grams of the treated finely divided pulp was added to the oil and water. The bottle was then shaken for 2 minutes after which the pulp is allowed to drain away, and for 2 minutes after which it one hour at 140 ⁰ C was dried, intended to remove water adhering to, and finally dio Ülabsorption by weighing. It

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the pulp was found to have taken up oil in an amount of 2.080 % of its original weight. There was no evidence that the pulp was soaking water and no sinking was observed.

Example 2

Unbleached pine kraft pulp was slurried in water to a liquor ratio of about 1 % . 36.24 kg of rosin size (Paper Products 2409) per ton of dry pine pulp was added to the slurry. The slurry was stirred and then 45.3 kg of alum per ton of dry pulp was added. This Aufechlämmung was applied to a liquor ratio of 0.1 weight -% diluted with water and produced on a laboratory paper machine paper.. The wet sheets were pressed between quenchers, dried to the water to remove and place in oven at 105 ⁰ C. The dry sheets of hydrophobized pulp were then pulverized in a Fitz mill to increase the surface area. The density was 7.208 kg / er ⁵ . When testing for oil absorption, as indicated in Example 1, it was found that the hydrophobized, finely divided pulp absorbed 1.990% of its own weight in oil. The pulp with the absorbed

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Oil was then squeezed to remove excess oil, and the oil test was repeated on this pressed pulp. The treated pulp took up 1,370% of its original weight in this second attempt. The pulp was then recompressed to remove excess oil and subjected to the oil absorption test a third shark. The pulp absorbed 1,420% of its original weight in oil. The fourth, fifth and sixth texts were made alike and showed an oil absorption of 1,160% or 1,175% and 1,085%, respectively. The pulp "did not tend to soak up water and did not sink in any test." established.

In the sixth attempt, the oil-laden pulp was pressed into blocks and used as fuel.

Example 3

Unbleached pine kraft pulp was slurried in water to an oily ratio of about 1%, and 11.3 kg of carmin glue (Paper Products 2409) and 14.04 kg of alum were added per ton of dry pulp. The pulp was centrifuged and ^{dried in the oven at 105 °} C. Then it was

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pulverized in a Fitz mill. The density was 10.73 kg / m. This hydrophobized fluff pulp showed an oil absorption of 1.590% of its own weight than it the vortex oil test described in Example 1 was subjected. No sinking of the pulp was found.

Example 4

NSSC pulp and. Ground wood pulps were treated as described in Example 3, except that 36.24 kg of rosin size (Paperproducts 2409) and 45.3 kg of alum were used per ton of dry pulp and the pulp, after drying, was defibrated and pulverized by hand, so not in the Fitz mill. The density of the hydrophobized NSSC cellulose was 13.61 kg / m ³ , that of the wood pulp 19 »22 kg / m 3. These treated finely divided pulps were tested for their ability to remove oil from calm water. In this test, a 6.35 mm thick layer of oil was applied to water in a bowl. The treated fine wood pulps were applied to the oil and allowed to stand for 5 minutes. These pulps showed no tendency to sink to the bottom of the jar during the test. The treated

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Pulps with the oil they had absorbed were removed with a scraper and weighed to determine the oil uptake. The test showed that the treated NSSC pulp and the ground wood pulp had absorbed 1,040% and 850% of their own weight in oil, respectively.

Example 5

Bleached Kraft pulp became drier with 2.26 kg of a synthetic sizing product (Neuphor 100) per tonne Pulp treated and dried on a Psp machine. This The hydrophobized pulp sheet was then ground and flaked in a Fitz mill, so that the density of the pulp 10.41 kg / nr. This finely divided water-repellent pulp was then with regard to oil absorption, as described in Example 1, tested and found that it had absorbed 655% of its own weight of oil. Bleached pulps with 4.53 kg of Cyanasize 400, a synthetic sizing agent, and 3.424 kg of Aquapel 360C, a synthetic sizing product, per ton of dry pulp treated dried in a conventional paper machine and then pulverized in a Fitzmühle. The densities of these pulps were: 12.33 kg / nr or 12.17 kg / m. Then, as in Example 1, checked for oil absorption capacity; the finely divided, with Cyanasize 400 water-repellent pulp took up 1.075% of its own

