EP0996592A2

EP0996592A2 - Method for removing pollutant organic fluids from surface water

Info

Publication number: EP0996592A2
Application number: EP98936379A
Authority: EP
Inventors: Michael Voigt; Ernst Grigat; Wolfgang Schulz-Schlitte; Hans-Peter Esser
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1997-07-05
Filing date: 1998-06-22
Publication date: 2000-05-03
Also published as: NO996181L; CN1261863A; NO996181D0; DE19728833A1; JP2002510249A; AU728449B2; AU8540298A; CA2294726A1; WO1999002457A2; WO1999002457A3; KR20010015536A

Abstract

The invention relates to a method for removing pollutant organic fluids, especially oil, from surface waters. According to the inventive method, a suitable binding agent is applied to the water surface, said organic fluid binding with or being absorbed by said binding agent. The binding agent is then removed together with the bound or absorbed fluid.

Description

Process for the removal of organic liquids polluting surface waters

The present invention relates to a method for removing surface contaminating organic liquids, in particular oil, in which a binding agent binding the organic liquid is applied to the surface of the water and the binding agent with the attached or absorbed liquid is subsequently removed.

Oil carpets floating on water, for example, pose a serious environmental threat. A particular problem is that even the slightest oil content can poison water and pose a deadly danger to fish and other life forms. When removing such oil spills, it is very important that the oil is removed practically completely and that the oil is removed very quickly so that the oil spill cannot spread or can only spread slightly.

Oil carpets are generally removed by applying a binder to the surface of the water that absorbs the oil and then removing the binder with the bound or absorbed oil.

Materials with a high oil affinity, such as, for example, special plastics or materials with a macroscopically porous structure in liquid or solid form, are generally used as binders, which are applied to the surface of the water, the binder particles binding or absorbing the oil before it floats. form a carpet on the surface of the water, which can then be easily removed.

Since the polymer itself is not dispersed in water or seawater, so that oil droplets floating in the water cannot be removed by the polymer, it is also known from JP 59-039 381 A, an aqueous dispersion of the polymer on the one hand and water containing alcohol as Solvent on the other hand to deliver, which has an excellent dispersibility in water, so that the polymer also gets under the water surface to absorb 01 there

In practice, a large number of different binders are used which, in addition to the polymer, also contain other oil-absorbing components, for example

Sawdust, peat, cork and the like may furthermore be known to add components to the polymer which allow the oil to agglomerate into lumps or the like (JP 54-033 887 A), which can be easily removed

However, the problem with the removal of such oil carpets is still that the 01 spreads quickly, especially in wind and / or strong waves on the open sea, and that a coherent carpet - even from the already bound 01 - is driven apart

Accordingly, it is the object of the present invention, the above

To improve methods for removing surface water polluting organic liquids so that the spread of the organic liquid can be prevented or at least reduced and a later removal, for example by

Suction is made easier

According to the invention, this object is essentially achieved in that a solution or made of a polymer and a water-miscible and / or volatile solvent, which has a lower density than water, is applied to the surface of the water in order to delimit a soiled surface area is therefore a process for the removal of organic liquids which pollute surface water, in order to limit a contaminated surface area, a solution / dispersion of a polymer or a mixture of polymers and a water-miscible and / or volatile solvent which has a lower density than water, is applied to the surface of the water, wherein a binding the organic liquid

Binder before or after the application of the polymer solution / dispersion, is applied to the water surface and then the binder with the bound or absorbed liquid is eliminated, the polymers being biodegradable and selected from aliphatic or partially aromatic polyester, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides

The invention is based on the consideration of placing a barrier around a soiled surface area in order to hold the surface area together and thus counteract a further spread of the contaminants. This ring-shaped barrier is formed according to the invention in that a polymer solution or dispersion is applied to the water surface which is due to their low density and the affinity for organic pollution to form a closed ring along the pollution spreads on the water surface. The solvent mixes with the water or evaporates, causing the polymer to form the desired annular barrier on the water surface, which precipitates the contaminated surface area limited and holds together so that the pollution can hardly spread

