Patent ID: 12258539

DETAILED DESCRIPTION OF THE INVENTION

Features and benefits of the present invention will become apparent from the following description, which includes examples intended to give a broad representation of the invention. Various modifications will be apparent to those skilled in the art from this description and from practice of the invention. The scope is not intended to be limited to the particular forms disclosed and the invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.

As used herein, articles such as “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.

As used herein, the terms “include”, “includes” and “including” are meant to be non-limiting.

As used herein, the term “waste plastic feedstock” means waste plastic that has been depolymerized via pyrolysis conditions, which may be catalytic or non-catalytic, continuous or batch.

As used herein, the term “LAS” refers to linear alkylbenzene sulfonate.

As used herein, the term “LAB” refers to linear alkylbenzene.

As used herein, the term “fatty alcohol” refers to a linear alcohol derived from natural oil via reduction of the oil to alcohol (specifically, transesterification of triglycerides to give methyl esters which in turn are hydrogenated to the alcohols). Fatty alcohols are essentially 100% linear.

As used herein, the term “detergent alcohol” is broader than the term fatty alcohol and encompasses fatty alcohols as well as synthetic alcohols. Detergent alcohols may be linear, branched, or a mixture thereof. For example, synthetic alcohols may contain varying levels of 2-alkyl branched content, depending on the process used to make the synthetic alcohols. Synthetic alcohols may also contain branched content due to the feedstock containing branched paraffins or olefins.

As used herein, the term “MTA” refers to metric tons annual.

As used herein, the term “paraffin sulfonate” refers to a surfactant derived from sulfoxidation of paraffins.

As used herein, the term “olefin sulfonate” refers to a surfactant derived from direct sulfonation of olefin.

The terms “kerosene-based” (as in “kerosene-based alkylbenzene”) and “petrol-based” (as in “petrol-based alkylbenzene”) are used interchangeably to refer to a material (or the production thereof) that is produced from kerosene or another petrochemical that is extracted from the earth, such as crude oil, natural gas, or ethylene oligomers derived from ethylene from various sources, such as natural gas, crude oil, coal, or the like. Any of these petrol-based feedstocks may be blended with a waste plastic feedstock to produce alkylbenzene, oxo alcohol, or any of the other surfactant intermediates or surfactants disclosed herein.

The term “another source(s) of hydrocarbon” includes feedstock derived from natural gas, crude oil, coal, biomass, fats or oils, or waste fats or oils. Feedstocks derived from natural gas, crude oil, coal, biomass, fats or oils, or waste fats or oils contain a hydrocarbon stream similar to that of kerosene or an olefin stream. For example, the Neodene® products sold by Shell include linear alpha and internal olefins that are made via ethylene. Other olefins, such as alpha olefins, may come from processes known to one skilled in the art, such as Ziegler chemistry. Another source of olefins may be vinylidene-type, which may come from short chain olefin dimerization (also known to one skilled in the art) and may be blended with waste plastic-based olefins and/or paraffins.

The term “substantially free of” or “substantially free from” as used herein 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 about 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the component.

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.

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.

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.

The methods and systems disclosed herein relate to producing linear or branched alkylbenzene, linear or branched paraffin, linear or branched olefin, and/or linear or branched oxo alcohol from waste plastic feedstock alone or waste plastic feedstock in combination with kerosene and/or another source(s) of hydrocarbons, as disclosed herein. The methods and systems disclosed herein provide an alternative use for waste plastic, which may otherwise end up in landfills or in the environment. The waste plastic feedstock is made by pyrolyzing waste plastic, either catalytically or non-catalytically and via a continuous or a batch process. The pyrolysis of waste plastic is well known in the art. Multiple variations of pyrolysis are practiced to produce waste plastic feedstocks. The following are non-limiting examples of companies that are piloting waste plastic pyrolysis, practicing it commercially, or selling equipment to pyrolize waste plastic to produce a feedstock for fuel or chemical use: PARC; Resynergi; Vadxx; Green Enviro Tech Holdings; J.U.M Global; ReGEN Fuels and Energy LLC; Green Mantra Technologies; Climax Global Energy; Envion; Nexus Fuels;JBI, Inc.; Recarbon Corp; Anhui Oursun Environmental Technologies; ECO Int'l Marketing; P-fuel, ltd.; Polymer Energy; PLastOil; Promeco; T Technology; ROYCO FUEL CHINA; AYU Global Resources, Inc. and Plastic2Fuel.

The waste plastic used in the various available pyrolysis processes is derived from plastics designated by #1-#6). It may be desirable to use plastic waste designated by #1, #2, #4 and #6, though all grades may be used depending on the nature of the pyrolysis and subsequent processing steps.. # 1 plastic waste is polyethylene terephthalate, #2 plastic waste is high density polyethylene, #4 plastic waste is low density polyethylene), and #5 plastic waste is polypropylene. If, for example, a pyrolysis plant desires to produce a waste plastic feedstock having a low sulfur, oxygen, and nitrogen content, then), then #2, #4, and #5 plastic wastes may be most desirable. If a pyrolysis plant desires to minimize the aromatic content of the pyrolyzed product, then reducing #1 plastic waste and #6 plastic waste may achieve lower levels of aromatics in the product of the pyrolysis process. Other plastics, such as #3 (PVC), may also be used but require additional processing units to remove the chlorine produced by pyrolysis.

Plastics in category #7 (unknown material) may also be used, particularly if the #7 plastic waste is identified as containing #2 plastic waste, #4 plastic waste, #5 plastic waste, a mixture or copolymer thereof, or a mixture or copolymer of polyethylene and polypropylene. #7 plastic waste may not be recycled because of its unusual size of a #7 container, because the #7 plastic waste comes from industrial. When the #7 plastic waste contains other materials, such as polyacrylonitrile, polyacrylic acid, polyvinyl sulfonate, which can introduce undesirable impurities (e.g., nitrogen, oxygen, sulfur), these impurities may be managed by a hydrotreatment unit in a LAB and/or LAB/oxo alcohol facility (e.g., if the impurity content is deemed to be low for the particular facility).

It has been found that the waste plastic feedstock may produce an increased level of linear paraffin and linear olefin, as compared to petroleum-based kerosene feedstock. Also, the sulfur, oxygen, and nitrogen content of the waste plastic feedstock may be reduced, depending on the type(s) of plastic waste that are used; a reduced content of sulfur, oxygen, and nitrogen may be advantageous for a feed stream entering a linear alkylbenzene plant or a combined linear alkylbenzene and oxo alcohol plant or for other surfactant intermediates and surfactants.

Paraffin and olefin are key feedstocks for alkylbenzene and oxo alcohols. When linear alkylbenzene was first produced in the 1960s, it contained an increased content of linear paraffins and linear olefins (from light crude oil), as described in the literature. Over the past 50 years, crude oil has come to include heavier crude, which requires more aggressive processing and thus contains less linear paraffin and linear olefin, which results in lower throughput in processing plants that convert kerosene to linear alkylbenzene and oxo alcohols. By supplementing kerosene and/or another source(s) of hydrocarbons with a waste plastic feedstock source or by using a waste plastic feedstock source alone, a producer can greatly increase the throughput in a linear alkylbenzene plant or oxo alcohol production, in the case of a plant that produces both linear alkylbenzene and oxo alcohol, thereby improving the efficiency of the process, and the surfactant made from such waste plastic-derived linear alkylbenzene or oxo alcohol may then be used to make detergent formulations for consumers.

One may also use both the linear and branched feedstocks derived from waste plastic alone or waste plastic in combination kerosene and/or another source(s) of hydrocarbons to make linear and/or branched mixtures of alkylbenzenes, oxo alcohols, and surfactants derived therefrom.

