Chemical recovery of thermoset resins

Abstract

Various systems and methods are disclosed, including, in one embodiment, a method of coking a combined feed comprising: combining a resin feedstock with a coker feedstock having a T10 distillation point of about 343 DEG 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 the coking reactor to form at least coke and a coker effluent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 331,049, filed April 14, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0003] Systems and methods are provided for recovering thermosetting resins in a coker. Background Art

[0004] Windmills on land and offshore generate a large amount of electrical energy and supply 6% of the electricity consumed in the world. Typically, windmill blades are made of glass fiber and carbon fiber reinforced thermosetting resins (including epoxy resins, vinyl esters, unsaturated polyesters and polydicyclopentadiene (PDCPD)). The global demand for polymer matrices for windmill blades exceeds 295 kT / a. In addition to windmill blades, fiber-reinforced thermosetting resins are also needed for building construction, transportation industry, aviation, roads, consumer products and many other applications.

[0005] However, it is challenging to recycle thermosetting resins and particularly fiber-reinforced resins into new and useful products. For example, thermosetting resins are formed by a cross-linked polymer network that cannot be melted or extruded. In addition, it has been proposed to recycle these materials by grinding them to reuse as solid fillers, but the applications in which these fillers can be used without negative effects on performance and properties are limited. In chemical recycling, high fiber content is problematic due to the large amount of residues or charges generated by these reinforcing fibers. Therefore, windmill blades and other products containing fiber-reinforced thermosetting resins are often burned or landfilled. In the absence of burning or landfilling, expensive and energy-consuming methods are often used to separate reinforcing fibers from thermosetting resins. Summary of the invention

[0006] Disclosed herein is an example method for coking a combined feed, comprising: combining a resin feed with a coker feed having a T10 distillation point of about 343° C. or greater to form a combined feed, wherein the resin feed comprises a thermosetting resin having a median particle size of about 5 mm or less; and exposing at least a portion of the combined feed to coking conditions in a coking reactor to form at least coke and a coker effluent.

[0007] Further disclosed herein are example petroleum cokes comprising a carbonaceous solid material comprising silicon in an amount of about 1000 parts per million by weight (wppm) or more.

[0008] These and other features and properties of the disclosed methods and systems of the present disclosure, as well as their advantageous applications and / or uses, will be apparent from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] In order to help ordinary technicians in the relevant field to implement and use the subject matter of this article, reference is made to the accompanying drawings, in which:

[0010] Figure 1 An example of a fluidized bed coking system is shown, which includes a coker, a heater, and a gasifier.

[0011] Figure 2 An example of a fluidized bed coking system is shown, which includes a coker and a gasifier.

[0012] Figure 3 An example of a system and process flow is shown for co-processing of resin feed and coker feed.

[0013] Figure 4 Shown is the mass loss curve from thermogravimetric analysis of a PDCPD thermoset polymer sample.

[0014] Figure 5 Shown is the mass loss curve from thermogravimetric analysis of another PDCPD thermoset polymer sample.

[0015] Detailed Description

[0016] In various embodiments, systems and methods are provided for co-processing resin feedstock in a coking environment. In some embodiments, the resin feedstock may be incorporated into a fluidized coking environment (e.g., Flexicoking TM In other embodiments, the resin feedstock may be incorporated into the feedstock for a delayed coking environment.

[0017] For example, co-processing of resin raw materials in a coking environment can be carried out by carrying out several treatments on thermosetting waste. First, the thermosetting resin in the resin raw material can be conditioned by changing the size of the thermosetting resin to improve the adaptability of the thermosetting resin for co-processing. Second, the thermosetting resin particles in the resin raw material can be entrained in a carrying fluid and / or a base coker raw material. In an embodiment using a carrying fluid, the carrying fluid may correspond to a refinery stream, such as a refinery stream formed by co-processing of the resin raw material in a coking environment. Third, a slurry of the resin raw material can be sent to a coking environment, such as a fluidized coking environment or a delayed coking environment. The slurry of the thermosetting waste can be introduced as a separate stream, or the slurry can be mixed with a conventional coker raw material before entering the coking environment. Fourth, the thermosetting waste can then be co-processed in a coking environment to produce a coke liquid product.

[0018] In some embodiments, co-processing thermosetting resins in a coking environment can provide advantages over coking of conventional feeds. Since thermosetting resins have no melting point and cannot be extruded, it is challenging to recycle thermosetting resins. In addition, the inclusion of reinforcing materials (e.g., carbon fibers and glass fibers) in thermosetting resins increases the challenge of recycling. Advantageously, by co-processing in a coking environment, thermosetting resin waste can be recovered while producing coke and desired liquid products. Therefore, example embodiments of the present technology provide the recovery of thermosetting resins (e.g., windmill blades) without the need for pretreatment to separate reinforcing fibers.

[0019] As used herein, the naphtha boiling range is defined as from about the boiling point of C5 alkanes (about 30° C.) to 177° C. The distillate boiling range is defined as from 177° C. to 343° C. The gas oil boiling range is defined as from 343° C. to 566° C. The vacuum residue boiling range corresponds to temperatures above 566° C.

[0020] raw material

[0021] In various embodiments, coking can be used to co-process a combination of raw materials corresponding to a mixture of conventional coker feedstock and resin feedstock. Conventional coker feedstock can correspond to one or more types of petroleum and / or renewable feedstocks with a boiling range suitable for processing in a coker. The resin feedstock can correspond to one or more types of reinforced resins, such as one or more thermosetting resins, and other components that are generally used to prepare fiber-reinforced thermosetting resins. The amount of the enhanced thermosetting resin in the combined feedstock can correspond to 1.0% to 25% by weight of the combined feedstock sent to the coker, or 3.0% to 25% by weight, or 10% to 25% by weight, or 3.0% to 15% by weight. Optionally, a carrying fluid can also be included in the resin feedstock to help introduce the resin feedstock into the coking environment. The combined amount of the resin feedstock and the carrying fluid in the combined feedstock can correspond to 1.0% to 30% by weight of the combined feedstock sent to the coker, or 3.0% to 30% by weight, or 10% to 30% by weight, or 3.0% to 15% by weight. Conventional coker feedstocks may correspond to 70 wt % to 99 wt % of the combined feed to the coker.

[0022] In some embodiments, the coker feedstock for co-processing with the resin feedstock may correspond to a conventional petroleum feedstock having a relatively high boiling point fraction, such as a heavy oil feedstock. For example, the coker feedstock portion of the feedstock may have a T10 distillation point of 343°C or higher, or 371°C or higher. In some embodiments, the coker feedstock has a T10 distillation point of 343°C to 650°C. Heavy oils suitable for inclusion in the coker feedstock include, but are not limited to, atmospheric petroleum heavy oil (reduced petroleum crude); petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms, or residual oil; tar (pitch); asphalt (asphalt); natural asphalt (bitumen); other heavy hydrocarbon residues; oil sands oil; shale oil; or even coal slurry or coal liquefaction products such as coal liquefaction bottoms. Such a feed will typically have a Conradson carbon residue value (ASTM D189-165) of at least 5% by weight, typically 5% to 50% by weight. In some embodiments, the feedstock is a petroleum vacuum residue.

