CN117836393A - Apparatus and process for pyrolysis of plastic feedstock - Google Patents

Apparatus and process for pyrolysis of plastic feedstock Download PDF

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CN117836393A
CN117836393A CN202280052363.2A CN202280052363A CN117836393A CN 117836393 A CN117836393 A CN 117836393A CN 202280052363 A CN202280052363 A CN 202280052363A CN 117836393 A CN117836393 A CN 117836393A
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catalyst
reactor
separator
conduit
introducing
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卡洛·巴迪奥拉
王松
S·B·雷迪·卡利
约翰·芬德利
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E2 Technology Co ltd
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E2 Technology Co ltd
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Priority claimed from US17/698,174 external-priority patent/US20230002681A1/en
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Abstract

The present disclosure relates to apparatus and processes for pyrolysis of a feedstock, such as a plastic feedstock. In at least one embodiment, a process includes introducing a plastic melt having a plastic component into a reactor via a nozzle coupled to the reactor. The process includes introducing a catalyst into the reactor via a first conduit coupling the reactor with a riser or regenerator. The process includes pyrolyzing the plastic component to form a pyrolysis product. The process includes removing the pyrolysis product from the reactor via a second conduit disposed at an upper 1/2 height of the reactor. The process includes removing the catalyst from the reactor via a third conduit disposed at a lower 1/2 height of the reactor.

Description

Apparatus and process for pyrolysis of plastic feedstock
Cross Reference to Related Applications
The present application claims priority from U.S. non-provisional patent application Ser. No. 17/698,174, filed 3/18/2022, which claims the benefit and priority from U.S. provisional patent application Ser. No. 63/217,051, filed 6/2021, and assigned to the assignee hereof, the contents of which are incorporated herein by reference in their entirety.
Technical Field
The present disclosure relates to apparatus and processes for pyrolysis of a feedstock, such as a plastic feedstock.
Background
Most of the waste plastics are transferred to a landfill site or burned, and a small part is transferred to recycling. However, over the years, as regulations and collection of landfills have increased, the percentage of post-consumer waste that is recycled or burned for energy recovery has gradually increased.
Attempts have been made to crack plastics into usable products using conventional cracking equipment for cracking petroleum derived feeds such as diesel. For example, plastic feeds in powder form or pellets are introduced into fluid catalytic cracking reactors, which require high temperatures for the plastic feeds.
In addition, the presence of chlorine in the waste plastic (e.g., polyvinyl chloride) promotes corrosion of the reactor internals, requiring a separate dechlorination process before the dechlorinated product can be introduced into the reactor and other components of the plant. These additional dechlorination steps (and reactors for dechlorination) reduce the throughput and yield of the desired cracked product.
The spent catalyst (formed in the pyrolysis reactor during pyrolysis) further reduces throughput and yield. Spent catalyst can be regenerated in conventional regenerators, but the amount of regeneration is insufficient, especially when using plastic feeds containing chlorine and trace metals.
It is desirable to provide high throughput equipment and processes for feeds such as plastic feeds that can be converted by pyrolysis and catalytic upgrading to form hydrocarbon products with high yields.
Disclosure of Invention
The present disclosure relates to apparatus and processes for pyrolysis of a feedstock, such as a plastic feedstock.
In at least one embodiment, the process includes introducing a plastic melt including a plastic component into a reactor via a nozzle coupled to the reactor. The process includes introducing a catalyst into a reactor via a first conduit coupling the reactor with a riser, standpipe, or regenerator. The process includes pyrolyzing the plastic component to form a pyrolysis product. The process includes removing pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor. The process includes removing catalyst from the reactor via a third conduit disposed at a lower 1/2 height of the reactor, wherein the catalyst removed from the reactor comprises ash. The process includes introducing catalyst from the third conduit into the separator to form a catalyst rich phase and an ash rich phase in the separator.
In at least one embodiment, the process includes removing catalyst from the reactor, wherein the catalyst comprises ash. The process includes introducing catalyst into the separator via a conduit to form a catalyst-rich phase and an ash-rich phase in the separator. The process includes introducing a catalyst rich phase into a regenerator to form a regenerated catalyst. The conduit has an end disposed within the separator at 1/4 to 3/4 the height of the separator and the end contains a plurality of outlets.
In at least one embodiment, the process includes introducing a plastic melt having a plastic component into a reactor via a nozzle coupled to the reactor. The process includes introducing a catalyst into a reactor via a first conduit coupling the reactor with a riser or regenerator. The process includes pyrolyzing the plastic component to form a pyrolysis product. The process includes removing pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor. The process includes removing catalyst from the reactor via a third conduit disposed at the lower 1/2 height of the reactor.
These and other features and attributes of embodiments of the present invention, as well as its advantageous applications and/or uses, will be apparent from the detailed description that follows.
Drawings
So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to aspects, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical aspects of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective aspects.
FIG. 1 is an apparatus and process flow for pyrolysis of a plastic feedstock according to one embodiment.
Fig. 2A is a nozzle according to one embodiment.
Fig. 2B is a nozzle according to one embodiment.
Fig. 3 is a separator according to one embodiment.
To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. The drawings are not to scale and may be simplified for clarity. It is contemplated that elements and features of one aspect may be beneficially incorporated in other aspects without further recitation.
Detailed Description
The present disclosure relates to apparatus and processes for pyrolysis of a feedstock, such as a plastic feedstock.
In some embodiments, a process is provided that includes introducing a plastic melt including a plastic component into a reactor via one or more nozzles coupled with the reactor. The process includes introducing the catalyst into the reactor using a dilute phase pneumatic transfer of regenerated catalyst coupled to the reactor via a cyclone, standpipe, or vessel dipleg system. The process includes pyrolyzing the plastic component to form a pyrolysis product. The process includes removing pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor. The process includes removing catalyst from the reactor via a third conduit disposed at a lower 1/2 height of the reactor, wherein the catalyst removed from the reactor comprises ash. The process includes introducing catalyst from the third conduit into the separator to form a catalyst rich phase and an ash rich phase in the separator.
In some embodiments, an apparatus is provided that includes one or more nozzles coupled to a reactor. The nozzle includes an inlet disposed substantially perpendicular to a horizontal conduit disposed in the nozzle. The apparatus includes a riser coupled to the reactor. The apparatus comprises a first outlet conduit arranged at the upper 1/2 height of the reactor. The first outlet duct is coupled to the cyclone separator. The apparatus comprises a second outlet conduit arranged at the lower 1/2 height of the reactor. The second outlet conduit is coupled to the second separator. The apparatus includes a regenerator coupled to the second separator and the riser.
The apparatus and process of the present disclosure provide high throughput of pyrolysis products formed using plastic pyrolysis. The process may be performed as a single stage process, providing a higher yield than conventional processes for treating waste plastics. The apparatus and process of the present disclosure provides for elutriation of char, char ash, attrition catalyst, and coinjection materials such that spent catalyst can be easily regenerated, providing improved throughput of pyrolysis products in addition to higher purity of catalyst recycled to the reactor. In addition, the use of a catalyst having a narrower size distribution and a larger average diameter than the coinjection material allows the coinjection material to elutriate from the catalyst in the reactor. In addition, the use of a catalyst having a larger average diameter in addition to the reactor configured to provide bubble control results in reduced plugging and wear of vessel piping, valves, and other equipment components, thereby maintaining the integrity and longer service life of the equipment of the present disclosure.
In addition, the use of the separator of the present disclosure provides improved throughput of pyrolysis products as the separation of spent catalyst from components such as ash is improved. The use of the separator improves throughput, particularly because the catalyst can remain viable (e.g., the catalyst can be regenerated) such that the time interval between plant shutdowns can be prolonged. The separators of the present disclosure may also provide improved regeneration of spent catalyst (as ash is removed at the separator), thereby further improving the throughput and yield of pyrolysis products.
Reactor conditions
In some embodiments, a process is provided that includes introducing a plastic melt including a plastic component into a reactor via one or more nozzles coupled with the reactor. The process includes introducing a catalyst into the reactor by pneumatic transfer via a first conduit coupling the reactor with a riser. For example, the process may include introducing the catalyst into the reactor using a dilute phase pneumatic transfer of regenerated catalyst coupled to the reactor via a cyclone dipleg system. The process includes pyrolyzing the plastic component to form a pyrolysis product. The process includes removing pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor and removing catalyst from the reactor via a third conduit disposed at a lower 1/2 height of the reactor.
Apparatus and process flow
Fig. 1 is an apparatus 100 and process flow for pyrolysis of a plastic feedstock according to one embodiment. The apparatus 100 includes a pyrolysis reactor 102, a riser 102a, a first separator 104, a second separator 106, and a regenerator 108.