Table 1, below, shows an illustration of the benefits that may be realized by supplementing a kerosene feed with waste plastic feedstock (Example 1 versus Example 2). Table 1 also illustrates an example that uses 100% waste plastic feedstock (Example 3). Table 1 is provided merely for illustration, and is not limiting on the possible benefits, compositions, or plastic waste-derived feed/kerosene feed amounts realizable in accordance with the present disclosure. The information in Table 1 is calculated based on potential production volumes and analysis of a typical kerosene feedstock and a waste plastic feedstock, using the 2D-GC/TOFMS and GC methods described herein.

TABLE 1Feed TypeExample 1Example 2Example 3Heart Cut Waste651820133,149Plastic Pyrolysate inMTAKerosene in MTA229883500,0000TOTAL MTA Feeds295065500,000133,149Extract MTA (linear700857008570085paraffin)Product Purity0.9850.9850.985Product Aromatics0.0050.0050.005Product C#DistributionnC9000nC1010.0015.2113.84nC1132.3233.3228.37nC1230.1128.3628.86nC1326.9622.6928.29nC140.610.430.72AMW Target Range166.95168.2166.8

As shown in Table 1, in Example 1, 65,182 MTA of waste plastic feedstock (heart cut) are provided with 229883 MTA kerosene feed. In Example 2, however, a greater amount of MTA, 500,000 MTA, is needed to achieve a similar production quantity of linear paraffin, when only heart cut kerosene feed is used. Example 3 shows the production quantity of linear paraffin produced from waste plastic feedstock alone. Thus, Table 1 shows that by blending waste plastic feedstock in the heart cut range with kerosene, the same production quantity of linear paraffin may be obtained while using about 40% less total feedstock in the production facility. Example 3 shows that by using waste plastic feedstock (heart cut) alone, the same amount of linear paraffin product may be produced using about 28% of the amount of feedstock as compared to using kerosene feedstock alone. In other words, more than 3.5 times as much linear paraffin can be produced using waste plastic feedstock (heart cut) alone.

Table 2 shows an analysis of waste plastic feedstock (derived from plastic waste via pyrolysis) in the heart cut range (middle distillate) and an analysis of a kerosene feedstock in the heart cut range. Table 2 also shows the analysis for a hydrotreated sample of waste plastic feedstock (middle distillate). Table 2 shows that the conversion of olefin in the original middle distillate fraction of the waste plastic feedstock has almost doubled the linear paraffin content as compared to the kerosene feedstock, which has less linear olefin to contribute to total paraffin after hydrotreatment. The compositions in Table 2 are non-limiting examples of compositions and the content of olefins and paraffins, linear and branched, and aromatics, as identified by the 2D-GC/TOFMS method described herein. The information in Table 2 is calculated based on the analysis of a typical kerosene feedstock and a waste plastic feedstock, using the 2D-GC/TOFMS and GC methods described herein. The information in Table 2 is reported in GC area %. Average chain length is calculated from the GC area %.

TABLE 2Analysis of waste plastic feedstock compared to Petrol Kero K1PetrolWaste PlasticDerivedFeedstockKeroseneMiddleK1 (fromMiddledistillateCompound ClassSunoco)DistillatehydrotreatedLinear Paraffin24.225.557.9Total Paraffin58.029.972.5Linear Olefin4.728.01.7Total Olefin +27.060.917.1CyclicsAromatic15.09.16.4PhenolNone0.10.2DetectedBranched33.814.820.1HydrocarbonsAve chain length12.415.115.0for linear paraffincompositionTotal Potential29.061.557.9Linear Paraffin posthydrotreatment
Methods for Producing Surfactant Intermediates and Surfactants Derived from Waste Plastic Feedstock

The present invention relates to improved, highly efficient processes for making surfactant intermediates and surfactants, which may be used in various cleaning products. More specifically, the present invention relates to methods and systems for producing a linear alkylbenzene, paraffin, or olefin from waste plastic feedstock alone or in combination with a kerosene feedstock.

In addition to the sustainability benefits of using waste plastic feedstock (e.g., removal of waste plastic from the environment), it has been found that waste plastic feedstock has very desirable properties for making surfactant intermediates, such as alkylbenzene and oxo alcohols. For example, waste plastic feedstock has a much greater content of linear paraffin than traditional kerosene feedstock; waste plastic feedstock has a greater content of linear olefin; it has a reduced content of aromatics, sulfur, and oxygen components. These properties provide for a desirable feedstock, which can either be used alone or blended with kerosene feedstock.

A method for producing a paraffin from a waste plastic feedstock in combination with kerosene and/or another suitable source(s) of hydrocarbons as defined herein may include providing a first feed stream comprising kerosene and/or another suitable source(s) of hydrocarbons, pre-fractionating the first feed stream to produce a heart cut paraffin stream comprising paraffins in a heart cut range, and combining the heart cut paraffin stream with a second feed stream comprising waste plastic feedstock to form a combined stream. The method may further include one or more of the steps of hydrotreating the combined stream, fractionating the hydrotreated stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, and separating branched and cyclic hydrocarbons from the second heart cut paraffin stream to form a linear heart cut paraffin stream. Hydrotreating is a well known process that removes oxygen, nitrogen, and sulfur and also reduces any remaining olefins to paraffins. The waste plastic feedstock may also be pre-fractionated to provide a heart cut stream of waste plastic feedstock prior to combining the waste plastic feedstock stream with the kerosene-based heart cut stream. When the method for producing paraffin from waste plastic feedstock in combination with kerosene and/or another suitable source(s) of hydrocarbons includes the separating step, the paraffin product is linear, as branched and cyclic hydrocarbons are removed via the separating step. The separating step may optionally produce two streams of paraffins—branched paraffins and linear paraffins. When the method for producing paraffin from waste plastic feedstock in combination with kerosene and/or another suitable source(s) of hydrocarbons does not include the optional separating step, the paraffin product is a blend of linear, branched, and cyclic paraffins.

A method for producing paraffin from a waste plastic feedstock alone may include providing a feed stream comprising waste plastic feedstock and pre-fractionating the feed stream to produce a first heart cut paraffin stream comprising paraffins in a heart cut range. The method may further include one or more of the steps of hydrotreating the first heart cut paraffin stream, fractionating the hydrotreated feed stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, separating branched and cyclic hydrocarbons from the second heart cut paraffin stream to form a linear heart cut paraffin stream. When the method for producing paraffin from waste plastic feedstock alone includes the optional separating step, the paraffin product is linear, as branched and cyclic hydrocarbons are removed via the separating step. The separating step may optionally produce two streams of paraffins—branched paraffins and linear paraffins. When the method for producing paraffin from waste plastic feedstock does not include the optional separating step, the paraffin product is a blend of linear, branched, and cyclic paraffins.

A method for producing an olefin from waste plastic feedstock in combination with kerosene and/or another suitable source(s) of hydrocarbons may include providing a first feed stream comprising kerosene and/or another suitable source(s) of hydrocarbons, pre-fractionating the first feed stream to produce a first heart cut paraffin stream comprising paraffins in a heart cut range, and combining the first heart cut paraffin stream with a second feed stream comprising waste plastic feedstock to form a combined stream. The method may further include the steps of hydrotreating the combined stream, fractionating the hydrotreated stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, separating branched and cyclic hydrocarbons from the second heart cut paraffin stream, and dehydrogenating the (optionally separated) second heart cut paraffin stream to form a stream comprising olefins. When the method for producing olefin includes the optional separating step, namely separation of linear paraffin from branched and cyclic paraffin, the step of dehydrogenating produces linear olefins, which may be desirable for some oxo alcohols and for linear alkylbenzene production. When the method for producing olefin does not include the optional separating step, the step of dehydrogenating produces a blend of linear, branched, and cyclic olefins.

