CN117580929A

CN117580929A - Chemical recovery facility and method with enhanced integration

Info

Publication number: CN117580929A
Application number: CN202280046120.8A
Authority: CN
Inventors: 武显春; 达里尔·贝汀; 肯尼·伦道夫·帕克; 迈克尔·加里·波拉塞克; 大卫·尤金·斯莱文斯基
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2021-06-30
Filing date: 2022-06-24
Publication date: 2024-02-20
Also published as: EP4363523A1; WO2023278261A1

Abstract

Methods and apparatus for providing a recovered component hydrocarbon product (r-product) from a recovered component pyrolysis oil (r-pyrolysis oil) and a recovered component pyrolysis gas (r-pyrolysis gas). The treatment schemes provided herein maximize the use of the recycled component pyrolysis products to provide a variety of recycled component end products.

Description

Chemical recovery facility and method with enhanced integration

Background

Pyrolysis of waste plastics plays a role in a variety of chemical recycling techniques. Pyrolysis of waste plastics produces heavy components (e.g., wax, tar, and char) and recovered component pyrolysis oil (r-pyrolysis oil) and recovered component pyrolysis gas (r-pyrolysis gas). When the pyrolysis facility is located near another processing facility (e.g., cracker facility), it is desirable to send as much r-pyrolysis oil and r-pyrolysis gas as possible to downstream processing facilities for use as feedstock to form other recovered component products (e.g., olefins, paraffins, etc.).

However, in some cases, particularly when it is part of an existing infrastructure, a single downstream processing facility may not be configured to receive both r-pyrolysis oil and r-pyrolysis gas, or may not be configured to receive the entire volume of r-pyrolysis oil and/or r-pyrolysis gas produced by the pyrolysis facility. In this case, it may be cost effective to burn or otherwise dispose of r-pyrolysis oil as fuel, but this is contrary to one of the main objectives of chemical recovery, which is to convert as much waste plastic as possible into a new product. Thus, there is a need to provide a treatment scheme that provides better utilization of r-pyrolysis oil and r-pyrolysis gas formed from pyrolysis of waste plastics.

Disclosure of Invention

In one aspect, the present technology relates to a chemical recovery process comprising: (a) Pyrolyzing the waste plastics to provide a recycle component pyrolysis effluent (r-pyrolysis effluent); (b) Separating at least a portion of the r-pyrolysis effluent to provide a recovered component pyrolysis gas (r-pyrolysis gas) and a recovered component pyrolysis oil (r-pyrolysis oil); (c) Introducing at least a portion of the r-pyrolysis gas into a cracker facility; and (d) introducing at least a portion of the r-pyrolysis oil to another downstream location, wherein the downstream location is not within a cracker facility.

In one aspect, the present technology relates to a chemical recovery process comprising: (a) Pyrolyzing the waste plastics to provide a recycle component pyrolysis effluent (r-pyrolysis effluent); (b) Separating at least a portion of the r-pyrolysis effluent to provide a recovered component pyrolysis gas (r-pyrolysis gas) and a recovered component pyrolysis oil (r-pyrolysis oil); and (c) introducing at least a portion of the r-pyrolysis oil into (i) a storage vessel at one or more of the following locations (i) to (x); (ii) a delivery device; (iii) a fluid catalytic cracker; (iv) a carbon reformer; (v) a distillation column or distillation zone; (vi) fine chemical facilities; (vii) a burner; (viii) an MTO facility; and (ix) a refinery.

Drawings

FIG. 1 is a flow diagram illustrating the major steps of a method and facility for utilizing a recovered constituent pyrolysis gas (r-pyrolysis gas) and a recovered constituent pyrolysis oil (r-pyrolysis oil) formed by pyrolysis of waste plastics in one or more downstream processing facilities.

Detailed Description

We have discovered a novel method and system for utilizing recycled component pyrolysis gas (r-pyrolysis gas) and recycled component pyrolysis oil (r-pyrolysis oil). In particular, we have found that r-pyrolysis gas can be directed to a cracker facility, and that r-pyrolysis oil can be used in a processing facility other than the cracker facility. As a result, maximum utilization of both r-pyrolysis gas and r-pyrolysis oil can be achieved regardless of the configuration of the cracking or other downstream processing facilities.

FIG. 1 illustrates one embodiment of a method and system for chemical recycling of waste plastic. The process/facility shown in fig. 1 includes a pyrolysis step/facility 20 and a cracking step/facility 40, and the pyrolysis facility 20 and the cracker facility 40 may co-operate or may be located remotely from each other. As used herein, the term "co-operate with" refers to a characteristic of at least two objects being located on a common physical site and/or within 0.5 or 1 mile of each other. As used herein, the term "remotely located" refers to a distance between two facilities, sites, or reactors that is greater than 1 mile, greater than 5 miles, greater than 10 miles, greater than 50 miles, greater than 100 miles, greater than 500 miles, greater than 1000 miles, or greater than 10,000 miles.

When two or more facilities co-operate together, the facilities may be integrated in one or more ways. Examples of integration include, but are not limited to, heat integration, utility integration, wastewater integration, mass flow integration via pipes, office space, cafeterias, factory management, IT departments, maintenance departments, and common utility and component (e.g., seals, gaskets, etc.) integration.

In some embodiments, the pyrolysis facility/process 20 is a commercial scale facility/process that receives the waste plastic feedstock 110 at an average annual feed rate of at least 100, or at least 500, or at least 1,000, at least 2,000, at least 5,000, at least 10,000, at least 50,000, or at least 100,000 pounds per hour on average over a year. Further, the pyrolysis facility may produce r-pyrolysis oil 114 and r-pyrolysis gas 116 in combination at an average annual rate of at least 100, or at least 1,000, or at least 5,000, at least 10,000, at least 50,000, or at least 75,000 pounds per hour on average over a year.

