CA1060874A - Process for producing oil-absorbing materials - Google Patents
Process for producing oil-absorbing materialsInfo
- Publication number
- CA1060874A CA1060874A CA252,878A CA252878A CA1060874A CA 1060874 A CA1060874 A CA 1060874A CA 252878 A CA252878 A CA 252878A CA 1060874 A CA1060874 A CA 1060874A
- Authority
- CA
- Canada
- Prior art keywords
- fibres
- oil
- water
- olefin polymer
- mat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Wood Science & Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Removal Of Floating Material (AREA)
- Road Paving Structures (AREA)
- Cleaning Or Clearing Of The Surface Of Open Water (AREA)
- Water Treatment By Sorption (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Oil-absorbing material having the ability to hold oils in water for long periods and good combustibility after oil absorption and which do not produce hazardous substances during combustion are formed by mixing vegetable fibres with not more than 35% by weight of the fibres of a solid poly-olefin and heating the resulting mixture to melt the poly-olefin and impregnate the vegetable fibres with the molten polyolefin.
Oil-absorbing material having the ability to hold oils in water for long periods and good combustibility after oil absorption and which do not produce hazardous substances during combustion are formed by mixing vegetable fibres with not more than 35% by weight of the fibres of a solid poly-olefin and heating the resulting mixture to melt the poly-olefin and impregnate the vegetable fibres with the molten polyolefin.
Description
7 ~
`
This invention relates to a process ~or producing oil-absorbing materials which are use~ul for collecting oils flowing on the surface of water or those dispersed in water as oil particles.
Various types of oil-absorbing materials have pre~iously been used ~or collecting and removing various oils that have flowed onto the water surface, for example, the ~lowing of heavy oils on the surface of the sea. Oil-ab~orbing materials in general use are structures composed of natural fibers or synthetic fibers in the form of~ for example~ a ~at or a fence.
Known natural fibers used for th~s purpose include~ ~or example, grass peat fibers, wood wool7 and straws, and polypropylene and polyethylene fibers, for example, are known as the synthetic ~iberq .
Since these oil-absorbing materials are evaluated not only by their ability to absorb oils, but also by their combustibility after oil absorption, oil-absorbing materials composed of the natural fibers are preferred to those made of the synthetic fibers.
The oil-absorbing materials of the synthetic fibers melt during combustion, and it is difficult to burn them o~f. Furthermore;
they produce black smoke or hazardous substances during combustion, and there~ore, a special combustion Eurnace or special equipment for the removal of the hazardous substances are required.
On the other hand, since oil-absorbing materials made o~
natural fibers are hydrophilic, they absorb not only oils ~but 8t7'~
also water when put into a water area polluted by oils, and consequently, their ability to absorb oils is restricted to not a small extent.
This defect can be overcome to some extent b~ subjecting the natural fibers to a water-repelling treatment using a chemical consisting mainly of an emulsion-type water repellent of, for example, the aliphatic wax or silicone type. However, when oil-absorbing materials produced from the natural ~ibers ~o treated ~loat on the water surface for long period~ of time while being tossed abouk in the waves o~ the sea and in contact with oils, the water-repellent itself is dissolved and removed out of the oil-absorbing materials so that the water-repelling effect does not last sufficiently. In addition, the emulsifier, heavy metal salts, etc. contained in the treating chemicals may dissolve in the water, and cause adverse effects. Accordingly, the use of the water-repelling chemicals cannot be an appropriate measure.
It is an object of this invention therefore to pro~ide a process -~or producing oil-absorbing materials which rekain the ability to hold oils in water for long periods o~ time, have good combustibility after oil absorption, and do not produce hazardous substances during combuskion.
According to this invention, there is provided a proces~
for producing an oil-absorbing material which comprises mixing vegetable ~ibers with not more than 35% by weight, based on the ~C~608~7~3 fibres, of a solid ole~in polymer, and heating the resul-ting mixture to melt the olefin polymer, and thereby impre~nate the vegetable ~ibres with the molten olefin polymer.
The vegetable fibres used in this invention are fibres separated from grass peat, fibres of coconut shell fibres, flax fibres, straws, and grass fibres.
Examples of the solid olefin polymers used in this inven-tion are homopolymers or copolymers preferably having a weight average molecular weight of at least 15,000 of ethylene, propylene, isobutylene and butene, copolymers of ethylene with vinyl acetate, acrylic acid, acrylates, methacrylic acid, methacrylates, and mixtures of these polymers and copolymers. When olefin polymers having a molecular weight of less than 15,000 are used, the dura-bility of the water-repellency of the resulting oil-absorbing materials is somewhat reduced. Desirably, these olefin polymers are crystalline. The amount of the solid olefin polymer is not more than 35% by weight, 2Q preferably 2 to 30% by weight, based on the vegetable fibres.
Mixing of the vegetable fibres and the solid olefin polymer is performed, for example, by using a stirrer or card. Preferably, the solid olefin polymer is used in -the form of a powder having a size of not greater than 50 mesh, or fibres having a length of not more than 10 mm. Water contained in the vegetable fibres evaporates off during a heating operation, and therefore, lO~
~ 4 it is not necessary to restrict the moisture content of the vegetable fibres. The vegetable fibres well mixed with ~e solid olefin polymer are heated preferably to a temperature above the melting point of the solid olefin polymer. This heating results in the melting of the solid olefin polymer and consequently its impregnation in the vegetable fibres.
