WO2023057526A1

WO2023057526A1 - Composition

Info

Publication number: WO2023057526A1
Application number: PCT/EP2022/077734
Authority: WO
Inventors: Venkataraghavan Rajanarayana
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2021-10-08
Filing date: 2022-10-05
Publication date: 2023-04-13

Abstract

A detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS) and wherein said P-LAS comprises at least 30%wt C12.

Description

COMPOSITION

The present invention relates to improved detergent formulations comprising linear alkyl benzene sulphonate (LAS).

WO 2017/027271 (P&G) discloses methods for producing detergent compounds from waste plastic feedstocks. More specifically, the invention relates to methods for producing detergent intermediates, including alkylbenzenes, paraffins, olefins, oxo alcohols, and surfactant derivatives thereof from waste plastic feedstock

Despite the prior art there remains a need for improved detergent formulations comprising linear alkyl benzene sulphonate (LAS). Commercial LAS is manufactured as complex mixtures of various homologues having different linear alkyl chain lengths. It is generally made from petrochemicals.

Accordingly, and in a first aspect of the invention there is provided a detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS) and wherein said P-LAS comprises at least 30%wt C12.

In a further aspect of the invention there is provided a method of making a detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS), the method incorporating the steps of a. producing P-LAS by pyrolysis of waste plastic wherein said P-LAS comprises at least 30%wt C12; and b. incorporating the P-LAS from step a. into a detergent composition.

In a further aspect of the invention there is provided a method of treating fabrics with a detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS) and wherein said P-LAS comprises at least 30%wt C12, comprising the step of immersing at least a part of a fabric in an aqueous wash liquor comprising water and the detergent composition. We have surprisingly found that inclusion of P-LAS obtained from waste plastic feedstock which is rich in C12 can in the context of detergent compositions have a surprising and desirable performance characteristic as follows.

Foaming is also a key physical characteristic which affects the sensorial experience of a detergent formulation and also affects how much water is used during rinsing. In many countries, clean water is in increasingly shorter supply and therefore foam performance can be important in water usage management.

Improvements in fragrance performance/choice are also highly desirable. The odour of a composition is for many consumers the most persuasive sensory component in a product.

Improvement in visuals, in particular colour perception through film is also a sensitive formulation constraint. The light absorbance spectrum of a product is a key factor in a product’s colour stability. Not only can this lead to a variety in colour offerings between different products (where different products are affected differently by extraneous ultraviolet light, e.g. from the sun) but also the physical behaviour, in particular physical stability.

Components which help decrease the absorption of light of the composition at around 335 to 400 nm in the product are highly desirable.

Ingredients which improve performance against bacteria, moulds and mites are also highly desirable.

For liquids, viscosity is also a key physical characteristic that can be affected by a change in raw material. A higher viscosity means improved product use confidence. Components that can deliver a higher viscosity without having to add expensive viscosity modifiers are highly desired.

LAS from sources other than plastic waste

The detergent composition may further comprise LAS from sources other than plastic waste, such as LAS obtained from fossil fuel, natural oils, waste oils (from any source) etc.

Preferably LAS from fossil fuel as a %wt. of total LAS is no more than 75%, more preferably no more than 50 %wt even more preferably no more than 30%wt.

The detergent composition may further comprise LAS obtained from natural oils. As used herein, “natural oils” are those derived from plant or algae matter, and are often referred to as renewable oils. Natural oils are not based on kerosene or other fossil fuels. In certain embodiments, the natural oils include, but are not limited to, one or more of coconut oil, babassu oil, castor oil, algae 1 byproduct, beef tallow oil, borage oil, camelina oil, Canola (R) oil, choice white grease, coffee oil, corn oil, Cuphea Viscosissima oil, evening primrose oil, fish oil, hemp oil, hepar oil, jatropha oil, Lesquerella Fendleri oil, linseed oil, Moringa Oleifera oil, mustard oil, neem oil, palm oil, perilla seed oil, poultry fat, rice bran oil, soybean oil, stillingia oil, sunflower oil, tung oil, yellow grease, cooking oil, and other vegetable, nut, or seed oils. Other natural oils will be known to those having ordinary skill in the art. The natural oils typically include triglycerides, free fatty acids, or a combination of triglycerides and free fatty acids, and other trace compounds. Processes for making LAS using such oils are disclosed in WO13141979A

The detergent composition may comprise LAS obtained from renewable glyceride feedstock which is preferably rich in triglycerides. This feedstock may be an oil rich in triglycerides with C to C14 fatty acids. The oil rich in triglycerides with C to C14 fatty acids is preferably selected from the group consisting of: coconut oil; palm kernel oil; laurel oil; babassu oil; microbial oils; and mixtures thereof. Processes for making LAS using such oils are described in US2017029347.