Similarly, cracker facility/process 40 can be a commercial scale facility/process that receives hydrocarbon feed 120 at an average annual feed rate of at least 100, or at least 500, or at least 1,000, at least 2,000, at least 5,000, at least 10,000, at least 50,000, or at least 75,000 pounds per hour on average over a year. Further, the cracker facility can produce at least one recovered component product stream (r-product) at an average annual rate of at least 100, or at least 1,000, or at least 5,000, at least 10,000, at least 50,000, or at least 75,000 pounds per hour on average over a year. When more than one r-product stream is produced, these rates may be applied to the combined rates of all r-products.

As shown in fig. 1, the process begins with a pyrolysis step wherein waste plastics 110 are pyrolyzed in a pyrolysis reactor 22. The pyrolysis reaction includes chemical decomposition and thermal decomposition of the classified waste plastics introduced into the reactor 22. While all pyrolysis processes may generally be characterized by a substantially oxygen-free reaction environment, the pyrolysis process may be further defined by, for example, a pyrolysis reaction temperature within the reactor, a residence time in the pyrolysis reactor, a reactor type, a pressure within the pyrolysis reactor, and the presence or absence of a pyrolysis catalyst.

The pyrolysis reactor 22 shown in fig. 1 may be, for example, a membrane reactor, a screw extruder, a tubular reactor, a tank, a stirred tank reactor, a riser reactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, a vacuum reactor, a microwave reactor, or an autoclave.

The pyrolysis reaction may include heating and converting the waste plastic feedstock in a substantially oxygen-free atmosphere or in an atmosphere containing less oxygen relative to ambient air. For example, the atmosphere within pyrolysis reactor 22 may contain no more than 5 wt.%, no more than 4 wt.%, no more than 3 wt.%, no more than 2 wt.%, no more than 1 wt.%, or no more than 0.5 wt.% oxygen.

The temperature in pyrolysis reactor 22 may be adjusted to facilitate the production of certain end products. In some embodiments, the peak pyrolysis temperature in the pyrolysis reactor may be at least 325 ℃, or at least 350 ℃, or at least 375 ℃, or at least 400 ℃. Additionally or alternatively, the peak pyrolysis temperature in the pyrolysis reactor may be no more than 800 ℃, no more than 700 ℃, or no more than 650 ℃, or no more than 600 ℃, or no more than 550 ℃, or no more than 525 ℃, or no more than 500 ℃, or no more than 475 ℃, or no more than 450 ℃, or no more than 425 ℃, or no more than 400 ℃. More particularly, the peak pyrolysis temperature in the pyrolysis reactor may be in the range of 325 ℃ to 800 ℃, or 350 ℃ to 600 ℃, or 375 ℃ to 500 ℃, or 390 ℃ to 450 ℃, or 400 ℃ to 500 ℃.

The residence time of the feedstock within pyrolysis reactor 22 may be at least 1, or at least 5, or at least 10, or at least 20, or at least 30, or at least 60, or at least 180 seconds. Additionally or alternatively, the residence time of the feedstock within pyrolysis reactor 22 may be less than 2, or less than 1, or less than 0.5, or less than 0.25, or less than 0.1 hours. More particularly, the residence time of the feedstock within pyrolysis reactor 22 may range from 1 second to 1 hour, or from 10 seconds to 30 minutes, or from 30 seconds to 10 minutes.

Pyrolysis reactor 22 may be maintained at a pressure of at least 0.1, or at least 0.2, or at least 0.3 bar and/or no more than 60, or no more than 50, or no more than 40, or no more than 30, or no more than 20, or no more than 10, or no more than 8, or no more than 5, or no more than 2, or no more than 1.5, or no more than 1.1 bar. The pressure within pyrolysis reactor 22 may be maintained at atmospheric pressure or in the range of 0.1 to 60, or 0.2 to 10, or 0.3 to 1.5 bar.

The pyrolysis reaction in the reactor may be pyrolysis performed in the absence of a catalyst or catalytic pyrolysis performed in the presence of a catalyst. When a catalyst is used, the catalyst may be homogeneous or heterogeneous and may include, for example, certain types of zeolites and other mesostructured catalysts.

As shown in FIG. 1, pyrolysis effluent 112 is removed from reactor 22 and may be separated in separator 24 to produce a recovered component pyrolysis oil (r-pyrolysis oil) 114, a recovered component pyrolysis gas (r-pyrolysis gas) 116, and a recovered component pyrolysis residue (r-pyrolysis residue) 118. As used herein, the term "r-pyrolysis gas" refers to a composition obtained from pyrolysis of waste plastics that is gaseous at 25 ℃ at 1 atm. As used herein, the term "r-pyrolysis oil" refers to a composition obtained from pyrolysis of waste plastics that is liquid at 25 ℃ and 1 atm. As used herein, the term "r-pyrolysis residue" refers to a composition obtained from pyrolysis of waste plastics, which is not r-pyrolysis gas or r-pyrolysis oil, and mainly comprises pyrolytic carbon and pyrolytic heavy wax. As used herein, the term "pyrolytic carbon" refers to a carbonaceous composition obtained from pyrolysis that is solid at 200 ℃ and 1 atm. As used herein, the term "pyrolysis heavy wax" refers to c20+ hydrocarbons obtained from pyrolysis that are not pyrolytic carbon, pyrolysis gas, or pyrolysis oil.

