WO2014161701A1

WO2014161701A1 - Use of abrasive fibres which accumulate when transporting polymer material through conveyor pipes, as absorption agents for hydrophobic substances

Info

Publication number: WO2014161701A1
Application number: PCT/EP2014/054366
Authority: WO
Inventors: Dietrich Von Der Wense
Original assignee: Innospec Ltd.; Innospec Leuna Gmbh
Priority date: 2013-04-04
Filing date: 2014-03-06
Publication date: 2014-10-09
Also published as: DE102013103352A1

Abstract

The invention relates to the use of abrasive fibres, also known as angel hair, which accumulate when transporting polymer material through conveyor pipes, as absorption agents for hydrophobic substances.

Description

Use of Abriebfasern, which are incurred in the transport of polymer material through delivery lines, as adsorbent for hydrophobic substances

The invention relates to the use of abrasive fibers, so-called angel hair, which are obtained during the transport of polymer material through delivery lines, as adsorbents for hydrophobic substances.

The problem of contaminating land and water with oil products and various chemicals has become increasingly important over the last decades. Pollution sources include accidents in the transport and shipping sectors, impurities from industrial petroleum processing or storage of oils, and inadmissible disposal of used oils from vehicles and machinery.

There are several approaches to eliminating impurities once formed, with many disposal measures being unsatisfactory, especially with oil contaminants. In the case of impurities on solid ground, for example, the soil is removed over a large area or it is worked with oil-absorbing or oil-binding agents. Pollution of the water and especially the sea are almost always acute disasters. The heretofore known oil binders are often only of little effect, such. As the Oilsink known mixture of bleaching earth, diatomaceous earth and cement, which binds the floating oil on the water and then sinks to the bottom of the sea or the water.

Other, more efficient oil binders are known, but must be prepared with greater effort or with multi-step process.

For example, an oil binder for binding petroleum or petroleum products floating on or at the surface of the water according to DE 4320908 A1 is known. Here, polyethylene is used in finely divided form, which is obtained from various waste products by processing measures such as cutting, scraping, etc. in fine-fiber form. Although this option offers the advantage that waste products can be reused, it requires a more or less elaborate processing step to produce a material, ie fibers with a sufficiently large surface area. Also known from EP 2392630 A1 is a spray product of waxes in the form of a fibrous felted wax wool, which can be used to clean a wide variety of media. The product is commercially available as Deurex®Pure. Used here are spray products of polyethylene wax or polypropylene wax, wherein molten low-viscosity waxes of the raw materials are atomized under pressure to fibrous felted polymer wool. Consequently, for this purpose, the raw materials, which are present for example in granular form, must be melted, liquefied and then sprayed under pressure. Defined conditions must be observed for all steps in order to obtain a wool-like product with a sufficiently large, receptive surface at the end.

The required, relatively complex processing steps cause the already known binders are expensive.

The object of the invention was therefore to provide an adsorbent for oily or total for hydrophobic impurities, which does not have the disadvantages mentioned above. In particular, it should be less expensive than the already known products and easier to produce.

The object is achieved by the use of abrasive fibers, which are obtained during transport of polymer material through delivery lines, as adsorbents for hydrophobic substances according to claim 1. Further preferred embodiments emerge from the subclaims.

The abrasion fibers of the invention represent the resulting in the production of plastics abrasion in the form of so-called "angel hair" (angel hair). This abrasion occurs when the granules usually produced in the production of polymer materials are transported in the tubes of production, which in Standard case pneumatic. The pneumatic transport is preferably carried out by means of air, in particular hot air at temperatures above 25 ° C. In this case, abrasion of the granules on the tube walls causes abrasion, with a closed abrasion layer, the so-called "snake skin", first forming on the tube wall of the conveying lines and by contact with the tube wall and the granulate particles. Depending on the load and structure of this layer, individual fibers, largely longitudinal, are torn out, which are referred to as angel hair.

This abrasion occurs in most polymeric materials, especially in polymers such as polyethylene, but also, for example, ethylene vinyl acetate. The abrasion is in the form of long Fibers having a substantially round cross section, in particular having a length of 5 mm to 10 m, preferably cm to 5 m, and a diameter of 50 nm to 100 mm, preferably 1 mm to 10 mm. These fibers interweave with each other (agglomeration), whereby delivery lines or their internals can be added. Angel's hair is usually present as a ball of long threads or in the form of fibrous felted wool, is separated from the granules at the end of production.

Angel hair, i. fibrous abrasion has heretofore been considered a pure waste product, i. it did not have any use and had to be removed and disposed of, in part costly and labor intensive. In contrast to all adsorbents and oil binders described above, angel hair is, however, a product which does not have to be produced separately by costly work steps.