A method for producing an olefin from waste plastic feedstock alone may include providing a feed stream comprising waste plastic feedstock and pre-fractionating the feed stream to produce a first heart cut paraffin stream comprising paraffins in a heart cut range. The method may further include one or more of the steps of hydrotreating the first heart cut paraffin stream, fractionating the hydrotreated feed stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, separating branched and cyclic hydrocarbons from the second heart cut paraffin stream, and dehydrogenating the (optionally separated) second heart cut paraffin stream to form a stream comprising olefins. When the method for producing olefin includes the optional separating step, namely separation of linear paraffin from branched and cyclic paraffin, the step of dehydrogenating produces linear olefins, which may be desirable for some oxo alcohols and for linear alkylbenzene production. When the method for producing olefin does not include the optional separating step, the step of dehydrogenating produces a blend of linear, branched, and cyclic olefins.

A method for producing a alkylbenzene from waste plastic feedstock in combination with kerosene and/or another suitable source(s) of hydrocarbons may include providing a first feed stream comprising kerosene and/or another suitable source(s) of hydrocarbons, pre-fractionating the first feed stream to produce a first heart cut paraffin stream comprising paraffins in a heart cut range, and combining the first heart cut paraffin stream with a second feed stream comprising waste plastic feedstock to form a combined stream. The waste plastic feedstock may also be pre-fractionated to provide a heart cut stream of waste plastic feedstock prior to combining. This pre-fractionating may be performed at the site where the waste plastic feedstock is produced or at the site where the alkylbenzene is produced. The method may further include one or more of the steps of hydrotreating the combined stream, fractionating the hydrotreated stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, dehydrogenating the second heart cut paraffin stream to form a stream comprising olefins, and alkylating the stream comprising olefins with a third feed stream comprising benzene to form a stream comprising alkylbenzenes that are linear, branched, or a mixture thereof. The aromatic portion may be derived from a traditional petroleum-based feedstock. Alternatively, the aromatic portion may be derived from a renewable feedstock, e.g., natural oil, or from the naphtha fraction of waste plastic feedstock.

A method for producing alkylbenzene from waste plastic feedstock alone may include providing a feed stream comprising waste plastic feedstock, pre-fractionating the feed stream comprising waste plastic feedstock to produce a first heart cut paraffin stream comprising paraffins in a heart cut range. The method may further include one or more of the steps of hydrotreating the first heart cut paraffin stream, fractionating the hydrotreated stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, dehydrogenating the second heart cut paraffin stream to form a stream comprising olefins, and alkylating the stream comprising olefins with a third feed stream comprising benzene to form a stream comprising alkylbenzenes that are linear, branched, or a mixture thereof. Thus, the non-aromatic portion of the alkylbenzene is derived from plastic waste. The aromatic portion may be derived from a traditional petroleum-based feedstock. Alternatively, the aromatic portion may be derived from a renewable feedstock, e.g., natural oil, or from the naphtha fraction of waste plastic feedstock.

A method for producing an oxo alcohol from waste plastic feedstock in combination with kerosene and/or another suitable source(s) of hydrocarbons may include providing a first feed stream comprising kerosene and/or another suitable source(s) of hydrocarbons, pre-fractionating the first feed stream to produce a first heart cut paraffin stream comprising paraffins in a heart cut range, and combining the first heart cut paraffin stream with a second feed stream comprising waste plastic feedstock to form a combined stream. The waste plastic feedstock may also be pre-fractionated to provide a heart cut stream of waste plastic feedstock prior to combining; this pre-fractionating may be performed at the site where the waste plastic feedstock is produced or at the site where the oxo alcohol is produced. The method may further include one or more of the steps of hydrotreating the combined stream, fractionating the hydrotreated stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, dehydrogenating the second heart cut paraffin stream to form a stream comprising olefins, and hydroformylating the stream comprising olefins in the presence of syngas to form a stream comprising oxo alcohols that are linear, branched, or a mixture thereof. The oxo alcohols may be further purified by known means in the art. Alternatively, this method for producing an oxo alcohol may utilize waste plastic feedstock alone (without kerosene) to produce an oxo alcohol that is derived from only waste plastic feedstock and syngas (produced by any means).

A method for producing oxo alcohol from waste plastic feedstock alone may include providing a feed stream comprising waste plastic feedstock, pre-fractionating the feed stream comprising waste plastic feedstock to produce a first heart cut paraffin stream comprising paraffins in a heart cut range. The method may further include one or more of the steps of hydrotreating the first heart cut paraffin stream, fractionating the hydrotreated stream to remove paraffins that are heavier and/or lighter than the heart cut range to form a second heart cut paraffin stream, dehydrogenating the second heart cut paraffin stream to form a stream comprising olefins, and hydroformylating the stream comprising olefins in the presence of syngas to form a stream comprising oxo alcohols that are linear, branched, or a mixture thereof.

InFIG.1, a system100utilizing an example process for producing a linear alkylbenzene, paraffin, and/or olefin is shown. A feedstock containing kerosene and/or another source(s) of hydrocarbons102is fed into a pre-fractionator104. The pre-fractionator104fractionates the kerosene feed102into three streams106,108, and110product. Stream106is a light hydrocarbon stream that may include C9hydrocarbons and lighter hydrocarbons (hydrocarbons having fewer carbons) that are separated from the kerosene feed102. Or, stream106may include C8and lighter hydrocarbons, or C10and lighter hydrocarbons, depending on the desired product composition of linear alkylbenzenes, paraffins, and olefins. Stream108is a distillate, or heavy hydrocarbon stream, that may include C14and heavier hydrocarbons (hydrocarbons having more carbons) that are separated from the kerosene feed102. Or stream108may include anywhere from C13-C19and heavier hydrocarbons, depending on the desired product composition of linear alkylbenzenes, paraffins, and olefins. Stream110includes hydrocarbons that are selected for further processing into the desired linear alkylbenzenes, paraffins, and olefins, and is referred to as the “heart cut.” The heart cut stream110may include C10-C13hydrocarbons that are separated from the kerosene feed102. Or, stream110may include C10-C18hydrocarbons. Generally, the heart cut may include any range of hydrocarbons within the C9-C19range. Light hydrocarbon stream106and distillate stream108are removed from the system100and may be used in other processes.

InFIG.1, the heart cut stream110continues within system100for further processing in a kero-hydrotreater (KHT)112. Hydrotreatment (also referred to as hydroprocessing) is a class of catalytic processes that comprise a set of reactions. Hydrotreating generally employs mild temperature and hydrogen pressures, such that only the more unstable compounds that might lead to the formation of gums, or insoluble materials, are converted to more stable compounds. Hydrotreament is used to substantially remove sulfur, oxygenates, nitrogen, and aromatics. KHT112is employed to treat the heart cut stream of hydrocarbons110to reduce the naturally occurring nitrogen and sulfur content in kerosene to acceptable levels for use in detergents and also to hydrogenate any olefins present in the feed. KHT112is a catalyst-based apparatus, and various catalysts (hydrotreating catalysts) for denitrification and desulfurization are known to those having ordinary skill in the art. InFIG.1, the KHT112also receives a feed stream of waste plastic feedstock114. In examples where, as inFIG.1, the waste plastic feedstock feed114and the kerosene heart cut110are combined in the KHT112, the KHT is also configured to hydrotreat the waste plastic feedstock and kerosene blend, which may contain some level of oxygen, sulfur, or nitrogen, depending on the kerosene feed and the source of the waste plastic for the waste plastic feedstock114. Waste plastic feedstock114typically contains olefins, unless it is hydrotreated prior to entering the system. Thus, the KHT apparatus112may produce paraffins, by using a catalyst that is suitable for hydrogenation, deoxygenation, and denitrification/desulfurization or a mix of catalysts that each accomplish one or more of hydrogenation, deoxygenation, denitrification/desulfurization. A suitable KHT112apparatus for use is sold by UOP LLC and others.

A treated stream of paraffins116aexiting KHT112may be fed to a separator118to separate the desirable linear paraffins from branched or cyclic compounds that may be included in the stream116a.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. Depending on the composition of the kerosene feed102and/or the waste plastic feedstock feed114, separation of linear paraffins from branched and cyclic paraffins may not be necessary, and a treated stream of paraffins116bfrom the KHT112may be directed downstream for further processing to produce linear and branched surfactant intermediates and linear and branched surfactants.