In some embodiments, the r-pyrolysis gas comprises C2 and/or C3 components in amounts of 5wt% to 60wt%, 10wt% to 50wt%, or 15wt% to 45wt%, C4 components in amounts of 1wt% to 60wt%, 5wt% to 50wt%, or 10wt% to 45wt%, and C5 components in amounts of 1wt% to 25wt%, 3wt% to 20wt%, or 5wt% to 15wt%, respectively.

In some embodiments, the r-pyrolysis oil comprises at least 50wt%, at least 75wt%, at least 90wt%, or at least 95wt% of C4 to C30, C5 to C25, C5 to C22, or C5 to C20 hydrocarbon components. The r-pyrolysis oil may have a 90% boiling point in the range of 150 ℃ to 350 ℃, 200 ℃ to 295 ℃, 225 ℃ to 290 ℃, or 230 ℃ to 275 ℃, as used herein, "boiling point" refers to the boiling point of the composition as determined by ASTM D2887-13. Additionally, as used herein, "90% boiling point" refers to the boiling point at which 90% by weight of the composition boils according to ASTM D2887-13.

In some embodiments, the r-pyrolysis oil may comprise heteroatom-containing compounds in an amount of less than 20wt, less than 10wt, less than 5wt, less than 2wt, less than 1wt, or less than 0.5 wt. As used herein, the term "heteroatom-containing" compound includes any compound or polymer containing nitrogen, sulfur, or phosphorus. Any other atom is not considered a "heteroatom" in order to determine the amount of heteroatom, heteroatom compound or heteroatom polymer present in the r-pyrolysis oil. Heteroatom-containing compounds include oxygenated compounds. Typically, when the pyrolysis waste plastics include polyethylene terephthalate (PET) and/or polyvinyl chloride (PVC), such compounds are present in the pyrolysis oil. Thus, little to no PET and/or PVC in the waste plastic 110 results in little to no heteroatom-containing compounds in the pyrolysis oil.

As shown in fig. 1, at least a portion of the r-pyrolysis gas 116 may be introduced into the cracker facility 40, and in some embodiments, at least 50%, at least 75%, at least 90%, or at least 95% of the r-pyrolysis gas 116 from the pyrolysis facility 20 may be introduced into the cracker facility. All or a portion of the r-pyrolysis gas 116 may be introduced to at least one location upstream of the furnace 42. Additionally or alternatively, all or a portion of the r-pyrolysis gas 116 may be introduced to at least one location downstream of the furnace 42.

When introduced to a location downstream of the cracker furnace 42, the r-pyrolysis gas 116 may be introduced into one or more of the following locations: (i) a quench zone 44 that cools and partially condenses the furnace effluent; (ii) A compression zone 46 that compresses a vapor portion of the furnace effluent in two or more compression stages; and (iii) a separation zone 48 that separates the compressed stream into two or more recovered component products (r-products). In some cases, the r-pyrolysis gas 116 may be introduced into only one of these locations, while in other cases, the r-pyrolysis gas 116 may be divided into additional fractions, with each fraction being introduced into a different location. In this case, the fraction of r-pyrolysis gas 116 may be introduced to at least two, three, or all of the locations shown in FIG. 1.

When introduced into the quench zone 44, the r-pyrolysis gas 116 may be introduced into a separation or quench vessel, or into an inlet or effluent of the quench zone 44. In some cases, this may include heating and/or compressing the r-pyrolysis gas 116 such that it has a temperature within about 150 ℃, about 125 ℃ or about 100 ℃ and/or a pressure within about 75, about 50 or about 25psi in the stream or vessel into which the r-pyrolysis gas 116 is introduced.

When introduced into the compression section 46, the r-pyrolysis gas 116 may be introduced upstream of the first compression stage, upstream or downstream of the last compression stage, or upstream of one or more intermediate compression stages.

When introduced into separation zone 48, r-pyrolysis gas 116 can be introduced to the inlet of one or more separation columns (including the first column or the last column) or can be combined with a stream (e.g., a top stream or a bottom stream) withdrawn from one or more separation columns.

When introduced upstream of the furnace 42, the r-pyrolysis gas 116 may be combined with a hydrocarbon feed 120 introduced to the inlet of the cracker furnace 42. The hydrocarbon feed 120 may comprise predominantly C3 to C5 hydrocarbon components, C5 to C22 hydrocarbon components, or C3 to C22 hydrocarbon components, or even predominantly C2 components. The hydrocarbon feed 120 may include recovered components from one or more sources, or it may include non-recovered components. Additionally, in some cases, hydrocarbon feed 120 may not include any recovery components.

As shown in fig. 1, a combined stream comprising r-pyrolysis gas and hydrocarbon feed may be introduced into a cracker furnace 42, where it may be thermally cracked to form lighter hydrocarbon effluents. The effluent stream may then be cooled in quench zone 44 and compressed in compression zone 46. The compressed stream from compression zone 46 can be further separated in separation zone 48 to produce at least one recovered component product (r-product) 122. Examples of recovery component products include, but are not limited to, recovery component ethane (r-ethane), recovery component ethylene (r-ethylene), recovery component propane (r-propane), recovery component propylene (r-propylene), recovery component butane (r-butane), recovery component butene (r-butene), recovery component butadiene (r-butadiene), and recovery component pentane and heavier (r-C5+). In some embodiments, at least a portion of the recovered component stream (e.g., r-ethane or r-propane) may be returned to the inlet of the cracker furnace as a reaction recovery stream.

