Chemical recovery of artificial turf

Abstract

The present disclosure provides systems and methods for chemical recovery of artificial turf, including, in one embodiment, a method comprising: providing a turf feed comprising a dimensioned carpet composition; and cracking at least the turf feed to produce at least a cracking product comprising hydrocarbons.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 403,377, filed on September 2, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure provides systems and methods for chemical recycling of artificial turf. Background Art

[0004] Artificial turf is used as a ground covering in many applications, including sports fields, playgrounds, and residential and commercial ground coverings. Artificial turf generally includes a carpet portion, one or more backing materials, one or more filling materials, and an optional shock-absorbing pad. The carpet portion includes vertical fibers or upright ribbons that are similar to the blades of artificial turf and are often made of thermoplastic materials. The fibers of the carpet portion will be referred to as "turf fibers" in this article. The one or more backing materials may include a primary backing material and a secondary backing material. The primary backing material may include thermoplastics such as polypropylene, and the secondary backing material may include polyurethane or latex, etc. The one or more filling materials simulate the soil in natural turf and may include inorganic fillers such as sand. The one or more filling materials may also include a second filling material, such as granular thermosetting rubber. Artificial turf optionally includes a shock-absorbing pad below the backing material.

[0005] Although artificial turf is a suitable alternative to natural turf, it has a limited service life and is often removed and replaced with new turf material. Due to the huge amount of artificial turf currently in use, there is a need to reuse and / or recycle some or all of the turf components. However, the options for turf recycling are limited. Due to the composite nature of artificial turf, which typically includes thermoplastic components (such as turf fibers, primary backing materials, etc.) and thermosetting components (such as secondary backing materials), mechanical recycling is difficult. These mixtures are known to produce low values ​​in mechanical recycling. Moreover, since artificial turf typically includes inorganic fillers as filling materials, the turf fibers are contaminated by such inorganic fillers, making traditional carpet mechanical recycling processes inapplicable. In addition, it is also known that thermosetting rubber is difficult to recycle mechanically, especially when contaminated by inorganic filler materials. Since artificial turf can also include thermosetting rubber as a second filling material, mechanical recycling is further complicated.

[0006] Overview

[0007] Disclosed herein is an exemplary method of chemically reclaiming artificial turf comprising: providing a turf feed comprising a sized carpet composition; and cracking at least the turf feed to produce at least a cracking product comprising hydrocarbons.

[0008] Also disclosed herein is an exemplary method of chemically recycling artificial turf, the method comprising: providing a turf feed comprising infill material from artificial turf, wherein the infill material comprises a polymeric material; and cracking the turf feed to produce at least a cracking product comprising hydrocarbons.

[0009] These and other features and properties of the methods and systems disclosed in the present disclosure as well as their advantageous applications and / or uses will be apparent from the following detailed description.

[0010] BRIEF DESCRIPTION OF THE DRAWINGS

[0011] To assist one of ordinary skill in the relevant art in making and using the subject matter herein, reference is made to the accompanying drawings, in which:

[0012] Figure 1 is an illustrative depiction of artificial turf according to certain embodiments of the present disclosure.

[0013] Figure 2 is an illustrative description of a method for artificial turf separation and sizing according to certain embodiments of the present disclosure.

[0014] Figure 3 is an illustrative description of another method for artificial turf separation and sizing, according to certain embodiments of the present disclosure.

[0015] Figure 4 is an illustrative description of a fluidized bed coking system including a coker, a heater, and a gasifier, according to certain embodiments of the present disclosure.

[0016] Figure 5 is an illustrative description of a fluidized bed coking system including a coker and a gasifier, according to certain embodiments of the present disclosure.

[0017] Figure 6 is an illustrative description of a delayed coking system including a coker and a gasifier, according to certain embodiments of the present disclosure.

[0018] Figure 7 is a graph showing mass loss curves from thermogravimetric analysis of sample turf feed according to certain embodiments of the present disclosure.

