CN116368206A

CN116368206A - Recovery of aliphatic hydrocarbons

Info

Publication number: CN116368206A
Application number: CN202180069888.2A
Authority: CN
Inventors: J-P·A·M·J·G·兰格; G·范罗萨姆; W·德尔克斯; K·J·费希尔; T·J·奥尔索夫; J·P·哈恩
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2020-10-16
Filing date: 2021-10-12
Publication date: 2023-06-30
Also published as: JP2023545519A; KR20230086710A; EP4229154A1; CA3197061A1; US20230374398A1; WO2022079059A1

Abstract

The present invention relates to a process for recovering aliphatic hydrocarbons from a liquid stream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds and optionally aromatic hydrocarbons, the process comprising: a) Subjecting the liquid stream to liquid-liquid extraction with an extraction solvent; b) Mixing an extract stream comprising an extraction solvent, a heteroatom-containing organic compound, and optionally an aromatic hydrocarbon with a layering solvent to remove a portion of the heteroatom-containing organic compound and optionally the aromatic hydrocarbon; and c) separating the remaining stream into a layered solvent stream and an extraction solvent stream, wherein before and/or after step c) further heteroatom-containing organic compounds and optionally aromatic hydrocarbons are removed from the remaining stream and/or from the stream resulting from step c), respectively, by contacting the subsequent stream with a sorbent agent. Furthermore, the present invention relates to a process for recovering aliphatic hydrocarbons from plastics, which comprises the above-mentioned process; and to a process for steam cracking a hydrocarbon feed comprising aliphatic hydrocarbons recovered in one of the above processes.

Description

Recovery of aliphatic hydrocarbons

Technical Field

The present invention relates to a process for recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons; to a process for recovering aliphatic hydrocarbons from plastics, which comprises the above-mentioned process; and to a process for steam cracking a hydrocarbon feed comprising aliphatic hydrocarbons recovered in one of the above processes.

Background

Waste plastics can be converted to high value chemicals, including olefins and aromatic hydrocarbons, via cracking of the plastics (e.g., by pyrolysis). Pyrolysis of plastics can produce product streams containing hydrocarbons in a wide boiling range. Hydrocarbons from such pyrolysis product streams may be further cracked in a steam cracker to produce high value chemicals, including monomers that can be used to make new plastics, ethylene and propylene.

WO2018069794 discloses a process for producing olefins and aromatic hydrocarbons from plastics, wherein a liquid pyrolysis product stream is separated into a stream having<A first fraction having a boiling point of 300 ℃ and a second fraction having a boiling point of ≡300 ℃. Feeding only the first fraction to a liquid steam cracker while feeding the first fractionThe secondary fraction is recycled to the pyrolysis unit. In the process shown in figure 1 of WO2018069794, the separation is carried out in a hydrocarbon liquid distillation unit. The separation of the liquid pyrolysis product stream into two fractions is cumbersome (e.g., energy intensive). Another disadvantage is that a heavier portion of the liquid pyrolysis product stream must be sent back to the pyrolysis unit for deeper pyrolysis. This can result in yield loss through the formation of gas and an increase in the amount of solid by-products (coke) that are not ultimately sent to the steam cracker. In one embodiment of the process of WO2018069794 described above (see FIG. 2), the process will first have <The first fraction having a boiling point of 300 ℃ is sent to a hydrotreating unit along with hydrogen to produce a treated hydrocarbon liquid stream, which is then fed to a liquid steam cracker. This hydrotreating is also cumbersome because it is capital intensive and requires the use of expensive hydrogen (H ₂ )。

Furthermore, US20180355256 discloses a method for obtaining fuel from plastics, the method comprising subjecting a quantity of plastics to a pyrolysis process, thereby converting at least a portion of these plastics into a raw fuel; and extracting the fuel in a directly usable form by: 1) A first extraction step comprising countercurrent liquid-liquid extraction using one or more extraction solvents to extract one or more impurities from the crude fuel; and 2) a second extraction step comprising countercurrent extraction of the contaminated extraction solvent resulting from the first extraction step. In the process shown in fig. 2 of US20180355256, a raw fuel (i.e. gas oil) produced by pyrolysis of plastics is first extracted with N-methyl-2-pyrrolidone (NMP) to extract one or more impurities, including sulphur compounds and aromatic compounds, from the raw fuel. The contaminated NMP from the first extraction step is then subjected to a second extraction step using water to increase the polarity of the contaminated extraction solvent, thereby separating the impurities. In the final step, water contaminated NMP from the second extraction step is distilled using a standard distillation column, which produces recycled water and recycled NMP.

The feed to the distillation column as disclosed in US20180355256 (fig. 2) above may still contain some amount of heteroatom-containing organic and aromatic contaminants. The distillation may result in a portion of the contaminants being separated out with the recycled water because water and such contaminants may form azeotropes, thereby reducing the quality of the recycled water stream. If the recycled water is recycled to the column used in the second extraction step, the concentration of these contaminants in the recycled water will increase in a so-called "build-up" manner, in addition to the build-up of these contaminants in the recycled NMP to be used in the first extraction step. This may result in a lower efficiency of the first extraction step and the second extraction step. US20180355256 relates to a method for obtaining fuel from plastics. This accumulation of these contaminants (in the recycled NMP) may result in the purified oil still containing relatively large amounts of these contaminants, which is particularly alarming when such purified oil is fed to a steam cracker rather than used as fuel, as these contaminants can negatively impact the yield, selectivity and reliability of the steam cracker.

There is a continuing need to develop improved processes for recovering aliphatic hydrocarbons from liquid streams containing aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons, which may originate from cracked waste plastics, particularly mixed waste plastics, especially prior to feeding such recovered aliphatic hydrocarbons to a steam cracker. It is an object of the present invention to provide such a process for recovering aliphatic hydrocarbons from such liquid streams which is technically advantageous, efficient and affordable, in particular without one or more of the above-mentioned disadvantages, as discussed above in connection with WO2018069794 and US 20180355256. Such a technically advantageous process would preferably result in relatively low energy requirements and/or relatively low capital expenditure.

Disclosure of Invention

Surprisingly, the inventors have found that this process can be carried out by: a) Subjecting a liquid stream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds and optionally aromatic hydrocarbons to liquid-liquid extraction with an extraction solvent a), the extraction solvent containing one or more heteroatoms; b) Mixing the stream comprising extraction solvent a), heteroatom-containing organic compound and optionally aromatic hydrocarbon resulting from step a) with a layering solvent b) to remove a portion of the heteroatom-containing organic compound and optionally aromatic hydrocarbon, wherein the layering solvent b) contains one or more heteroatoms and is less miscible in heptane than extraction solvent a); and c) separating at least a portion of the stream comprising extraction solvent a), layering solvent b), heteroatom-containing organic compound and optionally aromatic hydrocarbon resulting from step b) into a stream comprising layering solvent b) and a stream comprising extraction solvent a), wherein (i) at least a portion of the stream resulting from step b) is contacted with a sorbent (or sorbent) prior to step c); and/or (ii) after step c), contacting at least a portion of the stream produced by step c) comprising the layering solvent b), the heteroatom-containing organic compound, and optionally an aromatic hydrocarbon with a sorbent agent (or sorbent), wherein the sorbent agent removes at least a portion of the heteroatom-containing organic compound and optionally the aromatic hydrocarbon from the subsequent stream.

Accordingly, the present invention relates to a process for recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds and optionally aromatic hydrocarbons, said process comprising the steps of:

a) Contacting at least a portion of the liquid hydrocarbon feedstream with an extraction solvent a) containing one or more heteroatoms, and subjecting the liquid hydrocarbon feedstream to liquid-liquid extraction with the extraction solvent a) to produce a first stream comprising aliphatic hydrocarbons and a second stream comprising extraction solvent a), heteroatom-containing organic compounds, and optionally aromatic hydrocarbons;

b) Mixing at least a portion of the second stream resulting from step a) with a layering solvent b) and separating the resulting mixture into a first stream comprising heteroatom-containing organic compounds and optionally aromatic hydrocarbons and a second stream comprising extraction solvent a), layering solvent b), heteroatom-containing organic compounds and optionally aromatic hydrocarbons, wherein the layering solvent contains one or more heteroatoms and the miscibility in heptane is lower than the miscibility of extraction solvent a) in heptane;

c) Separating at least part of the second stream resulting from step b) into a first stream comprising the layering solvent b), optionally heteroatom-containing organic compounds and optionally aromatic hydrocarbons and a second stream comprising the extraction solvent a);

d) Recycling at least a portion of the extraction solvent a) from the second stream produced in step c) to step a); and

e) Optionally recycling at least a portion of the layered solvent b) from the first stream produced in step c) to step b),

wherein:

(i) Removing heteroatom-containing organic compounds and optionally aromatic hydrocarbons from the second stream resulting from step b) by contacting at least a portion of the second stream with a sorbent agent prior to step c); and/or

(ii) After step c), removing heteroatom-containing organic compounds and optionally aromatic hydrocarbons from the first stream produced by step c) by contacting at least a portion of the first stream with a sorbent agent, wherein the first stream comprises layering solvent b), heteroatom-containing organic compounds and optionally aromatic hydrocarbons.

Advantageously, in the present invention, no hydrotreatment (with H) is required due to the liquid-liquid extraction in step a) ₂ And (3) processing. Furthermore, advantageously, liquid hydrocarbon streams having a wide boiling range, such as plastic pyrolysis oil, can be treated in the present process, with relatively low yield losses and feed degradation. This means that the cost of the hydrocarbon feed to the steam cracker can be significantly reduced by the application of the present invention.

Furthermore, the heteroatom-containing organic compound and any aromatic hydrocarbon may ultimately be partitioned into the stream comprising extraction solvent a) and layering solvent b) produced by step b) of the present process. The heteroatom-containing organic and aromatic compounds may comprise the component having the strongest polarity of all the heteroatom-containing organic and aromatic compounds extracted in step a) of the present process. In this case, advantageously, by the sorption step in the process of the invention, it is then still possible to deliver a relatively pure layered solvent b) recycle stream and a relatively pure extraction solvent a) recycle stream, which recycle streams are substantially free of heteroatom-containing organic compounds and aromatic hydrocarbons. This pure layered solvent b) stream can then advantageously be recycled in step a) itself or in another additional step and used for extraction of the extraction solvent a), thereby preventing the extraction solvent a) from entering the final hydrocarbon raffinate stream without contaminating this raffinate stream with heteroatom-containing organic compounds and aromatic hydrocarbons. Again, this pure extraction solvent a) stream can then advantageously be recycled to step a) and used for extracting further heteroatom-containing organic compounds and optionally aromatic hydrocarbons from the fresh feed. Thus, in the present invention, contaminants not removed in step b) will advantageously be concentrated into the sorbent agent used in such a sorption step, thereby preventing accumulation of such contaminants in the recycle stream in the present process.

Because of the above-described use of sorbent in the present invention, the need to apply other cumbersome methods to mitigate the accumulation of these contaminants is no longer present or is substantially reduced. For example, the need to discharge a portion of the recycle stream prior to recycling is no longer present or substantially reduced, where (i) such discharge stream is discarded, resulting in loss of extraction solvent, or (ii) extraction solvent can be recovered from such discharge stream, for example by distillation of such discharge stream, but this is cumbersome.

