Extraction of harmful compounds from materials containing such harmful compounds
09718940 · 2017-08-01
Assignee
Inventors
Cpc classification
C08J11/02
CHEMISTRY; METALLURGY
C08J2319/00
CHEMISTRY; METALLURGY
International classification
Abstract
A composition and method for extracting, recovering, removing, and/or reducing at least one harmful compound selected from a harmful polycyclic aromatic hydrocarbon (PAH), bisphenol A (BPA), a harmful phthalate, a harmful polychlorinated biphenyl (PCB), a harmful dioxin, a harmful hexachlorobenzene, or a harmful organotin from a harmful compound-containing material using harmful compound-extracting composition comprising a turpentine fluid.
Claims
1. A method for extracting, reducing and/or removing a harmful polycyclic aromatic hydrocarbon (PAH) from a PAH-containing material selected from water, oils, plants, wood, fats, rubber, plastics, or consumer goods that contain a PAH to obtain a material from which said PAH has been separated comprising the steps of: a) providing a liquid PAH-extracting composition comprising a turpentine liquid selected from the group consisting of natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, 3-carene, anethole, dipentene (p-mentha-1,8-diene), terpene resins, alpha-terpene, beta-terpene, gamma terpene, nopol, pinane, camphene, p-cymene, anisaldehyde, 2-pinane hydroperoxide, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, terpin hydrate, ocimene, 2-pinanol, dihydromyrcenol, isoborneol, alloocimene, alloocimene alcohols, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, p-menthan-8-ol, alpha-terpinyl acetate, citral, citronellol, 7-methoxydihydrocitronellal, 10-camphorsulphonic acid, p-menthene, p-menthan-8-yl acetate, citronellal, 7-hydroxydihydrocitronellal, menthol, menthone, polymers thereof, and mixtures thereof, b) contacting said PAH-containing material selected from water, oils, plants, wood, fats, rubber, plastics, or consumer goods that contain a PAH with said liquid PAH-extracting composition such that an extraction mixture is formed, and a residual material is formed of material from the PAH-containing material that is not soluble in the liquid PAH-extracting composition, wherein the extraction mixture comprises at least a portion of said PAH extracted into and dissolved in the turpentine liquid, c) separating the turpentine liquid from said residual material, and d) after step c, removing the turpentine liquid from the residual material using methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, or a mixture thereof.
2. The method of claim 1, wherein said liquid PAH-extracting composition further comprises a fluid selected from Dimethyl Sulfoxide (DMSO), 2-ethoxyethanol, alkanes, aliphatic amines, aromatic amines, carbon bisulfide, vegetable oils, solvents manufactured in petroleum refining, dry distilling coal, fractionating liquefied coal, and fractionating extracted hydrocarbons from oil sands and oil shale, or a mixture thereof.
3. The method of claim 2, wherein the ratio of turpentine liquid in the liquid PAH-extracting composition to the fluid selected from Dimethyl Sulfoxide (DMSO), 2-ethoxyethanol, alkanes, aliphatic amines, aromatic amines, carbon bisulfide, vegetable oils, solvents manufactured in petroleum refining, dry distilling coal, fractionating liquefied coal, and fractionating extracted hydrocarbons from oil sands and oil shale, or a mixture thereof is greater than or equal to about 1:1 by volume.
4. The method of claim 1, wherein said PAH-containing material is contacted with said liquid PAH-extracting composition in a ratio range of about 1:6 to about 4:1 by weight.
5. The method of claim 4, wherein the PAH-containing containing material is contacted with said liquid PAH-extracting composition in a ratio of about 1:4 to about 2:1 by weight.
6. The method of claim 5, wherein the PAH-containing material is contacted with said liquid PAH-extracting composition in a ratio of about 1:3 to about 1:1 by weight.
7. The method of claim 1, wherein said contacting is carried out at a temperature within the range of about 2° C. to about 400° C.
8. The method of claim 1, wherein said contacting is carried out at a temperature within the range of about 15° C. to about 150° C.
9. The method of claim 1, wherein said contacting is carried out at a temperature within the range of about 90° C. to about 120° C.
10. The method of claim 1, wherein said PAH-containing material is contacted with said liquid PAH-extracting composition for about 1 to about 300 minutes.
11. The method of claim 1, wherein said PAH-containing material is contacted with said liquid PAH-extracting composition for about 15 to about 90 minutes.
12. The method of claim 1, wherein said contacting step is repeated about 1 to about 10 times.
13. The method of claim 1, wherein said liquid PAH-extracting composition comprises at least 50% of a turpentine fluid or mixture of turpentine fluids.
14. The method of claim 1, wherein said liquid PAH-extracting composition comprises at least 90% of a turpentine fluid or mixture of turpentine fluids.
15. The method of claim 1, wherein said contacting extracts at least about 80% of PAH contained within said PAH-containing material before said contacting.
16. The method of claim 1, wherein said contacting extracts at least about 95% of PAH contained within said PAH-containing material before said contacting.
17. The method of claim 1, wherein said turpentine fluid is selected from the group consisting of alpha-terpineol, beta-terpineol, gamma-terpineol, 3-carene, anethole, nopol, pinane, camphene, p-cymene, anisaldehyde, 2-pinane hydroperoxide, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, terpin hydrate, ocimene, 2-pinanol, dihydromyrcenol, isoborneol, alloocimene, alloocimene alcohols, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, p-menthan-8-ol, alpha-terpinyl acetate, citral, citronellol, 7-methoxydihydrocitronellal, 10-camphorsulphonic acid, p-menthene, p-menthan-8-yl acetate, citronellal, 7-hydroxydihydrocitronellal, menthol, menthone, polymers thereof, and mixtures thereof.
18. The method of claim 1, wherein the liquid PAH-extracting composition is surfactant free.
19. The method of claim 1, wherein the liquid PAH-extracting composition is non-aqueous.
20. A method for removing a harmful polycyclic aromatic hydrocarbon (PAH) from a PAH-containing material selected from oils, plants, wood, fats, rubber, plastics, or consumer goods that contain a PAH to obtain a material from which said PAH has been removed comprising the steps of: a) providing a liquid PAH-extracting composition comprising a turpentine liquid, b) contacting said PAH-containing material selected from oils, plants, wood, fats, rubber, plastics, or consumer goods that contain a PAH with said liquid PAH-extracting composition such that an extraction mixture is formed, and a residual material is formed of material from the PAH-containing material that is not soluble in the liquid PAH-extracting composition, wherein the extraction mixture comprises at least a portion of said PAH extracted into and dissolved in the turpentine liquid, c) separating the turpentine liquid from said residual material, and d) after step c, removing the turpentine liquid from the residual material using methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, or a mixture thereof.
Description
DETAILED DESCRIPTION OF THE INVENTION
(1) In one aspect, the present invention relates to a readily deployed composition for the dissolution, extraction, removal or reduction of at least one harmful compound from a harmful compound-containing material.