[0019] Detailed Description

[0020] In various embodiments, systems and methods for chemical recovery of artificial turf are provided. In some embodiments, the chemical recovery method of artificial turf includes cracking turf feed to produce hydrocarbons. In some embodiments, the turf feed is co-processed with conventional cracking feedstocks such as petroleum vacuum residue in a cracking environment. Although the systems and methods disclosed herein are suitable for cracking turf feedstocks in various different cracking embodiments, they may be particularly suitable for cracking turf feedstocks in coking environments such as delayed coking and fluidized bed coking environments.

[0021] Chemical recovery of artificial turf using cracking can be carried out by, for example, performing several processes on the artificial turf. First, the artificial turf can be conditioned to provide a turf feed. The turf feed includes one or more components of artificial turf, including turf fibers adjusted in size, primary backing materials adjusted in size, and secondary backing materials adjusted in size. The turf feed can also include at least a portion of a filling material (e.g., a first filling material of an inorganic filler or a second filling material of a thermosetting rubber). Secondly, the turf feed can enter a hydrolysis environment, such as a fluidized bed coking environment or a delayed coking environment. The turf feed can enter a hydrolysis environment as a separate stream or in a slurry (e.g., with a carrier fluid and / or conventional cracking raw materials). Third, the turf feed can then be processed in a cracking environment to generate cracking products. The cracking products produced are valuable products that can be further processed, such as gas, naphtha, gas oil, and / or coke. In some embodiments, the turf feed is co-processed in the cracking environment with one or more co-feeds such as conventional cracking raw materials in the method.

[0022] In some embodiments, chemical recovery of artificial turf using cracking has advantages over mechanical processing. As previously mentioned, due to the complex nature of artificial turf containing many different materials such as thermosetting materials, thermoplastic materials, rubber particles and / or inorganic fillers, the mechanical processing of artificial turf is challenging. Advantageously, some exemplary embodiments provide a technology for chemical recovery of artificial turf while producing desired products. Since the chemical composition of artificial turf is chemically compatible with the cracking environment (e.g., coking), the turf is processed in the cracking environment to produce desired products, such as gas, naphtha, gas oil and / or coke. In addition, when the coking feed is processed in the coking environment according to one or more embodiments, the inorganic filler in the coking feed is separated into the coke, thereby allowing the turf feed contaminated by the inorganic filler to be recovered, and the inorganic filler will bring problems to the recovery in other ways. By processing the inorganic filler in chemical recovery, some exemplary embodiments solve a key problem of artificial turf recovery.

[0023] Although artificial turf is a suitable alternative to natural turf, it has a limited service life and is often removed and replaced with new turf material. Due to the huge amount of artificial turf currently in use, there is a need to reuse and / or recycle some or all of the turf components. However, the options for turf recycling are limited. Due to the composite nature of artificial turf, which typically includes thermoplastic components (such as turf fibers, primary backing materials, etc.) and thermosetting components (such as secondary backing materials), mechanical recycling is difficult. These mixtures are known to produce low values ​​in mechanical recycling. Moreover, since artificial turf typically includes inorganic fillers as filling materials, the turf fibers are contaminated by such inorganic fillers, making traditional carpet mechanical recycling processes inapplicable. In addition, it is also known that thermosetting rubber is difficult to recycle mechanically, especially when contaminated by inorganic filler materials. Since artificial turf can also include thermosetting rubber as a second filling material, mechanical recycling is further complicated.

[0024] Artificial turf

[0025] Artificial turf is used as a ground covering in many applications, including sports fields, playgrounds, and residential and commercial ground coverings, etc. Artificial turf generally includes multiple components, including turf fibers, a primary backing material, a secondary backing material, a filling material, and / or a shock-absorbing pad. In some embodiments, the turf fibers are combined with the primary backing material and extend upward from the top side of the primary backing material, similar to blades of grass. In some embodiments, the filling material is dispersed between the turf fibers extending from the primary backing material. In some embodiments, the secondary backing material is coupled to the bottom side of the primary backing material to keep the turf fibers on the primary backing material. Artificial turf also includes the optional shock-absorbing pad located below the secondary backing material.