Since the amount of the olefin polymer impregnated in the vegetable fibres is not more than 35%
by weight, preferably 2 to 30% by weight, the porosity and surface roughness of the vegetable fibres themselves remain in the resulting structure. A microscopic obser-vation of this structure shows that adhesion of fibres to one another asribable to the impregnated olefin polymer occurs only to a small extent, and the olefin polymer does not cover the surface of the vegetable fibres. Accordingly, the oil-holding ability of the vegetable fibres themselves is not reduced, and the olefin polymer once impregnated into the fibres is not likely to dissolve even during its long-term residence in water. Thus, a long-las$ing stable water-repellency is imparted to the vegetable fibres. When the amount o the olefin polymer exceeds 35% by weight, the wick effect of the vegetable fibres becomes insufficient during burning so that the fibres generate a black smoke and the olefin polymer partly drips from the vegetable fibres.
The oil-absorbing material obtained by the ~`
~i(38t7~
4a process of this invention can be used as packed in a suitable receptacle so as to collect oils dispersed as oil d~oplets in water. Or it can be press-formed into a mat-like structure, or further wrapped by a ~`
net to prevent the breakage of -the mat in water, and in this form, can be used to absorb oils on the water surface. Or the mat so obtained may be placed on the water sur~ace as an oil fence with a suitable float so as to use it to pre~ent the S diffusion of floating oils on the water surface.
According to the process of this invention, there ~an easily be obtained an oil-absorbing material which has water-repellency durable for long period~ of time in water~ good oil~absorbing ability inherent to the vegetable fibers, and good combustibility after oil absorption, and does not produce a hazardous substance during combustion.
The following examples illustrate the present inventionO
Tt should be noted that the invention is not limited to these examples alone Example 1 Polypropylene powder (lOOg) having a size o~ not greater than 100 mesh and an average molecular weight of 25JOOO was added to 1.4 Kg of grass peat fibers (water content 40% by weight~ obtained by beating grass peat in water and separating the fibers from the humus. They were thoroughly mixed by a card. The resulting mixture was maintained in a hot air dryer at 180C for 15 minutes to melt the polypropylene and impregnate it in the peat fibers. The resulting polypropylene-impregnated peat fibers are designated as an oil-absorbing material A.
The above procedure was repeated using 42 g o~ an ethylene/
_ 5 _ ~10ti,C~7~L
vinyl acetate copolymer powder (lO~o by weight of vinyl acetate; melting point 95C) with the heat-meltingtemperature being maintained at 105C. Thus, grass peat fibers impregnated with the above copolymer were obtained. These fibers are designated as an oil-absorbing material B.
When the above procedure was repeated using 42 g of an ethylene/zinc methacrylate copolymer powder (10% of zinc methacrylate; melting point 113C) with the heat-melting tem-perature being maintained at 12~C, grass peat fibers impregnated with the above copolymer were obtained. These fibers are designated as an oil-absorbing materi~l C.
Example 2 1.2 Kg of grass peat ~ibers (water content 20% by weight) obtained by the same method as set forth in Example 1 and 100 g of fibrillated fibers oP polypropylene having an average molecular weight of ~0,000 with an average fiber diameter of 3 mm were thoroughly mixed in a Henschei mixer. The resulting mixture was maintained in a hot air dryer at 180C for 15 minutes to melt the polypropyle~e fibers and impregnate them in the peat fibers. The rssulting polypropylene-impregnated peat ~ibers are designated as an oil-absorbing material D.
The above procedure was repeated using 48 g of fibrillated fiber~ of polyethylene ha~ing an average molecular weight of 20~000 with an average fiber length of 2 mm with the heat-melting temperature being maintained at 140~C. Thus, polyethylene-a cle f~Ar k 0~'7'~
impregnated grass peat fibers were obtained. These ~ibers are designated as an oil-absorbing material E.
; Exam~,l,e 3 0.~ Kg of flax fibers twater content 40%) and 160 g o~
polybutene-l powder having an average molecular weight of 50,000 and a size of not greater than 100 mesh were mixed, and maintained in a far-infrared furnace at 150C for 15 minute~ to melt the polybutene-l and impregnate it into the ~lax ~ibers.
The resulting impregnated flax fibers are designated as an oil-absorbing material F.
Comparative ,Exa,mple A paraffin wax emulsion having the composition indicated below was diluted with water, and the same grass peat fibers as used in Example 1 were immersed in the diluted emulsion.
Then~ the immersed peat fibers ~re squee~ed by rolls to the desired paraffin wax content, and heated at 100C to melt the paraffin wax adhering to the peat ~ibers and impregnate it into the peat fibers. In this manner, products with a paraf~in wax content of 2% by weight and 4% by weight were obtained. These '20 products are designated as oil-absorbing materials I and II, respectively.
~ 7 ~
~10~37~
Formulation_of the para~in wax emulsion Paraf-~in (m.p. 54 5~C~ 90%
Beef tallow free fatty acid 38.8%
Monoethanolamine 3.35%
Water 48.85%
Com~arative Example 2 A commercially available silicone emulsion for water-repellent ~inishing o~ textiles (To~hiba TS~ 831) and a ~ commercially available catalyst (Toshiba CW 80~ were mixed in a volume ratio of 1:1. The same grass peat ~ibers as used in Example 1 were immersed in the mixture, dried at 100C for 10 minutes, and then heat-treated at 180C for 5 minutes to form a product having a silicone pick-up o~ 3% by weight based on the peat ~ibers. The product is designated as an oil-absorbing materila III.
ComParative Example 3 A waxy substance having an average molecular weight of 6,ooo obtained as a by-product in the production o~ polyethy~ene was dissolved in naphtha by heating to ~orm a 30% by weight solution. The same grass peat fibers as used in Example 1 were immersed in the resulting solution, squeezedg cooled, and then crumpled to remove the excess o~ the waxy substance and thereby to obtain a product with a waxy substance pick-up of 150%. The product is designated as an oil-absorbing material IV.
The above procedure was repeated using a 10% by weight ~ `I rad~ ~Or~S
'7~
solution of the ~axy substance, thereby to obtain a product having a waxy substance pick-up of 1~ which is designated as an oil-absorbing material V.
