KR20010015536A - Method for Removing Pollutant Organic Fluids from Surface Water - Google Patents

Abstract

The present invention relates to a method for removing organic fluids, in particular oils, from the water surface. According to the method of the present invention, a suitable binder is added to the water to bind the binder or the organic fluid is absorbed by the binder. The binder is then removed together with the bound or absorbed fluid.

Description

Method for removing pollutant organic fluids from surface water

The present invention relates to a method of removing an organic liquid contaminating the water surface, in particular an oil, by adding a binder to the water surface which binds the organic liquid and then removing the binder together with the bound or absorbed liquid.

For example, oil films floating on water cause serious harm to the environment. One particular problem is that even small amounts of oil contaminate a wide range of water and cause fatal harm to fish and other organisms. Therefore, when removing such an oil film, it is very important to remove the oil substantially completely and very quickly so that the oil film cannot spread or only slightly spreads.

The oil film is generally removed by adding an oil absorbing binder to the water and then removing the binder together with the bound or absorbed oil. Materials generally used as binders include highly lipophilic materials such as specialty plastics or materials with pore structures of visually identifiable size (in solid or liquid form). By adding these binder materials to the water surface, the binder on the water combines with or absorbs the oil before forming the oil film floating on the water surface, which can then be easily removed.

In addition, since the polymer itself is not dispersed in water or seawater, oil droplets floating in water cannot be removed by the polymer, and JP 59-039 381 contains a polymer on the one hand and an alcohol as the solvent on the other. It is known that an aqueous dispersion comprising water can be prepared, which exhibits excellent water dispersibility, so that the polymer is present under the water to absorb the oil below the surface.

Indeed, numerous different binders are used, which may contain other oil absorbing constituents in addition to the polymer, such as sawdust, peat, cork and the like. Moreover, it is known that these components can be added to the polymer to form agglomerates or similar aggregates in which the oil can be easily removed (JP 54-033 887 A).

However, as before, the removal of the oil film has problems such as the oil spreading rapidly and even the already combined cohesive oil film is scattered due to the severe movement of sea winds and / or waves in the high seas.

Accordingly, it is an object of the present invention to provide a method for removing organic liquids that contaminate the water surface so as to prevent or at least reduce the spread of organic liquids and to facilitate the removal of subsequent organic liquids, for example by absorption. One way is to improve.

This object is achieved in accordance with the invention in that it adds to the surface a solution / dispersion with a polymer or mixture of polymers and a water-miscible and / or volatilizable solvent that is less dense than water to substantially contaminate the contaminated sleeping area. do. Accordingly, the present invention is directed to biodegradable and aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, or aliphatic or partially aromatic polyester amides to limit contaminated sleeping areas. Adding a solution / dispersion with water-miscible and / or volatile solvent which is less dense than water and a polymer selected from to combine with the organic liquid before or after adding the polymer solution / dispersion A method of removing an organic liquid contaminating water, comprising the step of adding a binder, followed by removing the binder together with the bound or absorbed liquid.

The present invention is based on the concept of placing a barrier wall around the contaminated sleeping area to keep the contaminated sleeping area together to counteract further spread of contaminants. According to the present invention, the annular barrier wall is formed by adding a polymer solution or dispersion to the water surface, where the solution and dispersion spread along the water contamination while forming a closed ring due to low density and affinity to organic pollutants. . During this process, the solvent is mixed or evaporated with water, as a result of which the polymer condenses on the water while forming the desired annular barrier wall, defining and contaminating the contaminated sleeping area so that the contamination can no longer spread.

The range of the cyclic barrier wall depends substantially on the amount of solution / dispersion applied to the water surface and is limited by the evaporation of the solvent or the solvent mixing with water.

The polymer content of the solution / dispersion is generally up to 50% by weight (relative to the total solution or dispersion). Higher concentrations are inadequate because the free flow of solution / dispersion becomes insufficient. The polymer content is preferably up to 30% by weight, in particular from 5 to 10% by weight.

In order to promote uniform ring formation, it is advantageous to add the solution to the water surface as uniformly as possible. This can be achieved, for example, by spraying the solution onto the water surface.

The solution or dispersion preferably contains a biodegradable polymer or a mixture of biodegradable polymers so that the solution / dispersion or the polymer contained therein can be processed without problems.

Suitable biodegradable polymers include aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, or aliphatic or partially aromatic polyester amides, or mixtures thereof.