(2) According to one embodiment, a method is provided including the steps of dissolving, extracting, recovering, removing, and/or reducing at least one harmful compound from a harmful compound-containing material. As used herein, a “harmful compound” is a compound selected from Polycyclic Aromatic Hydrocarbons (PAHs), Bisphenol A (BPA), phthalates, Polychlorinated Biphenyls (PCBs), dioxins, organotins such as dibutyltin (DBT), triphenyltin (TphT), dioctyltin (DOT), hexachlorobenzene, or tributyltin (TBT). Examples of harmful compound-containing materials are water, soil, air, a gas, oils, plants, wood, fats, rubber, plastics, consumer goods, raw materials, or any other type of material or other medium that contains harmful compounds including the materials listed in the background section. Dissolving, extracting, recovering, removing, and/or reducing at least one harmful compound from a harmful compound-containing material includes the step of providing a harmful compound-extracting composition comprising, consisting essentially of, or consisting of turpentine fluid and contacting the harmful compound-containing material with the harmful compound-extracting composition such that an extraction mixture is formed, as well as a harmful compound-reduced or harmful compound-free residual material.
(3) According to the present invention, the quantity of harmful compound contained within the harmful compound-containing material is substantially reduced. At least one species of harmful compound is reduced according to the inventive method. In one embodiment, the harmful compound to be reduced or eliminated from the harmful compound-containing material is a harmful compound identified as being associated with health and safety risks. For example, the harmful compound may be carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or an irritant. As used herein, the term “harmful PAHs” refers to one or more PAH compounds having carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or irritant characteristics. Similarly, as used herein, the term “harmful organotin” refers to one or more organotin compounds having carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or irritant characteristics. Similarly, as used herein, the term “harmful phthalate” refers to one or more phthalate compounds having carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or irritant characteristics. Similarly, as used herein, the term “harmful PCB” refers to one or more polychlorinated biphenyl compounds having carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or irritant characteristics. Similarly, as used herein, the term “harmful dioxin” refers to one or more dioxin compounds having carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or irritant characteristics. As used herein, the term “harmful hexachlorobenzene” refers to one or more hexachlorobenzene compounds having carcinogenic, immunogenic, mutagenic, teratogenic, reprotoxic and/or irritant characteristics.
(4) In one embodiment, the invention includes a method of treating a harmful compound-containing material that contains levels of one or more harmful compounds, alone or in combination, that violate standards set by one or more regulatory agencies as acceptably safe, such that the level of the one or more harmful compounds are reduced from an unacceptably high level to below an acceptably safe threshold level as set by regulations. For example, the method involves reducing levels of one or more PAHs selected from benz[a]anthracene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, benzo[a]pyrene, chrysene, cyclopenta[cd]pyrene, dibenz[a,h]anthracene, dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, dibenzo[a,i]pyrene, dibenzo[a,l]pyrene, indeno[1,2,3-cd]pyrene, or 5-methylchrysene, in order to comply with European Union Scientific Committee for Food regulations for acceptably low levels of PAHs.
(5) The following table lists the names and structures of some PAHs frequently monitored according to recommendations by the EU Scientific Committee for Food Safety (SCF), the European Union (EU) and the U.S. Environmental Protection Agency (EPA).
(6) TABLE-US-00003 List Common Name Structure EPA, SCF, EU Benzo[a] pyrene
(7) PAHs that can be removed using the invention include, but are not limited to the PAHs listed in the following table.
(8) TABLE-US-00004 # of # of Benzene PAH Rings Rings Acenaphthene 3 2 Acenaphthylene 3 2 Anthracene 3 3 Benzo[a]anthracene 4 4 Benzo[a]pyrene 5 5 Benzo[e]pyrene 5 5 Benzo[b]fluoranthene 5 4 Benzo[ghi]perylene 6 6 Benzo[j]fluoranthene 5 4 Benzo[k]fluoranthene 5 4 Benzo[c]fluorene 4 3 Chrysene 4 4 Cyclopenta[cd]pyrene 5 4 Dibenzo(a,h)anthracene 5 5 Dibenzo[a,e]pyrene 6 6 Dibenzo[a,h]pyrene 6 6 Dibenzo[a,i]pyrene 6 6 Dibenzo[a,l]pyrene 6 6 Fluoranthene 3 4 Fluorene 3 2 Indeno[1,2,3-cd]pyrene 6 5 5-Methylchrysene 4 4 Naphthalene 2 2 Phenanthrene 3 3 Pyrene 4 4
(9) For example, the method involves reducing levels of one or more organotin compounds. The European Union Regulation Commission has banned the use of tri-substituted organostannic compounds such as TBT compounds and TPT compounds after Jul. 1, 2010, in articles where the concentration in the article, or part thereof, is greater than the equivalent of 0.1% by weight of tin.
(10) The European Union Regulation Commission has also banned the use of DBT compounds after Jan. 1, 2012, in mixtures and articles for supply to the general public where the concentration in the mixture or the article, or part thereof, is greater than the equivalent of 0.1% by weight of tin.
(11) The European Union Regulation Commission has also banned the use of Dioctyltin (DOT) compounds Jan. 1, 2012, in the following articles for supply to, or use by, the general public, where the concentration in the article, or part thereof, is greater than the equivalent of 0.1% by weight of tin: textile articles intended to come into contact with the skin, gloves, footwear or part of footwear intended to come into contact with the skin, wall and floor coverings, childcare articles, female hygiene products, nappies, and two-component room temperature vulcanization molding kits (RTV-2 molding kits).
(12) Triphenyltin compounds are organotin compounds with the general formula (C.sub.6H.sub.5).sub.3SnX. They contain the triphenyltin group, (C.sub.6H.sub.5).sub.3Sn, or Ph.sub.3Sn, which consists of an atom of tin bonded to three phenyl groups. Examples of triphenyltins include: Triphenyltin hydride, Ph.sub.3SnH, Triphenyltin hydroxide, Ph.sub.3SnOH, Triphenyltin chloride, Ph.sub.3SnCl, Triphenyltin acetate, Ph.sub.3SnOAc.
(13) Tributyltin compounds are a group of compounds containing the (C.sub.4H.sub.9).sub.3Sn moiety, such as tributyltin hydride or tributyltin oxide. The EPA has released a final ambient water quality criteria document for tributyltin (TBT), which is found at water.epa.gov/scitech/swguidance/standards/criteria/aqlife/pollutants/tributyltin/upload/2004_01_05_criteria_tributyltin_tbt-final.pdf and is incorporated herein by reference in its entirety. Generally, the one-hour average concentration of TBT should not exceed 0.46 μg/L more than once every three years on the average (acute criterion) and the four-day average concentration of TBT should not exceed 0.072 μg/l more than once every three years on the average (chronic criterion) in order to protect freshwater aquatic life. Further, the one-hour average concentration of TBT should not exceed 0.42 μg/L more than once every three years on the average (acute criterion) and the four-day average concentration of TBT should not exceed 0.0074 μg/L more than once every three years on the average (chronic criterion) in order to protect saltwater aquatic life.
(14) Thus, in one embodiment, the invention includes a method of treating an organotin-containing material that contains levels of one or more organotins, alone or in combination, that violate standards set by one or more regulatory agencies, e.g., the EU Commission, as acceptably safe, such that the level of the one or more organotins are reduced from an unacceptably high level to below an acceptably safe threshold level as set by regulations.
