WO2023222550A1

WO2023222550A1 - Methods for producing ingredients from waste plastic pyrolysis oil

Info

Publication number: WO2023222550A1
Application number: PCT/EP2023/062814
Authority: WO
Inventors: Venkataraghavan Rajanarayana
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2022-05-20
Filing date: 2023-05-12
Publication date: 2023-11-23

Abstract

A method for producing a hydrocarbon feedstock from waste plastic feedstock and crude oil comprising the steps of: A. providing a first feed stream comprising crude oil; B. providing a second feed stream comprising waste plastic pyrolysis oil; C. combining the first and second feed streams to provide a combined feed stream D. pre-treating said combined feed stream; E. fractionating the combined stream to provide multiple output streams, said multiple output streams comprising hydrocarbons in the range C1-C20; and F. Separating from at least one of said multiple output streams, by further fractionation of said at least one of said multiple output streams, at least one target output stream.

Description

METHODS FOR PRODUCING INGREDIENTS FROM WASTE PLASTIC PYROLYSIS OIL

The present invention relates generally to 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, polymers and other ingredients for use in home care compositions from waste plastic feedstock.

WO2017027271 discloses methods for producing detergent intermediates, including alkylbenzenes, paraffins, olefins, oxo alcohols, and surfactant derivatives thereof from waste plastic feedstock. The process involves pre-fractionating fossil-based kerosene before mixing this with a second feed of waste plastic.

Despite the prior art, there is a need for improved process for making surfactants and surfactant intermediates and other useful chemicals using pyrolysis oil, preferably from waste plastic feedstocks (i.e. pyrolyzed plastic waste).

The inventors have found that the precise point at which the pyrolysis oil is combined with other feedstocks allows for surprising advantages as are described below.

Accordingly, the invention provides a method for producing a hydrocarbon feedstock from waste plastic pyrolysis oil and crude oil comprising the steps of:

A. providing a first feed stream comprising crude oil;

B. providing a second feed stream comprising waste plastic pyrolysis oil;

C. combining the first and second feed streams to provide a combined feed stream

D. optionally pre-treating said combined feed stream;

E. fractionating the combined stream to provide multiple output streams, said multiple output streams comprising hydrocarbons in the range C1-C20; and

F. Separating from at least one of said multiple output streams, by further fractionation of said at least one of said multiple output streams, at least one output stream being a target output stream.

The waste plastic pyrolysis oil is thus co-fractionated with crude oil (so before any fractionating the crude). Fractionating the waste plastic (pyrolysis oil) feedstock at this crude distillation stage allows for greater freedom in the type of plastic and its contamination levels. This is highly advantageous because plastic waste is highly variable in practice. Whilst waste plastic waste is generally sorted and processed (pyrolyzed) by type (type is discussed below under ‘Plastic Type’) the quality of that waste plastic feedstocks may vary in terms of contamination / impurities. Plastic waste processing is not, in the main, a neat scientific process.

The prior art processes disclose mixing waste plastic pyrolysis oil into at least partly refined oil and additional impurity removal steps are necessary to ensure that any impurities do not overload the catalysts used at that or later stage, since these are designed for refined feedstocks.

WO2017027271 discloses treatment by a kero-hydrotreater, which is a hydrotreater which is configured for treatment of kerosene - a refined cut from petroleum. However, this can only be used if the level of impurities are sufficiently low. If the waste plastic is highly contaminated, the catalysts of the kero-hydrotreater would be overloaded which would be sub-optimal. By contrast, the method of the invention, the waste plastic feedstock is combined and pre-treated prior to fractionation.

Fractionation

Fractionation preferably takes place in a one or more a distillation unit/s or column/s of a crude distillation unit, including one or more atmospheric and/or vacuum distillation units.

The fractionation has at least two stages whereby the first fractionates crude oil and waste plastic feedstock and the second then refines further a cut taken from that first fractionation. The first fractionation and furhter fractionation may themselves be multi-stage.

