WO2023201169A1 - Chemical recycling of thermoset resins - Google Patents

Abstract

A variety of systems and methods are disclosed, including, in one embodiment, a method of performing coking on a combined feed, comprising: combining a resin feedstock with a coker feedstock comprising a T10 distillation point of about 343°C or higher to form a combined feedstock, wherein the resin feedstock comprises a thermoset resin having a median particle size of about 5 mm or less; and exposing at least a portion of the combined feedstock to coking conditions in a coking reactor to form at least coke and a coker effluent.

Description

CHEMICAL RECYCLING OF THERMOSET RESINS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to US Provisional Application No. 63/331,049 filed April 14, 2022, the disclosure of which is incorporated herein by reference.

FIELD

[0002] Systems and methods are provided for recycling of thermoset resins in cokers.

BACKGROUND

[0003] Onshore and offshore windmills generate significant electric energy and supply 6% of the electricity consumed in the world. Typically, windmill blades are made from fiberglass and carbon-fiber reinforced thermoset resins, including epoxies, vinyl esters, unsaturated polyesters, and polydicyclopentadiene (PDCPD). The global polymer matrix demand for windmill blades exceeded 295 kT/a. In addition to windmill blades, fiber-reinforced thermoset resins are also in demand for building construction, transportation industry, aviation, roads, consumer products, and numerous other applications.

[0004] However, thermoset resins and especially fiber-reinforced resins can be challenging to recycle into new and useful products. For instance, thermoset resins are formed of a crosslinked polymer network that cannot be melted or extruded. In addition, it has been proposed to recycle these materials by grinding them for reuse as a solid filler, but the applications that are available to use these fillers without a negative impact on performance and properties are limited. In chemical recycling, the high fiber content is problematic because of the large amounts of residue or charge these reinforcing fibers produce. As a result, windmill blades and other products containing fiber-reinforced thermoset resins are often burned or landfilled. Where not burned or landfilled, expensive and energy-intensive processes are often used for separation of the reinforcing fibers from the thermoset resin.

SUMMARY

[0005] Disclosed herein is an example method of performing coking on a combined feed, comprising: combining a resin feedstock with a coker feedstock comprising a T10 distillation point of about 343°C or higher to form a combined feedstock, wherein the resin feedstock comprises a thermoset resin having a median particle size of about 5 mm or less; and exposing at least a portion of the combined feedstock to coking conditions in a coking reactor to form at least coke and a coker effluent. [0006] Further disclosed herein is an example petroleum coke comprising a carbonaceous solid material comprising silicon in an amount of about 1000 weight parts per million (wppm) or more.

[0007] These and other features and attributes of the disclosed methods and systems of the present disclosure and their advantageous applications and/or uses will be apparent from the detailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0009] FIG. 1 shows an example of a fluidized bed coking system including a coker, a heater, and a gasifier.

[0010] FIG. 2 shows an example of a fluidized bed coking system including a coker and a gasifier.

[0011] FIG. 3 shows an example of a system and process flow for co-processing of a resin feedstock and a coker feedstock.

[0012] FIG. 4 shows a mass loss profile from thermogravimetric analysis of a PDCPD thermoset polymer sample.

[0013] FIG. 5 shows a mass loss profile from thermogravimetric analysis of another PDCPD thermoset polymer sample.

DETAILED DESCRIPTION

[0014] In various embodiments, systems and methods are provided for co-processing of resin feedstock in a coking environment. In some embodiments, the resin feedstock can be incorporated into the feed for a fluidized coking environment, such as a Flexicoking™ reaction environment. In other embodiments, the resin feedstock can be incorporated into the feed for a delayed coking environment.

[0015] The co-processing of a resin feedstock in a coking environment can be performed, for example, by performing several processes on the thermoset waste. First, the thermoset resins in the resin feedstock can be conditioned by sizing of the thermoset resins to improve the suitability of the thermoset resins for co-processing. Second, the thermoset resin particles in the resin feedstock can be entrained into a carrier fluid and/or the base coker feedstock. In embodiments where a carrier fluid is used, the carrier fluid can correspond to a refinery stream, such as a refinery' stream formed by the co-processing of the resin feedstock in the coking environment. Third, the sluny of resin feedstock can be passed into a coking environment, such as a fluidized coking environment or a delayed coking environment. The slurry of thermoset waste can be introduced as a separate stream, or the slurry can be mixed with a conventional coker feedstock prior to entering the coking environment. Fourth, the thermoset waste can then be co-processed in the coking environment to generate coke liquid products.

[0016] In some embodiments, co-processing of thermoset resins in a coking environment can provide advantages relative to coking of a conventional feed. Thermoset resins can be challenging to recycle due their lack of a melting point and inability to extrude. In addition, the inclusion of reinforcing materials, such as carbon fibers and fiberglass, in thermoset resins increase the challenges for recycling. Advantageously by coprocessing in a coking environment thermoset resin waste can be recycled while producing coke and desirable liquid products. Accordingly, examples embodiments of the present techniques provide for recycling of thermoset resins (e.g., windmill blades) without the need for pre-processing to separate reinforcing fibers.

[0017] As used herein, the naphtha boiling range is defined as roughly the boiling point of a C5 alkane (roughly 30°C) to 177°C. The distillate boiling range is defined as 177°C to 343°C. The gas oil boiling range is defined as 343°C to 566°C. The vacuum resid boiling range corresponds to temperatures greater than 566°C.

Feedstock

[0018] In various embodiments, coking can be used to co-process a combined feedstock corresponding to a mixture of a conventional coker feedstock and a resin feedstock. The conventional coker feedstock can correspond to one or more types of petroleum and/or renewable feeds with a suitable boiling range for processing in a coker. The resin feedstock can correspond to one or more types of reinforced resins, such as one or more thermoset resins, along with other components typically used in formulation of fiber-reinforced thermoset resins. The amount of reinforced thermoset resin in the combined feedstock can correspond to 1.0 wt% to 25 wt% of the combined feed to the coker, or 3.0 wt% to 25 wt%, or 10 wt% to 25 wt%, or 3.0 wt% to 15 wt%. Optionally, a earner fluid can also be included in the resin feedstock to assist with introducing the resin feedstock into the coking environment. The combined amount of resin feedstock and carrier fluid in the combined feed can correspond to 1.0 wt% to 30 wt% of the combined feed to the coker, or 3.0 wt% to 30 wt°/o, or 10 wt°/o to 30 wt%, or 3.0 wt% to 15 wt%. The conventional coker feedstock can correspond to 70 wt% to 99 wt% of the combined feed to the coker.

[0019] In some embodiments, the coker feedstock for co-processing with the resin feedstock can correspond to a conventional petroleum feedstock having a relatively high boiling fraction, such as a heavy oil feed. For example, the coker feedstock portion of the feed can have a T10 distillation point of 343°C or more, or 371°C or more. In some embodiments, the cooker feedstock has a T10 distillation point of 343°C to 650°C. Examples of suitable heavy oils for inclusion in the coker feedstock include, but are not limited to, reduced petroleum crude; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms, or residuum; pitch; asphalt; bitumen; other heavy hydrocarbon residues; tar sand oil; shale oil; or even a coal slurry or coal liquefaction product such as coal liquefaction bottoms. Such feeds will typically have a Conradson Carbon Residue (ASTM DI 89-165) of at least 5 wt%, generally from 5 wt% to 50 wt%. In some embodiments, the feed is a petroleum vacuum residuum.