(15) In one embodiment, the invention includes a method of removing bisphenol A (BPA) and/or phthalates from a BPA and/or phthalate-containing material. For example, the BPA and/or phthalate-containing material is a plastic to be recycled. The method involves contacting the BPA and/or phthalate-containing material with a BPA and/or phthalate-extracting fluid containing an effective amount of a turpentine fluid to extract, remove, and/or reduce the BPA and/or phthalates from the BPA and/or phthalate-containing material such that a recovery mixture is formed, as well as residual material. The recovery mixture contains at least a portion of the BPA and/or phthalates that were in the BPA and/or phthalate-containing material. The residual material includes material that is not dissolved into the turpentine fluid. The residual material can be totally free or include a reduced portion of the BPA and/or phthalates in the circumstance where all such BPA and/or phthalates have not been solubilized by the BPA and/or phthalate-extracting fluid. The residual material is then separated from the recovery mixture. The recovery mixture is further separated into a first portion and a second portion. The first portion of the recovery mixture includes a BPA and/or phthalate stream that includes at least a portion of the BPA and/or phthalate extracted from the BPA and/or phthalate-containing material.
(16) In one embodiment, the invention includes a method of removing hexachlorobenzene from a hexachlorobenzene-containing material. For example, the hexachlorobenzene-containing material is rubber, fungicide, soil or water. The method involves contacting the hexachlorobenzene-containing material with a hexachlorobenzene-extracting fluid containing an effective amount of a turpentine fluid to extract, remove, and/or reduce the hexachlorobenzene from the hexachlorobenzene-containing material such that a recovery mixture is formed, as well as residual material. The recovery mixture contains at least a portion of the hexachlorobenzene that was in the hexachlorobenzene-containing material. The residual material includes material that is not dissolved into the turpentine fluid. The residual material can be totally free or include a reduced portion of the hexachlorobenzene in the circumstance where all such hexachlorobenzene has not been solubilized by the hexachlorobenzene-extracting fluid. The residual material is then separated from the recovery mixture. The recovery mixture is further separated into a first portion and a second portion. The first portion of the recovery mixture includes a hexachlorobenzene stream that includes at least a portion of the hexachlorobenzene extracted from the hexachlorobenzene-containing material.
(17) In one embodiment, at least one harmful compound is dissolved, extracted, recovered, or removed using a PAH-extracting composition. The harmful compound-extracting composition contains one or more turpentine fluids selected from natural turpentine, synthetic turpentine, mineral turpentine, pine oil, alpha-pinene, beta-pinene, alpha-terpineol, beta-terpineol, gamma-terpineol, 3-carene, anethole, dipentene (p-mentha-1,8-diene), terpene resins, alpha-terpene, beta-terpene, gamma terpene, nopol, pinane, camphene, p-cymene, anisaldehyde, 2-pinane hydroperoxide, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, terpin hydrate, ocimene, 2-pinanol, dihydromyrcenol, isoborneol, alloocimene, alloocimene alcohols, geraniol, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, p-menthan-8-ol, alpha-terpinyl acetate, citral, citronellol, 7-methoxydihydrocitronellal, 10-camphorsulphonic acid, p-menthene, p-menthan-8-yl acetate, citronellal, 7-hydroxydihydrocitronellal, menthol, menthone, polymers thereof, or mixtures thereof. In certain embodiments, the harmful compound-extracting composition comprises, consists essentially of, or consists of a turpentine fluid having more than eight carbon atoms. In certain embodiments, the harmful compound-extracting composition comprises, consists essentially of, or consists of a turpentine fluid having nine, ten, or more than ten carbon atoms. In certain embodiments, the harmful compound-extracting composition comprises, consists essentially of, or consists of a synthetic turpentine fluid or a blend of synthetic turpentine fluids. The turpentine fluid may be a liquid, vapor, gas, supercritical fluid, or a combination thereof.
(18) In one embodiment, the harmful compound-extracting composition contains one or more acyclic or cyclic alcohols. For example, the alcohols can be simple alcohols such as methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), isopropanol, butanol, isobutanol, pentanol and its eight more isomers (1-Pentanol, 3-Methyl-1-butanol, 2-Methyl-1-butanol, 2,2-Dimethyl-1-propanol, 3-Pentanol, 2-Pentanol, 3-Methyl-2-butanol, 2-Methyl-2-butanol) and hexanol and its sixteen more isomers (1-Hexanol, 2-Hexanol, 3-Hexanol, 2-Methyl-1-pentanol, 3-Methyl-1-pentanol, 4-Methyl-1-pentanol, 2-Methyl-2-pentanol, 3-Methyl-2-pentanol, 4-Methyl-2-pentanol, 2-Methyl-3-pentanol, Tertiary 3-Methyl-3-pentanol, Primary 2,2-Dimethyl-1-butanol, 2,3-Dimethyl-1-butanol, 3,3-Dimethyl-1-butanol, 2,3-Dimethyl-2-butanol, 3,3-Dimethyl-2-butanol, 2-Ethyl-1-butanol), lower aliphatic alcohols, or a mixture thereof. In certain embodiments, the alcohol is methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), isopropanol, butanol, isobutanol, pentanol, hexanol, or a mixture thereof. In another embodiment, the harmful compound-extracting composition contains no acyclic or cyclic alcohol.
(19) As used herein, the term “lower aliphatic alcohols” refers to primary, secondary and tertiary monohydric and polyhydric alcohols of between 2 and 12 carbon atoms. As used herein, the term alkanes refers to straight chain and branched chain alkanes of between 5 and 22 carbon atoms. As used herein, the term aromatics refers to monocyclic, heterocyclic and polycyclic compounds. As used herein, “aliphatic amines” refers to primary, secondary and tertiary amines having alkyl substituents of between 1 and 15 carbon atoms.
(20) In another embodiment, the harmful compound-extracting composition further contains an organic compound with a hydroxyl functional group, e.g., benzene, toluene, hexane and xylene, or a mixture thereof. In some embodiments, the PAH-extracting composition contains no organic compound with a hydroxyl functional group, e.g., no benzene, toluene, hexane, and xylene.
(21) In yet another embodiment, the harmful compound-extracting composition contains a second fluid selected from Dimethyl sulfoxide (DMSO) (also termed as Dimethyl sulfoxide, Methyl sulfoxide, or Methylsulfinylmethane), CELLOSOLVE™ (also termed as 2-Ethoxyethanol, Ethylene glycol, Ethyl ether, Oxitol, or EthylCellosolve), alkanes, aromatics, aliphatic amines, aromatic amines, carbon bisulfide, vegetable oils, solvents manufactured in petroleum refining, dry distilling coal, fractionating liquefied coal, and fractionating extracted hydrocarbons from oil sands and oil shale, or a mixture thereof.
(22) In certain embodiments, the ratio of turpentine fluid in the harmful compound-extracting composition to the second fluid is greater than or equal to about 1:1 by volume. In one embodiment, the ratio of turpentine fluid in the harmful compound-extracting composition to the second fluid is greater than or equal to about 3:1 by volume.
