WO2020232435A1

WO2020232435A1 - Compositions and methods for the removal of hydrocarbon residues

Info

Publication number: WO2020232435A1
Application number: PCT/US2020/033392
Authority: WO
Inventors: Lloyd Marshall LUDLOW; David Wheeler
Original assignee: Rutpen Ltd; Soteria Group Inc
Current assignee: Rutpen Ltd; Soteria Group Inc
Priority date: 2019-05-16
Filing date: 2020-05-18
Publication date: 2020-11-19
Anticipated expiration: 2021-11-16

Abstract

Disclosed are compositions for use in the removal of bitumen residues, as well as methods of using these compositions to remediate materials containing harmful particulate matter.

Description

COMPOSITIONS AND METHODS FOR THE REMOVAL OF

HYDROCARBON RESIDUES

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of priority of U.S. Provisional Application No.

62/848,730, filed May 16, 2019, which is incorporated by reference in its entirety.

BACKGROUND

Bitumen-containing substances or residues may be removed from objects or substrates using various methods. For instance, chemical solvents may be used to remove unwanted residues from machinery, unwanted particles from products, or otherwise. Solvents may also be used to extract residues or substances from chemical compositions, products, or materials. For instance, a solvent may be used to separate a particular chemical compound from a mixture of chemical compounds. However, many of the solvents typically used by industry are not environmentally friendly. In fact, many of the solvents are hazardous materials and are expensive to use, maintain, control, and dispose of.

Therefore, there is an ongoing need for improved methods for safe removal bitumen- containing materials, such as bitumen-containing materials from surfaces including building surfaces.

SUMMARY

Disclosed are composition for use in the removal of hydrocarbon residues, such as bitumen. The compositions can comprise (a) a surfactant package; (b) an organic solvent; and (c) a taggant.

The surfactant package can be present in the composition in an amount of from greater than 0% by weight to 25% by weight (e.g., from 1% by weight to 15% by weight), based on the total weight of the composition. The surfactant package can comprise a primary surfactant and optionally one or more secondary surfactants. For example, the primary surfactant can comprise from 25% by weight to 100% by weight of the surfactant package, and the one or more secondary surfactants comprise from 0% by weight to 75% by weight of the surfactant package.

The primary surfactant can comprise a non-ionic surfactant. In some embodiments, the primary surfactant can comprise an ethoxylated alkyl phenol (e.g., an ethoxylated

nonylphenol). The primary surfactant can be present in an amount of from greater than 0% by weight to 15% by weight (e.g., from greater than 0% by weight to 10% by weight), based on the total weight of the composition. When present, the one or more secondary surfactants comprise one or more anionic surfactants, one or more cationic surfactants, one or more zwitterionic surfactants, one or more non-ionic surfactants, or a combination thereof.

The organic solvent can be present in the composition in an amount of greater than 50% by weight (e.g., from 75% by weight to 98% by weight), based on the total weight of the composition. In some embodiments, the organic solvent can comprise a bio-based solvent. In certain embodiments, the organic solvent can comprise a vegetable oil derivative. For example, the organic solvent can comprise a soybean oil derivative (e.g., methyl soyate).

The taggant can be present in the composition in an amount of from greater than 0% by weight to 10% by weight, based on the total weight of the composition. The taggant can comprise any suitable taggant or combination of taggants. The taggant can be organo-soluble or organo-dispersible. In some embodiments, the taggant can comprise a blend of marker materials, optionally in combination with one or more light-emitting materials.

In some embodiments, the composition can further comprise D-Limonene. When present, the D-Limonene can be present in the composition an amount of from greater than 0% by weight to 5% by weight, based on the total weight of the composition.

Also provided are methods for the removal of hydrocarbon residues (e.g., bitumen, graffiti, etc.) The methods can comprise (a) contacting the hydrocarbon residue (e.g., the bitumen) with a composition described herein; (b) agitating the hydrocarbon residue (e.g., the bitumen) in the presence of the composition; and (c) removing the hydrocarbon residue (e.g., the bitumen) and the composition from the surface. In certain embodiments, the surface can comprise a wall, a floor, or a structural support. In certain embodiments, the surface can comprise metal, cement, concrete, stone, wood, a polymeric material, a composite, or a combination thereof. In some embodiments, step (a) can comprise applying a standing layer of the composition to the hydrocarbon residue (e.g., the bitumen). For example, the hydrocarbon residue can be present on a floor, and step (a) can comprise pouring or spraying the composition onto the floor.

In some embodiments, step (b) can comprise scrubbing the hydrocarbon residue (e.g., with a bristled brush). In some embodiments, the hydrocarbon residue can be contacted with the composition for at least 1 hour prior to agitation.

The hydrocarbon residue (e.g., bitumen) can be contacted with the composition for at least 2 hours (e.g., at least 4 hours) following agitation and prior to removal. In some embodiments, step (c) can comprise applying a solid absorbent (e.g., a sweeping compound) to the bitumen and the composition, and collecting the absorbent to remove the bitumen and the composition.

In some embodiments, the method can further comprise applying a stain remover to the surface.

DETAILED DESCRIPTION

Disclosed are composition for use in the removal of hydrocarbon residues, such as bitumen. The compositions can comprise (a) a surfactant package; (b) an organic solvent; and (c) a taggant. Also provided are methods of using the compositions described herein for the removal of hydrocarbon residues (e.g., bitumen).

Compositions

Compositions for use in the removal of hydrocarbon residues can comprise (a) a surfactant package; (b) an organic solvent; and (c) a taggant. The composition can optionally include one or more additional components as discussed below, including viscosity modifiers (e.g., thickening agents), pH modifying agents, co-solvents, colorants, adhesion promoters, stabilizers, chelating agents, fungicides, biocides, insecticides, and fragrances.