The plastic melt is introduced into the pyrolysis reactor 102 via a nozzle 110. The plastic melt may comprise any suitable plastic material, such as plastic scrap, automotive plastic waste, thermoplastic, thermoset, or a combination thereof. The plastic melt may comprise one or more plastics such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, or combinations thereof. The plastic may be obtained from a recyclable plastic. For example, a bale comprising plastic may be sorted into portions, wherein at least one of the portions comprises one or more plastics. In some embodiments, the plastic melt is introduced into the reactor at a rate of about 60,000lb/hr to about 100,000lb/hr, such as about 75,000lb/hr to about 85,000lb/hr, or about 30,000lb/hr to about 50,000 lb/hr. The plastic melt may be provided to the nozzle 110 by a plastic melt source (not shown) that may be configured to provide heat to the plastic to form the plastic melt. In some embodiments, the plastic melt, after introduction into the reactor, has a solids (e.g., char) content of about 20wt% or less, such as about 15wt% or less, such as about 10wt% or less, e.g., about 5wt% or less, such as about 1wt% or less, after introduction into the reactor 102.
The plastic melt may further comprise a viscosity-reducing agent. For example, the viscosity-reducing agent can be a recycled portion of the pyrolysis product, such as an organic compound (e.g., aromatic or mono-olefin), such as ethylene, propylene, butylene, benzene, toluene, xylene, or a combination thereof. The viscosity reducing agent may additionally or alternatively include a paraffinic organic compound such as C 4 -C 100 Paraffin wax such as C 6 -C 50 Paraffin wax such as C 10 -C 30 Paraffin wax. The viscosity-reducing agent may be introduced into the plastic melt in a plastic melt source (not shown) or nozzle 110. In some embodiments, the weight ratio of plastic to viscosity reducing agent (after introduction into the reactor) is from about 0.5:1 to about 1.5:1, such as about 1:1. In some embodiments in which the plastic melt includes a viscosity-reducing agent, the plastic melt is introduced into the reactor at a rate of about 60,000lb/hr to about 200,000lb/hr, such as about 120,000lb/hr to about200,000lb/hr, such as about 148,000lb/hr to about 172,000lb/hr.
The catalyst may be introduced into the pyrolysis reactor 102 via a first conduit 112. Conduit 112 couples reactor 102 to riser 102a. The conduit 112 may be disposed at the upper 1/2 height of the reactor (as shown in fig. 1) or alternatively may be a dipleg coupled with the riser 102a at a first end and coupled with the reactor 102 at a second end back such that the second end of the dipleg return (conduit 112) is disposed at the lower 1/2 height of the reactor.
The plastic melt and catalyst in the reactor 102 pyrolyzes the plastic to form pyrolysis products. In some embodiments, the catalyst is introduced into the reactor 102 via the first conduit 112 at a catalyst flow rate of about 5.5 ton minutes to about 13.8 ton minutes, such as about 7.5 ton minutes to about 12.4 ton minutes, or about 2.5 ton minutes to about 8.8 ton minutes. In some embodiments, the catalyst disposed in riser 102a has a minimum gas fluidization velocity of about 0.4ft/sec to about 0.6 ft/sec. In some embodiments, the weight ratio of catalyst to feed (e.g., plastic melt with or without viscosity-reducing agent) in reactor 102 is about 15:1 to about 5:1, such as about 11:1 to about 7:1, such as about 9:1.
Pyrolysis products are removed from the reactor 102 via a second conduit 114 disposed at the upper 1/2 height of the reactor. The catalyst is removed from the reactor 102 via a third conduit 116 disposed at the lower 1/2 height of the reactor. For example, the catalyst may be removed from the reactor via a third conduit 116, wherein the third conduit 116 is disposed at a bottom surface of the reactor 102.
In some embodiments, the reactor 102 is a bubbling bed reactor. Alternatively, a fluidized bed reactor, slurry reactor, rotary furnace reactor, or packed bed reactor may be used. During introduction of the plastic melt into the reactor, the plastic melt (e.g., without the viscosity-reducing agent) may have a viscosity of about 900 ° F to about 1,100 ° F, such as about 1,000 ° F to about 1,050 ° F, or about 900 ° F to about 1,020 ° F temperature. Alternatively, during introduction of the plastic melt into the reactor, the plastic melt (e.g.,with viscosity-reducing agent) may have a viscosity of about 300 ° F to about 700 ° F, such as about 350 ° F to about 665 ° F temperature.
In some embodiments, the reactor temperature during pyrolysis of the plastic melt is about 900 f ° F to about 1,100 ° F, such as about 1,000 ° F to about 1,050 ° F, or about 900 ° F to about 1,020 ° F. For example, the plastic may be pyrolyzed at about 900 f ° F to about 1,100 ° F, such as about 1,000 ° F to about 1,050 ° F, and/or a reactor pressure of from about 20psig to about 40psig, such as from about 27psig to about 33 psig.
Pyrolysis of the present disclosure may provide pyrolysis products such that the pyrolysis products include valuable monomers of light gas olefins and aromatics, such as benzene, toluene, xylenes, or combinations thereof. The process yield can be tuned to the desired yields of olefins and aromatics by using a combination of catalyst, reactor setup, and process operating conditions. The pyrolysis products may include organic compounds, such as C 2 -C 12 And (3) hydrocarbons. In some embodiments, the pyrolysis product comprises an organic compound selected from the group consisting of ethylene, propylene, and combinations thereof. In some embodiments, the pyrolysis product comprises an organic compound selected from the group consisting of ethylene, propylene, butene, benzene, toluene, xylene, and combinations thereof.
In some embodiments, coinjection particles are introduced into the reactor 102 in addition to the catalyst. For example, coinjection particles can be introduced into the reactor 102 through the nozzle 110 at a rate of about 1,000lb/hr to about 3,000 lb/hr. In some embodiments, the coinjected particles are particles configured to entrap halogen (e.g., fluorine, chlorine, bromine, or iodine present in the polymer or contaminants of the plastic melt). These halogens may be present in the desired pyrolysis product as undesirable contaminants during the pyrolysis process, or they may be deposited on or react with the pyrolysis catalyst components, thereby reducing desirable catalyst properties such as activity and selectivity for the desired pyrolysis product. In addition, these halogens may deposit on or react with mechanical components of the pyrolysis system, resulting in damage, reduced efficiency, or mechanical failure. Furthermore, these halogens may be present as toxic gases or as liquid effluents from the outlet of the pyrolysis system. Co-injected particles configured to entrap or sequester halogens may include, but are not limited to, oxides, carbonates, calcium oxides, calcium carbonates, limestone, metal oxides, mixed metal oxides, clays, sand, earth, zeolites, or any other material or combination of materials capable of being combined with or sequestered in a reversible or irreversible manner with one or more halogens, thereby reducing the halogens or eliminating them from the desired pyrolysis product, or thereby reducing or eliminating the deleterious deposition thereon or reaction therewith, on mechanical components of the pyrolysis system, or thereby reducing or eliminating the appearance thereof as a toxic gas or liquid effluent from the outlet of the pyrolysis system. For example, the coinjection particles can be an oxide, carbonate, calcium oxide, calcium carbonate, limestone, metal oxide, mixed metal oxide, clay, sand, earth, zeolite, or any other material or combination of materials capable of combining with and chelating the halogen.
In some embodiments, the coinjection particles comprise a material or combination of materials configured to entrap or sequester metals and semi-metals that may be present in the plastic melt. Various metals and semi-metals may be present in plastic waste, especially post-consumer plastic waste. These metals and semi-metals may include, but are not limited to, alkali metals, alkaline earth metals, transition metals, rare earths, iron, silver, copper, zinc, gray tin, lead, phosphorus, and aluminum, and may be present as free elements or may be present as inorganic or organic or organometallic molecules, compounds, polymers, mixtures, or other combinations. These metals and semi-metals may appear in the desired pyrolysis product as undesirable contaminants during the pyrolysis process, or they may deposit on or react with the pyrolysis catalyst components, thereby reducing desirable catalyst properties such as activity and selectivity for the desired pyrolysis product. In addition, these metals and semi-metals may deposit on or react with mechanical components of the pyrolysis system, resulting in damage, reduced efficiency, or mechanical failure. Coinjection particles configured to entrap or sequester metals and semi-metals can include, but are not limited to, oxides, carbonates, calcium oxides, calcium carbonates, limestone, metal oxides, mixed metal oxides, clays, sand, earth, zeolites, or any other material or combination of materials capable of being combined or sequestered in a reversible or irreversible manner with one or more metals and semi-metals, thereby reducing or eliminating these metals and semi-metals from the desired pyrolysis product, or thereby reducing or eliminating their detrimental deposition onto or reaction with the pyrolysis catalyst components, or thereby reducing or eliminating their detrimental deposition onto or reaction with mechanical components of the pyrolysis system.