In some embodiments, the r-pyrolysis gas 116 may be introduced into the cracker facility 40 at multiple locations both upstream and downstream of the cracker furnace 42. In this case, the furnace effluent formed by cracking at least a portion of one of the r-pyrolysis gas fractions may be combined with another r-pyrolysis gas fraction introduced downstream of the cracker furnace 42.

As shown in fig. 1, at least a portion or all of the r-pyrolysis oil may be introduced to a downstream location 50. The downstream location 50 may not be within the cracker facility 40, as shown in FIG. 1. In some embodiments, at least 75wt%, at least 85wt%, at least 90wt%, at least 95wt%, at least 97wt%, or at least 98wt% of the r-pyrolysis oil 114 may not be sent to the cracker facility 40.

The downstream location 50 may include one or more downstream processing, storage, and/or transport facilities adapted to react, separate, store, and/or move at least a portion of the r-pyrolysis oil 114. In some embodiments, the downstream location 50 may include at least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, or all of a storage vessel, a transfer device, a Fluid Catalytic Cracker (FCC), a carbon reformer, a distillation column or zone, a fine chemical facility, a combustor, a methanol-to-olefins (MTO) facility, and a refinery. In some cases, the downstream location 50 may be a cracker facility that is different from the cracker facility 40 into which the r-pyrolysis gas is introduced.

In some embodiments, the downstream location 50 may include a storage and/or transport device. The storage/delivery means may be insulated, cooled and/or pressurized tanks, pipes and/or tubes. The tank may be a stationary tank or a tank located on a rail car, truck, trailer or ship. As used herein, the term "pipe" when applied to a conveying device refers to a pipe for conveying more than 2, more than 5, more than 10, more than 100, more than 1000, or more than 2500 miles of material. This piping to move material from one station to another is different from in-facility piping to move material between co-operating reactors, vessels and facilities.

In some embodiments, downstream location 50 may comprise a refinery. Refineries are multiprocessing facilities that convert crude oil or similar heavy hydrocarbons into lighter hydrocarbon products such as gasoline, diesel, jet fuel, and C4 and lighter hydrocarbons and heavier streams such as gas oil. When a portion of the r-pyrolysis oil 114 is introduced to a refinery, it may undergo one or more processing steps to produce a recovered constituent fuel (r-fuel).

In some embodiments, r-pyrolysis oil introduced to a refinery may be subjected to a cracking step to reduce the molecular weight of hydrocarbon molecules by catalytic and/or thermal cracking. Examples of catalytic crackers include fluid bed or fixed bed catalytic crackers. Cokers are one example of thermal crackers.

Additionally or alternatively, the r-pyrolysis oil may be introduced into a reformer, such as a naphtha reformer, and/or an isomerization unit, wherein the molecular structure of the hydrocarbons may be rearranged, typically in the presence of a catalyst. For example, the paraffin/alkane component of the r-pyrolysis oil may be converted to an alkene/alkene component in a reformer. The resulting recovered component product streams from these units may be used as r-fuels or as blending components to form one or more of the aforementioned r-fuels.

In some embodiments, the r-pyrolysis oil may be introduced into at least one separation vessel, such as a distillation column. The column may be configured to separate various components from the r-pyrolysis oil, and one or more of these components may be used or as r-fuel. Examples of distillation columns in a refinery may include, but are not limited to, crude columns, FCC main fractionators, coker main fractionators, naphtha splitters, and combinations of these.

Examples of r-fuel products from refineries may include, but are not limited to, a recovery component gasoline range fuel (r-gasoline) having a 50% boiling point of 100 ℃ to 250 ℃, a recovery component diesel range fuel (r-diesel) having a 50% boiling point of 250 ℃ to 300 ℃, a recovery component gas oil range fuel (r-gas oil) having a 50% boiling point of 300 ℃ to 400 ℃, a residuum range fuel (r-residuum) having a 50% boiling point of 400 ℃ to 500 ℃, and a recovery component solid product such as bitumen or coke (r-bitumen or r-coke). As used herein with respect to fuels, the term "50% boiling point" refers to the temperature at which 50% of the fuel mixture has evaporated as determined by ASTM D-86.

In some embodiments, the downstream location 50 may include a fine chemical facility for producing starting materials for pharmaceuticals, agrochemicals, pesticides, pigments, and other end products. The fine chemical facility may utilize one or more of amination, condensation, esterification, friedel-Crafts, grignard, halogenation, and/or hydrogenation to provide one or more recovered component fine chemicals (r-chemicals), including one or more of the types listed previously.

In some embodiments, downstream location 50 may comprise a distillation column. The distillation column may be a single distillation column for separating one or more components from the r-pyrolysis oil stream, or it may comprise two or more columns configured in series to form a plurality of recovered component hydrocarbon streams. The distillation column may be present in another type of facility (e.g., a refinery or fine chemical facility) or may be present in a separation facility configured only to form recovered component hydrocarbon products.

In some embodiments, the downstream location 50 may include a burner, such as a burner of a furnace or other energy generation facility. The furnace may be used to generate energy for the pyrolysis facility 20 shown in fig. 1 or for other types of facilities, including, for example, refineries or fine chemical facilities. In other embodiments, when, for example, r-pyrolysis oil is used directly as a fuel source (e.g., a ship or train), the burner may be used to produce energy in a motor or engine.

In some embodiments, the downstream location 50 may include a carbon reformer such that the r-pyrolysis oil 114 may be subjected to carbon reforming to produce a recovered component synthesis gas (r-synthesis gas) and a recovered component hydrogen (r-H) ₂ ). In one embodiment, carbon reforming is partial oxidative gasification with non-recovered liquid or gaseous hydrocarbons and r-pyrolysis oil feed. In some embodiments, carbon reforming may include catalytic reforming, while in other embodiments, carbon reforming may include steam reforming.