.A linear paraffin stream116cexiting the separator118, or the hydrotreated stream of linear and branched paraffins116b,is fed to a fractionator122. As discussed above, the pre-fractionator104removed light and heavy hydrocarbons from the kerosene feed102; however, the waste plastic feedstock feed114may include hydrocarbons that are heavier and/or lighter than the heart cut range, and as such the fractionator122is optionally provided to fractionate hydrocarbons that are heavier and/or lighter than the desired heart cut range. Hydrocarbons that are C14 and heavier may be removed from system100in a heavy paraffins stream124, and may be used in other processes, as in stream108. Alternatively, hydrocarbons anywhere in the range from C15-C18 and heavier may be removed from system100in the heavy paraffins stream124. The paraffins in the desired heart cut range exit the fractionator122in a stream126afor further processing into alkylbenzene, paraffin, and/or olefin products in subsystem10, as will be described in greater detail below.

Alternatively, if the waste plastic feedstock feed114does not require fractionation, then the stream126bmay be directed downstream for further processing.

Alternatively, waste plastic feedstock114may be used as the only feedstock and not blended with any other feedstock (thereby eliminating feedstock102and process104inFIG.1.FIG.6illustrates and example of such a process. All the numbers shown inFIG.6are the same as the numbers inFIG.1and are assigned the same meanings as inFIG.1(described above).

InFIG.2, a subsystem10utilizing a process for producing a linear and/or branched alkylbenzene, linear and/or branched paraffin, or linear and/or branched olefin is depicted. Subsystem10receives as its feed stream the stream126afrom the fractionator122or stream126b,which is not fractionated, including the heart cut linear paraffins. Stream126aor stream126bis fed to a separator22. The separator22may be a multi-stage fractionation unit, distillation system, or similar known apparatus. The separator22provides a means to separate the paraffins into various desirable fractions or into various portions for producing one or more of linear and/or branched alkylbenzenes, linear and/or branched paraffins, linear and/or branched olefins, or linear and/or branched oxo alcohols (with further processing). For example, as shown inFIG.2, a first portion of paraffins24and a second portion of paraffins26are illustrated, although any number of paraffin portions may be provided. Portion24may include the same hydrocarbon range as portion26, or they may be separated into different fractions. For example, where the heart cut is selected as C10-C18, portion24may include C10- C13 paraffins, whereas portion26may include C14- C18 paraffins. Alternatively, they may both include C10- C18 paraffins. In another example, where the heart cut is selected as C10- C13, both portions24and26may include hydrocarbons in that range. Numerous other examples are possible, depending on the quantity and the hydrocarbon content of the desired linear alkylbenzenes, paraffins, olefins, or oxo alcohols (produced downstream of subsystem10). For example, it may be desirable to provide a C10-C13heart cut fraction or a C10-C12heart cut fraction and also provide a C14-C15(two carbon-cut) fraction or a C13-C14(two carbon-cut) fraction, respectively, which may be further processed downstream of subsystem10to make an oxo alcohol, using a known two carbon-cut process.

Either or both paraffin portions24or26(or other portions, if more are present) may thereafter be purified to remove trace contaminants, resulting in a purified paraffin product. When only paraffin production is desired, the entire paraffin product (i.e., all of the one or more portions) may be purified at this stage. Alternatively, some of the paraffin product may be directed to further processing stages for the production of alkylbenzenes and/or olefins. Alternatively, when only olefin and/or alkylbenzene production is desired, the entire paraffin product (i.e., all of the one or more portions) may be directed to further processing stages. As shown in the example subsystem10illustrated inFIG.2, the second paraffin portion26is directed to a purification system80to remove any remaining trace contaminants, such as oxygenates, nitrogen compounds, and sulfur compounds, among others, that were not previously removed in the processing steps described above. In one example, purification system80is an adsorption system. Alternatively or additionally, a PEP unit82, available from UOP LLC, may be employed as part of purification system80. Subsequent to purification, a purified paraffin stream13may be removed from subsystem10as the paraffin product. As further shown inFIG.2, the first portion of paraffins24(e.g., that portion of paraffins directed for further processing to alkylbenzenes and/or olefins, when desired) may be introduced to an alkylbenzene and olefin production zone28. Specifically, the first portion of paraffins24may be fed into a dehydrogenation unit30in the alkylbenzene and olefin production zone28. In the dehydrogenation unit30, the first portion of paraffins24is dehydrogenated into mono-olefins of the same carbon numbers as the first portion of paraffins24. Typically, dehydrogenation occurs through known catalytic processes, such as the commercially popular Pacol® process. Conversion is typically less than 30%, for example less than 20%, leaving greater than 70% paraffins unconverted to olefins. Di-olefins (e.g., dienes) and aromatics may also be produced, as expressed in the following equations:
Mono-olefin formation: CxH2x+2→CxH2x+H2
Di-olefin formation: CxH2x→CxH2x−2+H2
Aromatic formation: CxH2x−2→CxH2x−6+2H2

InFIG.2, a dehydrogenated stream32may exit the dehydrogenation unit30comprising mono-olefins and hydrogen, unconverted paraffins, as well as some di-olefins and aromatics. The dehydrogenated stream32is delivered to a phase separator34for removing the hydrogen from the dehydrogenated stream32. The removed hydrogen can be directed away from system100, or it can be used as fuel or as a source of hydrogen (H2) for a hydrotreatment process.

At the phase separator34, a liquid stream38is formed and includes the mono-olefins, the unconverted paraffins, and any di-olefins and aromatics formed during dehydrogenation. The liquid stream38exits the phase separator34and enters a selective hydrogenation unit40. The hydrogenation unit40may be a DeFine® reactor (or a reactor employing a DeFine® process), available from UOP LLC. The hydrogenation unit40selectively hydrogenates at least a portion of the di-olefins in the liquid stream38to form additional mono-olefins. As a result, an enhanced stream42is formed with an increased mono-olefin concentration.

As shown, the enhanced stream42may pass from the hydrogenation unit40to a light hydrocarbons separator44, such as a stripper column, which removes a light end stream46containing any light hydrocarbons, such as butane, propane, ethane and methane, which may result from cracking or other reactions during upstream processing. With the light hydrocarbons46removed, stream48is formed and may be delivered to an aromatic removal apparatus50, such as a PEP unit available from UOP LLC. As indicated by its name, the aromatic removal apparatus50removes aromatics from the stream48and forms a stream of mono-olefins and unconverted paraffins52.

InFIG.2, to produce alkylbenzenes, the stream of mono-olefins52and a stream of benzene54are fed into an alkylation unit56. The benzene may be sourced from petroleum, it may be sourced from renewable feedstocks described in the art, or it may be obtained from known processes for isolating benzene from waste plastic feedstocks that are referred to as naphtha grade. Furthermore the benzene may be sourced via waste plastic pyrolysis in the waste plastic pyrolysis naphtha fraction. The alkylation unit56holds a catalyst58, such as a solid acid catalyst, which supports alkylation of the benzene54with the mono-olefins52. Hydrogen fluoride (HF) and aluminum chloride (AlCl3) are two major catalysts in commercial use for the alkylation of benzene with mono-olefins and may be used in the alkylation unit56. Additional catalysts include 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 alkylbenzene (LAB), may be formed according to the reaction:
C6H6+CXH2X→C6H5CXH2X+4
and may be present in the alkylation effluent60. To optimize the alkylation process, surplus amounts of benzene54may be supplied to the alkylation unit56. Therefore, the alkylation effluent60exiting the alkylation unit56may contain alkylbenzene and unreacted benzene. Further, the alkylation effluent60may also include some unreacted paraffins. InFIG.2, the alkylation effluent60is passed to a benzene separation unit62, such as a fractionation column, for separating the unreacted benzene from the alkylation effluent60. This unreacted benzene may exit the benzene separation unit62in a benzene recycle stream64that is delivered back into the alkylation unit56to reduce the volume of fresh benzene needed in stream54.