[0026] The turf fibers include any material suitable for making artificial turf. Examples of materials suitable for turf fibers include thermoplastic materials such as polyolefins, polyesters, polyamides or other suitable thermoplastics and blends thereof. In some embodiments, the turf fibers include polyethylene, polypropylene, polyamide 6, polyamide 6,6, polyethylene terephthalate, or combinations thereof.

[0027] In some embodiments, the turf fibers are coupled to the primary backing material. The turf fibers can be coupled to the primary backing material by any suitable means. For example, the turf fibers can be tufted or stitched into the primary backing material. For another example, an adhesive can be used to fix the turf fibers. In some embodiments, the primary backing material includes one or more thermoplastic materials. Examples of thermoplastic materials suitable for use in the primary backing material include polyolefins, polyamides, and polyesters. In some embodiments, the primary backing material includes polyethylene, polypropylene, polyamide, polyethylene terephthalate, or a combination thereof.

[0028] In some embodiments, artificial turf also includes a secondary backing material. The secondary backing material is coupled to the bottom side of the primary backing material to keep turf fibers on the primary backing material. In some embodiments, the secondary backing material is applied to the bottom side of the primary backing material. The example of suitable secondary backing material includes thermosetting materials. In some embodiments, the secondary backing material includes polyurethane, thermosetting elastomer (for example natural or synthetic rubber latex), acrylic adhesive or a combination thereof.

[0029] In some embodiments, artificial turf also includes filling material. Filling material is dispersed between turf fibers, for example, plays the role of ballast. Filling material can include a single filling material or a combination of filling materials. In some embodiments, filling material includes a first filling material and a second filling material. The example of a suitable first filling material includes an inorganic material, such as sand, gravel or other inorganic materials. The example of a suitable second filling material includes cork and polymer materials, such as polymer beads, thermosetting rubber, thermoplastic elastomer, thermoplastic vulcanizate, thermoplastic material and a combination thereof. In some embodiments, the second filling material includes ground tire rubber, granular rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene propylene diene monomer (EPDM) rubber, chloroprene rubber and a combination thereof. In some embodiments, a combination of suitable filling materials is used.

[0030] In some embodiments, the artificial turf further comprises a shock absorbing pad. When in use, the shock absorbing pad may be placed, for example, under the secondary backing material. The shock absorbing pad acts as a vibration absorbing material. In some embodiments, the shock absorbing pad comprises polyurethane, polyvinyl chloride foam, polyurethane foam, rubber, closed-cell cross-linked polyethylene foam, polyurethane base pad with voids, elastomeric foam of polyvinyl chloride, polyethylene, polyurethane and polypropylene, and combinations thereof.

[0031] Figure 1 A cross-sectional view of an artificial turf 100 according to one or more embodiments is illustrated. In the illustrated embodiment, the artificial turf 100 includes turf fibers 102 coupled to a primary backing material 104. The turf fibers 102 extend from a top side 106 of the primary backing material 104, and a fill material 108 is dispersed between the turf fibers 102. A secondary backing material 110 is coupled to a bottom side 112 of the primary backing material 104. Although not shown, the artificial turf 100 may include an optional shock absorbing pad located below the secondary backing material 110.

[0032] Artificial Turf Conditioning

[0033] Exemplary embodiments include conditioning artificial turf into turf feed. In some embodiments, the turf feed includes a carpet composition, such as artificial turf from which at least a portion of the filling material is separated. The artificial turf can be obtained from a variety of sources. In some embodiments, the artificial turf is obtained from a collection station after it is removed from the ground or other installation location. The collection station includes post-consumer artificial turf suitable for conditioning into turf feed. In some embodiments, the artificial turf is sorted according to the type of turf fiber. In some embodiments, the artificial turf is packaged.