The extent of the annular barrier depends essentially on the amount of solution / dispersion that is applied to the surface of the water, and is limited by the fact that the solvent evaporates or mixes with the water

The polymer content of the solution / dispersion is generally up to 50% by weight (based on the total solution or dispersion). Higher concentrations are less suitable because of the insufficient flowability. The polymer contents are preferably 1 to 30% by weight, in particular 5 to 10% by weight -%

In order to support a uniform ring formation, it is advantageous that the solution is applied as uniformly as possible to the water surface. This can be achieved, for example, by spraying the solution onto the water surface The solution or dispersion preferably contains a biodegradable polymer or mixtures of polymers, so that the solution / dispersion or the polymer contained therein can be disposed of without problems.

Suitable biodegradable polymers are 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:

Aliphatic or partially aromatic polyester

A) aliphatic bifunctional alcohols, preferably linear C to Cio-dialcohols such as ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 carbon atoms in the cycloaliphatic ring, such as cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C ₃ -C ₂ -Alkyldiolen, such as neopentyl glycol, and in addition, if necessary, small amounts of higher-functional alcohols such as 1,2,3-propanetriol or trimethylolpropane and from aliphatic bifunctional acids, preferably C -C ₂ -alkyl dicarboxylic acids, such as and preferably succinic acid, Adi pinic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or B) from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of A and B,

the aromatic acids making up no more than 50% by weight, based on all acids;

Aliphatic or partially aromatic polyester urethanes

C) aliphatic bifunctional alcohols, preferably linear C ₂ to cio dialcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably with a C ₅ - or Cβ-cycloaliphatic ring, such as for example Cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C ₃ - C ₂ alkyl diols, such as neopentyl glycol, and in addition, if necessary, small amounts of higher-functional alcohols, preferably C3-C ₂ alkyl polyols, such as 1,2,3-propanetriol or trimethylol propane, and from aliphatic bifunctional acids, preferably C ₂ -C ₂ alkyl dicarboxylic acids, such as ise and preferably succinic acid, adipic acid, and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or D) from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of C and D,

the aromatic acids making up no more than 50% by weight, based on all acids;

E) from the reaction product of C and / or D with aliphatic and / or cycloaliphatic bifunctional and additionally optionally higher-functional isocyanates, preferably with 1 to 12 C atoms or 5 to 8 C atoms in the case of cycloaliphatic isocyanates, for example tetramethylene diisocyanate, hexamethylene diisocyanate , Isophorone diisocyanate, optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher-functional alcohols, preferably C ₃ -C 8 -alkyldi- or -polyols or 5 to 8 C atoms in the case of cycloaliphatic alcohols, for example ethanediol, Hexanediol, butanediol, cyclohexanedimethanol, and / or optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher functional amines and / or amino alcohols with preferably 2 to 12 C atoms in the alkyl chain, for example Ethylenediamine or aminoethanol, and / or optionally further modified amines or alcohols such as for example ethylenediaminethanesulfonic acid, as free acid or as salt,

wherein the ester fraction C) and / or D) is at least 75% by weight, based on the sum of C), D) and E),

Aliphatic or aliphatic-aromatic polyester carbonates

F) aliphatic bifunctional alcohols, preferably linear C ₂ to C ₀ dialkols such as ethanediol, butanediol, hexanediol or especially preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms in the cycloaliphatic ring, such as, for example, cyclohexanedimethanol, and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers therefrom with molecular weights of up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably with C ₂ -C ₂ -alkyldicarboxylic acids, such as, for example, neopentyl glycol and additionally, if appropriate, small amounts of higher-functional alcohols, for example 1,2,3-propanetriol, Trimethylolpropane as well as from aliphatic bifunctional