Surprisingly, it has been found that this fibrous abrasion can be used without further processing steps as adsorbent (synonym: binder) for hydrophobic substances. Such suitability of the simple angel hair as an adsorbent or its adsorption capacity has hitherto been completely unknown and is therefore completely new. The terms abrasion, fibrous abrasion and abrasion fibers and angel hair are used synonymously here.

The term "comprising" used below means in a preferred form in each case "consist of".

The polymeric material from which the abrasive fibers are made comprises synthetic products such as polyethylene (PE), polypropylene (PP) or ethylene vinyl acetate (EVA) or degradation products made by thermal, catalytic or radioactive degradation, as well as natural products. Preference is given to PE and EVA. Since the abrasion occurs at a later time to the conveyed product, it can consist of pure polymer material, but also of mixtures of different polymer materials. Also included are physical mixtures in all mixing ratios, for example 1: 100 to 100: 1, preferably 1:10 to 10: 1 (by weight), and synthetic copolymer mixtures of the respective monomers. The polymer materials may have an average molecular weight distribution of 200 to 1,000 g / mole.

According to the invention, PE comprises in particular PE-HD, PE-LD and PE-LLD according to the definitions below.

PE-HD (HDPE, high-density PE): density between 0,94 g / cm ³ and 0,97 g / cm ³ , PE-LD (LDPE, low-density PE): Density between 0.915 g / cm ³ and 0.935 g / cm ³ , PE-LLD (LLDPE): linear low-density polyethylene whose polymer molecule has only short branching. These branches are prepared by copolymerization of ethene and higher C ₃ -C ₈ -α-olefins (typically butene, hexene or octene), content of alpha-olefin: 5 -12% by mass.

The EVA comprises vinyl acetate contents of from 1 to 99% by weight, preferably from 5 to 90% by weight. In one embodiment, mixtures of different EVAs having average molecular weights between 100,000 and 300,000 g / mol and vinyl acetate contents between 9% and 18% are used. Preference is given to using EVAs which were produced by means of high-pressure polymerization.

PP and PE are preferably produced by the Ziegler-Natta process, the Fischer-Tropsch process or the metallocene process or are synthetic polymers which are produced by thermal, catalytic or radioactive degradation or are produced in the production of polyolefins as low molecular waxy wastes. and synthetic polymers made from alpha-olefin by the high pressure process. Also included are mixtures of said polymers containing up to 25% EVA. In a broader sense, the polymeric material also includes microcrystalline waxes.

By "hydrophobic substances" are substances with a log K ₀ w (logarithmic distribution coefficient between n-octanol and water) greater than 1 (between 1 and 10), preferably greater than 2 (between 2 and 9), most preferably greater than 3 (between 3 and 8) In particular, hydrophobic substances are oils or hydrophobic chemicals.

The term "oils" includes in particular water-immiscible liquids such as oil wastes, waste oils and heavy oils but also gasoline such as light gasoline and jet fuel and diesel, and fatty oils, essential oils, mineral oils, silicone oils, heavy oils, engine oils, fuel oil, kerosene, Rapeseed oil, thistle oil, soybean oil, corn oil, peanut oil, olive oil, hering oil, palm oil, sunflower oil, cottonseed oil, etc. alone or in a mixture. In summary, all synthetic and vegetable oils are adsorptive.

"(Hydrophobic) chemicals" include in particular nonpolar organic solvents such as low molecular weight branched and unbranched, saturated and unsaturated hydrocarbons, preferably having 5 to 12 carbon atoms, more preferably having 5 to 10 carbon atoms, most preferably pentane, n- or cyclohexane, n - or cyclo-heptane, octane, nonane and decane and aromatic ring compounds, preferably with 6 to 10 Carbon atoms which optionally carry further aliphatic or aromatic substituents or functional groups such as hydroxyl groups, for example benzene, toluene, xylene, Me sytilen, phenol. In general, nonpolar organic solvents are understood to mean those which have a log _Kow as defined above for hydrophobic substances in general, or a polarity index of Snyder of from 5 to 1, in particular from 4 to 2, preferably from 3.5 to 2.5, exhibit. Furthermore, the term "(hydrophobic) chemicals" includes in particular dioxins (in particular polyfluorinated, polychlorinated, polybrominated dibenzodioxins and dibenzofurans) and anilines.