"4A zeolite" (also referred to as LTA zeolite) means a zeolite having pore openings of about 4 angstroms; and the term "5A zeolite" means a zeolite having pore openings of about 5 angstroms.
4A zeolite (Na) 2 O·Al 2 O 3 ·2SiO 2 ·9/2H 2 O) a continuous three-dimensional network of channels having a diameter of about 4 angstroms, except for aboutOutside the larger "cage" of diameter. The 4A zeolite may have one or more of the following properties: (1) an average particle size of about 3 microns; and/or (2) a silicon to aluminum ratio of about 1.
5A zeolite (3/4 CaO.1/4 Na) 2 O·Al 2 O 3 ·2SiO 2 ·9/2H 2 O) is a three-dimensional network of intersecting channels. The channel inlets are controlled by eight oxygen atoms from which the channels are formed (aboutDiameter). When the channels intersect, they are formed with +.>Larger holes or cages of diameter. The 5A zeolite may have about 0.7g/cm 3 To about 0.75g/cm 3 Such as about 0.72g/cm 3 Is a bulk density of (c).
If calcium oxide is used, the calcium oxide may react with the chlorine content of the polymer melt to form calcium chloride and gaseous products such as carbon dioxide. In some embodiments, the weight ratio of catalyst to co-injected particles in reactor 102 is from about 10:1 to about 30:1, such as from about 15:1 to about 25:1, such as about 20:1.
After sequestering the one or more halogens, or after sequestering the one or more metals or semi-metals, or after sequestering a combination of the one or more halogens, metals, or semi-metals, the coinjection particles, or products thereof, can be removed from the reactor via a second conduit 114 and introduced into the first separator 104 along with the pyrolysis product.
In some embodiments, the coinjection particles have a smaller average diameter compared to the average diameter of the pyrolysis catalyst. In these embodiments, in combination with other parameters of the pyrolysis reactor 102, co-injected particles, or reaction products thereof (and/or char and attrition catalyst) can be removed from the reactor 102 (via a conduit disposed at the upper 1/2 height of the reactor) to the first separator 104, while larger catalyst particles are removed from the reactor 102 via a third conduit 116 disposed at the lower 1/2 height of the reactor. In some embodiments, the coinjection particles have an average diameter of less than 400 microns, such as less than 200 microns, such as from about 50 microns to about 400 microns, such as from about 75 microns to about 200 microns, and/or the catalyst has an average diameter and/or narrower particle size distribution of from about 500 microns to about 600 microns. For example, the catalyst may have a D1% value of about 400 microns and a D99% value of about 700 microns.
The first separator 104 may be a cyclone separator configured to separate coinjection particles or products thereof from pyrolysis products. The coinjected particles or products thereof are removed from the first separator 104 via a fifth conduit 120 for storage or further processing (e.g., disposal or regeneration). Pyrolysis products are removed from the first separator 104 via conduit 118 for storage or further processing (e.g., additional cyclone separation and/or distillation of the products). For example, a second stage cyclone for secondary removal may be used to increase separation efficiency. Subsequent means for separating solids and gases from the pyrolysis products may include cyclones, hot gas filters, vortex separators, electrostatic separation, or combinations thereof, which may be further added to achieve the desired solids removal efficiency.
Catalyst (e.g., spent catalyst) from the reactor 102 is introduced into the separator 106. In some embodiments, separator 106 is a solid-solid separator. Coinjection particles from pyrolysis products, or products thereof, may also be removed from separator 106 via sixth conduit 122.
Spent catalyst and ash enter the middle portion of separator 106. The spent catalyst and ash may further include any residual coinjection particles that are not separated from the catalyst/ash in the reactor 102. Fig. 3 is a separator 106 of the present disclosure. As shown in fig. 3, the second end of the third conduit 116 is at about 60 ° Or at a greater angle to facilitate gravity flow of the mixture of spent catalyst and ash into the separator 106 via the third conduit 116. Although an angle of about 60 is shown ° But any suitable angle may be used, such as about 10 ° Up to about 90 ° (vertical inlet), such as about 30 ° Up to about 75 ° Such as about 45 ° To about 60 ° . Additionally or alternatively, gas may be introduced into the third conduit 116 to facilitate the flow of the mixture of spent catalyst and ash in the third conduit 116 and into the separator 106.
In some embodiments, the mixture of spent catalyst and ash entering the reactor 106 includes about 90wt% or more spent catalyst and about 10wt% or less ash, such as about 0.5wt% to about 4wt% ash and about 96wt% to about 99.9wt% spent catalyst. At about 800 ° F to about 1,200 ° F, such as about 950 ° F to about 1,050 ° F, the spent catalyst and ash are introduced into separator 106. In some embodiments, spent catalyst and ash are introduced into separator 106 at a rate of from about 1 million pounds per hour to about 2 million pounds per hour, such as from about 1.3 million pounds per hour to about 1.7 million pounds per hour, such as from about 1.4 million pounds per hour to about 1.7 million pounds per hour.
The third conduit 116 has a first end coupled to the reactor 102 (fig. 1) and a second end coupled to the separator 106. As shown in fig. 3, the second end of the third conduit 116 has a plurality of outlets 310a, 310b, and 310c for providing a mixture of spent catalyst and ash into the separator 106. Although three outlets 310a-310c are shown in fig. 3, the second end of the third conduit 116 may have any suitable number of outlets, such as a single outlet or from about 2 to about 20 outlets, such as from about 3 to about 10 outlets, such as from about 4 to about 6 outlets. The outlet may be fully or partially open towards the separator. The plurality of outlets disposed at the second end of the third conduit 116 facilitate uniform distribution of the mixture of spent catalyst and ash into the separator 106, which, in combination with one or more other features of the separator 106, facilitates separation of the spent catalyst from the ash. Further, during use, the second end of the third conduit 116 is disposed in the ash-rich phase 304 (e.g., the second end is disposed in a middle portion of the separator 106, such as at 1/4 to 3/4 height of the separator), facilitating ash separation of the spent catalyst from the mixture introduced into the separator 106 via the outlets 310a-c by allowing the spent catalyst to separate from the ash, followed by settling of the spent catalyst. Once introduced into the separator 106, the ash separates from the spent catalyst and the ash settles to form an ash-rich phase 304. Likewise, spent catalyst separates from ash and the spent catalyst settles from a middle portion of the separator 106 toward a bottom portion of the separator 106 to form a catalyst rich phase 302. The "catalyst-rich phase" is rich in spent catalyst and may optionally include some amount of non-deactivated catalyst.
The gas is introduced into the separator 106 via a seventh conduit 306 to fluidize the mixture of spent catalyst and ash. The gas may be provided at a rate of about 0.1ft/s to about 1.5ft/s, such as about 0.3ft/s to about 0.7ft/s, such as about 0.5 ft/s. The gas may have a composition of about 150 ° F to about 1050 ° F temperature. The gas may have a lower temperature than the spent catalyst and ash entering the separator 106 via the third conduit 116 such that the gas may promote cooling of the spent catalyst and ash. In some embodiments, the introduced gas may replace the entrapped reaction gas present prior to introduction into the regenerator combustion system. The rate of gas introduced into separator 106 via seventh conduit 306 may be such that the gas promotes the ability of the spent catalyst to separate from the ash and such that the spent catalyst is able to self-extract from the ashA fine balance is achieved between separation/gravity settling. The gas in the separator 106 may exit the separator 106 via the sixth conduit 122 and/or the dipleg conduit 308. Ash from ash-rich phase 304 is removed from separator 106 via dipleg outlet 308.
As shown in fig. 3, the catalyst rich phase 302 is shown as the bottom phase below the ash rich phase 304 because in the embodiment of fig. 3, the spent catalyst has a higher density and/or larger particle size than the ash of the ash rich phase 304. In alternative embodiments, the catalyst-rich phase 302 may have a lower density and/or smaller particle size than the ash-rich phase 304, and the catalyst-rich phase 302 may be above the ash-rich phase 304 in the separator 106. In these embodiments, the catalyst rich phase 302 is removed from the separator 106 via a conduit (not shown) disposed in a middle portion of the separator 106, and the spent catalyst removed via the conduit (not shown) provides the spent catalyst to the regenerator 108 of fig. 1. Further in these embodiments, ash of ash-rich phase 302 is disposed toward a bottom portion of separator 106, and ash is removed from separator 106 for disposal or further processing by a conduit (not shown) disposed at the bottom portion of separator 106.