[0034] The conditioning of artificial turf includes the step of carrying out physical processing to artificial turf, so that it is ready for experiencing cracking environment. In some embodiments, conditioning includes adjusting the size of artificial turf to reduce its particle size. For example, smaller particle size can be conducive to the transportation of solid and / or reduce the possibility of incomplete conversion in cracking. The example of physical processing can include adjusting the size of artificial turf, for example, by crushing, chopping, shredding and grinding (including cryogenic grinding). In some embodiments, physical processing can be used to reduce the median particle size to 0.01 millimeter (" mm ")-50mm, 0.1-50mm, 0.1-30mm, 0.1-20mm, 5.0mm, or 0.1mm-5.0mm, or 0.01mm-3.0mm, or 0.1mm-3.0mm, or 0.01mm-3.0mm, or 0.1mm-3.0mm, or 1.0mm-5.0mm, or 1.0mm-3.0mm, to reduce the maximum particle size. To determine the median particle size, the particle size is defined as the diameter of the smallest bounding sphere containing the particle. Optionally, after physical processing, the thermosetting resin may be sieved or filtered to remove larger particles. In some embodiments, the sieving or filtering may be used to reduce the maximum particle size to 10 mm or less, or 5.0 mm or less.

[0035] In some embodiments, the turf feed for cracking includes artificial turf that has been sized without any additional separation. In other embodiments, the artificial turf that has been sized is separated into one or more components to provide a turf feed. The components can be separated, for example, according to specific gravity, size and / or shape. Examples of suitable separation techniques include screening, specific screening by specific gravity and / or separation by air rotation (e.g., cyclone separator). Different fractions of the artificial turf that has been sized can be obtained, which contain one or more different components of artificial turf. According to one or more embodiments, the polymer turf component is suitable for chemical recovery by cracking. It should be understood that certain components (e.g., sand) will not be converted, but distributed with coke. The turf feed can include, for example, one or more of turf fibers that have been sized, primary backing materials that have been sized, secondary backing materials that have been sized, first filling materials, second filling materials, and / or shock pads that have been sized. Although it may be desirable to separate turf fibers from artificial turf to provide a turf feed consisting solely of turf fibers, the turf fibers may be contaminated with other components of the artificial turf such that the individual turf fibers also include additional components, such as a primary backing material, a secondary backing material, a first filling material, a second filling material, and / or a shock pad. In some embodiments, the filling material is separated from the other turf components to form a carpet composition for turf feed, wherein the carpet composition comprises one or more of turf fibers, a primary backing material, a secondary backing material, and / or a shock pad. It should be understood that although it may be desirable to separate the carpet composition from the filling material for recycling, the carpet composition may be contaminated with the filling material, such as the first filling material, thereby providing an inorganic filler to the turf feed.

[0036] Figure 2A method 200 for conditioning artificial turf is illustrated. As illustrated, the method 200 includes providing artificial turf, as shown in block 202. The artificial turf is then sized at block 204 to provide sized artificial turf. As previously described, the size of the artificial turf may be adjusted using any suitable technique to provide sized artificial turf having a reduced particle size, including crushing, chopping, cutting, shredding, and grinding. In some embodiments, the sized artificial turf is used as a turf feed for cracking without further separation, as shown in block 206. The sized artificial turf may be pyrolyzed alone, in combination with one or more turf fractions, or pyrolyzed together with conventional cracking feedstock. In some embodiments, the sized artificial turf is separated into one or more fractions, as shown in block 206. For example, the filler material is separated from the sized carpet composition to provide at least a separated second filler material at block 210, a separated first filler material (e.g., shown as a separated inorganic filler) at block 212, and a sized composition at block 214. The sized carpet composition at block 214 may include one or more of turf fiber, primary backing material, secondary backing material, and / or a shock pad. In some embodiments, the sized carpet composition may also be separated into different fractions, such as a turf fiber fraction, a primary backing fraction, and / or a secondary backing fraction. As illustrated, an exemplary embodiment includes pyrolyzing the sized carpet composition and / or the second filler material at block 206, which may be pyrolyzed separately, in combination with each other, or in combination with conventional pyrolysis feedstocks.