(23) In another embodiment, the ratio of turpentine fluid in the harmful compound-extracting composition to the second fluid is between about 1:5 to about 5:1 by volume. In one embodiment, the ratio of turpentine fluid in the harmful compound-extracting composition to the second fluid is between about 1:2 to about 2:1 by volume.
(24) In one embodiment, the harmful compound-extracting composition contains at least about 10% alcohol, toluene, methylene chloride, or a mixture thereof. In another embodiment, the turpentine-extracting composition contains at least about 30% alcohol, toluene, methylene chloride, or a mixture thereof. In another embodiment, the harmful compound-extracting composition contains up to about 50% alcohol, toluene, methylene chloride, or a mixture thereof. In another embodiment, the method involves not contacting the harmful compound-containing material with any alcohol, toluene, or methylene chloride.
(25) In one embodiment, the quantity of the harmful compound contained within the harmful compound-containing material is reduced by at least about 10% and up to about 100%. In one embodiment, the quantity of the harmful compound contained within the harmful compound-containing material is reduced by at least about 50%. In one embodiment, the quantity of the harmful compound contained within the harmful compound-containing material is reduced by at least about 75%. In one embodiment, the quantity of the harmful compound contained within the harmful compound-containing material is reduced by about 100%.
(26) In certain embodiments, the concentration of at least one harmful compound or the sum total quantity of a selected group of harmful compounds in a harmful compound-containing material is reduced from an unacceptably high level to an acceptably low level, e.g., to meet regulatory guidelines, which reduction step is herein referred to as “satisfactorily reducing” the level of harmful compound. These guidelines are well-known to a person skilled in the art. For example, the level of one or more PAHs is reduced to less than 200 mg/kg, 20 mg/kg, 10 mg/kg, 5 mg/kg, 1 mg/kg, 0.5 mg/kg, or 0.2 mg/kg by weight of the PAH-containing material. In certain embodiments, the level of one or more PAHs is reduced to below a detectable level.
(27) As used herein, the term “substantially reduces” shall mean that the amount of at least one harmful compound contained in the harmful compound-containing material is reduced by at least about 50%.
(28) As used herein, the term “sufficiently reduces” shall mean that the amount of at least one harmful compound contained in the harmful compound-containing material is reduced to below a relevant regulatory level for the material that is being treated, for example, for PAHs, below 10 mg/kg or below 0.2 mg/kg. Similarly, for organotins, below 0.1%.
(29) As used herein, the term “devulcanized recycle rubber” refers to scrap rubber that has been obtained for recycling purposes and has been devulcanized for this purpose.
(30) The harmful compound-extracting composition is said to consist essentially of the turpentine fluid if the turpentine fluid is the essential active ingredient for substantially all of the harmful compound-extraction and the other ingredients in the composition are essentially inactive or non-active in extracting harmful compounds. Thus, in certain embodiments, the basic and novel characteristics of the present invention include a composition consisting essentially of a turpentine fluid that excludes other active harmful compound-extracting ingredients.
(31) As used herein, the term “non-active” shall mean that the ingredient is not present in an effective active amount for harmful compound extraction.
(32) In another embodiment, the inventive composition is substantially non-aqueous or the method involves contacting said material with a substantially non-aqueous harmful compound-extracting composition. In one embodiment the harmful compound-extracting composition is non-aqueous.
(33) In certain embodiments, one or more surfactants may be added to the harmful compound-extracting composition. Yet in other embodiments, the harmful compound-extracting composition is surfactant-free or substantially surfactant-free.
(34) In certain embodiments, the ratio of the harmful compound-extracting composition to harmful compound-containing material is in a range of about 1:6 to about 6:1 by weight, or in a range of about 1:2 to about 4:1 by weight. In another embodiment the ratio of the harmful compound-extracting composition to the harmful compound-containing material is in a range of about 1:1 to about 3:1 by weight.
(35) In other embodiments, the amount of the harmful compound-extracting composition used is about 10 to about 2500 wt. % of the harmful compound-containing material. In certain embodiments, the amount of the harmful compound-extracting composition used is about 30 to about 200 wt. % of the harmful compound-containing material. In other embodiments, the amount of the harmful compound-extracting composition used is about 50 to about 150 wt. % of the harmful compound-containing material. In one embodiment, the amount of the harmful compound-extracting composition used is about 100 wt. % of the harmful compound-containing material.
(36) In one embodiment, the harmful compound-containing material is selected from one or more materials that contain levels of harmful compound that are unacceptably high and are in need of reduction. For example, the harmful compound-containing material may be devulcanized rubber or rubber that has not been vulcanized. In one embodiment, the harmful compound-containing material is rubber that has not been devulcanized by the method disclosed in U.S. Pat. No. 7,767,722. In another embodiment, the harmful compound-containing material may be fabrics, wastewater, groundwater, seawater, tobacco products and harmful compound(s) formed from lighted tobacco products, carbon black, wood, coal, diesel, vegetable oil and fats, animal oils and fats, soil, capacitors, electrical devices, adhesives, biocides, paints, coatings, soaps, detergents, pesticides, herbicides, fungicides, fertilizers, coal-tar seal coatings, used motor oil, or incense. In particular, the harmful compound-containing material may be a consumer good or raw material for manufacturing a consumer good, e.g., plastics, elastomers, rubber, lacquers, varnishes, paints, lubricants, antirust oils, leather and coatings. Examples of consumer goods are a shoe, a boot, a sandal, a recycled tire, athletic equipment, clothing, a playground surface material, playground equipment, a wetsuit, a cable or wire sheath, rubber mulch, an office supply, office equipment, an office furnishing, a sports field surface, a sports track material, a glove, a backpack, luggage, a floor mat, a floor covering, bedding, a tobacco product, a tool handle, bicycle handles, stroller handles, a steering wheel or steering wheel cover, a gear-shift knob, a plastic toy, a bicycle handlebar, a watch strap, a toy, a videogame controller, a mobile device, a mobile device cover or protector, a water recreational device a water flotation device, scuba diving equipment, a scuba mask, snorkeling equipment, a scuba fin, swimming goggles, a swim cap, a shower cap, a toothbrush handle, camping gear, a strap, a rain suit, an adhesive, a glue, an agricultural adjuvant, a building material, a personal-care product, a medical device, a surfactants, packaging, modeling clay, a wax, printing ink, a pharmaceutical, a food product, a textile, a compact disc, impact-resistant safety equipment, a lacquer to coat metal products such as food cans, bottle tops, and water supply pipes, a dental sealant, transformers, capacitors, voltage regulators, switches, reclosers, bushings, and electromagnets, used hydraulic oil, fluorescent light ballasts, cable insulation, fiberglass, felt, foam, cork, caulking, carbonless copy paper, floor finish, contaminated soil or water, an electronic and electrical device, and a food container.