[0023] Some examples of conventional petroleum feedstocks suitable for processing in a delayed coker or fluidized bed coker may have compositions and properties within the ranges listed in Table 1 below.

[0024] Table 1 - Examples of Coker Feedstocks

[0025] In addition to petroleum feedstocks, renewable feedstocks derived from biomass with a suitable boiling range may also be used as part of the coker feed. Such renewable feedstocks include feedstocks with a T10 boiling point of 340°C or higher and a T90 boiling point of 600°C or lower. An example of a suitable renewable feedstock derived from biomass may be a pyrolysis oil feedstock derived at least in part from biomass.

[0026] When the resin raw material is combined as a part of the total feed of the coking method, the resin raw material may include one or more types of thermosetting resins. Thermosetting resins are three-dimensional cross-linked networks, which are formed by converting liquid resins (liquid resin) into solids through the cross-linking of resin molecules. The conversion (or curing) can be initiated by heat or radiation and can be promoted by pressure and / or catalysts. The catalyst used to cure the resin is often referred to as a hardener. Examples of resins that form a cross-linked 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, thermosetting resins include thermosetting resin waste. Examples of thermosetting resin waste include thermosetting resins from windmill blades (e.g., materials that change the size of windmill blades) and production waste from windmill blade production. Because they are often enhanced and cannot be melted or extruded, the recovery of these thermosetting resin wastes is challenging. However, by co-processing thermosetting resins with conventional coker feedstocks, coking can be performed with reduced or minimized changes in coker operating conditions due to changes in feed composition.

[0027] Any suitable amount of thermosetting resin may be included in the resin raw material. In some embodiments, the amount of thermosetting resin in the resin raw material corresponds to 1.0% to 100% by weight, or 1.0% to 99% by weight, or 1.0% to 95% by weight, 1.0% to 90% by weight, or 1.0% to 50% by weight, or 10% to 100% by weight, or 10% to 90% by weight, or 10% to 50% by weight, or 40% to 100% by weight, or 40% to 90% by weight, or 50% to 100% by weight, or 50% to 90% by weight of the resin raw material.

[0028] In some embodiments, the resin raw material comprises a PDCPD resin. In such embodiments, the PDCPD resin corresponds to any suitable amount of the resin raw material, for example, 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 %.

[0029] In some embodiments, thermosetting resin is a thermosetting resin enhanced so that the resin forming a cross-linked network is enhanced with a reinforcing material. The example of suitable reinforcing material includes fiber, such as carbon fiber, glass fiber (for example, E-glass, ECR-glass, R-glass or S-glass), basalt fiber, quartz fiber, aramid fiber and combination thereof. The reinforcing material of any suitable amount may be included in the enhanced thermosetting resin. In some embodiments, the amount of the reinforcing material in the enhanced thermosetting resin corresponds to 1.0 wt % to 25 wt %, 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 of any suitable amount may be included in the enhanced thermosetting resin. In some embodiments, the amount of resin in the reinforced thermosetting resin corresponds to 75% to 99% by weight, or 75% to 95% by weight, or 75% to 90% by weight, or 80% to 99% by weight, or 80% to 95% by weight, or 80% to 90% by weight of the reinforced thermosetting resin.

[0030] In some embodiments, the reinforcing material comprises glass fiber. Where used, the enhanced thermosetting resin comprises any suitable amount of glass fiber, for example, 1.0 wt % to 25 wt %, 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 % of the enhanced thermosetting resin.

[0031] In some embodiments, the reinforcing material comprises carbon fibers. Where used, the enhanced thermosetting resin comprises any suitable amount of carbon fibers, such as 1.0% to 25% by weight, or 1.0% to 20% by weight, or 1.0% to 15% by weight, or 1.0% to 10% by weight, or 5.0% to 25% by weight, or 5% to 20% by weight, 5% to 15% by weight, or 5% to 10% by weight, or 10% to 25% by weight of the enhanced thermosetting resin.

[0032] In some embodiments, the thermosetting resin includes a fiber-reinforced PDCPD resin. Examples of suitable fiber-reinforced PDCD resins include PDCPD resins reinforced with fibers (e.g., carbon fibers, glass fibers (e.g., E-glass, ECR-glass, R-glass or S-glass), basalt fibers, quartz fibers, aramid fibers and combinations thereof). In some embodiments, the PDCPD resin is reinforced with carbon fibers. In some embodiments, the PDCPD resin is reinforced with glass fibers.

[0033] In some embodiments, the thermosetting resin comprises waste windmill blades. Examples of suitable waste windmill blades include thermosetting resins reinforced with reinforcing materials (e.g., fibers, including fibers such as carbon fibers, glass fibers (e.g., E-glass, ECR-glass, R-glass or S-glass), basalt fibers, quartz fibers, aramid fibers, and combinations thereof). The thermosetting resin in the waste windmill blades includes any suitable thermosetting resin, including unsaturated polyester resins, vinyl ester resins, epoxy resins, phenolic resins, urethane resins, polyurethane resins, furan resins, and polydicyclopentadiene (PDCPD) resins.

[0034] Except thermosetting resin and reinforcing material, resin raw material can comprise various other components.Such other components can comprise filler, additive, modifier, packaging dye and / or other components that are usually added to thermosetting material during preparation and / or afterwards.The example of the filler that is suitable for thermosetting resin comprises metal salt, for example TiO , talcum, CaCO , Mg, SiO , Al, TiCl , CaCl , and NaCl.The example of resin raw material further comprises any component that is usually present in thermosetting resin waste.Finally, the example of resin raw material further comprises one or more carrying fluids, so that the raw material sent to coking method corresponds to the slurry of thermosetting resin.

[0035] In this discussion, unless otherwise indicated, the weight of the resin or reinforcing material in the feed / stock corresponds to the weight relative to the total thermosetting resin content in the feed / stock. This weight includes any additives / modifiers / other components contained in the thermosetting resin. However, unless otherwise indicated, the weight percentages described herein do not include any carrier fluid used.

[0036] In various embodiments, a thermosetting resin (which may be reinforced) is prepared for mixing with a coker feedstock and / or feeding into a coker reactor. Methods of preparing a thermosetting resin may include reducing the particle size of the thermosetting resin and mixing the thermosetting resin with a carrier fluid.