ComParative Example 4 5 ' Atactic polypropylene having an average molecular",`weight of 10,000 obtained as a by-product in the production of polypro-pylene was dissolved in toluene by heating to form a 30% by weight solution of the atactic polypropylene. The same grass peat fibers as used in Example 1 were immersed in the solution, and dried in air to remove the toluene and thereby to obtain a product with an atactic polypropylene pick-up of 100%. The product is designated as an oil-absorbing material VI.
The above procedure was repeated using a lO~o by weight toluene solution of the atactic polypropylene thereby to form a product having an atactic polypropylene pick-up of 10%.
The product is designated as an oil-absorbing material ~II.
ComParative Example 5 - The same procë'dure as in Example 3 was repeated except that the amount of the polybutene-l added was changed to 220 g.
Thus, flax fibers impregnated with polybutene-l were obtained.
This product is designated as an oil-absorbing material VIII.
Test ExamPle 1 ttest ~or the durability of water rePellenc~) 128 g each of the oil-absorbing materials obtained in Examples 1 to 3 and Comparative Examples 1 to S was wrapped in a net made of polyethylene filaments and formed into a square _ ~ _ 0~7'~
mat measuring 40 cm i~ each side and 1 cm in thickness. The mats obtained were each tested for the durability of water repellency in the following manner, The mat was allowed to stand in a water tank in which waves with a height o~ 30 cm, a length of 200 cm and a ~eriod o~
1.2 seconds were artifieially produced, The time that elapsed until the mat completely submerged in water was measured.
When the mat did not submerge~ the state of the mat after per~orming the test ~or 78 hours was obser~ed.
The-same grass peat fiber~ (a) and ~lax fibers (b) as used in Examples 1 and 3 respectiv ly were also tested in the same way as above. The results are shown in Table 1.
Table 1 . . _ . . ~
Oil-absorbing Time that elapsed State of the mat after material until the eomplete the end of the test submerging of the __ _ _ mat ~Hours ? ~
A _ Completely floating B _ Submerged to about 1j8 C _ Submerged to about 1/8 D _ Submerged to about l~lO
E _ Submerged to about l/lO
~5 ~ _ ~ Col Ipletely Ploating ~8t~
V 45 Submerged to aobut 3/4 VI _ Submerged to about 1/4 VIII Completely ~loating Test Exam~ple_2~ (test for the abilitY _o~absorb oils and water) 10 g each of the oil-absorbing materials ohtained in Examples 1 to 3 and Comparative Examples 1 to 5 was wrapped in a net made of polyethylene ~ilaments and formed into a square mat measuring 10 cm in each side and 1 cm in thickness.
The mats obtained were each tested for the ability to absorb oils and water in the following manner.
me mat was ~mmersed ~orcibly in water for a predetermined period o~ time, and oscillated with an amplitude of 4 cm at 100 strokes/minute. The mat so treated was allowed to stand for 5 minutès so as to remove water, and then put into a waker`tank in which a ~loating film o heavy oil A with a thickneæs o~
0.5 mm was formed on the water surace to cause it to absorb the oil, The mat was pulled up from the tank, and al~owed to stand for 5 minutes. The ~inal contents of the oil and water in the mat were determined on the basis of the weight of the mat.
The same grasæ peat fibers (a) and flax fibers (b) as :`
~lJ16~8~7~
used in Examples 1 and 3 were ,tested in the same way as above, The results obtained are shown in Table 2, Table 2 Time for Oil-absorbing Amount of the Amount o~
immersing material oil held by water held the mat in the mat by the mat water __ _ _ (~-oil, ~-ma,t) l~,-wa_er/~ at) A 9.13 0.50 B 9 .51 O .48 . C 9.5 o.55 D 9.55 o.4~
E 9.70 0.40 .
O F 9.38 0.58 (in the dry state) a 6.58 1,27 , b 7.48 1.71 I 6.13 1.50 II 7.26 1.08 III 7.83 0.95 IV 4.58 o.55 V ~.o6 .59 VI 5,05 0.37 VII 8.59 - 0.56 VIII 8, 23 O . 45 A 9.66 0,70 5 minutes B 9.62 o~73 C 9.00 0.68 10ti08'74 D 9 . 60 o ~ 7o E 9.35 0 .65 F 9 .65 0 .59 a 0 .54 7 .34 5minutes b 0 . 63 7 . 2 4 I 6.27 2 .05 II 6 . 66 2 .13 III 7 . 5 0 1 . 24 IV 4.38 o.65 VI 74 5837 l 651 VII 8 . 13 1 . 2 4 VIII 8 .16 0 . 5 6 _ A 9 . 50 0 . 75 B 9 .55 0 .78 C 8.92 0.72 1day D 9.52 0.70 E 9.67 o.66 F 9 38 0.62 b O . 55 8 . 2 2 I 3 .59 5 .3 II 4 . 06 4 . 3 7 III 5 .32 3 .48 IV 4.08 1.19 ,, ~ 8~7~
V 6.47 2,31 VI 4.75 0088 1 day VII 7.,49 2.05 VIII 8.08 0.70 _ .. ..... _ . _ A 9.22 0.81 B 9.23 0.83 C 8.53 o.85 D 9.15 0.80 E 9.68 0.68 F 9.30 0,71 10 days a 0.43 8.93 b 0,48 8.35 I 1.15 7.~8 II 1.52 7.11 III 2.19 6.65 IV 3.81 1.86 V 2.89 6.14 VI 4 .Sl 1. 25 VII 3 . 2 6 6.~7 VIII -~.01 o~7~
.. .. _ . . . _ ~est_ExamPle 3 (test ~or combustibility) Mats were produced in the same way as in Test Example 1 using the oil-absorbing màterials obtained in Examples 1 and 3. Each o~ the mats was placed on a wire gauze, and ignited.