(37) In certain embodiments, the invention is directed to the recycle of rubber. Such a method involves obtaining devulcanized or never-before vulcanized rubber containing one or more harmful compounds at unacceptably high levels, reducing the levels of harmful compound in the devulcanized rubber or non-vulcanized rubber to satisfactorily low levels according to the method described above, separating the harmful compound-extracting composition from the devulcanized or never-before vulcanized rubber, optionally further treating the devulcanized or never-before vulcanized rubber with one or more washing steps using alcohols or organic compounds, then vulcanizing or revulcanizing the rubber for use as a recycled rubber product.
(38) In certain embodiments, the invention is directed to the recycle of motor oil. Such a method involves obtaining used motor oil containing one or more harmful compounds at unacceptably high levels, reducing the levels of harmful compound in the used motor oil to satisfactorily low levels according to the method described above, separating the harmful compound-extracting composition from the used motor oil, then performing further processing steps to convert the harmful compound-reduced motor oil into a useful recycled product that has reduced harmful compound levels compared to conventional recycled motor oil and recycled products conventionally made from used motor oil.
(39) In certain embodiments, the dissolution, removal, reduction and/or extraction of harmful compounds can be carried out at a temperature within the range of about 2° C. to about 400° C. In certain embodiments, the harmful compound-containing material is contacted with the harmful compound-extracting composition at a temperature of less than about 280° C., or less than about 160° C. In other embodiments, the contacting temperatures can be within the range of about 15° C. to about 150° C.
(40) In certain embodiments, it has surprisingly been found that PAHs are extracted most effectively and efficiently at a contacting temperature between about 90° C. to about 120° C.
(41) The contacting step for dissolution, removal, recovery, and/or reduction of the levels of harmful compound in the harmful compound-containing material can involve one or more steps including mixing, stirring, in-line static mixing, dipping, submerging, and/or any other means of contacting the PAH-containing material with the harmful compound-extracting composition.
(42) The contacting step can occur over a period of about 1 to about 300 minutes. In one embodiment, the contacting step can occur over a period of about 5 to about 60 minutes, at a pressure between about 1 and about 10 atm.
(43) In certain embodiments, it has surprisingly been found that PAHs are extracted most effectively and efficiently, e.g., from rubber, over a contacting period between about 10 minutes to about 90 minutes, particularly between about 20 minutes to about 60 minutes. The contacting step may be repeated once or multiple times. For example, the contacting step may be repeated 1 to 10 times. The extraction of harmful compound from a harmful compound-containing material can be monitored over time by various methods including, but not limited to High Resolution, Single-Column Gas Chromatography (GC-FID), Multi-Dimensional Gas Chromatography (GC-FID), Gas Chromatography-Mass Spectrometry (GC-MS), Fluorescent Indicator Absorption (FIA), High Performance Liquid Chromatography (HPLC), Gas Chromatography-Fourier Transform Infrared Spectroscopy (GC-FTIR), Supercritical Fluid Chromatography (SFC), Nuclear Magnetic Resonance Spectroscopy (NMR), and/or Clay-Gel Absorption Chromatography. Thus, in one embodiment, a harmful compound-containing material may be treated with the harmful compound-extracting composition and monitored so as to determine the contacting time necessary to reduce the levels of harmful compound(s) in the harmful compound-containing material to acceptable levels.
(44) After contacting the harmful compound-containing material with the harmful compound-extracting composition, the resultant material, which has reduced levels of harmful compound, is separated from the harmful compound-extracting composition. Separation can occur through any suitable means including, but not limited to, vacuum or pressure filtration, and/or gravity separation. After one or more separation steps, the resultant material which has reduced levels of harmful compound(s) may be further processed to remove the harmful compound-extracting composition by washing the resultant material with one or more acyclic or cyclic alcohols. For example, the alcohol can be simple alcohols such as methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), isopropanol, butanol, isobutanol, pentanol and its eight more isomers (1-Pentanol, 3-Methyl-1-butanol, 2-Methyl-1-butanol, 2,2-Dimethyl-1-propanol, 3-Pentanol, 2-Pentanol, 3-Methyl-2-butanol, 2-Methyl-2-butanol) and hexanol and its sixteen more isomers (1-Hexanol, 2-Hexanol, 3-Hexanol, 2-Methyl-1-pentanol, 3-Methyl-1-pentanol, 4-Methyl-1-pentanol, 2-Methyl-2-pentanol, 3-Methyl-2-pentanol, 4-Methyl-2-pentanol, 2-Methyl-3-pentanol, Tertiary 3-Methyl-3-pentanol, Primary 2,2-Dimethyl-1-butanol, 2,3-Dimethyl-1-butanol, 3,3-Dimethyl-1-butanol, 2,3-Dimethyl-2-butanol, 3,3-Dimethyl-2-butanol, 2-Ethyl-1-butanol), lower aliphatic alcohols, or a mixture thereof. In certain embodiments, the alcohol is methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), isopropanol, butanol, isobutanol, pentanol, hexanol, or a mixture thereof. The washing step or washing steps may also include contacting the treated material with an organic compound with a hydroxyl functional group, for example, benzene, toluene, hexane and xylene, or a mixture thereof to remove the harmful compound-extracting composition.
(45) The turpentine fluid can be separated from the harmful compound-extracting composition via any suitable means including, but not limited to, flash evaporation or distillation. Any turpentine fluid extracted into the acyclic or cyclic alcohols may be separated therefrom via any suitable means including, but not limited to, flash evaporation or distillation.
(46) In one embodiment, the invention includes a method of obtaining a consumer good having reduced levels of at least one harmful compound by obtaining a consumer good or a raw material for manufacturing a consumer good having an unacceptably high level of at least one harmful compound, providing a harmful compound-extracting composition comprising a turpentine fluid, contacting said a consumer good or a raw material for manufacturing a consumer good having an unacceptably high level of at least one harmful compound with said harmful compound-extracting composition such that a reduced-harmful compound material and an extraction mixture are formed, the extraction mixture comprising at least a portion of at least one harmful compound extracted into the turpentine fluid, separating the extraction mixture from the reduced-harmful compound material, and using the reduced-harmful compound material as a consumer good or as a raw material for manufacturing a consumer good. The consumer good may be any suitable material including, but not limited to, a shoe, boot, sandal, tire, or tire part. The raw material may be any suitable material including, but not limited to, devulcanized recycle rubber, plastic, coal-tar, or carbon black. In certain embodiments, the contacting may occur for about 15 to about 90 minutes at about 60° C. to about 140° C.
(47) In certain embodiments, after optionally processing the resultant material by contacting it with one or more acyclic or cyclic alcohols, the material, now having reduced levels of harmful compound(s), may be used as a consumer good or as a raw material for producing a consumer good. For example, the invention includes a method of producing a shoe, boot, or sandal by obtaining devulcanized rubber or non-vulcanized rubber for use as a recycled product, reducing the levels of harmful compound in the devulcanized rubber or non-vulcanized rubber to satisfactorily low levels according to the method described above, separating the harmful compound-extracting composition from the devulcanized rubber to satisfactorily low levels, optionally further treating the devulcanized rubber with one or more washing steps using alcohols, then vulcanizing or revulcanizing the rubber and using it to manufacture a shoe, boot, or sandal according to industry practices for doing so. The invention also includes a method of producing a recycled tire or retread tire by reducing levels of harmful compound in devulcanized rubber or non-vulcanized rubber to satisfactorily low levels according to the method described above, separating the harmful compound-extracting composition from the treated rubber to satisfactorily low levels, optionally further treating the rubber with one or more washing steps using alcohols, then vulcanizing or revulcanizing the rubber and using it to manufacture a recycled tire or to retread a tire.