Surprisingly, the abrasive fiber can also be used to separate from mixtures of polar substances, in particular from liquid mixtures of polar substances, preferably from aqueous mixtures, the less polar / least polar component. In other words, the abrasive fibers are used as adsorbents for the separation of a polar substance from a mixture with at least one second, more polar substance. In this embodiment, the term "hydrophobic substance" also includes substances with a polarity less than that of water or with a log K _ow <1, preferably between -1 and +1.

Thus, the abrasion fiber from a mixture of water and alcohol may be separated by adsorption alcohol completely (ethanol log K _ow: -0.30). This also works with surfactants, ie surfactants are separated from mixtures with water by adsorption in the abrasive fiber.

The abrasive fibers have an extremely low bulk density of up to 0.02 g / cm ³ and a surface area up to 5 m ² / g, therefore they adsorb the above-mentioned substances, such as. As gasolines, diesel and waste oils up to 5 times, preferably 10 times, most preferably 100 times the amount of its own weight.

The adsorption of the hydrophobic substances is used to separate them from, in particular liquid, mixtures with hydrophilic / polar substances, in particular from water or aqueous mixtures (hydrophilic: log K _ow <0; polar: polarity index from 4 to 8, in particular from 5 to 7, preferably from 5.5 to 6.5, according to Snyder).

Alternatively, the adsorption can also be used to separate hydrophobic substances from mixtures with solids, in particular from all types of soils / substrates, for example from sandy, muddy and earthy soils. Initially, this requires an order, preferably a mechanical incorporation, so that the clumping and binding property, the hydrophobic substances contained in the solids / soils / substrates can be easily removed.

In summary, the abrasive fibers are used as adsorbents for liquid mixtures of hydrophobic and hydrophilic substances or for mixtures with solids containing hydrophobic substances to separate the hydrophobic substances by adsorption in the abrasive fiber. In other words, the abrasive fibers are used particularly for land applications or for applications in water / waters.

When used in water / waters, it is advantageous that the abrasive fibers are inert, i. there are no reactions. A water absorption does not take place, and the product is easy to separate and residue-free from the water. The separation is still very easy as the product floats on the water.

Important areas of application are preventive water protection, prevention or direct absorption of oil or solvent pollution shortly after the formation of pollution, cleaning and keeping clean of shipping lanes, cleaning and keeping clean of oil spills, eg. For example, at locks, boat docks or harbors, preventive cleaning of oil separators, oil separation and recycling of oils in filter technology, separation of difficult or non-water soluble solvents (chemical separation) and their recycling in filter technology, oil separation in wastewater treatment and wastewater treatment, oil separation and their recycling in the oil-naphtha recovery, oil separation and recycling of waste oils / waste, oil separation or recovery of oils used in the production of vegetable oils, and many applications in the chemical industry that produce or recycle water-insoluble fluids.

The most important application is the cleaning of oil polluted waters, rivers, seas and their beaches. The abrasive fiber can also be used in high seas on seas or oceans for the environmentally friendly disposal of oil spills. The swell positively influences the absorption of the oil pollution. Due to the intensive movement process, the oil pollution is absorbed faster.

The abrasion fibers are particularly suitable as binders for waste oil, heavy oil, oil wastes, vegetable oils, animal oils, but also for crude oil, as it comes from the earth and is explored under the seas, and can be used as a binder for underwater applications, because They can also bind these oils or crude oils under the water surface and thus environmentally friendly from contaminated areas such as from the seabed or sea bottom, or they can also be used preventively because they float for years on the water, can not dissolve and thus preventively contribute to the prevention of oil contamination in biotopes, in locks, in harbors, on oil rigs or to protect against oil pollution in inland waters and can also be used in high seas on lakes or seas for environmentally friendly disposal of oil and solvent pollution, because the absorption of oil or solvent pollution is positively influenced by an intense swell. The abrasive fibers may be contained in a package which is permeable to water and preferably floats on water. Floating on water may be due to the packaging itself or due to the abrasive fibers providing sufficient buoyancy. The more they are moved in a water-permeable packaging by the waves, the faster the oil spills or solvent contaminants are absorbed and because the soaked with the contaminants abrasion fiber does not sink in the water, so floating, the packaging unit can be removed mechanically from the water easily.