[0020] Some examples of conventional petroleum feedstock suitable for processing in a delayed coker or fluidized bed coker can have a composition and properties within the ranges set forth below in Table 1.

Table 1 - Example of Coker Feedstock

[0021] In addition to petroleum feedstocks, renewable feedstocks derived from biomass having a suitable boiling range can also be used as part of the coker feed. Such renewable feedstocks include feedstocks with a T10 boiling point of 340°C or more and a T90 boiling point of 600°C or less. An example of a suitable renewable feedstock derived from biomass can be a pyrolysis oil feedstock derived at least in part from biomass.

[0022] When integrating a resin feedstock as part of a total feed for a coking process, the resin feedstock can include one or more types of thermoset resins. Thermoset resins are a three-dimensional, crosslinked network formed from transformation of a liquid resin to a solid through crosslinking of resin molecules. This transformation (or curing) can be induced by heat or radiation and can be promoted with pressure and/or a catalyst. Catalyst for curing resins are often referred to as hardeners. Examples of resins forming the crosslinked network include unsaturated polyester resins, vinyl ester resins, epoxy resins, phenolic resins, urethane resins, polyurethane resins, furan resins, and polydicyclopentadiene (PDCPD) resins. In some embodiments, the thermoset resin includes thermoset resin waste. Example of thermoset resin waste include thermoset resin from windmill blades (e.g., sized material from a windmill blade) and production scrap from windmill blade production. These thermoset resin wastes can be challenging to recycle as they are often reinforced and cannot be melted or extruded. However, by co-processing of the thermoset resin with a conventional coker feedstock, coking can be performed with reduced or minimized variations in coker operating conditions due to changes in feed composition.

[0023] The thermoset resin can be included in the resin feedstock in any suitable amount. In some embodiments, the amount of thermoset resin in the resin feedstock corresponds to 1.0 wt% to 100 wt% of the resin feedstock, or 1.0 wt% to 99 wt%, or 1.0 wt% to 95 wt%, 1.0 wt% to 90 wt%, or 1.0 wt% to 50 wt%, or 10 wt% to 100 wt%, or 10 wt% to 90 wt%, or 10 wt% to 50 wt%, or 40 v % to 100 wt%, or 40 wt% to 90 wt%, or 50 wt% to 100 wt%, or 50 wt% to 90 wt%.

[0024] In some embodiments, PDCPD resin is included in the resin feedstock. In such embodiments, the PDCPD resin corresponds to any suitable amount of the resin feedstock, such as 0.1 wt% to 100 wt%, or 0.1 wt% to 95 wt%, or 0.1 wt% to 90 wt%, or 0.1 wt% to 80 wt%, or 0.1 wt% to 50 wt%, or 0.1 wt% to 20 wt%, or 1.0 wt% to 75 wt%, or 1.0 wt% to 50 wt%, or 10 wt% to 20 wt%, or 10 wt% to 100 wt%, or 10 wt% to 50 wt%.

[0025] In some embodiments, the thermoset resin is a reinforced thermoset resin such that the resin forming the crosslinked network is reinforced with a reinforcing material. Examples of suitable reinforcing materials include fibers, such as carbon fiber, fiberglass (e.g., E-glass, ECR-glass, R-glass, or S-glass), basalt fibers, quartz fibers, aramid fiber, and combinations thereof. The reinforcing material can be included in the reinforced thermoset resin in any suitable amount. In some embodiments, the amount of the reinforcing material in the reinforced thermoset resin corresponds to 1.0 wt% to 25 wt% of the reinforced thermoset resin, or 1.0 wt% to 20 wt%, or 1.0 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 5.0 wt% to 25 wt%, or 5 wt% to 20 wt%, 5 wt% to 15 wt%, or 5 wt% to 10 wt%, or 10 wt% to 25 wt%. The resin can be included in the reinforced thermoset resin in any suitable amount. In some embodiments, the amount of the resin in the reinforced thermoset resin corresponds to 75 wt% to 99 wt% of the reinforced thermoset resin, or 75 wt% to 95 wt%, or 75 wt% to 90 wt%, or 80 wt% to 99 wt%, or 80 wt% to 95 wt%, or 80 wt% to 90 wt%.

[0026] In some embodiments, the reinforcing material comprises fiberglass. Where used, the fiberglass is included in the reinforced thermoset resin in any suitable amount, such as 1.0 wt% to 25 wt% of the reinforced thermoset resin, or 1.0 wt% to 20 wt%, or 1.0 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 5.0 wt% to 25 wt%, or 5 wt% to 20 wt%, 5 wt% to 15 wt%, or 5 wt% to 10 wt%, or 10 wt% to 25 wt%.

[0027] In some embodiments, the reinforcing material comprises carbon fiber. Where used, the carbon fiber is included in the reinforced thermoset resin in any suitable amount, such as 1.0 wt% to 25 wt% of the reinforced thermoset resin, or 1.0 wt% to 20 wt%, or 1.0 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 5.0 wt% to 25 wt%, or 5 wt% to 20 wt%, 5 wt% to 15 wt%, or 5 wt% to 10 wt%, or 10 wt% to 25 wt%.

[0028] In some embodiments, the thermoset resin includes a fiber-reinforced PDCPD resin.

Examples of suitable fiber-reinforced PDCD resins include a PDCPD resin reinforced with a fiber, such as carbon fiber, fiberglass (e.g., E-glass, ECR-glass, R-glass, or S-glass), basalt fibers, quartz fibers, aramid fiber, and combinations thereof. In some embodiments, the PDCPD resin is reinforced with a carbon fiber. In some embodiments, the PDCPD resin is reinforced with fiberglass.

[0029] In some embodiments, the thermoset resin includes waste windmill blades.

Examples of suitable waste windmill blades include a thermoset resin reinforced with a reinforcing material, such as fiber, including a fiber, such as carbon fiber, fiberglass (e.g., E-glass, ECR-glass, R-glass, or S-glass), basalt fibers, quartz fibers, aramid fiber, and combinations thereof. The thermoset resin in the waste windmill blade includes any suitable thermoset resin, including unsaturated polyester resins, vinyl ester resins, epoxy resins, phenolic resins, urethane resins, polyurethane resins, furan resins, and polydicyclopentadiene (PDCPD) resins.

[0030] In addition to thermoset resins and reinforcing materials, a resin feedstock can include a variety of other components. Such other components can include fillers, additives, modifiers, packaging dyes, and/or other components typically added to a thermoset during and/or after formulation. Examples of suitable fillers for the thermoset resins include metal salts, such as TiO2, talc, CaCO3, Mg, SiO2, Al, TiC14, CaC12, and NaCl. Examples of the resin feedstock further include any components typically found in thermoset resin waste. Finally, examples of the resin feedstock further include one or more carrier fluids so that the feedstock to the coking process corresponds to a slurry of the thermoset resin. [0031] In this discussion, unless otherwise specified, weights of resin or reinforcing material in a feed / feedstock correspond to weights relative to the total thermoset resin content in the feed / feedstock. Any additives / modifiers / other components included in a thermoset resin are included in this weight. However, unless otherwise specified, the weight percentages described herein exclude any carrier fluids used.

