DE2358808A1 - METHOD OF OBTAINING OIL - Google Patents

Description

K 2272 FP-Dr.P-df 24, November 1973

description to register the

KALLE SHARE NG ESEL LS CH AF T Wiesbaden-Biebrich

for a patent

Method of sucking up oil

The invention relates to a method for sucking up Ql, in particular of hydrocarbon oils to a large extent Sense, such as crude oil, heating oil, diesel oil and other motor fuels from water surfaces, from water or from the ground,

The removal of oil from oil-polluted water surfaces or from oil-polluted water or from oil-polluted soil is in particular a difficult task when sucking up the oil

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largely fully feasible. Because it In many cases, large amounts of oil are involved and correspondingly large amounts of absorbent agents must be used, the absorbent agent should be used Possibility also be relatively cheap.

There are already numerous means for picking up, in particular those floating on water surfaces oil has been suggested. Most often, means are proposed, which mainly consist of mineral or consist of other inorganic powders which may have been made superficially hydrophobic; she only absorb relatively small amounts of oil and also have the disadvantage that sooner or later they sink to the bottom with the adsorbed oil through the water, where the oil then poses a latent risk of re-contamination of the water surface because it is unlikely to remain adsorbed on the inorganic adsorbent forever. Other Proposals relate to the use of crushed newsprint or sawdust made hydrophobic, whereby as water repellant, especially organic silicon compounds, as well as paraffin, fatty acid Magnesium and fatty acid oils are suggested.

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These known oil-absorbing agents hold the oil soaked up only inadequately, so that after some Lingering of the absorbent loaded with oil in the water Part of the oil is recovered, especially in moving water is delivered. It is also difficult to do with the oil to collect loaded newspaper or sawdust from the surface of the water, because the powder particles just let them clump together a little. ·

The object of the present invention is to provide a method for sucking up oil from S1 contaminated water surfaces, from oil contaminated water or from oil contaminated soil, in which the oil is largely completely removed from the surface of the water or from the bottom, "the one used absorbent means that hold oil for a long time and it can easily be collected even from the surface of water.

In solving the problem is known from the Process assumed in which the sucking up of the oil happens by means of a small, modified pulp mass, but according to the invention this is the solution The method leading to the task, characterized in that a "/ kl einteilige'ZeVT material mass is used which

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with an organic isocyanate, a higher molecular one Fatty acid, an ester of a higher molecular weight fatty acid, a complex compound of a higher molecular weight fatty acid with basic chromium chloride or one higher molecular fatty acid group containing melamine resin precondensate is modified.

Man. uses, for example, ground or unground Cellulose or cellulose glass, wood flour and ground or shredded paper, mainly newspapers and others Recovered paper in the modified form.

The organic isocyanates are preferably bivalent or polyvalent. The pulp masses reacted with isocyanates are distinguished by the fact that they the Ql as quickly as possible completely from water surfaces or pick up from the ground. The use of pulp pulp reacted with isocyanates also has the advantage that these can be reacted with the isocyanates in many cases in the presence of water, so that one no organic solvent to be used as the reaction medium needs. This applies, for example, to isocyanate compounds, produced by the condensation of three molecules of a diisocyanate, for example, through the condensation of three molecules of hexamethylene diisocyanate, and for stearyl isocyanate.

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In the case of the higher molecular fatty acids, their esters, their complex compounds with basic chromium chloride and with them substituted melamine resin precondensates they are fatty acids with at least 14 carbon atoms in the molecule. The use of fatty acids and the specified derivatives prepared with them has the advantage that one can modify the cellulose masses relatively small amounts of the fatty acid compounds needed. The complex compounds with basic chromium chloride and the melamine precondensates modified with fatty acid lead to modified cellulose masses with a comparatively high oil absorption capacity.

The method according to the invention is effective oil absorption and results in masses laden with oil, which are in solid aggregates clump together, are buoyant and therefore collect them with simple means without leaving any residue permit. In addition, some of the oil-absorbing parts are modified Cellulose masses are completely biodegradable, and they are therefore able to rapidly biodegrade .0 residues * »also from to promote those that are in hard-to-reach places. Another advantage is that the oil used in the process

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taking modified cellulose compositions are relatively simple and therefore cheap to produce.

The method according to the invention makes it possible at

Removing oil from oil contaminated water surfaces 01 to bind firmly to the oil-absorbing mass. The procedure is also beneficial in the event of oil spills in the countryside apply. Due to the ability to assemble of the cellulose masses loaded with Dl, the Ql can be absorbed very easily from the soil. The procedure can Also applied to oil contaminated water from the oil to free while it runs through a container in to which the oil-absorbing modified cellulose mass is located, which acts there as a cleaning compound.