The mats made of the o~l-absorbing materials A to F, I to III, V and VII showed a good burning state without producing any smoke, But the mat mad~ of the oil-absorbing material VIII
burned while generating some black smoke. The mats made of the oil-absorbing materials IV and VI produced a large quantity of black smoke, and a part of the polymer impregnated melted, and dripped from the wire gauze.
ExamPle_d
`
This invention relates to a process ~or producing oil-absorbing materials which are use~ul for collecting oils flowing on the surface of water or those dispersed in water as oil particles.
Various types of oil-absorbing materials have pre~iously been used ~or collecting and removing various oils that have flowed onto the water surface, for example, the ~lowing of heavy oils on the surface of the sea. Oil-ab~orbing materials in general use are structures composed of natural fibers or synthetic fibers in the form of~ for example~ a ~at or a fence.
Known natural fibers used for th~s purpose include~ ~or example, grass peat fibers, wood wool7 and straws, and polypropylene and polyethylene fibers, for example, are known as the synthetic ~iberq .
Since these oil-absorbing materials are evaluated not only by their ability to absorb oils, but also by their combustibility after oil absorption, oil-absorbing materials composed of the natural fibers are preferred to those made of the synthetic fibers.
The oil-absorbing materials of the synthetic fibers melt during combustion, and it is difficult to burn them o~f. Furthermore;
they produce black smoke or hazardous substances during combustion, and there~ore, a special combustion Eurnace or special equipment for the removal of the hazardous substances are required.
On the other hand, since oil-absorbing materials made o~
natural fibers are hydrophilic, they absorb not only oils ~but 8t7'~
also water when put into a water area polluted by oils, and consequently, their ability to absorb oils is restricted to not a small extent.
This defect can be overcome to some extent b~ subjecting the natural fibers to a water-repelling treatment using a chemical consisting mainly of an emulsion-type water repellent of, for example, the aliphatic wax or silicone type. However, when oil-absorbing materials produced from the natural ~ibers ~o treated ~loat on the water surface for long period~ of time while being tossed abouk in the waves o~ the sea and in contact with oils, the water-repellent itself is dissolved and removed out of the oil-absorbing materials so that the water-repelling effect does not last sufficiently. In addition, the emulsifier, heavy metal salts, etc. contained in the treating chemicals may dissolve in the water, and cause adverse effects. Accordingly, the use of the water-repelling chemicals cannot be an appropriate measure.
It is an object of this invention therefore to pro~ide a process -~or producing oil-absorbing materials which rekain the ability to hold oils in water for long periods o~ time, have good combustibility after oil absorption, and do not produce hazardous substances during combuskion.
According to this invention, there is provided a proces~
for producing an oil-absorbing material which comprises mixing vegetable ~ibers with not more than 35% by weight, based on the ~C~608~7~3 fibres, of a solid ole~in polymer, and heating the resul-ting mixture to melt the olefin polymer, and thereby impre~nate the vegetable ~ibres with the molten olefin polymer.
The vegetable fibres used in this invention are fibres separated from grass peat, fibres of coconut shell fibres, flax fibres, straws, and grass fibres.
Examples of the solid olefin polymers used in this inven-tion are homopolymers or copolymers preferably having a weight average molecular weight of at least 15,000 of ethylene, propylene, isobutylene and butene, copolymers of ethylene with vinyl acetate, acrylic acid, acrylates, methacrylic acid, methacrylates, and mixtures of these polymers and copolymers. When olefin polymers having a molecular weight of less than 15,000 are used, the dura-bility of the water-repellency of the resulting oil-absorbing materials is somewhat reduced. Desirably, these olefin polymers are crystalline. The amount of the solid olefin polymer is not more than 35% by weight, 2Q preferably 2 to 30% by weight, based on the vegetable fibres.
Mixing of the vegetable fibres and the solid olefin polymer is performed, for example, by using a stirrer or card. Preferably, the solid olefin polymer is used in -the form of a powder having a size of not greater than 50 mesh, or fibres having a length of not more than 10 mm. Water contained in the vegetable fibres evaporates off during a heating operation, and therefore, lO~
~ 4 it is not necessary to restrict the moisture content of the vegetable fibres. The vegetable fibres well mixed with ~e solid olefin polymer are heated preferably to a temperature above the melting point of the solid olefin polymer. This heating results in the melting of the solid olefin polymer and consequently its impregnation in the vegetable fibres.
Since the amount of the olefin polymer impregnated in the vegetable fibres is not more than 35%
by weight, preferably 2 to 30% by weight, the porosity and surface roughness of the vegetable fibres themselves remain in the resulting structure. A microscopic obser-vation of this structure shows that adhesion of fibres to one another asribable to the impregnated olefin polymer occurs only to a small extent, and the olefin polymer does not cover the surface of the vegetable fibres. Accordingly, the oil-holding ability of the vegetable fibres themselves is not reduced, and the olefin polymer once impregnated into the fibres is not likely to dissolve even during its long-term residence in water. Thus, a long-las$ing stable water-repellency is imparted to the vegetable fibres. When the amount o the olefin polymer exceeds 35% by weight, the wick effect of the vegetable fibres becomes insufficient during burning so that the fibres generate a black smoke and the olefin polymer partly drips from the vegetable fibres.
The oil-absorbing material obtained by the ~`
~i(38t7~
4a process of this invention can be used as packed in a suitable receptacle so as to collect oils dispersed as oil d~oplets in water. Or it can be press-formed into a mat-like structure, or further wrapped by a ~`
net to prevent the breakage of -the mat in water, and in this form, can be used to absorb oils on the water surface. Or the mat so obtained may be placed on the water sur~ace as an oil fence with a suitable float so as to use it to pre~ent the S diffusion of floating oils on the water surface.