Acids such as and preferably succinic acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or

G) from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of F and G,

the aromatic acids making up no more than 50% by weight, based on all acids,

H) a carbonate component which is produced from aromatic bifunctional phenols, preferably bisphenol-A, and carbonate donors, for example phosgene

or a carbonate fraction which is produced from aliphatic carbonic acid esters or their derivatives such as, for example, chlorocarbonic acid esters or aliphatic carboxylic acids or their derivatives such as salts and carbonate donors, for example phosgene, where

the ester fraction F) and / or G) is at least 70% by weight, based on the sum of F), G) and H);

Aliphatic or partially aromatic polyester amides

I) aliphatic bifunctional alcohols, preferably linear C ₂ to cio dialcohols such as, for example, ethanediol, butanediol, hexanediol, particularly preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 C atoms, such as, for example, cyclohexanedimethanol , and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C3-Cι ₂ -Alkyldiolen, such as neopentylglycol and additionally optionally small amounts of higher functional alcohols, preferably C3-Cι -Alkylpolyole, such as 1,2,3-propanetriol, trimethylolpropane and from aliphatic bifunctional acids, preferably with 2 to 12 carbon atoms in the alkyl chain, such as and preferably Berns tartaric acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid,

Isophthalic acid, naphthalenedicarboxylic acid and, if necessary, small amounts of higher functional acids such as trimellitic acid or

K) from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the carbon chain, for example hydroxybutyric acid,

Hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide, or a mixture and / or a copolymer of I) and K),

the aromatic acids making up no more than 50% by weight, based on all acids,

L) an amide portion of aliphatic and / or cycloaliphatic bifunctional and / or optionally small amounts of branched bifunctional amines, linear aliphatic C ₂ to Cio-diamines are preferred, and additionally optionally small amounts of higher-functional amines, among the amines preferably hexamethylenediamine, Isophoronediamine and particularly preferably hexamethylenediamine, as well as from linear and / or cycloaliphatic bifunctional acids, preferably with 2 to 12 carbon atoms in the alkyl chain or C ₅ - or Cβ ring in the case of cycloaliphatic acids, preferably adipic acid, and / or optionally small Amounts of branched bifunctional and / or optionally aromatic bifunctional acids such as, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher-functional acids, preferably having 2 to 10 carbon atoms, or

M) from an amide portion of acid- and amine-functionalized building blocks, preferably with 4 to 20 carbon atoms in the cycloaliphatic chain, preferably ω-laurolactam, ε-caprolactam, particularly preferably ε-caprolactam,

or a mixture of L) and M) as an amide component, wherein

the ester fraction I) and / or K) is at least 30% by weight, based on the sum of I), K), L) and M), preferably the weight fraction of the ester structures is 30 to 70% by weight, the fraction of Amide structures is 70 to 30 wt .-%.

All acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters. The biodegradable polyesteramides according to the invention can be synthesized either by the "polyamide method" by stoichiometric mixing of the starting components, if appropriate with the addition of water and subsequent removal of water from the reaction mixture, or by the "polyester method" by stoichiometric mixing of the starting components and addition an excess of diol with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In this second case, the excess diol is distilled off in addition to water. Synthesis by the described “polyester method” is preferred.

The polycondensation can be further accelerated by using known catalysts. Both the known phosphorus compounds which accelerate polyamide synthesis and acidic or organometallic catalysts for the esterification, as well as combinations of the two, are possible for accelerating the polycondensation.

Care must be taken to ensure that the catalysts do not adversely affect the biodegradability or compostability or the quality of the resulting compost.

Furthermore, the polycondensation to polyesteramides can be influenced by the use of lysine, lysine derivatives or other amidically branching products such as, for example, aminoethylaminoethanol, which both accelerate the condensation and lead to branched products (see, for example, DE 3831709).