[0037] Figure 3A method 300 for conditioning artificial turf is illustrated. As illustrated, the method 300 includes providing artificial turf, as shown at block 202. The artificial turf is then sized at block 204 to provide sized artificial turf. As previously described, the size of the artificial turf may be adjusted using any suitable technique to provide sized artificial turf having a reduced particle size, including crushing, chopping, shredding, and grinding. In some embodiments, the sized artificial turf is used as a turf feed for cracking without further separation, as shown in block 206. The sized artificial turf may be pyrolyzed alone, in combination with one or more turf fractions, or pyrolyzed together with conventional cracking feedstock. In some embodiments, the sized artificial turf is separated into one or more fractions, as shown in block 206. For example, the filler material is separated from the sized carpet composition to provide at least a separated second filler material at block 210, a separated first filler material (e.g., shown as a separated inorganic filler) at block 212, and a sized carpet composition at block 214. The sized carpet composition at block 214 may include one or more of turf fiber, primary backing material, secondary backing material, and / or a shock pad. In some embodiments, the sized carpet composition may also be separated into different fractions, such as a turf fiber fraction, a primary backing fraction, and / or a secondary backing fraction. As illustrated, an exemplary embodiment includes pyrolyzing the sized carpet composition and / or the separated second filler material at block 206, which may be pyrolyzed separately, in combination with each other, or in combination with conventional pyrolysis feedstocks.

[0038] In some embodiments, the size-adjusted artificial turf from block 204 is provided to a second turf size adjustment at block 302 for further size reduction. In some embodiments, the size-adjusted carpet composition separated in block 208 is provided to a second turf size adjustment at block 302 for further size reduction. According to some embodiments of the present disclosure, the further size-reduced output of block 302 is provided to a second turf separation at block 304. In the second turf separation at block 304, a first filler material (e.g., an inorganic filler) may be separated from the size-adjusted turf composition to provide a turf composition at block 306, which may then be lysed at block 206. The separated first filler material from block 304 is optionally returned to the separation at block 208.

[0039] Cracking feed

[0040] According to some embodiments of the present disclosure, a turf feed is pyrolyzed to produce hydrocarbons. In some embodiments, the turf feed is co-pyrolyzed with a conventional cracking feed. The turf feed includes one or more components of an artificial turf. For example, the turf feed includes a size-adjusted carpet composition that includes one or more of turf fibers, a primary backing material, a secondary backing material, and / or a size-adjusted backing pad. In some embodiments, the carpet composition is contaminated with a filler material such that the turf feed also includes a filler material, such as a first filler material of an inorganic material.

[0041] In some embodiments, the sized carpet composition is included in the turf feed in any suitable amount. For example, the sized carpet composition can be included in the turf feed in an amount of 0.1% to 100% by weight of the turf feed. In some embodiments, the sized carpet composition is included in the turf feed in an amount of 1%-99%, 1%-95%, 1%-90%, 1%-50%, 10%-100%, 10%-90%, 10%-50%, 40%-100%, 40%-90%, 50%-100%, or 50%-90% by weight of the turf feed.

[0042] In some embodiments, the sized turf fibers are included in the carpet composition in any suitable amount. For example, the sized turf fibers can be included in the carpet composition in an amount of 0.1% to 100% by weight of the carpet composition. In some embodiments, the sized turf fibers are included in the carpet composition in an amount of 1%-99%, 1%-95%, 1%-90%, 1%-50%, 10%-100%, 10%-90%, 10%-50%, 40%-100%, 40%-90%, 50%-100%, or 50%-90% by weight of the carpet composition.

[0043] In some embodiments, a resized primary backing material is included in a carpet composition. For example, a resized primary backing material can be included in a carpet composition in an amount of 0.1% to 100% by weight of the turf feed. In some embodiments, a resized primary backing material is included in a carpet composition in an amount of 1%-100%, 1%-95%, 1%-90%, 1%-80%, 1%-50%, 1%-20%, or 1%-75%, 1%-50%, 10%-20%, 10%-100%, 10%-50% by weight of the carpet composition.

[0044] In some embodiments, a resized secondary backing material is included in the carpet composition. For example, the resized secondary backing material can be included in the carpet composition in an amount of 0.1%-100% by weight of the carpet composition. In some embodiments, the resized secondary backing material is included in the carpet composition in an amount of 1%-100%, 1%-95%, 1%-90%, 1%-80%, 1%-50%, 1%-20%, or 1%-75%, 1%-50%, 10%-20%, 10%-100%, 10%-50% by weight of the carpet composition.