[0032] In various embodiments, the thermoset resin, which can be reinforced, is prepared for mixing with the coker feedstock and/or delivery into the coker reactor. Methods for preparing the thermoset resin can include reducing the particle size of the thermoset resin and mixing the thermoset resin with a carrier fluid.

[0033] In various embodiments, a physical processing step is performed to prepare the thermoset resin for a coking environment. For example, having a small particle size can facilitate transport of the solids and/or reduce the likelihood of incomplete conversion in the coking reactor. Examples of physical processing can include crushing, chopping, shredding, and grinding (including cryogenic grinding). In some embodiments, the physical processing can be used to reduce the median particle size to 0.01 mm to 5.0 mm, or 0.1 mm to 5.0 mm, or 0.01 mm to 3.0 mm, or 0.1 mm to 3.0 mm, or 0.01 mm to 3.0 mm, or 0.1 mm to 3.0 mm, or 1.0 mm to 5.0 mm, or 1.0 mm to 3.0 mm. to reduce the maximum particle size. For determining a median particle size, the particle size is defined as the diameter of the smallest bounding sphere that contains the particle. Optionally, after the physical processing, the thermoset resin can be sieved or filtered to remove larger particles. In some embodiments, the sieving or filtering can be used to reduce the maximum particle size to 10 mm or less, or 5.0 mm or less. [0034] Additionally or alternately, a carrier fluid can be added to the resin feedstock. For introduction into a coking environment, it can be convenient for the feedstock to be in the form of a slurry. If a carry fluid is used for transporting the resin feedstock, any suitable fluid can be used. Examples of suitable earner fluids can include (but are not limited to) a wide range of petroleum or petrochemical products. For example, some suitable earner fluids include crude oil, naphtha, kerosene, diesel, light or heavy cycle oils, catalytic slurry oil, and gas-oils. Other potential carrier fluids can correspond to naphthenic and/or aromatics solvents, such as toluene, benzene, methylnaphthalene, cyclohexane, methylcyclohexane, and mineral oil. Still other carrier fluids can correspond to refinery fractions, such as a gas oil fraction or naphtha fraction from a coker. As yet another example, a distillate and/or gas oil boiling range fraction can be used that generated by coking of the combined feedstock (i.e., combined resin feedstock and coker feedstock). Another example of suitable carrier fluid includes coker feedstock, as described above. Mixing and Pre-Heating of Feedstocks

[0035] In some particular embodiments, the resin feedstock and the coker feedstock are mixed to form a combined feedstock prior to entering the coking environment. More generally, however, any convenient method for introducing both the resin feedstock and the coker feedstock into the coking environment can be used.

[0036] In embodiments where the coker feedstock and the resin feedstock are mixed to form a combined feedstock prior to entering the coking environment, mixing the feedstocks can be beneficial for assisting with heating of the resin feedstock. Resins have relatively poor heat transfer properties. By mixing the resin feedstock with the coker feedstock, the smaller portion of resin feedstock can be distributed in the larger portion of coker feedstock. This dispersal of the resin feedstock in the petroleum / biomass portion of the feedstock can increase the surface area for transferring heat, thereby increasing the speed of the heat transfer.

[0037] Prior to being introduced into the coking environment, the feedstocks (optionally in the form of a combined feedstock) are pre-heated. Pre-heating the feedstocks in one or more heating stages can increase the temperature of the feedstocks to a mixing and storage temperature, to a temperature related to the coking temperature, or to another convenient temperature.

[0038] In some embodiments, a portion of the pre-heating of a resin feedstock can be performed by mixing the resin feedstock with a coker feedstock in a mixing tank and heating the mixture in the mixing tank. For example, a resin feedstock and a coker feedstock can be mixed in a heated stirred tank for storage operating at 200°C to 325°C, or 275°C to 325°C. Tank agitation aids in uniform dispersal of waste fiber-reinforced resin into resid and maintains slurry suspension. Heating in a mixing tank provides heat to the combined feedstock prior to introducing the combined feedstock into the coking reaction environment. This can reduce or minimize additional coker heat duty that would otherwise be required to heat the resin feedstock to thermal cracking temperatures. In addition to heating, stripping of the combined resin feedstock and coker feedstock using a stripping gas can be performed in a mixing tank. Passing a stripping gas through the combined feedstock can assist with removing HC1 that is entrained in the combined feedstock. Such HC1 can be created, for example, by exposing chlorine-containing polymers to heat. More generally, stripping can remove other gases that are entrained in the combined feedstock.

[0039] Still another option can be to mix the resin feedstock with the coker feedstock after the pre-heater furnace for the coker. In these embodiments, the coker feedstock can be heated to a higher temperature in the pre-heater, and then the resin feedstock can be added to the preheated coker feedstock to heat the reinforced resin.

Coking Conditions - Fluidized Coking

[0040] Coking processes in modem refinery settings can typically be categorized as delayed coking or fluidized bed coking. Fluidized bed coking is a petroleum refining process in which heavy petroleum feeds, typically the non-distillable residues (resids) from the fractionation of heavy oils are converted to lighter, more useful products by thermal decomposition (coking) at elevated reaction temperatures, typically 480°C to 590°C, and in most cases from 500°C to 550°C. Example heavy oils suitable for processing by the fluid coking process include heavy atmospheric resids, petroleum vacuum distillation bottoms, aromatic extracts, asphalts, and bitumens from tar sands, tar pits and pitch lakes of Canada (Athabasca, Alta ), Trinidad, Southern California (La Brea (Los Angeles), McKittrick (Bakersfield, Calif.), Carpinteria (Santa Barbara County, Calif), Lake Bermudez (Venezuela) and similar deposits such as those found in Texas, Peru, Iran, Russia and Poland.

[0041] The Flexicoking™ process, developed by Exxon Research and Engineering Company, is a type of fluid coking process that is operated in a unit including a reactor and a heater, but also including a gasifier for gasifying the coke product by reaction with an air/steam mixture to form a low heating value fuel gas. A stream of coke passes from the heater to the gasifier where all but a small fraction of the coke is gasified to a low-BTU gas ("120 BTU/standard cubic feet) by the addition of steam and air in a fluidized bed in an oxy gendeficient environment to form fuel gas comprising carbon monoxide and hydrogen. In a conventional Flexicoking™ configuration, the fuel gas product from the gasifier, containing entrained coke particles, is returned to the heater to provide most of the heat required for thermal cracking in the reactor with the balance of the reactor heat requirement supplied by combustion in the heater. A small amount of net coke (1 percent of feed) is withdrawn from the heater to purge the system of metals and ash. The liquid yield and properties are comparable to those from fluid coking. The fuel gas product is withdrawn from the heater following separation in internal cyclones which return coke particles through their diplegs.

[0042] In this description, the term “Flexicoking” (trademark of ExxonMobil Research and Engineering Company) is used to designate a fluid coking process in which heavy petroleum feeds are subjected to thermal cracking in a fluidized bed of heated solid particles to produce hydrocarbons of lower molecular weight and boiling point along with coke as a by-product which is deposited on the solid particles in the fluidized bed. References to fluidized cokers are intended to include conventional fluidized cokers as well as flexicokers. The resulting coke can then be converted to a fuel gas by contact at elevated temperature with steam and an oxy gen-containing gas in a gasification reactor (gasifier). This type of configuration can more generally be referred to as an integration of fluidized bed coking with gasification. FIGS. 1 and 2 provide examples of fluidized coking reactors that include a gasifier.