The production of polyesters, polyester carbonates and polyester urethanes is generally known or is carried out analogously by known processes (cf., 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 further contain 0.1 to 5% by weight, preferably 0.1 to 1% by weight, of branching agents (see also description of the polymers). These branches can, for example, trifunk tional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid. The branching agents increase the melt viscosity of the polyester amides according to the invention to such an extent that extrusion blow molding with these polymers is possible. This does not hinder the biodegradation of these materials.

The biodegradable compostable polyester urethanes, polyesters, polyester carbonates and polyester amides generally have a molecular weight of at least 10,000 g / mol and generally have a statistical distribution of the starting materials in the polymer. In the case of a typical polymer structure, possibly from C) and D) and from E), a completely statistical distribution of the monomer units is not always to be expected.

Biodegradable polymers are commercially available and are offered, for example, by Bayer AG under the product names BAK 1095 and BAK 2195.

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

Other environmentally compatible, water-miscible solvents are dimethyl sulfoxide (DMSO) or N-methyl-2-pyrrolidinone (NMP). Furthermore, the

Solvents mixed with water can be used, eg ethanol / water mixture. The solubility of the solvent in water can also be increased by adding alcohol. The alcohol can have different specifications. For example, methanol, ethanol, propanol (iso-, n-), butanol (n-, iso-, tert.-), or ketones (acetone, 2-butanone) are conceivable. It is essential that the polymer dissolve or be dispersed in the solvent, but is not soluble in water. A solvent mixture containing a solvent has proven particularly suitable a C1-C4 alcohol, a Ci-Cg ketone and / or an aromatic carboxylic acid or a salt thereof is highlighted, which is specifically referred to in particular by the method described in the unpublished German patent application 19 640 032.5 .

To bind the organic liquid, the usual binders can be used, which can be sprayed or poured onto the surface of the water as well as the solution. Examples of such binders are gum powder, peat, cork or latices, which can be used individually or in combination.

The binder can be applied to the surface of the water before or after the solution. In a preferred manner, however, the solution is first applied in order to limit and fix a defined, soiled surface area, which can then subsequently be freed from the oil or another organic liquid. As a result, a time advantage is achieved in particular, by means of which the further spread of the organic liquid polluting the surface water can be minimized.

Claims

claims

1. Process for the removal of organic liquids which pollute surface waters, a solution / dispersion of a polymer or a mixture of polymers and a water-miscible and / or volatile solvent which has a lower density than water being used to delimit a contaminated surface area , is applied to the surface of the water, a binder which binds the organic liquid being applied to the surface of the water before or after the application of the polymer solution / dispersion, and then the binder with the bound or absorbed liquid is removed, the polymers being biodegradable and selected are made of aliphatic or partially aromatic polyester, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides.

2. The method of claim 1, wherein a solution with a polymer content of up to 50 wt .-% is used.

3. The method according to any one of the preceding claims, wherein a solution with a polymer content of 1 to 30 wt .-% is used.

4. The method according to any one of the preceding claims, wherein the polymers used are: Aliphatic or partially aromatic polyesters

A) aliphatic bifunctional alcohols and / or optionally cycloaliphatic bifunctional alcohols and / or partially or completely instead of the diols based on monomeric or oligomeric polyols

Ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000 and / or possibly small amounts of branched bifunctional alcohols and additionally optionally small amounts of higher functional alcohols and from aliphatic bifunctional acids and / or optionally aromatic bifunctional acids and additionally optionally small amounts of higher functional acids or

B) from acid- and alcohol-functionalized building blocks or their derivatives,

or a mixture and / or a copolymer of A and B,

the aromatic acids making up no more than 50% by weight, based on all acids;

Aliphatic or partially aromatic polyester urethanes

C) aliphatic bifunctional alcohols and / or optionally cycloaliphatic bifunctional alcohols and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000 and / or optionally small amounts of branched bifunctional alcohols and additionally optionally small amounts of higher functional alcohols and from aliphatic bifunctional acids and / or optionally aromatic bifunctional and additionally optionally small amounts of higher functional acids or