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weight of oil on, the flaked, with Aquapel 360 C hydrophobized pulp assumed 8809ο its own weight Oil on. None of the pulps sank. '

Example 6

Unbleached Kraft pine pulp was slurried in water to a liquor ratio of about V / a and 5.66 kg of alum and 4.53 kg of Al wax 251-H wax emulsion per ton of dry pulp were added with stirring. The pulp was then centrifuged to remove the excess water and dried in an oven at 105 ° C. The hydrophobized pulp was then flocculated in a Fitzmühle by riverization. The density was 4.8 kg / m. This fluffy hydrophobized pulp was then tested for its oil absorption capacity as described in Example 1 and it was found that it took up 1100% of its own weight in oil.

It. it should be noted that the invention does not apply to the special expressions used here is limited. In addition, numerous modifications are possible in the frame fall of the invention.

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Claims (18)

Patent claims: j Procedures for the removal of oil pollution from bodies of water, ' characterized in that on the contaminated with oil Water-repellent wood pulp is distributed and then the wood pulp with that absorbed by it Oil is removed from the surface of the body of water, the water repellency of the wood pulp by treatment with a synthetic or natural sizing agent, such as a resin glue, a wax emulsion, an emulsion a dimeric alkyl ketene, a stearic anhydride emulsion or another natural or synthetic Sizing agent, and if rosin glue is used, also with alum, aluminum chloride, sodium aluminate, a water-soluble aluminum salt or a chromium, alkaline earth, iron or manganese SaIζ is made. 2. The method according to claim 1, characterized in that a wood pulp is used which has a density between 24.027 and 3.2 kg / m ⁵ . 3. The method according to claim 1, characterized in that the wood pulp is distributed in water and by adding from rosin glue and alum to aqueous slurry - 20 - 0 9 8 4 7/0646 is hydrqhobiert, whereby the alum is deposited in a Sufficient amount of the rosin size is added to the surface of the wood pulp, after which the water is removed and the hydrophobized pulp is dried. 4. The method according to claim 1, 2 or 3 »characterized in that the wood pulp is flocculated after drying, by drying them quickly in a high-velocity stream of warm air. 5. The method according to claim 1, 2 or 3, characterized in that the wood pulp is flocculated after drying becomes that it is pulverized in a mill. 6. The method according to claim 1, characterized in that the wood pulp is so strongly hydrophobized that it is more light absorbed than 30% moisture, tested by the TAPPI test method T491-Su63. 7. The method according to claim 4, characterized in that the flash drying is performed at a temperature of 121-649 ⁰ C. - 21 - 209847/0646 8. The method according to claim 4, characterized in that the rapid drying at a flow rate between 140 and 840 nr / sec. is carried out. 9. The method according to any one of the preceding claims, characterized in that the alum in an amount of about 1.25 to 1.5 parts by weight per part of resin is used 10. The method according to claim 1, characterized in that the resin glue used for hydrophobing the wood pulp is used in an amount of at least 4.53 kg per ton of dry pulp. 11. The method according to claim 9, characterized in that " the alum is used in an amount of at least 6.79 kg per ton of dry pulp. 12. The method according to claim 9, characterized in that the resin glue is used in an amount of at least 11.32 kg per ton of dry wood pulp. 13. The method according to claims 9 to 12, characterized in that that the alum is used in an amount of at least 22.65 kg per ton of dry wood pulp. - 22 - 209847/0646 14. The method according to claim 1, characterized in that the wood pulp by treatment with a dimeric alkyl ketene is hydrophobized. 15. The method according to claim 1, characterized in that the wood pulp by treatment with a stearic anhydride emulsion is hydrophobized. 16. The method according to claim 1, characterized in that the wood pulp is made hydrophobic by treating it with a wax emulsion, 17. The method according to claim 1, characterized in that the resin glue and the alum by spraying a solution these substances are applied to the wood pulp. 18. Briquette, characterized in that it consists of wood pulp and the oil absorbed by it. 209847/0 646