(48) In certain embodiments, the ratio of the harmful compound-extracting composition to a harmful compound-containing fabric is between about 0.1:1 to about 3:1, about 0.5:1 to about 2:1, or about 1:1. In other embodiments, the ratio of the harmful compound-extracting composition to a harmful compound-containing devulcanized or non-vulcanized rubber is between about 0.1:1 to about 10:1, about 0.5:1 to about 6:1, about 2:1 to about 5:1, or about 4:1.
(49) According to an aspect of the present invention, the harmful compound-containing material is contacted with a heterogeneous fluid including a harmful compound-extracting composition. In other embodiments, the harmful compound-containing material is contacted with a homogeneous, one-phase fluid. The homogeneous, one-phase fluid can comprise, consist essentially of, or consist of the harmful compound-extracting composition.
(50) Various standardized methods for determining the level of harmful compounds such as PAHs have been developed by regulatory agencies worldwide. The ISO 21461 method provides for the selective determination of polyaromaticity of oil in vulcanized rubber compounds. The method is based on Nuclear Magnetic Resonance (NMR) Spectrometry. Specifically, the rubber material is cut into small pieces and is extracted using acetone for 8 hours in a soxhlet apparatus. After drying by a stream of nitrogen, the dried extract is dissolved in methylene chloride. The methylene chloride is subjected to a clean-up step by means of solid phase extraction. The dried, non-polar eluate of the solid phase extract is analyzed by NMR spectrometry to determine the percentage of Bay Region Hydrogens (% Hbay), which gives an indication of the aromaticity of the used oil. Directive 2005/69/EC provides that a vulcanized rubber compound may be placed on the market for the production of tires or parts of tires if the % Hbay is below 0.35%.
(51) In the ZEK method for determining the level of PAHs, which was developed in Germany and has been adopted in Europe, 500 mg of sample is cut into particles 2-3 mm in size, and placed in an ultrasonic bath at a temperature of 60° C. for one hour with 20 mL of toluene mixed with internal standards: Standard 1: naphthalene-d8; Standard 2: pyren-d10, anthracene-d10, or phenanthrene-d10; Standard 3: benzo(a)pyrene-d12, perylene-d12, or triphenylbenzene. After cooling to room temperature, an aliquot is taken from the extract and quantified using a gas chromatrograph with a mass specific detector (GC-MSD) in the SIM method. Category 1 materials must have total sum of harmful PAH levels<0.2 mg/kg (undetectable) and benzo[a]pyrene levels<0.2 mg/kg (undetectable), Category 2 materials must have total sum of harmful PAH levels<10 mg/kg and benzo[a]pyrene levels<1 mg/kg, and Category 3 materials must have total sum of harmful PAH levels<200 mg/kg and benzo[a]pyrene levels<10 mg/kg. A Category 1 material is material intended to be put in the mouth or material for toys with normal skin contact for children aged<36 months. A Category 2 material is material not included within Category 1, but with predictable contact with skin for longer than 30 seconds. A Category 3 material is material not included within Categories 1 or 2, but with predictable contact with skin for up to 30 seconds.
(52) The U.S. EPA has developed various methods for determining PAH levels including EPA 8100, 8310, and 8270D. Method 8100 is used to determine the concentration of certain PAHs. Compounds that may be determined by this method are: Acenaphthene, Acenaphthylene, Anthracene, Benzo(a)anthracene, Benzo(a)pyrene, Benzo(b)fluoranthene, Benzo(j)fluoranthene, Benzo(k)fluoranthene, Benzo(ghi)perylene, Chrysene, Dibenz(a,h)acridine, Dibenz(a,j)acridine, Dibenzo(a,h)anthracene, 7H-Dibenzo(c,g)carbazole, Dibenzo(a,e)pyrene, Dibenzo(a,h)pyrene, Dibenzo(a,i)pyrene, Fluoranthene, Fluorene, Indeno(1,2,3-cd)pyrene, 3-Methylcholanthrene, Naphthalene, Phenanthrene, and Pyrene. The methods for such testing have been published by the EPA and are available at www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8100.pdf, which is incorporated herein by reference in its entirety.
(53) Method 8310 is used to determine the concentration of certain PAHs in ground water and wastes. Specifically, Method 8310 is used to detect the following substances: Acenaphthene, Acenaphthylene, Anthracene, Benzo(a)anthracene, Benzo(a)pyrene, Benzo(b)fluoranthene, Benzo(ghi)perylene, Benzo(k)fluoranthene, Chrysene, Dibenzo(a,h)anthracene, Fluoranthene, Fluorene, Indeno(1,2,3-cd)pyrene, Naphthalene, Phenanthrene, and Pyrene. The methods for such testing have been published by the EPA and are available at www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8310.pdf, which is incorporated herein by reference in its entirety.
(54) Method 8270D is used to determine the concentration of semivolatile organic compounds in extracts prepared from many types of solid waste matrices, soils, air sampling media and water samples. The methods for such testing have been published by the EPA and are available at www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8270d.pdf, which is incorporated herein by reference in its entirety.