According to the process of this invention, there ~an easily be obtained an oil-absorbing material which has water-repellency durable for long period~ of time in water~ good oil~absorbing ability inherent to the vegetable fibers, and good combustibility after oil absorption, and does not produce a hazardous substance during combustion.
The following examples illustrate the present inventionO
Tt should be noted that the invention is not limited to these examples alone Example 1 Polypropylene powder (lOOg) having a size o~ not greater than 100 mesh and an average molecular weight of 25JOOO was added to 1.4 Kg of grass peat fibers (water content 40% by weight~ obtained by beating grass peat in water and separating the fibers from the humus. They were thoroughly mixed by a card. The resulting mixture was maintained in a hot air dryer at 180C for 15 minutes to melt the polypropylene and impregnate it in the peat fibers. The resulting polypropylene-impregnated peat fibers are designated as an oil-absorbing material A.
The above procedure was repeated using 42 g o~ an ethylene/
_ 5 _ ~10ti,C~7~L
vinyl acetate copolymer powder (lO~o by weight of vinyl acetate; melting point 95C) with the heat-meltingtemperature being maintained at 105C. Thus, grass peat fibers impregnated with the above copolymer were obtained. These fibers are designated as an oil-absorbing material B.
When the above procedure was repeated using 42 g of an ethylene/zinc methacrylate copolymer powder (10% of zinc methacrylate; melting point 113C) with the heat-melting tem-perature being maintained at 12~C, grass peat fibers impregnated with the above copolymer were obtained. These fibers are designated as an oil-absorbing materi~l C.
Example 2 1.2 Kg of grass peat ~ibers (water content 20% by weight) obtained by the same method as set forth in Example 1 and 100 g of fibrillated fibers oP polypropylene having an average molecular weight of ~0,000 with an average fiber diameter of 3 mm were thoroughly mixed in a Henschei mixer. The resulting mixture was maintained in a hot air dryer at 180C for 15 minutes to melt the polypropyle~e fibers and impregnate them in the peat fibers. The rssulting polypropylene-impregnated peat ~ibers are designated as an oil-absorbing material D.
The above procedure was repeated using 48 g of fibrillated fiber~ of polyethylene ha~ing an average molecular weight of 20~000 with an average fiber length of 2 mm with the heat-melting temperature being maintained at 140~C. Thus, polyethylene-a cle f~Ar k 0~'7'~
impregnated grass peat fibers were obtained. These ~ibers are designated as an oil-absorbing material E.
; Exam~,l,e 3 0.~ Kg of flax fibers twater content 40%) and 160 g o~
polybutene-l powder having an average molecular weight of 50,000 and a size of not greater than 100 mesh were mixed, and maintained in a far-infrared furnace at 150C for 15 minute~ to melt the polybutene-l and impregnate it into the ~lax ~ibers.
The resulting impregnated flax fibers are designated as an oil-absorbing material F.
Comparative ,Exa,mple A paraffin wax emulsion having the composition indicated below was diluted with water, and the same grass peat fibers as used in Example 1 were immersed in the diluted emulsion.
Then~ the immersed peat fibers ~re squee~ed by rolls to the desired paraffin wax content, and heated at 100C to melt the paraffin wax adhering to the peat ~ibers and impregnate it into the peat fibers. In this manner, products with a paraf~in wax content of 2% by weight and 4% by weight were obtained. These '20 products are designated as oil-absorbing materials I and II, respectively.
~ 7 ~
~10~37~
Formulation_of the para~in wax emulsion Paraf-~in (m.p. 54 5~C~ 90%
Beef tallow free fatty acid 38.8%
Monoethanolamine 3.35%
Water 48.85%
Com~arative Example 2 A commercially available silicone emulsion for water-repellent ~inishing o~ textiles (To~hiba TS~ 831) and a ~ commercially available catalyst (Toshiba CW 80~ were mixed in a volume ratio of 1:1. The same grass peat ~ibers as used in Example 1 were immersed in the mixture, dried at 100C for 10 minutes, and then heat-treated at 180C for 5 minutes to form a product having a silicone pick-up o~ 3% by weight based on the peat ~ibers. The product is designated as an oil-absorbing materila III.
ComParative Example 3 A waxy substance having an average molecular weight of 6,ooo obtained as a by-product in the production o~ polyethy~ene was dissolved in naphtha by heating to ~orm a 30% by weight solution. The same grass peat fibers as used in Example 1 were immersed in the resulting solution, squeezedg cooled, and then crumpled to remove the excess o~ the waxy substance and thereby to obtain a product with a waxy substance pick-up of 150%. The product is designated as an oil-absorbing material IV.
The above procedure was repeated using a 10% by weight ~ `I rad~ ~Or~S
'7~
solution of the ~axy substance, thereby to obtain a product having a waxy substance pick-up of 1~ which is designated as an oil-absorbing material V.
ComParative Example 4 5 ' Atactic polypropylene having an average molecular",`weight of 10,000 obtained as a by-product in the production of polypro-pylene was dissolved in toluene by heating to form a 30% by weight solution of the atactic polypropylene. The same grass peat fibers as used in Example 1 were immersed in the solution, and dried in air to remove the toluene and thereby to obtain a product with an atactic polypropylene pick-up of 100%. The product is designated as an oil-absorbing material VI.
The above procedure was repeated using a lO~o by weight toluene solution of the atactic polypropylene thereby to form a product having an atactic polypropylene pick-up of 10%.
The product is designated as an oil-absorbing material ~II.
ComParative Example 5 - The same procë'dure as in Example 3 was repeated except that the amount of the polybutene-l added was changed to 220 g.
Thus, flax fibers impregnated with polybutene-l were obtained.
This product is designated as an oil-absorbing material VIII.