In some embodiments, the surfactant package can be present in the composition in an amount greater than 0% by weight (e.g., at least 5% by weight, at least 10% by weight, at least 15% by weight, or at least 20% by weight), based on the total weight of the composition. In some embodiments, the surfactant package can be present in the composition in an amount of 25% by weight or less (e.g., 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less), based on the total weight of the composition.

The surfactant package can be present in the composition in an amount ranging from any of the minimum values described above to any of the maximum values described above.

For example, the surfactant package can be present in the composition in an amount of from greater than 0% by weight to 25% by weight (e.g., from 1% by weight to 15% by weight), based on the total weight of the composition.

In some embodiments, the organic solvent can be present in the composition in an amount of at least 50% by weight (e.g., at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, or at least 85% by weight, at least 90% by weight, or at least 95% by weight), based on the total weight of the composition. In some embodiments, the organic solvent can be present in the composition in an amount of 98% by weight or less (e.g., 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less), based on the total weight of the composition.

The organic solvent can be present in the composition in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, the organic solvent can be present in the composition in an amount of from 50% by weight to 98% by weight (e.g., from 75% by weight to 98% by weight), based on the total weight of the composition.

In some embodiments, the taggant can be present in the composition in an amount greater than 0% by weight (e.g., at least 0.5% by weight, at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 4% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, or at least 9% by weight), based on the total weight of the composition. In some embodiments, the taggant can be present in the composition in an amount of 10% by weight or less (e.g., 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less), based on the total weight of the composition. The taggant can be present in the composition in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, the taggant can be present in the composition in an amount of from greater than 0% by weight to 10% by weight, based on the total weight of the composition.

Surfactant Package

The surfactant package can comprise a primary surfactant and optionally one or more secondary surfactants.

The primary surfactant can comprise a non-ionic surfactant, an anionic surfactant, a cationic surfactant, or a zwitterionic surfactant. In some embodiments, the primary surfactant can comprise a non-ionic surfactant. In some embodiments, the primary surfactant can comprise an anionic surfactant.

When present, the one or more secondary surfactants can comprise one or more non ionic surfactants, one or more additional anionic surfactants, one or more cationic surfactants, one or more zwitterionic surfactants, or any combination thereof.

In some embodiments, the primary surfactant can comprise at least 25% by weight (e.g., at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight) of the surfactant package, based on the total weight of the surfactant package. In some embodiments, the primary surfactant can comprise 100% by weight or less (e.g., 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, or 30% by weight or less) of the surfactant package, based on the total weight of the surfactant package.

The primary surfactant can be present in the surfactant package in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the primary surfactant can comprise from 25% to 100% by weight (e.g., from 50% by weight to 100% by weight, or from 75% by weight to 100% by weight) of the surfactant package, based on the total weight of the surfactant package. In some examples, the primary surfactant can be present in an amount of from greater than 0% by weight to 15% by weight (e.g., from greater than 0% by weight to 10% by weight), based on the total weight of the composition.

In some embodiments, the one or more secondary surfactants can comprise greater than 0% by weight (e.g., at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, or at least 70% by weight) of the surfactant package, based on the total weight of the surfactant package. In some embodiments, the one or more secondary surfactants can comprise 75% by weight or less (e.g., 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less) of the surfactant package, based on the total weight of the surfactant package.

The one or more secondary surfactants can be present in the surfactant package in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the one or more secondary surfactants can comprise from greater than 0% to 75% by weight (e.g., from greater than 0% by weight to 50% by weight, from 10% by weight to 75% by weight, or from 10% by weight to 50% by weight) of the surfactant package, based on the total weight of the surfactant package.

Suitable anionic surfactants for use as a primary surfactant and/or a secondary surfactant include a hydrophobic tail that comprises from 6 to 60 carbon atoms. In some embodiments, the anionic surfactant can include a hydrophobic tail that comprises at least 6 carbon atoms (e.g., at least 7 carbon atoms, at least 8 carbon atoms, at least 9 carbon atoms, at least 10 carbon atoms, at least 11 carbon atoms, at least 12 carbon atoms, at least 13 carbon atoms, at least 14 carbon atoms, at least 15 carbon atoms, at least 16 carbon atoms, at least 17 carbon atoms, at least 18 carbon atoms, at least 19 carbon atoms, at least 20 carbon atoms, at least 21 carbon atoms, at least 22 carbon atoms, at least 23 carbon atoms, at least 24 carbon atoms, at least 25 carbon atoms, at least 26 carbon atoms, at least 27 carbon atoms, at least 28 carbon atoms, at least 29 carbon atoms, at least 30 carbon atoms, at least 31 carbon atoms, at least 32 carbon atoms, at least 33 carbon atoms, at least 34 carbon atoms, at least 35 carbon atoms, at least 36 carbon atoms, at least 37 carbon atoms, at least 38 carbon atoms, at least 39 carbon atoms, at least 40 carbon atoms, at least 41 carbon atoms, at least 42 carbon atoms, at least 43 carbon atoms, at least 44 carbon atoms, at least 45 carbon atoms, at least 46 carbon atoms, at least 47 carbon atoms, at least 48 carbon atoms, at least 49 carbon atoms, at least 50 carbon atoms, at least 51 carbon atoms, at least 52 carbon atoms, at least 53 carbon atoms, at least 54 carbon atoms, at least 55 carbon atoms, at least 56 carbon atoms, at least 57 carbon atoms, at least 58 carbon atoms, or at least 59 carbon atoms). In some embodiments, the anionic surfactant can include a hydrophobic tail that comprises 60 carbon atoms or less (e.g., 59 carbon atoms or less, 58 carbon atoms or less, 57 carbon atoms or less, 56 carbon atoms or less, 55 carbon atoms or less, 54 carbon atoms or less, 53 carbon atoms or less, 52 carbon atoms or less, 51 carbon atoms or less, 50 carbon atoms or less, 49 carbon atoms or less, 48 carbon atoms or less, 47 carbon atoms or less, 46 carbon atoms or less, 45 carbon atoms or less, 44 carbon atoms or less, 43 carbon atoms or less, 42 carbon atoms or less, 41 carbon atoms or less, 40 carbon atoms or less, 39 carbon atoms or less, 38 carbon atoms or less, 37 carbon atoms or less, 36 carbon atoms or less, 35 carbon atoms or less, 34 carbon atoms or less, 33 carbon atoms or less, 32 carbon atoms or less, 31 carbon atoms or less, 30 carbon atoms or less, 29 carbon atoms or less, 28 carbon atoms or less, 27 carbon atoms or less, 26 carbon atoms or less, 25 carbon atoms or less, 24 carbon atoms or less, 23 carbon atoms or less, 22 carbon atoms or less, 21 carbon atoms or less, 20 carbon atoms or less, 19 carbon atoms or less, 18 carbon atoms or less, 17 carbon atoms or less, 16 carbon atoms or less, 15 carbon atoms or less, 14 carbon atoms or less, 13 carbon atoms or less, 12 carbon atoms or less, 11 carbon atoms or less, 10 carbon atoms or less, 9 carbon atoms or less, 8 carbon atoms or less, or 7 carbon atoms or less).