This first fractionation may obtain a wide range of hydrocarbons, from which can be selected those of the desired boiling point range (i.e. carbon chain length) - the target output stream/s.

Preferably fractionation comprises by fractional distillation and may include the steps of distilling (the feedstocks) under atmospheric pressure and/or under a vacuum.

Co-fractonation can also remove non-boiling components like inorganics, metals etc. Levels

Preferably, the waste plastic is present in the combined stream at a level from 0.01 %wt, more preferably 0.1% wt and most preferably from 1%wt (as a wt% of the total wt of the combined stream).

Preferably the waste plastic is present in the combined stream at a level not exceeding 8%wt, more preferably not exceeding 15%wt, even more preferably not exceeding 25%wt and most preferably not exceeding 50%wt (as a wt% of the total wt of the combined stream).

Advantageously, the waste plastic is present in the combined stream at a levelof 0.01% to 50%, preferably 0.1% to 25%, most preferably 1% to 15%

PRE-FRACTIONATION TREATMENT

The crude oil and waste plastic may be pre-treated before fractionation, separately or in combination. Waste plastic may contain impurities and also generally many crude oils usually contain besides the basic elements of its chemical composition hydrocarbons such as sulfur, oxygen, nitrogen, and mechanical impurities and so pre-treatment is highly preferred before the first fractionation step.

Pre-treatment may include anyone of : de-gassing, de-watering, de-emulsification e.g. chemical de-emulsification by surfactants, desalting.

Certain pre-treatment may be carried out prior to fractionation e.g. at the well if water content of oil is high as may be the case in older oil fields, de-emulsification by surfacts may take place as is known in the art.

The CDU may comprise pre-treatment units located upstream of (i.e. so the feed stream enters prior to entering) the distillation unit/column. Preferably the CDU comprises at least an electrostatic desalter pre-treatment and may be a vertical, horizontal, and ball electrostatic desalter. Multiple output streams

Preferably these comprises streams differentiated by boiling point (carbon chain length) and comprise any /all of the following: Gases, Naphtha, Kerosene, Diesel/Light Gas Oil, Heavy gas oil, but at least naptha, kerosene, diesel.

Target Output () stream

The term “target output stream” refers to the output from the separation step F and is a stream of target hydrocarbons. Preferably, the target output stream comprises C6-C19 hydrocarbons.

Preferably, the target output stream comprises C10-13 hydrocarbons.

Preferably, the target output stream comprises C5-C9 hydrocarbons (the naptha fraction).

Preferably, the target output stream comprises C6 hydrocarbons.

In petroleum-based crude oils, various types of molecules are present. Per their chemical structure, molecules can be classified as a paraffin, olefin, naphthene (a cyclic paraffin), and aromatic. Preferably, the target output stream comprises paraffin hydrocarbons, linear and branched, more specifically linear n-paraffins.

Preferably, the target output stream comprises aromatic hydrocarbons.

The target output stream may undergo further refining steps , including further of distillation, separation, de-coking, re-forming, de-aromatization, alkylation, visbreaking, coking; cracking e.g. catalytic cracking, hydrocracking, isomerization aromatic ring opening, hydrotreating, hydroprocessing, or hydrodesulfurization.

Crude Oil

Crude oil, as used herein is crude oil that is unprocessed and has not been fractionated. Preferably the crude oil is fossil fuel.

Hydrotreating

The target output stream may be hydrotreated.

Hydrotreating is a process that removes oxygen, nitrogen, and sulfur and also reduces any remaining olefins to paraffins. Separation of branched and cyclic hydrocarbons

Optionally branched and cyclic hydrocarbons may be separated from the target output stream.

The separating step may optionally produce two streams of hydrocarbons - branched and linear hydrocarbons.

Olefins.

The linear stream may be dehydrogenated the optionally separated second heart cut paraffin stream to form a stream comprising olefins.

Surfactants

Linear Alkylbenzenes, Branched Alkylbenzenes, Or Mixtures Thereof

According to a further method of the invention linear alkylbenzenes, branched alkylbenzenes, or mixtures thereof as well as surfactants derived from such alkylbenzenes (e.g., sulfonated linear alkylbenzene, sulfonated branched alkylbenzene, or mixtures thereof) are made from the target hydrocarbons.