Furthermore, the invention relates to a process for recovering aliphatic hydrocarbons from plastics, wherein at least a portion of these plastics comprises heteroatom-containing organic compounds, said process comprising the steps of:

(I) Cracking the plastics and recovering hydrocarbon products comprising aliphatic hydrocarbons, heteroatom-containing organic compounds and optionally aromatic hydrocarbons; and

(II) subjecting a liquid hydrocarbon feedstream comprising at least a portion of the hydrocarbon product obtained in step (I) to the above-described process for recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream.

Still further, the present invention relates to a process for steam cracking a hydrocarbon feed comprising aliphatic hydrocarbons recovered in one of the above processes for recovering aliphatic hydrocarbons.

Drawings

Fig. 1 shows an embodiment of a process for recovering aliphatic hydrocarbons according to the invention.

Fig. 2 shows another embodiment of the above method.

Detailed Description

Each of the methods of the present invention includes a plurality of steps. Additionally, the method may include one or more intermediate steps between successive steps. Furthermore, the method may comprise one or more additional steps before the first step and/or after the last step. For example, where the method comprises steps a), b) and c), the method may comprise one or more intermediate steps between step a) and step b) and between step b) and step c). Furthermore, the method may comprise one or more additional steps before step a) and/or after step c).

Within this specification, the phrase "step y) comprises" conducting at least a portion of the stream resulting from step x) "means" step y) comprises "conducting a portion or all of the stream resulting from step x)" or "step y) comprises" conducting a portion or all of the stream resulting from step x). For example, the stream resulting from step x) may be separated into one or more portions, wherein step y) may be performed on at least one of these portions. Furthermore, for example, the stream resulting from step x) may be subjected to an intermediate step between step x) and step y), thereby producing a further stream, at least a portion of which may be subjected to step y).

Although the processes of the present invention and the streams and compositions used in the processes are described in terms of "comprising," "containing," or "including," respectively, one or more of the different steps or components, they may also "consist essentially of" or "consist of" respectively, the one or more of the different steps or components.

In the context of the present invention, where the stream comprises two or more components, these components are selected in a total amount of not more than 100%.

Further, where upper and lower limits are recited for a property, a range of values defined by a combination of any of the upper limits with any of the lower limits is also implied.

Within this specification, "substantially free" in relation to the amount of a particular component in a stream means that the amount of the component in question is at most 1,000ppmw (per million parts by weight), preferably at most 500ppmw, more preferably at most 100ppmw, more preferably at most 50ppmw, more preferably at most 30ppmw, more preferably at most 20ppmw, and most preferably at most 10ppmw, based on the amount (i.e. weight) of the stream.

Within this specification, a "top stream" or a "bottom stream" from a column refers to a stream exiting the column from the top or bottom of the column at a position of between 0% and 30%, more suitably between 0% and 20%, even more suitably between 0% and 10%, respectively, based on the total column length.

Unless otherwise indicated, when boiling point is mentioned in this specification, this refers to boiling point at 760mm hg pressure (101.3 kPa).

Liquid hydrocarbon feed stream

In the present invention, the liquid hydrocarbon feedstream comprises aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons.

Preferably, the liquid hydrocarbon feed stream comprises both aliphatic hydrocarbons having a boiling point of from 30 ℃ to 300 ℃ and aliphatic hydrocarbons having a boiling point of from greater than 300 ℃ to 600 ℃, the weight ratio of the two aliphatic hydrocarbons being from 99:1 to 1:99. The amount of aliphatic hydrocarbons having a boiling point of 30 ℃ to 300 ℃ may be up to 99 wt%, or up to 80 wt%, or up to 60 wt%, or up to 40 wt%, or up to 30 wt%, or up to 20 wt%, or up to 10 wt%, based on the total amount of aliphatic hydrocarbons having a boiling point of 30 ℃ to 600 ℃. Further, the amount of aliphatic hydrocarbons having a boiling point of 30 ℃ to 300 ℃ may be at least 1 wt%, or at least 5 wt%, or at least 10 wt%, or at least 20 wt%, or at least 30 wt%, based on the total amount of aliphatic hydrocarbons having a boiling point of 30 ℃ to 600 ℃.

Thus, advantageously, the liquid hydrocarbon feed stream may comprise varying amounts of aliphatic hydrocarbons over a wide boiling point range of 30 ℃ to 600 ℃. Thus, as well as the boiling point, the carbon number of the aliphatic hydrocarbon in the liquid hydrocarbon feed stream may also vary within wide limits, for example from 5 to 50 carbon atoms. The aliphatic hydrocarbon in the liquid hydrocarbon feed stream may have a carbon number of at least 4, or at least 5, or at least 6, and may have a carbon number of at most 50, or at most 40, or at most 30, or at most 20.

The amount of aliphatic hydrocarbons in the liquid hydrocarbon feed stream may be at least 30 wt%, or at least 50 wt%, or at least 80 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt%, and may be less than 100 wt%, or at most 99 wt%, or at most 90 wt%, or at most 80 wt%, or at most 70 wt%, based on the total weight of the liquid hydrocarbon feed stream. Aliphatic hydrocarbons may be cyclic, linear and branched.

The aliphatic hydrocarbons in the liquid hydrocarbon feedstream may include non-olefinic (paraffinic) aliphatic compounds and olefinic aliphatic compounds. The amount of paraffinic aliphatic compound in the liquid hydrocarbon feedstream may be at least 20 wt%, or at least 40 wt%, or at least 60 wt%, or at least 80 wt%, and may be less than 100 wt%, or at most 99 wt%, or at most 80 wt%, or at most 60 wt%, based on the total weight of the liquid hydrocarbon feedstream. Furthermore, the amount of olefinic aliphatic compound in the liquid hydrocarbon feedstream may be less than 100 wt%, or at least 20 wt%, or at least 40 wt%, or at least 60 wt%, or at least 80 wt%, and may be up to 99 wt%, or up to 80 wt%, or up to 60 wt%, based on the total weight of the liquid hydrocarbon feedstream.

Further, the olefinic compound may include an aliphatic compound (mono-olefin) having one carbon-carbon double bond and/or an aliphatic compound having two or more carbon-carbon double bonds, the latter compound may be conjugated or non-conjugated. That is, the two or more carbon-carbon double bonds may be conjugated or non-conjugated. Aliphatic compounds having two or more carbon-carbon double bonds may include compounds having double bonds in the alpha and omega positions. The amount of mono-olefin in the liquid hydrocarbon feed stream may be at least 20 wt%, or at least 40 wt%, or at least 60 wt%, or at least 80 wt%, and may be less than 100 wt%, or at most 99 wt%, or at most 80 wt%, or at most 60 wt%, based on the total weight of the liquid hydrocarbon feed stream. Furthermore, the amount of conjugated aliphatic compound having two or more carbon-carbon double bonds in the liquid hydrocarbon feed stream may be greater than 0 wt%, or at least 10 wt%, or at least 20 wt%, or at least 40 wt%, or at least 60 wt%, and may be up to 80 wt%, or up to 60 wt%, or up to 40 wt%, based on the total weight of the liquid hydrocarbon feed stream.

Within this specification, aliphatic hydrocarbons containing one or more heteroatoms are "heteroatom-containing organic compounds," as described further below. Unless indicated otherwise, either explicitly or by context, within this specification the term "aliphatic hydrocarbon" does not include aliphatic hydrocarbons containing heteroatoms. Furthermore, unless specified otherwise, either explicitly or by context, within this specification the term "aliphatic hydrocarbon" does not include conjugated aliphatic compounds having two or more carbon-carbon double bonds.

In addition to the aliphatic hydrocarbons described above, the liquid hydrocarbon feed stream also comprises heteroatom-containing organic compounds and optionally aromatic hydrocarbons.

The amount of aromatic hydrocarbons in the liquid hydrocarbon feed stream may be 0 wt%, or greater than 0 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, and may be up to 50 wt%, or up to 40 wt%, or up to 30 wt%, or up to 20 wt%, based on the total weight of the liquid hydrocarbon feed stream. The aromatic hydrocarbons may include monocyclic aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons. An example of a monocyclic aromatic hydrocarbon is styrene. The polycyclic aromatic hydrocarbon may include a non-condensed polycyclic aromatic hydrocarbon and/or a condensed polycyclic aromatic hydrocarbon. An example of a non-fused polycyclic aromatic hydrocarbon is an oligopolystyrene. Styrene and oligostyrene may be derived from polystyrene. Examples of condensed polycyclic aromatic hydrocarbons are naphthalene and anthracene, and alkyl naphthalene and alkyl anthracene. One or more aromatic rings in an aromatic hydrocarbon may be substituted with one or more hydrocarbon groups including alkyl groups (saturated) and alkylene groups (unsaturated).

Within this specification, aromatic hydrocarbons containing one or more heteroatoms are "heteroatom-containing organic compounds," as described further below. Unless indicated otherwise, either explicitly or by context, within this specification the term "aromatic hydrocarbon" does not include aromatic hydrocarbons containing heteroatoms.

Furthermore, the amount of heteroatom-containing organic compound in the liquid hydrocarbon feed stream is greater than 0 wt%, and may be at least 0.5 wt%, or at least 1 wt%, or at least 3 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, and may be up to 30 wt%, or up to 20 wt%, or up to 10 wt%, or up to 5 wt%, based on the total weight of the liquid hydrocarbon feed stream.

The heteroatom-containing organic compound in the liquid hydrocarbon feedstream contains one or more heteroatoms which may be oxygen, nitrogen, sulfur and/or halogen (such as chlorine), suitably oxygen, nitrogen and/or halogen. The heteroatom-containing organic compound may comprise one or more of the following moieties: amines, imines, nitriles, alcohols, ethers, ketones, aldehydes, esters, acids, amides, carbamates (sometimes referred to as urethanes) and ureas.

In addition, the above-mentioned heteroatom-containing organic compounds may be aliphatic or aromatic. An example of a heteroatom-containing aliphatic organic compound is oligomeric polyvinyl chloride (PVC). The oligomeric PVC may be derived from polyvinyl chloride. The heteroatom-containing aromatic organic compound may include a heteroatom-containing monocyclic aromatic organic compound and/or a heteroatom-containing polycyclic aromatic organic compound. Examples of heteroatom-containing monocyclic aromatic organic compounds are terephthalic acid and benzoic acid. An example of a polycyclic aromatic organic compound containing heteroatoms is oligomeric polyethylene terephthalate (PET). Terephthalic acid, benzoic acid, and oligomeric PET may be derived from polyethylene terephthalate. Examples of nitrogen-containing organic compounds are compounds derived from polyurethanes and polyamides, including nylons.

Unless indicated otherwise, either explicitly or by context, within this specification the term "heteroatom-containing organic compound" refers to a heteroatom-containing organic compound in or derived from a liquid hydrocarbon feedstream. Furthermore, unless explicitly or otherwise indicated by context, within the present specification the term "heteroatom-containing organic compound" does not include extraction solvents, layering solvents and/or washing solvents as defined in the present specification.

In addition, the liquid hydrocarbon feedstream may comprise salts. The salts may include organic salts and/or inorganic salts. These salts may contain ammonium, alkali metal, alkaline earth metal or transition metal as cation and carboxylate, sulfate, phosphate or halide as anion.

