WO2016082873A1

WO2016082873A1 - Oil adsorbent, process for producing such an oil adsorbent and method of selective adsorption of oils

Info

Publication number: WO2016082873A1
Application number: PCT/EP2014/075679
Authority: WO
Inventors: Gerhard Michael KREUDER; Arno Cordes
Original assignee: Kreuder Gerhard Michael
Priority date: 2014-11-26
Filing date: 2014-11-26
Publication date: 2016-06-02

Abstract

The invention relates to a process for producing an oil adsorbent from renewable raw materials, comprising the comminution of material consisting of renewable raw materials by means of suitable comminution machines to give a granular material and a treatment of the granular material with a reaction mixture comprising enzymes for enzymatic treatment of the granular material. It further relates to an oil adsorbent producible by the process, to a method of selective adsorption of used oils using the oil adsorbent, and to the use of an enzymatic treatment of granular materials made from renewable raw materials for improving particular properties.

Description

OIL ADHESIVES, METHOD FOR PRODUCING SUCH OIL ADSORPTION AGENTS AND METHOD FOR THE SELECTIVE ADSORPTION OF OILS

Technical field of the invention

The invention relates to the enzymatic modification of particle surfaces for

Improvement of aggregation and buoyancy on water. More particularly, it relates to a process for producing an oil sorbent, an oil sorbent which can be produced by the process, a process for selectively adsorbing oils using the oil sorbent, and the use of enzymatic treatment of granules to improve aggregation, buoyancy and reduction the exit of organic matter from the granules.

State of the art

Both our own experiments and various publications show that particles made from renewable materials such as leather are very suitable for removing hydrocarbons from both solid and liquid surfaces (DE 2810140 A 1 and DE 19849427 A 1).

Unfortunately, the legal requirements regarding the discharge of organic dry matter (OTS) into the water (limit value <20 mg / l, test method according to

Ölbinder ", Joint Ministerial Gazette G3191 A, Federal Minister for the Environment,

Conservation and Nuclear Safety (1998)).

Even after repeated washing of the leather granules with water, these values are above 100 mg / l (own experiments of the inventors). Thus, an application by ASA Spezialenzyme GmbH to the Materialprüfungsamt Nordrhein-Westfalen, Dortmund, for a license to use leather granulate as an oil binder for use in waters was not granted.

Oil binders are used in large quantities in various industrial sectors

Absorbing spilled oil used on floors. Fire departments and

Water guards use oil binders for oil spills on land and water. Oil binders, which are universally applicable to water and land, and at the same time a high

Oil binding capacity are also due to the strict legal

Requirements for use in waters currently not commercially available. The enzymatic action of phenol oxidases is as follows today: mono- and polyhydric phenols, their derivatives (halogen, amino, nitro compounds) and aromatic amino acids (tyrosine) are oxidized in the presence of oxygen. In this case, radicals that form a polymerization of the reaction products to form

humin substance-like, dark brown colored polymers (Haider, K., Arch. Microbiol., 64, (1969) 338-348).

Also Ligninabbauprodukte, ligninartige wastes, wastes from the

Wood bark utilization, proteins and tannins or constituents of these materials can be converted by phenol oxidases and / or incorporated into the polymers. It was thus possible to use phenol oxidases and lignosulfonate to develop a binder for the bonding of chipboard (see DE 3644397 C1).

In view of the prior art, it is an object of the present invention to provide a process for producing oil sorbents which is capable of providing such agents having excellent oil absorbing ability, improved buoyancy and aggregating ability on surfaces of liquids show and at the same time only small amounts of organic

Discharge dry matter in the surrounding medium and also do not pose a burden on the environment by a content of potentially toxic inorganic compounds. Furthermore, it is an object of this compound to improve such

To provide oil adsorbents and methods for the selective separation of oils from liquids.

Subject of the invention

These objects have been achieved by the present invention and its embodiments set forth below.

The invention relates in a first aspect to a method for producing a

Oil adsorbent from renewable raw materials of plant origin, comprising the comminution of material consisting of renewable raw materials of vegetable origin by means of suitable crushing into granules and a treatment of the granules with a reaction mixture containing enzymes for the enzymatic treatment of the granules.