A method of the invention may produce alkylbenzene by dehydrogenating a target output stream of C10-C14 hydrocarbons to provide an olefin stream of C10-C14 hydrocarbons 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.

Benzene

The aromatic portion may be derived as follows:

1. directly from the aromatic hydrocarbons extracted from the first fractionation (A)

2. by further cracking the crude fraction from the first fractionation step

3. by reforming the naptha fraction from the first fractionation step

Other Surfactants

Preferably the method further includes the step of producing linear oxo alcohols, branched oxo alcohols, or mixtures thereof as well as surfactants derived from such oxo alcohols. Such surfactants include sulfated linear detergent alcohols, sulfated branched detergent alcohols, ethoxylated and sulfated linear detergent alcohols, ethoxylated sulfated branched detergent alcohols, ethoxylated linear detergent alcohols, ethoxylated branched detergent alcohols, or mixtures thereof.

Oxo alcohol may be produced by - dehydrogenating the target output hydrocarbon (chain length?) to form a stream comprising olefins, - hydroformulating 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.

Preferably the method further includes the step of converting said target output stream to linear paraffin sulfonates, branched paraffin sulfonates, or mixtures thereof, as well as linear olefin sulfonates, branched olefin sulfonates, or mixtures thereof.

Preferably the method further includes the step of converting target output stream to linear amines, branched amines, or mixtures thereof derived as well as surfactant derivatives of such amines, including linear or branched amine oxide.

The present invention also relates to a detergent composition comprising one or more of the surfactants or ingredients produced from the target output stream, according to the methods disclosed herein and methods of making such detergent compositions.

Waste plastics

The waste plastic used in the method may be from any suitable waste plastics. The waste plastic used in the method of the invention is preferably a liquid and more preferably this liquid is obtained by pyrolysis (pyrolised waste plastic). Advantageously it is the liquid oil (or liquid from condensed vapour) obtained from pyrolysis of waste plastic herein also termed pyrolysis oil or pyrolysate).

Waste Plastic Type

Preferably the waste plastic which is pyrolysed comprises any of polyethylene such as high- density polyethylene (HDPE), low-density polyethylene (LDPE); polypropylene (PP) and polystyrene. 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 polyethylene terephthalate (PET) (based on total weight of plastic).

Pyrolysis of Plastic Waste

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 pyrolysate may be from fast-pyrolysed waste plastic. Fast pyrolysis may be conducted at high temperature ( 400 - 900 degrees C).

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, or used for providing energy to the pyrolysis process. Preferably, the char from pyrolysis is not 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.

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.

Impurities

The output feeds 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. 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. 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. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically illustrates a system utilizing a process for producing alkylbenzenes, paraffins, and/or olefins from waste plastic feedstock co-refined with crude oil

FIG. 2 schematically illustrates a subsystem of the system shown in FIG. 1 for producing alkylbenzenes, paraffins, and/or olefins; and

FIG 3 shows a subsystem utilizing a process for producing a linear and/or branched alkylbenzene, linear and/or branched paraffin, or linear and/or branched olefin.

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 "olefin sulfonate" refers to a surfactant derived from direct sulfonation of olefin. The terms "kerosene” is taken to refer to the fraction or ‘cut’ taken from a crude distillation unit that is in a boiling point in the range of 130°C to 300°C, at atmospheric pressure, “fossil” or "petrol” or “petroleum” (as in, respectively, "fossil-based alkylbenzene" or "petrolbased alkylbenzene" or “petroleum-based”) are used interchangeably to refer to a material (or the production thereof) that is produced from a 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 according to the methods of the invention.

“home care composition” means any composition for treating surfaces and articles in the home, such as fabric substrates or household surfaces. “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. “Household surface” such as 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 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. Household surfaces in elude “dishes” which is meant generically and encompasses essentially any items which may be found in a hand dishwash or machine dishwashing load, including crockery chinaware, glassware, plasticware, hollowware and cutlery, pots, pans, baking dishes and flatware made from any material or combination of hard surface materials commonly used in the making of articles used for eating and/or cooking.