Preferably, at least a portion of the components in the liquid hydrocarbon feedstream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons are synthetic compounds other than natural compounds found in petroleum, for example. For example, such synthetic compounds include compounds derived from the pyrolysis of plastics synthesized from biomass, such as polyethylene synthesized from bioethanol by dehydration of the ethanol and subsequent polymerization of the ethylene formed therefrom.

Furthermore, since heteroatom-containing organic compounds are readily removed in the present process, the feed to the present process may advantageously permit relatively large amounts of such heteroatom-containing organic compounds. Thus, waste plastics that may be pyrolyzed to produce the feedstock of the present process may include heteroatom-containing plastics such as polyvinyl chloride (PVC), polyethylene terephthalate (PET), and Polyurethane (PU). In particular, the pyrolytically-mixable waste plastics contain relatively large amounts of such heteroatom-containing plastics in addition to heteroatom-free plastics such as Polyethylene (PE) and polypropylene (PP).

Step a) -extraction with extraction solvent a)

In step a) of the present process, at least a portion of a liquid hydrocarbon feedstream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons is contacted with an extraction solvent a) containing one or more heteroatoms, and the liquid hydrocarbon feedstream is subjected to liquid-liquid extraction with the extraction solvent a), thereby producing a first stream comprising aliphatic hydrocarbons and a second stream comprising extraction solvent a), heteroatom-containing organic compounds, and optionally aromatic hydrocarbons.

In step a) of the present process, the liquid hydrocarbon feedstream may be fed to a first column (first extraction column). Furthermore, a first solvent stream comprising extraction solvent a) may be fed to the first column at a higher location than the location of the liquid hydrocarbon feed stream feed, thereby enabling countercurrent liquid-liquid extraction and producing an overhead stream from the first column comprising aliphatic hydrocarbons (the "first stream" described above) and a bottom stream from the first column comprising extraction solvent a), heteroatom-containing organic compounds and optionally aromatic hydrocarbons (the "second stream" described above).

In step a), the weight ratio of extraction solvent a) to liquid hydrocarbon feed stream may be at least 0.05:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, and may be at most 5:1, or at most 3:1, or at most 2:1, or at most 1:1. Further, the temperature in step a) may be at least 0 ℃, or at least 20 ℃, or at least 30 ℃, or at least 40 ℃, or at least 50 ℃, and may be at most 200 ℃, or at most 150 ℃, or at most 100 ℃, or at most 70 ℃, or at most 60 ℃, or at most 50 ℃, or at most 40 ℃. The pressure in step a) may be at least 100mbar, or at least 500mbar, or at least 1bara, or at least 1.5bara, or at least 2bara, and may be at most 50bara, or at most 30bara, or at most 20bara, or at most 15bara, or at most 10bara, or at most 5bara, or at most 3bara, or at most 2bara, or at most 1.5bara. The temperature and pressure in step a) are preferably such that both the hydrocarbons from the feed stream and the extraction solvent a) are liquid.

In step a), aliphatic hydrocarbons are recovered by liquid-liquid extraction of the heteroatom-containing organic compound and optionally aromatic hydrocarbons with an extraction solvent a). Further, preferably, the recovered aliphatic hydrocarbon comprises an aliphatic hydrocarbon having a boiling point of 30 ℃ to 300 ℃ and an aliphatic hydrocarbon having a boiling point of higher than 300 ℃ to 600 ℃, the weight ratio of the two aliphatic hydrocarbons being 99:1 to 1:99. The above description of the weight ratio of aliphatic hydrocarbons having a boiling point of 30 ℃ to 300 ℃ to aliphatic hydrocarbons having a boiling point of greater than 300 ℃ to 600 ℃ with respect to aliphatic hydrocarbons in the liquid hydrocarbon feed stream also applies to the recovered aliphatic hydrocarbons.

In step a), the liquid-liquid extraction produces a first stream comprising aliphatic hydrocarbons and a second stream comprising extraction solvent a), heteroatom-containing organic compounds and optionally aromatic hydrocarbons. Within this specification, the former stream (first stream) comprising recovered aliphatic hydrocarbons may also be referred to as "raffinate stream", and the latter stream (second stream) may also be referred to as "extract stream". The content of aromatic hydrocarbons, conjugated aliphatic compounds having two or more carbon-carbon double bonds, and heteroatom-containing organic compounds in such raffinate streams is reduced. Such raffinate streams contain no or up to 10 wt%, or up to 5 wt%, or up to 1 wt% aromatic hydrocarbons, or substantially no aromatic hydrocarbons. Furthermore, such a raffinate stream does not comprise or comprises up to 15 wt%, or up to 10 wt%, or up to 5 wt%, or up to 1 wt% of conjugated aliphatic compounds having two or more carbon-carbon double bonds, or substantially does not comprise such aliphatic compounds. Furthermore, such raffinate stream contains no or up to 1 wt.% of heteroatom-containing organic compounds, or substantially no such organic compounds.

The extraction solvent a) used in step a) of the present process, which may be fed as a first solvent stream to the first column in step a), preferably has a density at least 3%, or at least 5%, or at least 8%, or at least 10%, or at least 15%, or at least 20% higher than the density of the liquid hydrocarbon feed stream. Further, the density may be up to 50%, or up to 40%, or up to 35%, or up to 30% higher than the density of the liquid hydrocarbon feedstream.

In addition, the extraction solvent a) used in step a) contains one or more heteroatoms, which may be oxygen, nitrogen and/or sulfur. Still further, it is preferred that the extraction solvent a) is thermally stable at a temperature of 200 ℃. Still further, the extraction solvent a) may have a boiling point of at least 50 ℃, or at least 80 ℃, or at least 100 ℃, or at least 120 ℃ and at most 300 ℃, or at most 200 ℃, or at most 150 ℃. Still further, it is preferred that the extraction solvent a) is not miscible or has relatively low miscibility in heptane. Preferably, the extraction solvent a) has such miscibility in heptane that at most 30 wt.%, or at most 20 wt.%, or at most 10 wt.%, or at most 3 wt.%, or at most 1 wt.% of the extraction solvent a) is miscible in heptane, based on the weight of the heptane. The miscibility of one compound in another compound (such as heptane) can be determined by any of the common methods known to those skilled in the art, including ASTM method D1476. When reference is made in this specification to the miscibility of one compound in another, this refers to miscibility at 25 ℃.

Furthermore, the extraction solvent a) in step a) has a hansen solubility parameter distance R relative to heptane determined at 25 ℃ _{a, heptane} May be at least 3MPa ^1/2 Preferably at least 5MPa ^1/2 More preferably at least 10MPa ^1/2 More preferably at least 15MPa ^1/2 . Furthermore, extracting the R of solvent a) _{a, heptane} Can be lower than 45MPa ^1/2 Or at most 40MPa ^1/2 Preferably at most 35MPa ^1/2 More preferably at most 30MPa ^1/2 More preferably at most 25MPa ^1/2 . For example, the R of N-methylpyrrolidone (NMP) _{a, heptane} 15MPa of ^1/2 。

Further, the extraction solvent a) has a hansen solubility parameter distance R relative to heptane measured at 25 DEG C _{a, heptane} Distance R from Hansen solubility parameter relative to toluene _{Toluene (a)} Differences (i.e. R _{a, heptane} -R _{Toluene (a)} ) May be at least 1.5MPa ^1/2 Preferably at least 2MPa ^1/2 . In addition, R of the extraction solvent a) _{a, heptane} And R is R _{Toluene (a)} Can be up to 4.5MPa ^1/2 Preferably at most 4MPa ^1/2 。

Hansen Solubility Parameters (HSPs) may be used as a phase for predicting one component from another componentSimilarity means. More specifically, each component is characterized by three hansen parameters, each typically in MPa ^0.5 The representation is: delta _d Energy representing the dispersion force between molecules; delta _p Representing the energy of the dipole intermolecular forces between the molecules; and delta _h Represents the energy of hydrogen bonds between molecules. The affinity between compounds can be described as Hansen Solubility Parameter (HSP) distance R using multidimensional vectors that quantify these solvent atom and molecule interactions _a It is defined in formula (1):

(R _a ) ² ＝4(δ _d2 –δ _d1 ) ² +(δ _p2 –δ _p1 ) ² +(δ _h2 –δ _h1 ) ² (1)

wherein the method comprises the steps of

R _a Distance in HSP space of compound 1 and compound 2 (MPa ^0.5 )

δ _d1 、δ _p1 、δ _h1 Hansen (or equivalent) parameters of =compound 1 (in MPa ^0.5 In units of

δ _d2 、δ _p2 、δ _h2 Hansen (or equivalent) parameters of compound 2 (in MPa ^0.5 In units of

Thus, R for a given solvent calculated relative to the compound to be recovered _a The smaller the value (i.e., compound 1 and compound 2 as the solvent to be recovered, or vice versa), the higher the affinity of the solvent to be recovered.

Hansen solubility parameters for many solvents can be found, for example, in the following documents: allan F.M. Barton, CRC Handbook of Solubility Parameters and Other Cohesion Parameters, second edition, CRC press 1991; charles M.Hansen, hansen Solubility Parameters: A User's Handbook, CRC press 2007.

In particular, the extraction solvent a) used in step a) of the present process may comprise ammonia or preferably one or more organic solvents selected from the group consisting of: diols and triols including monoethylene glycol (MEG), monopropylene glycol (MPG), any isomer of butanediol and glycerol; glycol ethers including oligoethylene glycols including diethylene glycol, triethylene glycol, and tetraethylene glycol, and monoalkyl ethers thereof including diethylene glycol diethyl ether; amides, including N-alkylpyrrolidones, wherein the alkyl group can contain from 1 to 8 or 1 to 3 carbon atoms, and including formamide, dialkylformamide and acetamide, and monoalkylformamide and acetamide, wherein the alkyl group can contain from 1 to 8 or 1 to 3 carbon atoms, including N-methylpyrrolidone (NMP), such dialkylformamide and acetamide, and monoalkylformamide and acetamide, including Dimethylformamide (DMF), methylformamide and dimethylacetamide; dialkyl sulfoxides, wherein the alkyl group can contain from 1 to 8 or from 1 to 3 carbon atoms, including dimethyl sulfoxide (DMSO); sulfones, including sulfolane; n-formyl morpholine (NFM); furan ring-containing components and derivatives thereof, including furfural, 2-methyl-furan, furfuryl alcohol, and tetrahydrofurfuryl alcohol; hydroxy esters, including lactic acid esters, including methyl lactate and ethyl lactate; trialkyl phosphates including triethyl phosphate; phenolic compounds including phenol and guaiacol; benzyl alcohol-based compounds, including benzyl alcohol; amine compounds including ethylenediamine, monoethanolamine, diethanolamine, and triethanolamine; nitrile compounds including acetonitrile and propionitrile; trioxane compounds including 1,3, 5-trioxane; carbonate compounds including propylene carbonate and glycerol carbonate; and cycloalkanone compounds including dihydro-l-glucosone.