In a preferred embodiment of this process, the renewable raw materials of plant origin are cellulose-containing materials. In another preferred embodiment of this process, the renewable raw materials of plant origin are hemicellulose-containing materials.

In a further preferred embodiment of this process, the enzymes for the enzymatic treatment of the granules are enzymes for the enzymatic treatment of the surface of the granules, preferably enzymes for the cross-linking of residues on the surface of the granules.

In a preferred embodiment of this process, the enzymes for the enzymatic treatment of the granules are enzymes from the groups phenol oxidases, peroxidases and transglutaminases. In a further preferred embodiment of this process, the enzymes for the enzymatic treatment of the granules from the group of phenol oxidases are the enzymes laccase, polyphenol oxidase and tyrosinase.

In another preferred embodiment of this method, the

Reaction mixture for the treatment of the granules one or more substances from the group comprising monohydric or polyhydric phenols, their derivatives, lignin degradation products, lignin-type waste materials, waste from the utilization of wood bark, proteins,

proteinaceous wastes, tannins and other tannins were added.

In a preferred embodiment of this process, in particular one or more of the following compounds from the group comprising caffeic acid, hydroquinone, the reaction mixture for carrying out the enzymatic reaction

Pyrocatechol, pyrogallol, guaiacol, 2,6-dimethoxyphenol, 3-methylcatechol,

Syringaldehyde, vanillic acid, vanillin, methylsyringic acid, 4-methylcatechol,

Sulfite waste liquor, sulfate lignin, lignin sulfonic acid, 1-hydroxybenzotriazole, tyrosine,

Phenylalanine, tryptophan, casein, casein peptone, gelatin, whey added. In a second aspect, the present invention relates to an oil adsorbent obtainable by a process according to the first aspect of the present invention.

In a third aspect, the present invention relates to a process for the selective adsorption of mineral oils, petroleum, gear oils, motor oils, hydraulic oils, rapeseed oil and waste oils of various kinds using an oil adsorbent according to the second aspect of the present invention.

In a preferred embodiment of this process, the process serves to remove said oils from the surface of an aqueous liquid, in particular from a water surface. - -

In another preferred embodiment of this method, the method is for removing said oils from solid surfaces.

In a fourth aspect, the present invention relates to the use of an enzymatic treatment of granules of renewable raw materials of plant origin for improving the aggregation of the granules on surfaces of

Liquids and / or to improve the buoyancy of the granules and / or to reduce the escape of organic matter from the granules.

Description of the invention

It has now surprisingly been found, compared with the known state of the art, that the properties of granules of renewable raw materials, such as e.g.

cellulosic and hemicellulose containing materials by the superficial

Treatment with enzymes without the risk of toxic loading of these materials can be significantly improved.

By the treatment of e.g. Wood granules with the enzymes described herein and optionally with the addition of phenolic compounds, aromatic

Amino acids or waste materials, the following effects are achieved: the surface of the granules is sealed by the cross-linking of superficial residues, the leakage of organic matter and the abrasion of very small particles is minimized and thus falls below the legal limit for use in waters and the buoyancy of the granules on water will be improved.

The surface of the renewable raw material is modified according to the present invention by enzymatic reactions so that when used in waters, an improved aggregation of the oil-binding particles during and after oil absorption is enabled. Thus, a widespread distribution of the oil-binding particles, which may arise due to weather influences and the prevailing flow conditions, avoided on the water. Preferably, the aggregation of the particles on water surfaces is improved by 20% to 500%. Furthermore, the buoyancy of the oil-binding particles is improved. Preferably, the amount of particles floatable on water surfaces is reduced to <1%. In addition, the deposition of oil-laden particles in riparian areas and on aquatic plants is avoided, thereby protecting the environment. - -

In addition, the leakage of organic matter from the oil binder is significantly reduced.

By treating granules such as wood granules with the herein

described enzymes and in particular with the addition of phenolic

Compounds (e.g., hydroxybenzotriazole), aromatic amino acids, or waste create covalent bonds and thus achieve true close meshing. In contrast, in a hydrophobization by tanning or alum only an impregnation of the granules and no permanent chemical bonds. While the use of chromium (III) sulfate produces consistent chemical bonds, the toxicity of chromium is a major problem here. As renewable raw materials of plant origin within the meaning of the present

The invention preferably uses cellulosic or hemicellulose-containing materials. In a particularly preferred embodiment of the present invention, cellulose-containing materials are used. In a further particularly preferred embodiment of the present invention, hemicellulose-containing materials are used.