[0037] In various embodiments, a physical treatment step is performed to prepare the thermosetting resin for a coking environment. For example, having a small particle size can promote the transportation of solids and / or reduce the possibility of incomplete conversion in the coking reactor. The example of physical treatment may include crushing, chopping, shredding and grinding (including frozen grinding). In some embodiments, physical treatment 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 the median particle size, particle size is defined as the diameter of the minimum surrounding sphere containing particles. Optionally, after the physical treatment, the thermosetting resin can be sieved or filtered to remove larger particles. In some embodiments, sieving or filtering may be used to reduce the maximum particle size to 10 mm or less, or 5.0 mm or less.

[0038] Additionally or alternatively, a carrier fluid may be added to the resin feedstock. It is convenient for the feedstock to be in the form of a slurry for introduction into a coking environment. If the carrier fluid is used to transport the resin feedstock, any suitable fluid may be used. Examples of suitable carrier fluids may include, but are not limited to, a wide range of petroleum or petrochemical products. For example, some suitable carrier fluids include crude oil, naphtha, kerosene, diesel, light or heavy cycle oil, catalytic oil slurry and gas oil. Other possible carrier fluids may correspond to cycloalkane and / or aromatic solvents, such as toluene, benzene, methylnaphthalene, cyclohexane, methylcyclohexane and mineral oil. Still other carrier fluids may correspond to refinery fractions, such as gas oil fractions or naphtha fractions from a coker. As yet another example, distillates and / or gas oil boiling range fractions produced by the coking of a combined feedstock (i.e., a combined resin feedstock and coker feedstock) may be used. Another example of a suitable carrier fluid includes a coker feedstock, as described above.

[0039] Mixing and preheating of raw materials

[0040] In some specific embodiments, the resin feed and the coker feed are mixed prior to entering the coking environment to form a combined feed. More generally, however, any convenient method of introducing both the resin feed and the coker feed into the coking environment may be used.

[0041] In embodiments where the coker feedstock and the resin feedstock are mixed to form a combined feedstock prior to entering the coking environment, the mixed feedstock can be beneficial in assisting the heating of the resin feedstock. Resins have relatively poor heat transfer properties. By mixing the resin feedstock with the coker feedstock, a smaller portion of the resin feedstock can be distributed in a larger portion of the coker feedstock. This dispersion of the resin feedstock in the petroleum / biomass portion of the feedstock can increase the surface area for heat transfer, thereby increasing the rate of heat transfer.

[0042] Prior to introduction into the coking environment, the feedstock is preheated (optionally in the form of a combined feedstock). Preheating the feedstock in one or more heating stages can raise the temperature of the feedstock to a mixing and storage temperature, to a temperature related to the coking temperature, or to another convenient temperature.

[0043] In some embodiments, a part of the preheating of the resin raw material can be carried out by mixing the resin raw material with the coker raw material in a mixing tank and heating the mixture in the mixing tank. For example, the resin raw material and the coker raw material can be mixed in a heated stirring tank for storage, and the stirring tank is operated at 200°C to 325°C, or 275°C to 325°C. Tank stirring helps the waste fiber reinforced resin to be evenly dispersed in the residual oil and maintains the slurry suspension. Before the combined raw material is introduced into the coking reaction environment, the heating in the mixing tank provides heat for the combined raw material. This can reduce or minimize the additional coker heat load that is originally required to heat the resin raw material to the thermal cracking temperature. In addition to heating, stripping the combined resin raw material and the coker raw material can be carried out in the mixing tank using a stripping gas. Passing the stripping gas through the combined raw material can help remove the HCl entrained in the combined raw material. Such HCl can be produced, for example, by exposing chlorine-containing polymers to heat. More generally, stripping can remove other gases entrained in the combined raw material.

[0044] Yet another option may be to mix the resin feed with the coker feed after the preheater furnace for the coker. In these embodiments, the coker feed may be heated to a higher temperature in the preheater, and then the resin feed may be added to the preheated coker feed to heat the enhanced resin.

[0045] Coking conditions - fluid coking

[0046] Coking processes in modern refinery arrangements can generally be classified as delayed coking or fluidized bed coking. Fluidized bed coking is a petroleum refining process in which heavy petroleum feeds, typically the non-distillable residue (residue) 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 500°C to 550°C. Example heavy oils suitable for treatment by the fluid coking process include heavy atmospheric residues, petroleum vacuum distillation bottoms, aromatic extracts, asphalt, and natural bitumen from oil sands, tar pits, asphalt lakes, produced in Canada (Athabasca, Alta.), Trinidad, Southern California (La Brea (Los Angeles), McKittrick (Bakersfield, California), Carpinteria (Santa Barbara County, California), Lake Bermudez (Venezuela), and similar deposits, such as those found in Texas, Peru, Iran, Russia and Poland.

[0047] Flexicoking developed by Exxon Research and Engineering TM The process is a type of fluidized coking process that is operated in an apparatus that includes a reactor and a heater, and also includes a gasifier (for gasifying the coke product by reacting with an air / steam mixture to form a low heating value fuel gas). The coke stream is passed from the heater to the gasifier, where all of the coke, except for a small portion of the coke, is gasified into a low BTU gas (~120 BTU / standard cubic foot) by adding steam and air in a fluidized bed in an oxygen-deficient environment to form a fuel gas containing carbon monoxide and hydrogen. In conventional Flexicoking TM In the 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, the balance of the reactor heat requirement being supplied by combustion in the heater. A small amount of clean coke (1% of the feed) is withdrawn from the heater to remove metals and ash from the system. Liquid yields and properties are comparable to those from fluid coking. The fuel gas product is withdrawn from the heater after separation in an internal cyclone separator, which returns the coke particles through their legs.

[0048] In this specification, the term "Flexicoking" (a trademark of ExxonMobil Research and Engineering Company) is used to designate a fluidized coking process in which a heavy petroleum feed is subjected to thermal cracking in a fluidized bed of heated solid particles to produce lower molecular weight and boiling point hydrocarbons and coke as a by-product, which is deposited on the solid particles in the fluidized bed. Reference to a fluidized coker is intended to include conventional fluidized cokers and flexible cokers. The resulting coke can then be converted to fuel gas by contact with steam and an oxygen-containing gas at elevated temperatures in a gasification reactor (gasifier). This type of configuration may be more generally referred to as the integration of fluidized bed coking with gasification. Figure 1 and 2 An example of a fluid coking reactor including a gasifier is provided.