More preferably, the extraction solvent a) comprises one or more of the following: the above dialkyl sulfoxides, in particular DMSO; sulfones, in particular sulfolane; the above-mentioned N-alkylpyrrolidones, in particular NMP; and furan ring-containing components, in particular furfural. Even more preferably, the extraction solvent a) comprises one or more of the above-mentioned N-alkyl pyrrolidinone (in particular NMP) and furan ring-containing component (in particular furfural). Most preferably, the extraction solvent a) comprises NMP.

Aqueous solutions of quaternary ammonium salts, in particular trioctyl methyl ammonium chloride or methyltributylammonium chloride, can also be used as extraction solvent a) in step a).

In addition to the extraction solvent a), a washing solvent such as water may be added to step a). This washing solvent is referred to herein as washing solvent c) and is described further below. In this case, step a) preferably produces a first stream comprising aliphatic hydrocarbons and a second stream comprising washing solvent c), extraction solvent a), heteroatom-containing organic compounds and optionally aromatic hydrocarbons. Advantageously, therefore, said washing solvent c) added in step a) acts as an extraction solvent to extract the extraction solvent a) and thereby makes it possible that no or substantially no extraction solvent a) is eventually present in the first stream produced by step a) and comprising recovered aliphatic hydrocarbons. In case wash solvent c) is also added to step a), the weight ratio of extraction solvent a) to wash solvent c) in step a) may be at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, and may be at most 30:1, or at most 25:1, or at most 20:1, or at most 15:1, or at most 10:1, or at most 5:1, or at most 3:1, or at most 2:1.

In case wash solvent c) is also added to step a), the second solvent stream comprising wash solvent c) may be fed to the above-mentioned first column (first extraction column) at a higher position than the position where the above-mentioned first solvent stream comprising extraction solvent a) is fed, thereby enabling countercurrent liquid-liquid extraction and producing an overhead stream from the first column comprising aliphatic hydrocarbons (the above-mentioned "first stream") and a bottom stream from the first column comprising wash solvent c), extraction solvent a), organic compounds comprising heteroatoms and optionally aromatic hydrocarbons (the above-mentioned "second stream"). In the above case, the first solvent stream in extraction step a) may comprise, in addition to extraction solvent a), a layering solvent b) such as water and/or the above-described optional washing solvent c). The layering solvent b) is also described further below. The delamination solvent b) and the washing solvent c) may originate from one or more recycle streams after step c) of the process.

In case the washing solvent c) is also added to step a), it is preferred that the stream comprising the washing solvent c) to be added comprises no or substantially no heteroatom-containing organic compounds originating from the liquid hydrocarbon feed stream. This preferred requirement is especially applicable in the case where the stream is fed to the first extraction column at a relatively high position as described above, wherein these heteroatom-containing organic compounds may again contaminate the raffinate (overhead) stream resulting from step a). Advantageously, in the present invention, at least a portion of the stream containing the layered solvent b) resulting from step c) or at least a portion of the treated stream containing the layered solvent b) resulting from the sorption step (ii), which may contain no or substantially no heteroatom-containing organic compound, may be used as such a stream for feeding (recycling) to the washing solvent c) of step a), in particular in case the layered solvent b) is identical to the washing solvent c), in particular water.

As mentioned above, the second stream produced by step a) for the first (extraction) column described above corresponds to the bottom stream from this column, comprising the extraction solvent a), the heteroatom-containing organic compound and optionally the aromatic hydrocarbon. In the case where salts and/or conjugated aliphatic compounds having two or more carbon-carbon double bonds are present in the liquid hydrocarbon feed stream, the second stream may also comprise such salts and/or compounds.

In the present invention, by means of steps b), c) and d) of the process, the extraction solvent a) is recovered from the second stream resulting from step a) and is then advantageously recycled to step a).

Step b) -delamination with a delamination solvent b)

In step b) of the present process, at least a portion of the second stream comprising the extraction solvent a), the heteroatom-containing organic compound and optionally the aromatic hydrocarbon resulting from step a) is mixed with the layering solvent b) and the resulting mixture is separated into a first stream comprising the heteroatom-containing organic compound and optionally the aromatic hydrocarbon and a second stream comprising the extraction solvent a), the layering solvent b), the heteroatom-containing organic compound and optionally the aromatic hydrocarbon, wherein the layering solvent contains one or more heteroatoms and the miscibility in heptane is lower than the miscibility of the extraction solvent a) in heptane. Depending on the partition coefficient, a certain amount of heteroatom-containing organic compounds and any aromatic hydrocarbons are also eventually present in the second stream, wherein the first stream is more hydrophobic than the second stream. Thus, the second stream also comprises heteroatom-containing organic compounds and optionally aromatic hydrocarbons.

The layering solvent b) used in step b) contains one or more heteroatoms, which may be oxygen, nitrogen and/or sulfur. Still further, it is preferred that the delamination solvent b) is not miscible or has a relatively low miscibility in heptane just like the extraction solvent a). Preferably, the layering solvent b) has such miscibility in heptane that at most 10 wt%, or at most 3 wt%, or at most 1 wt%, or at most 0.5 wt%, or at most 0.1 wt% of the layering solvent b) is miscible in heptane, based on the weight of the heptane. In the present invention, the miscibility of the layering solvent b) in heptane is lower than the miscibility of the extraction solvent a) in heptane. The miscibility of the solvents a) and b) in heptane can be determined by any of the common methods known to those skilled in the art, including ASTM method D1476, described above. Furthermore, suitably, the layering solvent b) is miscible in the extraction solvent a). This means that up to 50% by weight of the layering solvent b) based on the total amount of layering solvent b) and extraction solvent a) can be mixed in extraction solvent a).

Furthermore, the delamination solvent b) in step b) is determined at 25 ℃ from the hansen solubility parameter distance R with respect to heptane _{a, heptane} May be at least 10MPa ^1/2 Preferably at least 20MPa ^1/2 More preferably at least 30MPa ^1/2 More preferably at least 40MPa ^1/2 . Furthermore, the R of the delamination solvent b) _{a, heptane} May be up to 55MPa ^1/2 More preferably at most 50MPa ^1/2 More preferably at most 45MPa ^1/2 . For example, the R of water _{a, heptane} 45MPa of ^1/2 。

As mentioned above, the miscibility of the extraction solvent a) and the delamination solvent b) in heptane is different. Thus, the solvent a) and the solvent b) are not identical. In particular, the delamination solvent b) has a hansen solubility parameter distance R relative to heptane measured at 25 DEG C _{a, heptane} Said R being greater than the extraction solvent a) _{a, heptane} . Preferably, the method comprises the steps of,r of the solvents a) and b) _{a, heptane} Is at least 1MPa ^1/2 More preferably at least 5MPa ^1/2 More preferably at least 10MPa ^1/2 More preferably at least 15MPa ^1/2 More preferably at least 20MPa ^1/2 More preferably at least 25MPa ^1/2 . Furthermore, preferably, R of the solvents a) and b) _{a, heptane} Is at most 55MPa ^1/2 More preferably at most 50MPa ^1/2 More preferably at most 45MPa ^1/2 More preferably at most 40MPa ^1/2 More preferably at most 35MPa ^1/2 More preferably at most 30MPa ^1/2 。

In particular, the layered solvent b) used in step b) of the present process may comprise one or more solvents selected from the group of solvents as defined above for extraction solvent a) and water. Preferably, the layering solvent b) comprises water and one or more of the above diols and triols, in particular monoethylene glycol (MEG) and glycerol. More preferably, the layering solvent b) comprises water, most preferably consists of water. The other preferred requirements and embodiments described above with reference to extraction solvent a) used in step a) also apply to the layering solvent b), except that layering solvent b) is different from extraction solvent a) (because it has lower miscibility in heptane), and layering solvent b) may and preferably does contain water.

In addition, the second stream resulting from step b) may also comprise salts. Any conjugated aliphatic compound having two or more carbon-carbon double bonds may be eventually present in the first stream or the second stream resulting from step b) together with the heteroatom-containing organic compound and optionally an aromatic hydrocarbon. Generally, in the present invention, the conjugated aliphatic compounds may have similar behavior to aromatic compounds, such that these conjugated aliphatic compounds may ultimately be present in the same stream or streams as the optional aromatic hydrocarbons.

In step b), the layering solvent b) is added separately from the second stream resulting from step a) in addition to any layering solvent b) that may be present in the latter stream and is mixed with the latter stream. In step b), at least a portion of the second stream comprising washing solvent c), such as water, and extraction solvent a) resulting from the optional additional extraction step (in which at least a portion of the first stream resulting from step a) comprising recovered aliphatic hydrocarbons and extraction solvent a)) is subjected to liquid-liquid extraction with washing solvent c) may be added to provide said layered solvent b) that needs to be added in step b).

The mixing in step b) may be carried out in any manner known to the person skilled in the art. For example, a mixer may be used upstream of the phase separation apparatus as described below. Further, for example, in-line (or static) mixing may be performed upstream of such a phase separation device. Still further, mixing may be accomplished in a column as described below.

By adding the layering solvent b) and mixing in step b) as such, different phases are formed, including a first phase which is more hydrophobic and a second phase which comprises the extraction solvent a), the layering solvent b), the heteroatom-containing organic compound and optionally the aromatic hydrocarbon, which phases are less hydrophobic, which phases are separated into the first and second streams, respectively, in step b). Thus, advantageously, said delamination solvent b) added in step b) independently of the second stream resulting from step a) acts as a so-called "delamination agent" (or "anti-solvent") to remove the more hydrophobic compounds from the extraction solvent a) to be recovered and recycled.

The phase separation in step b) may be carried out by any device capable of separating two phases, including decanters, flotation devices, coalescers and centrifuges, suitably decanters. Preferably, the phase separation in step b) is carried out in a single stage, for example in a decanter, flotation device, coalescer or centrifuge. For example, when a decanter is used in step b), a first upper phase comprising a more hydrophobic compound and a second lower phase comprising an extraction solvent a), a layering solvent b) and a less hydrophobic (i.e. less hydrophobic than the compounds in the first phase) compound may be separated into the first and second streams, respectively.

In addition, step b) may be carried out in a column comprising a plurality of separation trays. In the latter case, step b) comprises mixing at least part of the second stream resulting from step a) with the layering solvent b) in a column, respectively, and separating the resulting mixture into the above-mentioned first stream and second stream, thereby suitably producing an overhead stream from the column (the above-mentioned "first stream") and a bottom stream from the column (the above-mentioned "second stream"). Preferably, the layering solvent b) and the further extraction solvent a) rich stream are fed co-currently into the column at the bottom of the column.

The internals in the column described above facilitate the mixing of the extraction solvent a) rich stream with the layering solvent b). Such tower internals are known in the art. The tower internals may include packing such as raschig rings, pall rings, lux rings, torsemide rings, dirichlet rings; a sieve plate; or random packing, etc., as described in Perry's Chemical Engineer's Handbook. Furthermore, the tower may be provided with stirring means. For example, the shaft may extend along the tower and may be provided with a rotor and a stator fixed to the tower.