The following polymers are suitable:

A) aliphatic difunctional alcohols, preferably linear C ₂ to C ₁₀ dialcohols such as ethanediol, butanediol or hexanediol, most preferably butanediol and / or optionally alicyclic difunctional alcohols, preferably Difunctional alcohols having 5 or 6 carbon atoms in the alicyclic ring, such as cyclohexanedimethanol and / or monomers or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or Copolymers thereof of 4000 or less, preferably 1000 or less, and / or optionally small amounts of branched difunctional alcohols, preferably C ₃ -C ₁₂ alkyl diols such as neopentyl glycol and optionally also small amounts of higher functionalities It degrees alcohols, such as 1,2,3-propanetriol or trimethylolpropane, and aliphatic bifunctional acids, preferably C ₂ -C ₁₂ alkyl dicarboxylic acids, Preferably preferably succinic or adipic acid and / or optionally aromatic difunctional acids such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid, and optionally also small amounts of higher functional acids such as trimellitic acid. ; or

B) acid- and alcohol-functionalized components, preferably those having 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid or lactic acid, or derivatives thereof, for example ε- Caprolactone or dilactide; or

Mixtures and / or copolymers of A) and B)

Aliphatic or partially aromatic polyesters formed from wherein the proportion of aromatic acid is 50% by weight or less for all acids;

C) aliphatic difunctional alcohols, preferably linear C ₂ to C ₁₀ dialcohols such as ethanediol, butanediol or hexanediol, most preferably butanediol and / or optionally alicyclic difunctional alcohols, preferably Those having 5 or 6 carbon atoms in the alicyclic ring such as cyclohexanedimethanol and / or monomeric or oligomeric polyols based on propylene glycol, propylene glycol, tetrahydrofuran or molecular weight of 4000 or less, in whole or in part instead of diol, Of copolymers and / or optionally small amounts of branched difunctional alcohols, preferably C ₃ -C ₁₂ alkyl diols, such as neopentyl glycol, and optionally also small amounts of higher Alcohols, preferably C ₃ -C ₁₂ alkyl polyols, such as 1,2,3-propanetriol or trimethylolpropane, and aliphatic difunctional acids, preferably C ₂ -C ₁₂ alkyl dicarboxylic acids, such as preferably succinic acid or adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid and optionally also small amounts of higher Acids of functionality such as trimellitic acid; or

D) acid- and alcohol-functionalized components, preferably those having 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid or lactic acid, or derivatives thereof, for example ε- Caprolactone or dilactide; or

Mixtures and / or copolymers of C) and D), wherein the proportion of aromatic acids is up to 50% by weight relative to all acids;

E) higher functionalities of 1 to 12 or 5 to 8 carbon atoms in the case of C and / or D, aliphatic and / or alicyclic difunctional isocyanates and optionally also preferably alicyclic isocyanates; Reaction products with isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate, optionally linear and / or branched and / or alicyclic difunctional alcohols and / or also higher With functionalities of alcohols, preferably C ₃ -C ₁₂ alkyl diols or polyols or alicyclic alcohols, such as those having from 5 to 8 carbon atoms, for example ethanediol, hexanediol, butanediol or cyclohexane-dimethanol Reaction products and / or lines with reaction products and / or optionally linear and / or branched and / or alicyclic difunctional amines and / or amino alcohols And / or branched and / or alicyclic amines and / or also higher functional amino alcohols, preferably those having 2 to 12 carbon atoms in the alkyl chain, for example ethylenediamine or aminoethanol Reaction products and / or optionally other modified amines or alcohols, for example as free acids or salts, such as ethylenediaminoethane-sulfonic acid

Aliphatic or partially aromatic polyester urethanes formed from wherein the ester fraction represented by C) and / or D) is at least 75% by weight relative to the sum of C), D) and E);

F) aliphatic difunctional alcohols, preferably linear C ₂ to C ₁₀ dialcohols such as ethanediol, butanediol or hexanediol, most preferably butanediol and / or optionally alicyclic difunctional alcohols, preferably Those having 5 or 8 carbon atoms in the alicyclic ring, such as cyclohexanedimethanol and / or monomeric or oligomeric polyols based on propylene glycol, propylene glycol, tetrahydrofuran or molecular weights of 4000 or less, in whole or in part instead of diol, Its copolymer is preferably 1000 or less and / or optionally small amounts of branched difunctional alcohols, preferably C ₂ -C ₁₂ alkyl dicarboxylic acids such as neopentyl glycol, and optionally also small amounts of higher Functionalities of alcohols such as 1,2,3-propanetriol or trimethylolpropane, and aliphatic difunctional acids, preferably C ₂ -C ₁₂ alkyl dicarboxylic acids, Such as preferably succinic acid or adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid, and optionally also small amounts of higher functional acids such as trimellitic acid ; or