[0049] Figure 1 An example of a flexible coker unit (i.e., a system including a gasifier thermally integrated with a fluidized bed coker) having three reaction vessels (reactor, heater, and gasifier) ​​is shown. The unit includes a reactor section 10 having a coking zone and its associated stripping and scrubbing sections (not shown separately), a heater 11, and a gasifier 12. The relationship of the coking zone, scrubbing zone, and stripping zone in the reactor section is shown, for example, in U.S. Patent No. 5,472,596, which is cited for the purpose of describing a flexible coking unit and its reactor sections. A combined feed of a coker feed (e.g., a heavy oil feed) and a resin feed is introduced into the unit via line 13, and cracked hydrocarbon products are withdrawn via line 14. Although Figure 1Combination feedstocks are shown, but example embodiments also include separate introduction of coker feedstock and resin feedstock into reactor section 10. Fluidizing and stripping steam is supplied via line 15. Cold coke is taken out from the stripping section at the bottom of reactor section 10 by means of line 16 and conveyed to heater 11. The term "cold" applied to the temperature of the extracted coke is, of course, undoubtedly relative since it is much higher than the environment at the operating temperature of the stripping section. Hot coke is recycled from heater 11 to reactor section 10 via line 17. Coke from heater 11 is transferred to gasifier 12 via line 21 and particles of hot, partially gasified coke are recycled back to the heater from the gasifier via line 22. Excess coke is extracted from heater 11 via line 23. In a conventional configuration, gasifier 12 is provided with its steam and air supply via line 24 and hot fuel gas is taken out from the gasifier to the heater via line 25. In some alternative embodiments, a stream of oxygen having a purity of 95 vol% or more, such as an oxygen stream from an air separation unit, may be provided instead of supplying air to the gasifier 12 via line 24. In such an embodiment, in addition to the stream of oxygen supplied, a stream of additional diluent gas may be supplied via line 31. The additional diluent gas may correspond to, for example, CO2 separated from the fuel gas produced during gasification. The fuel gas is taken from the device via line 26 on the heater; coke fines are removed from the fuel gas in a heater cyclone system 27, which includes a primary and secondary cyclone separator connected in series and a feed leg that returns the separated fines to the fluidized bed in the heater. The fuel gas from line 26 may then undergo further processing. For example, in some embodiments, the fuel gas from line 26 may be fed to a separation stage for separating CO2 (and / or H2S). This may produce a stream of syngas with an increased concentration, which may then be conveyed to a conversion stage for converting syngas into methanol.

[0050] It is noteworthy that in some optional embodiments, the heater cyclone system 27 may be located in a separate container (not shown) rather than in the heater 11. In such an aspect, the pipeline 26 may extract the fuel gas from the separate container, and the pipeline 23 for removing excess coke may correspond to the pipeline for transporting coke fines away from the separate container. Compared to the raw material, these coke fines and / or other partially gasified coke particles discharged from the heater (or gasifier) ​​may have an increased metal content. For example, the weight percentage of metal in the coke particles discharged from the system (relative to the weight of the discharged particles) may be greater than the weight percentage of metal in the raw material (relative to the weight of the raw material). In other words, the metal from the raw material is concentrated in the discharged coke particles. Since the gasifier conditions do not produce slag, the discharged coke particles correspond to a mechanism for removing metals from the coker / gasifier environment. In some embodiments, the metal may correspond to a combination of nickel, vanadium and / or iron. Additionally or alternatively, the gasifier conditions may result in substantially no deposition of metal oxides on the interior walls of the gasifier, such as deposition of less than 0.1 wt %, or less than 0.01 wt % of the metal present in the feedstock introduced into the coker / gasifier system.

[0051] In e.g. Figure 1 In the configuration of FIG. 1 , the system elements shown in the figure can be characterized based on the fluid communication between the elements. For example, the reactor section 10 is directly in fluid communication with the heater 11. The reactor section 10 is also indirectly in fluid communication with the gasifier 12 via the heater 11.

[0052] As an alternative, the integration of a fluidized bed coker with a gasifier can also be achieved without the use of an intermediate heater. In such an alternative, the cold coke from the reactor can be transferred directly to the gasifier. The transfer will, in almost all cases, be a clearly direct transfer, with one end of a tubular transfer line connected to the coke outlet of the reactor and its other end connected to the coke inlet of the gasifier, without an intermediate reaction vessel, i.e., a heater. However, the presence of means other than a heater is not excluded, for example, an inlet for lifting gas, etc. Similarly, although the hot, partially gasified coke particles from the gasifier are returned directly from the gasifier to the reactor, this only means that there is no intermediate reaction vessel, i.e., a heater, as in a conventional three-vessel Flexicoker. TM There may be an intermediate heater in the reactor, while other devices may exist between the gasifier and the reactor, for example, a gas lift inlet and outlet.

[0053] Figure 2 An example of integration of a fluidized bed coker with a gasifier is shown without a separate heater vessel. Figure 2In the configuration shown in , the cyclone separator used to separate the fuel gas from the catalyst fines is located in a separate vessel. In other aspects, the cyclone separator can be included in the main gasifier vessel 41.

[0054] exist Figure 2 In the configuration shown in FIG. 4 , the configuration includes a reactor 40, a main gasifier vessel 41 and a separator 42. A combined feed of a coker feed (e.g., a heavy oil feed) and a resin feed is introduced into the reactor 40 via line 43 and a fluidizing / stripping gas is introduced into the reactor 40 via line 44; cracked hydrocarbon products are removed via line 45. Although Figure 2 Combination feedstocks are shown, but example embodiments also include introducing the coker feedstock and resin feedstock separately into the reactor 40. Cold, stripped coke is sent directly from the reactor 40 to the main gasifier vessel 41 via line 46, and hot coke is returned to the reactor in line 47. Steam and oxygen are supplied via line 48. A stream of gas containing coke fines is sent to the separator vessel 42 via line 49 (which is connected to the gas outlet of the main gasifier vessel 41). Fines are separated from the gas stream in a cyclone separator system 50, which includes a primary and secondary cyclone separator connected in series, which has a feed leg that returns the separated fines to the separator vessel. The separated fines are then returned to the main gasifier vessel 41 via return line 51, and the fuel gas product is taken out via line 52. Coke is removed from the separator via line 53. The fuel gas from line 52 can then undergo further processing to separate CO2 (and / or H2S) and convert the synthesis gas into methanol.

[0055] Cokers and gasifiers can be operated according to the parameters necessary for the desired coking process. Thus, the heavy oil feed in the coker feed will typically be a heavy (high boiling) atmospheric petroleum heavy oil; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms, or residual oil; tar; asphalt; natural asphalt; other heavy hydrocarbon residues; oil sands oil; shale oil; or even coal slurry or coal liquefaction products such as coal liquefaction bottoms. Such feeds will typically have a Conradson carbon residue value (ASTM D189-165) of at least 5% by weight, generally 5 to 50% by weight. In some embodiments, the coker feed is a petroleum vacuum residue.