Furthermore, the above description of the temperature and pressure in extraction step a) also applies to step b). Still further, in step b), the weight ratio of the layering solvent b) to the extraction solvent a) may be at least 0.005:1, or at least 0.01:1, or at least 0.5:1, or at least 1:1, or at least 2:1, and may be at most 10:1, or at most 7:1, or at most 5:1, or at most 4:1, or at most 2:1, based on the amount of extraction solvent a) in the second stream resulting from step a). Suitably, the amount of the layering solvent b) added in step b) (based on the total of (i) said amount of layering solvent b) and (ii) the amount of extraction solvent a) in the second stream resulting from step a) may be from 0.1 to 45 wt%, more suitably from 1 to 40 wt%, more suitably from 5 to 35 wt%, more suitably from 10 to 30 wt%.

Thus, advantageously, in step b), a portion of the heteroatom-containing organic compounds and optionally aromatic hydrocarbons is removed from the extraction solvent a) to be recycled, so that it is not necessary to separate the extraction solvent a) from such removed compounds in a subsequent step, for example by cumbersome and energy-consuming distillation. Further, advantageously, any aromatic hydrocarbons and conjugated aliphatic compounds having two or more carbon-carbon double bonds removed in step b) may be blended with pyrolysis gasoline and processed into fuel or used for the production of aromatic compounds. Likewise, the heteroatom-containing organic compounds removed in step b) may also optionally be converted to fuel after hydrotreating to remove heteroatoms. Furthermore, the compounds removed in step b) may be further separated into various fractions which may be used as solvents.

Step c) -separation of extraction solvent a) and delamination solvent b)

In step c) of the process, at least a portion of the second stream produced by step b) and comprising extraction solvent a) and layering solvent b) is separated into a first stream comprising layering solvent b) and a second stream comprising extraction solvent a). In the case of the optional washing solvent c) described below for use in the present invention, this washing solvent c) may be the same or different, preferably the same, as the layering solvent b), such washing solvent c) may eventually be present in said second stream resulting from step b) and subsequently in said first stream resulting from step c).

Thus, the feed stream of step c) comprises at least a portion of the second stream resulting from step b). In step c), the layering solvent b) and the extraction solvent a) may be separated from each other in any known manner, preferably by evaporation, for example by distillation. The latter separation may be carried out in a distillation column. Advantageously, in the distillation, at least a portion of any heteroatom-containing organic compounds and aromatic hydrocarbons in the feed stream of step c) are azeotropically removed with the layering solvent b), in particular water.

Thus, it is preferred that step c) comprises separating at least part of the second stream resulting from step b) by distillation into a top stream comprising the layered solvent b) and a bottom stream comprising the extraction solvent a). In case the feed stream of step c) further comprises heteroatom-containing organic compounds and optionally aromatic hydrocarbons, the top stream further comprises such compounds.

In addition, where the feed stream of step c) also comprises salts, the second stream resulting from step c) also comprises such salts. If the feed stream of step c) or the second stream resulting from step c) contains any solid salts, these salts can be removed therefrom by any method, including filtration.

In the present invention, the amount of layering solvent b) in the feed stream of step c) may be at least 10 wt% or at least 20 wt%, and may be at most 70 wt%, or at most 50 wt%, or at most 40 wt%. The second stream resulting from step c) may still comprise a delamination solvent b) in an amount of, for example, up to 10 wt.%, or up to 5 wt.%, or up to 3 wt.%, or up to 1 wt.%. Advantageously, in case the amount of the delamination solvent b) in the second stream is relatively low, e.g. at most 5 wt%, such delamination solvent b) does not need to be removed before recycling the extraction solvent a) from the same stream to step a) of the process.

As mentioned above, in case the feed stream of the above-described distillation step as step c) in the present process comprises, in addition to the extraction solvent a) and the layering solvent b), a heteroatom-containing organic compound and optionally an aromatic hydrocarbon, the top stream resulting from the distillation step comprises layering solvent b), a heteroatom-containing organic compound and optionally an aromatic hydrocarbon. Advantageously, at least a portion of the organic heteroatom-containing compound and aromatic hydrocarbon are removed azeotropically with the layering solvent b), especially water, in the distillation. In the latter case, the top stream may be separated into two phases, one of which comprises the layering solvent b) and the other phase comprises the heteroatom-containing organic compound and optionally an aromatic hydrocarbon. Such phase separation may be carried out by any device capable of separating the two phases, including decanters, flotation devices, coalescers and centrifuges, suitably decanters. Advantageously, the stratified solvent b) from such separated phase comprising stratified solvent b) may be recycled as further described below, while the other phase may be withdrawn from the process, thereby reducing the risk of any accumulation of organic compounds containing heteroatoms and aromatic hydrocarbons in the process.

A sorption step (i) and a sorption step (ii)

In the present invention, advantageously, a sorption agent is used in step (i) and step (ii) to remove the organic compounds containing heteroatoms and optionally aromatic hydrocarbons which are not completely removed in step b) but are entrained in the second stream resulting from step b), which comprises the extraction solvent a) and the layering solvent b) to be separated from each other in the subsequent step c). By this sorption, accumulation of these contaminants in the recycle stream in the present process is advantageously avoided.

It is envisaged that the removal of heteroatom-containing organic compounds and optionally aromatic hydrocarbons by the above-described sorption is applied in the present process to either or both of the following steps:

(i) Before step c): contacting at least a portion of the second stream resulting from step b) with a sorbent agent, the second stream comprising extraction solvent a), layering solvent b), heteroatom-containing organic compound and optionally aromatic hydrocarbon; and/or

(ii) After step c): contacting at least a portion of the first stream resulting from step c) with a sorbent agent, wherein the first stream comprises the layering solvent b), the heteroatom-containing organic compound, and optionally an aromatic hydrocarbon.

Furthermore, the sorption step (ii) is carried out prior to any recycling of at least a portion of the layered solvent b) from the first stream resulting from step c), for example in an optional recycling step e). Furthermore, step (ii) is preferably carried out prior to any recycling of at least a portion of the first stream resulting from step c) to step c).

In this way, at least a portion of the contaminants will advantageously be concentrated into the sorbent agent used in such a sorption step, thereby preventing accumulation of such contaminants in the recycle stream in the present process. The sorbent thus retains contaminants, which can eventually be regenerated or removed from the process and replaced by fresh sorbent, thereby avoiding the risk of heteroatom-containing organic compounds and aromatic hydrocarbons accumulating in the process.

The treated stream resulting from the sorption step (i) and the sorption step (ii) preferably contains no or substantially no heteroatom-containing organic compounds and aromatic hydrocarbons.

In the case of the sorption step (i), at least a portion of the treated stream resulting from the sorption step (i) and comprising the layering solvent b) and the extraction solvent a) may be fed to step c), in which step c) the at least a portion is separated into a first stream comprising the layering solvent b) and a second stream comprising the extraction solvent a). Recycling at least a portion of the extraction solvent a) from the second stream produced in step c) as further described below. Advantageously, there is no need to separate heteroatom-containing organic compounds and aromatic hydrocarbons from the first stream, as a major portion of these contaminants have been removed in the sorption step (i). Thus, at least a portion of the layered solvent b) from the first stream may be recycled as further described below.

Furthermore, in the case of sorption step (ii), at least a portion of the layered solvent b) from the treated stream resulting from the sorption step (ii) may be recycled as further described below. As described above, in step c), the extraction solvent a) and the layering solvent b) may be separated from each other by distillation, wherein at least a portion of any heteroatom-containing organic compounds and aromatic hydrocarbons in the feed stream to step c) are azeotropically removed with layering solvent b). In general, the relative amount of the layering solvent b) in the overhead stream resulting from such distillation is relatively high compared to the amount of contaminants comprising the heteroatom-containing organic compound and optionally aromatic hydrocarbon, such that removal of these contaminants by phase separation can be cumbersome, whereby such contaminants are less prone to forming a separate phase upon condensation. In the present invention, such troublesome phase formation and separation can be advantageously prevented by performing the above-described adsorption step (i) and/or adsorption step (ii).

In this specification, sorption refers to a process in which one substance (a sorbent agent) absorbs or retains another substance by absorption, adsorption, or a combination of both. Preferably, the sorbent used in the present invention is a sorbent that preferentially sorbs organic compounds containing heteroatoms and optionally aromatic hydrocarbons. In particular, it is preferred that the heteroatom-containing organic compound and optionally aromatic hydrocarbon are preferentially sorbed compared to the extraction solvent, the layering solvent and/or the washing solvent as defined in the present specification. In this way, the quality of the extraction solvent a) recycle stream, any stratification solvent b) recycle stream and/or any washing solvent c) recycle stream can be advantageously improved in the present process.

Suitably, the sorbent separates the heteroatom-containing organic compound and optionally the aromatic hydrocarbon by affinity. In addition, the sorbent reagent may have a relatively low polarity.

In the present invention, the organic compound containing heteroatoms and the optional aromatic hydrocarbon to be removed may be relatively large molecules compared to the extraction solvent a), the delamination solvent b) and the optional washing solvent c). In the present invention, suitable sorbent reagents preferably have a pore size large enough to partially or fully sorb the heteroatom-containing organic compound and optionally aromatic hydrocarbon.

The sorbent reagents used in step (i) and step (ii) of the present process suitably have a porous structure consisting of micropores, mesopores or macropores or a combination thereof. According to IUPAC nomenclature, the microporous structure has a thickness of less than 2nm

Angstroms) with a mesoporous structure having a pore size of 2nm to 50nm (/ a)>

To->

) And the macroporous structure has a pore size of greater than 50nm +.>

Is a pore size of the polymer.

The sorbent reagents applicable to step (i) and step (ii) are not limited to the specific materials listed in this specification. In general, any material characterized by a relatively high specific surface area, by a porous structure comprising micropores, mesopores or macropores or a combination thereof, from natural or synthetic sources, from mineral or organic sources, by a treated or untreated surface and in any form can be used in the present invention Is bright. The specific surface area can be 1m ² /g to 3000m ² /g, preferably 50m ² /g to 2000m ² /g, more preferably 100m ² /g to 1000m ² In the range of/g. The specific surface area may be at least 1m ² /g, or at least 10m ² /g, or at least 50m ² And/g. Furthermore, it may be up to 3000m ² /g, or up to 1000m ² /g, or up to 500m ² And/g. Furthermore, suitable sorbent reagents for step (i) and step (ii) have a concentration of at least 0.001cm ³ /g, or at least 0.01cm ³ /g, or at least 0.1cm ³ /g, and at most 1cm ³ Per g, or up to 3cm ³ Per gram, or up to 5cm ³ Per gram, or up to 10cm ³ Void volume per gram. Suitable sorbent reagents for step (i) and step (ii) may satisfy both of the above characteristics, namely pore size and surface area, or pore size and pore volume, or surface area and pore volume. As mentioned above, it is preferred that the sorbent agent has a relatively high affinity for the heteroatom-containing organic compound and optionally the aromatic hydrocarbon.

The sorbent agent conveniently used in step (i) and step (ii) of the process of the invention may be a molecular sieve of inorganic origin (such as a metal oxide, wherein the metal is one or more of an alkaline earth metal, a transition metal and a post-transition metal, such as Al, si, zn, mg, ti, zr); or may be molecular sieves of organic origin (such as activated carbon, crosslinked and porous polymers, carbonaceous materials); or may be a hybrid molecular sieve such as a metal-organic framework. The sorbent agent may be dispersed in a porous amorphous inorganic or organic matrix (also referred to as a binding material) having channels and cavities therein that allow liquid to enter the sorbent agent. Alternatively, the sorbent agent may be used without a binding material.