The anionic surfactant can include a hydrophobic tail that comprises a number of carbon atoms ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the anionic surfactant can comprise a hydrophobic tail comprising from 6 to 15, from 16 to 30, from 31 to 45, from 46 to 60, from 6 to 25, from 26 to 60, from 6 to 30, from 31 to 60, from 6 to 32, from 33 to 60, from 6 to 12, from 13 to 22, from 23 to 32, from 33 to 42, from 43 to 52, from 53 to 60, from 6 to 10, from 10 to 15, from 16 to 25, from 26 to 35, or from 36 to 45 carbon atoms. The hydrophobic (lipophilic) carbon tail may be a straight chain, branched chain, and/or may comprise cyclic structures. The hydrophobic carbon tail may comprise single bonds, double bonds, triple bonds, or any combination thereof. In some embodiments, the anionic surfactant can include a branched hydrophobic tail derived from Guerbet alcohols. The hydrophilic portion of the anionic surfactant can comprise, for example, one or more sulfate moieties, one or more sulfonate moieties, one or more sulfosuccinate moieties, one or more carboxylate moieties, or any combination thereof.

In some embodiments, the anionic surfactant can comprise, for example a sulfonate, a sulfate, a sulfosuccinate, or a carboxylate. In some examples, the anionic surfactant can comprise an internal olefin sulfonate (IOS), an alfa olefin sulfonate (AOS), an alkyl aryl sulfonate (ARS), an alkane sulfonate, a petroleum sulfonate, an alkyl diphenyl oxide sulfonate, an alcohol sulfate, an alkoxy sulfate, an alkoxy sulfonate, an alkoxy carboxylate, an alcohol phosphate, or an alkoxy phosphate. In some embodiments, the anionic surfactant can comprise an alkoxy carboxylate surfactant, an alkoxy sulfate surfactant, an alkoxy sulfonate surfactant, an alkyl sulfonate surfactant, an aryl sulfonate surfactant, or an olefin sulfonate surfactant.

In some embodiments, the anionic surfactant can comprise a rosin-based surfactant (e.g., a carboxylate-containing rosin-based surfactant, a sulfate-containing rosin-based surfactant, a sulfonate-containing rosin-based surfactant, a phosphate-containing rosin-based surfactant, or a combination thereof). Examples of rosin-based surfactants include those described in the attached Appendix, the contents of which are incorporated herein by reference.

In some embodiments, the anionic surfactant can comprise an alkyl benzene sulfonate.

In some embodiments, the anionic surfactant can comprise an alpha olefin sulfonate.

An "alkoxy carboxylate surfactant" or "alkoxy carboxylate" refers to a compound having an alkyl or aryl attached to one or more alkoxylene groups (typically -CH2-CH(ethyl)- 0-, -CH2-CH(methyl)-0-, or -CH2-CH2-O-) which, in turn is attached to -COO or acid or salt thereof including metal cations such as sodium. In embodiments, the alkoxy carboxylate

surfactant can be defined by the formulae below: or

wherein R¹ is substituted or unsubstituted C6-C36 alkyl or substituted or unsubstituted aryl; R² is, independently for each occurrence within the compound, hydrogen or unsubstituted C1-C6 alkyl; R³ is independently hydrogen or unsubstituted C1-C6 alkyl, n is an integer from 0 to 175, z is an integer from 1 to 6 and M⁺ is a monovalent, divalent or trivalent cation. In some of these embodiments, R¹ can be an unsubstituted linear or branched C6-C36 alkyl.

An“alkoxy sulfate surfactant” or“alkoxy sulfate” refers to a surfactant having an alkyl or aryl attached to one or more alkoxylene groups (typically -CH2-CH(ethyl)-0-, -CEb- CH(methyl)-0-, or -CH2-CH2-O-) which, in turn is attached to -SO3 or acid or salt thereof including metal cations such as sodium. In some embodiment, the alkoxy sulfate surfactant has the formula R-(B0)_e-(P0)f-(E0) -S03 or acid or salt (including metal cations such as sodium) thereof, wherein R is C6-C32 alkyl, BO is -CH2-CH(ethyl)-0-, PO is -CH2-CH(methyl)-0-, and EO is -CH2-CH2-O-. The symbols e, f and g are integers from 0 to 50 wherein at least one is not zero.