As used herein, the term "partial oxidation" refers to the high temperature conversion of a carbonaceous feed to synthesis gas (carbon monoxide, hydrogen and carbon dioxide), wherein the conversion isComplete oxidation of carbon to CO with ratio ₂ The amount of oxygen required is small in stoichiometric amount. The feed to the POX gasification may comprise solids, liquids and/or gases.

In some embodiments, the carbon reforming may include a gasifier, which may include a gas feed gasifier, a liquid feed gasifier, a solid feed gasifier, or a combination thereof. More particularly, carbon reforming may include partial oxidative gasification of a liquid feed. As used herein, "liquid feed partial oxidation gasification" refers to a partial oxidation gasification process wherein the feed to the process consists essentially of components that are liquid at 25 ℃ and 1 atm. Additionally, carbon reforming may include partial oxidative gasification of the gas feed. As used herein, "gas feed partial oxidation gasification" refers to a partial oxidation gasification process wherein the feed to the process consists essentially of components that are gaseous at 25 ℃ and 1 atm.

In some embodiments, carbon reforming comprises partial oxidation gasification. In a partial oxidation gasification process, the gasifier is operated in an oxygen-lean environment, relative to the amount required to fully oxidize 100% of the carbon and hydrogen bonds. For example, the total oxygen demand of the gasifier may exceed the amount theoretically required to convert the carbon content of the gasification feedstock to carbon monoxide by at least 5%, 10%, 15% or 20%. In general, satisfactory operation can be obtained at a total oxygen supply of 10% to 80% over theoretical requirements. Examples of suitable amounts of oxygen per pound of carbon may be, for example, in the range of 0.4 to 3.0, 0.6 to 2.5, 0.9 to 2.0, or 1.2 to 2.0 free oxygen per pound of carbon.

When partial oxidation gasification is used in the carbon reforming step, the type of gasification technique employed may be a partial oxidation entrained flow gasifier that produces synthesis gas. This technology differs from fixed bed (alternatively referred to as moving bed) and fluidized bed gasifiers. In a fixed bed (or moving bed gasifier), the feed stream is moved in countercurrent flow with the oxidant gas, and the oxidant gas typically used is air. The feed stream falls into the gasification chamber, accumulating and forming a feed bed. Air (or alternatively oxygen) continuously flows upward through the bed of feedstock material from the bottom of the gasifier while fresh feedstock continuously falls from the top due to gravity to refresh the bed as it burns. The combustion temperature is typically below the melting temperature of the ash and does not slag.

In some embodiments, when carbon reforming includes gasification, the gasifier may include at least the following characteristics: (i) a single stage; (ii) slagging; (iii) downstream; (iv) entraining the stream; (v) high pressure; (vi) elevated temperature; (vii) slurry feed; (viii) a coal or PET feed; and/or (ix) quenching the gasifier.

In some embodiments, the downstream location 50 may include a methanol-to-olefins (MTO) facility. In such embodiments, the r-pyrolysis oil is first converted to methanol, which is then reacted to form olefins such as ethylene and propylene. The r-pyrolysis oil may optionally undergo an initial reaction, such as gasification and separation, prior to use in forming methanol. In some embodiments, the r-pyrolysis oil fed to the carbon reformer may then be introduced into an MTO facility for conversion to methanol and olefins.

In some embodiments, the r-pyrolysis oil 114 may be combined with at least one non-recovered component hydrocarbon-containing stream, and the combined stream may be subjected to further processing at a downstream location. When combined with another stream, the r-pyrolysis oil 114 may comprise 5wt% to 95wt%, 10wt% to 80wt%, or 25wt% to 75wt% of the combined stream. Combining the r-pyrolysis oil 114 with other streams maximizes the use of existing facilities when processing the r-pyrolysis oil into other products.

In some embodiments, the r-pyrolysis oil 114 may be split into two or more fractions, and each fraction may be introduced to a different downstream location 50. In some cases, the r-pyrolysis oil 114 may be split such that one fraction includes 5wt% to 95wt%, 10wt% to 80wt%, 15wt% to 75wt%, or 25wt% to 60wt% of the total amount of r-pyrolysis oil removed from the pyrolysis facility 20. In other embodiments, at least 90%, at least 95%, at least 97%, or at least 99% of the r-pyrolysis oil 114 from the pyrolysis facility 20 may be introduced to a single downstream location 50.

Definition of the definition

It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions may be provided in the foregoing description, for example, when defined terms are used in the context of the accompanying usage.

The terms "a," "an," and "the" as used herein mean one or more.

As used herein, the term "and/or" when used in a list of two or more items means that any one of the listed items can be used alone, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B and/or C, the composition may contain a alone; b alone; c alone; a combination of A and B; a and C in combination, B and C in combination; or a combination of A, B and C.

As used herein, the phrase "at least a portion" includes at least a portion, and up to and including the entire amount or period of time.

As used herein, the term "chemical recovery" refers to a waste plastic recovery process that includes the step of chemically converting waste plastic polymers into lower molecular weight polymers, oligomers, monomers and/or non-polymer molecules (e.g., hydrogen, carbon monoxide, methane, ethane, propane, ethylene, and propylene) that are useful per se and/or that can be used as feedstock for another chemical production process.

As used herein, the term "co-operate with" refers to a characteristic of at least two objects being located on a common physical site and/or within one mile of each other.