Suitable sorbent reagents for use in the present invention having a predominantly microporous structure are zeolites, porous glass, activated carbon, char coke ("char" stands for "charcoal"), clays (such as bauxite, preferably activated clay), activated alumina, aerogels, graphene-based nanomaterials and single-or multi-walled carbon nanotubes. Suitable sorbent reagents for use in the present invention having a predominantly mesoporous structure are Ordered Mesoporous Carbon (OMC), mesoporous activated carbon, mesoporous zeolites, activated alumina, silica gel and mesoporous silica such as M-41-S, MAS-5, MCM-41, SBA-15, SBA-16, TUD-1, HMM-33, FSM-16, MSM-48. A suitable sorbent for use in the present invention having a predominantly macroporous structure is macroporous silica.

As described above, the sorbent agent comprising carbon (such as activated carbon and char) may consist essentially of carbon, for example a substance comprising 80 to 100 wt% carbon, preferably 90 to 100 wt% carbon, more preferably 95 to 100 wt% carbon, most preferably 98 to 100 wt% carbon, and highly preferably 99 to 100 wt% carbon.

Preferred activated carbon as a sorbent agent for removing heteroatom-containing organic compounds and optionally aromatic hydrocarbons in step (i) and step (ii), especially step (ii), has an iodine value of 500mg/g to 1200mg/g and a molasses value in the range of 95 to 1500, more preferably in the range of 200 to 1500. "iodine value" is a relative measure of pores having a size of 10 angstroms to 28 angstroms. It is expressed in milligrams of elemental iodine per gram of granular activated carbon and determines the area of activated carbon available for the sorption of low molecular weight organic compounds. Iodine number can be determined according to ASTM D4607. The "molasses value" measures the extent to which activated carbon removes color from the raw solution. It measures pores greater than 28 angstroms. These pores are those responsible for removing the higher molecular weight organic compounds. In this case, the amount of the absorbed molasses was quantified.

Furthermore, suitable activated carbon for use in the present invention has a particle size of 600m ² /g to 2000m ² Total specific surface area in the range of/g and total pore volume in the range of 0.9mL/g to 2.5 mL/g. Further, preferred activated carbons for use in the present invention have a pore size of greater than 20 angstroms of greater than 100m ² Specific surface area per gram and pore volume exceeding 0.5 mL/g. These properties facilitate the removal of relatively large molecules comprising the heteroatom-containing organic compound and optionally aromatic hydrocarbon to be removed in step (i) and step (ii).

Activated carbon and char, the surface of which is modified and/or functionalized, may also be suitably used in step (i) and step (ii). Suitable methods for producing functional properties on the surface of carbon materials include: oxidation by liquid and gaseous oxidants, grafting of functional groups onto the material surface, physical sorption of ligands, vapor deposition and/or functional groups formed during carbon activation.

Zeolites are also suitable sorbing agents for removing heteroatom-containing organic compounds and optionally aromatic hydrocarbons in step (i) and step (ii). Zeolites can be produced in several aluminosilicate ring arrangements and any framework type of zeolite can be suitably used in the present invention. Exemplary zeolites for step (i) and step (ii) are faujasite type (such as 13X (sodium form of zeolite X) or 10X and NaX), LTA type (such as pore-blocking zeolite 4A and zeolite 4A), ZSM type, and mixtures thereof. Preferably, the zeolite used in the present invention to remove heteroatom-containing organic compounds has pores and/or surface cavities with cross-sectional dimensions greater than 5.6 angstroms. Examples of such zeolites include MFI-type (such as ZSM-5 and Pentasil zeolites), mordenite (MOR-type), zeolite L (LTL-type), FAU-type zeolites (such as X and Y), dealuminated zeolite Y, low sodium ultrastable Y (USY), MTW-type (such as ZSM-12), zeolite beta (BEA-type) and zeolite omega (MAZ-type). In addition, sorbent reagents having surface cavities with cross-sectional dimensions greater than 5.6 angstroms are also suitable for sorbing heteroatom-containing organic compounds, regardless of the size of the pores. Examples of such sorbent agents having such surface cavities are MWW-type zeolites (such as MCM-22, PSH-3, SSZ-25, MCM-41, MCM-49 and MCM-56), IFR-type zeolites (such as MCM-58), MEL-type zeolites (such as ZSM-11), FER-type zeolites (such as ZSM-35) and clinoptilolite, ferrierite, stilbite, EU-1, NU-87, mordenite, faujasite, natrolite and cancrinite.

Preferred molecular sieve zeolite-based sorbent reagents suitable for use in step (i) and step (ii) of the present invention have relatively low polarity and low affinity for polar components, which may include heteroatom-containing organic compounds. The polarity of a molecular sieve zeolite is determined by its Si/Al ratio, with low ratios resulting in high polarity and vice versa. Preferred sorbent reagents for use in the present invention include zeolites having Si/Al ratios greater than 20. Such zeolites are relatively organophilic and may advantageously adsorb compounds such as phenol. A suitable example of such a preferred sorbent agent is MCM-22 with a Si/Al ratio of 30. Alternatively, preferred sorbent reagents for use in the present invention include zeolites having a Si/Al ratio of less than 20 which have been treated, such as cation exchanged or surface modified, to enhance their affinity for heteroatom-containing organic compounds and/or aromatic compounds.

In addition, molecular sieve zeolites suitable for use as a sorbent in step (i) and step (ii) may be modified by cation exchange. For example, the cationic sites may be filled by ion exchange with one or more metal cations selected from the metals of groups I-A, I-B, II-B and II-A of the periodic Table (

IUPAC

1, 11, 12 and 2). Preferred metal cations for ion exchange include beryllium, lithium, sodium, magnesium, potassium, calcium, rubidium, strontium, cesium, barium, gold, copper, silver, zinc, and cadmium.

Furthermore, the sorbent reagents suitable for step (i) and step (ii) may be silicalite-type, organosilicate or crystalline silica polymorphs. Silicalite type sorbent has very high silica to alumina ratio>1000). Silicalite-type sorbent agents are not zeolites because they lack ion exchange capacity. The organosilicates are synthesized from reaction systems substantially free of aluminum-containing reagents and are completely free of framework AlO ^4- Tetrahedra, or absence of crystallographically significant amounts of framework AlO ^4- Tetrahedra. The organosilicates may be made from a combination of alkali metal cations (preferably sodium, potassium or lithium), silica and Tetraethylammonium (TEA) cations. Due to their organophilic nature, silicalites advantageously selectively sorb organic molecules, including heteroatom-containing organic compounds and any aromatic hydrocarbons, from a polar medium (such as water) or a mixture of polar medium and an organic solvent.

Crystalline hybrid porous materials may also be used as the sorbent in step (i) and step (ii). These materials may be characterized by high porosity, large surface area, and low density. There are two classes of hybrid porous materials: covalent Organic Frameworks (COFs) consisting purely of organic materials, and metal-organic frameworks (MOFs) consisting of metal cations alone or of clusters of cations interconnected by polyfunctional organic molecules. Both types may be suitably used in the present invention.

Preferably, the sorption agent used in step (i) of the present invention preferentially sorbs the heteroatom-containing organic compound and optionally the aromatic hydrocarbon and does not or substantially not sorb the layered solvent b) and the extraction solvent a), thereby ultimately improving the quality of the recycled stream of the layered solvent b) and the recycled stream of the extraction solvent a). Preferred sorbent reagents in step (i) include zeolites such as ZSM-12, silicalite and/or MCM-22.

Preferably, the sorption agent used in step (ii) of the present invention preferentially sorbs the heteroatom-containing organic compound and aromatic hydrocarbon and does not or substantially not sorb the layered solvent b), thereby ultimately improving the quality of the recycled stream of layered solvent b). Preferred sorbent materials in step (ii) include activated carbon.

The temperature in step (i) and step (ii) may be in the range of from ambient temperature to about 160 ℃, preferably 40 ℃ to 90 ℃, more preferably 40 ℃ to 60 ℃. In step (i) and step (ii) of the present invention, the pressure is not critical to the performance of the sorbent, and it may vary from atmospheric to 100 bar.

The heteroatom-containing organic compounds and optional aromatic hydrocarbons accumulate in the sorbent material, thereby producing a "spent sorbent". As known in the art, the sorbent eventually needs to be replaced or regenerated. In either case, the corresponding container containing spent sorbent will be out of service. In the case of regeneration, the spent sorbent is contacted with a stream free of heteroatom-containing organic compounds and optionally aromatic hydrocarbons. Preferably, the stream is heated to promote desorption of the heteroatom-containing organic compound and optionally aromatic hydrocarbon. The regeneration stream may be a gas, a liquid, or a supercritical fluid. It may be inert, such as nitrogen, or reactive, such as hydrogen, oxygen and hydrogen peroxide. Depending on the regeneration method, the regeneration temperature is in the range of 20 ℃ to 350 ℃. Regeneration of the sorbent material may be performed by stripping with a stream of material, such as steam or nitrogen, or by heating the sorbent in air to burn off the sorbed material. Alternatively, in the event that the sorbent material used in the present invention cannot be fully regenerated, it must be discarded when its sorbent capacity is reached.

Recycle step

In step d) of the process, at least a portion of the extraction solvent a) from the second stream produced in step c) is recycled to step a).

The second stream resulting from step c) may also comprise aromatic hydrocarbons and/or heteroatom-containing organic compounds. In case the stream comprising extraction solvent a) to be recycled to step a) comprises relatively large amounts of such compounds, an additional layering solvent b) may be added to step b) in order to prevent any accumulation of these contaminants in such recycled stream recycled to step a). Furthermore, these contaminants may be removed by discharging a portion of the stream comprising the extraction solvent a) to be recycled to step a) before recycling the extraction solvent a) to step a), wherein such discharged stream may be discarded or the extraction solvent a may be recovered from such discharged stream, for example by distillation of such discharged stream.

Furthermore, in optional step e) of the present process, at least a portion of the layered solvent b) from the first stream produced in step c) is recycled to step b). In case of performing the sorption step (ii) in the present process, at least a portion of the layered solvent b) from the treated stream resulting from the sorption step (ii) may be recycled in step e) to step b).

This subsequent recycling to step b) in step e) is suitable in case the first stream resulting from step c) or the treated stream resulting from the sorption step (ii) still comprises relatively large amounts of heteroatom-containing organic compounds and/or aromatic hydrocarbons originating from the liquid hydrocarbon feed stream. However, in case such a stream does not or substantially does not contain or contains relatively small amounts of heteroatom-containing organic compounds and/or aromatic hydrocarbons, which is advantageously achieved by the sorption step in the present process, it is preferred that at least a portion of the layered solvent b) is recycled from such a stream to step a) in case a washing solvent c), such as water, is added to step a) as described above, or to the following optional additional extraction step, in which such a washing solvent c) is added.

Separating extraction solvent a) from the raffinate stream

In the case where the stream (raffinate stream) comprising recovered aliphatic hydrocarbons resulting from the liquid-liquid extraction of extraction solvent a) in step a) also comprises extraction solvent a), it is preferred that extraction solvent a) is separated from the stream as the first stream resulting from step a) and optionally recycled to step a). In this way, the recovered aliphatic hydrocarbon is advantageously separated from any extraction solvent a) in the raffinate stream described above, and the separated extraction solvent a) may advantageously be recycled to step a).