“Paraffin” means alkanes of general formula of C_nH2n+2 . Paraffins may be normal or isoparaffins. Normal paraffins (n-paraffins or n-alkanes) are open, straight-chain saturated hydrocarbons. Isoparaffins, are branched-type hydrocarbons, e.g. isobutane (also called methylpropane). Paraffins are found in petroleum and beginning with the simplest compound, methane.

“stream” may mean a feedstock moving through a communication device such as a pipe, or it may be a feedstock stored in e.g. a CDU. So that e.g. a target output stream may be fed by pipes from a refining unit, and then stored in a storage unit e.g. tank.

Under standard conditions of temperature and pressure (STP), the first four members of the alkane series (methane, ethane, propane, and butane) are in gaseous form, and compounds starting from C5H12 (pentane) to n-heptadecane (C17H36) are liquids (constituting large fractions of hydrocarbons found in liquid fuels (e.g., gasoline, jet fuel, and diesel fuel), whereas n-octadecane (C Hss) or heavier compounds exist in isolation as wax-like solids at STP. These heavier paraffins are soluble in lighter paraffins or other hydrocarbons and can be found in diesel fuel and fuel oils. Paraffins from Ci to C40 usually appear in crude oil (heavier alkanes in liquid solution, not as solid particles) and represent up to 20% of crude by volume.

“Refining” as used herein is intended to mean the processes used to refine feedstocks and includes any of including further of distillation, separation, de-coking, re-forming, dearomatization, alkylation, visbreaking, coking; cracking e.g. catalytic cracking, hydrocracking, isomerization aromatic ring opening, hydrotreating, hydroprocessing, or hydrodesulfurization whereby a crude, unprocessed oil is ‘refined’.

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 by-product 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.

Figure 1 shows a schematic of a Crude Distillation Unit for use in a method for producing a hydrocarbon feedstock from pyrolysed waste plastic feedstock i.e. pyrolysis oil (liquid) and crude oil comprising the steps of:

A. providing a first feed stream comprising crude oil;

B. providing a second feed stream comprising liquid waste plastic pyrolysis oil;

D. pre-treating said combined feed stream;

F. Separating from at least one of said multiple output streams, by further fractionation of at least one of said multiple output streams at least one target output stream.

The first and second feed streams are combined, pre-treated then fractionated. Pretreatment of the combined stream takes place in the de-salter. The individual streams may be pre-treated prior to combination. Pre-treatment of individual and/or combined stream may include de-gassing, de-watering, de-emulsification e.g. chemical de-emulsification by surfactants (not shown) e.g. crude may be pre-treated by de-emulsification agents e.g. surfactants, at the well if water content of oil is high.

After de-salting, the combined feed stream undergoes fractional distillation according to the art and is carried out in two units, first in an Atmospheric Distillation Unit with further processing of the residue from atmospheric distillation in the Vacuum Distillation Unit (VDU), as illustrated in Figure 1. The system also includes exchangers and pump located in loops to pre-heat the desalted crude before it is fed into the fired furnace - not shown for simplicity but these are well known in the art. The combined feed stream is heated in the heater to 700-750° F to produce a two-phase mixture which enter the flash zone of the ADU for separartion of liquid and vapours. Heat removed from the overhead vapor provides a temperature gradient and the column condenses and separates out fractions according to boiling point (corresponding to carbon chain length) and comprise Gases, Naphtha, Kerosene, Diesel/Light Gas Oil, Heavy gas oil. Stream strippers on the side of the column also provide reflux to the main column to help with clean separation of the distillate products. Additional reflux is provided to the main column by pump around loops associated with heat exchanger.

Further fractionation steps are then used to provide target output streams comprising any of: C6-C19 hydrocarbons and/or C10-13 hydrocarbons and/or C5-C9 hydrocarbons and/or C6 hydrocarbons.