For the purposes of the present invention, granulate is preferably understood to be comminuted material, more preferably material having a particle size of less than 5 mm.

The enzymes for enzymatic treatment of the granules are preferably suitable for enzymatically converting residues on the surface of the granules. More preferably, the enzymes are suitable peptide chains or sugar chains on the

Cross-link surface of the granules, in particular polysaccharides such as cellulose or hemicellulose. The skilled person is with the help of his general

Expertise able to select without inventive step suitable enzymes for the particular substrate, which are able to the surface of the material

cross-linking and sealing, thus achieving the advantageous results of the present invention.

Preferably here enzymes from the group of oxidoreductases, in particular phenol oxidases such as polyphenol oxidases, laccases and tyrosinases are used. These enzymes are capable of using certain Cosubstrate the granule surface to modify it to cause an aggregation effect and to agglomerate the oil-laden particles on aqueous surfaces. The oil binding capacity of the particles remains unchanged or is slightly improved. Our own experiments showed that cellulose- and hemicellulose-containing materials in

Granular form have a high oil absorption capacity. However, use on waters is currently not possible due to characteristics such as poor buoyancy and retrievability from the water. Surprisingly, however, it was possible to demonstrate that the granule surface can be modified by the use of certain enzymes in such a way that an aggregation of the oil-binding particles occurs, thus significantly improving the retrievability of the oil-laden granule particles from the water and thus their reusability. A positive side issue is that leakage of organic matter from the oil binder is minimized.

As cosubstrates for the purposes of the present invention are particularly preferred

Lignin degradation products such. Caffeic acid or hydroquinone, ligninous wastes such as e.g. Sulfite waste liquor or sulphate lignin and waste from the utilization of wood bark. As raw material for the manufacturing process cellulose-containing residues such as

Shrub cut, Kaff, waste from pulp production, straw grave and wood particles, but also fermentation residues from biogas production and grains are used.

The method of selective adsorption of mineral oils, petroleum, gear oils, motor oils, hydraulic oils, rapeseed oil and waste oils of various kinds according to the present invention is basically suitable for any kind of separation of a nonpolar solvent from a polar solvent such as water. One of the advantages of the present invention is that the oil sorbent of the present invention can be used on both dry surfaces and solid surfaces.

The present invention further provides the use of an enzymatic

Treatment of granules of renewable raw materials of plant origin, in particular cellulose- and / or hemicellulose-containing materials, to improve the aggregation of these granules on surfaces of liquids and / or to

Improving the buoyancy of the granules and / or reducing the leakage of organic matter from the granules available. In a preferred embodiment of this use, the purpose of the use is to improve the aggregation of these granules on surfaces of liquids. In , In another preferred embodiment of this use, the object of use is to improve the buoyancy of the granules. In a further preferred embodiment of this use, the aim of the use is to reduce the leakage of organic matter from the granules.

The manufacturing process for the oil binder consists of:

1. Pre-shredding the renewable raw material of plant origin with a shredder to a grain size <4 cm,

2. removal of the metals,

3. Granulation of the material with a granulator to a particle size <5 mm, and

4. Enzymatic conversion.

Examples

The invention is further illustrated by the non-limiting examples below:

Example 1 - Preparation of an oil binder from wood granules

500 kg of wood chips are shredded in a shredder (Alpine company, sieve size 3 cm) and transported on a conveyor belt on which a

Magnetic separator metals are removed. After that, the material is in one

Cutting mill (Rapid) crushed to a particle size <5 mm. Over a

Sprayer is then a mixture of 20 units of laccase and 2 g

Hydroxybenzotriazole per kg of wood applied to the material. Thereafter, an incubation of 4 hrs. At 40 ° C with stirring and oxygen addition.