[0056] Fluid coking is carried out in an apparatus having a large reactor containing hot coke particles, wherein the coke particles are maintained in a fluidized state at the desired reaction temperature, steam is injected at the bottom of the vessel, and the average direction of motion of the coke particles is downward through the bed. In a particular embodiment, 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 a plurality of feed nozzles arranged at several successive heights in the reactor. Steam is injected into a stripping section at the bottom of the reactor and the steam passes upward through the coke particles, which are descending through the dense phase of the fluidized bed in the main part of the reactor above the stripping section. In the fluidized bed part of the feed liquid covers the coke particles and it is subsequently cracked into a solid coke layer and lighter products, which are formed as gas or vaporized liquid. The residence time of the feed in the coking zone (where the temperature is suitable for thermal cracking) is about 1 to 30 seconds. The reactor pressure is relatively low in order to facilitate the vaporization of hydrocarbon vapors, which are conveyed upward from the dense phase into the dilute phase of the fluidized bed in the coking zone and into the cyclone separators at the top of the coking zone, wherein most of the entrained solids are separated from the gas phase by centrifugal force in one or more cyclone separators, and the entrained solids are returned to the dense fluidized bed by gravity through the cyclone separator legs. The mixture of steam and hydrocarbon vapor from the reactor is then discharged from the cyclone separator gas outlet to a scrubber section in a pressure ventilation system (plenum) located above the coking zone and separated from it by a partition. The mixture is quenched in the washing section by contact with liquid descending from the shed. A pumping circulation loop circulates the condensed liquid to an external cooler and returns to the top shed row of the washing section to provide cooling for the quenching and condensation of the heaviest fraction of the liquid product. The heavy fraction is usually recycled until it disappears by being sent back to the coking zone in the reactor.

[0057] During the fluidized coking process, a combined feedstock preheated to a temperature at which it can flow and can be pumped is introduced toward the top of the reactor vessel through an injection nozzle (which is configured to produce a spray of feedstock that enters a bed of coke particles fluidized in the vessel) into a coking reactor. The temperature in the coking zone of the reactor is typically in the range of 450°C to 650°C and the pressure is maintained at a relatively low level, typically in the range of 0 kPag to 700 kPag, and most typically at 35 kPag to 320 kPag, in order to promote rapid drying of the coke particles and prevent sticky, adherent high molecular weight hydrocarbons from forming deposits on the particles (which can cause reactor fouling). In some embodiments, the temperature within the coking zone can be 450°C to 600°C, or 450°C to 550°C. Conditions can be selected so that the desired amount of conversion of the feedstock occurs in the fluidized bed reactor. For example, conditions may be selected to achieve at least 10 wt% conversion relative to 343°C (or 371°C), or at least 20 wt% conversion relative to 343°C (or 371°C), or at least 40 wt% conversion relative to 343°C (or 371°C), for example up to 80 wt% conversion or possibly even higher. The light hydrocarbon products of the coking (thermal cracking) reaction vaporize, mix with the fluidizing steam and pass upward through the dense phase of the fluidized bed to the dilute phase region above the dense fluidized bed of coke particles. This mixture of vaporized hydrocarbon products formed in the coking reaction flows upward through the dilute phase, with the superficial velocity of the steam being about 1 to 2 m / s (~3 to 6 ft / s), entraining some fine coke solid particles separated from the cracking vapor in the reactor cyclone separator, as described above. In an embodiment where steam is used as a fluidizing agent, the weight of the steam introduced into the reactor may be selected relative to the weight of the feedstock introduced into the reactor. For example, the mass flow rate of the steam entering the reactor may correspond to 6.0% of the mass flow rate of the raw material, or 8.0% or more, such as up to 10% or possibly even higher. If the activated light hydrocarbon stream is used as a part of the stripping and / or fluidizing gas in the reactor, the amount of steam may be reduced. In such an embodiment, the mass flow rate of steam may correspond to 6.0% or less of the mass flow rate of the raw material, 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 also be lower, such as corresponding to 1.0% or less of the mass flow rate of the raw material, or 0.8% or less, or 0.6% or less, such as low to substantially all steam is replaced by the activated light hydrocarbon stream. The cracked hydrocarbon vapor is sent out of the cyclone separator into the washing section of the reactor and then arrives at product fractionation and recovery.

[0058] In a typical fluid coking process, the coke particles formed in the coking zone pass downward in the reactor and exit the bottom of the reactor vessel through a stripper section where they are exposed to steam to remove adsorbed hydrocarbons. The solid coke from the reactor, consisting primarily of carbon with lesser amounts of hydrogen, sulfur, nitrogen and trace amounts of vanadium, nickel, iron and other elements derived from the feed, passes through the stripper and is conveyed out of the reactor vessel to a burner or heater where it is partially combusted with air in a fluidized bed to raise its temperature from 480°C to 700°C to supply the heat required for the endothermic coking reaction, after which a portion of the hot coke particles is recycled to the fluidized bed reaction zone to transfer heat to the reactor and to serve as a core for coke formation. The remainder is withdrawn as a coke product. The net coke yield is only 65% ​​of that produced by delayed coking.

[0059] For a coking process including a gasification zone, the cracking process is carried out in a reactor, the coke particles pass downward through the coking zone, through a stripping zone, where they are freed of adsorbed hydrocarbons by an upward flow of fluidizing gas (steam). They then leave the coking reactor and are conveyed to a gasification reactor (gasifier), which contains a fluidized bed of solid particles and operates at a temperature higher than that of the coking zone of the reactor. In the gasifier, the coke particles are converted together with steam and an oxygen-containing gas into a fuel gas containing carbon monoxide and hydrogen by reaction at elevated temperatures.

[0060] The gasification zone is generally maintained at a high temperature ranging from 850°C to 1000°C and a pressure of 0 kPag to 1000 kPag, preferably 200 kPag to 400 kPag. Steam and oxygen-containing gas are introduced to provide fluidization and a source of oxygen for gasification. In some embodiments, the oxygen-containing gas may be air. In other embodiments, the oxygen-containing gas may have a low nitrogen content, such as oxygen from an air separation unit or another oxygen stream containing 95 vol% or more of oxygen, or 98 vol% or more of oxygen, which is sent to the gasifier to react with solid particles, which are contained in the coke deposited on them in the coking zone. In embodiments where the oxygen-containing gas has a low nitrogen content, a separate dilution stream, such as a recycled CO2 or H2S stream derived from the fuel gas produced by the gasifier, may also be sent to the gasifier.

[0061] The reaction between coke and steam and oxygen-containing gas in the gasification zone produces fuel gas containing hydrogen and carbon monoxide and partially gasified residual coke product. The conditions in the gasifier are selected accordingly to produce these products. Steam and oxygen rate (and any optional CO2 rate) will depend on the rate at which cold coke enters from the reactor and to a lesser extent on the composition of coke, which in turn will change according to the severity of the composition of the heavy oil feed and the cracking conditions in the reactor, which are selected according to the range of feed and required liquid products. In some embodiments, the fuel gas product from the gasifier contains entrained coke solids and is removed by cyclone separators or other separation techniques in the gasifier section of the device. Suitable cyclone separators are included in the internal cyclone separators in the main gasifier container itself or in a separate, smaller container outside, as described below. The fuel gas product is taken out as a top material from the gasifier cyclone separator. Remove the partially gasified solids obtained from the gasifier and introduce it directly into the coking zone of the coking reactor at a certain height in the dilute phase above the lower dense phase.