The separation performed in separator 106 to form the multiple phases may be performed at any suitable pressure and temperature. In some embodiments, the pressure in separator 106 is from about 20psig to about 50psig, such as from about 25psig to about 40psig, such as from about 30psig to about 35psig. In some embodiments, the temperature in separator 106 is about 700 degrees f ° F to about 1,200 ° F, such as about 850 ° F to about 1,050 ° F, such as about 950 ° F to about 1,000 ° F。
In some embodiments, the spent catalyst obtained from the separator 106 is about 90wt% or more, such as about 96wt% to about 99.9wt% spent catalyst, relative to the mixture of spent catalyst and ash introduced into the separator 106. Likewise, the ash obtained from the separator 106 is about 10wt% or less, such as about 0.5wt% to about 4wt% ash, relative to the mixture of spent catalyst and ash introduced into the separator 106.
In embodiments in which sand is also used in the reactor 102 in addition to catalyst, the sand may be separated in the separator 106 (e.g., as part of the catalyst-rich phase or as a third phase in addition to the catalyst-rich phase and ash-rich phase). For example, sand may be disposed in a sand-rich phase disposed above or below catalyst-rich phase 302, and a sand-rich phase may be disposed below ash-rich phase 304. In these embodiments, the sand-rich phase is removed from separator 106 via a conduit (not shown) disposed below ash-rich phase 304 and sand of the sand-rich phase is removed from separator 106 via a conduit (not shown) disposed below the conduit that removes ash from separator 106.
Additionally or alternatively, in embodiments trace metals (such as chromium) are separated from spent catalyst in separator 106. Because the trace metals may be denser than the spent catalyst, the trace metals may separate from the spent catalyst and settle in the separator 106 into a metal-rich phase disposed below the catalyst-rich phase 302. In these embodiments, the metal-rich phase is removed from the separator 106 via a conduit (not shown) disposed below the catalyst-rich phase 302 and the spent catalyst of the catalyst-rich phase 302 is removed from the separator 106 via a conduit (not shown) disposed above the conduit that removes trace metals from the separator 106.
In some embodiments, the conduit for removing the ash rich phase from the separator may be positioned towards another separator or a dividing wall acting in series or in stages. Each series or stage geometry may be configured as a separate container or as discrete chambers integrated into one container. The gas may be provided at a rate of about 0.05ft/s to about 1.5ft/s, such as about 0.1ft/s to about 0.3ft/s, such as about 0.1ft/s, wherein separation of the third or fourth phases within the ash rich phase may be achieved so as to increase the separation efficiency of the catalyst rich phase.
From separator 106, catalyst (e.g., spent catalyst) is introduced via conduit 140 into regenerator 108 configured to form regenerated catalyst. An oxygen-carrying gas, such as air, may be introduced into the regenerator 108 to regenerate the spent catalyst and combust material (e.g., carbonaceous material such as ash disposed on the catalyst). In some embodiments, air is introduced into regenerator 108 at a rate of about 107,000lb/hr to about 165,000lb/hr, such as about 133,000lb/hr to about 151,000lb/hr, such as about 145,000 lb/hr.
The regenerated catalyst formed in regenerator 108 is then introduced into riser 102 a.
In some embodiments, the plastic melt is not introduced into riser 102 a. Gases such as cracking gases, product gases, reactant gases, recycle gases, or a combination thereof are introduced into riser 102a via inlet 132. For example, the gas is introduced into riser 102a at a rate of about 18,000lb/hr to about 23,000lb/hr, such as about 21,000lb/hr to about 22,000 lb/hr.
In some embodiments, gas is introduced into the reactor 102 via inlet 130. For example, the gas may be introduced into the reactor 102 via a nozzle at a rate of about 3,000lb/hr, about 12,000lb/hr, such as about 7,750lb/hr about 10,250 lb/hr. The nozzle may have an outlet of a diameter of about 6mm to about 20mm, such as about 13 mm.
The gas introduced into riser 102a and/or reactor 102 may be a refining, product recycle fluid (e.g., gas or liquid). The gas provides a fluidizing medium in the reactor 102 and also provides improved conversion/yield of the reactor feed to the pyrolysis products. For example, in embodiments in which the gas is a recycle fluid, the recycle fluid may contain a paraffin material that provides conversion toward pyrolysis products, such as aromatics, thereby increasing the yield of the target product.
In some embodiments, the gas (and/or coinjection material and/or recycle oil) is introduced into the reactor indirectly via the inlet of the nozzle 110 and the nozzle 110 has an outlet diameter that is less than the nozzle inner diameter (as shown in fig. 2B). For example, the nozzle may have a maximum inner diameter of about 10mm to about 20mm, such as about 15mm, and the nozzle may have an outlet of about 4mm to about 12mm, such as about 8mm, diameter. The gas injected into the nozzle inlet (in combination with the recycled oil) helps to initially shear the plastic melt into fine droplets. The narrower outlet again shears the material into fine droplets, e.g., 70-80 microns, and disperses the droplets. The fine droplets allow the material to be heated rapidly for pyrolysis (and less undesirable byproducts are formed due to the reduced residence time required in the reactor).
During use, the catalyst particles in the reactor 102 may be in the form of an emulsion. Because gas is introduced into the reactor 102 via the riser 102a and the chemical reaction effluent, bubbles may form within the reactor 102. The reactor 102 may be configured to break up bubbles formed in the reactor 102. Mass transfer of the plastic melt to the catalyst is promoted by breaking up bubbles in the reactor 102. For example, the entry of pyrolyzed plastic molecules into the pores of the catalyst is promoted, thereby promoting better conversion of the plastic into pyrolysis products. In addition, the formation of larger bubbles promotes mechanical vibration within the reactor, and thus breaking bubbles may reduce or eliminate the occurrence of mechanical vibration contributed by larger bubbles.
In some embodiments, the reactor 102 has a plurality of plates, nets, or structural grid sheds (not shown) disposed within the reactor. For example, a plurality of plates, webs, or structured grids may have an arrangement of first columns and second columns of plates, webs, or structured grids, wherein the first columns are offset from the second columns in a horizontal direction. In some embodiments, one or more nets or cell sheds have an angular apex cover in a vertical direction and one or more openings along their covers.
Catalyst
The catalyst used for the pyrolysis of the plastic melt may be any suitable pyrolysis catalyst. In some embodiments, the catalyst is a composite body having multiple components. These components may include one or more materials that are catalytically active in the conversion of the plastic in the reactor feed to the desired pyrolysis product. These components may include, for example, but are not limited to, zeolites, clays, acid-impregnated clays, alumina, silica-alumina, spent FCC catalyst, equilibrium FCC catalyst, metal oxides, mixed metal oxides, or combinations thereof. The catalyst components may also include one or more materials that bind the catalyst components together so as to improve their physical strength. These binder materials may include, for example, but are not limited to, various aluminas, silicas, magnesias, clays, and other clays and minerals. The catalyst component may also include one or more materials that define other aspects of the composite catalyst body, such as density, porosity, and pore size distribution. These modifying materials may include, but are not limited to, various aluminas, aluminum hydroxides, aluminum oxyhydroxides, clays, earth, fillers, or combinations thereof. In addition, these modifying materials may act as hardeners, densification agents, porosity enhancing burnout materials, stabilizers, diluents, activity promoters, activity stabilizers, or combinations thereof. Further these modifying materials may include one or more components that sequester feed contaminants such as metals, semi-metals, or halogens. In addition, these modifying materials may include one or more components that reduce emissions of sulfur oxides, nitrogen oxides, or acid gases from the pyrolysis system. In addition, these modifying materials may include one or more components that control and regulate the combustion of carbon and the emissions of oxidized carbon from the pyrolysis system regenerator. In some embodiments, the additive material is a matrix formed from an active material, such as an active alumina material (amorphous or crystalline), a binder material (such as alumina or silica), an inert filler (such as kaolin), or a combination thereof. For example, the catalyst may comprise a zeolite material disposed in a matrix.
In some embodiments, the various catalyst components are in the bulk of a homogeneous composition. In other embodiments, the various components are distributed between two or more bodies, which may be physically mixed so as to achieve the total desired amount of the various individual components.