The extraction solvent a) may be separated from the above-described first stream resulting from step a) by any means, including distillation, extraction, absorption and membrane separation, wherein the stream comprises aliphatic hydrocarbons and the extraction solvent a).

In particular, in the above case where the first stream produced from step a) comprises aliphatic hydrocarbons and extraction solvent a), in an additional step at least a portion of said first stream is contacted with washing solvent c) and this at least a portion is subjected to liquid-liquid extraction with washing solvent c), thereby producing a first stream comprising aliphatic hydrocarbons and a second stream comprising washing solvent c) and extraction solvent a).

In the present invention, the optional washing solvent c) may be the same or different, preferably the same, as the layering solvent b), which may be used for the additional extraction step described above, or may be added separately to step a), or may be added to step a) together with the extraction solvent a) in the stream. The preferred requirements and embodiments described above with reference to the delamination solvent b) also apply to the optional washing solvent c). Preferably, the washing solvent c) comprises water, more preferably consists of water. Furthermore, preferably, both the layering solvent b) and the washing solvent c) comprise water, more preferably consist of water.

In the additional step described above, the first stream produced by step a) and comprising aliphatic hydrocarbons and extraction solvent a) may be fed to a second column (second extraction column). Furthermore, a second solvent stream comprising washing solvent c) may be fed to the second column at a higher position than the position fed by said first stream produced by step a), thereby enabling countercurrent liquid-liquid extraction and producing a top stream from the second column comprising aliphatic hydrocarbons (the "first stream" described above) and a bottom stream from the second column comprising washing solvent c) and extraction solvent a) (the "second stream" described above).

Thus, advantageously, said washing solvent c) added in the additional step described above acts as an extraction solvent for extracting the extraction solvent a), thereby advantageously making it possible for no or substantially no extraction solvent a) to be eventually present in the recovered aliphatic hydrocarbon. In the additional step described above, the weight ratio of extraction solvent a) to washing solvent c) may be at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, and may be at most 30:1, or at most 25:1, or at most 20:1, or at most 15:1, or at most 10:1, or at most 5:1, or at most 3:1, or at most 2:1. Furthermore, the above description of the temperature and pressure in extraction step a) also applies to the additional (extraction) step described above. In the case where the process comprises the additional step described above, the first solvent stream in extraction step a) may comprise a layering solvent b) in addition to the extraction solvent a), in which case the bottom stream from the first extraction column also comprises a layering solvent b).

In the above-described additional step of adding the washing solvent c), it is preferred that the stream comprising the washing solvent c) to be added does not comprise or substantially does not comprise heteroatom-containing organic compounds derived from the liquid hydrocarbon feed stream. This preferred requirement is particularly applicable where the stream is fed to the second extraction column at a relatively high location as described above, where these heteroatom-containing organic compounds may again contaminate the raffinate (overhead) stream. Advantageously, in the present invention, at least a portion of the first stream produced by step c) and comprising the layering solvent b) and optionally the washing solvent c), and, in the case of carrying out the sorption step (ii) in the present process, at least a portion of the treated streams produced by the sorption step (ii), which streams may contain no or substantially no heteroatom-containing organic compounds originating from the liquid hydrocarbon feed stream, may be used as such a stream of washing solvent c) for feeding (recycling) to said additional step, in particular in the case that layering solvent b) is identical to washing solvent c), in particular water.

Furthermore, at least part of the second stream comprising washing solvent c) and extraction solvent a) resulting from the additional (extraction) step described above may be fed to step b) to provide at least part of the layering solvent b) that needs to be added in step b), especially if layering solvent b) is identical to washing solvent c). Advantageously, therefore, such a washing solvent c) can act both as extraction solvent for extraction solvent a) in said additional step and as so-called "delamination agent" (or "anti-solvent") in step b), i.e. as delamination solvent b), as discussed further above.

In the case where a washing solvent other than water is fed to the extraction column for extracting the extraction solvent a) used in step a), whether in the additional step described above or in step a) itself as described above, it may be preferable to feed water to the extraction column at a position higher than the position at which such other solvent is fed, in addition to such other solvent. In this way, advantageously, water fed at a higher location can extract any wash solvent other than water, thereby preventing such other wash solvent from entering the (final) raffinate stream. Alternatively, the latter raffinate stream may be washed with water in a separate step.

Upstream and downstream integration

In the present invention, the liquid hydrocarbon feedstream may comprise at least a portion of the hydrocarbon products formed in a process comprising cracking plastics, preferably waste plastics, more preferably mixed waste plastics, wherein at least a portion of these plastics comprise heteroatom-containing organic compounds.

The invention therefore also relates to a process for recovering aliphatic hydrocarbons from plastics, at least a portion of which comprises organic compounds containing heteroatoms, comprising the steps of:

The preferred requirements and embodiments described above with reference to the aliphatic hydrocarbon recovery process of the present invention are equally applicable to step (II) of the process for recovering aliphatic hydrocarbons from plastics of the present invention. In step (I) above, the hydrocarbon product obtained may be a liquid, or a solid or wax. In the latter case, the solid or wax is first heated to make it liquid and then subjected to the aliphatic hydrocarbon recovery process in step (II).

In the above process, at least a portion of the plastics fed to step (I) comprise heteroatom-containing organic compounds, these plastics preferably being waste plastics, more preferably mixed waste plastics. In said step (I), the cracking of the plastic may involve a thermal cracking process and/or a catalytic cracking process. The cracking temperature in step (I) may be from 300 ℃ to 800 ℃, suitably from 400 ℃ to 800 ℃, more suitably from 400 ℃ to 700 ℃, more suitably from 500 ℃ to 600 ℃. In addition, any pressure may be applied, which may be subatmospheric, atmospheric or superatmospheric. The heat treatment in step (I) causes the plastic to melt and crack its molecules into smaller molecules. The cracking in step (I) may be carried out as pyrolysis or as liquefaction. A continuous liquid phase is formed during both pyrolysis and liquefaction. Furthermore, a discontinuous gas phase is formed in the pyrolysis, which escapes from the liquid phase and separates into a continuous gas phase. In liquefaction, there is no significant gas phase because of the relatively high pressure applied.

Furthermore, in step (I), subsequent gas phase condensation and/or liquid phase cooling provides a hydrocarbon product, which may be liquid, or solid or wax, and which comprises aliphatic hydrocarbons, heteroatom-containing organic compounds and optionally aromatic hydrocarbons, at least a portion of which is subjected to the above-described aliphatic hydrocarbon recovery process in step (II).

The above step (I) may be carried out in any known manner, for example as disclosed in the above-mentioned WO2018069794 and WO2017168165, the disclosures of which are incorporated herein by reference.

Advantageously, the aliphatic hydrocarbons recovered in one of the above described processes for recovering aliphatic hydrocarbons, which may comprise different amounts of aliphatic hydrocarbons over a wide boiling point range, may be fed to the steam cracker without further pretreatment, such as with hydrogen treatment (hydrotreating or hydrotreating), as disclosed in WO2018069794 above. In addition to being used as a feed to a steam cracker, the recovered aliphatic hydrocarbons may also be advantageously fed to other refinery processes including hydrocracking, isomerisation, hydrotreating, thermocatalytic cracking and fluid catalytic cracking. Furthermore, in addition to being used as a feed to a steam cracker, the recovered aliphatic hydrocarbons may also be advantageously separated into different fractions, each of which may have different applications, such as diesel, marine fuel, solvents, etc.

Accordingly, the present invention also relates to a process for steam cracking a hydrocarbon feed comprising aliphatic hydrocarbons recovered in one of the above processes for recovering aliphatic hydrocarbons. In addition, the present invention is therefore also directed to a process for steam cracking a hydrocarbon feed comprising the steps of: recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream in one of the above-described processes for recovering aliphatic hydrocarbons; and steam cracking the hydrocarbon feed comprising the aliphatic hydrocarbons recovered in the previous step. In the present specification, the phrase "steam cracking a hydrocarbon feed comprising aliphatic hydrocarbons recovered in the previous step" may refer to "steam cracking a hydrocarbon feed comprising at least a portion of the recovered aliphatic hydrocarbons". In addition to the process for recovering aliphatic hydrocarbons of the present invention, the hydrocarbon feed to the steam cracking process may also contain hydrocarbons from another source. Such other sources may be naphtha, wax oil or a combination thereof.

Advantageously, where the liquid hydrocarbon feedstream comprises aromatic hydrocarbons (especially polycyclic aromatic compounds), heteroatom-containing organic compounds, conjugated aliphatic compounds having two or more carbon-carbon double bonds, or combinations thereof, these contained compounds have been removed by the aliphatic hydrocarbon recovery process of the present invention as described above prior to feeding the recovered hydrocarbons to the steam cracking process. This is particularly advantageous because the removed compounds, especially polycyclic aromatic compounds, no longer cause fouling in the preheating, convection and radiation sections of the steam cracker and downstream heat exchange and/or separation equipment of the steam cracker, for example in an in-line heat exchanger (transfer line exchanger, TLE) for rapid cooling of the effluent from the steam cracker. As hydrocarbons condense, they can thermally decompose into a coke layer that can cause fouling. This fouling is a major factor in determining the length of time the cracker is operated. Reducing the amount of fouling extends the run time without maintenance downtime and improves heat transfer in the heat exchanger.

Steam cracking may be performed in any known manner. The hydrocarbon feed is typically preheated. The feed may be heated using a heat exchanger, a furnace, or any other combination of heat transfer and/or heating devices. The feedstock is steam cracked in a cracking zone under cracking conditions to produce at least olefins (including ethylene) and hydrogen. The cracking zone may comprise any cracking system known in the art as being suitable for cracking a feedstock. The cracking zone may include one or more heating furnaces, each dedicated to a particular feed or fraction of the feed.

The cracking is carried out at elevated temperature, preferably at a temperature in the range of 650 ℃ to 1000 ℃, more preferably 700 ℃ to 900 ℃, most preferably 750 ℃ to 850 ℃. Steam is typically added to the cracking zone to act as a diluent to reduce the hydrocarbon partial pressure and thereby increase the olefin yield. The steam also reduces the formation and deposition of carbonaceous material or coke in the cracking zone. Cracking occurs in the absence of oxygen. The residence time under cracking conditions is very short, typically in the order of milliseconds.

A cracker effluent is obtained from the cracker, which may comprise aromatics (as produced in a steam cracking process), olefins, hydrogen, water, carbon dioxide, and other hydrocarbon compounds. The specific product obtained depends on the composition of the feed, the hydrocarbon to steam ratio, the cracking temperature and the in-furnace residence time. The cracked product from the steam cracker is then passed through one or more heat exchangers, commonly referred to as TLE ("in-line heat exchangers"), to rapidly reduce the temperature of the cracked product. TLE preferably cools the cracked product to a temperature in the range of 400 ℃ to 550 ℃.

Drawings

Figures 1 and 2 further illustrate the process of the present invention for recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream.