As an example of further refining, Figure 2 shows a system 100 utilizing an example process for producing a linear alkylbenzene LAB (and ultimately a linear alkylbenzene sulphonate LAS) from the output kerosene stream (one the multiple output streams) with target stream C9-C13.

The output kerosene stream is separated from the CDU above and then again fractionated in a fractionator 104. The fractionator 104 fractionates the feed 102 into three streams 106, 108, and 110 product. Stream 106 is the hydrocarbon stream of C9 hydrocarbons and lighter hydrocarbons (hydrocarbons having fewer carbons) that are separated from the kerosene feed 102. Stream 108 is a distillate, or heavy hydrocarbon stream, that may include C13 (and heavier hydrocarbons (hydrocarbons having more carbons) that are separated from the kerosene feed 102. Stream 110 is the target output stream selected for further processing into the desired linear alkylbenzenes. The target output cut stream 110 of C9 -C13 hydrocarbons that are separated from the kerosene feed 102. Streams 106, 108 are removed from the system 100 (and may be re-used). In FIG.2, the target output stream 110 is hydrotreated in the 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. KHT 112 is employed to treat the heart cut stream of hydrocarbons 110 to 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. KHT 112 is a catalyst-based apparatus, and various catalysts (hydrotreating catalysts) for denitrification and desulfurization are known to those having ordinary skill in the art.

KHT 112 may also be configured to hydrotreat a feedstock containing olefins (to produce paraffins) or the feedstock may be hydrotreated prior to entering the system. Thus, the KHT apparatus 112 may produce paraffins from olefins, by using a catalyst that is suitable for hydrogenation. The catalyst may be suitable for e.g. deoxygenation, and denitrification/desulfurization or there may be a mix of catalysts that each accomplish one or more of hydrogenation, deoxygenation, denitrification/desulfurization. A suitable KHT 112 apparatus for use is sold by UOP LLC and others.

A treated stream of paraffins 116a exiting KHT 112 may be fed to a separator 118 to separate the desirable linear paraffins from branched or cyclic compounds that may be included in the stream 116a. 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 output kerosene feed 102, separation of linear paraffins from branched and cyclic paraffins may not be desired, and a treated stream of paraffins 116b from the KHT 112 may be directly fed downstream for further processing to produce linear and branched LAB. In this embodiment stream 116b and/or 116c are directed to the LAB processing subsystem 10, as will be described in greater detail below.

In FIG. 3, a subsystem 10 utilizing a process for producing a linear and/or branched alkylbenzene, linear and/or branched paraffin, or linear and/or branched olefin is depicted. Subsystem 10 receives as its feed stream the stream 116b or116c from the fractionation process of fig 1. Stream is fed to a separator 22. The separator 22 may be a multi-stage fractionation unit, distillation system, or similar known apparatus. The separator 22 provides 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. Here, a first portion of paraffins 24 and a second portion of paraffins 26 are illustrated, although any number of paraffin portions may be provided. Portion 24 may include the same hydrocarbon range as portion 26, or they may be separated into different fractions. For example, where the target output is selected as C1O -C13, portion 24 may include C1O - C13 paraffins, whereas portion 26 may include C14 - C18 paraffins. Alternatively, they may both include C1O - C13 paraffins. In another example, where the heart cut is selected as C10 - C13, both portions 24 and 26 may include hydrocarbons in that range. Numerous other examples are possible, depending on the quantity and the hydrocarbon content of the desired linear alkylbenzenes, For example, it may be desirable to provide a C10 -C13 heart cut fraction or a C10 -C12 heart cut fraction.