(55) In another embodiment, the invention includes a method of removing bisphenol A (BPA) and/or phthalates from a BPA and/or phthalate-containing material. BPA has a structure of
(56) ##STR00033##
and phthalates have a core structure of
(57) ##STR00034##
(58) Some common phthalates are listed in the following table:
(59) TABLE-US-00005 CAS Name Abbreviation Structural formula No. Dimethyl phthalate DMP C.sub.6H.sub.4(COOCH.sub.3).sub.2 131-11-3 Diethyl phthalate DEP C.sub.6H.sub.4(COOC.sub.2H.sub.5).sub.2 84-66-2 Diallyl phthalate DAP C.sub.6H.sub.4(COOCH.sub.2CH═CH.sub.2).sub.2 131-17-9 Di-n-propyl DPP C.sub.6H.sub.4[COO(CH.sub.2).sub.2CH.sub.3].sub.2 131-16-8 phthalate Di-n-butyl phthalate DBP C.sub.6H.sub.4[COO(CH.sub.2).sub.3CH.sub.3].sub.2 84-74-2 Diisobutyl phthalate DIBP C.sub.6H.sub.4[COOCH.sub.2CH(CH.sub.3).sub.2].sub.2 84-69-5 Butyl cyclohexyl BCP CH.sub.3(CH.sub.2).sub.3OOCC.sub.6H.sub.4COOC.sub.6H.sub.11 84-64-0 phthalate Di-n-pentyl DNPP C.sub.6H.sub.4[COO(CH.sub.2).sub.4CH.sub.3].sub.2 131-18-0 phthalate Dicyclohexyl DCP C.sub.6H.sub.4[COOC.sub.6H.sub.11].sub.2 84-61-7 phthalate Butyl benzyl BBP CH.sub.3(CH.sub.2).sub.3OOCC.sub.6H.sub.4COOCH.sub.2C.sub.6H.sub.5 85-68-7 phthalate Di-n-hexyl DNHP C.sub.6H.sub.4[COO(CH.sub.2).sub.5CH.sub.3].sub.2 84-75-3 phthalate Diisohexyl DIHxP C.sub.6H.sub.4[COO(CH.sub.2).sub.3CH(CH.sub.3).sub.2].sub.2 146-50-9 phthalate Diisoheptyl DIHpP C.sub.6H.sub.4[COO(CH.sub.2).sub.4CH(CH.sub.3).sub.2].sub.2 41451-28-9 phthalate Butyl decyl BDP CH.sub.3(CH.sub.2).sub.3OOCC.sub.6H.sub.4COO(CH.sub.2).sub.9CH.sub.3 89-19-0 phthalate Di(2-ethylhexyl) DEHP, DOP C.sub.6H.sub.4[COOCH.sub.2CH(C.sub.2H.sub.5)(CH.sub.2).sub.3CH.sub.3].sub.2 117-81-7 phthalate Di(n-octyl) DNOP C.sub.6H.sub.4[COO(CH.sub.2).sub.7CH.sub.3].sub.2 117-84-0 phthalate Diisooctyl phthalate DIOP C.sub.6H.sub.4[COO(CH.sub.2).sub.5CH(CH.sub.3).sub.2].sub.2 27554-26-3 n-Octyl n-decyl ODP CH.sub.3(CH.sub.2).sub.7OOCC.sub.6H.sub.4COO(CH.sub.2).sub.9CH.sub.3 119-07-3 phthalate Diisononyl DINP C.sub.6H.sub.4[COO(CH.sub.2).sub.6CH(CH.sub.3).sub.2].sub.2 28553-12-0 phthalate Di(2-Propyl Heptyl) DPHP C.sub.6H.sub.4[COOCH.sub.2CH(CH.sub.2CH.sub.2CH.sub.3)(CH.sub.2).sub.4CH.sub.3].sub.2 53306-54-0 phthalate Diisodecyl DIDP C.sub.6H.sub.4[COO(CH.sub.2).sub.7CH(CH.sub.3).sub.2].sub.2 26761-40-0 phthalate Diundecyl DUP C.sub.6H.sub.4[COO(CH.sub.2).sub.10CH.sub.3].sub.2 3648-20-2 phthalate Diisoundecyl DIUP C.sub.6H.sub.4[COO(CH.sub.2).sub.8CH(CH.sub.3).sub.2].sub.2 85507-79-5 phthalate Ditridecyl phthalate DTDP C.sub.6H.sub.4[COO(CH.sub.2).sub.12CH.sub.3].sub.2 119-06-2 Diisotridecyl DIUP C.sub.6H.sub.4[COO(CH.sub.2).sub.10CH(CH.sub.3).sub.2].sub.2 68515-47-9 phthalate
(60) In one embodiment, the invention includes a method of removing BPA and/or phthalates from a plastic to be recycled. The method involves contacting the BPA and/or phthalate-containing material, e.g., plastics including polyvinyl chloride (PVC), with a BPA and/or phthalate-extracting fluid containing an effective amount of a turpentine fluid to extract, remove, and/or reduce the BPA and/or phthalates from the BPA and/or phthalate-containing material such that a recovery mixture is formed, as well as residual material. The recovery mixture contains at least a portion of the BPA and/or phthalates that were in the BPA and/or phthalate-containing material. The residual material includes material that is not dissolved into the turpentine fluid. The residual material can be totally free or include a reduced portion of the BPA and/or phthalates in the circumstance where all such BPA and/or phthalates have not been solubilized by the BPA and/or phthalate-extracting fluid. The residual material is then separated from the recovery mixture. The recovery mixture is further separated into a first portion and a second portion. The first portion of the recovery mixture includes a BPA and/or phthalate stream that includes at least a portion of the BPA and/or phthalate extracted from the BPA and/or phthalate-containing material. A method and composition for recycling plastics is described in WO 2012/033742, which is incorporated herein by reference in its entirety.
(61) Still other aspects and advantages of the present invention will become easily apparent by those skilled in the art from this description, wherein certain embodiments of the invention are shown and described simply by way of illustration of the best mode contemplated of carrying out the invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, without departing from the invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
EXAMPLES
Example 1: Removal of Harmful PAHs—Test 1
(62) Crumb rubber samples were tested according to the EPA 8270D method for removal of PAHs by an independent NELAP accredited laboratory. For PAH level determination, the samples were subjected to 3 minute ultrasonic extraction with methylene chloride at room temperature and then the levels of PAHs were obtained using GC-MSD. As a control, a sample of untreated crumb rubber was found to contain:
(63) TABLE-US-00006 Name of PAH Concentration (mg/kg) Acenaphthene BRL Acenaphthylene 0.105 Anthracene BRL Benzo[a]anthracene BRL Benzo[a]pyrene BRL Benzo[b]fluoranthene BRL Benzo[ghi]perylene BRL Benzo[k]fluoranthene BRL Chrysene 0.237 Dibenzo[a,h]anthracene BRL Fluoranthene 0.625 Fluorene BRL Indeno[1,2,3-cd]pyrene BRL Naphthalene 0.092 Phenanthrene 0.45 Pyrene 1.76 TOTAL 3.269 Detection (Reporting) Limit 0.083 BRL = Below Reporting Limit
(64) Crumb rubber was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 90° C. for 20 minutes. The crumb rubber was then separated from the turpentine fluids blend and was tested by the same EPA method. No detectable concentration of any of the PAHs was found in the treated sample. The detection limit was 0.332.
Example 2: Removal of Harmful PAHs—Test 2
(65) A different batch of crumb rubber samples from those tested in Example 1 was tested according to the ZEK method for removal of PAHs by the same independent NELAP accredited laboratory as in Example 1. For PAH level determination, the samples were subjected to 1 hour ultrasonic extraction with toluene at 60° C.
(66) A first test sample of crumb rubber was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 90° C. for 20 minutes. A second test sample of crumb rubber was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 120° C. for 60 minutes. For each sample, crumb rubber was then separated from the turpentine fluids blend and was tested by the same ZEK method. The concentrations of PAHs in a sample of crumb rubber before and after treatment are tabulated below. As is clear from the data, no detectable concentration of any of the PAHs was found in either treated sample.
(67) TABLE-US-00007 Concentration (mg/kg) Concentration (mg/kg) Name of PAH Before Treatment After Treatment Acenaphthene BRL BRL Acenaphthylene BRL BRL Anthracene BRL BRL Benzo[a]anthracene BRL BRL Benzo[a]pyrene BRL BRL Benzo[b]fluoranthene BRL BRL Benzo[ghi]perylene BRL BRL Benzo[k]fluoranthene BRL BRL Chrysene BRL BRL Dibenzo[a,h]anthracene BRL BRL Fluoranthene BRL BRL Fluorene BRL BRL Indeno[1,2,3-cd]pyrene BRL BRL Naphthalene BRL BRL Phenanthrene BRL BRL Pyrene 10.4 BRL TOTAL 10.4 0 Detection (Reporting) 1.584 1.287 Limit
Example 3: Removal of Harmful PAHs—Test 3
(68) A different batch of crumb rubber samples from those tested in Examples 1-2 was tested according to the ZEK method for removal of PAHs by the same independent NELAP accredited laboratory as in Examples 1 and 2. For PAH level determination, the samples were subjected to 1 hour ultrasonic extraction with toluene at 60° C.