In embodiments, the alkoxy sulfate surfactant can be an aryl alkoxy sulfate surfactant. The aryl alkoxy surfactant can be an alkoxy surfactant having an aryl attached to one or more alkoxylene groups (typically -CH2-CH(ethyl)-0-, -CH2-CH(methyl)-0-, or -CH2-CH2-O-) which, in turn is attached to -SO3 or acid or salt thereof including metal cations such as sodium.

An“alkyl sulfonate surfactant” or“alkyl sulfonate” refers to a compound an alkyl group (e.g., a branched or unbranched C6-C32 alkyl group) attached to -SO3 or acid or salt thereof including metal cations such as sodium.

An“aryl sulfate surfactant” or“aryl sulfate” refers to a compound having an aryl group attached to -O-SO3 or acid or salt thereof including metal cations such as sodium. An“aryl sulfonate surfactant” or“aryl sulfonate” refers to a compound having an aryl group attached to -SO3^' or acid or salt thereof including metal cations such as sodium. In some cases, the aryl group can be substituted, for example, with an alkyl group (an alkyl aryl sulfonate).

An“internal olefin sulfonates” or“IOS” refers to an unsaturated hydrocarbon compound comprising at least one carbon-carbon double bond and at least one SO4 group, or a salt thereof. As used herein, a“C20-28 internal olefin sulfonate” or“C20-28 IOS” refers to an IOS, or a mixture of IOSs with an average carbon number of 20 to 28, or of 23 to 25. The C20- 28 IOS may comprise at least 80% of IOS with carbon numbers of 20 to 28, at least 90% of IOS with carbon numbers of 20 to 28, or at least 99% of IOS with carbon numbers of 20 to 28. As used herein, a“Cl 5- 18 internal olefin sulfonate” or“Cl 5- 18 IOS” refers to an IOS or a mixture of IOSs with an average carbon number of 15 to 18, or of 16 to 17. The Cl 5- 18 IOS may comprise at least 80% of IOS with carbon numbers of 15 to 18, at least 90% of IOS with carbon numbers of 15 to 18, or at least 99% of IOS with carbon numbers of 15 to 18. The internal olefin sulfonates may be alpha olefin sulfonates, such as an isomerized alpha olefin sulfonate. The internal olefin sulfonates may also comprise branching. The IOS may be at least 20% branching, 30% branching, 40% branching, 50% branching, 60% branching, and 65% branching. In some embodiments, the branching is between 20-98%, 30-90%, 40-80%, or around 65%. Examples of internal olefin sulfonates and the methods to make them are found in U.S. Pat. No. 5,488,148, and U.S. Patent Application Publication 2009/0112014, all incorporated herein by reference.

In embodiments, the anionic surfactant can be an alkylbenzene sulfonate or a dibenzene disufonate. In embodiments, the anionic surfactant can be benzenesulfonic acid,

decyl(Sulfophenoxy)-disodium salt; linear or branched C6-C36 alkyl :PO(0-65):EO(0- 100) sulfate; or linear or branched C6-C36 alkyl :PO(0-65):EO(0- 100) carboxylate. In embodiments, the anionic surfactant is an isomerized olefin sulfonate (C6-C30), internal olefin sulfonate (C6- C30) or internal olefin disulfonate (C6-C30). In some embodiments, the anionic surfactant is a Guerbet-PO(0-65)-EO(0-100) sulfate (Guerbet portion can be C6-C36). In some embodiments, the anionic surfactant is a Guerbet-PO(0-65)-EO(0-100) carboxylate (Guerbet portion can be C6-C36). In some embodiments, the anionic surfactant is alkyl PO(0-65) and EO(O-IOO) Sulfonate: where the alkyl group is linear or branched C6-C36. In some embodiments, the anionic surfactant is a sulfosuccinate. In some embodiments, the anionic surfactant is an alkyl aryl sulfonate (ARS) (e.g. an alkyl benzene sulfonate (ABS)), a C10-C30 internal olefin sulfate (IOS), or an alkyl diphenyl oxide sulfonate.

Suitable non-ionic surfactants for use as a secondary surfactant include compounds that can be added to increase to increase wettability. In embodiments, the HLB of the non-ionic surfactant is greater than 10 (e.g., greater than 9, greater than 8, or greater than 7. In some embodiments, the HLB of the non-ionic surfactant is from 7 to 10.

The non-ionic surfactant can comprise a hydrophobic tail comprising from 6 to 36 carbon atoms. In some embodiments, the non-ionic surfactant can include a hydrophobic tail that comprises at least 6 carbon atoms (e.g., at least 7 carbon atoms, at least 8 carbon atoms, at least 9 carbon atoms, at least 10 carbon atoms, at least 11 carbon atoms, at least 12 carbon atoms, at least 13 carbon atoms, at least 14 carbon atoms, at least 15 carbon atoms, at least 16 carbon atoms, at least 17 carbon atoms, at least 18 carbon atoms, at least 19 carbon atoms, at least 20 carbon atoms, at least 21 carbon atoms, at least 22 carbon atoms, at least 23 carbon atoms, at least 24 carbon atoms, at least 25 carbon atoms, at least 26 carbon atoms, at least 27 carbon atoms, at least 28 carbon atoms, at least 29 carbon atoms, at least 30 carbon atoms, at least 31 carbon atoms, at least 32 carbon atoms, at least 33 carbon atoms, at least 34 carbon atoms, or at least 35 carbon atoms). In some embodiments, the non-ionic surfactant can include a hydrophobic tail that comprises 36 carbon atoms or less (e.g., 35 carbon atoms or less, 34 carbon atoms or less, 33 carbon atoms or less, 32 carbon atoms or less, 31 carbon atoms or less, 30 carbon atoms or less, 29 carbon atoms or less, 28 carbon atoms or less, 27 carbon atoms or less, 26 carbon atoms or less, 25 carbon atoms or less, 24 carbon atoms or less, 23 carbon atoms or less, 22 carbon atoms or less, 21 carbon atoms or less, 20 carbon atoms or less, 19 carbon atoms or less, 18 carbon atoms or less, 17 carbon atoms or less, 16 carbon atoms or less, 15 carbon atoms or less, 14 carbon atoms or less, 13 carbon atoms or less, 12 carbon atoms or less, 11 carbon atoms or less, 10 carbon atoms or less, 9 carbon atoms or less, 8 carbon atoms or less, or 7 carbon atoms or less).