As shown, a benzene-stripped stream66exits the benzene separation unit62and enters a paraffinic separation unit68, such as a fractionation column. In the paraffinic separation unit68, unreacted paraffins may be removed from the benzene-stripped stream66in a recycle paraffin stream70, and may be routed to and mixed with the first portion of paraffins24before dehydrogenation as described above, or may optionally be directed to the second portion26for purification of product paraffins.

Further, an alkylbenzene stream72that is separated by the paraffinic separation unit68may be fed to an alkylate separation unit74. The alkylate separation unit74, which may be, for example, a multi-column fractionation system, separates a heavy alkylate bottoms stream76from the alkylbenzene stream72.

After the post-alkylation separation processes, the alkylbenzene product12, which contains some portion derived from waste plastic feedstock, may be isolated and exit the subsystem10. It is noted that such separation processes are not necessary in all cases in order to isolate the alkylbenzene product12. For instance, the alkylbenzene product12may be desired to have a wide range of carbon chain lengths and not require any fractionation to eliminate carbon chains longer than desired, e.g., heavies or carbon chains shorter than desired, e.g., lights. Further, the feed114may be of sufficient quality that no fractionation is necessary for the desired chain length range.

InFIG.2, to produce olefins, a stream53, which may include all or a portion of stream52, may be directed to a separator57for separating the unconverted paraffins from the olefins. The separator57may be an Olex ® separator, available from UOP LLC. The Olex ® process involves the selective adsorption of a desired component (i.e., olefins) from a liquid-phase mixture by continuous contacting with a fixed bed of adsorbent. Alternatively, the separator57may be a direct sulfonation separator, which makes olefin sulfonate surfactants (containing some fraction that is derived from waste plastic feedstock) directly. The separated, unconverted paraffins may optionally be directed back to the second paraffin portion26for purification (stream73) and/or back to the first paraffin portion24for dehydrogenation for conversion to olefins (stream71). InFIG.2, an olefin stream61may exit the separator57and may be fed to a separator63. The separator63may be a multi-stage fractionation unit, distillation system, or similar known apparatus. The separator63may provide a means to separate the olefins into various desirable fractions. For example, as shown inFIG.2, a first portion of olefins65and a second portion of olefins67are illustrated, although any number of olefin portions may be provided, depending on how many olefin fractions are desired. The first portion of olefins65may have carbon chain lengths of C10 to C14. Alternatively, the first portion of olefins65may have carbon chain lengths having a lower limit of CL, where L is an integer from four (4) to thirty-one (31), and an upper limit of Cu, where U is an integer from five (5) to thirty-two (32). The second portion of olefins67may have carbon chains shorter than, longer than, or a combination of shorter and longer than, the chains of the first portion of olefins65. The first portion of olefins65may include olefins with C10to C14chains and the second portion of olefins67may include olefins with C18to C20chains. Alternatively, the first portion of olefins65may include olefins with C10to C13chains and the second portion of olefins67may include olefins with C14to C18chains. Alternatively, the first portion of olefins65and/or the second portion of olefins67may include 2-carbon-cut olefins, such as C14to C15.Subsequent to separation, the purified olefins portions65and67are removed from the subsystem10as the olefin product. The olefin products65and67may be used directly to produce oxo alcohols by known hydroformylation processes or fractionated further into 2- or 3-carbon-cuts prior to hydroformylation.

FIG.3depicts a system200using another example of a process for producing a alkylbenzene, paraffin, or olefin from waste plastic feedstock and kerosene and/or another source(s) of hydrocarbons as disclosed herein,. InFIG.3, the heavy paraffins stream124is not directed out of the system200for optional use in other processes, as inFIG.1, but rather is directed to a second subsystem10b(stream126being directed to a first subsystem10a) for the production of alkylbenzenes, paraffins, and/or olefins that are heavier than the heart cut. Subsystems10aand10boperate in the same manner as described above with regard to subsystem10. For example, subsystems10aand10bmay be separate systems for the simultaneous processing of the heart cut and the heavier paraffins, respectively. Alternatively, subsystems10aand10bmay be the same system, where the heart cut and heavier paraffins are processed at different times.

FIG.4depicts a system300using yet another example of a process for producing a alkylbenzene, paraffin, or olefin from waste plastic feedstock and kerosene and/or another source(s) of hydrocarbons as disclosed herein,. InFIG.4, the waste plastic feedstock feed stream114may be hydrotreated (to form paraffins) in a hydrotreatment apparatus113prior to being combined with the paraffins from the kerosene feed102. As such, the KHT112need not be configured for extensive hydrogenation, and a catalyst used therein may be selected solely for denitrification and desulfurization purposes. For example, a stream115aof paraffins may exit the hydrotreatment apparatus113and feed into the separator118, to separate branched and aromatic compounds. Alternatively, if such separation is not performed, a stream115bof paraffins may be combined with the paraffins derived from the kerosene and/or another source(s) of hydrocarbons downstream of the separator118. In this example, the heavy paraffins may either be removed from system300as discussed above with regard toFIG.1(stream124a), further processed into alkylbenzenes, paraffins, and/or olefins (10b), as discussed above with regard toFIG.3.

FIG.5depicts a system400using still another example of a process for producing a alkylbenzene, paraffin, or olefin from waste plastic feedstock and kerosene and/or another source(s) of hydrocarbons. InFIG.5, a heavy paraffin stream124is directed to an isomerization reactor125. The isomerization reactor125is provided to convert the heavy paraffins stream124into a stream of branched paraffins and other compounds127, which may have other industrial uses, such as fuel and/or for making branched oxo alcohols.

As noted above,FIG.6illustrates an example of a system utilizing a process for producing alkylbenzenes, paraffins, and/or olefins from waste plastic feedstock alone. In contrast toFIG.1, inFIG.6feed102, the kerosene feed, and unit104are eliminated. Only feed114, the waste plastic feed, is fed into the hydrotreater112. InFIG.6, the hydrotreater112treats the feed114to reduce the olefin content and to reduce any impurities that may be present in the feed114in order to produce paraffin. The hydrotreater112employs a catalyst that is suitable for hydrogenation, deoxygenation and denitrification/desulfurization or a mix of catalysts that each accomplish one or more of hydrogenation, deoxygenation, denitrification, and desulfurization. A suitable KHT112apparatus for use in embodiments of the present disclosure is sold by UOP LLC.

A treated stream of paraffins116aexiting the hydrotreater112may be fed to a separator118to separate linear paraffins from branched or cyclic paraffins that may be included in the stream116a.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.

Depending on the composition of the waste plastic feed114(e.g., waste plastic feedstock derived from pure polyethylene), separation of linear paraffins from branched and cyclic components may not be necessary, and a hydrotreated stream of paraffins116bfrom the hydrotreater112may be directed downstream for further processing.

A linear paraffin stream116cexiting the separator118or the treated stream of paraffins116bmay be fed to a fractionator122. The waste plastic feed114may include hydrocarbons that are heavier and/or lighter than the heart cut range, and as such the fractionator122may be provided to fractionate hydrocarbons that are heavier and/or lighter than the desired heart cut range in the waste plastic stream. Hydrocarbons that are C14and heavier may removed from system100in a heavy paraffins stream124and may be used in other processes. Hydrocarbons anywhere in the range from C15- C18and heavier may be removed from system100in the heavy paraffins stream124. The paraffins in the desired heart cut range exit the fractionator122in a stream126for further processing into alkylbenzene, paraffin, and/or olefin in subsystem10(FIG.2). Paraffins produced by the system ofFIG.6and fed to subsystem10, however, are derived from 100% waste plastic feedstock. Previous disclosed details aboutFIG.2and subsystem10may apply downstream ofFIG.6as well to produce, for example, alkylbenzene, where the non-aromatic portion of the alkyl benzene is derived entirely from waste plastic.