(69) A first test sample of the crumb rubber was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 90° C. for 20 minutes. A second test sample of crumb rubber was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 120° C. for 60 minutes. For each sample, crumb rubber was then separated from the turpentine fluids blend and was tested by the same ZEK method. As is clear from the table below, no detectable concentration of any of the PAHs was found in either treated sample.
(70) TABLE-US-00008 Concen- Concen- tration tration Concen- (mg/kg) (mg/kg) tration After After (mg/kg) Treatment at Treatment at Before 90° C. for 120° C. for Name of PAH Treatment 20 minutes 60 minutes Acenaphthene BRL BRL BRL Acenaphthylene BRL BRL BRL Anthracene BRL BRL BRL Benzo[a]anthracene BRL BRL BRL Benzo[a]pyrene BRL BRL BRL Benzo[b]fluoranthene BRL BRL BRL Benzo[ghi]perylene BRL BRL BRL Benzo[k]fluoranthene BRL BRL BRL Chrysene BRL BRL BRL Dibenzo[a,h]anthracene BRL BRL BRL Fluoranthene 2.3 BRL BRL Fluorene BRL BRL BRL Indeno[1,2,3-cd]pyrene BRL BRL BRL Naphthalene BRL BRL BRL Phenanthrene BRL BRL BRL Pyrene 7.7 BRL BRL TOTAL 10.0 0 0 Detection (Reporting) 0.495 0.495 0.495 Limit
Example 4: Removal of Harmful PAHs—Test 4
(71) A different batch of crumb rubber samples from those tested in Examples 1-3 was tested according to the ZEK method for removal of PAHs. These sample measurements were performed by a different independent A2LA accredited and ISO 9001:2008 registered laboratory as further independent verification of the unexpected results described above. For PAH level determination, the samples were subjected to one hour ultrasonic extraction with toluene at 60° C. A control sample of untreated crumb rubber, a first test sample of the crumb rubber that was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 90° C. for 20 minutes, and a second test sample of crumb rubber that was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 120° C. for 60 minutes, were each tested by the same method. For each test sample, the crumb rubber was then separated from the turpentine fluids blend. The samples were each tested by the same ZEK method and the results of this testing is tabulated below:
(72) TABLE-US-00009 Control First Test Second Test Sample Sample Sample Concen- Concen- Concen- tration tration tration Name of PAH (mg/kg) (mg/kg) (mg/kg) Acenaphthene BRL BRL BRL Acenaphthylene BRL BRL BRL Anthracene BRL BRL BRL Benzo[a]anthracene BRL BRL BRL Benzo[a]pyrene BRL BRL BRL Benzo[b]fluoranthene BRL BRL BRL Benzo[ghi]perylene BRL BRL BRL Benzo[k]fluoranthene BRL BRL BRL Chrysene BRL BRL BRL Dibenzo[a,h]anthracene BRL BRL BRL Fluoranthene 2.4 0.6 0.5 Fluorene BRL BRL BRL Indeno[1,2,3-cd]pyrene BRL BRL BRL Naphthalene BRL BRL BRL Phenanthrene 1.2 0.2 0.2 Pyrene 8 2 1.8 TOTAL 11.6 2.8 2.5 Detection (Reporting) ≦0.2 ≦0.2 ≦0.2 Limit
Example 5: Removal of Harmful PAHs—Test 5
(73) A different batch of crumb rubber samples from those tested in Examples 1-4 was tested according to the EPA 8270D method for removal of PAHs by the same independent A2LA accredited and ISO 9001:2008 registered laboratory that performed the tests in Example 4. For PAH level determination, the samples were subjected to one hour ultrasonic extraction with toluene at 60° C. A control sample of untreated crumb rubber and a test sample of the crumb rubber that was mixed with a blend of turpentine fluids containing α-terpineol, β-terpineol, and β-pinene at 90° C. for 20 minutes were each tested by the same method. For the test sample, the crumb rubber was then separated from the turpentine liquids blend. The samples were each tested by the same ZEK method and the results of this testing is tabulated below.
(74) TABLE-US-00010 Control Sample Test Sample Concentration Concentration Name of PAH (mg/kg) (mg/kg) Acenaphthene BRL BRL Acenaphthylene BRL BRL Anthracene BRL BRL Benzo[a]anthracene BRL BRL Benzo[a]pyrene BRL BRL Benzo[b]fluoranthene BRL BRL Benzo[ghi]perylene BRL BRL Benzo[k]fluoranthene BRL BRL Chrysene BRL BRL Dibenzo[a,h]anthracene BRL BRL Fluoranthene 2.5 BRL Fluorene BRL BRL Indeno[1,2,3-cd]pyrene BRL BRL Naphthalene BRL BRL Phenanthrene 1.7 BRL Pyrene 7.3 1.5 TOTAL 11.5 1.5 Detection (Reporting) ≦0.2 ≦0.2 Limit
Example 6: Extraction of the Turpentine Fluid from PAH-Reduced Rubber
(75) To remove turpentine fluid trapped within the pores of the PAH-reduced rubber sample, the rubber sample was mixed with isopropyl alcohol (IPA) at a 1:1 mass ratio under ambient pressure and at about 15° C. for about 5 minutes. The mixing procedure was repeated twice such that the amount of turpentine fluid remaining in the pores of the rubber sample was reduced from 200 wt. % to essentially nil (0.001 wt. % of the rubber).
Example 7: Use of a PAH-Reduced Rubber for Producing Consumer Products
(76) Recycle rubber that was treated the PAH-extracting composition of the invention to reduce PAH levels was used in the manufacture of shoe soles and hockey pucks by making a 50/50 mixture of the recycled rubber and virgin rubber and molding. The molding was done by conventional means. A comparison of the quality of the shoe soles and hockey pucks made using 100% virgin rubber to the 50% recycled and PAH-reduced rubber mixture surprisingly revealed essentially no detriment to quality. Thus, an appreciable cost savings, environmental benefit, and increase in safety are obtained from the invention.
(77) The results for the reduction of PAH levels in PAHs-containing materials described in the specification, and especially in the Examples above, were unexpected. Surprising advantages were realized in processing or recycling materials containing unacceptably high levels of harmful PAHs into safe and useful new products and raw materials through practicing the claimed invention.
(78) As used herein, the terms about and approximately should be interpreted to include any values which are within 5% of the recited value. Furthermore, recitation of the term about and approximately with respect to a range of values should be interpreted to include both the upper and lower end of the recited range. As used herein, the terms first, second, third and the like should be interpreted to uniquely identify elements and do not imply or restrict to any particular sequencing of elements or steps.
(79) While the invention has been shown or described in only some of its embodiments, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the spirit and scope of the invention.