As used herein, the term "commercial scale facility" refers to a facility having an average annual feed rate of at least 500 pounds per hour averaged over the course of a year.

As used herein, the term "comprising" is an open transition term for transitioning from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

As used herein, the term "cracking" refers to the breakdown of complex organic molecules into simpler molecules by the cleavage of carbon-carbon bonds.

As used herein, the term "comprising" has the same open-ended meaning as "comprising" provided above.

As used herein, the term "remotely located" refers to a distance of at least 1, 5, 10, 50, 100, 500, 1000, or 10000 miles between two facilities, sites, or reactors.

As used herein, the term "predominantly" means more than 50% by weight. For example, a stream, composition, feedstock or product that is predominantly propane is a stream, composition, feedstock or product that contains more than 50wt% propane.

As used herein, the term "pyrolysis" refers to the thermal decomposition of one or more organic materials at elevated temperatures in an inert (i.e., substantially oxygen-free) atmosphere.

As used herein, the term "pyrolysis gas" (pyrolysis gas and pygas) refers to a composition obtained from pyrolysis that is gaseous at 25 ℃.

As used herein, the term "pyrolysis oil" refers to a composition obtained from pyrolysis that is liquid at 25 ℃ and 1 atm.

As used herein, the term "pyrolysis residue" refers to a composition obtained from pyrolysis that is not pyrolysis gas or pyrolysis oil, and that comprises primarily pyrolytic carbon and pyrolytic heavy wax.

As used herein, the term "recovery component" refers to or comprises a composition that is directly and/or indirectly derived from a recovery material.

As used herein, the term "scrap" refers to used, discarded, and/or discarded materials.

As used herein, the terms "waste plastic" and "plastic waste" refer to used, waste, and/or discarded plastic materials.

Description of the appended claims-first embodiment

In a first embodiment of the present technology, a chemical recovery method is provided, the method comprising: (a) Pyrolyzing the waste plastics in a pyrolysis facility to provide a recycle component pyrolysis effluent (r-pyrolysis effluent); (b) Separating at least a portion of the r-pyrolysis effluent to provide a recovered component pyrolysis gas (r-pyrolysis gas) and a recovered component pyrolysis oil (r-pyrolysis oil); (c) Introducing at least a portion of the r-pyrolysis gas into a cracker facility; and (d) introducing at least a portion of the r-pyrolysis oil to a downstream location, wherein the downstream location is not within a cracker facility.

The first embodiment described in the previous paragraph may also include one or more additional aspects/features listed in the following paragraphs. Each of the following additional features of the first embodiment may be a separate feature or may be combined with one or more of the other additional features to a consistent extent. In addition, the following paragraphs specifying bullets may be considered as dependent claim features having a level of dependency indicated by the degree of indentation in the bullets list (i.e., features indented farther than the features listed above are considered to be dependent on the features listed above).

● Wherein the pyrolysis facility and the cracker facility are co-operating.

● Wherein at least 50%, 75%, 90% or 95% of the r-pyrolysis gas formed in the pyrolysis facility is introduced into the cracker facility.

● Wherein the r-pyrolysis gas is introduced into the cracker facility at a location downstream of the cracker furnace.

Wherein r-pyrolysis gas is introduced into the quench section of the cracker facility.

Wherein r-pyrolysis gas is introduced into the compression section of the cracker facility.

■ Wherein the r-pyrolysis gas is introduced upstream of the first compression stage.

■ Wherein r-pyrolysis gas is introduced upstream of the final compression stage.

Wherein the r-pyrolysis gas is introduced into the separation section of the cracker facility.

■ Wherein the r-pyrolysis gas is introduced upstream of the first column of the separation section.

● Wherein at least a portion of the r-pyrolysis gas is introduced to a cracker facility upstream of the cracker furnace, and further comprising cracking at least a portion of the r-pyrolysis gas to form a recovery component furnace effluent (r-furnace effluent).

Further comprising combining another portion of the r-pyrolysis gas with the r-furnace effluent and introducing the combined stream to at least one of a quench section, a compression section, and a separation section of the cracker facility.

● Also included is dividing the r-pyrolysis oil into two or more portions and introducing a first portion of the r-pyrolysis oil to a downstream location.

Wherein a second portion of the r-pyrolysis oil is introduced to the inlet of the cracker furnace.

Wherein the first portion of r-pyrolysis oil is at least 5%, 20%, 45% and/or no more than 90%, 75%, 50% of the total r-pyrolysis oil removed from the pyrolysis facility.

● Wherein the r-pyrolysis oil comprises at least 50wt%, 75wt%, 90wt%, 95wt% of C4 to C30 (C5 to C25, C5 to C22, or C5 to C20) hydrocarbon compounds.

● Wherein the r-pyrolysis oil has a 90% boiling point in the range of 150 ℃ to 350 ℃, 200 ℃ to 295 ℃, 225 ℃ to 290 ℃, or 230 ℃ to 275 ℃.

● Wherein the r-pyrolysis oil comprises no more than 20wt%, 10wt%, 2wt%, 0.5wt%, or 0.1wt% heteroatom-containing compounds.

● Wherein the r-pyrolysis gas comprises a C2 hydrocarbon component in an amount of 5wt% to 60wt%, 10wt% to 50wt%, or 15wt% to 45wt%, a C3 hydrocarbon component in an amount of 5wt% to 60wt%, 10wt% to 50wt%, or 15wt% to 45wt%, a C4 hydrocarbon component in an amount of 1wt% to 60wt%, 5wt% to 50wt%, or 10wt% to 45wt%, and a C5 hydrocarbon component in an amount of 1wt% to 25wt%, 3wt% to 20wt%, or 5wt% to 15 wt%.