Virgin or waste oils may be used.

Levels

The LAS obtained from waste plastic feedstock comprises from 0.001 to 8% wt. preferably from 0.01 to 5% wt., most preferably 1-4%wt of the total LAS.

Preferably, the detergent composition comprises from 1 to 40% LAS, more preferably from 2 to 10% wt. LAS.

Carbon Chain Distribution

The P-LAS may also comprise alkyl chains comprising carbon chain lengths other than C12. These non-C12 alkyl chains may include any of C8-C16, preferably C10, C11 , C13, C14, and these other carbon chain lengths may be in any ratio, provided there is at least 30%wt C12 (based on total weight of all P-LAS present).

Preferably however, P-LAS also comprises at least 30%wt of C11 (based on total weight of all P-LAS present).

The total LAS in the detergent composition may comprise alkyl chains of any carbon chain length number (C9, C10, C11 , C12 or C13).

Total LAS in the detergent composition may comprise at least 30%wt C10. C10 may be the dominant component.

Total LAS in the detergent composition may comprise at least 30%wt C11. C11 may be the dominant component. Total LAS in the detergent composition may comprise at least 30%wt C12. C12 may be the dominant component.

Total LAS in the detergent composition may comprise at least 30%wt C13. C13 may be the dominant component.

Alternatively, the total LAS in the detergent composition may comprise at least 50%wt, preferably at least 60%, preferably at least 70% of two carbon chain lengths (the dominant pair) which may be any of C10 and C11 , C10 and C12, C10 and C13, C11 and C12, C11 and C13, or C12 and C13, and preferably C11 and C12. In the case of a dominant pair, the remaining LAS of other carbon chain lengths are all present at a lower level than the level of either of the dominant pair.

Preferably, the average carbon chain length of the alkyl chains of the (total) LAS is from 8 to 16, more preferably from 10 to 14 and most preferably from 11 to 12. 11.5 to 11.7 is a particularly preferred range. Preferably the (total) LAS contains more than 80wt% of the C10, C11 , C12 and C13 alkyl chains. Preferably the weight ratio of C10:C11 is from 1 :2 to 1 :5. Preferably the weight ratio of C10:C12 is from 1 :2 to 1 :5. Preferably the weight ratio of C10:C13 is from 1 :1 to 1:3.

Advantageously, the high C12 P-LAS may be combined with high C10, C12, C13 or C14 streams from other sources as described herein to provide a required average carbon chain length.

Preferably the level of tetralins is less than 8wt%, more preferably less than 0.5wt%.

Preferably the level of isoalkylbenzenes is less than 6wt% more preferably less than 1wt%.

Pyrolysis of waste plastic to provide components of P-LAS

Preferably, the P-LAS is obtained from pyrolyzed waste plastic.

Plastic waste for pyroylysis (or indeed any chemical de-polymerisation action) is preferably pre- treated by any of the steps of washing, drying, shredding and sieving.

Pyrolysis, as used herein, means the thermal decomposition or de-polymerisation of the plastic at elevated temperatures, either catalytically or non- catalytically and via a continuous or a batch process, in a controlled atmosphere to form what is termed a what is term “pyrolysate”. The atmosphere for pyrolysis preferably has minimal oxygen, more preferably is oxygen free, and may contain inert gases.

Preferably the pyrolysis is carried out at a temperature between 300 and 900 degrees C. The P-LAS may be obtained from the pyrolysate of fast-pyrolysed waste plastic. Fast pyrolysis may be conducted at high temperature ( 400 - 900 degrees C).

Preferably the waste plastic which is pyrolysed comprises any of polyethylene such as high- density polyethylene (HDPE), low-density polyethylene (LDPE); polypropylene (PP).