FIG.7schematically illustrates an example of a system utilizing a process for producing linear and/or branched oxo alcohols, linear and/or branched paraffins, and/or linear and/or branched olefins from waste plastic feedstock and kerosene and/or another source(s) of hydrocarbons. The steps prior to entering subsystem10inFIG.7are diagrammed inFIG.1and discussed above. InFIG.7, in contrast toFIG.2, instead of feeding a stream of mono-olefins52and a stream of benzene54into an alkylation unit56, a stream53, which may include all or a portion of stream52, is directed to a separator57for separating unconverted paraffins from the olefins. The separator57may be an Olex ® separator, available from UOP LLC. The Olex ® process involves the selective adsorption of a desired component (i.e., olefins) from a liquid-phase mixture by continuous contacting with a fixed bed of adsorbent. The separator57may be a direct sulfonation separator. The separated, unconverted paraffins may optionally be directed back to the second paraffin portion26for purification (stream73) and/or back to the first paraffin portion24for dehydrogenation for conversion to olefins (stream71). InFIG.7, an olefins stream61may exit the separator57and may be fed to a separator63. The separator63may be a multi-stage fractionation unit, distillation system, or similar known apparatus. The separator63may provide a means to separate the olefins into various desirable fractions. For example, as shown inFIG.7, a first portion of olefins65and a second portion of olefins67are illustrated, although any number of olefin portions may be provided, depending on how many olefin fractions are desired. The first portion of olefins65may have carbon chain lengths of C10 to C14. The first portion of olefins65may have carbon chain lengths having a lower limit of CL, where L is an integer from four (4) to thirty-one (31), and an upper limit of Cu, where U is an integer from five (5) to thirty-two (32).

The second portion of olefins67may have carbon chains shorter than, longer than, or a combination of shorter and longer than, the chains of the first portion of olefins65. The first portion of olefins65may include olefins with C10to C14chains and the second portion of olefins67may include olefins with C18to C20chains. Subsequent to separation, the purified olefins portions65and67are removed from the subsystem10as the olefin product. Alternatively, the separator63produces two-carbon-cut olefins, such as C14-C15,C16-C17or C17-C18, or any combination of the above. Alternatively, when the first portion of olefins65includes C10-C14olefins, this portion may be further fractionated to produce C11-C12, C13-C14, or both, depending on the separator configuration and the need for further processing. These olefin portions65,67may be fed into oxo units201,202to produce oxo alcohols, using known hydroformylation processes. Suitable oxo catalysts for hydroformylation include rhodium and/or cobalt catalysts, which may be modified or unmodified. The two streams of oxo alcohols may then be fed into a separator203,204to remove hydroformylation catalyst from the stream and produce purified streams of oxo alcohols205,206.

FIG.8schematically illustrates an example of a system utilizing a process for producing linear or branched oxo alcohols, linear or branched paraffins, and/or linear or branched olefins from waste plastic feedstock alone (FIG.8represents a combination ofFIG.6andFIG.7).FIG.6illustrates a process of producing paraffin from waste plastic feedstock alone.FIG.6coupled withFIG.7, which illustrates a system10utilizing a process for producing linear and/or branched oxo alcohols, linear and/or branched paraffins, and/or linear and/or branched olefins, illustrates a process for producing a linear or branched oxo alcohol that is derived only from plastic waste feedstock and, for example, syngas.

In another example, which is not illustrated, linear and/or branched paraffin, produced according to any of the above-described processes, may be converted to a linear and/or branched paraffin sulfonate, using known sulfoxidation processes, and may be included in a detergent formulation.

In another example, which is not illustrated, linear and/or branched olefin may be sulfonated, using known processes (e.g., SO3, oleum, or other sulfonating agents) to produce a linear and/or branched olefin sulfonate surfactant, which may also be used in detergent formulations.

In another example, which is not illustrated, the linear and/or branched oxo alcohol product shown inFIG.7orFIG.8, is converted to a linear and/or branched tertiary amine, using known reaction conditions (e.g., using dimethyl amine in the presence of a catalyst under low hydrogen conditions). The linear and/or branched tertiary amine may be converted (under known conditions via oxidation) to a linear and/or branched amine oxide.

While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims and their legal equivalents.

Detergent Compositions

The detergent compositions described herein may comprise a surfactant in an amount sufficient to provide desired cleaning properties. The detergent compositions may comprise from about 1% to about 75%, by weight of the composition, of a surfactant. The detergent compositions may comprise from about 2% to about 35%, by weight of the composition, of a surfactant. The detergent compositions may comprise from about 5% to about 10%, by weight of the composition, of a surfactant.

The detergent compositions may comprise a plastic waste-derived surfactant content of at least about 50%, or at least about 70%, or at least about 80%, or at least about 90% (meaning that at least about 50%, or at least about 70%, or at least about 80%, or at least about 90% of the total surfactant in the detergent composition is plastic waste-derived).

In particular, the detergent compositions may comprise a plastic waste-derived surfactant produced according to the methods described herein. The detergent compositions may comprise a plastic waste-derived sulfonated linear alkylbenzene, a plastic waste-derived sulfated detergent alcohol, and/or a plastic waste-derived paraffin sulfonate produced according to the method(s) described herein. The detergent compositions may comprise a plastic waste-derived surfactant produced by the method(s) disclosed herein in combination with natural alcohol sulfates and/or natural alcohol ethoxylated sulfates, such as those derived from the reduction of methyl esters to fatty alcohols.

The detergent compositions may comprise a plastic waste-derived surfactant produced by the method(s) disclosed herein in combination with a conventional kerosene-based surfactant. The conventional kerosene-based surfactant may be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof.

Combinations of Surfactants

The detergent compositions may comprise a plastic waste-derived anionic surfactant and a plastic waste-derived or conventional kerosene-based nonionic surfactant, e.g., C12-C18 alkyl ethoxylate. The detergent compositions may comprise a plastic waste-derived alkyl benzene sulfonates (LAS) and another, optionally plastic waste-derived, anionic surfactant, e.g., C10-C18 alkyl alkoxy sulfates (AExS), where x is from 1-30, where the plastic waste-derived surfactants are produced according to the methods described herein. The detergent compositions may comprise a plastic waste-derived anionic surfactant and a cationic surfactant, for example, dimethyl hydroxyethyl lauryl ammonium chloride. The detergent compositions may comprise a plastic waste-derived anionic surfactant and a zwitterionic surfactant, for example, C12-C14dimethyl amine oxide.

Adjunct Cleaning Additives

The detergent compositions of the invention may also contain adjunct cleaning additives. Suitable adjunct cleaning additives include builders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease cleaning agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibiting agents, chelating agents, suds supressors, softeners, and perfumes.

Processes of Making Detergent Compositions

The detergent compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator.

Methods of Use

The present disclosure includes methods for cleaning soiled material. As will be appreciated by one skilled in the art, the detergent compositions of the present invention are suited for use in laundry pretreatment applications, laundry cleaning applications, and home care applications.

Such methods include, but are not limited to, the steps of contacting detergent compositions in neat form or diluted in wash liquor, with at least a portion of a soiled material and then optionally rinsing the soiled material. The soiled material may be subjected to a washing step prior to the optional rinsing step.

For use in laundry pretreatment applications, the method may include contacting the detergent compositions described herein with soiled fabric. Following pretreatment, the soiled fabric may be laundered in a washing machine or otherwise rinsed.

Machine laundry methods may comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. An “effective amount” of the detergent composition means from about 20 g to about 300 g of product dissolved or dispersed in a wash solution of volume from about 5 L to about 65 L. The water temperatures may range from about 5° C. to about 100° C. The water to soiled material (e.g., fabric) ratio may be from about 1:1 to about 30:1. The compositions may be employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. In the context of a fabric laundry composition, usage levels may also vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water, and the type of washing machine (e.g., top-loading, front-loading, top-loading, vertical-axis Japanese-type automatic washing machine).