Either or both paraffin portions 24 or 26 (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 subsystem 10 illustrated in FIG. 2, the second paraffin portion 26 is directed to a purification system 80 to 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 system 80 is an adsorption system. Alternatively, or additionally, a PEP unit 82, available from UOP LLC, may be employed as part of purification system 80. Subsequent to purification, a purified paraffin stream 13 may be removed from subsystem 10 as the paraffin product. As further shown in FIG. 2, the first portion of paraffins 24 (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 zone 28. Specifically, the first portion of paraffins 24 may be fed into a dehydrogenation unit 30 in the alkylbenzene and olefin production zone 28. In the dehydrogenation unit 30, the first portion of paraffins 24 is dehydrogenated into mono-olefins of the same carbon numbers as the first portion of paraffins 24. 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: Cx H2x+2 —>Cx H2x +H2

Di-olefin formation: Cx H2x —>Cx H2x-2 +H2

Aromatic formation: Cx H2x-2 —>Cx H2x-6 +2H2

Dehydrogenated stream 32 may exit the dehydrogenation unit 30 comprising mono-olefins and hydrogen, unconverted paraffins, as well as some di- olefins and aromatics. The dehydrogenated stream 32 is delivered to a phase separator 34 for removing the hydrogen from the dehydrogenated stream 32. The removed hydrogen can be directed away from system 100, or it can be used as fuel or as a source of hydrogen (H2 ) for a hydrotreatment process.

At the phase separator 34, a liquid stream 38 is formed and includes the mono- olefins, the unconverted paraffins, and any di-olefins and aromatics formed during dehydrogenation. The liquid stream 38 exits the phase separator 34 and enters a selective hydrogenation unit 40. The hydrogenation unit 40 may be a DeFine® reactor (or a reactor employing a DeFine® process), available from UOP LLC. The hydrogenation unit 40 selectively hydrogenates at least a portion of the di-olefins in the liquid stream 38 to form additional mono-olefins. As a result, an enhanced stream 42 is formed with an increased mono-olefin concentration.

As shown, the enhanced stream 42 may pass from the hydrogenation unit 40 to a light hydrocarbons separator 44, such as a stripper column, which removes a light end stream 46 containing any light hydrocarbons, such as butane, propane, ethane and methane, which may result from cracking or other reactions during upstream processing. With the light hydrocarbons 46 removed, stream 48 is formed and may be delivered to an aromatic removal apparatus 50, such as a PEP unit available from UOP LLC. As indicated by its name, the aromatic removal apparatus 50 removes aromatics from the stream 48 and forms a stream of mono-olefins and unconverted paraffins 52.

Stream 52, of mono-olefins and a stream of benzene 54 are fed into an alkylation unit 56.

The aromatic portion of LAB may be derived as follows: 1. from the aromatic hydrocarbons extracted from the first fractionation

2. by cracking the fraction from the first fractionation step

3. by reforming the naptha fraction from the first fractionation step

Furthermore, the benzene may be sourced via pure crude or pure (no crude) waste plastic pyrolysis in the waste plastic pyrolysis naphtha fraction. The alkylation unit 56 holds a catalyst 58, such as a solid acid catalyst, which supports alkylation of the benzene 54 with the mono-olefins 52. Also, Hydrogen fluoride (HF) and aluminum chloride (A1C13 ) are two other major catalysts in commercial use for the alkylation of benzene with mono-olefins and may be used in the alkylation unit 56. 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:

C6 H6 +CX H2X -^C6 H5 CX H2X+4 and may be present in the alkylation effluent 60. To optimize the alkylation process, surplus amounts of benzene 54 may be supplied to the alkylation unit 56. Therefore, the alkylation effluent 60 exiting the alkylation unit 56 may contain alkylbenzene and unreacted benzene. Further, the alkylation effluent 60 may also include some unreacted paraffins. In FIG. 2, the alkylation effluent 60 is passed to a benzene separation unit 62, such as a fractionation column, for separating the unreacted benzene from the alkylation effluent 60. This unreacted benzene may exit the benzene separation unit 62 in a benzene recycle stream 64 that is delivered back into the alkylation unit 56 to reduce the volume of fresh benzene needed in stream 54.

As shown, a benzene- stripped stream 66 exits the benzene separation unit 62 and enters a paraffinic separation unit 68, such as a fractionation column. In the paraffinic separation unit 68, unreacted paraffins may be removed from the benzene- stripped stream 66 in a recycle paraffin stream 70 and may be routed to and mixed with the first portion of paraffins 24 before dehydrogenation as described above, or may optionally be directed to the second portion 26 for purification of product paraffins.