Preferably the waste plastic comprises less than 10 %wt, more preferably less than 5%, even more preferably less than 1% wt of any of polyvinylchloride (PVC) or polystyrene (PS) or polyethylene terephthalate (PET) (based on total weight of plastic).

Waste plastics may be pyrolised in any suitable reactor, for example, fluidized bed reactors (Bubbling Fluidised Bed, BFB, Circulated Fluidised Bed, CFB) which are advantageous for temperature control; kilns such as rotary kilns e.g. screw kilns where screw or an auger placed coaxially in a fixed kiln transports the feed through the heated reactor which is advantageous for complex waste; vacuum pyrolysis; melting vessels or stirred-tank reactors (STR) as used in various chemical processes have also been used to pyrolyze plastic; microwaves reactors or any combination thereof.

Catalysts may be used and may be selected from zeolite (which may be natural (NZ) or and zeolite-based catalysts such as zeolite beta (BEA), ZSM-5, Y-zeolite, FCC, and MCM-41 (Ratnasari, D. K., Nahil, M. A., and Williams, P. T. (2017). Other catalysts include metalbased catalysts such as ZnO.

Catalysts may be microporous or mesoporous.

The catalytic reaction during the pyrolysis of plastic waste on solid acid catalysts may include cracking, oligomerization, cyclization, aromatization and isomerization reactions.

Liquid pyrolysate (or oil) may be obtained. Alternatively or additionally pyrolysate vapours may be condensed to form a liquid and this liquid can (also) be used.

For pyrolysis vapour, this may be subjected to a quenching process. This involves the rapid cooling and condensation of the products to stop the reaction and to allow further processing.

Liquid pyrolysate is then preferably refined to a paraffin suitable for use in a P-LAS manufacturing process.

The liquid pyrolsis oil is preferably fractionated e.g. in a distillation column to obtain selectively hydrocarbons of the desired boiling point range (i.e. carbon chain length). The fractionation process may be a multi-stage process involving multiple fractionation steps. Individual feedstocks may be pre-fractionated prior to combining with other feedstocks and there may be further fractionation steps where the combined feedstocks are co-fractionated.

For example, the pyrolysate from the waste plastic may be fractionated separately from other feedstocks to produce the required cuts ( hydrocarbons of desired carbon chain length, preferably C8 - C16, more preferably C10-C14) which are thus wholly plastic derived.

Alternatively the pyrolysate liquid may be combined and fractionated together with other feedstocks, but again the desired cuts or desired carbon chain length is preferably C8 - C16, more preferably C10-C14.

Impurities

The plastic pyrolysate feedstock may comprise impurities and such impurities may be removed or at least reduced by various treatments such as hydrotreatment.

Hydrotreatment using e.g. a UoP kero-hydrotreator to operate the Unionrefining® process, may be used to reduce the for example, nitrogen, sulfur, oxyen, olefin content, and aromatics. To make the alkyl chain of the P-LAS from waste plastic and aliphatic feedstock is required so aromatics are preferably removed/reduced for this. Where the phenyl moiety is also obtained from the waste plastic feedstock, the aromatics may be removed and further utilized to provide such benzene. The kero-treater is a catalyst-based apparatus, and various catalysts for denitrification and desulfurization are known to those having ordinary skill in the art.

Sulfur removal, also referred to as desulfurization or hydrodesulfurization (HDS) may be used and this may convert sulfur compounds to hydrogen sulfide. Nitrogen removal, also referred to as denitrogenation or hydrodenitrogenation (HDN) may be used and this may convert convert organic nitrogen compounds to ammonia. Metal (organometallics) removal, also referred to as demetallation or hydrodemetallation (HDM) may be used and this may convert organometallics to the respective metal sulfides. Oxygen removal, also referred to as hydrodeoxygenation, may be used and this may convert organic oxygen compounds to water. Olefin saturation may take place in which organic compounds containing double bonds are converted to their saturated homologues. Aromatic saturation, also referred to as hydrodearomatization, may take place in which some of the aromatic compounds are converted to naphthenes. Halides such as chlorine removal may take place, also referred to as hydrodehalogenation, in which the organic halides are converted to hydrogen halides. The pyrolysis oil may be filtered in a filtration zone configured to remove particulates or other materials from the pyrolysis oil. The contaminant removal zone may comprise an ion exchange zone to remove metals from the pyrolysis oil.