The non-ionic surfactant can include a hydrophobic tail that comprises a number of carbon atoms ranging from any of the minimum values described above to any of the maximum values described above. For example, the non-ionic surfactant can comprise a hydrophobic tail comprising from 6 to 15, from 16 to 30, from 31 to 36, from 6 to 25, from 26 to 30, from 6 to 32, from 6 to 12, from 13 to 22, from 23 to 32, from 33 to 36, from 6 to 10, from 10 to 15, from 16 to 25, or from 26 to 36 carbon atoms. In some cases, the hydrophobic tail may be a straight chain, branched chain, and/or may comprise cyclic structures. The hydrophobic carbon tail may comprise single bonds, double bonds, triple bonds, or any combination thereof. In some cases, the hydrophobic tail can comprise an alkyl group, with or without an aromatic ring (e.g., a phenyl ring) attached to it. In some embodiments, the hydrophobic tail can comprise a branched hydrophobic tail derived from Guerbet alcohols.

Example non-ionic surfactants include alkyl aryl alkoxy alcohols, alkyl alkoxy alcohols, or any combination thereof. In embodiments, the non-ionic surfactant may be a mix of surfactants with different length lipophilic tail chain lengths. For example, the non-ionic surfactant may be C9-C11 :9EO, which indicates a mixture of non-ionic surfactants that have a lipophilic tail length of 9 carbon to 11 carbon, which is followed by a chain of 9 EOs. The hydrophilic moiety is an alkyleneoxy chain (e.g., an ethoxy (EO), butoxy (BO) and/or propoxy (PO) chain with two or more repeating units of EO, BO, and/or PO). In some embodiments, 1- 100 repeating units of EO are present. In some embodiments, 0-65 repeating units of PO are present. In some embodiments, 0-25 repeating units of BO are present. For example, the non ionic surfactant could comprise 10EO:5PO or 5EO. In embodiments, the non-ionic surfactant may be a mix of surfactants with different length lipophilic tail chain lengths. For example, the non-ionic surfactant may be C9-C11 :P09:E02, which indicates a mixture of non-ionic surfactants that have a lipophilic tail length of 9 carbon to 11 carbon, which is followed by a chain of 9 POs and 2 EOs. In specific embodiments, the non-ionic surfactant is linear C9- C11 :9EO. In some embodiments, the non-ionic surfactant is a Guerbet PO(0-65) and EO(0- 100) (Guerbet can be C6-C36); or alkyl PO(0-65) and EO(O-IOO): where the alkyl group is linear or branched C1-C36. In some examples, the non-ionic surfactant can comprise a branched or unbranched C6-C32:PO(0-65):EO(0-100) (e.g., a branched or unbranched C6- C30:PO(30-40):EO(25-35), a branched or unbranched C6-C12:PO(30-40):EO(25-35), a branched or unbranched C6-30:EO(8-30), or any combination thereof).

Example cationic surfactants include surfactant analogous to those described above, except bearing primary, secondary, or tertiary amines, or quaternary ammonium cations, as a hydrophilic head group. "Zwitterionic" or "zwitterion" as used herein refers to a neutral molecule with a positive (or cationic) and a negative (or anionic) electrical charge at different locations within the same molecule. Example zwitterionic surfactants include betains and sultains.

Examples of suitable surfactants are disclosed, for example, in U.S. Patent Nos.

3,811,504, 3,811,505, 3,811,507, 3,890,239, 4,463,806, 6,022,843, 6,225,267, 7,629,299 7,770,641, 9,976,072, 8,211, 837, 9,422,469, 9,605,198, and 9,617,464; WIPO Patent

Application WO/2008/079855, WO/2012/027757 and WO /2011/094442; as well as U.S.

Patent Application Nos. 2005/0199395, 2006/0185845, 2006/018486, 2009/0270281,

2011/0046024, 2011/0100402, 2011/0190175, 2007/0191633, 2010/004843. 2011/0201531, 2011/0190174, 2011/0071057, 2011/0059873, 2011/0059872, 2011/0048721, 2010/0319920,

2010/0292110, and 2017/098202, each of which is hereby incorporated by reference herein in its entirety for its description of example surfactants.

In certain embodiments, the surfactant package can comprise a non-ionic primary surfactant. In some embodiments, the primary surfactant can comprise an ethoxylated alkyl phenol (e.g., an ethoxylated nonylphenol).