[0043] FIG. 1 shows an example of a Flexicoker unit (i.e., a system including a gasifier that is thermally integrated with a fluidized bed coker) with three reaction vessels: reactor, heater and gasifier. The unit comprises reactor section 10 with the coking zone and its associated stripping and scrubbing sections (not separately indicated), heater 11 and gasifier 12. The relationship of the coking zone, scrubbing zone and stripping zone in the reactor section is shown, for example, in US Pat. No. 5,472,596, to which reference is made for a description of the Flexicoking unit and its reactor section. A combined feedstock of coker feedstock (e.g., heavy oil feed) and resin feedstock is introduced into the unit by line 13 and cracked hydrocarbon product withdrawn through line 14. While FIG. 1, shows a combined feedstock, example embodiments also include separate introduction of the coker feedstock and resin feedstock to the reactor section 10. Fluidizing and stripping steam is supplied by line 15. Cold coke is taken out from the stripping section at the base of reactor section 10 by means of line 16 and passed to heater 11. The term “cold” as applied to the temperature of the withdrawn coke is, of course, decidedly relative since it is well above ambient at the operating temperature of the stripping section. Hot coke is circulated from heater 11 to reactor section 10 through line 17. Coke from heater 11 is transferred to gasifier 12 through line 21 and hot, partly gasified particles of coke are circulated from the gasifier back to the heater through line 22. The excess coke is withdrawn from the heater 11 by way of line 23. In conventional configurations, gasifier 12 is provided with its supply of steam and air by line 24 and hot fuel gas is taken from the gasifier to the heater though line 25. In some alternative embodiments, instead of supplying air via a line 24 to the gasifier 12, a stream of oxygen with 95 vol% purity or more can be provided, such as an oxygen stream from an air separation unit. In such embodiments, in addition to supplying a stream of oxygen, a stream of an additional diluent gas can be supplied by line 31. The additional diluent gas can correspond to, for example, CO2 separated from the fuel gas generated during the gasification. The fuel gas is taken out from the unit through line 26 on the heater; coke fines are removed from the fuel gas in heater cyclone system 27 comprising serially connected primary and secondary cyclones with diplegs which return the separated fines to the fluid bed in the heater. The fuel gas from line 26 can then undergo further processing. For example, in some embodiments, the fuel gas from line 26 can be passed into a separation stage for separation of CO2 (and/or H2S). This can result in a stream with an increased concentration of synthesis gas, which can then be passed into a conversion stage for conversion of synthesis gas to methanol.

[0044] It is noted that in some optional embodiments, heater cyclone system 27 can be located in a separate vessel (not shown) rather than in heater 11. In such aspects, line 26 can withdraw the fuel gas from the separate vessel, and the line 23 for purging excess coke can correspond to a line transporting coke fines away from the separate vessel. These coke fines and/or other partially gasified coke particles that are vented from the heater (or the gasifier) can have an increased content of metals relative to the feedstock. For example, the weight percentage of metals in the coke particles vented from the system (relative to the weight of the vented particles) can be greater than the weight percent of metals in the feedstock (relative to the weight of the feedstock). In other words, the metals from the feedstock are concentrated in the vented coke particles. Since the gasifier conditions do not create slag, the vented coke particles correspond to the mechanism for removal of metals from the coker / gasifier environment. In some embodiments, the metals can correspond to a combination of nickel, vanadium, and/or iron. Additionally, or alternately, the gasifier conditions can cause substantially no deposition of metal oxides on the interior walls of the gasifier, such as deposition of less than 0. 1 wt% of the metals present in the feedstock introduced into the coker I gasifier system, or less than 0.01 wt%.

[0045] In configurations such as FIG. 1, the system elements shown in the figure can be characterized based on fluid communication between the elements. For example, reactor section 10 is in direct fluid communication with heater 11. Reactor section 10 is also in indirect fluid communication with gasifier 12 via heater 11.

[0046] As an alternative, integration of a fluidized bed coker with a gasifier can also be accomplished without the use of an intermediate heater. In such alternative aspects, the cold coke from the reactor can be transferred directly to the gasifier. This transfer, in almost all cases, will be unequivocally direct with one end of the tubular transfer line connected to the coke outlet of the reactor and its other end connected to the coke inlet of the gasifier with no intervening reaction vessel, i.e., heater. The presence of devices other than the heater is not however to be excluded, e.g., inlets for lift gas etc. Similarly, while the hot, partly gasified coke particles from the gasifier are returned directly from the gasifier to the reactor this signifies only that there is to be no intervening heater as in the conventional three-vessel Flexicoker™ but that other devices may be present between the gasifier and the reactor, e.g., gas lift inlets and outlets. [0047] FIG. 2 shows an example of integration of a fluidized bed coker with a gasifier but without a separate heater vessel. In the configuration shown in FIG. 2, the cyclones for separating fuel gas from catalyst fines are located in a separate vessel. In other aspects, the cyclones can be included in a main gasifier vessel 41.

[0048] In the configuration shown in FIG. 2, the configuration includes a reactor 40, main gasifier vessel 41 and a separator 42. The combined feedstock of coker feedstock (e.g., heavy oil feed) and resin feedstock is introduced into reactor 40 through line 43 and fluidizing/stripping gas through line 44; cracked hydrocarbon products are taken out through line 45. While FIG. 2, shows a combined feedstock, example embodiments also include separate introduction of the coker feedstock and resin feedstock to the reactor 40. Cold, stripped coke is routed directly from reactor 40 to main gasifier vessel 41 by way of line 46 and hot coke returned to the reactor in line 47. Steam and oxygen are supplied through line 48. The flow of gas containing coke fines is routed to separator vessel 42 through line 49 which is connected to a gas outlet of the main gasifier vessel 41. The fines are separated from the gas flow in cyclone system 50 comprising serially connected primary and secondary cyclones with diplegs which return the separated fines to the separator vessel. The separated fines are then returned to the main gasifier vessel 41 through return line 51 and the fuel gas product taken out by way of line 52 Coke is purged from the separator through line 53. The fuel gas from line 52 can then undergo further processing for separation of CO2 (and/or H2S) and conversion of synthesis gas to methanol.

[0049] The coker and gasifier can be operated according to the parameters necessary for the required coking processes. Thus, the heavy oil feed in the coker feedstock will typically be a heavy (high boiling) reduced petroleum crude; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms, or residuum; pitch; asphalt; bitumen; other heavy hydrocarbon residues; tar sand oil; shale oil; or even a coal slurry or coal liquefaction product such as coal liquefaction bottoms. Such feeds will typically have a Conradson Carbon Residue (ASTM D189-165) of at least 5 wt%, generally from 5 to 50 v %. In some embodiments, the coker feedstock is a petroleum vacuum residuum.