In some embodiments, the catalyst is a group VIII metal or compound thereof, a group VIB metal or compound thereof, a group VIIB metal or compound thereof, or a group IIB metal or compound thereof, or a combination thereof. For example, the group VIB metal or compound thereof can comprise molybdenum and/or tungsten. The group VIII metal or compound thereof may include nickel and/or cobalt. The group VIIB metal or compound thereof may comprise manganese and/or rhenium. The group IIB metal or compound thereof may include zinc and/or cadmium. In some embodiments, the catalyst is a sulfided catalyst. In some embodiments, the catalyst is a cobalt-molybdenum catalyst, a nickel-molybdenum catalyst, a tungsten-molybdenum catalyst, sulfides thereof, or combinations thereof. In some embodiments, the catalyst is a platinum-molybdenum catalyst, a tin-platinum catalyst, a platinum-gallium catalyst, a platinum-chromium catalyst, a platinum-rhenium, or a combination thereof. In some embodiments, the catalyst comprises cobalt and molybdenum, nickel and molybdenum, iron and molybdenum, palladium and molybdenum, platinum and molybdenum, or nickel and platinum. The group IIIB metal or compound thereof may include lanthanum and/or cerium.
In some embodiments, the catalytically active component may comprise one or more zeolites, which may include, but are not limited to, X-type, Y-type, mordenite which may be X-type zeolite, Y-type zeolite, USY-type zeolite, mordenite, faujasite, nanocrystalline zeolite, MCM mesoporous material, SBA-15, silico-aluminophosphate, gallium phosphate, titanium phosphate. In some embodiments, the catalyst may include one or more zeolites (or metal-loaded zeolites). In some embodiments, the zeolite is ZSM-5, ZSM-11, aluminosilicate zeolite, ferrierite, heulandite, zeolite A, erionite, chabazite, or a combination thereof.
In some embodiments, the catalytically active component is a zeolite, such as a medium pore zeolite, such as a ZSM-5 zeolite. ZSM-5 zeolite is a molecular sieve, i.e., a porous material having an intersecting two-dimensional pore structure with 10-membered oxygen containing rings. Zeolitic materials having such 10-membered oxygen ring pore structures are generally classified as mesoporous zeolites. These medium pore zeolites typically have a pore size of 5.0 angstromsTo->Is a pore size of the polymer. ZSM-5 zeolite has about +.>To about->A mesoporous size zeolite of pore size.
Other properties of the ZSM-5 zeolite may include one or more of the following: (1) About 20 to about 600, such as about 30, of SiO 2 /Al 2 O 3 Molar ratio; (2) About 320 or greater, such as about 340 or greater, such asSuch as about 320 to about 380, a Brunauer-Emmett-Teller (BET) surface area (m 2 /g); and/or (3) in hydrogen or ammonium ion exchanged form.
The catalysts of the present disclosure may have particle sizes small enough to achieve the following goals (1) allow for uniform reactor and regenerator fluidization without the need for extreme velocities, (2) provide good contact of the catalyst with the feed (e.g., plastic melt, recycle cracked gas, etc.) and reduce/minimize external diffusion barriers, (3) allow for smooth regeneration without hot spots that may occur when the particles are too large, and/or (4) allow for smooth pneumatic transport without the need for higher gas velocities. The catalysts of the present disclosure may have a sufficiently large particle size and density (1) to allow for a higher ratio of catalyst to feed during pyrolysis, (2) to allow for higher space velocity (throughput) while minimizing entrainment, (3) to allow for good catalyst separation and release from the bottom of the reactor and the bottom of the regenerator, and/or (4) to allow for an effective separation or separable phase (non-catalyst solids such as char, co-injected material) with lighter, smaller ash when a separator is used. In some embodiments, the catalyst has an average diameter of about 450 microns to about 650 microns, such as about 500 microns to about 600 microns, such as about 540 microns to about 560 microns.
In some embodiments, the catalyst may have a narrower diameter distribution. For example, the catalyst may have a diameter distribution of about +/-200 microns, such as about +/-150 microns, such as about +/-75 microns, of the average diameter of the catalyst. In some embodiments, the catalyst has a D1% value of about 380 microns to about 420 microns, such as about 400 microns. D1% is the diameter of the catalyst such that 99wt% of the catalyst has a diameter greater than the value of D1%. In some embodiments, the catalyst has a d99% value of about 680 microns to about 720 microns, such as about 700 microns. D99% is the diameter of the catalyst such that 99wt% of the catalyst has a diameter less than the d99% value. The narrower size (e.g., diameter) distribution of the catalyst may (1) reduce or minimize dense phase separation in the reactor and regenerator, (2) reduce or minimize preferential and dilute phase transport at higher feed or regenerator air rates, and/or (3) reduce or minimize plugging at vessel discharge ports, slide valves, Y-junctions, etc.
In some embodiments, the catalyst has an average particle density of about 300g/l to about 1,200g/l, such as about 500g/l to about 1,000g/l, such as about 600g/l to about 800 g/l.
In some embodiments, the catalyst has a sphericity of about 0.9 or greater, such as about 0.95 or greater, such as about 0.99 or greater.
In some embodiments, the catalyst has an active catalyst (e.g., zeolite) loading of about 50wt% or greater, such as about 60wt% or greater, such as about 75wt% or greater, such as about 85wt% or greater, wherein the balance of the catalyst comprises the additive material. For example, the additive material may include any suitable binder material.
The catalysts of the present disclosure may have a attrition resistance, referred to as attrition resistance index, of less than 10 when measured in a jet cup apparatus at an air jet velocity of 200 ft/sec.
The catalysts of the present disclosure may have a crush strength of greater than 1 newton, such as greater than 5 newtons, as measured in a single bead anvil test apparatus.
In some embodiments, the catalyst is in the form of particles, pellets, extrudates, cut extrudates, linked extrudates, beads, lozenges, spheres, or a combination thereof.
The catalysts of the present disclosure may be obtained by any suitable process (such as spray drying) and/or may be obtained from commercial sources. For example, the catalyst may be formed by spray drying, pelletizing, oil and water dripping, granulating, fluidized bed coacervation, spray coating a compact, extrusion, or any combination thereof. The catalyst may be cut, crushed, ground, or screened to provide any suitable size (e.g., diameter) distribution. The catalyst may be further prepared by polishing, densification, or spheronization in a rotating disk, rotating drum, or the like.
More than one type of catalyst may be introduced into the reactor 102. For example, a first catalyst is introduced into the reactor 102 through a conduit and a second catalyst is introduced into the reactor 102 through a different conduit. The first catalyst and the second catalyst may be introduced into the reactor 102 at the same or different flow rates in order to control the relative amounts of catalyst in the reactor 102 at any given time. The balance of the first catalyst and/or the second catalyst may include an additive material, such as a binder material.
Additionally or alternatively, the first catalyst and the second catalyst are introduced into the reactor 102 via a single conduit (as a mixture of catalysts). For example, the mixture of catalysts may be a single-body catalyst comprising both catalysts. The balance of the unitary body catalyst may include additive materials, such as binder materials.
In some embodiments, sand having a density of about 1450g/l to about 1680g/l may be mixed with the catalyst. Examples of sand include quartz sand, silica sand, sand containing a metal or metal oxide, or combinations thereof. The use of sand can inhibit contamination of the catalyst by contaminants generated during pyrolysis. The sand may also provide thermal and catalytic activity that controls the pyrolysis occurring in the reactor. Sand may be used in an amount of up to about 99wt% based on the total amount of sand + catalyst.
Additional aspects
The present disclosure provides, inter alia, that each of the following aspects can be considered to include any alternative aspects as appropriate.
Clause 1. A process comprising:
introducing a plastic melt comprising a plastic component into the reactor via a nozzle coupled to the reactor;
introducing a catalyst into the reactor via a first conduit coupling the reactor with a riser or regenerator;
pyrolyzing the plastic component to form a pyrolysis product;
removing pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor;
removing catalyst from the reactor via a third conduit disposed at a lower 1/2 height of the reactor, wherein the catalyst removed from the reactor comprises ash; and
the catalyst from the third conduit is introduced into the separator to form a catalyst rich phase and an ash rich phase in the separator.
Clause 2. The process of clause 1, wherein the third conduit is disposed at an angle of about 30 ° to about 90 ° relative to the substantially vertical side of the separator.
Clause 3 the process of clause 1 or 2, further comprising introducing a gas into the third conduit.
The process of any of clauses 1-3, wherein the catalyst introduced into the separator when introduced into the separator has a temperature of about 950°f to about 1,050°f and is introduced into the separator at a rate of about 1.3 million pounds per hour to about 1.7 million pounds per hour.
Clause 5 the process of any of clauses 1 to 4, wherein the third conduit has an end disposed within the separator and the end comprises a plurality of outlets.
Clause 6 the process of any of clauses 1 to 5, wherein the end of the third conduit is positioned at 1/4 to 3/4 of the height of the separator.