Organic Solvents

The organic solvent can comprise any suitable organic solvent. Examples of organic solvents include lactones such as g-butyrolactone, g-valerolactone, g-caprolactone, g- heptalactone, a-acetyl -g-butyrol actone, and e-caprolactone; ethers such as dioxane, 1,2- dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether,

tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; carbonates such as ethylene carbonate and propylene carbonate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone; phenols such as phenol, cresol, and xylenol; esters such as ethyl acetate, butyl acetate, methyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; hydrocarbons such as toluene, xylene, diethylbenzene, and cyclohexane;

halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene; organic solvents such as petroleum type solvents (e.g. petroleum ether, petroleum naphtha); fluoro-alcohols such as 2H,3H-tetrafluoropropanol; hydrofluoroethers such as perfluorobutyl methyl ether and perfluorobutyl ethyl ether; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-propyl alcohol; and diacetone alcohols combing performances of both of ketone and alcohol.

In some embodiments, the organic solvent can comprise a bio-based solvent. As used herein, the term“bio-based” refers to a solvent that is either derived from a biological source (e.g., a plant such as soybeans), is biodegradable, or a combination thereof.

In certain embodiments, the organic solvent can comprise a vegetable oil or derivative thereof. For example, the organic solvent can comprise soybean oil, rape seed oil, corn oil, sunflower oil, palm kernel oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, nut oils, melon seed oils, gourd seed oils, flax seed oil, hemp oil, wheat germ oil, castor oil, rice bran oil, tung oil, other vegetable/fruit oils, animal fat (including tallow, lard, yellow grease and fish-oil), algae oil, copaiba, oil from halophytes, oil from fungi, or derivatives thereof. Derivatives of these oils include, for example esters (e.g., methyl esters) and epoxidized esters of fatty acid obtained from one of these biological sources. Derivatives are also described, for example, in U.S. Patent No. 7,951,766, which is hereby incorporated herein by reference. Other examples of bio-based surfactants include lactate esters (e.g., produced from processes using sugar, starches and oils and high-performance microbial fermentation), such as ethyl lactate.

In some examples, the organic solvent can comprise a soybean oil derivative (e.g., methyl soy ate).

Taggants

The compositions described herein further include a taggant. The term“tag” or “taggant” is well known in the art, and generally refers to a component or composition that is suitable for the purpose of detecting or identifying an article or composition to which taggant is applied or incorporated. The taggant can be overt, covert, or invisible or otherwise difficult to detect on individual entities or small numbers of entities, yet having an overt signal detectable from all or a larger number of entities. For example, the entity can be labeled with one or more colors, fluorescent dyes, ultraviolet radiation dyes, luminescent compositions, haptens, nucleotides, polypeptides, or scents. A single entity can be labeled with more than one tag of the same or different types. For example, a particle can be labeled with two or more discretely distinguishable dyes in varying proportion; or a particle can be labeled with a nucleotide and a fluorescent dye. Any of the known tags and the combinations of the tags with entities can be used. Methods known to those skilled in the art can be used to label an entity with one or more taggants. For example, U.S. Pat. No. 6,632,526 teaches methods of dyeing or staining microspheres with at least two fluorescent dyes in such a manner that intra-sample variation of dye concentrations are substantially minimized. The entity can be a segmented particle whose composition is varied along the diameter or the length of the particle. U.S. Pat. No. 6,919,009 teaches methods of manufacture of rod-shaped particles.

In some embodiments, the taggant can comprise an organo-soluble or organo- dispersible taggant. In some embodiments, the taggant can comprise a blend of marker materials, optionally in combination with one or more light-emitting materials.

Marker materials are materials that can be identified using known analytical techniques including, without limitation, spectroscopic and chromatographic techniques, for example mass spectrometry, atomic emission spectroscopy, laser induced breakdown spectroscopy, gas chromatography and gel electrophoresis.

A unique marker composition may be formed by varying parameters including, without limitation, identity of a marker; combination of different marker materials; concentration of an individual marker within the composition; and relative concentrations of two marker materials.

The taggant may include a single marker material, but preferably contains a plurality of different marker materials at least two, at least three, at least four, at least five or at least ten, at least twenty different marker materials. Optionally, the taggant comprises up to forty or up to thirty different marker materials. Concentration of marker materials may be measured by ICP- mass spectrometry or ICP atomic emission spectroscopy as a weight per volume of the marker material.

The greater the number of marker materials used, the greater the number of unique combinations available for use. Furthermore, a greater number of marker materials in a taggant may provide a greater degree of certainty in identification of the source of the composition.

The concentration of each marker material may be between 0.0000001%-15% (1 ppb- 150,000 ppm) for each component, optionally 5-100,000 pm, optionally 100-10,000 ppm. Optionally each marker material is provided in an amount of at least 25 ppm, optionally at least 50 ppm.

A marker composition may be formed as described in UK Patent GB 2413674, the contents of which are incorporated herein by reference. The formulation of unique combinations of marker materials can be prepared using a binary method; however other methods comprising octal and hexadecimal strings can also be used. Each marker composition is held on a database of forensic codes and assigned to a specific owner and/or location. With this database, forensic analysis of a marker composition in a composition or on material treated with a composition can be used to verify the authenticity of a composition or to verify that a material was properly remediated using a composition described herein.

Preferably, the or each marker is an uncommon material provided at a concentration that would not normally be present in the field of use. Exemplary marker materials are metal compounds and organic compounds.

Exemplary metals of metal compound markers include alkaline earth metals, d-block metals, lanthanides, for example Lanthanum, Europium and Holmium; and p-block metals, for example Tellurium and Gallium.

Exemplary organic marker compounds include, tetrahydrocarbazole derivatives and methoxybenzonitrile derivatives.

The or each marker material may be dissolved or dispersed in the composition.

Preferably, the or each marker material is dissolved and the metal salt may be selected accordingly. Exemplary metal compound markers include metal oxides, metal triflates, metal halides, metal nitrates, metal sulfates, and metal sulfides.