G) acid- and alcohol-functionalized components, preferably those having 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid or lactic acid, or derivatives thereof, for example ε- Caprolactone or dilactide; or

Mixtures and / or copolymers of F) and G), wherein the proportion of aromatic acids is up to 50% by weight relative to all acids;

H) carbonate fractions prepared from aromatic difunctional phenols, preferably bisphenol A, and carbonate donors such as phosgene, or esters of aliphatic carbonates or derivatives thereof, such as esters of chlorocarboxylic acid, or aliphatic carboxylic acids Esters or derivatives thereof such as salts and carbonate donors such as phosgene

Aliphatic or aliphatic-aromatic polyester carbonates formed from wherein the ester fraction represented by F) and / or G) is at least 70% by weight relative to the sum of F), G) and H);

I) aliphatic difunctional alcohols, preferably linear C ₂ to C ₁₀ dialcohols such as ethanediol, butanediol or hexanediol, most preferably butanediol and / or optionally alicyclic difunctional alcohols, preferably Those having 5 or 8 carbon atoms, such as cyclohexanedimethanol and / or completely or partially diols instead of diols, monomers or oligomeric polyols based on propylene glycol, tetrahydrofuran or molecular weights of 4000 or less, preferably 1000 or less Copolymers thereof, and / or optionally small amounts of branched difunctional alcohols, preferably C ₃ -C ₁₂ alkyl polyols such as neopentyl glycol, and optionally also small amounts of higher functional alcohols, preferably is C ₃ -C ₁₂ alkyl polyols, such as 1,2,3-propanetriol or trimethylolpropane, and aliphatic bifunctional acids, preferably C ₂ -C ₁₂ alkyl-di Carboxylic acids, such as preferably succinic acid or adipic acid, and / or optionally aromatic difunctional acids such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid, and optionally also small amounts of higher functional acids Such as trimellitic acid; or

K) Acid- and alcohol-functionalized components, preferably those having 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid or lactic acid, or derivatives thereof, for example ε- Caprolactone or dilactide; or

Mixtures and / or copolymers of I) and K), wherein the proportion of aromatic acids is up to 50% by weight for all acids;

L) aliphatic and / or alicyclic difunctional amines and / or optionally small amounts of branched difunctional amines, preferably linear aliphatic C ₂ to C ₁₀ diamines, and optionally also small amounts of higher functionality Amines, preferably amines which are hexamethylenediamine or isophorone diamine, most preferably hexamethylene-diamine, and linear and / or alicyclic difunctional acids, preferably 2 to 12 carbon atoms in the alkyl chain. In the case of individuals or alicyclic acids, those containing a C ₅ or C ₆ ring and / or optionally small amounts of branched difunctional acids and / or optionally aromatic difunctional acids such as terephthalic acid, isophthalic acid Or an amide fraction formed from naphthalene dicarboxylic acid, and optionally also small amounts of higher functional acids, preferably those having from 2 to 10 carbon atoms.

Formed from; or

M) acid- and amine-functionalized components, preferably those having 4 to 20 carbon atoms in the alicyclic chain, preferably ω-laurolactam or ε-caprolactam, most preferably ε-caprolactam ; or

Mixture of L) and M) as amide fraction

The ester fraction represented by aliphatic or partially aromatic polyester amides (wherein I) and / or K) is at least 30% by weight relative to the sum of I), K), L) and M), and the ester structure The weight ratio of 30 to 70% by weight and the weight ratio of the amide structure is 70 to 30% by weight).

All acids can also be used in the form of derivatives, such as acid chlorides or esters (including both monomeric and oligomeric esters).

The biodegradable polyester amides according to the present invention optionally comprise the "polyamide process" or esterification of the acid groups or the resulting acid groups comprising stoichiometric mixing of the starting components with the addition of water followed by removal of the water from the reaction mixture. It can be synthesized by a "polyester method" which involves stoichiometric mixing of the starting components with the subsequent transesterification or amide exchange of the ester and the addition of excess diol. In the case of the "polyester process", not only water but also excess diols are also removed by distillation. Synthesis is preferably performed by the "polyester method" mentioned above.

The condensation polymerization process can also be accelerated using known catalysts. It is possible to use both known phosphorus compounds which accelerate the synthesis of polyamides and organometallic catalysts or acids for esterification processes. It is also possible to use a combination of two types of catalysts to accelerate the condensation polymerization process.