The abrasive fiber is in particular as a binder for all fuels, gasolines, diesel but also for light gasoline or aviation gasoline and as a binder for oil-contaminated sands, mud, earth, beaches, sandy beaches, in which the binder, however, must be mechanically incorporated, lakes, seas or rivers or for cleaning oil-contaminated biotopes. In particular, it is also suitable for removing oil or solvent contamination in ice water or in the Arctic Ocean, while it can be used both on the water surface, as well as under water. Furthermore, the abrasive fiber can be used as a binder, in particular as a binder for oil- or solvent-contaminated roads after car accidents or other accidents in which water-insoluble or water-poorly soluble solvents have leaked, and used as a binder for numerous environmentally harmful aliphatic solvents and surface-active surfactants, in particular water-insoluble or sparingly soluble low molecular weight, branched or unbranched and cyclic hydrocarbons (eg., Pentane, n- or cyclohexane, n- or cyclo-heptane, octane, nonane, decane, etc.) adsorbed and thus after receiving the Pollutants are environmentally friendly from contaminated buildings, company premises, land areas and rivers, lakes and seas are removed.

After adsorption, separation of the abrasive fibers is possible, for example by separation by means of a centrifuge, which allows the reuse of both the abrasive fibers and the hydrophobic substances. In the following, the invention will be explained by way of examples without being limited thereto.

Examples

example 1

100 g of polyethylene abrasion fiber prepared by the Fischer-Tropsch method having an average molecular weight distribution of 400 to 1,000 g / mol are mixed with waste oil and alternatively with diesel fuel at room temperature (20 ° C). Subsequently, the abrasive fibers are removed and the adsorption is determined by weighing:

Example 2

100 g of abrasive fiber, obtained in the production of polyethylene by the Ziegler method with an average molecular weight distribution of 400 to 2,500 g / mol, are mixed with hexane at room temperature (20 ° C). Then the abrasive fibers are removed and weighed:

Example 3

100 g of abrasion fiber ethylene-vinyl acetate copolymer (EVA: CAS: 24937-78-8; high-pressure polymerization) are treated at room temperature (20 ° C) with hexane for 1 h (304.2 g of hexane) and then quickly separated via filters. The adsorption is determined by weighing: hydrophobic substance amount of absorbed hydrophobic

Substance [g]

Hexane 156.3 Example 4

100 g of abrasion fiber ethylene-vinyl acetate copolymer (EVA: CAS: 24937-78-8; high-pressure polymerization) are at room temperature (20 ° C) for 1 h with xylene added (527.5 g of xylene) and then quickly separated via filters. The adsorption is determined by weighing:

Example 5

100 g of abrasive fiber ethylene-vinyl acetate copolymer (EVA: CAS: 24937-78-8; high-pressure polymerization) are treated at room temperature (20 ° C) with olive oil for 1 h (303.4 g olive oil) and then quickly separated via filters. The adsorption is determined by weighing:

After 24 h almost 60g of oil had leaked out, then remaining oil intake: 241 g.

In Examples 3, 4, 5, a mixture of different EVAs with average molecular weights between 100,000 and 300,000 g / mol and vinyl acetate contents between 9% and 18% was preferably used.

Claims

claims

1 . Use of Abriebfasern, which are incurred in the transport of polymer material through delivery lines, as adsorbent for hydrophobic substances.

2. Use of abrasive fibers as adsorbents for hydrophobic substances according to claim 1, characterized in that the abrasive fibers of polyethylene, polypropylene or ethylene vinyl acetate or degradation products, which were produced by thermal, catalytic or radioactive degradation and natural products or mixtures thereof.

3. The use of Abriebfasernais adsorbent for hydrophobic substances according to claim 1 or 2, characterized in that the abrasive fibers of polyethylene or ethylene vinyl acetate or mixtures thereof.

Use of abrasive fibers as adsorbents for hydrophobic substances according to one or more of claims 1-3, characterized in that the hydrophobic substances are oils or hydrophobic chemicals.

Use of abrasive fibers as adsorbents for hydrophobic substances according to one or more of claims 1-4, characterized in that the hydrophobic chemicals are nonpolar organic solvents.

6. The use of abrasive fibers as adsorbents for hydrophobic substances according to one or more of claims 1-5, characterized in that the abrasive fibers are present in Knäulform and / or in the form of fibrous felted wool.

7. Use of abrasive fibers as adsorbents for hydrophobic substances according to one or more of claims 1-6, characterized in that the adsorbent for liquid mixtures of hydrophobic and hydrophilic substances or for mixtures with solids, in which hydrophobic substances are used to to separate the hydrophobic substances by adsorption in the abrasive fiber.

8. Use of abrasive fibers as adsorbents for hydrophobic substances according to one or more of claims 1-7, characterized in that the adsorbent for land applications or for applications in water / waters is used.

9. Use of abrasive fibers as adsorbents for hydrophobic substances according to one or more of claims 1-8, characterized in that the adsorbent for the separation of a polar substance from a mixture with at least one second, more polar substance is used.