The detergent compositions herein may be used for laundering of fabrics at reduced wash temperatures. These methods of laundering fabric comprise the steps of delivering a laundry detergent composition to water to form a wash liquor and adding a laundering fabric to said wash liquor, wherein the wash liquor has a temperature of from about 0° C. to about 20° C., or from about 0° C. to about 15° C., or from about 0° C. to about 9° C. The fabric may be contacted to the water prior to, or after, or simultaneous with, contacting the laundry detergent composition with water.

Another method includes contacting a nonwoven substrate, which is impregnated with the detergent composition, with a soiled material. As used herein, “nonwoven substrate” can comprise any conventionally fashioned nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those marketed under the tradenames SONTARA® by DuPont and POLYWEB® by James River Corp.

Hand washing/soak methods, and combined handwashing with semi-automatic washing machines, are also included.

Machine Dishwashing Methods

Methods for machine-dishwashing or hand dishwashing soiled dishes, tableware, silverware, or other kitchenware, are included. One method for machine dishwashing comprises treating soiled dishes, tableware, silverware, or other kitchenware with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from about 8 g to about 60 g of product dissolved or dispersed in a wash solution of volume from about 3 L to about 10 L.

One method for hand dishwashing comprises dissolution of the detergent composition into a receptacle containing water, followed by contacting soiled dishes, tableware, silverware, or other kitchenware with the dishwashing liquor, then hand scrubbing, wiping, or rinsing the soiled dishes, tableware, silverware, or other kitchenware. Another method for hand dishwashing comprises direct application of the detergent composition onto soiled dishes, tableware, silverware, or other kitchenware, then hand scrubbing, wiping, or rinsing the soiled dishes, tableware, silverware, or other kitchenware. In some examples, an effective amount of detergent composition for hand dishwashing is from about 0.5 ml. to about 20 ml. diluted in water.

Packaging for the Compositions

The detergent compositions described herein can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials, and any suitable laminates.

Multi-Compartment Pouch Additive

The detergent compositions described herein may also be packaged as a multi-compartment detergent composition.

ANALYSIS METHODS AND EXAMPLES

GC Sample Prep:

In order to identify the various products of the process, derivatization is performed. All data reported herein on the Agilent Technologies Gas Chromatograph 7890A instrument are in area %.

Derivatized samples are prepared by drying a 1 ml sample of the reactor effluent over MgSO4, filtering, and adding 20 μl of resultant to a vial followed by 1.5 ml of 14% BF3 in MeOH and heating to 65° C. for 30 minutes. 1.5 ml of water is then added followed by 2.0 ml of hexane. This is then shaken and the organic layer is allowed to separate. Once separated, the top organic layer is dried through a MgSO4plug into a GC vial. The resultant sample is analyzed by GC using the following:

Agilent Technologies Gas Chromatograph 7890A equipped with a split/splitless injector and FID;

J&W Scientific capillary column DB-1HT, 30 meter, 0.25 mm id, 0.1 μm film thickness cat# 1221131;

EMD Chemicals HPLC grade Chloroform, cat# EM-CX1058-1 or equivalent;

2 ml GC autosampler vials with screw tops, or equivalent.

GC Parameters:

Carrier Gas: Helium

Column Head Pressure: 18.5 psi

Flows: Column Flow @ 1.6 ml/min.Split Vent @ 19.2 ml/min.Septum Purge @ 3 ml/min.

Injection: Agilent Technologies 7693 Series Autosampler, 10 ul syringe, 1 ul injection

Injector Temperature: 275° C.

Detector Temperature: 340° C.

Oven Temperature Program: initial 70° C. hold 1 min.rate 10° C./min.final 320° C. hold 5 min.

Another procedure to analyze for impurities in the paraffin is 2D GCMS. This system is well known in the analytical literature as providing the best way to separate complex compositions and to identify by mass spectroscopy the types of materials separated.

2D GCMS Analysis Procedure:

2D-GC/FID—Relatively Quantitative Comparison

Equipment:

Leco Comprehensive 2-dimensional Gas ChromatographAgilent 7890 GC System (Leco modified) w/split/splitless injector &flame ionization detector (FID)Leco Secondary ovenLeco LN2 modulator and controllerCTC Combi-PAL Autosampler (or equivalent)Columns:Supelco Gamma DEX 120 (30×0.25 mm ID×0.25 um df)Deactivated transfer line Restek ‘Siltek’(0.66 m×0.25 mm ID)Varian VF-5ms (2m×0.15 mm ID×0.15 um df)In the following configuration:

FilmInt.MaxThick-LengthDiameterTempness#TypeLocation(m)(μ)(° C.)(μ)Phase1InletFront2CapillaryGC Oven30.000250.00235.00.25G-DEX1203CapillaryModulator0.660250.00350.00.00Deact-ivatedFS4CapillarySecondary1.770150.00360.00.15VF-Oven5ms5CapillaryDetector0.330150.00360.00.15VF-or MS5msTransferLine

Sample Preparation:

Dilute sample 100:1 in dichlormethane (DCM) as follows:Pipette 10 uL of paraffin or kerosene sample into 2mL GC vialPipette 990 uL DCM into same GC vialCap with septa seal and mix (vortex mixer) 20 seconds.

Instrument Parameters:

Carrier Gas: Helium @ 1.1mL/min (constant flow mode)

Injection: 1 uL Split 50:1 @200° C.

Primary Oven:Initial 35° C. hold 2 min.Ramp 1—1° C./min to 200° C.Ramp 2—5° C./min to 220° C.

Secondary Oven: +10° C. offset tracking primary oven

Modulator Temp: +25° C. offset tracking primary oven

Modulator Program:Entire run—18.5 second modulation periodHot pulse time—8.75 secondsCool time between stages 0.5 seconds

Detector: (FID)Temp. 300° C.Data collection rate: 200HzMakeup 25 mL/min Nitrogen (Makeup +column)Hydrogen: 40 mL/minAir: 450 mL/min
2D-GC/TOFMS—Qualitative Composition

Equipment:

Leco Pegasus 4D—Comprehensive 2-D GC+Time-of-Flight Mass Spectrometer

Leco Comprehensive 2-dimensional Gas Chromatograph

Agilent 7890 GC System (Leco modified) w/split/splitless injector & flame ionization detector (FID)

Leco Secondary oven

Leco LN2 modulator and controller

CTC Combi-PAL Autosampler (or equivalent)

Columns:Supelco Gamma DEX 120 (30m ×0.25mm ID×0.25um df)Deactivated transfer line ‘Restek Siltek’ (0.4m×0.25mm ID)Restek rxi-XLB (2.1m×0.18mm ID×0.18um df)In the following configuration:

FilmInt.MaxThick-LengthDiameterTempness#TypeLocation(m)(μ)(° C.)(μ)Phase1InletFront2CapillaryGC Oven30.000250.00250.00.25G-DEX1203CapillaryModulator0.400250.00360.00.00Deact-ivatedFS4CapillarySecondary2.000180.00360.00.18rxi-BOvenXL5CapillaryDetector0.100180.00360.00.18rxi-or MSXLBTransferLine6*DetectorTOF

Sample Preparation:Dilute sample 100:1 in dichlormethane (DCM) eg. as follows:Pipette 10 uL of paraffin or kerosene sample into 2 mL GC vialPipette 990 uL DCM into same GC vialCap with septa seal and mix (vortex mixer) 20 seconds

Instrument Parameters:Carrier Gas: Helium @ 1.1 mL/min (constant flow mode)Injection: 1 uL Split 50:1 @200° C.Primary Oven:Initial 35° C. hold 2 min.Ramp 1—1° C./min to 200° C.Ramp 2—5° C./min to 220° C.Secondary Oven: +10° C. offset tracking primary ovenModulator Temp: +25° C. offset tracking primary ovenModulator Program:Entire run—18.5 second modulation periodHot pulse time—8.75 secondsCool time between stages 0.5 secondsDetector: (TOF-MS)Tranfer line Temperature: 250° C.Data collection rate: 200 spectra/secondElectron Energy: −70VMass Range 45-450 m/zSolvent Delay: 150 secondsSource Temperature: 210° C.
HT-GC/FID—High Temp Fast GC for High Boilers (FFE & Residual Triglyceride)