[0062] In some embodiments, coking conditions may be selected to provide a desired amount of conversion relative to 343° C. Typically desired conversions may correspond to 10 wt % or more, or 50 wt % or more, or 80 wt % or more relative to 343° C., for example until substantially complete conversion of the feedstock.

[0063] The volatile products from the coke drum are directed away from the process for further processing. For example, the volatiles may be directed to a coker fractionator to distill and recover coker gas, coker naphtha, light gas oil, and heavy gas oil. Such fractions may typically (but not always) be used in a blend of fuel and lubricant products (e.g., motor gasoline, motor diesel, fuel oil, and lubricant oil) after upgrading. Upgrading may include separation, removal of heteroatoms via hydrotreating and non-hydrotreating methods, dearomatization, solvent extraction, and the like. The process is compatible with a process wherein at least a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator is captured for recycling and combined with fresh feed (coker feed components) to form a coker heater or coker furnace charge. The combined feed ratio ("CFR") is the volume ratio of the furnace charge (fresh feed plus recycle oil) to the fresh feed to a continuous fluid coker operation. Fluid coking operations typically employ 5 vol% to 35% vol% recycle (1.05 to 1.35 CFR). In some embodiments, there may be no recycle and sometimes in special applications the recycle may be up to 200%.

[0064] Coking conditions - delayed coking

[0065] Delayed coking is a method for thermally converting heavy oils such as petroleum residue (also referred to as "residual oil") to produce liquid and vapor hydrocarbon products and coke. In a specific embodiment, a combined feedstock of a coker feedstock (e.g., residual oil) and a resin feedstock is subjected to delayed coking to produce liquid and vapor hydrocarbon products and coke. In some embodiments, the residual oil is from heavy and / or acidic (high sulfur) crude oil. Delayed coking of the combined feedstock is performed by converting part of the combined feedstock into more valuable hydrocarbon products. The resulting coke has value as a fuel (fuel grade coke), as an electrode for aluminum manufacturing (anode grade coke), etc., depending on its grade.

[0066] Typically, the combined feedstock (e.g., the residue portion and the fiber-reinforced resin) is pumped to a preheater where the combined feedstock is preheated, e.g., to a temperature of 480° C. to 520° C. The preheated feedstock is directed to a coking zone, which is typically a vertically oriented, insulated coker vessel, e.g., a drum, through an inlet at the bottom of the drum. The pressure in the drum is typically relatively low, e.g., 100 kPa-g to 550 kPa-g, or 100 kPa-g to 240 kPa-g to allow volatiles to be removed at the top. The typical operating temperature of the drum will be approximately 400° C. to 445° C., but may be as high as 475° C. The hot feedstock is thermally cracked in the coke drum over a period of time (“coking time”), releasing volatiles, primarily comprising hydrocarbon products, which continuously rise through the coke bed (which consists of channels, pores, and paths) and are collected at the top. The volatile product is directed to a coker fractionator to distill and recover coker gas, gasoline boiling range materials 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 collected to recycle it and combine it with fresh feed (coker feed components) to form a coker heater or coker furnace charge. In addition to the volatile product, the method also results in the accumulation of coke in the drum. When the coke drum is full of coke, the heated feed is transferred to another drum and hydrocarbon vapors are purged from the coke drum with steam. The drum is then cooled with water to reduce the temperature to 95°C to 150°C, after which the water is discharged. When the discharge step is completed, the drum is opened and the coke is removed by drilling and / or cutting ("hydraulic decoking") using a high-speed water jet.

[0067] Configuration Example

[0068] Figure 3 An example of a configuration for co-processing of resin feedstock during fluid coking is shown. Figure 3In the resin feed preparation stage 56, the resin feedstock 54 is physically treated. Physically treating the feedstock may include one or more methods to reduce the median particle size of the particles in the feed; to remove particles larger than a target particle size from the feedstock; to form particles of a desired size (e.g., by grinding, crushing, chopping, or other suitable means of changing the size). The physically treated resin feedstock 58 may then be combined with the coker feedstock 60 in a mixing stage 62. The mixing stage 62 includes any suitable type of mixing equipment, including a stirred tank reactor, a melt extruder, a heated batch mixer, and a tubular heating furnace, among others. Optionally, the resin feedstock is combined with an optional carrying fluid 64. Optionally, the combined feedstock 66 may be heated prior to leaving the mixing stage 62. This optional heating may be performed in addition to any heating performed by a preheater that is part of the coker 68. The coker 68 may correspond to a fluidized coker or a delayed coker, such as, for example, Figure 1 and 2 Coker 68 may produce at least a solid coke product 70 and a coker effluent 72. In embodiments where coker 68 comprises a gasifier, coker 68 may further produce a low BTU fuel gas (not shown) comprising a syngas component.

[0069] The coker effluent 72 may be passed to a fractionation stage 74 that includes one or more types of fractionators and / or separators. The fractionation stage 74 may separate the fluid products into one or more vapor products 76 and one or more liquid products 78. Optionally, additional liquid products may be produced to serve as a carrier fluid 64. For example, a diesel or gas oil boiling range product may be used as a carrier fluid 64. Alternatively, the carrier fluid 64 may correspond to a solvent from another source.

[0070] Examples of coking products

[0071] Coking of the combined feedstocks produces products including coke and coker effluent. Many types of thermosetting resins have relatively low sulfur contents. This can provide advantages by reducing the sulfur content of the coker products, thereby reducing the severity required for any subsequent sulfur removal treatment of the resulting coker effluent.

[0072] The coke produced in the coking process is generally a carbonaceous solid material, most of which is carbon. Because coke is produced in a coker from a petroleum cracking process, it may also be referred to as petroleum coke or petroleum coke (petcoke). The specific composition of coke depends on several factors, including a specific coking process (e.g., delayed coker) or in some embodiments, based on the gross weight of coke, coke comprises carbon in an amount of 80% by weight to 95% by weight. Additional components in coke include hydrogen, nitrogen, sulfur 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, the coke produced by the combined raw materials further comprises residues from the coking of enhanced thermosetting resins, such as glass residues in some embodiments of thermosetting resins reinforced with glass fibers. For further example, additional fillers in thermosetting resins may cause coke to have additional amounts of impurities, such as titanium, magnesium, calcium, silicon dioxide, aluminum and sodium.