The taggant can further include at least one light-emitting material, preferably a photoluminescent light-emitting material. The or each light-emitting material may

independently be fluorescent or phosphorescent. This material can act as a preliminary indicator to indicate the presence of the taggant in the composition or on a material. Upon preliminary identification, the composition may be analyzed in detail to identify the markers in the composition.

This indicator can be either overt and/or covert. Overt indicators emit light in the visible wavelength that can be seen without any apparatus and may be selected from, for example, microdots, pigments and dyes. Covert indicators can be viewed only with the use of a suitable stimulus, for example photoluminescent materials that only emit visible radiation when excited by radiation other than visible light, for example upon excitation with a UV lamp.

Preferably, the light-emitting material is water soluble or water dispersible. More than one light-emitting material may be present in the composition, for example materials that emit radiation of different wavelengths, for initial identification of the composition.

Exemplary covert indicators are coumarins, oxazinones, stilbenes, fluoresceins and derivatives thereof. Coumarins, oxazinones, stilbenes and derivatives thereof are preferred.

The or each light-emitting material may be used in a concentration of between 0.05 to 40% by weight of the composition.

Suitable taggants include those sold under the tradename SMARTWATER by

SmartWater Technology Ltd. (Shropshire, U.K.). Examples include“Index Solutions” (a water based solution containing low level additives, such as metals (rare-earth lanthanides), which are blended using a binary sequence to ensure uniqueness);“Indsol Tracer” (a polymer emulsion that blends different chemical agents according to a binary code), and“SmartWater Instant (fragments of a copolymer of vinyl acetate in isopropyl alcohol). Such taggants are described, for example, in U.S. Patent No. 5,811,152; U.S. Patent No. 10,035,951, and U.S. Patent Application Publication No. 2015/0332613, all of which are incorporated herein by reference.

Additional Components

The composition can optionally include one or more additional components, including viscosity modifiers (e.g., thickening agents), pH modifying agents, co-solvents, colorants, adhesion promoters, stabilizers, chelating agents, fungicides, biocides, insecticides, and fragrances.

In some embodiments, the composition can further comprise a viscosity modifier, such as a polymer. When present, the viscosity modifier can be present in the composition an amount of from greater than 0% by weight to 10% by weight, based on the total weight of the composition.

In some embodiments, the composition can further comprise a pH modifying agent (e.g., an acid, a base, or a combination thereof). In some embodiments, the composition can have an effective amount of a pH modifying agent to provide a pH of from 7.5 to 10. In certain embodiments, the pH modifying agent can comprise sodium hydroxide, potassium hydroxide, or a combination thereof. In some embodiments, the composition can further comprise D-Limonene. When present, the D-Limonene can be present in the composition an amount of from greater than 0% by weight to 5% by weight, based on the total weight of the composition.

In some embodiments, the composition further comprises a co-solvent. The co-solvent comprises an alcohol or an ether. For example, the co-solvent can comprise butylene glycol, hexylene glycol, ethoxydiglycol, dipropylene glycol, ethylene glycol, propylene glycol, ethanol, isopropanol, or a combination thereof. When present, the co-solvent can be present in the composition an amount of from greater than 0% by weight to 20% by weight (e.g., from greater than 0% by weight to 10% by weight), based on the total weight of the composition.

In some embodiments, the composition can further include a chelating agent, such a ethylenediamine tetraacetic acid (EDTA) or a salt thereof.

Methods of Use

Also provided are methods for the removal of hydrocarbon residues (e.g., bitumen, graffiti, etc.) The methods can comprise (a) contacting the hydrocarbon residue (e.g., the bitumen) with a composition described herein; (b) agitating the hydrocarbon residue (e.g., the bitumen) in the presence of the composition; and (c) removing the hydrocarbon residue (e.g., the bitumen) and the composition from the surface. In certain embodiments, the surface can comprise a wall, a floor, or a structural support. In certain embodiments, the surface can comprise metal, cement, concrete, stone, wood, a polymeric material, a composite, or a combination thereof.

In some embodiments, step (a) can comprise applying a standing layer of the composition to the hydrocarbon residue (e.g., the bitumen). For example, the hydrocarbon residue can be present on a floor, and step (a) can comprise pouring or spraying the

composition onto the floor.

In some embodiments, step (b) can comprise scrubbing the hydrocarbon residue (e.g., with a bristled brush). In some embodiments, the hydrocarbon residue can be contacted with the composition for at least 1 hour (e.g., at least 2 hours, at least 3 hours, or at least 4 hours) prior to agitation.

The hydrocarbon residue (e.g., bitumen) can be contacted with the composition for at least 2 hours (e.g., at least 4 hours, or at least 6 hours) following agitation and prior to removal. In some embodiments, step (c) can comprise applying a solid absorbent (e.g., a sweeping compound) to the bitumen and the composition, and collecting the absorbent to remove the bitumen and the composition.

The presence of a taggant in the compositions described herein provides a mechanism for the authentication of the composition, a mechanism for confirmation that a hydrocarbon residue has been properly cleaned and removed using a composition described herein, a mechanism for tracking removed hydrocarbon residue, or a combination thereof.

Accordingly, provided herein are methods for confirming that a hydrocarbon residue has been properly cleaned and removed. These methods can comprise (a) interrogating waste comprising the hydrocarbon residue for the presence of a taggant; and (b) assessing the identity of the taggant to confirm that hydrocarbon residue was removed using a composition described herein. Assessing the identity of the taggant can comprise, by way of example,

spectroscopically and/or spectrometrically interrogating the taggant in the composition to identify the taggant present in the composition. Assessing the identity of the taggant can further comprise consulting a tracking registry to confirm the identity of the composition used to remove the hydrocarbon residue.