[0045] In some embodiments, a resized backing pad is included in the carpet composition. For example, the resized backing pad can be included in the carpet composition in an amount of 0.1%-100% by weight of the carpet composition. In some embodiments, the resized backing pad is included in the carpet composition in an amount of 1%-100%, 1%-95%, 1%-90%, 1%-80%, 1%-50%, 1%-20%, or 1%-75%, 1%-50%, 10%-20%, 10%-100%, 10%-50% by weight of the carpet composition.

[0046] In some embodiments, a filler material is included in the turf feed. The filler material includes a first filler material (e.g., an inorganic filler) and / or a second filler material (e.g., a thermosetting rubber, a thermosetting elastomer, etc.). If present, the filler material may be included in the turf feed in an amount of 0.1%-100% by weight of the turf feed. In some embodiments, the filler material is included in the turf feed in an amount of 1%-100%, 1%-95%, 1%-90%, 1%-80%, 1%-50%, 1%-20% or 1%-75%, 1%-50%, 10%-20%, 10%-100%, 10%-50% by weight of the turf feed. In some embodiments, it may be desirable to limit the amount of the first filler material of the inorganic filler in the turf feed. For example, the first filler material may be present in the turf feed in an amount of 50% or less by weight of the turf feed. In some embodiments, the first filler material is present in the turf feed in an amount of 40%, 30%, 20%, 15%, 10% or less by weight of the turf feed. For example, the first turf filler may be present in an amount of about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to about 20%, about 0.1% to about 15%, about 0.1% to about 10%, about 0.1% to about 5%, about 1% to about 20%, about 1% to about 10%, about 1% to about 5%, or about 1% to about 3% by weight of the turf feed. In some embodiments, the second filler may be present in the turf feed in an amount of 0.1% to 100% by weight of the turf feed. In some embodiments, the second fill material is included in the turf feed in an amount of 1%-100%, 1%-95%, 1%-90%, 1%-80%, 1%-50%, 1%-20%, or 1%-75%, 1%-50%, 10%-20%, 10%-100%, 10%-50% by weight of the turf feed.

[0047] In some embodiments, the turf feed comprises a sized carpet composition and a filling material, wherein the sized carpet composition comprises one or more of turf fibers, a primary backing material, a secondary backing material, and / or a backing pad. For example, the turf feed comprises a sized carpet composition and a second filling material of an inorganic filler in an amount of about 50% or less of the weight of the turf feed. In some embodiments, the turf feed comprises sized turf fibers, a sized primary backing material, a sized secondary backing material, and a filling material, wherein the filling material is present in the turf feed in an amount of about 20% or less of the weight of the turf feed.

[0048] In some embodiments, the turf feed includes a first filler material of an inorganic filler and a second filler of a polymeric material, wherein the first filler material is present in the turf feed in an amount of about 30% or less by weight of the turf feed. In some embodiments, the turf feed also includes at least one of sized turf fibers, sized primary backing materials, or sized secondary backing materials.

[0049] As previously described, one or more components of the artificial turf may be sized to reduce the median particle size for cracking. In some embodiments, the turf feed has a median particle size of 0.01 mm-50 mm, 0.1-50 mm, 0.1-30 mm, 0.1-20 mm, 5.0 mm, or 0.1 mm-5.0 mm, or 0.01 mm-3.0 mm, or 0.1 mm-3.0 mm, or 0.01 mm-3.0 mm, or 0.1 mm-3.0 mm, or 1.0 mm-5.0 mm, or 1.0 mm-3.0 mm to reduce the maximum particle size. In some embodiments, the turf feed has a maximum particle size of 20 mm or less, 10 mm or less, or 5.0 mm or less.