Hydroprocessing conditions and reactors are disclosed in for example, U.S. application Ser. Nos. 14/551,797 and 14/101,842 filed Nov. 24, 2014 and Dec. 10, 2013, respectively, and both of which are incorporated herein by reference.

Separation Process

The plastic pyrolysate liquid may undergo separation process to separate the desirable linear paraffins from branched or cyclic compounds that may be included in the stream. A suitable separator for this purpose is a separator that operates using the UOP LLC Molex® process, which is a liquid-state separation of normal paraffins from branched and cyclic components using UOP LLC Sorbex® technology. Other separators known in the art are suitable for use herein as well.

The plastic pyrolysate liquid may undergo separation alone or in combination with feedstocks other than plastic waste feedstocks (e.g. fossil feedstocks or plant or algae feedstocks as mentioned herein)

Such separation processes may take place after the plastic pyrolysate (and any other feedstocks if combined) has been fractionated, e.g after a pre-fractionation step.

Processes other than pyrolysis may be used to convert waste plastic feedstock to LAS or LAS components (n-olefins, benzene) e.g., gasification, hydrothermal liquifaction etc..

The stream of n-paraffins (having selected carbon chain lengths preferably C8 - C16, more preferably C10-C14)) obtained from the above treatments may then be used to make P-LAS as described below.

Method of making P-LAS from refined pyrolysate.

The P-LAS obtained from the waste plastic feedstock may utilize known methods. Broadly, this involves taking the n-paraffins obtained from fractionating, separating, the pyrolysate etc as described above, converting said n-paraffins to n-olefins (by de-hydrogenation) e.g. broadly, firstly alkylation of benzene with an n-olefin (typically converted from n-paraffin homologue), followed by sulphonation in the conventional manner. For the present invention, at least the n-olefin is derived from the plastic feedstock. P-LAS manufacturing may incorporate, at any stage, further removal of impurities I purification steps to remove any remaining trace contaminants, such as oxygenates, nitrogen compounds, and sulfur compounds, chlorine compounds among others, that were not previously removed in the processing steps described above. Purification may comprise an adsorption system. Alternatively or additionally, a UoP PEP unit in which selected aromatics can be removed, may be employed as part of purification system.

Preferably the purification takes place prior to de-hydrogenation.

During dehydrogenation, the paraffins are dehydrogenated into mono-olefins of the same carbon numbers. Dehydrogenation may be a catalytic process, e.g. UoP’s Pacol process. Conversion is typically less than about 30%, for example less than about 20%, leaving greater than about 70% paraffins unconverted to olefins. Di-olefins (i.e., dienes) and aromatics are also produced as an undesired result of the dehydrogenation reactions as expressed in the following equations:

Mono-olefin formation: CX H2X+2 -^CX H2X +H2

Di-olefin formation: CX H2X -^CX H2X-2 +H2

Aromatic formation: CX H2X-2 -^CX H2X-6 +2H2

Preferably the hydrogen is removed and maybe re-used e.g. in hydrogenation units.

This stream may be selectively hydrogenated e.g. by a DeFine® hydrogenation reactor (or a reactor employing a DeFine® process), available from UOP LLC, to selectively hydrogenate at least a portion of the di-olefins to form additional mono-olefins. As a result, an enhanced stream is formed with an increased mono-olefin concentration.

The enhanced stream may undergo further fractionation, separation, to remove unwanted e.g. light hydrocarbons, such as butane, propane, ethane and methane, that may result from cracking or other reactions during upstream processing or PEP process to remove unwanted aromatics.

To form linear alkylbenzenes, mono-olefins are used to alkylate a stream of benzene, which benzene may be obtained from aromatics removed in earlier stages or obtained previous. The benzene may alternatively be sourced from fossil or natural oils.