The following examples further illustrate the process according to the invention. The examples describe the preparation of the oil-absorbing modified cellular compositions to be used in the process. In In each of the examples below, the oil absorbency of the manufactured product was then assessed established. To do this, each time in a 250 ml Beaker filled with 100 g of water and added 2 g of oil (a waste oil drained from an automobile) is poured. Subsequently, from a weighed amount of the produced oil-absorbing modified pulp mass were so

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eft small portions taken and stirring with a glass rod on the oil contaminated water surface sprinkled, until all of the oil from the sprinkled powder mass was recorded, i.e. until there is no more oil film on the Could see water, and up the agglomerates of oil and ©! Absorbing mass-were clumped together enough, that one could lift them out of the water with the glass rod. The amount of oil absorbing material consumed - ". Was determined and from this the amount of oil taken up j® g of the mass is calculated. These amounts are in the menu following the examples Given in the table. :

example 1

While continuously kneading is moistened 17 g of ground newsprint (particle size under 0.5 mm) with 50 ml of isopropanol (100 jFig) to "© rwärmt it to 80 ⁰ C ₉ adds 5 g of diphenyl-methane-4 ₀ 4'-diisocyanate dissolved in 20 ml of isoprepanol, dropwise _; add and knead 60 min. at 80 ⁰ C in a closed kneading apparatus on, "The product is dried at 6O ⁰ C.

Example 2 .

As in Example 1 above, 17 g of ground pulp are obtained (Particle size below 0.25 mm) with 5 g of diphenylmethane-4-4'-diisocyanate, which are dissolved in 20 ml of isopropanol, reacted and the product obtained is dried.

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Example 3

Are sprayed with mixing 17 grams of ground pulp (particle size below 0.25 mm) at room temperature with a solution of 17 g of a triisocyanate, which is prepared by condensation of 3 molecules of hexamethylene diisocyanate, in 20 ml of xylene, and then stirred for 30 min. At 12O ⁰ C react in the drying cabinet.

Example 4

17 g of ground pulp (particle size below 0.25 mm) are sprayed at room temperature with 17 g of water and then reacts as in Example 3 above with 17 g of triisocyanate dissolved in xylene.

Example 5

With continued kneading is moistened 17 g of ground pulp (particle size below 0.025 mm) in a kneading apparatus (Drais-kneader) with 50 ml of xylene to heated to 8O ⁰ C, spraying a solution of 17 g of the mentioned in Example 3 above triisocyanate in 20 ml of xylene, and kneaded for 60 minutes at 8O ⁰ C. long on.

Example 6

Is moistened 17 g of ground newsprint (particle size under 0.5 mm) with 50 ml of xylene as in Example 5 above to, sprayed with a solution of 17 g triisocyanate (as in Example 3 above) and kneaded at 80 ⁰ C for 60 min. Further.

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Example 7

In a toothed disk mill (space between the teeth 3 to 5 mm), 17 g of wet-ground, unpainted cellophane are moistened with 50 ml of gasoline while kneading in a kneading machine and sprayed with 17 g of diphenylmethane-4,4'- with continuing kneading at room temperature. diisocyanate, which are yellow in 20 ml of gasoline. After 15 minütigern further kneading the product is 15 hrs. Dried at 100 ⁰ C.

The product obtained is well suited for cleaning Water containing a small amount of oil, i.e. less than 1% Ql is contaminated, in a continuous process.

Example 8

As in Example 7 above, 17 g of wet-ground, unpainted cell glass are moistened with gasoline and sprayed at room temperature with 17 g of the triisocyanate mentioned in Example 3 above, dissolved in 20 ml of gasoline. Kneading for another 15 min. And then dried 15 hrs. At 10Q ⁰ C.

Example 9

While kneading in a kneading device, 20 g of ground cellulose (particle size below 0.25 mm) are mixed with 1 g of distilled water. Water, Ig of triethylamine and 100 ml of benzene heated to 8O ⁰ C, dropwise 10 g of stearyl isocyanate, the ml in 20 gasoline are solved, and to "TABT 60 min. To react at 8Q ^Q £. The product obtained is sucked off, with benzene and dried at 6O ⁰ C. 5D9823 / 0413

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Example 10

While kneading in a kneading device, 20 g of ground pulp (max. Particle size 0.25 mm) are mixed with 1 g of distilled water. Water, 1 g of triethylamine, 100 ml of benzene and 10 g of stearyl isocyanate dissolved in 20 ml of benzene, heated to 80 ⁰ C and kneaded for 60 minutes at this temperature. Long. The product obtained is filtered off, washed with benzene and dried at 60.degree.