The process of any of clauses 1-6, further comprising introducing a gas into the separator via a fourth conduit at a rate of about 0.3ft/s to about 0.7ft/s, wherein the gas has a temperature of about 150°f to about 1050°f.
The process of any of clauses 1-7, wherein forming the catalyst-rich phase and the ash-rich phase in the separator is performed at a pressure of about 25psig to about 40psig and a temperature of about 850°f to about 1,050°f.
The process of any one of clauses 1 to 8, further comprising introducing the catalyst rich phase into a regenerator.
The process of any of clauses 10, 1 to 9, wherein the catalyst introduced into the reactor comprises zeolite and sand and the catalyst introduced into the separator from the third conduit comprises zeolite, sand and ash.
The process of any of clauses 1-10, wherein introducing the catalyst from the third conduit into the separator further forms a sand-rich phase in the separator, the process further comprising removing the sand-rich phase from the separator via a fourth conduit.
The process of any one of clauses 1-11, further comprising sorting the bale comprising the plastic component into a plurality of portions, wherein at least one of the portions comprises the plastic component.
The process of any of clauses 1-12, wherein the reactor is a bubbling bed reactor and the plastic melt has a temperature of about 900°f to about 1,100°f during introduction of the plastic melt into the reactor.
The process of any of clauses 1-14, wherein the plastic group is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, and combinations thereof.
The process of any of clauses 1-14, wherein the pyrolysis product comprises an organic compound selected from the group consisting of ethylene, propylene, butene, benzene, toluene, xylene, and combinations thereof.
The process of any one of clauses 1 to 15, further comprising introducing co-injected particles into the reactor.
The process of any of clauses 1-16, wherein the coinjection particles are introduced into the reactor through a nozzle at a rate of about 1,000lb/hr to about 3,000 lb/hr.
The process of any one of clauses 1 to 17, further comprising removing the coinjection particles, or the product thereof, from the reactor via a second conduit.
The process of any one of clauses 1 to 18, wherein the coinjection particles are calcium oxide, and the process comprises removing the calcium chloride from the reactor via a second conduit.
The process of any of clauses 1-19, wherein the coinjection particles are a zeolite selected from the group consisting of a 4A zeolite, a 5A zeolite, and a combination thereof.
The process of any one of clauses 1 to 20, wherein the coinjection particles have an average diameter of less than 400 microns.
The process of any one of clauses 1 to 21, wherein the coinjection particles have an average diameter of less than 200 microns.
Clause 23 the process of any of clauses 1 to 22, further comprising:
introducing coinjected particles or products thereof into the cyclone separator via a second conduit;
separating the coinjection particles or their products from the pyrolysis products using a cyclone separator;
removing pyrolysis products from the cyclone via a fourth conduit; and
via a fifth conduit, the coinjection particles or their products are removed from the cyclone.
The process of any one of clauses 1 to 23, further comprising introducing a cracking gas into the reactor.
The process of any of clauses 25, 1 to 24, wherein introducing the cracking gas into the reactor is performed via a nozzle at a rate of about 6,000lb/hr to about 12,000 lb/hr.
The process of any of clauses 1 to 25, wherein introducing the plastic melt into the reactor is performed at a rate of about 60,000lb/hr to about 100,000 lb/hr.
The process of any of clauses 27, 1 to 26, wherein removing the catalyst from the reactor comprises removing the catalyst from the reactor via a third conduit disposed at a bottom surface of the reactor.
The process of any one of clauses 1 to 27, further comprising introducing catalyst from the reactor into the separator and the regenerator to form regenerated catalyst.
The process of any one of clauses 1 to 28, further comprising introducing the regenerated catalyst into a riser or vessel.
The process of any one of clauses 1 to 29, wherein the plastic melt is not introduced into a riser.
The process of any one of clauses 1 to 30, further comprising introducing a gas into the riser.
The process of any of clauses 1-31, wherein the cracked gas is introduced into the riser at a rate of about 9,000lb/hr to about 11,500 lb/hr.
The process of any one of clauses 33, 1 to 32, wherein the nozzle coupled to the reactor is further coupled to a source of plastic melt, wherein the source of plastic melt is not a riser.
The process of any of clauses 1-33, wherein the plastic melt further comprises a viscosity-reducing agent.
The process of any of clauses 1-34, wherein the viscosity-reducing agent comprises an aromatic liquid selected from the group consisting of benzene, toluene, xylene, and combinations thereof.
The process of any of clauses 1-35, wherein pyrolyzing the plastic component is performed at a reactor temperature of about 900°f to about 1,100°f and a reactor pressure of about 20psig to about 40 psig.
The process of any of clauses 37, 1 to 36, wherein the cracked gas is introduced into the reactor via a nozzle and the nozzle has an outlet diameter less than the nozzle inner diameter.
The process of any of clauses 38, wherein introducing the catalyst into the reactor via the first conduit is performed at a catalyst flow rate of about 5.5 ton minutes to about 13.8 ton minutes.
The process of any of clauses 39, 1 to 38, wherein introducing the catalyst into the reactor via the first conduit is performed at a catalyst flow rate of about 7.5 ton minutes to about 12.4 ton minutes.
Clause 40 the process of any of clauses 1 to 39, wherein prior to introducing into the reactor, the catalyst is disposed in a riser and the catalyst has a minimum gas fluidization velocity of about 0.4ft/sec to about 0.6 ft/sec.
The process of any one of clauses 41, 1 to 40, wherein the catalyst is a zeolite.
Clause 42 the process of any of clauses 1 to 41, wherein the zeolite is a ZSM-5 zeolite.
The process of any one of clauses 1 to 42, wherein the catalyst has an average diameter of about 500 microns to about 600 microns.
Clause 44 the process of any of clauses 1 to 43, wherein the catalyst has a D1% value of about 400 microns and a D99% value of about 700 microns.
Clause 45 the process of any of clauses 1 to 44, wherein the catalyst has a density of about 600g/l to about 800 g/l.
Clause 46 the process of any of clauses 1 to 45, wherein the catalyst has a sphericity of about 0.95 or greater.
The process of any of clauses 47, 1 to 46, wherein the catalyst has a zeolite loading of about 50 weight percent or greater, wherein the balance of the catalyst comprises the additive material.
Clause 48 the process of any of clauses 1 to 47, wherein the catalyst has a zeolite loading of about 75 weight percent or greater.
Clause 49 the process of any of clauses 1 to 48, wherein the additive material comprises a binder material.
The process of any one of clauses 1 to 49, wherein the reactor comprises a plurality of plates, webs, or square grids, including a first strake, web, or square grid and a second strake, web, or square grid, wherein the first columns are horizontally offset from the second columns.
Clause 51 the process of any of clauses 1 to 50, wherein each plate, net, or square of the plurality of plates, nets, or square grids has a tent-shaped angular apex cover in a vertical direction and has one or more openings along the cover.
Clause 52 the process of any of clauses 1 to 51, wherein the plastic melt has a solids content of about 10 weight percent or less.
Clause 53, an apparatus comprising:
a nozzle coupled to the reactor, the nozzle including an inlet disposed substantially perpendicular to a horizontal conduit disposed in the nozzle.
A riser coupled to the reactor;
a first outlet conduit disposed at an upper 1/2 height of the reactor, the first outlet conduit coupled to the cyclone; and
a second outlet conduit disposed at a lower 1/2 height of the reactor, the second outlet conduit coupled to the second separator;
a regenerator coupled to the second separator and the riser.
Clause 54 the apparatus of clause 53, wherein the reactor comprises a plurality of plates, webs, or square grids comprising a first column and a second column of plates, webs, or square grids, wherein the first column is horizontally offset from the second column.
Clause 55. The apparatus of clause 53 or 54, wherein the second outlet conduit is positioned at the bottom surface of the reactor.
Clause 56. A process comprising:
removing the catalyst from the reactor, wherein the catalyst comprises ash;
introducing catalyst into the separator via a conduit to form a catalyst-rich phase and an ash-rich phase in the separator; and
the catalyst rich phase is introduced into a regenerator to form a regenerated catalyst,
wherein the conduit has an end disposed within the separator at 1/4 to 3/4 the height of the separator and the end comprises a plurality of outlets.
Clause 57 the process of any of clauses 1 to 52 or 56, wherein the conduit is at about 30 relative to the substantially vertical side of the separator ° Up to about 90 ° Is arranged at an angle to the axis of the lens.
The process of any one of clauses 1 to 52, 56, or 57, further comprising introducing a gas into the conduit.