Alkylation catalysts include any suitable solid acid catalyst, that supports alkylation of the benzene with the mono-olefins. Examples include hydrogen fluoride (HF) and aluminum chloride (AICI3 as major catalysts in commercial use for the alkylation of benzene with linear mono-olefins, also, zeolite-based or fluoridate silica alumina-based solid bed alkylation catalysts (for example, FAU, MOR, UZM-8, Y, X RE exchanged Y, RE exchanged X, amorphous silica-alumina, and mixtures thereof, and others known in the art). As a result of alkylation, alkylbenzene, typically called linear alkylbenzene (LAB), is formed according to the reaction:

C6 H6 +CX H2X -^C6 H5 CX H2X+1

To optimize the alkylation process, surplus amounts of benzene may be supplied to the alkylation unit. In this case, the reaction products may include as well as alkylbenzene, some unreacted benzene which may be removed by a benzene separation unit, which may comprise a fractionation column. The benzene extracted may be reused e.g. delivered back into the alkylation unit to reduce the volume of fresh benzene needed in stream.

Any unreacted paraffins may be removed via a paraffinic separation unit which may comprise a fractionation column. Such unreacted paraffins can be reused in this process.

Alkylbenzenes, following separation from excess benzene and unreacted paraffins if so necessary, may undergo further fractionation via for example, a multi-column fractionation system to separate any alkylbenzene with carbon chain lengths still present that are outside the target range.

Finally, the alkyl benzene is sulphonated to form P-LAS.

For detergent compositions where the total LAS contains less than 100% P-LAS, the n- above processing pyrolysis oil from of waste plastic feedstock may be conducted with oils from feedstocks obtained from sources other than waste plastic feedstock (e.g. from fossil feedstocks, or natural oils as described herein). In such case, the above descriptions would involve mixed streams.

Alternatively, the P-LAS may be processed in isolation from other feedstocks for all or part of the processes described above. Thus, pyrolysis oil may be processed in a separate stream from say, fossil or natural oil streams, up to any point and then combined.

P-LAS may be processed entirely in isolation and added to a detergent composition as a separate ingredient to LAS from other sources and/or pre-mixed with LAS from other sources. Phenyl isomer

The (total) LAS may comprise multiple positional isomers, with regard to the position of the phenyl moiety on the alkyl chain. Such positional isomers may comprise any of 2-phenyl, 3- phenyl, 4-phenyl, 5-phenyl, and the like and any combination.

Preferably, the linear alkylbenzene has a 2-phenyl isomer content between about 15 percent and 45 percent, based on the weight of the alkylated aryl compound.

Preferably, the weight ratio of 2-phenyl isomer: 3-phenyl isomer : is from 2:1 to 1 :2, more preferably from 3:2 to 1 :2, most preferably 5:4 to 4:5. Preferably these two isomers represent from 20 to 70wt% of the P-LAS, more preferably from 30 to 40wt% .

Solid alkylation catalysts, such as those used in the Detal™ process, produce products with 2-phenyl isomer content between 25 and 30 percent. HF-catalyzed processes typically yield a 2-phenyl isomer content less than 20 percent, and AlCh typically between 30 and 33 percent. One process for controlling the 2-phenyl isomer content of linear alkylbenzene is disclosed in EP2616176 B. In this process LAB is obtained by alkylating a benzene with an olefin comprising reacting under alkylation reaction conditions a substantially linear olefin with benzene in a process stream comprising water and in the presence of a catalyst and controlling the water concentration in the range from bone dry to 100 ppm, said catalyst comprising a first catalyst component zeolite selected from the group consisting of rare earth-containing faujasite and blends thereof, and a second catalyst component zeolite selected from the group consisting of UZM-8, Zeolite MWW, Zeolite BEA, Zeolite OFF, Zeolite MOR, Zeolite LTL, Zeolite MTW, BPH/UZM-4, and blends thereof.*

Definitions

As used herein, the following terms are defined:

The articles “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described; and "include", "includes" and "including" are meant to be nonlimiting.

“Alkyl” means an unsubstituted or substituted saturated hydrocarbon chain having from 1 to 18 carbon atoms. The chain may be linear or branched. "biodegradable" means the ability of a compound to ultimately be degraded completely into CO2 and water or biomass by microorganisms and/or natural environmental factors, preferably within 6 months.

“detergent composition” in the context of this invention means cleaning compositions, generally containing detersive surfactants, optionally other treatment ingredients, intended for and capable of treating substrates as defined herein.