Further, an alkylbenzene stream 72 that is separated by the paraffinic separation unit 68 may be fed to an alkylate separation unit 74. The alkylate separation unit 74, which may be, for example, a multi-column fractionation system, separates a heavy alkylate bottoms stream 76 from the alkylbenzene stream 72.

After the post-alkylation separation processes, the alkylbenzene product 12, which contains some portion derived from waste plastic feedstock, may be isolated and exit the subsystem 10. It is noted that such separation processes are not necessary in all cases in order to isolate the alkylbenzene product 12. For instance, the alkylbenzene product 12 may 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 feed 114 may be of sufficient quality that no fractionation is necessary for the desired chain length range.

To produce olefins, a stream 53, which may include all or a portion of stream 52, may be directed to a separator 57 for separating the unconverted paraffins from the olefins. The separator 57 may 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 separator 57 may 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 portion 26 for purification (stream 73) and/or back to the first paraffin portion 24 for dehydrogenation for conversion to olefins (stream 71). In FIG. 2, an olefin stream 61 may exit the separator 57 and may be fed to a separator 63. The separator 63 may be a multistage fractionation unit, distillation system, or similar known apparatus. The separator 63 may provide a means to separate the olefins into various desirable fractions. For example, as shown in FIG. 2, a first portion of olefins 65 and a second portion of olefins 67 are illustrated, although any number of olefin portions may be provided, depending on how many olefin fractions are desired. The first portion of olefins 65 may have carbon chain lengths of C10 to C14. Alternatively, the first portion of olefins 65 may 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 olefins 67 may have carbon chains shorter than, longer than, or a combination of shorter and longer than, the chains of the first portion of olefins 65. The first portion of olefins 65 may include olefins with do to C14 chains and the second portion of olefins 67 may include olefins with C18 to do chains. Alternatively, the first portion of olefins 65 may include olefins with do to C13 chains and the second portion of olefins 67 may include olefins with C14 to C18 chains. Alternatively, the first portion of olefins 65 and/or the second portion of olefins 67 may include 2-carbon-cut olefins, such as C14 to C15. Subsequent to separation, the purified olefins portions 65 and 67 are removed from the subsystem 10 as the olefin product. The olefin products 65 and 67 may be used directly to produce oxo alcohols by known hydroformylation processes or fractionated further into 2- or 3-carbon-cuts prior to hydroformylation.

As well as LAB (and LAS), the invention can provide paraffins, olefins, oxo alcohols, and surfactant derivatives, polymers, and other ingredients for home care compositions.

Home care compositions

Home care compositions preferably comprise one or more ingredients which are derived I converted from the target hydrocarbons made according to the method of the invention.

The home care composition comprising said one or more ingredients (derived I converted from the target hydrocarbons made according to the method of the invention) may be formulated for any home care function as defined herein.

The ingredient derived I converted from the target hydrocarbons made according to the method of the invention may be a surfactant, preferably a detersive surfactant. The surfactant may include any of a sulfonated linear alkylbenzene (LAS), a sulfated detergent alcohol, a paraffin sulfonate, any anionic surfactant, e.g., C10-C18 alkyl alkoxy sulfates (AExS), where x is from 1-30 or nonionic surfactant, e.g., C12-C18 alkyl ethoxylate, nonionic surfactant, e.g., C12-C18 alkyl ethoxylate, cationic surfactant, for example, dimethyl hydroxyethyl lauryl ammonium chloride, a zwitterionic surfactant, for example, C12-C14 dimethyl amine oxide.

The one or more ingredient derived I converted from the target hydrocarbons made according to the method of the invention may comprise a combination of surfactants including but not limited to any anionic surfactant and any nonionic surfactant e.g. C12-C18 alkyl ethoxylate; a alkyl benzene sulfonates (LAS) and another, optionally an anionic surfactant, e.g., C10-C18 alkyl alkoxy sulfates (AExS), where x is from 1-30; a anionic surfactant and a cationic surfactant, for example, dimethyl hydroxyethyl lauryl ammonium chloride; a anionic surfactant and a zwitterionic surfactant, for example, C12-C14 dimethyl amine oxide.