D) from acid- and alcohol-functionalized building blocks or their derivatives,

or a mixture and / or a copolymer of C and D,

the aromatic acids making up no more than 50% by weight, based on all acids; E) from the reaction product of C and / or D with aliphatic and / or cycloaliphatic bifunctional and additionally optionally higher-functional isocyanates, optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher-functional alcohols and / or optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher functional amines and / or amino alcohols and / or optionally further modified amines or alcohols as free acid or as salt,

wherein the ester fraction C) and / or D) is at least 75% by weight, based on the sum of C), D) and E);

Aliphatic or aliphatic-aromatic polyester carbonates

F) aliphatic bifunctional alcohols and / or optionally cycloaliphatic bifunctional alcohols and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000 and / or optionally small amounts of branched bifunctional alcohols and additionally optionally small amounts of higher functional alcohols and from aliphatic bifunctional acids and / or optionally aromatic bifunctional acids and additionally optionally small amounts of higher functional acids or

G) from acid and alcohol functionalized building blocks or their derivatives

or a mixture and / or a copolymer of F and G, the aromatic acids making up no more than 50% by weight, based on all acids,

H) a carbonate portion, which is made from aromatic bifunctional phenols, and carbonate donors

or

a carbonate portion, which is made from aliphatic carbonic acid esters or their derivatives or aliphatic carboxylic acids or their derivatives and carbonate donors, wherein

Aliphatic or partially aromatic polyester amides

I) aliphatic bifunctional alcohols and / or optionally cycloaliphatic bifunctional alcohols and / or partially or completely instead of the diols based on monomeric or oligomeric polyols

Ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000 and / or optionally small amounts of branched bifunctional alcohols and additionally optionally small amounts of higher functional alcohols and from aliphatic bifunctional acids and / or optionally aromatic bifunctional acids and additionally optionally small amounts of higher functional acids or

K) from acid- and alcohol-functionalized building blocks or their derivatives,

or a mixture and / or a copolymer of I) and K), the aromatic acids making up no more than 50% by weight, based on all acids,

L) an amide component from aliphatic and / or cycloaliphatic bifunctional and / or optionally small amounts of branched bifunctional amines and additionally optionally small amounts of higher functional amines and from linear and / or cycloaliphatic bifunctional acids and / or optionally small amounts of branched bifunctional and / or optionally aromatic bifunctional Acids and, if necessary, small amounts of higher functional acids or

M) from an amide component from acid- and amine-functionalized building blocks,

or a mixture of L) and M) as an amide component, wherein

the ester content I) and / or K) is at least 30% by weight, based on the sum of I), K), L) and M).

5. The method according to any one of the preceding claims, wherein alcohols, ketones, ethers, halogenated or halogen-free hydrocarbons, toluene, dimethyl sulfoxide, N-methyl-2-pyrrolidinone or mixtures thereof, if appropriate in a mixture with water, are used as solvents.

6. The method according to any one of the preceding claims, wherein as a solvent ethanol, methanol, propanol, (n- / iso-), butanol (n-, iso-, tert.-), acetone, 2-butanone, ethyl acetate, dichloromethane, chloroform , Tetrahydrofuran, toluene, dimethyl sulfoxide, N-methyl-3-pyrrolidinone, optionally in a mixture with water.

7. The method according to any one of the preceding claims, wherein a solvent mixture containing a -CC alcohol, a C _r C ₆ ketone and / or an aromatic carboxylic acid or a salt thereof is used as the solution.

8. The method according to any one of the preceding claims, wherein the solution is sprayed onto the surface of the water.

9. The method according to any one of the preceding claims, wherein the binder is sprayed or poured onto the surface of the water.

10. The method according to any one of the preceding claims, wherein rubber powder, peat, cork and / or latices is used as a binder.