“detersive surfactant” in the context of this invention denotes a surfactant which provides a detersive (i.e. cleaning) effect to a substrate such as fabric treated as part of a domestic treatment e.g. laundering process or dishwashing process or hard surface washing process.

“C12” refer to the length of the alkyl chains (12) of the alkyl chain of the P-LAS. Similarly C9 means the alkyl chain has 9 carbon atoms and so forth.

“washing operation” as used herein generally denotes a method of laundering fabric using a laundry treatment composition according to the invention.

"substantially free of” or "substantially free from" refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient. A composition that is "substantially free" of/from a component means that the composition comprises less than 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the component.

"Substrate” preferably is any suitable substrate and includes but is not limited to fabric substrates and dishes. Fabric substrates includes clothing, linens and other household textiles etc. In the context of fabrics, wherein the term “linen” is used to describe certain types of laundry items including bed sheets, pillow cases, towels, tablecloths, table napkins and uniforms and the term “textiles” can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends. “Dishes” is meant generically and encompasses essentially any items which may be found in a dishwashing load, including crockery chinaware, glassware, plasticware, hollowware and cutlery, including silverware. Substrate may also include any inanimate “household surface”, “household hard surface”, it is meant herein any kind of surface typically found in and around houses like kitchens, bathrooms, e.g., floors, walls, tiles, windows, cupboards, sinks, showers, shower plastified curtains, wash basins, WCs, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox®, Formica®, vitroceramic, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like. Household hard surfaces also include household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on. Such hard surfaces may be found both in private households as well as in commercial, institutional and industrial environments.

“Treatment” in the context of treating substrates may include cleaning, washing, conditioning, lubricating, care, softening, easy-ironing, anti-wrinkle, fragrancing, de-pilling, rejuvenation including colour rejuvenation, soaking, pretreatment of substrates, bleaching, colour treatments, soil removal, stain removal and any combination thereof.

“total LAS present in the detergent composition” means all the LAS present, regardless of feedstock source. This may be P-LAS and LAS from fossil fuel and LAS from plant and/or algae and any other LAS.

“Linear alkylbenzene sulphonate obtained from waste plastic feedstock” or “P-LAS” is distinguished from LAS which is linear alkylbenzene sulphonate from other sources such as petrochemical, natural oils etc. It is obtained from pyrolysis of waste plastic.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

Dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a value disclosed as "50 microns’ is intended to mean "about 50 microns."

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated. It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

Further Anionic-surfactants

Other non-soap anionics include salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Anionic Surfactant are described in Anionic Surfactants Organic Chemistry (Surfactant Science Series Volume 56) edited By H.W.Stache (Marcel Dekker 1996).

Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. The alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. The counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed. Sodium and potassium are preferred.

Some alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.

Mixtures of any of the above-described materials may also be used.

Also commonly used in laundry liquid compositions are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with a mole average of 3EO units per molecule.

The alkyl ether sulphate may be provided in a single raw material component or by way of a mixture of components. Alcohol ethoxylates

The surfactant preferably comprises a non-ionic surfactant. Preferably the composition comprises from 0.1 to 20% wt. non-ionic surfactant based on the total weight of composition. Such nonionic surfactants include, for example, polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include Cs to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.

A preferred class of additional nonionic surfactant for use in the invention includes aliphatic C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.

The alcohol ethoxylate may be provided in a single raw material component or by way of a mixture of components.

A composition of the invention may contain one or more further surfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above.

The detergent composition may comprise further ingredients as below.

Sequestrant

The detergent compositions may also preferably comprise a sequestrant material. Examples include the alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.

Cleaning Polymers

The detergent composition may further comprise one or more anti-redeposition polymers e.g. alkoxylated polyethyleneimines, preferably an ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.

Soil Release Polymers

The detergent composition may further comprise one or more soil release polymers.

Suitable soil release polymers are described in greater detail in U. S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007/079850 and WO2016/005271. If employed, soil release polymers will typically be incorporated into the liquid laundry detergent compositions herein in concentrations ranging from 0.01 percent to 10 percent, more preferably from 0.1 percent to 5 percent, by weight of the composition.

Hydrotropes

A composition of the invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers e.g. C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (M_w) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates) or mixtures thereof.