Clause 59 the process of any of clauses 1 to 52 or 56 to 58, wherein the catalyst introduced into the separator when introduced into the separator has a temperature of about 950°f to about 1,050°f and is introduced into the separator at a rate of about 1.3 million pounds per hour to about 1.7 million pounds per hour.
Clause 60 the process of any of clauses 1 to 52 or 56 to 59, further comprising introducing the gas into the separator via the second conduit at a rate of about 0.3ft/s to about 0.7ft/s, wherein the gas has a temperature of about 150°f to about 1050°f.
Clause 61 the process of any of clauses 1 to 52 or 56 to 60, wherein forming the catalyst-rich phase and the ash-rich phase in the separator is performed at a pressure of about 25psig to about 40psig and a temperature of about 850°f to about 1,050°f.
Clause 62 the process of any of clauses 1 to 52 or 56 to 61, wherein the catalyst introduced into the reactor comprises zeolite and sand and the catalyst introduced from the conduit into the separator comprises zeolite, sand and ash.
Clause 63. The process of any of clauses 1 to 52 or 56 to 62, wherein introducing the catalyst from the conduit into the separator further forms a sand-rich phase in the separator, the process further comprising removing the sand-rich phase from the separator via a second conduit.
Clause 64 the process of any of clauses 1 to 52 or 56 to 63, further comprising introducing the ash-rich phase into a second separator to form a second catalyst-rich phase and a second ash-rich phase.
Clause 65 the process of clause 64, wherein the second separator is a stage volume within the first separator.
Clause 66, a process comprising:
introducing a plastic melt comprising a plastic component into the reactor via a nozzle coupled to the reactor;
introducing a catalyst into the reactor via a first conduit coupling the reactor with a riser or regenerator;
Pyrolyzing the plastic component to form a pyrolysis product;
removing pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor; and
the catalyst was removed from the reactor via a third conduit disposed at the lower 1/2 height of the reactor.
Clause 67 the process of clause 66, further comprising sorting the bale comprising the plastic component into a plurality of portions, wherein at least one of the portions comprises the plastic component.
Clause 68 the process of clause 66 or 67, wherein the reactor is a bubbling bed reactor and the plastic melt has a temperature of about 900°f to about 1,100°f during introduction of the plastic melt into the reactor.
Clause 69 the process of any of clauses 66 to 68, wherein the plastic group is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, and combinations thereof.
Clause 70 the process of any of clauses 66 to 69, wherein the pyrolysis product comprises an organic compound selected from the group consisting of ethylene, propylene, butene, benzene, toluene, xylene, and combinations thereof.
Clause 71 the process of any of clauses 66 to 70, further comprising introducing co-injected particles into the reactor.
The process of any one of clauses 66 to 71, wherein the coinjection particles are introduced into the reactor through a nozzle at a rate of about 1,000lb/hr to about 3,000 lb/hr.
Clause 73 the process of any of clauses 66 to 72, further comprising removing the coinjection particles, or the product thereof, from the reactor via a second conduit.
The process of any one of clauses 74, 66 to 73, wherein the co-injected particle is calcium oxide, and the process comprises removing calcium chloride from the reactor via a second conduit.
The process of any of clauses 66 to 74, wherein the coinjection particles are a zeolite selected from the group consisting of a 4A zeolite, a 5A zeolite, and a combination thereof.
The process of any one of clauses 66 to 75, wherein the coinjection particles have an average diameter of less than 400 microns.
The process of any one of clauses 66 to 76, wherein the coinjection particles have an average diameter of less than 200 microns.
Clause 78 the process of any one of clauses 66 to 77, further comprising:
introducing coinjected particles or products thereof into the cyclone separator via a second conduit;
separating the coinjection particles or their products from the pyrolysis products using a cyclone separator;
removing pyrolysis products from the cyclone via a fourth conduit; and
Via a fifth conduit, the coinjection particles or their products are removed from the cyclone.
Clause 79 the process of any of clauses 66 to 78, further comprising introducing a cracked gas into the reactor.
The process of any one of clauses 66 to 79, wherein introducing the cracking gas into the reactor is performed at a rate of about 3,000lb/hr to about 5,000lb/hr via a nozzle.
Clause 81 the process of any of clauses 66 to 80, wherein introducing the plastic melt into the reactor is performed at a rate of about 30,000lb/hr to about 50,000 lb/hr.
The process of any of clauses 82, 66 to 81, wherein removing the catalyst from the reactor comprises removing the catalyst from the reactor via a third conduit disposed at a bottom surface of the reactor.
Clause 83. The process of any of clauses 66 to 82, further comprising introducing the catalyst from the reactor into a separator and a regenerator to form a regenerated catalyst.
The process of any one of clauses 66 to 83, further comprising introducing the regenerated catalyst into a riser or vessel.
Clause 85 the process of any of clauses 66 to 84, wherein the plastic melt is not introduced into the riser.
The process of any one of clauses 66 to 85, further comprising introducing a gas into the riser.
The process of any one of clauses 66 to 86, wherein the cracked gas is introduced into the riser at a rate of about 9,000lb/hr to about 11,500 lb/hr.
The process of any one of clauses 88, wherein the nozzle coupled to the reactor is further coupled to a source of plastic melt, wherein the source of plastic melt is not a riser.
Clause 89 the process of any of clauses 66 to 88, wherein the plastic melt further comprises a viscosity reducing agent.
The process of any of clauses 66 to 89, wherein the viscosity reducing agent comprises an aromatic liquid selected from the group consisting of benzene, toluene, xylene, and combinations thereof.
The process of any of clauses 66 to 25, wherein pyrolyzing the plastic component is performed at a reactor temperature of about 900°f to about 1,100°f and a reactor pressure of about 20psig to about 40 psig.
The process of any one of clauses 66 to 91, wherein the cracked gas is introduced into the reactor via a nozzle and the nozzle has an outlet diameter less than the nozzle inner diameter.
The process of any one of clauses 66 to 92, wherein introducing the catalyst into the reactor via the first conduit is performed at a catalyst flow rate of about 2.5 ton minutes to about 8.8 ton minutes.
The process of any one of clauses 66 to 93, wherein introducing the catalyst into the reactor via the first conduit is performed at a catalyst flow rate of about 3.5 ton minutes to about 4.4 ton minutes.
The process of any of clauses 66 to 94, wherein the catalyst disposed in the riser has a minimum gas fluidization velocity of about 0.4ft/sec to about 0.6 ft/sec.
The process of any one of clauses 66 to 95, wherein the catalyst is a zeolite.
The process of any one of clauses 66 to 96, wherein the zeolite is a ZSM-5 zeolite.
The process of any one of clauses 66 to 97, wherein the catalyst has an average diameter of about 500 microns to about 600 microns.
The process of any one of clauses 66 to 98, wherein the catalyst has a D1% value of about 400 microns and a D99% value of about 700 microns.
The process of any one of clauses 66 to 99, wherein the catalyst has a density of about 600g/l to about 800 g/l.
Clause 101 the process of any of clauses 66 to 100, wherein the catalyst has a sphericity of about 0.95 or greater.
The process of any one of clauses 66 to 101, wherein the catalyst has a zeolite loading of about 50 weight percent or greater, wherein the balance of the catalyst comprises the additive material.
Clause 103 the process of any of clauses 66 to 102, wherein the catalyst has a zeolite loading of about 75 weight percent or greater.
The process of any one of clauses 66 to 103, wherein the additive material comprises a binder material.
The process of any one of clauses 66 to 104, wherein the reactor comprises a plurality of plates, webs, or square grids, including a first strake, web, or square grid and a second strake, web, or square grid, wherein the first columns are horizontally offset from the second columns.
The process of any one of clauses 66 to 105, wherein each plate, net, or square of the plurality of plates, nets, or square grids has a tent-shaped angular apex cover in a vertical direction and has one or more openings along the cover.
Clause 107 the process of any of clauses 66 to 106, wherein the plastic melt has a solids content of about 10 weight percent or less.
In general, the apparatus and processes of the present disclosure provide high throughput pyrolysis, such as plastic pyrolysis, to form pyrolysis products. The process may be performed as a single stage process, providing a higher yield than conventional processes for treating waste plastics. The apparatus and process of the present disclosure provides for elutriation of char, attrition catalyst, and coinjection materials so that spent catalyst can be easily regenerated, providing improved throughput for pyrolysis of plastics in addition to higher purity of catalyst recycled to the reactor. In addition, the use of a catalyst having a narrower size distribution and a larger average diameter than the coinjection material allows the coinjection material to elutriate. In addition, the use of a catalyst having a larger average diameter in addition to the reactor configured to provide bubble control results in reduced plugging and wear of vessel piping, valves, and other equipment components, thereby maintaining the integrity and longer service life of the equipment of the present disclosure. In addition, the use of the separator of the present disclosure provides improved throughput of pyrolysis products as the separation of spent catalyst from components such as ash is improved. The use of the separator improves throughput, particularly because the catalyst can remain viable (e.g., the catalyst can be regenerated) such that the time interval between plant shutdowns can be prolonged. The separators of the present disclosure may also provide improved regeneration of spent catalyst (as ash is removed at the separator), thereby further improving the throughput and yield of pyrolysis products.