[0050] Fluidized coking is carried out in a unit with a large reactor containing hot coke particles which are maintained in the fluidized condition at the required reaction temperature with steam injected at the bottom of the vessel with the average direction of movement of the coke particles being downwards through the bed. In particular embodiments, the combined feedstock is heated to a pumpable temperature, typically in the range of 350°C to 400°C, mixed with atomizing steam, and fed through multiple feed nozzles arranged at several successive levels in the reactor. Steam is injected into a stripping section at the bottom of the reactor and passes upwards through the coke particles descending through the dense phase of the fluid bed in the main part of the reactor above the stripping section. Part of the feed liquid coats the coke particles in the fluidized bed and is subsequently cracked into layers of solid coke and lighter products which evolve as gas or vaporized liquid. The residence time of the feed in the coking zone (where temperatures are suitable for thermal cracking) is on the order of 1 to 30 seconds. Reactor pressure is relatively low in order to favor vaporization of the hydrocarbon vapors which pass upwards from dense phase into dilute phase of the fluid bed in the coking zone and into cyclones at the top of the coking zone where most of the entrained solids are separated from the gas phase by centrifugal force in one or more cyclones and returned to the dense fluidized bed by gravity through the cyclone diplegs. The mixture of steam and hydrocarbon vapors from the reactor is subsequently discharged from the cyclone gas outlets into a scrubber section in a plenum located above the coking zone and separated from it by a partition. It is quenched in the scrubber section by contact with liquid descending over sheds. A pump-around loop circulates condensed liquid to an external cooler and back to the top shed row of the scrubber section to provide cooling for the quench and condensation of the heaviest fraction of the liquid product. This heavy fraction is typically recycled to extinction by feeding back to the coking zone in the reactor.

[0051] During a fluidized coking process, the combined feedstock, pre-heated to a temperature at which it is flowable and pumpable, is introduced into the coking reactor towards the top of the reactor vessel through injection nozzles which are constructed to produce a spray of the feed into the bed of fluidized coke particles in the vessel. Temperatures in the coking zone of the reactor are typically in the range of 450°C to 650°C and pressures are kept at a relatively low level, typically in the range of 0 kPag to 700 kPag, and most usually from 35 kPag to 320 kPag, in order to facilitate fast drying of the coke particles, preventing the formation of sticky, adherent high molecular weight hydrocarbon deposits on the particles which could lead to reactor fouling. In some embodiments, the temperature in the coking zone can be 450°C to 600°C, or 450°C to 550°C. The conditions can be selected so that a desired amount of conversion of the feedstock occurs in the fluidized bed reactor. For example, the conditions can be selected to achieve at least 10 wt% conversion relative to 343°C (or 371°C), or at least 20 wt% conversion relative 343°C (or 371°C), or at least 40 wt% conversion relative to 343°C (or 371°C), such as up to 80 wt% conversion or possibly still higher. The light hydrocarbon products of the coking (thermal cracking) reactions vaporize, mix with the fluidizing steam and pass upwardly through the dense phase of the fluidized bed into a dilute phase zone above the dense fluidized bed of coke particles. This mixture of vaporized hydrocarbon products formed in the coking reactions flows upwardly through the dilute phase with the steam at superficial velocities of roughly 1 to 2 meters per second (~ 3 to 6 feet per second), entraining some fine solid particles of coke which are separated from the cracking vapors in the reactor cyclones as described above. In embodiments where steam is used as the fluidizing agent, the weight of steam introduced into the reactor can be selected relative to the weight of feedstock introduced into the reactor. For example, the mass flow rate of steam into the reactor can correspond to 6.0% of the mass flow rate of feedstock, or 8.0% or more, such as up to 10% or possibly still higher. The amount of steam can potentially be reduced if an activated light hydrocarbon stream is used as part of the stripping and/or fluidizing gas in the reactor. In such embodiments, the mass flow rate of steam can correspond to 6.0% of the mass flow rate of feedstock or less, or 5.0% or less, or 4.0% or less, or 3.0% or less. Optionally, in some embodiments, the mass flow rate of steam can be still lower, such as corresponding to 1.0% of the mass flow rate of feedstock or less, or 0.8% or less, or 0.6% or less, such as down to substantially all of the steam being replaced by the activated light hydrocarbon stream. The cracked hydrocarbon vapors pass out of the cyclones into the scrubbing section of the reactor and then to product fractionation and recovery.

[0052] In a general fluidized coking process, the coke particles formed in the coking zone pass downwards in the reactor and leave the bottom of the reactor vessel through a stripper section where they are exposed to steam in order to remove occluded hydrocarbons. The solid coke from the reactor, consisting mainly of carbon with lesser amounts of hydrogen, sulfur, nitrogen, and traces of vanadium, nickel, iron, and other elements derived from the feed, passes through the stripper and out of the reactor vessel to a burner or heater where it is partly burned in a fluidized bed with air to raise its temperature from 480°C to 700°C to supply the heat required for the endothermic coking reactions, after which a portion of the hot coke particles is recirculated to the fluidized bed reaction zone to transfer the heat to the reactor and to act as nuclei for the coke formation. The balance is withdrawn as coke product. The net coke yield is only 65 percent of that produced by delayed coking.

[0053] Fora coking process that includes a gasification zone, the cracking process proceeds in the reactor, the coke particles pass downwardly through the coking zone, through the stripping zone, where occluded hydrocarbons are stripped off by the ascending current of fluidizing gas (steam). They then exit the coking reactor and pass to the gasification reactor (gasifier) which contains a fluidized bed of solid particles and which operates at a temperature higher than that of the reactor coking zone. In the gasifier, the coke particles are converted by reaction at the elevated temperature with steam and an oxy gen-containing gas into a fuel gas comprising carbon monoxide and hydrogen.

[0054] The gasification zone is typically maintained at a high temperature ranging from 850°C to l,000°C and a pressure ranging from 0 kPag to 1000 kPag, preferably from 200 kPag to 400 kPag. Steam and an oxygen-containing gas are introduced to provide fluidization and an oxygen source for gasification. In some embodiments, the oxygen-containing gas can be air. In other embodiments, the oxygen-containing gas can have a low nitrogen content, such as oxygen from an air separation unit or another oxygen stream including 95 vol% or more of oxygen, or 98 vol% or more, are passed into the gasifier for reaction with the solid particles comprising coke deposited on them in the coking zone. In embodiments where the oxygencontaining gas has a low nitrogen content, a separate diluent stream, such as a recy cled CO2 or H2S stream derived from the fuel gas produced by the gasifier, can also be passed into the gasifier.

[0055] In the gasification zone the reaction between the coke and the steam and the oxy gencontaining gas produces a hydrogen and carbon monoxide-containing fuel gas and a partially gasified residual coke product. Conditions in the gasifier are selected accordingly to generate these products. Steam and oxygen rates (as well as any optional CO2 rates) will depend upon the rate at which cold coke enters from the reactor and to a lesser extent upon the composition of the coke which, in turn will vary according to the composition of the heavy oil feed and the severity of the cracking conditions in the reactor with these being selected according to the feed and the range of liquid products which is required. In some embodiments, the fuel gas product from the gasifier contains entrained coke solids and these are removed by cyclones or other separation techniques in the gasifier section of the unit. Suitable cyclones include internal cyclones in the main gasifier vessel itself or external in a separate, smaller vessel as described below. The fuel gas product is taken out as overhead from the gasifier cyclones. The resulting partly gasified solids are removed from the gasifier and introduced directly into the coking zone of the coking reactor at a level in the dilute phase above the lower dense phase.

[0056] In some embodiments, the coking conditions can be selected to provide a desired amount of conversion relative to 343 °C. Typically a desired amount of conversion can correspond to 10 wt% or more, or 50 wt% or more, or 80 wt% or more, such as up to substantially complete conversion of the feedstock relative to 343°C.