It should be ensured that the catalyst does not adversely affect the biodegradability or compostability or the quality of the resulting degradation products.

Condensation polymerization processes to form polyester amides may also be affected when using lysine, lysine derivatives, or other products that promote branching of the amides, such as aminoethyl-aminoethanol (eg DE 3831709). Reference).

The preparation of polyesters, polyester carbonates and polyester urethanes can be similarly carried out by methods which are generally known or known (for example EP-A 304 787, WO 95/12629, WO 93/13154, EP-A 682 054, EP-A 593 975).

The polyesters, polyester urethanes, polyester carbonates or polyester amides according to the invention may also contain from 0.1 to 5% by weight, preferably from 0.1 to 1% by weight of the branching agent. Reference). This branching agent may be a trifunctional alcohol such as trimethylolpropane or glycerol, for example a tetrafunctional alcohol such as pentaerythritol, or a trifunctional carboxylic acid such as citric acid. The branching agent increases the melt viscosity of the polyester amide according to the invention to a value such that extrusion blow molding is possible using these polymers. This does not degrade the biodegradation of these materials.

Biodegradable / compostable polyester urethanes, polyesters, polyester carbonates and polyester amides generally comprise starting materials having a molecular weight of at least 10,000 g / mol and generally having a random distribution in the polymer. When synthesizing polyurethanes, optionally from C) and D), as well as from E), it is not always expected that the distribution of monomer components is completely random.

Biodegradable polymers are commercially available and are sold, for example, by Bayer AG under product codes BAK 1095 and BAK 2195.

Alcohols, ketones, ethers, halogenated or halogenated-free hydrocarbons, or mixtures thereof can be used as the solvent. Examples thereof include ethanol, acetone, ethyl acetate, isopropanol, methanol, dichloromethane, chloroform, tetrahydrofuran and toluene. Environmentally friendly solvents are preferably used.

Other environmentally compatible water miscible solvents include dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone. The solvent may also be used in admixture with water, for example in a mixture of ethanol and water. Solvent solubility in water may also be increased by adding alcohol. The specifications of the alcohols used herein may differ. Possible examples include methanol, ethanol, (iso-, n-) propanol, (n-, iso-, tert-) butanol or ketones (acetone, 2-butanone). It is important that the polymer is dissolved or dispersed in a solvent but insoluble in water. Solutions which prove to be particularly suitable include solvent mixtures containing C ₁ -C ₄ -alcohols, C ₁ -C ₆ -ketones and / or aromatic carboxylic acids or salts thereof, in particular not disclosed previously and described herein There is a solution prepared by the method described in German Patent Application No. 19 640 032.5, which is incorporated by reference.

Conventional binders can be used to bind the organic liquid. This binder can be sprayed or poured onto the surface like a solution. Examples of such binders include powdered rubber, peat, cork and / or latex, which can be used individually or in combination.

The binder may be added to the surface before or after adding the solution. However, preferably, solutions may be added first to define and fix defined contaminated sleeping areas and then remove them from oil or other organic liquids. As a result, the further spreading of the organic liquid contaminating the water surface is particularly advantageous in terms of time.

Claims (10)