Equipment:Agilent 7890 GC System w/split/splitless injector & flame ionization detector (FID)Agilent 7693 Autosampler (or equivalent)Columns:Agilent J&W DB1-HT (5m×0.25mm ID×0.1um df—cut from 30m Column # 122-1131)

Sample Preparation:Dilute sample 100:1 in dichlormethane (DCM) eg. as follows:Pipette 10 uL of paraffin or kerosene sample into 2mL GC vialPipette 990uL DCM into same GC vialCap with septa seal and mix (vortex mixer) 20 seconds

Instrument Parameters:Carrier Gas: Helium @ 1.4 mL/min (constant flow mode)Injection: luL Pulsed Split 25:1 @ 325° C.Pressure Pulse: lOpsi until 0.15min.Oven Program:Initial 40° C. hold 0.5 min.Ramp 1—40° C./min to 380° C. hold 3 min.Detector: (FID)Temp. 380° C.Data collection rate: 50HzMakeup 25 mL/min Heliumo Hydrogen: 40 mL/min

Air: 450 mL/min

DETERGENT FORMULATION EXAMPLES

Example 1

Heavy Duty Liquid Laundry Detergent Compositions

LiquidLiquidLiquidLiquidDetergentDetergentDetergentDetergentABCDIngredient(wt %)(wt %)(wt %)(wt %)Plastic waste-derived or1-1201-121-121-12conventional kerosene-basedAES10Plastic waste-derived or5-2015-301-510-201-5conventional kerosene-basedLAS11Sodium formate2.662.662.662.660.11Calcium formate————0.097Sodium hydroxide0.210.210.210.210.68Monoethanolamine (MEA)1.651.651.651.652.80Diethylene glycol (DEG)4.104.104.104.101.23Propylene glycol————8.39Plastic waste-derived or0.400.400.400.40—conventional kerosene-basedAE92C16AE73.153.153.153.15—NI 24-98————0.97Chelant30.180.180.180.180.29Citric Acid1.701.701.701.702.83C12-18Fatty Acid1.471.471.471.471.09Borax1.191.191.191.192.00Ethanol1.441.441.441.441.47Ethoxylated1.351.351.351.351.85Polyethyleneimine1Amphiphilic alkoxylated————0.940grease cleaning polymer7A compound having the0.400.400.400.401.40following general structure:bis((C2H5O)(C2H4O)n)(CH3)—N+—CxH2x—N+—(CH3)—bis((C2H5O)(C2H4O)n),wherein n = from 20 to 30,and x = from 3 to 8, orsulphated or sulphonatedvariants thereof1,2-Propanediol2.402.402.402.40—Protease (54.5 mg active/g)90.890.890.890.890.95Mannanase: Mannaway ®0.040.040.040.04—(25.6 mg active/g)5Xyloglucanase: Whitezyme ®————0.04(20 mg active/g)14Cellulase: Carezyme ™————0.10(11.63 mg active/g)14Amylase: Natalase ® (29 mg0.140.140.140.140.34active/g)5Fluorescent Whitening0.100.100.100.100.15Agents10Water, perfume, dyes & otherBalanceBalancecomponents1Polyethyleneimine (MW = 600) with 20 ethoxylate groups per —NH.2AE9 is C12-13alcohol ethoxylate, with an average degree of ethoxylation of 9, made according the methods disclosed herein or via a conventional kerosene-based process.3Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark4Natalase ®, Mannaway ® are all products of Novozymes, Bagsvaerd, Denmark.5Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime ®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase ®, Coronase ®).6Suitable Fluorescent Whitening Agents are for example, Tinopal ® AMS, Tinopal ® CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland7Amphiphilic alkoxylated grease cleaning polymer is a polyethyleneimine (MW = 600) with 24 ethoxylate groups per —NH and 16 propoxylate groups per —NH.8Huntsman, Salt Lake City, Utah, USA.9Novozymes A/S, Bagsvaerd, Denmark.10AES is C12-14alkyl ethoxy (3) sulfate, C14-15alkyl ethoxy (2.5) sulfate, or C12-15alkyl ethoxy (1.8) sulfate made according the methods disclosed herein or via a conventional kerosene-based process.11LAS is made according the methods disclosed herein or via a conventional kerosene-based process.

Example 2

Unit Dose Compositions—Unit dose laundry detergent formulations can comprise one or multiple compartments.

Ingredient(wt %)(wt %)(wt %)(wt %)(wt %)Ethoxylated glycerine40340(EO1-24)1,2 propanediol718.813.813.815.8Glycerine403.12.14.1Di Propylene Glycol40000Sodium cumene00002.0sulphonatePlastic waste-derived8189.512.510or conventionalkerosene-based AESPlastic waste-derived5189.514.57.5or conventionalkerosene-based LASPlastic waste-derived1505010or conventionalkerosene-basedIsalchem ® 156ASPlastic waste-derived13316213or conventionalkerosene-based AECitric Acid10.60.61.560.6C12-18Fatty Acid4.5104.514.84.5Enzymes1.01.71.72.01.7Ethoxylated1.41.44.06.04.0PolyethylenimineChelant0.60.61.21.23.0PEG-PVAc Polymer42.542.51.5Fluorescent Brightener0.150.40.30.30.3Monoethanolamine9.88.08.08.09.8TIPA002.000Triethanolamine02.0000Cyclohexyl dimethanol0002.00Water1210101010Structurant0.10.140.140.10.14Perfume0.21.911.91.9Hueing Agent00.10.0010.00010BuffersTo pH 8.0Other Solvents (ethanol)To 100%All enzyme levels are expressed as % enzyme raw material.

Raw Materials for Examples 2

AES is C12-14alkyl ethoxy (3) sulfate, C14-15alkyl ethoxy (2.5) sulfate, or C12-15alkyl ethoxy (1.8) sulfate made according the methods disclosed herein or via a conventional kerosene-based process.

Isalchem 156AS is an alcohol sulfate derived from the non-selective cobalt hydroformylation of an oxo alcohol, made according to the methods disclosed herein or via a conventional kerosene-based process.

AE is selected from C12-13with an average degree of ethoxylation of 6.5, C11-16with an average degree of ethoxylation of 7, C12-14with an average degree of ethoxylation of 7, C14-15with an average degree of ethoxylation of 7, or C12-14with an average degree of ethoxylation of 9, all made according the methods disclosed herein or via a conventional kerosene-based process.

PEG-PVAc polymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units. Available from BASF (Ludwigshafen, Germany).

Ethoxylated Polyethylenimine is a 600 g/mol molecular weight polyethylenimine core with 20 ethoxylate groups per —NH. Available from BASF (Ludwigshafen, Germany).

Amylases (Natalase®, Stainzyme®, Stainzyme Plus®) may be supplied by Novozymes, Bagsvaerd, Denmark.

Savinase®, Lipex®, Celluclean™, Mannaway®, Pectawash®, and Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark.

Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase®, Coronase®).

Suitable Fluorescent Whitening Agents are for example, Tinopal® TAS, Tinopal® AMS, Tinopal® CBS-X.

Chelant is selected from, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA, hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA; Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer (EDDS) supplied by Octel, Ellesmere Port, UK, Diethylenetriamine penta methylene phosphonic acid (DTPMP) supplied by Thermphos, or1,2-dihydroxybenzene-3,5-disulfonic acid supplied by Future Fuels Batesville, Arkansas, USA

Hueing agent is Direct Violet 9 or Direct Violet 99, supplied by BASF, Ludwigshafen, Germany.

Soil release agent is Repel-o-tex® PF, supplied by Rhodia, Paris, France.

Structurant is hydrogenated castor oil (e.g., Thixin®).