[0057] The volatile products from the coke drum are conducted away from the process for further processing. For example, volatiles can be conducted to a coker fractionator for distillation and recovery of coker gases, coker naphtha, light gas oil, and heavy gas oil. Such fractions can be used, usually, but not always, following upgrading, in the blending of fuel and lubricating oil products such as motor gasoline, motor diesel oil, fuel oil, and lubricating oil. Upgrading can include separations, heteroatom removal via hydrotreating and nonhydrotreating processes, de-aromatization, solvent extraction, and the like. The process is compatible with processes where at least a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator is captured for recycle and combined with the fresh feed (coker feed component), thereby forming the coker heater or coker furnace charge. The combined feedstock ratio (“CFR”) is the volumetric ratio of furnace charge (fresh feed plus recycle oil) to fresh feed to the continuous fluidized coker operation. Fluidized coking operations typically employ recycles of 5 vol% to 35% vol% (CFRs of 1.05 to 1.35). hi some embodiments, there can be no recycle and sometimes in special applications recycle can be up to 200%.

Coking Conditions - Delayed Coking

[0058] Delayed coking is a process for the thermal conversion of heavy' oils such as petroleum residua (also referred to as “resid”) to produce liquid and vapor hydrocarbon products and coke. In particular embodiments, delayed coking is performed on a combined feedstock of a coker feedstock (e.g., resids) and a resin feedstock to produce liquid and vapor hydrocarbon products and coke. In some embodiments, the resids are from heavy and/or sour (high sulfur) crude oils. Delayed coking of the combined feedstock is carried out by converting part of the combined feedstock to more valuable hydrocarbon products. The resulting coke has value, depending on its grade, as a fuel (fuel grade coke), electrodes for aluminum manufacture (anode grade coke), etc.

[0059] Generally, a combined feedstock (e.g., a residue fraction and fiber-reinforced resin) is pumped to a pre-heater where it is pre-heated, such as to a temperature from 480°C to 520°C. The pre-heated feed is conducted to a coking zone, typically a vertically oriented, insulated coker vessel, e.g., drum, through an inlet at the base of the drum. Pressure in the drum is usually relatively low, such as 100 kPa-g to 550 kPa-g, or 100 kPa-g to 240 kPa-g to allow volatiles to be removed overhead. Typical operating temperatures of the drum will be between roughly 400°C to 445°C, but can be as high as 475°C. The hot feed thermally cracks over a period of time (the “coking time”) in the coke drum, liberating volatiles composed primarily of hydrocarbon products that continuously rise through the coke bed, which consists of channels, pores and pathways, and are collected overhead. The volatile products are conducted to a coker fractionator for distillation and recovery' of coker gases, gasoline boiling range material such as coker naphtha, light gas oil, and heavy gas oil. In an embodiment, a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator can be captured for recycle and combined with the fresh feed (coker feed component), thereby forming the coker heater or coker furnace charge. In addition to the volatile products, the process also results in the accumulation of coke in the drum. When the coke drum is full of coke, the heated feed is switched to another drum and hydrocarbon vapors are purged from the coke drum with steam. The drum is then quenched with water to lower the temperature down to 95°C to 150°C, after which the water is drained. When the draining step is complete, the drum is opened, and the coke is removed by drilling and/or cutting using high velocity water jets (“hydraulic decoking”).

Configuration Examples

[0060] FIG. 3 shows an example of a configuration for co-processing of a resin feedstock during fluidized coking. In FIG. 3, a resin feedstock 54 is physically processed in a resin feed preparation stage 56. Physically processing the feedstock can include one or more processes to reduce the particle the median particle size of the particles in the feed; to remove particles larger than a target particle size from the feedstock; to create particles of a desired size (such as by grinding, crushing, shredding, or other suitable sizing). The physically processed resin feedstock 58 can then be combined with a coker feedstock 60 in mixing stage 62. The mixing stage 62 includes any suitable type of mixing equipment, including stirred tank reactors, melt extruders, heated batch mixeers, and tube heaters, among others. Optionally, the resin feedstock is combined with an optional carrier fluid 64. Optionally , the combined feedstock 66 can be heated prior to exiting mixing stage 62. This optional heating can be in addition to any heating that is performed by a pre-heater as part of coker 68. Coker 68 can correspond to a fluidized coker or a delayed coker, for example, as shown on FIGs. 1 and 2. Coker 68 can generate at least a solid coke product 70 and a coker effluent 72. In embodiments where coker 68 includes a gasifier, coker 68 can further generate a low BTU fuel gas (not shown) that includes synthesis gas components.

[0061] The coker effluent 72 can be passed into a fractionation stage 74 that includes one or more ty pes of fractionators and/or separators. Fractionation stage 74 can separate the fluid product into one or more gas phase products 76 and one or more liquid products 78. Optionally, an additional liquid product can be generated for use as carrier fluid 64. For example, a diesel or gas oil boiling range product can be used as carrier fluid 64. Alternatively, carrier fluid 64 can correspond to a solvent from another source.

Examples of Coking Products [0062] Coking of the combined feedstocks produces products including coke and a coker effluent. Many types of thermoset resins have a relatively low sulfur content. This can provide an advantage by reducing the sulfur content of the coker products, thus reducing the needed severity for any subsequent sulfur removal processes (such as hydroprocessing) on the resultant coker effluent.

[0063] Coke produced in the coking process is typically a carbonaceous solid material of which a majority is carbon. Since the coke is produced from petroleum cracking process in the coker, it can also be referred to as petroleum coke or petcoke. The particular composition of the coke depends on a number of factors, including the particular coking process, such as a delayed coker or in some embodiments, the coke includes carbon in an amount of 80 wt% to 95 wt% based on a total weight of the coke. Additional components in the coke include hydrogen, nitrogen, sulphur, and heavy metals, such as aluminum, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel, potassium, silicon, sodium, titanium, and/or vanadium. In addition to these conventional coke components, coke produced from the combined feedstock further includes residues from coking of reinforced thermoset resins, such as glass residues, in some embodiments, where the thermoset resins are reinforced with fiberglass. By way of further example, additional fillers in the thermoset resins can result in the coke having additional quantities of impurities, such as titanium, magnesium, calcium, silica, aluminum, and sodium.

[0064] In some embodiments, the coke produced originates at least in part from thermoset resins, which can include a reinforcing material. Examples of suitable reinforcing materials, include fiberglass, resulting in glass residues in the coke. In these embodiments, the fillers and reinforcing materials in the thermoset resins are diverted into the coke, resulting in the coke including glass residues, such as silicon, and other fillers from the thermoset resins in increased amounts as compared to conventional coke. For example, conventional coke can include silicon in amounts up to 600 wppm. However, the coke produced at least in part from fiber- reinforced thermoset resins can include silicon in an amount 1000 wppm or more. In some embodiments, the coke includes silicon in an amount of 1000 wppm to 2 wt%, 1000 wppm to 1 wt%, 5000 wppm to 2 wt%, or 1 wt% to 2 wt%. However, while the fillers and reinforcing materials are present in amounts sufficient to expel enough from the process to achieve steadystate operation, the coke should meet specification for petroleum coke.

[0065] A commonly expected yield of coke from coking of a conventional coker feedstock is 20 wt% to 40 wt% of the coker feedstock. However, because the resin feedstock can contain fibers or other reinforcing materials, as well as fillers, that are expelled in the coke, coking of the combined feedstock with the resin feedstock, can result in increased coke production. By way of example, yield of coke from coking of the combined feedstock of a coker feedstock and resin feedstock is 20 wt% to 50 wt% of the combined feedstock.