The detergent surfactant ingredient made by the invention may be 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 ingredient may be any ingredient comprising an alkyl chain or an aromatic moiety and may be any of: builders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease cleaning agents, 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 or any combination I mixture thereof.

Preferably the detersive surfactant is present 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 home care compositions preferably comprise at least 0.01 %wt, more preferably at least 0.1 %w, even more preferable at least 1 %wt, further more preferably at least 10%wt, most preferably at least 30%wt. content derived from target hydrocarbons.

The home care compositions preferably contain no more than 90%wt, more preferably no more than 70%wt, more preferably no more than 50% content derived from said target hydrocarbons.

The home care compositions may comprise other conventional (without plastic waste as a feedstock in manufacture) e.g. surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof; adjunct cleaning additives including 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

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

EXAMPLES

Below are formulations 1. Laundry Liquid, 2. Unit dose laundry liquid and 2 spray-dried powder which comprises LAS obtained from the method of the invention, wherein the combined feed comprised 1% wt. of liquid waste plastic to provide the alkyl chain. The aromatic portion of LAB may be derived as follows:

1. from the aromatic hydrocarbons extracted from the first fractionation

2. by cracking the fraction from the first fractionation step

3. by reforming the naptha fraction from the first fractionation step

Furthermore, the benzene may be sourced via pure crude or pure (no crude) waste plastic pyrolysis in the waste plastic pyrolysis naphtha fraction.

1. Laundry Liquid:

2. Unit dose laundry liquid formulations.

ried solid laundry composition

Table 2: Spray-dried solid laundry composition

Claims

1. A method for producing a hydrocarbon feedstock from waste plastic pyrolysis oil and crude oil comprising the steps of:

A. providing a first feed stream comprising crude oil;

B. providing a second feed stream comprising waste plastic pyrolysis oil;

D. pre-treating said combined feed stream;

F. Separating from at least one of said multiple output streams, by further fractionation of said at least one of said multiple output streams, at least one target output stream.

2. A method for producing a hydrocarbon feedstock according to claim 1 wherein the target output stream comprises C6-19 hydrocarbons.

3. A method for producing a hydrocarbon feedstock according to claim 1 wherein the target output stream comprises C10-13 hydrocarbons.

4. A method for producing a hydrocarbon feedstock according to claim 1 wherein the target output stream comprises C5-9 hydrocarbons, preferably C6 hydrocarbons.

5. A method for producing a hydrocarbon feedstock according to claim 1 wherein the target output stream comprises aromatic hydrocarbons, preferably benzene.

6. A method according to any preceding claim further including the step of hydrotreating the target ouptut stream.

7. A method according to any preceding claim further including the step of separating from the target output stream, branched and cyclic hydrocarbons to form a linear stream.

8. A method according to any preceding claim further including the step of dehydrogenating the target output hydrocarbon stream to form a stream comprising a stream of olefins.

9. A method according to any preceding claim further including the step of cracking the target output stream, said stream preferably comprising C5-C9 hydrocarbons to make benzene.

10. A method according to claim 8 further including the step of alkylating the olefin stream with benzene to form a stream comprising alkylbenzenes that are linear, branched, or a mixture thereof.

11. A method according to claim 10 wherein the benzene is the target output stream of claim 5.

12. A method according to claim 10 wherein the benzene is obtained from the method of claim 9.

13. The method according to any of claims 10 - 12 further comprising the step 10 of sulfonating the alkylbenzene to form an alkylbenzene sulfonate surfactant.

14. An alkylbenzene sulfonate surfactant produced according to the method of claim 13.

15. A detergent composition comprising an alkylbenzene sulfonate surfactant, wherein the alkylbenzene sulfonate surfactant is produced according to the method of claim