[0073] In some embodiments, the coke produced is derived at least in part from a thermosetting resin that may include a reinforcement. The example of a suitable reinforcement, including glass fiber, produces glass residues in the coke. In these embodiments, the filler and reinforcement in the thermosetting resin are transferred to the coke, causing the coke to include glass residues (such as silicon) and other fillers from the thermosetting resin compared to the amount increased by conventional coke. For example, conventional coke may include silicon at the most in an amount of 600 wppm. However, the coke produced at least in part by a fiber-reinforced thermosetting resin may include silicon in an amount of 1000 wppm or more. In some embodiments, the coke includes silicon in an amount of 1000 wppm to 2 weight %, 1000 wppm to 1 weight %, 5000 wppm to 2 weight % or 1 weight % to 2 weight %. However, when the amount of filler and reinforcement present is sufficient to be fully discharged from the process to reach steady-state operation, the coke should meet the specifications of petroleum coke.

[0074] The usual expected yield of coke from the coking of conventional coker feedstock is 20% to 40% by weight of the coker feedstock. However, because the resin feedstock may contain fibers or other reinforcing materials and fillers, which are discharged in the coke, the coking of a combination feedstock with the resin feedstock may result in an increased coke yield. For example, the yield of coke from the coking of a combination feedstock of the coker feedstock and the resin feedstock is 20% to 50% by weight of the combination feedstock.

[0075] In addition to coke, coking of the combined feedstock also produces a coker effluent. As discussed above, the coker effluent can be fractionated or otherwise separated to form a desired product stream, 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 thermosetting resin, the coker effluent further includes components derived from the thermosetting resin.

[0076] In some embodiments, the coker effluent is at least partially derived from the PDCPD resin in the resin feedstock. In these embodiments, the coker effluent comprises an increased amount of cycloolefins and / or cyclodienes. For example, the coker effluent comprises an increased amount of cyclopentene and cyclopentadiene. In some embodiments, the coker effluent comprises 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 wt % to 1 wt %, or 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 % of the amount of cyclopentene. In some embodiments, the coker effluent comprises cyclopentadiene in an amount between 0.01 wt% and 5 wt%, between 0.01 wt% and 2 wt%, between 0.01 wt% and 1 wt%, between 0.01 wt% and 0.1 wt%, between 0.1 wt% and 5 wt%, or between 0.5 wt% and 5 wt%, or between 1 wt% and 5 wt%, or between 0.1 wt% and 4 wt%, or between 0.1 wt% and 3 wt%, or between 0.1 wt% and 2 wt%, or between 0.1 wt% and 1 wt%, or between 0.5 wt% and 4 wt%, or between 0.5 wt% and 3 wt%, or between 0.5 wt% and 2 wt%, or between 0.5 wt% and 1 wt%.

[0077] Advantageously, in one or more embodiments, by attributing the cyclic olefins from the coker to the use of thermosetting resin waste (e.g., product waste from windmill blade production), such as by counting, allocating and / or offsetting or replacing other hydrocarbons in the mass or energy balance within the coker system, the cyclic olefins and cyclic dienes in the coker effluent are considered to be cyclic. For example, the cyclic cyclopentenes and cyclic cyclopentadienes are produced by PDCPD resins in the coker. In some embodiments, according to one or more embodiments, the cyclic olefins and cyclic dienes are separated and then polymerized. For example, the cyclic cyclopentenes and cyclic cyclopentadienes are polymerized to form PDCPD resins. In some embodiments, the coker effluent is used to produce cyclic polymers, such as cyclic thermosetting polymers (e.g., cyclic polydicyclopentadiene). In polymers formed by cyclic monomers, their cyclicity can be proven by third-party certification. An example of such certification is the mass balance chain of the regulatory method proposed by international sustainable development and carbon certification.

[0078] Additional Implementations

[0079] Thus, the present disclosure provides for coking of a combined feedstock comprising a coker feed and a resin feed.The methods and systems include any of the various features disclosed herein, including one or more of the following descriptions.

[0080] Embodiment 1. A method for coking a combined feed, comprising: combining a resin feed with a coker feed having a T10 distillation point of about 343°C or greater to form a combined feed, wherein the resin feed comprises a thermosetting resin having a median particle size of about 5 mm or less; and exposing at least a portion of the combined feed to coking conditions in a coking reactor to form at least coke and a coker effluent.

[0081] Embodiment 2. The method of Embodiment 1, further comprising reducing the particle size of the thermosetting resin to a median particle size of about 5 mm or less.

[0082] Embodiment 3. The method of embodiment 1 or 2, further comprising mixing the resin feedstock with a carrier fluid.

[0083] Embodiment 4. The method of any preceding embodiment, wherein at least a portion of the resin is combined with the coker feed in one or more mixing vessels, the method further comprising heating the combined feed to a temperature of about 200° C. or greater in the one or more mixing vessels.

[0084] Embodiment 5. The method of any one of Embodiments 1 to 3, wherein the resin feed is combined with the coker feed prior to introduction into the coking reactor.

[0085] Embodiment 6. The method of claim 1, wherein the thermosetting resin comprises a fiber reinforced resin.

[0086] Embodiment 7. The method of any preceding embodiment, wherein the thermosetting resin comprises a glass fiber reinforced resin.

[0087] Embodiment 8. The method of any preceding embodiment, wherein the thermosetting resin comprises a polydicyclopentadiene resin.

[0088] Embodiment 9. The method of any preceding embodiment, wherein the thermosetting resin is a dimensionally modified material from a windmill blade.

[0089] 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.

[0090] Embodiment 11. The method of any preceding embodiment, wherein the coke comprises silicon in an amount of about 1000 wppm or more.

[0091] Embodiment 12. The process of any preceding embodiment, wherein the coker effluent comprises cyclopentene in an amount from about 0.01 wt% to about 2 wt% and cyclopentadiene in an amount from about 0.01 wt% to about 5 wt%.

[0092] Embodiment 13. The method of any preceding embodiment, wherein the coker effluent comprises about 0.5 wt% to about 5 wt% cyclopentadiene, and the method further comprises separating at least a portion of the cyclopentadiene from the coker effluent and polymerizing at least a portion of the cyclopentadiene to form polydicyclopentadiene.

[0093] Embodiment 14. The method of any preceding embodiment, wherein the combined feedstock comprises the resin feedstock in an amount from about 1 wt % to about 25%.

[0094] Embodiment 15. The method of any preceding embodiment, further comprising reducing the particle size of the material from the windmill blades to form the thermosetting resin to a 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 wt %, and wherein the char comprises silicon in an amount of about 1000 wppm to about 2 wt %.

[0095] Embodiment 16. The method of any preceding embodiment, further comprising reducing the particle size of a polydicyclopentadiene resin used to form the thermoset resin to a median particle size of about 5 mm or less, wherein the combined feed comprises the resin feed in an amount of about 1 wt % to about 25 wt %, 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 %.

[0096] Embodiment 17. Petroleum coke, comprising: a carbonaceous solid material comprising silicon in an amount of about 1000 wppm or more.

[0097] Embodiment 18. The petroleum coke of Embodiment 17, wherein silicon is present in an amount from about 1000 wppm to about 2 wt%.