Test ExamPle 1 ttest ~or the durability of water rePellenc~) 128 g each of the oil-absorbing materials obtained in Examples 1 to 3 and Comparative Examples 1 to S was wrapped in a net made of polyethylene filaments and formed into a square _ ~ _ 0~7'~
mat measuring 40 cm i~ each side and 1 cm in thickness. The mats obtained were each tested for the durability of water repellency in the following manner, The mat was allowed to stand in a water tank in which waves with a height o~ 30 cm, a length of 200 cm and a ~eriod o~
1.2 seconds were artifieially produced, The time that elapsed until the mat completely submerged in water was measured.
When the mat did not submerge~ the state of the mat after per~orming the test ~or 78 hours was obser~ed.
The-same grass peat fiber~ (a) and ~lax fibers (b) as used in Examples 1 and 3 respectiv ly were also tested in the same way as above. The results are shown in Table 1.
Table 1 . . _ . . ~
Oil-absorbing Time that elapsed State of the mat after material until the eomplete the end of the test submerging of the __ _ _ mat ~Hours ? ~
A _ Completely floating B _ Submerged to about 1j8 C _ Submerged to about 1/8 D _ Submerged to about l~lO
E _ Submerged to about l/lO
~5 ~ _ ~ Col Ipletely Ploating ~8t~
V 45 Submerged to aobut 3/4 VI _ Submerged to about 1/4 VIII Completely ~loating Test Exam~ple_2~ (test for the abilitY _o~absorb oils and water) 10 g each of the oil-absorbing materials ohtained in Examples 1 to 3 and Comparative Examples 1 to 5 was wrapped in a net made of polyethylene ~ilaments and formed into a square mat measuring 10 cm in each side and 1 cm in thickness.
The mats obtained were each tested for the ability to absorb oils and water in the following manner.
me mat was ~mmersed ~orcibly in water for a predetermined period o~ time, and oscillated with an amplitude of 4 cm at 100 strokes/minute. The mat so treated was allowed to stand for 5 minutès so as to remove water, and then put into a waker`tank in which a ~loating film o heavy oil A with a thickneæs o~
0.5 mm was formed on the water surace to cause it to absorb the oil, The mat was pulled up from the tank, and al~owed to stand for 5 minutes. The ~inal contents of the oil and water in the mat were determined on the basis of the weight of the mat.
The same grasæ peat fibers (a) and flax fibers (b) as :`
~lJ16~8~7~
used in Examples 1 and 3 were ,tested in the same way as above, The results obtained are shown in Table 2, Table 2 Time for Oil-absorbing Amount of the Amount o~
immersing material oil held by water held the mat in the mat by the mat water __ _ _ (~-oil, ~-ma,t) l~,-wa_er/~ at) A 9.13 0.50 B 9 .51 O .48 . C 9.5 o.55 D 9.55 o.4~
E 9.70 0.40 .
O F 9.38 0.58 (in the dry state) a 6.58 1,27 , b 7.48 1.71 I 6.13 1.50 II 7.26 1.08 III 7.83 0.95 IV 4.58 o.55 V ~.o6 .59 VI 5,05 0.37 VII 8.59 - 0.56 VIII 8, 23 O . 45 A 9.66 0,70 5 minutes B 9.62 o~73 C 9.00 0.68 10ti08'74 D 9 . 60 o ~ 7o E 9.35 0 .65 F 9 .65 0 .59 a 0 .54 7 .34 5minutes b 0 . 63 7 . 2 4 I 6.27 2 .05 II 6 . 66 2 .13 III 7 . 5 0 1 . 24 IV 4.38 o.65 VI 74 5837 l 651 VII 8 . 13 1 . 2 4 VIII 8 .16 0 . 5 6 _ A 9 . 50 0 . 75 B 9 .55 0 .78 C 8.92 0.72 1day D 9.52 0.70 E 9.67 o.66 F 9 38 0.62 b O . 55 8 . 2 2 I 3 .59 5 .3 II 4 . 06 4 . 3 7 III 5 .32 3 .48 IV 4.08 1.19 ,, ~ 8~7~
V 6.47 2,31 VI 4.75 0088 1 day VII 7.,49 2.05 VIII 8.08 0.70 _ .. ..... _ . _ A 9.22 0.81 B 9.23 0.83 C 8.53 o.85 D 9.15 0.80 E 9.68 0.68 F 9.30 0,71 10 days a 0.43 8.93 b 0,48 8.35 I 1.15 7.~8 II 1.52 7.11 III 2.19 6.65 IV 3.81 1.86 V 2.89 6.14 VI 4 .Sl 1. 25 VII 3 . 2 6 6.~7 VIII -~.01 o~7~
.. .. _ . . . _ ~est_ExamPle 3 (test ~or combustibility) Mats were produced in the same way as in Test Example 1 using the oil-absorbing màterials obtained in Examples 1 and 3. Each o~ the mats was placed on a wire gauze, and ignited.
The mats made of the o~l-absorbing materials A to F, I to III, V and VII showed a good burning state without producing any smoke, But the mat mad~ of the oil-absorbing material VIII
burned while generating some black smoke. The mats made of the oil-absorbing materials IV and VI produced a large quantity of black smoke, and a part of the polymer impregnated melted, and dripped from the wire gauze.