● Wherein the downstream location is a carbon reformer.

Wherein the carbon reformer is a partial oxidation gasifier.

Wherein the carbon reformer is a steam reformer.

Wherein the carbon reformer is a plasma gasifier.

Wherein the carbon reformer is a catalytic reformer.

● Wherein the downstream location is a refinery and further comprising processing at least a portion of the r-pyrolysis oil to produce a recovered constituent fuel (r-fuel).

Wherein, r-fuel is a gasoline range fuel.

Wherein r-fuel is diesel range fuel.

Wherein, r-fuel is a gas oil range fuel.

Wherein r-fuel is residuum range fuel.

Wherein, r-fuel is pitch or coke.

The method further includes cracking at least a portion of the r-pyrolysis oil in the refinery to provide r-fuel.

■ Wherein cracking includes catalytic cracking.

■ Wherein cracking comprises thermal cracking.

● Wherein cracking comprises coking.

The method may further comprise reforming at least a portion of the r-pyrolysis oil to provide r-fuel.

■ Wherein reforming comprises catalytic reforming.

O further includes isomerizing at least a portion of the r-pyrolysis oil to provide r-fuel.

The method further includes fractionating at least a portion of the r-pyrolysis oil to form r-fuel.

● Wherein the downstream location is a burner of the furnace.

● Wherein the downstream location is a storage or transport device.

● Wherein the downstream location is another cracker facility.

Also included is introducing at least a portion of the r-pyrolysis oil into a cracker furnace of another cracker facility.

● Wherein the downstream location is a fine chemical production facility.

Further comprising treating at least a portion of the r-pyrolysis oil in one or more treatment zones of a fine chemical facility to produce a recovered constituent chemical (r-chemical).

● Also included is cracking a hydrocarbon feedstock in a cracker furnace of a cracker facility to produce a furnace effluent stream, and wherein the furnace effluent stream comprises a recovery component furnace effluent stream (r-furnace effluent).

The method further includes combining at least a portion of the r-pyrolysis gas with the furnace effluent stream to provide an r-furnace effluent.

Also included is introducing at least a portion of the r-pyrolysis gas to an inlet of a cracker furnace to provide an r-furnace effluent.

Wherein the hydrocarbon feedstock is predominantly a C2 to C4 hydrocarbon stream.

Wherein the hydrocarbon feedstock is predominantly a C5 to C22 stream.

Wherein the hydrocarbon feedstock comprises recovered components.

Wherein the hydrocarbon feedstock comprises non-recovered components.

● Also included is forming at least one recovery component product (r-product) from at least a portion of the r-pyrolysis oil.

● Also included is forming at least one recovery component product (r-product) from the r-pyrolysis gas from the cracker facility.

Wherein the r-product contains ethane (r-ethane) as a recovery component.

Wherein the r-product comprises the recovery component ethylene (r-ethylene).

Wherein the r-product comprises the recovered component propane (r-propane).

Wherein the r-product comprises propylene (r-propylene) as a recovery component.

Wherein the r-product comprises the recovered component butene (r-butene).

Wherein the r-product comprises the recovered component butane (r-butane).

Wherein the r-product comprises recovered component C5 and heavier (r-C5+).

Description of the attached claims-second embodiment

In a second embodiment of the present technology, a chemical recovery method is provided, the method comprising: (a) Pyrolyzing the waste plastics to provide a recycle component pyrolysis effluent (r-pyrolysis effluent); (b) Separating at least a portion of the r-pyrolysis effluent to provide a recovered component pyrolysis gas (r-pyrolysis gas) and a recovered component pyrolysis oil (r-pyrolysis oil); (c) Introducing at least a portion of the r-pyrolysis gas into a cracker facility; and (d) introducing at least a portion of the r-pyrolysis oil into one or more of the following locations (i) to (x): (i) a storage device; (ii) a delivery device; (iii) a fluid catalytic cracker; (iv) a carbon reformer; (v) a distillation column or distillation zone; (vi) fine chemical facilities; (vii) a burner; (viii) an MTO facility; (ix) different crackers; and (x) refineries.

The second embodiment described in the previous paragraph may also be included in one or more of the additional aspects/features listed in the following paragraphs of gist. Each of the following additional features of the first embodiment may be a separate feature or may be combined with one or more of the other additional features to a consistent extent. In addition, the following paragraphs specifying bullets may be considered as dependent claim features having a level of dependency indicated by the degree of indentation in the bullets list (i.e., features indented farther than the features listed above are considered to be dependent on the features listed above).

● Wherein the pyrolysis facility and the cracker facility are co-operating.

● Wherein at least a portion of the r-pyrolysis gas is introduced into the cracker facility upstream of the cracker furnace, and further comprising cracking at least a portion of the r-pyrolysis gas to form a recovery component furnace effluent (r-furnace effluent).

● Wherein the downstream location is a carbon reformer.

Wherein the carbon reformer is a partial oxidation gasifier.

Wherein, the carbon reformer is a steam reformer.

Wherein, the carbon reformer is a plasma gasifier.

Wherein, carbon reformer is catalytic reformer.

Wherein, r-fuel is a gasoline range fuel.

Wherein r-fuel is diesel range fuel.

Wherein, r-fuel is a gas oil range fuel.

Wherein r-fuel is residuum range fuel.

Wherein, r-fuel is pitch or coke.

■ Wherein cracking includes catalytic cracking.

■ Wherein cracking comprises thermal cracking.