Also provided are methods for tracking removal of a hydrocarbon residue. These methods can comprise (a) providing a composition described herein; (b) uniquely registering the taggant in the composition with a site comprising the hydrocarbon residue (e.g., bitumen) in a tracking registry; (c) contacting the hydrocarbon residue (e.g., the bitumen) with a composition described herein; (d) agitating the hydrocarbon residue (e.g., the bitumen) in the presence of the composition; (e) removing the hydrocarbon residue (e.g., the bitumen) and the composition from the surface; (e) transferring the hydrocarbon residue and associated waste to a storage device; (f) transporting the storage device containing the material to a waste disposal facility; and (g) disposing of the material at the waste disposal facility. In some cases, the method can further comprise interrogating the material for the presence of the taggant upon arrival at the waste disposal facility, uniquely registering the taggant with the waste disposal facility in the tracking registry, or a combination thereof. In some embodiments, the method can further comprise inputting additional

information related to removal of the material in the tracking registry. The additional materials can comprise, for example, a date of removal, a date of disposal, a monitoring person responsible for removal, a monitoring person responsible for disposal, an identity of the hydrocarbon residue, a quantity of the hydrocarbon residue in the storage device, or a combination thereof.

The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative components, compositions, and method steps disclosed herein are specifically described, other combinations of the

components, compositions, and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

The term“comprising” and variations thereof as used herein is used synonymously with the term“including” and variations thereof and are open, non-limiting terms. Although the terms“comprising” and“including” have been used herein to describe various embodiments, the terms“consisting essentially of’ and“consisting of’ can be used in place of“comprising” and“including” to provide for more specific embodiments of the invention and are also disclosed. Other than where noted, all numbers expressing geometries, dimensions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches.

Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference.

Claims

WHAT IS CLAIMED IS:

1. A composition for use in the removal of a hydrocarbon residue, the composition comprising:

(a) a surfactant package comprising a primary surfactant and optionally one or more secondary surfactants;

(b) an organic solvent; and

(c) a taggant.

2. The composition of claim 1, wherein the surfactant package is present in an amount of from greater than 0% by weight to 25% by weight, based on the total weight of the composition.

3. The composition of claim 2, wherein the surfactant package is present in an amount of from 1% by weight to 15% by weight, based on the total weight of the composition.

4. The composition of any of claims 1-3, wherein the primary surfactant is present in an amount of from greater than 0% by weight to 15% by weight, based on the total weight of the composition.

5. The composition of claim 4, wherein the primary surfactant is present in an amount of from greater than 0% by weight to 10% by weight, based on the total weight of the composition.

6. The composition of any of claims 1-5, wherein the primary surfactant comprises a non ionic surfactant

7. The composition of any of claims 1-6, wherein the primary surfactant comprises an ethoxylated alkyl phenol.

8. The composition of claim 7, wherein the ethoxylated alkyl phenol comprises an ethoxylated nonylphenol.

9. The composition of any of claims 1-8, wherein the one or more secondary surfactants comprise one or more anionic surfactants, one or more cationic surfactants, one or more zwitterionic surfactants, one or more non-ionic surfactants, or a combination thereof.

10. The composition of any of claims 1-9, wherein the organic solvent comprises a bio based solvent.

11. The composition of any of claims 1-10, wherein the organic solvent comprises a vegetable oil derivative.

12. The composition of any of claims 1-11, wherein the organic solvent comprises a soybean oil derivative.

13. The composition of claim 12, wherein the soybean oil derivative comprises methyl soy ate.

14. The composition of any of claims 1-13, wherein the organic solvent is present in an amount of greater than 50% by weight, based on the total weight of the composition.

15. The composition of any of claims 1-14, wherein the organic solvent is present in an amount of from 75% to 98% by weight, based on the total weight of the composition.

16. The composition of any of claims 1-15, wherein the taggant is present in an amount of from greater than 0% by weight to 10% by weight, based on the total weight of the composition.

17. The composition of any of claims 1-16, wherein the taggant comprises a blend of marker materials.

18. The composition of claim 17, wherein the taggant further comprises a light-emitting material.

19. The composition of any of claims 1-18, wherein the composition further comprises D- Limonene.

20. A method for removing a hydrocarbon residue from a surface, the method comprising:

(a) contacting the hydrocarbon residue with the composition of any of claims 1-19;

(b) agitating the hydrocarbon residue in the presence of the composition of any of claims 1- 19;

(c) removing the hydrocarbon residue and the composition from the surface.

21. The method of claim 20, wherein step (c) comprises applying a solid absorbent to the hydrocarbon residue and the composition, and collecting the absorbent to remove the hydrocarbon residue and the composition.

22. The method of any of claims 20-21, wherein step (a) comprises applying a standing layer of the composition of any of claims 1-19 to the hydrocarbon residue.

23. The method of any of claims 20-22, wherein the hydrocarbon residue is contacted with the composition of any of claims 1-19 for at least 1 hour prior to agitation.

24. The method of any of claims 20-23, wherein the hydrocarbon residue is contacted with the composition of any of claims 1-19 for at least 2 hours following agitation and prior to removal.

25. The method of any of claims 20-24, wherein the hydrocarbon residue is contacted with the composition of any of claims 1-19 for at least 4 hours prior to removal.

26. The method of any of claims 20-25, further comprising applying a stain remover to the surface.

27. The method of any of claims 20-26, wherein the hydrocarbon residue comprises bitumen.

28. The method of any of claims 20-26, wherein the hydrocarbon residue comprises graffiti.