The term "pyrolysis" includes the conversion of molecules into (i) atoms and/or (ii) molecules of smaller molecular weight, and/or optionally (iii) average endothermic reactions of molecules of larger molecular weight, e.g., forming, for example, ethylene, propylene, acetylene, benzene, toluene, di-Toluene or combinations thereof 2 -C 12 Process for unsaturated materials.
The term "catalyst activity" includes the weight of volatile material converted per weight of catalyst in a given amount of time.
The term "spent catalyst" includes any catalyst that is less active under the same reaction conditions (e.g., temperature, pressure, inlet flow) than the catalyst that was originally exposed to the process. Many non-limiting examples of reasons for catalyst deactivation are coking or carbon adsorption or accumulation, metal adsorption or accumulation, attrition, morphological changes including pore size changes, cationic or anionic substitution, and/or chemical or compositional changes. In addition to deactivated catalyst, spent catalyst may include some amount of non-deactivated (e.g., non-deactivated) catalyst.
The term "regenerated catalyst" includes the following catalysts: the catalyst has become deactivated as defined above and is then subjected to a process as defined above that increases its activity to a level greater than that it has as a spent catalyst. This may involve, for example, reversing the transformation or removing the contaminants outlined above as a possible cause of reduced activity. Regenerated catalysts may have an activity greater than or equal to that of fresh catalyst (often referred to herein as "catalyst" unless otherwise indicated), but typically regenerated catalysts have an activity between spent catalyst and fresh catalyst.
The term "pyrolysis gas" includes hydrocarbon fluids (gas or liquid) derived from waste plastic materials. The cleavage gas may be present in the form of fines recovered from the original effluent stream of the reactor or via a recycle stream for fluidization or further conversion in the reactor system.
The term "ash" includes ash removed from the reactor and separated from other materials. Ash is a solid phase that is not considered part of the group of particles of the catalyst that is circulated through the apparatus. The ash may be attrition catalyst fines, char from the plastic, and/or co-injected material, which may be metal oxide or catalyst, by material.
Although embodiments of the invention are described with respect to pyrolysis of plastic feedstock, embodiments of the invention may be used in any other suitable apparatus or process where applicable. For example, the separator of the present disclosure (e.g., separator 106) may be used in any suitable apparatus or process, such as solid-solid separation in conventional petrochemical processes that incorporate fluid catalytic cracking such as crude oil and the like.
Unless otherwise specified, the phrase "consisting essentially of (consists essentiallyof/consisting essentiallyof)" does not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in the present specification, as long as such steps, elements, or materials do not affect the basic and novel characteristics of the present disclosure, and in addition, it does not exclude impurities and variations normally associated with the elements and materials used.
For brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to recite a range not explicitly recited, and a range from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, as such a range from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, ranges include endpoints thereof between each point or individual value, although not explicitly stated. Thus, each point or individual value may serve as its own lower or upper limit, in combination with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
All numerical values within the embodiments herein are defined by "about" indicated values and take into account experimental errors and variations as would be expected by one of ordinary skill in the art.
All documents described herein are incorporated by reference herein, including any priority documents and or test procedures, so long as they are not inconsistent with this document. As is apparent from the foregoing general description and specific embodiments, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, the margin within this disclosure is not desired. Likewise, for purposes of united states law, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a transitional phrase "comprising" precedes a composition, element, or group of elements, it is understood that we also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of … …", "consisting of … …", "selected from the group consisting of … …", or "being" prior to the recitation of the composition, element, or elements, and vice versa.
Although the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims (20)

1. A process, comprising:
introducing a plastic melt comprising a plastic component into a reactor via a nozzle coupled to the reactor;
introducing a catalyst into the reactor via a first conduit coupling the reactor with a riser or regenerator;
pyrolyzing the plastic component to form a pyrolysis product;
removing the pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor;
removing the catalyst from the reactor via a third conduit disposed at a lower 1/2 height of the reactor, wherein the catalyst removed from the reactor comprises ash; and
the catalyst from the third conduit is introduced into a separator to form a catalyst rich phase and an ash rich phase in the separator.
2. The process of claim 1, wherein the third conduit is disposed at an angle of about 30 ° to about 90 ° relative to a substantially vertical side of the separator.
3. The process of claim 2, further comprising introducing a gas into the third conduit.
4. The process of claim 2, wherein the catalyst introduced into the separator when introduced into the separator has a temperature of about 950°f to about 1,050°f and is introduced into the separator at a rate of about 1.3 million pounds per hour to about 1.7 million pounds per hour.
5. The process of claim 1, wherein the third conduit has an end disposed within the separator and the end comprises a plurality of outlets.
6. The process of claim 5, wherein the end of the third conduit is positioned at 1/4 to 3/4 the height of the separator.
7. The process of claim 1, further comprising introducing a gas into the separator via a fourth conduit at a rate of about 0.3ft/s to about 0.7ft/s, wherein the gas has a temperature of about 150°f to about 1050°f.
8. The process of claim 1, wherein forming the catalyst-rich phase and the ash-rich phase in the separator is performed at a pressure of about 25psig to about 40psig and a temperature of about 850°f to about 1,050°f.
9. A process, comprising:
removing catalyst from the reactor, wherein the catalyst comprises ash;
Introducing the catalyst into a separator via a conduit to form a catalyst-rich phase and an ash-rich phase in the separator; and
introducing the catalyst-rich phase into a regenerator to form a regenerated catalyst,
wherein the conduit has an end disposed within the separator at 1/4 to 3/4 of the height of the separator and the end includes a plurality of outlets.
10. The process of claim 9, wherein the conduit is disposed at an angle of about 30 ° to about 90 ° relative to a substantially vertical side of the separator.
11. The process of claim 9, wherein the catalyst introduced into the separator when introduced into the separator has a temperature of about 950°f to about 1,050°f and is introduced into the separator at a rate of about 1.3 million pounds per hour to about 1.7 million pounds per hour.
12. The process of claim 9, further comprising introducing a gas into the separator via a second conduit at a rate of about 0.3ft/s to about 0.7ft/s, wherein the gas has a temperature of about 150°f to about 1050°f.
13. The process of claim 9, wherein forming the catalyst-rich phase and the ash-rich phase in the separator is performed at a pressure of about 25psig to about 40psig and a temperature of about 850°f to about 1,050°f.
14. A process, comprising:
introducing a plastic melt comprising a plastic component into a reactor via a nozzle coupled to the reactor;
introducing a catalyst into the reactor via a first conduit coupling the reactor with a riser or regenerator;
pyrolyzing the plastic component to form a pyrolysis product;
removing the pyrolysis products from the reactor via a second conduit disposed at an upper 1/2 height of the reactor; and
the catalyst was removed from the reactor via a third conduit disposed at the lower 1/2 height of the reactor.
15. The process of claim 14, further comprising sorting a bale comprising the plastic components into a plurality of portions, wherein at least one of the portions comprises the plastic components.
16. The process of claim 14, wherein the reactor is a bubbling bed reactor and the plastic melt has a temperature of about 900°f to about 1,100°f during introduction of the plastic melt into the reactor.
17. The process of claim 14, wherein the plastic group is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, and combinations thereof.
18. The process of claim 17, wherein the pyrolysis product comprises an organic compound selected from the group consisting of ethylene, propylene, butene, benzene, toluene, xylene, and combinations thereof.
19. The process of claim 14, further comprising introducing co-injected particles into the reactor, wherein the co-injected particles are calcium oxide, and the process comprises removing calcium chloride from the reactor via the second conduit.
20. The process of claim 14 wherein the catalyst is a zeolite having an average diameter of about 500 microns to about 600 microns.
CN202280052363.2A 2021-06-30 2022-06-29 Apparatus and process for pyrolysis of plastic feedstock Pending CN117836393A (en)

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US63/217,051 2021-06-30
US17/698,174 2022-03-18
US17/698,174 US20230002681A1 (en) 2021-06-30 2022-03-18 Apparatus and processes for pyrolysis of plastic feeds
PCT/US2022/073246 WO2023279016A1 (en) 2021-06-30 2022-06-29 Apparatus and processes for pyrolysis of plastic feeds

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