● Wherein cracking comprises coking.

The method may further comprise reforming at least a portion of the r-pyrolysis oil to provide the r-fuel.

■ Wherein reforming comprises catalytic reforming.

● Wherein the downstream location is a burner of the furnace.

● Wherein the downstream location is a storage or transport device.

● Wherein the downstream location is another cracker facility.

● Wherein the downstream location is a fine chemical production facility.

Wherein the hydrocarbon feedstock is predominantly a C5 to C22 stream.

Wherein the hydrocarbon feedstock comprises recovered components.

Wherein the hydrocarbon feedstock comprises non-recovered components.

Wherein the r-product contains ethane (r-ethane) as a recovery component.

Wherein the r-product comprises the recovery component ethylene (r-ethylene).

Wherein the r-product comprises recovered component propane (r-propane).

Wherein the r-product comprises the recovered component butene (r-butene).

Wherein the r-product comprises the recovered component butane (r-butane).

Wherein the r-product comprises recovered component C5 and heavier (r-C5+).

The claims are not limited to the disclosed embodiments

The preferred forms of the invention described above are to be used as illustration only, and should not be used in a limiting sense to interpret the scope of the present invention. Modifications to the above would be obvious to those of ordinary skill in the art, without departing from the spirit of the present invention.

The inventors hereby state their intent to rely on the doctrine of equivalents to determine and assess the reasonably fair scope of the present invention as it pertains to any apparatus not materially departing from but outside the literal scope of the invention as set forth in the following claims.

Claims

1. A chemical recovery process, the process comprising:

(a) Pyrolyzing the waste plastics in a pyrolysis facility to provide a recycle component pyrolysis effluent (r-pyrolysis effluent);

(b) Separating at least a portion of the r-pyrolysis effluent to provide a recovered component pyrolysis gas (r-pyrolysis gas) and a recovered component pyrolysis oil (r-pyrolysis oil);

(c) Introducing at least a portion of the r-pyrolysis gas into a cracker facility; and

(d) At least a portion of the r-pyrolysis oil is introduced to a downstream location, wherein the downstream location is not within the cracker facility.

2. The method of claim 1, wherein the pyrolysis facility and the cracker facility are co-operating.

3. The method of claim 1, wherein the r-pyrolysis gas is introduced into the cracker facility at a location downstream of a cracker furnace.

4. The method of claim 3, wherein the r-pyrolysis gas is introduced to at least one of a quench section, a compression section, and a separation section of the cracker facility.

5. The method of claim 1, wherein at least a portion of the r-pyrolysis gas is introduced into the cracker facility upstream of a cracker furnace, and further comprising cracking at least a portion of the r-pyrolysis gas to form a recovery component furnace effluent (r-furnace effluent).

6. The method of claim 1, further comprising dividing the r-pyrolysis oil into two or more portions and introducing a first portion of the r-pyrolysis oil to the downstream location.

7. The method of claim 1, wherein the r-pyrolysis oil comprises at least 50wt% C4 to C30 hydrocarbon compounds.

8. The method of claim 1, wherein the r-pyrolysis oil comprises heteroatom-containing compounds in an amount of not more than 20 wt%.

9. The method of claim 1, wherein the r-pyrolysis gas comprises 5wt% to 60wt% C2 hydrocarbon components, 5wt% to 60wt% C3 hydrocarbon components, 1wt% to 60wt% C4 hydrocarbon components, and 1wt% to 25wt% C5 hydrocarbon components.

10. The method of claim 1, wherein the downstream location is a carbon reformer.

11. The method of claim 1, wherein the downstream location is a refinery and further comprising processing at least a portion of the r-pyrolysis oil to produce a recovered component fuel (r-fuel).

12. The method of claim 1, wherein the downstream location is a burner of a furnace.

13. The method of claim 1, wherein the downstream location is another cracker facility.

14. The method of claim 1, wherein the downstream location is a fine chemical production facility.

15. The method of claim 1, further comprising cracking a hydrocarbon feedstock in a cracker furnace of the cracker facility to produce a furnace effluent stream, and wherein the furnace effluent stream comprises a recovery component furnace effluent stream (r-furnace effluent).

16. The method of any of claims 1-15, wherein the pyrolysis facility and the cracker facility are both commercial scale facilities.

17. A chemical recovery process, the process comprising:

(a) Pyrolyzing the waste plastics to provide a recycle component pyrolysis effluent (r-pyrolysis effluent);

(d) Introducing at least a portion of said r-pyrolysis oil into one or more of the following positions (i) to (x)

(i) A storage device;

(ii) A conveying device;

(iii) A fluid catalytic cracker;

(iv) A carbon reformer;

(v) A distillation column or distillation zone;

(vi) Fine chemical facilities;

(vii) A burner;

(viii) An MTO facility;

(ix) Different crackers; and

(x) And (3) an oil refinery.

18. The method of claim 17, wherein the r-pyrolysis oil comprises heteroatom-containing compounds in an amount of no more than 20wt, and wherein the r-pyrolysis gas comprises C2 hydrocarbon components in an amount of 5 wt-60 wt, C3 hydrocarbon components in an amount of 5 wt-60 wt, C4 hydrocarbon components in an amount of 1 wt-60 wt, and C5 hydrocarbon components in an amount of 1-25%.

19. The method of claim 17, wherein the introducing of step (c) comprises introducing at least a portion of the r-pyrolysis oil into two or more of locations (i) through (x).

20. The method of any of claims 17-19, wherein the pyrolysis facility and the cracker facility are co-operating and both the pyrolysis facility and the cracker facility are on a commercial scale.