ExamPle_d
2 . 5 ~Cg of the saDu~ grass peat f ibers (water content 40%
by weight3 as used in Example 1 a~d 120 g of a powder with a size of not greater than 100 mesh of a propylene/ethy~ene copolymer (ethylene conte~t 10%) ha~ing an average molecular ) weight of 40,000 were mixed, and maintained in a hot air oven at 160C for 15 minutes to melt the polymer and impregnate it into the peat f iber~ . The resulting oil-absorbing ma~eria~
was packed into a cylindrical receptacle haYing a diameter of 260 mm and a height sf 400 mmO Water having su~pended therein 40 ppm o~ a lubricating oil a~ ~ine particles was ~lowed at a rate of 700 liters/hour through the receptacle. Even after the pas~age of 15~ hours, the oi~d content at the exit o~ ~he ) receptacle did not exceed 5 ppm.
xam~le 5 200 g of a polyethylene powder having a size of not greater than 100 mesh and an a~erage molecular weight of 18,000 was added to 1.4 Kg of coconut shell fibers (water 8'7~
content 40% by weight), and they were thoroughly mixed by a Henschel mixer. The resulting mixture was hok-pressed a-t 125C, and maintained for 15 minutes in a compre~sed sta$e such that lO g o~ the mixture was converted to a ~quare mat measuring 10 cm in each side and l cm in thickness. Thus, a mat composed of the coconut shell fibers impregnated with the molten polyethylene (oil-absorbing material G) was obtained. The mat was tested for its abilit~ to absorb oils and water:~in the same way as in Test Example l using heavy oils B and C. The results are shown in Table 3.
For comparison) a square mat measuring lO cm in each side and 1 cm in thickness was made rom lO g of non-tr~ated coconut shell ~ibers tc), and its ability to absorb water and oils was test~,d in the same wayO The resul$s are also shown in Table 3.
Table 3 Time for Oil-absorbing Type of Amount of oil Amount o~
immersing material heavy held by the water held the mat oil mat (g-oil/ by the mat in wate~. .- g-mat) (g-water/
_ _ ~-mat) O G B 8.73 0,30 ~in the dry state)- C 11,53 0.28 C B 6.50 1,03 _ _ . _ C 9.85 0.97 G B 8,62 o,65 ~ C 11:,08 o.56 10 days _ _ ___ _ C _ ~ 2 53 7 5 lO~B74 The above mats were subjected to the same test for th0 durability of water repellency as in Test Example 1.
As a result, the mat prepared from the oil-absorbing material G submerged to a depth of only about l/lO, but the mat prepared from the oil-absorbing material C completely submerg0d in 12 hours.
After the test for the ability to absorb oils and water, the mat prepared from th~.oil-absorbing material G
showed a good burning state without the generation o~ any black smoke.
Test Exam~le A (test for the ability to absorb a fish oil~
A square mat measuring lO cm in each side and 1 cm in thiokness was made from lO g of the oil-absorbing material B
in the same way as in Test Example 2, and tested for its ability to absorb a sardine oil and water in the same way as in Example 2. The results are shown in Table 4.
Table 4 . _ . _ __ . . ........... .
Time for Amount of the Amount of water immersing sardine oil held by the mat the mat held by the (g-water/g-mat) in water mat ~g-oil/
_ _ ~-mat) .
in the 8.79 1.05 dry state~
_ . . _ 5 minutes 8.26 1.24 . .
4 days 7.95
by weight3 as used in Example 1 a~d 120 g of a powder with a size of not greater than 100 mesh of a propylene/ethy~ene copolymer (ethylene conte~t 10%) ha~ing an average molecular ) weight of 40,000 were mixed, and maintained in a hot air oven at 160C for 15 minutes to melt the polymer and impregnate it into the peat f iber~ . The resulting oil-absorbing ma~eria~
was packed into a cylindrical receptacle haYing a diameter of 260 mm and a height sf 400 mmO Water having su~pended therein 40 ppm o~ a lubricating oil a~ ~ine particles was ~lowed at a rate of 700 liters/hour through the receptacle. Even after the pas~age of 15~ hours, the oi~d content at the exit o~ ~he ) receptacle did not exceed 5 ppm.
xam~le 5 200 g of a polyethylene powder having a size of not greater than 100 mesh and an a~erage molecular weight of 18,000 was added to 1.4 Kg of coconut shell fibers (water 8'7~
content 40% by weight), and they were thoroughly mixed by a Henschel mixer. The resulting mixture was hok-pressed a-t 125C, and maintained for 15 minutes in a compre~sed sta$e such that lO g o~ the mixture was converted to a ~quare mat measuring 10 cm in each side and l cm in thickness. Thus, a mat composed of the coconut shell fibers impregnated with the molten polyethylene (oil-absorbing material G) was obtained. The mat was tested for its abilit~ to absorb oils and water:~in the same way as in Test Example l using heavy oils B and C. The results are shown in Table 3.
For comparison) a square mat measuring lO cm in each side and 1 cm in thickness was made rom lO g of non-tr~ated coconut shell ~ibers tc), and its ability to absorb water and oils was test~,d in the same wayO The resul$s are also shown in Table 3.
Table 3 Time for Oil-absorbing Type of Amount of oil Amount o~
immersing material heavy held by the water held the mat oil mat (g-oil/ by the mat in wate~. .- g-mat) (g-water/
_ _ ~-mat) O G B 8.73 0,30 ~in the dry state)- C 11,53 0.28 C B 6.50 1,03 _ _ . _ C 9.85 0.97 G B 8,62 o,65 ~ C 11:,08 o.56 10 days _ _ ___ _ C _ ~ 2 53 7 5 lO~B74 The above mats were subjected to the same test for th0 durability of water repellency as in Test Example 1.
As a result, the mat prepared from the oil-absorbing material G submerged to a depth of only about l/lO, but the mat prepared from the oil-absorbing material C completely submerg0d in 12 hours.
After the test for the ability to absorb oils and water, the mat prepared from th~.oil-absorbing material G
showed a good burning state without the generation o~ any black smoke.
Test Exam~le A (test for the ability to absorb a fish oil~
A square mat measuring lO cm in each side and 1 cm in thiokness was made from lO g of the oil-absorbing material B
in the same way as in Test Example 2, and tested for its ability to absorb a sardine oil and water in the same way as in Example 2. The results are shown in Table 4.
Table 4 . _ . _ __ . . ........... .