[0066] In addition to coke, coking of the combined feedstocks also results in a coker effluent. As discussed above, the coker effluent can be fractionated or otherwise separated to form desirable product streams, such as fuel gas (e.g., C4 and lighter hydrocarbons, naphtha, diesel, gasoline, light cycle oil, and/or heavy cycle oil. Because the combined feedstock also includes a thermoset resin, the coker effluent further include components derived from the thermoset resin.

[0067] In some embodiments, the coker effluent originate at least in part from a PDCPD resin in the resin feedstock. In these embodiments, the coker effluent includes an increased amount of cyclic olefins and/or cyclic diolefins. For example, the coker effluent includes an increase amount of cyclopentene and cyclopentadiene. In some embodiments, the coker effluent includes cyclopentene in an amount of 0.01 wt% to 2 wt%, 0.01 wt% to 1 wt%, 0.01 wt % to 0.1 wt%, 0.1 wt% to 2 wt%, or 0.1

0.2 wt% to 2 wt%, or 0.2 wt% to 1 wt%, or 0.1 wt% to 0.75 wt%, or 0.2 wt% to 0.75 wt%. In some embodiments, the coker effluent includes cyclopentadiene in an amount of 0.01

to 5 wt%, 0.01 wt% to 2 wt%, 0.01 wt% to 1 wt%, 0.01 wt% to 0.1 wt%, 0.1 wt% to 5 wt%, or 0.5 wt% to 5 wt%, or 1 wt% to 5 v %, or 0.1 wt% to 4 wt%, or 0.1 wt% to 3 wt%, or 0.1 wt% to 2 wt%, or 0.1 wt% to 1 wt%, or 0.5 wt% to 4 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%, or 0.5 wt% to 1 wt%. [0068] Advantageously, the cyclic olefins and cyclic diolefins in the coker effluent are considered circular, in one or more embodiments, by attributing the cyclic olefins from the coker to the use of thermoset resin waste (e g., product scrap from windmill blade production), such as determined by crediting, allocating, and/or offsetting or substituting for other hydrocarbons in a mass or energy balance within the coker system. For example, circular cyclopentene and circular cyclopentadiene are produced in the coker from the PDCPD resin. In some embodiments, circular cyclic olefins and circular diolefms are separated and then polymerized in accordance with one or more embodiments. For example, the circular cyclopentene and circular cyclopentadiene are polymerized to form the PDCPD resin. In some embodiments, coker effluent is used for production of circular polymers, such as circular thermoset polymers (e.g., circular poly dicyclopentadiene). In Polymers formed from circular monomers can be certified for their circularity by third party certification. One example of such certification is the mass balance chain of custody method set forth by the International Sustainability and Carbon Certification. Additional Embodiments

[0069] Accordingly, the present disclosure provides for coking of a combined feedstock including a coker feedstock and a resin feedstock. The methods and systems include any of the various features disclosed herein, including one or more of the following statements.

[0070] Embodiment 1. A method of performing coking on a combined feed, comprising: combining a resin feedstock with a coker feedstock comprising a T10 distillation point of about 343°C or higher to form a combined feedstock, wherein the resin feedstock comprises a thermoset resin having a median particle size of about 5 mm or less; and exposing at least a portion of the combined feedstock to coking conditions in a coking reactor to form at least coke and a coker effluent.

[0071] Embodiment 2. The method of embodiment 1, further comprising reducing a particle size of the thermoset resin to the median particle size of about 5 mm or less.

[0072] Embodiment 3. The method of embodiment 1 or 2, further comprising mixing the resin feedstock with a carrier fluid.

[0073] Embodiment 4. The method of any preceding embodiment, wherein the at least a portion of the resin is combined with the coker feedstock in one or more mixing vessels, the method further comprising heating the combined feed to a temperature of about 200°C or more in the one or more mixing vessels.

[0074] Embodiment 5. The method of any one of embodiments 1 to 3, wherein the resin feedstock is combined with the coker feedstock prior to introduction into the coking reactor.

[0075] Embodiment 6. The method of claim 1, wherein the thermoset resin comprises a fiber-reinforced resin.

[0076] Embodiment 7. The method of any preceding embodiment, wherein the thermoset resin comprises a fiberglass-reinforced resin.

[0077] Embodiment 8. The method of any preceding embodiment, wherein the thermoset resin comprises a polydicyclopentadiene resin.

[0078] Embodiment 9. The method of any preceding embodiment, wherein the thermoset resin is sized material from a windmill blade.

[0079] Embodiment 10. The method of any preceding embodiment, wherein the coking conditions comprise exposing the combined feed to a fluidized bed of coke particles at a temperature of about 450°C to about 650°C.

[0080] Embodiment 11. The method of any preceding embodiment, wherein the coke comprises silicon in an amount of about 1000 wppm or more. [0081] Embodiment 12. The method of any preceding embodiment, wherein the coker effluent comprises cyclopentene in an amount of about 0.01 wt% to about 2 wt% and cyclopentadiene in an amount of about 0.01 wt% to about 5 wt%.

[0082] Embodiment 13. The method of any preceding embodiment, wherein the coker effluent comprises cyclopentadiene in an amount of about 0.5 wt% to about 5 wt%, and the method further comprise separating at least a portion of the cyclopentadiene from the coker effluent and polymerizing the at least the portion of the cyclopentadiene to form poly dicyclopentadiene.

[0083] Embodiment 14. The method of any preceding embodiment, wherein the combined feedstock comprises the resin feedstock in an amount of about 1 wt% to about 25%.

[0084] Embodiment 15. The method of any preceding embodiment, further comprising reducing a particle size of a material from a windmill blade to form the thermoset resin to the median particle size of about 5 mm or less, wherein the combined feedstock comprises the resin feedstock in an amount of about 1 wt% to about 25%, wherein the coke comprises silicon in an amount of about 1000 wppm to about 2 wt%.

[0085] Embodiment 16. The method of any preceding embodiment, further comprising reducing a particle size of a polydicyclopentadiene resin to form the thermoset resin to the median particle size of about 5 mm or less, wherein the combined feedstock comprises the resin feedstock in an amount of about 1 wt% to about 25%, wherein the coker effluent comprises cyclopentene in an amount of about 0.01 wt% to about 2 wt% and cyclopentadiene in an amount of about 0.01 wt% to about 5 wt%.

[0086] Embodiment 17. A petroleum coke comprising: a carbonaceous solid material comprising silicon in an amount of about 1000 wppm or more.

[0087] Embodiment 18. The petroleum coke of embodiment 17, wherein the silicon is present in an amount of about 1000 wppm to about 2 wt%.

[0088] Embodiment 19. The petroleum coke of embodiment 17 or 18, wherein the petroleum coke is produced in a delayed coker.

[0089] Embodiment 20. The petroleum coke of embodiment 17 or 18, wherein the petroleum coke is produced in a fluidized coker.

[0090] Embodiment 21. The petroleum coke of any one of embodiments 17 to 20, wherein the petroleum coke is produced at least in part from coking fiberglass-reinforced thermoset resin.

[0091] Embodiment 22. The petroleum coke of any one of embodiment 21, wherein the fiberglass-reinforced thermoset resin comprises a polydicyclopentadiene resin. [0092] To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the entire scope of the disclosure.