Example U The treatment is carried out by kneading in a kneader

100 g of cellulose (particle size below 0.5 mm), with 300 g of a 1 wt Xi gen NaOH are mixed with 10 g of a 30 wt .-% solution of a Chrommyristinsäurekomplexes 1 hr. At 70 ⁰ C. The mixture is then the excess alkali neutralized with glacial acetic acid and then

dried in a drying cabinet at 70 ° C. The chromomyristic acid complex has the composition C ₁₃ H ₂₇ COOCrCl ₂ -Cr (OH) Cl ₂ . It is in a mixture of isopropanol, acetone and water (60: 30: 10 parts by weight)

solved. ,

Example 12

While mixing, 20 g of zeolite (particle size less than 0.5 mm) are dispersed in 150 ml of isopropanol (100%), in where 1 g of a stearic acid substituted tri-

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methylolmelamine are contained at 7O ⁰ C and then stirred for 1/2 hour. At 8O ⁰ C on. The mixture is then ^{dried at 100 °} C. in a drying cabinet.

Example 13 ■.

It is mixed in a kneader, 20 g cellulose (particle size under 0.5 mm) with a solution of 2 g of behenic acid in 100 ml of toluene and treated with it under kneading at 80 ⁰ C. Then the solvent is removed by drying at 12O ⁰ C,

Example 14

In a kneader, 20 g of cellulose is treated (particle size under 0.5 mm) with a solution of 2 g of pentaerythritol-tetrasteärat in 1Ό0 ml of toluene and treated with it under kneading 1/2 hr. At 8O ⁰ C. The mixture is then dried at 12O ⁰ C .

Example 15 \ . '■ - ■' .

Treating 20 g of cellulose (particle size below 0.25 mm) with a solution of ^{2 g-.Pentaerythrrttet.r.asteara:} t-in 100 ml of toluene 1/2 hours at 8O ⁰ C with kneading in a kneader. Is then dried at 12O ⁰ C.

Example 16 . -, · /.:,..■··.■, ■ ■ The unpainted time is crushed on a ZaJi η-

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Disk mill to particles of about 5 mm particle size, 150 g of the crushed cell glass are mixed with a suspension which contains 7.5 g of a trimethylolmelamine substituted with stearic acid in 450 ml of isopropanol (100%), and left in a kneading device while kneading act for 1 hr. at 8O ⁰ C. Thereafter C was dried at 100 ^0th

Example 17

It mixed homogeneously under kneading in a kneader 200 g coarse sawdust with 600 ml of isopropanol (100%) and 40 g of a dispersion of 20 g of molten, modified with stearic acid Trimethylolmelami η in 2 g of glacial acetic acid and 58 g of water at 7O ⁰ C. Afterwards a warm solution of 2 g of aluminum sulfate in 5 g of water is added. The mixture is allowed under further kneading 1 hr. Reaction at 7O ⁰ C. The mixture is then dried at 12O ⁰ C in a drying cabinet.

Example 18

While kneading in a kneading device, 100 g of finely ground newsprint (particle size below 0.25 mm), which is mixed with 300 g of isopropanol (100%), is treated with 25 g of a 30% strength by weight solution of a chromomyristic acid complex (see above example 11) 1 hr. at 7O ⁰ C, then the solvent is removed by drying.

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T a be .1. 1 e

Adsorbed oil quantities in g per g of modified cellulose mass

E.g. amount of oil E.g. amount of oil E.g. amount of oil

No. . No. No.

1 6.5 - 7 7th 4th 13th 8th 2 4th 8th 5: '■■ "-"' 14th 10 3 20th 9 7th 15th 7th 4th 10 10 8th 16 10 5 4th 11 17th 17- 5 6th 4 ^V 12th 10 18th 20th

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Claims (1)

Claim Process for sucking up oil from oil contaminated water surfaces, from oil contaminated water or soil contaminated with oil by means of a small piece modified pulp, characterized in that that one uses a small Zeil mass of substance, which with an organic isocyanate, a higher molecular fatty acid, an ester of a higher molecular fatty acid, a complex compound of a higher molecular fatty acid with basic chromium chloride or a higher molecular one Melamine resin precondensate modified with fatty acid group is. 509823/0413