Polymers or polymers selected from biodegradable and aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, or aliphatic or partially aromatic polyester amides to define contaminated sleeping areas A solution / dispersion with a water-miscible and / or volatilized solvent having a lower density than water and / or volatilization, adding a binder that binds the organic liquid before or after adding the polymer solution / dispersion, And then removing the binder together with the bound or absorbed liquid. The method of claim 1 wherein a solution having a polymer content of 50 wt% or less is used. The process according to claim 1 or 2, wherein a solution having a polymer content of 1 to 30% by weight is used. The method according to any one of claims 1 to 3, A) aliphatic difunctional alcohols and / or optionally alicyclic difunctional alcohols and / or monomers or oligomeric polyols based on propylene glycol or propylene glycol or tetrahydrofuran or molecular weights of 4000 or less instead of completely or partially diols Copolymers and / or optionally small amounts of branched difunctional alcohols and optionally also small amounts of higher functional alcohols and aliphatic difunctional acids and / or optionally aromatic difunctional acids and optionally also Small amounts of higher functional acids; or B) acid- and alcohol-functionalized components or derivatives thereof; or Mixtures and / or copolymers of A) and B) Aliphatic or partially aromatic polyesters formed from wherein the proportion of aromatic acid is 50% by weight or less for all acids; C) aliphatic difunctional alcohols and / or optionally alicyclic difunctional alcohols and / or monomers or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or molecular weights of 4000 or less, completely or partially instead of diols Copolymers and / or optionally small amounts of branched bifunctional alcohols and optionally also small amounts of higher functional alcohols and aliphatic difunctional acids and / or optionally aromatic difunctional acids and optionally also Small amounts of higher functional acids; or D) acid- and alcohol-functionalized components or derivatives thereof; or Mixtures and / or copolymers of C) and D), wherein the proportion of aromatic acids is up to 50% by weight relative to all acids; E) reaction products of C and / or D with aliphatic and / or alicyclic difunctional isocyanates, and optionally also with higher functional isocyanates, optionally linear and / or branched And / or reaction products with alicyclic difunctional alcohols and / or also higher functional alcohols, and / or optionally linear and / or branched and / or alicyclic difunctional amines and Reaction products with (or) amino alcohols, and / or reaction products with linear and / or branched and / or alicyclic amines and / or amino alcohols of higher functionality, and / or optionally Is the reaction product with other modified amines or alcohols as free acids or salts Aliphatic or partially aromatic polyester urethanes formed from wherein the ester fraction represented by C) and / or D) is at least 75% by weight relative to the sum of C), D) and E); F) aliphatic difunctional alcohols and / or optionally alicyclic difunctional alcohols and / or monomers or oligomeric polyols based on propylene glycol, propylene glycol, tetrahydrofuran or molecular weights of 4000 or less, completely or partially instead of diols Copolymers and / or optionally small amounts of branched bifunctional alcohols and optionally also small amounts of higher functional alcohols and aliphatic difunctional acids and / or optionally aromatic difunctional acids and optionally also Small amounts of higher functional acids; or G) acid- and alcohol-functionalized components or derivatives thereof; or Mixtures and / or copolymers of F) and G), wherein the proportion of aromatic acids is up to 50% by weight relative to all acids; H) carbonate fractions prepared from aromatic difunctional phenol and carbonate donors, or carbonate fractions prepared from esters of aliphatic carbonates or derivatives thereof or prepared from aliphatic carboxylic acids or derivatives thereof and carbonate donors (F) and ( Or) the ester fraction represented by G) is at least 70% by weight relative to the sum of F), G) and H). Aliphatic or aliphatic-aromatic polyester carbonates formed from; I) aliphatic difunctional alcohols and / or optionally alicyclic difunctional alcohols and / or monomers or oligomeric polyols based on propylene glycol, propylene glycol, tetrahydrofuran or molecular weights of 4000 or less, completely or partially instead of diols Copolymers and / or optionally small amounts of branched bifunctional alcohols and optionally also small amounts of higher functional alcohols and aliphatic difunctional acids and / or optionally aromatic difunctional acids and optionally also Small amounts of higher functional acids; or K) acid- and alcohol-functionalized components or derivatives thereof; or Mixtures and / or copolymers of I) and K), wherein the proportion of aromatic acids is up to 50% by weight for all acids; L) aliphatic and / or alicyclic difunctional amines and / or optionally small amounts of branched difunctional amines and optionally also small amounts of higher functional amines and linear and / or alicyclic bifunctional Amide fractions formed from acids and / or optionally small amounts of branched bifunctional acids and / or optionally aromatic difunctional acids and optionally also small amounts of higher functional acids; or M) amide fractions formed from acid- and amine-functionalized components The fraction of esters formed from or represented by aliphatic or partially aromatic polyester amides (wherein I) and / or K) comprising a mixture of L) and M) as the amide fraction are I), K), L) and At least 30% by weight relative to the sum of M)). 5. The alcohol according to claim 1, wherein the alcohol, ketone, ether, halogenated or halogenated-free hydrocarbon, toluene, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, or mixtures thereof is optionally water. Mixed with and used as a solvent. Ethanol, methanol, (n- / iso-) propanol, (n-, iso, -tert-) butanol, acetone, 2-butanone, ethyl acetate, dichloromethane, Chloroform, tetrahydrofuran, toluene, dimethyl sulfoxide or N-methyl-3-pyrrolidinone, optionally mixed with water and used as a solvent. The process according to any one of claims 1 to 6, wherein a solvent mixture containing C ₁ -C ₄ alcohols, C ₁ -C ₆ ketones and / or aromatic carboxylic acids, or salts thereof is used as the solution. 8. The method of any one of claims 1 to 7, wherein the solution is sprayed on the surface of the water. The method of claim 1, wherein the binder is sprayed or poured on the surface of the water. The method of claim 1, wherein powdered rubber, peat, cork and / or latex are used as binder.