[0098] Embodiment 19. The petroleum coke of Embodiment 17 or 18, wherein the petroleum coke is produced in a delayed coker.

[0099] Embodiment 20. The petroleum coke of Embodiment 17 or 18, wherein the petroleum coke is produced in a fluid coker.

[0100] 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 a glass fiber reinforced thermosetting resin.

[0101] Embodiment 22. The petroleum coke of any one of Embodiment 21, wherein the glass fiber reinforced thermosetting resin comprises a polydicyclopentadiene resin.

[0102] To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are provided.The following examples should not be construed as limiting or defining the entire scope of the present disclosure. Example 1

[0103] Laboratory scale experiments were conducted to determine the pyrolysis product distribution of thermosetting resin samples. Approximately 0.5 mg of PDCPD thermosetting resin sample #1 was loaded into a CDS 5150 micro-pyrolyzer and the temperature program was set to rapidly heat it to the pyrolysis temperature associated with the coker operation. The resin sample was pyrolyzed at 530°C for 20 seconds. The micro-pyrolyzer was connected to the inlet of a GC / MS by a transfer line that was heated to 250°C to avoid condensation. The pyrolysis products formed were identified by electron bombardment mass spectrometry. The pyrolysis products are provided in Table 2 below.

[0104] Table 2

[0105] As shown in Table 2, pyrolysis of neat PDCPD thermoset resin sample #1 resulted in the production of monomers including 1,3-cyclopentadiene, cyclopentene, and 3-methylcyclopentene. Advantageously, the production of these monomers by this resin sample indicates that resin charring should also produce corresponding resin monomers, which in turn can be reused in the production of resin, thereby providing a recycling process.

[0106] Thermogravimetric analysis (TGA) was used to further analyze the pyrolysis of PDCPD thermosetting resin sample #1. The resin sample was pyrolyzed in a controlled heating TGA under an inert nitrogen atmosphere. The temperature was increased from room temperature to 700°C at a thermal rate of 20°C / min and then held at 700°C for 1 hour. Figure 4 The mass loss curve from TGA is shown in . As illustrated in this figure, at 530° C., more than 80 wt % of the resin sample is converted to volatiles. Example 2

[0107] Conduct laboratory scale experiment to determine the pyrolysis product distribution of another thermosetting resin sample.Approximately 0.5 milligram of PDCPD thermosetting resin sample #2 is loaded into CDS 5150 micro-pyrolyzer and the temperature program is set to make it rapidly heated to the pyrolysis temperature relevant to the operation of the coker.This resin sample is pyrolyzed at 530 ℃ for 20 seconds.The micro-pyrolyzer is connected to the import of GC / MS by the transfer line that is heated to 250 ℃ to avoid condensation.The pyrolysis product formed is identified by electron bombardment mass spectrometry.The pyrolysis product is provided in the following table 3.

[0108] Table 3

[0109] As shown in Table 3, pyrolysis of neat PDCPD thermoset resin sample #2 resulted in the production of monomers including cyclopentadiene isomers. Advantageously, the production of these monomers by this resin sample indicates that resin charring should also produce corresponding resin monomers, which in turn can be reused in the production of resin, thereby providing a recycling process.

[0110] Thermogravimetric analysis (TGA) was used to further analyze the pyrolysis of PDCPD thermosetting resin sample #2. The resin sample was pyrolyzed in a controlled heating TGA under an inert nitrogen atmosphere. The temperature was increased from room temperature to 700°C at a thermal rate of 20°C / min and then maintained at 700°C for 1 hour. Figure 5 The mass loss curve from TGA is shown in . As illustrated in this figure, at 530° C., more than 85 wt % of the resin sample is converted to volatiles. Example 3

[0111] The above test uses two different PDCPD thermosetting resin samples. Before these tests, PDCPD thermosetting resin sample #1 is exposed to air for a long time. The CHNOS content of two resin samples is analyzed. The CHNOS analysis shows that, compared to PDCPD thermosetting resin sample #2, PDCPD thermosetting resin sample #1 has a larger amount of oxygen, as shown in Table 4. This is also consistent with the following fact: compared to PDCPD thermosetting resin sample #2, the amount of CO2 from the pyrolysis of PDCPD thermosetting resin sample #1 is larger.

[0112] Table 4

[0113] Although compositions, methods and processes are described herein in terms of "comprising," "containing," "having," or "including" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components and steps. Unless otherwise indicated, whether or not specifically mentioned in this specification, the phrases "consist essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, as long as such steps, elements, or materials do not affect the basic and novel characteristics of the disclosure, and further, they do not exclude impurities and differences normally associated with the elements and materials used.

[0114] All numerical values ​​within the detailed description are modified by "about" the indicated value, and take into account experimental errors and deviations that would be expected by a person of ordinary skill in the art.

[0115] Many variations, modifications and variations will be apparent to those skilled in the art based on the foregoing description without departing from the spirit or scope of the present disclosure, and when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

1. A method for coking a combined feed comprising: combining a resin feed with a coker feed having a T10 distillation point of about 343° C. or greater to form a combined feed, wherein the resin feed comprises a thermosetting resin having a median particle size of about 5 mm or less; and At least a portion of the combined feedstock is exposed 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 the particle size of the thermosetting resin to a 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 at least a portion of the resin is combined with the coker feed in one or more mixing vessels, the method further comprising heating the combined feed to a temperature of about 200°C or greater in the one or more mixing vessels.

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

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

7. The method of claim 1, wherein the thermosetting resin comprises a glass fiber reinforced resin.

8. The method of claim 1, wherein the thermosetting resin comprises polydicyclopentadiene resin.

9. The method of claim 1, wherein the thermosetting resin is a dimensionally modified 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 process of claim 1, wherein the coker effluent comprises cyclopentene in an amount from about 0.01 wt% to about 2 wt% and cyclopentadiene in an amount from about 0.01 wt% to about 5 wt%.

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

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

15. The method of claim 1, further comprising reducing the particle size of the material from the windmill blades to form the thermoset resin to a 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 wt %, and wherein the char comprises silicon in an amount of about 1000 wppm to about 2 wt %.

16. The method of claim 1 further comprising reducing the particle size of a polydicyclopentadiene resin used to form the thermoset resin to a median particle size of about 5 mm or less, wherein the combined feed comprises the resin feed in an amount of about 1 wt % to about 25 wt %, 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. Petroleum coke, including: A carbonaceous solid material comprising silicon in an amount of about 1000 wppm or more.

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

19. The petroleum coke according to 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 fluid coker.

21. The petroleum coke of claim 17, wherein the petroleum coke is produced at least in part by coking a glass fiber reinforced thermosetting resin.

22. The petroleum coke according to claim 21, wherein the glass fiber reinforced thermosetting resin comprises polydicyclopentadiene resin.

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