Example 2 - Use of the oil binder to remove oils from the

water surface

A pool of water is filled with 50 liters of brackish water and 100 ml of engine oil HD15-W40 added until an oil carpet forms. Thereafter, 20 g of enzymatically treated Olbindemittel be sprinkled according to Example 1 on the Olteppich. Based on the Olschlieren is observed that the oil is selectively absorbed by the Olbindemittel. The process takes 60 minutes. Thereafter, only the aggregated, laden on the surface floating Olbindemittel is skimmed off, dried and weighed. There is no visible oil on the water surface. Furthermore, the content of organic dry substance (oTS) in the water body is determined. The same experiment is carried out for comparison with untreated leather granules and with chemically treated leather granules.

The chemically treated granules used herein were prepared as follows. 100 g of leather granules are gently stirred in an aqueous suspension with the tanning agent tannin (100 g per liter) at 40 ° C. for 4 h. Thereafter, the supernatant is carefully poured off, the granules are washed three times with water and then dried.

The dry weight of the enzymatically treated and oil-laden wood granules is 92.4 g, which is 77% of the total oil-loaded granules. The rest of the oil-laden granules swim occasionally on the water surface or is attached to the glass wall. The dry weight of the untreated loaded with oil

Leather granules are 26.4 g, which is 22% of the total oil-loaded granules. Thus, the amount of oil binder aggregated to water was compared to

Untreated leather granules by the enzyme treatment increased by a factor of 3.5 (see Table 1). It can also be seen that the aggregated amount of oil binder in the case of enzymatic granules is markedly higher than that of tannin-treated granules.

The further results are shown in Table 1:

Tab. 1: Comparison of untreated and chemically crosslinked leather granules with enzymatically treated wood granules

These results show that only with the help of the enzymatic cross-linking the legal limit values for the organic dry substance for use in waters (20 mg / L) can be undercut.

Claims

claims

Process for the preparation of an oil sorbent from renewable raw materials of vegetable origin, comprising the comminution of material consisting of renewable raw materials of plant origin by means of suitable comminution machines into a granulate and a treatment of the granules with a reaction mixture containing enzymes for the enzymatic treatment of the granules.

A method according to claim 1, characterized in that the renewable raw materials of plant origin are cellulose-containing materials.

A method according to claim 1, characterized in that the renewable raw materials of plant origin are hemicellulose-containing materials.

Method according to at least one of the preceding claims, characterized in that the enzymes for the enzymatic treatment of the granules are enzymes for the enzymatic treatment of the surface of the granules, preferably enzymes for the cross-linking of residues on the surface of the granules.

Method according to at least one of the preceding claims, characterized in that the enzymes for enzymatic treatment of the granules are enzymes from the groups phenol oxidases, peroxidases and transglutaminases.

Method according to at least one of the preceding claims, characterized in that the enzymes for the enzymatic treatment of the granules from the group of phenol oxidases are the enzymes laccase, polyphenol oxidase and tyrosinase.

Method according to at least one of the preceding claims, characterized in that the reaction mixture for the treatment of granules one or more substances from the group comprising monohydric or polyhydric phenols, their derivatives, lignin degradation products, lignin-like waste, waste wood from bark utilization, proteins, proteinaceous waste, Tannins and other tannins are added.

Method according to at least one of the preceding claims, characterized in that the reaction mixture for carrying out the

enzymatic reaction, in particular one or more of the following

Compounds from the group comprising caffeic acid, hydroquinone, Pyrocatechol, pyrogallol, guaiacol, 2,6-dimethoxyphenol, 3-methylcatechol, syringaldehyde, vanillic acid, vanillin, methylsyringic acid, 4-methylcatechol, sulfite liquor, sulfate lignin, lignin sulfonic acid, 1-hydroxybenzotriazole, tyrosine, phenylalanine, tryptophan, casein, casein peptone, gelatin, Whey can be added.

Oil adsorbent preparable by a method according to any one of claims 1 to 8.

Selective adsorption of mineral oils, petroleum, gear oils, motor oils, hydraulic oils, rapeseed oil and waste oils of various kinds under

Use of an oil adsorbent according to claim 9.

A method according to claim 10, characterized in that the method for removing said oils from the surface of an aqueous liquid, in particular a water surface, is used.

A method according to claim 10, characterized in that the method serves to remove said oils from solid surfaces.

Use of an enzymatic treatment of granules

renewable raw materials of plant origin to improve the aggregation of the granules on surfaces of liquids and / or to improve the buoyancy of the granules and / or to reduce the escape of organic matter from the granules.