EXAMPLE 1

[0093] A laboratory scale experiment was performed to determine pyrolysis product distribution of a thermoset resin sample. Approximately 0.5 milligrams of a PDCPD Thermoset Resin Sample #1 was loaded into a CDS 5150 micropyrolyzer and the temperature program was set to rapidly heat it to pyrolysis temperatures relevant to coker operations. This resin sample was pyrolyzed at 530°C for 20 seconds. The micropyrolyzer was coupled to the inlet of a GC /MS by a transfer line that was heated to 250°C to avoid condensation. The evolved pyrolysis products were identified by the electron impact mass spectroscope. The pyrolysis products are provided in Table 2 below.

Table 2

[0094] As shown in Table 2, pyrolysis of the neat PDCPD Thermoset Resin Sample #1 results in production of monomers, including 1,3-cyclopentadiene, cyclopentene, and cyclopentene 3-methyl. Advantageously, production of these monomers from this resin sample indicates that resin coking should also produce the corresponding resin monomers that, in turn, can then be used to produce the resin, thus providing a circular process.

[0095] Thermogravimetric analysis (TGA) was used to further analyze pyrolysis of PDCPD Thermoset Resin Sample #1. This resin sample was pyrolyzed under inert nitrogen atmosphere in the TGA with controlled heating. The temperature was increased from room temperature to 700°C with a thermal rate of 20°C/minute and then held at 700°C for 1 hour. The mass loss profile from TGA is shown in FIG. 4. As illustrated in this figure, more than 80 wt% of the resin sample is converted to volatiles at 530°C.

EXAMPLE 2 [0096] A laboratory scale experiment was performed to determine pyrolysis product distribution of another thermoset resin sample. Approximately 0.5 milligrams of a PDCPD Thermoset Resin Sample #2 was loaded into a CDS 5150 micropyrolyzer and the temperature program was set to rapidly heat it to pyrolysis temperatures relevant to coker operations. Theis resin sample was pyrolyzed at 530°C for 20 seconds. The micropyrolyzer was coupled to the inlet of a GC /MS by a transfer line that was heated to 250°C to avoid condensation. The evolved pyrolysis products were identified by the electron impact mass spectroscope. The pyrolysis products are provided in Table 3 below.

Table 3

[0097] As shown in Table 3, pyrolysis of neat PDCPD Thermoset Resin Sample #2 results in production of monomers, including cyclopentadiene isomers. Advantageously, production of these monomers from this resin sample indicates that resin coking should also produce the corresponding resin monomers that, in turn, can then be used to produce the resin, thus providing a circular process.

[0098] Thermogravimetric analysis (TGA) was used to further analyze pyrolysis of PDCPD Thermoset Resin Sample #2. This resin sample was pyrolyzed under inert nitrogen atmosphere in the TGA with controlled heating. The temperature was increased from room temperature to 700°C with a thermal rate of 20°C/minute and then held at 700°C for 1 hour. The mass loss profde from TGA is shown in FIG. 5. As illustrated in this figure, more than 85 wt% of the resin sample is converted to volatiles at 530°C.

EXAMPLE 3

[0099] The preceding tests used two different PDCPD thermoset resin samples. PDCPD Thermoset Resin Sample #1 was exposed to air for a long time before these tests. Both resin samples were analyzed for CHNOS content. CHNOS analysis indicated that PDCPD Thermoset Resin Sample #1 had higher amount of oxygen compared to PDCPD Thermoset Resin Sample #2 as shown in Table 4. This is also consistent with higher amount of CO2 from pyrolysis of PDCPD Thermoset Resin Sample #1 compared to PDCPD Thermoset Resin Sample #2.

Table 4

[0100] While compositions, methods, and processes are described herein in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. The phrases, unless otherwise specified, “consists essentially of’ and “consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used. [0101] All numerical values within the detailed description are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary' skill in the art.

[0102] Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

CLAIMS:

1. A method of performing coking on a combined feed, comprising: combining a resin feedstock with a coker feedstock comprising a T10 distillation point of about 343°C or higher to form a combined feedstock, wherein the resin feedstock comprises a thermoset resin having a median particle size of about 5 mm or less; and exposing at least a portion of the combined feedstock to coking conditions in a coking reactor to form at least coke and a coker effluent.

2. The method of claim 1, further comprising reducing a particle size of the thermoset resin to the median particle size of about 5 mm or less.

3. The method of claim 1, further comprising mixing the resin feedstock with a carrier fluid.

4. The method of claim 1, wherein the at least a portion of the resin is combined with the coker feedstock in one or more mixing vessels, the method further comprising heating the combined feed to a temperature of about 200°C or more in the one or more mixing vessels.

5. The method of claim 1, wherein the resin feedstock is combined with the coker feedstock prior to introduction into the coking reactor.

6. The method of claim 1, wherein the thermoset resin comprises a fiber-reinforced resin.

7. The method of claim 1, wherein the thermoset resin comprises a fiberglass-reinforced resin.

8. The method of claim 1, wherein the thermoset resin comprises a poly dicyclopentadiene resin.

9. The method of claim 1, wherein the thermoset resin is sized material from a windmill blade.

10. The method of claim 1, wherein the coking conditions comprise exposing the combined feed to a fluidized bed of coke particles at a temperature of about 450°C to about 650°C.

11. The method of claim 1, wherein the coke comprises silicon in an amount of about 1000 wppm or more.

12. The method of claim 1, wherein the coker effluent comprises cyclopentene in an amount of about 0.01 wt% to about 2 wt% and cyclopentadiene in an amount of about 0.01 wt% to about 5 wt%.

13. The method of claim 1, wherein the coker effluent comprises cyclopentadiene in an amount of about 0.5 wt% to about 5 wt%, and the method further comprise separating at least a portion of the cyclopentadiene from the coker effluent and polymerizing the at least the portion of the cyclopentadiene to form poly di cyclopentadiene.

14. The method of claim 1, wherein the combined feedstock comprises the resin feedstock in an amount of about 1 wt% to about 25%.

15. The method of claim 1, further comprising reducing a particle size of a material from a windmill blade to form the thermoset resin to the median particle size of about 5 mm or less, wherein the combined feedstock comprises the resin feedstock in an amount of about 1 wt% to about 25%, wherein the coke comprises silicon in an amount of about 1000 wppm to about 2 wt%.

16. The method of claim 1, further comprising reducing a particle size of a polydicyclopentadiene resin to form the thermoset resin to the median particle size of about 5 mm or less, wherein the combined feedstock comprises the resin feedstock in an amount of about 1 wt% to about 25%, wherein the coker effluent comprises cyclopentene in an amount of about 0.01 wt% to about 2 wt% and cyclopentadiene in an amount of about 0.01 wt% to about 5 wt%.

17. A petroleum coke comprising: a carbonaceous solid material comprising silicon in an amount of about 1000 wppm or more.

18. The petroleum coke of claim 17, wherein the silicon is present in an amount of about 1000 wppm to about 2 wt%.

19. The petroleum coke of claim 17, wherein the petroleum coke is produced in a delayed coker.

20. The petroleum coke of claim 17, wherein the petroleum coke is produced in a fluidized coker.

21. The petroleum coke of claim 17, wherein the petroleum coke is produced at least in part from coking fiberglass-reinforced thermoset resin.

22. The petroleum coke of claim 21, wherein the fiberglass-reinforced thermoset resin compnses a polydicyclopentadiene resin.