Time for Amount of the Amount of water immersing sardine oil held by the mat the mat held by the (g-water/g-mat) in water mat ~g-oil/
_ _ ~-mat) .
in the 8.79 1.05 dry state~
_ . . _ 5 minutes 8.26 1.24 . .
4 days 7.95
Claims (5)
1. A process for producing an oil-absorbing material, which comprises mixing vegetable fibres selected from grass peat fibres, flax fibres, coconut shell fibres, straw and grass fibres, with not more than 35% by weight, based on the dry weight of the fibres, of a solid olefin polymer, and heating the resulting mixture to melt the olefin polymer and thereby impregnate the molten olefin polymer in the vegetable fibres.
2. A process as claimed in claim 1 wherein said olefin polymer has an average molecular weight of at least 15,000.
3. The process as claimed in claim 2 wherein said olefin polymer is a homopolymer or copolymer of ethylene, propylene, isobutylene or butene, a copolymer of ethylene with one or more of vinyl acetate, acrylic acid, acrylic acid salts, acrylic acid esters, methacrylic acid, a methacrylic acid salt or a methacrylic acid ester, or a mixture thereof.
4. The process as claimed in claim 2 or 3 wherein said olefin polymer is in the form of a powder having a size of not greater than 50 mesh, or fibres having a length of not more than 10 mm.
5. The process as claimed in claim 1 wherein the amount of said olefin polymer is 2 to 30% by weight based on the vegetable fibres.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50060201A JPS51136354A (en) | 1975-05-22 | 1975-05-22 | Method of producing oil collector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1060874A true CA1060874A (en) | 1979-08-21 |
Family
ID=13135292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA252,878A Expired CA1060874A (en) | 1975-05-22 | 1976-05-19 | Process for producing oil-absorbing materials |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS51136354A (en) |
| CA (1) | CA1060874A (en) |
| DE (1) | DE2621961A1 (en) |
| DK (1) | DK227276A (en) |
| FI (1) | FI761351A (en) |
| GB (1) | GB1513645A (en) |
| IE (1) | IE42690B1 (en) |
| NO (1) | NO761739L (en) |
| SE (1) | SE418155B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS534790A (en) * | 1976-07-05 | 1978-01-17 | Mitsui Toatsu Chem Inc | Production of oil collector |
| FR2433031A1 (en) * | 1978-08-11 | 1980-03-07 | Solvay | PROCESS FOR THE MANUFACTURE OF OBJECTS FROM COMPOSITIONS COMPRISING MODIFIED POLYOLEFINS AND CELLULOSIC FIBERS |
| DE3030956A1 (en) * | 1980-08-16 | 1982-03-25 | Chemische Fabrik Pfersee Gmbh, 8900 Augsburg | Oil slick absorber of peat made hydrophobic - by treating with cationic dispersion and/or pref. organo:polysiloxane(s) |
| SE8104567L (en) * | 1981-07-27 | 1983-01-28 | Alby Klorat Ab | SET TO MAKE A ABSORPTION MATERIAL FOR ORGANIC LIQUIDS, SPECIAL OIL |
| GB2211496A (en) * | 1987-10-26 | 1989-07-05 | James Alfred Jones | Substance for the sorption of oil and related compounds spilled on water and other substrates |
| WO1990011130A1 (en) * | 1989-03-17 | 1990-10-04 | L. Graf & Co. Pty. Ltd. | Oily domestic waste disposal |
| IT1250639B (en) * | 1991-07-04 | 1995-04-21 | Enichem Elastomers | METHOD FOR THE REMOVAL OF HYDROCARBON PRODUCTS FROM THE SURFACE OF A WATER MEDIUM |
| DE4320908A1 (en) * | 1993-06-18 | 1994-12-22 | Siegmund Piotrowski | Oil-binding agent |
| AU3267595A (en) * | 1994-08-18 | 1996-03-14 | Anatoly Alexeevich Bespalov | Method of removing crude oil or oil products from a surface, a method of regenerating and a method of using the used product |
| SI23548A (en) | 2010-11-17 | 2012-05-31 | Likon@Marko | The use of fibres obtained from seeds of populus trees for absorbent and filtering material and process and device for its producing |
| SG193251A1 (en) * | 2011-03-03 | 2013-10-30 | Siemens Energy Inc | Composite media for water treatment processes and methods of using same |
| FI127883B (en) * | 2016-08-26 | 2019-04-30 | Vapo Oy | Composite structure and method for producing the same |
| DE102021106840A1 (en) * | 2021-03-19 | 2022-09-22 | Frowin Puntsch | Textile product and use of the textile product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4836839A (en) * | 1971-09-14 | 1973-05-31 |
-
1975
- 1975-05-22 JP JP50060201A patent/JPS51136354A/en active Pending
-
1976
- 1976-05-03 SE SE7605029A patent/SE418155B/en unknown
- 1976-05-13 GB GB19649/76A patent/GB1513645A/en not_active Expired
- 1976-05-13 IE IE1018/76A patent/IE42690B1/en unknown
- 1976-05-13 FI FI761351A patent/FI761351A/fi not_active Application Discontinuation
- 1976-05-18 DE DE19762621961 patent/DE2621961A1/en not_active Withdrawn
- 1976-05-19 CA CA252,878A patent/CA1060874A/en not_active Expired
- 1976-05-21 NO NO761739A patent/NO761739L/no unknown
- 1976-05-21 DK DK227276A patent/DK227276A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2621961A1 (en) | 1977-04-21 |
| IE42690L (en) | 1976-11-22 |
| JPS51136354A (en) | 1976-11-25 |
| NO761739L (en) | 1976-11-23 |
| SE418155B (en) | 1981-05-11 |
| FI761351A (en) | 1976-11-23 |
| GB1513645A (en) | 1978-06-07 |
| IE42690B1 (en) | 1980-09-24 |
| DK227276A (en) | 1976-11-23 |
| SE7605029L (en) | 1976-11-23 |
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