In the process of fig. 1, the following streams are fed to extraction column 4: a liquid hydrocarbon feedstream 1 comprising aliphatic hydrocarbons (including conjugated aliphatic compounds having two or more carbon-carbon double bonds, hereinafter referred to as "dienes"), aromatic hydrocarbons, and heteroatom-containing organic compounds; a first solvent stream 2 comprising an organic solvent (e.g., N-methylpyrrolidone) as extraction solvent a) according to the invention; and a second solvent stream 3 comprising water as optional washing solvent c) according to the invention. In column 4, liquid hydrocarbon feed stream 1 is contacted with first solvent stream 2 (organic solvent) to recover aliphatic hydrocarbons by liquid-liquid extraction of dienes, aromatic hydrocarbons, and heteroatom-containing organic compounds with the organic solvent. In addition, the water in the second solvent stream 3 removes the organic solvent from the upper portion of column 4 by liquid-liquid extraction of the organic solvent with water. Stream 5 comprising recovered aliphatic hydrocarbons leaves column 4 at the top of the column. In addition, stream 6, which comprises organic solvent, water, dienes, aromatic hydrocarbons and organic compounds containing heteroatoms, leaves column 4 at the bottom of the column. Stream 6 and stream 14 comprising additional water (which is the layering solvent b) according to the invention) are combined, and the combined stream is fed to decanter 13. In decanter 13, the combined stream is separated into a stream 15 comprising dienes, aromatic hydrocarbons and organic compounds containing heteroatoms and a stream 16 comprising organic solvents, water, dienes, aromatic hydrocarbons and organic compounds containing heteroatoms.

Further, in the process of fig. 1, stream 16 may be fed to a sorption unit 10 containing a sorption agent that removes dienes, aromatic hydrocarbons, and heteroatom-containing organic compounds. The treated stream 11 from the adsorption unit 10 comprises an organic solvent and water. Stream 16 or treated stream 11 is fed to distillation column 7 where it is separated into a top stream 8 comprising water and a bottom stream 9 comprising organic solvent. In the case of stream 16 being fed to distillation column 7, top stream 8 also comprises dienes, aromatic hydrocarbons and heteroatom-containing organic compounds and is fed to a sorption unit 12 containing a sorption agent that removes the dienes, aromatic hydrocarbons and heteroatom-containing organic compounds. The treated stream 17 from the adsorption unit 12 comprises water, a portion of which stream (stream 17 a) is returned to the distillation column 7 as reflux stream, while another portion (stream 17 b) may be recycled via stream 14 and/or stream 3. In the case of feeding the treated stream 11 to the distillation column 7, the overhead stream 8 may be fed to a sorption unit 12. If in the latter case the top stream 8 is not fed to the sorption unit 12, a part of the top stream 8 (stream 17 a) is fed back to the distillation column 7 as reflux stream, while another part (stream 17 b) can be recycled via stream 14 and/or stream 3. The organic solvent from bottoms stream 9 is recycled via organic solvent stream 2.

In the process of fig. 2, the following streams are fed to a first extraction column 4a: a liquid hydrocarbon feedstream 1 comprising aliphatic hydrocarbons (including conjugated aliphatic compounds having two or more carbon-carbon double bonds, hereinafter referred to as "dienes"), aromatic hydrocarbons, and heteroatom-containing organic compounds; and a first solvent stream 2 comprising an organic solvent (e.g., N-methylpyrrolidone), wherein the organic solvent serves as extraction solvent a) according to the invention. In column 4a, liquid hydrocarbon feed stream 1 is contacted with a first solvent stream 2 (organic solvent) to recover aliphatic hydrocarbons by liquid-liquid extraction of dienes, aromatic hydrocarbons, and heteroatom-containing organic compounds with the organic solvent, thereby producing an overhead stream 5a comprising recovered aliphatic hydrocarbons and organic solvent and a bottom stream 6 comprising organic solvent, dienes, aromatic hydrocarbons, and heteroatom-containing organic compounds. Stream 5a and a second solvent stream 3 comprising water as optional scrubbing solvent c) according to the invention are fed to a second extraction column 4b. In column 4b, stream 5a is contacted with a second solvent stream 3 (water) to remove the organic solvent by liquid-liquid extraction with water. Stream 5b comprising recovered aliphatic hydrocarbons leaves column 4b at the top of the column. In addition, stream 14, which comprises organic solvent and water as the delamination solvent b according to the invention, leaves column 4b at the bottom of the column. Stream 6 and stream 14 are combined and the combined stream is fed to decanter 13. Regarding the processing in the decanter 13 and further downstream processing in the method of fig. 2, reference is made to the description above of the corresponding processing in the method of fig. 1.

Claims

1. A process for recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream comprising aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons, the process comprising the steps of:

a) Contacting at least a portion of the liquid hydrocarbon feed stream with an extraction solvent a) containing one or more heteroatoms and subjecting the liquid hydrocarbon feed stream to liquid-liquid extraction with the extraction solvent a) to produce a first stream comprising aliphatic hydrocarbons and an extraction solvent comprising

a) A second stream of organic compounds containing heteroatoms and optionally aromatic hydrocarbons;

b) Mixing at least a portion of the second stream resulting from step a) with a layering solvent b) and separating the resulting mixture into a first stream comprising heteroatom-containing organic compounds and optionally aromatic hydrocarbons and a second stream comprising extraction solvent a), layering solvent b), heteroatom-containing organic compounds and optionally aromatic hydrocarbons, wherein the layering solvent contains one or more heteroatoms and the miscibility in heptane is lower than that of extraction solvent a);

c) Separating at least part of the second stream resulting from step b) into a first stream comprising a layering solvent b), optionally a heteroatom-containing organic compound and optionally an aromatic hydrocarbon and a second stream comprising an extraction solvent a);

wherein:

(i) Removing heteroatom-containing organic compounds and optionally aromatic hydrocarbons from the second stream produced by step b) by contacting at least a portion of the second stream with a sorbent agent prior to step c); and/or

2. The method of claim 1, wherein step c) comprises:

separating at least part of the second stream resulting from step b) by distillation into a top stream comprising the layered solvent b), optionally heteroatom-containing organic compounds and optionally aromatic hydrocarbons and a bottom stream comprising the extraction solvent a), and

Wherein:

(i) Removing heteroatom-containing organic compounds and optionally aromatic hydrocarbons from the second stream produced by step b) by contacting at least a portion of the second stream with a sorbent agent, and feeding at least a portion of the treated stream produced by step (i) to step c); and/or

(ii) The top stream resulting from step c) comprises the layering solvent b), the heteroatom-containing organic compound and optionally an aromatic hydrocarbon, and heteroatom-containing organic compound and optionally an aromatic hydrocarbon are removed from the top stream by contacting at least a portion of the top stream with a sorbent agent.

3. The method according to claim 1 or 2, wherein:

the extraction solvent a) has the following formulaAt least 5MPa ^1/2 Preferably at least 10MPa ^1/2 R of (2) _{a, heptane} And the delamination solvent b) has a pressure of at least 20MPa ^1/2 Preferably at least 30MPa ^1/2 R of (2) _{a, heptane} Wherein R is _{a, heptane} Refers to the hansen solubility parameter distance relative to heptane measured at 25 ℃; and is also provided with

The R of the delamination solvent b) _{a, heptane} Said R being greater than said extraction solvent a) _{a, heptane} Wherein R of the solvent a) and the solvent b) _{a, heptane} Is at least 1MPa ^1/2 Preferably at least 5MPa ^1/2 More preferably at least 10MPa ^1/2 More preferably at least 15MPa ^1/2 。

4. A process according to any one of claims 1 to 3, wherein the extraction solvent a) comprises ammonia or preferably one or more organic solvents selected from the group consisting of: diols and triols including monoethylene glycol (MEG), monopropylene glycol (MPG), any isomer of butanediol and glycerol; glycol ethers including oligoethylene glycols including diethylene glycol, triethylene glycol, and tetraethylene glycol, and monoalkyl ethers thereof including diethylene glycol diethyl ether; amides, including N-alkylpyrrolidones, wherein the alkyl groups can contain from 1 to 8 or 1 to 3 carbon atoms, and including formamide, dialkylformamide and acetamide, and monoalkylformamide and acetamide, wherein the alkyl groups can contain from 1 to 8 or 1 to 3 carbon atoms, including N-methylpyrrolidone (NMP), and dialkylformamide and acetamide, and monoalkylformamide and acetamide, including Dimethylformamide (DMF), methylformamide and dimethylacetamide; a dialkyl sulfoxide, wherein the alkyl group can contain 1 to 8 or 1 to 3 carbon atoms, including dimethyl sulfoxide (DMSO); sulfones, including sulfolane; n-formyl morpholine (NFM); furan ring-containing components and derivatives thereof, including furfural, 2-methyl-furan, furfuryl alcohol, and tetrahydrofurfuryl alcohol; hydroxy esters, including lactic acid esters, including methyl lactate and ethyl lactate; trialkyl phosphates including triethyl phosphate; phenolic compounds including phenol and guaiacol; benzyl alcohol-based compounds, including benzyl alcohol; amine compounds including ethylenediamine, monoethanolamine, diethanolamine, and triethanolamine; nitrile compounds including acetonitrile and propionitrile; trioxane compounds including 1,3, 5-trioxane; carbonate compounds including propylene carbonate and glycerol carbonate; and cycloalkanone compounds including dihydro-l-glucosone.

5. The process according to any one of claims 1 to 4, wherein the layered solvent b) comprises one or more solvents selected from water and the solvents of the group of solvents as defined for extraction solvent a) in claim 4, and wherein the layered solvent b) preferably comprises water.

6. The method of any one of claims 1 to 5, wherein:

adding a washing solvent c) to step a) thereby producing a first stream comprising aliphatic hydrocarbons and a second stream comprising washing solvent c), extraction solvent a), heteroatom-containing organic compounds and optionally aromatic hydrocarbons; or alternatively

The first stream resulting from step a) comprises aliphatic hydrocarbons and an extraction solvent a), at least a portion of the first stream is contacted with a wash solvent c), and at least a portion of the first stream is subjected to liquid-liquid extraction with the wash solvent c), thereby producing a first stream comprising aliphatic hydrocarbons and a second stream comprising wash solvent c) and extraction solvent a).

7. The process according to claim 6, wherein the washing solvent c) is the same or different, preferably the same, as the layering solvent b), and the washing solvent c) preferably comprises water.

8. A process for recovering aliphatic hydrocarbons from a plastic, wherein at least a portion of the plastic comprises a heteroatom-containing organic compound, the process comprising the steps of:

(I) Cracking the plastic and recovering hydrocarbon products comprising aliphatic hydrocarbons, heteroatom-containing organic compounds, and optionally aromatic hydrocarbons; and

(II) performing the process according to any one of claims 1 to 7 on a liquid hydrocarbon feedstream comprising at least a portion of the hydrocarbon product obtained in step (I).

9. A process for steam cracking a hydrocarbon feed, wherein the hydrocarbon feed comprises aliphatic hydrocarbons recovered in the process according to any one of claims 1 to 8.

10. A process for steam cracking a hydrocarbon feed, the process comprising the steps of:

recovering aliphatic hydrocarbons from a liquid hydrocarbon feedstream in the process according to any one of claims 1 to 8; and

steam cracking a hydrocarbon feed comprising aliphatic hydrocarbons recovered in a previous step.