Non-aqueous carriers, are preferably included, may be present in an amount ranging from 1 to 50%, preferably from 10 to 30%, and more preferably from 15 to 25% (by weight based on the total weight of the composition). The level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such compositions. The preferred hydrotropes are monopropylene glycol and glycerol.

External Structurants

Compositions of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre. The presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid.

Enzymes

A composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present with corresponding enzyme stabilizers.

Product Form

The detergent composition may take any suitable form such as a liquid, gel, or a solid composition. Solid detergent compositions can take a variety of physical solid forms including forms such as powder, granule, ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet.

The detergent composition may be in the form of a unit dose formulation or contained on or in a porous substrate or nonwoven sheet, and other suitable forms.

Unit dose composition includes compositions enclosed within a water-soluble film.

Where the product is a liquid it may be a dilutable composition or an auto-dose composition. An auto-dose composition is one which is contained within a cartridge or such like and dispensed from within the washing machine when required.

Where the product is a dilutable it means that the consumer can purchase a concentrated product and take the concentrate home where it can be diluted to form a regular home care product. The dilution may require anything from 1 to 10 parts water to one part concentrate.

FURTHER OPTIONAL INGREDIENTS

A composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include fatty acids, foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, antishrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye, preservative. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the diluted composition) and so adjusted depending on the dilution ratio with water. Many of the ingredients used in embodiments of the invention may be obtained from so called black carbon sources or a more sustainable green source. The following provides a list of alternative sources for several of these ingredients and how they can be made into raw materials described herein.

EXAMPLES

The following detergent compositions are illustrated by way of example only.

Linear alkyl benzene sulfonate acid- P-LAS comprises LAS wherein alkyl chains are obtained from waste plastic and 30%wt comprises C12.

Claims

1. A detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS) and wherein said P-LAS comprises at least 30%wt C12.

2. A detergent composition according to claim 1 wherein the total LAS comprisesfrom 0.001 to 8 %wt P-LAS based on the total weight of any LAS present in the composition.

3. A detergent composition according to claim 1 or claim 2 where the P-LAS is obtained from pyrolyzed waste plastic.

4. A detergent composition according to any preceding claim wherein the waste plastic comprises any of polyethylene such as high-density polyethylene (HDPE), low- density polyethylene (LDPE); polypropylene (PP).

5. A detergent composition according to any preceding claim wherein the waste plastic comprises less than 10 %wt, more preferably less than 5%, even more preferably less than 1% wt of any of polyvinylchloride (PVC) or polystyrene (PS) or polyethylene terephthalate (PET) (based on total weight of plastic).

6. A detergent composition according to any preceding claim wherein the P-LAS comprises a phenyl moiety on the alkyl chain which is obtained from waste plastic.

7. A detergent composition according to any preceding claim further comprising LAS from sources other than plastic waste.

8. A detergent composition according to any preceding claim wherein the LAS from sources other than plastic waste comprises LAS obtained from natural oil.

9. A detergent composition according to any preceding claim wherein the LAS comprises LAS obtained from fossil sources.

10. A detergent composition according to any preceding claim wherein the detergent composition comprises from 1 to 40% LAS. A detergent composition according to any preceding claim wherein the total LAS in the detergent composition comprises at least 50%wt, preferably at least 60%, preferably at least 70% of two carbon chain lengths (the dominant pair) which may be any of C10 and C11 , C10 and C12, C10 and C13, C11 and C12, C11 and C13, or C12 and C13, and preferably any of any of C10 and C11 , C10 and C12, C10 and C13. A detergent composition according to any preceding claim comprising at least one further surfactant comprising an anionic and/or a nonionic surfactant. A detergent composition according to any preceding claim wherein the total LAS present in the composition is in the range from 50 to 100% wt. of the total anionic surfactant present in the composition. A method of a method of making a detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS), the method incorporating the steps of: a. producing P-LAS by pyrolysis of waste plastic wherein said P-LAS comprises at least 30%wt C12; and b. incorporating the P-LAS from step a. into a detergent composition. A method of treating fabrics with a detergent composition comprising linear alkylbenzene sulphonate obtained from waste plastic feedstock (P-LAS) and wherein said P-LAS comprises at least 30%wt C12, the method comprising the step of immersing at least a part of a fabric in an aqueous wash liquor comprising water and the detergent composition.