[0050] Optionally, a carrier fluid may also be included in the turf feed to help introduce the turf into the cracking environment. In order to introduce the cracking environment, it may be convenient for the raw material to be in the form of a slurry. If a carrier fluid is used to transport the turf feed, any suitable fluid may be used. Examples of suitable carrier fluids may include, but are not limited to, various petroleum or petrochemical products. For example, some suitable carrier fluids include crude oil, naphtha, kerosene, diesel, light or heavy cycle oil, catalytic slurry oil and gas oil. Other possible carrier fluids may be cycloalkane and / or aromatic solvents, such as toluene, benzene, methylnaphthalene, cyclohexane, methylcyclohexane and mineral oil. Other carrier fluids may correspond to refinery fractions, such as gas oil fractions or naphtha fractions from a coking plant. As another example, distillates and / or gas oil boiling range fractions produced by cracking the turf feed alone or with additional raw materials may be used.

[0051] In various embodiments, cracking can be used to co-process a combination feedstock corresponding to a mixture of a conventional cracking feedstock and a turf feedstock. In some embodiments, the conventional cracking feedstock is used as a carrier fluid for the turf feedstock. The conventional cracking feedstock can correspond to one or more types of petroleum and / or renewable feedstocks with a boiling range suitable for cracking (e.g., processing in a coker). The amount of turf feedstock in the combination feedstock can be equivalent to 0.1%-25%, or 3%-25%, or 10%-25%, or 3%-15% of the weight of the combination feedstock. The conventional cracking feedstock can be equivalent to 70% to 99% of the total feedstock weight of the coker.

[0052] In some embodiments, the cracking feedstock for co-processing with the turf feed may correspond to a conventional petroleum feedstock having a relatively high boiling point, such as a heavy oil feedstock. For example, the cracking feedstock portion of the feed may have a T10 distillation point of 343°C or higher, or a T10 distillation point of 371°C or higher. In some embodiments, the T10 distillation point of the coking feedstock is 343°C to 650°C. Examples of heavy oils suitable for inclusion in the cracking feedstock include, but are not limited to, topped crude oil; petroleum atmospheric distillation residue; petroleum vacuum distillation residue or residual oil; asphalt; tar; asphalt; other heavy hydrocarbon residues; tar sand oil; shale oil; or even coal slurry or coal liquefaction products, such as coal liquefaction residual oil. Such a feed typically has a Conradson carbon residue value (ASTM D189-165) of at least 5wt%, generally 5wt% to 50wt%. In some embodiments, the feed is a petroleum vacuum residue.

[0053] Some examples of conventional petroleum feedstocks suitable for processing in a delayed coker or a fluidized bed coker can have compositions and properties within the ranges described below in Table 1.

[0054] Table 1 - Examples of coking feedstocks

[0055] Conradson carbon residue 5-40 wt% API Weight -10 to 35° Boiling Point 340℃+ to 650℃+ sulfur 1.5 to 8 wt% hydrogen 9 to 11 wt% nitrogen 0.2 to 2 wt% carbon 80 to 86 wt% Metal 1 to 2000 wppm

[0056] In addition to petroleum feedstocks, renewable feedstocks derived from biomass with a suitable boiling range can also be used as part of the cracking 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 can be a cracking oil feedstock derived at least in part from biomass.

[0057] In some specific embodiments, the turf feed and the cracking feed (eg, coking feed) are mixed to form a combined feed prior to entering the cracking environment. However, more generally, any convenient method may be used to introduce the turf feed and cracking feed into the coking environment.

[0058] According to one or more embodiments, the feedstock (optionally in the form of a combined feedstock) is preheated prior to being introduced into the coking environment. Preheating the feedstock in one or more heating stages can raise the temperature of the feedstock to a mixing and storage temperature, a temperature related to the cracking temperature, or another convenient temperature.

[0059] In some embodiments, a portion of the preheating of the turf feed can be performed by mixing the turf feed with the cracking feed in a mixing tank and heating the mixture in the mixing tank. For example, the turf feed and the cracking feed can be mixed in a heated stirring tank and then stored at a temperature of 200°C to 325°C or 275°C to 325°C. In some embodiments, stirring in the tank helps the turf feed to be evenly dispersed in the residual oil and keep the slurry suspended. Heating in a mixing tank before the combined feed is introduced into the cracking reaction environment provides heat for the combined feed. This can reduce or minimize the additional cracking heat load required to heat the turf feed to the thermal cracking temperature. In addition to heating, the combined turf feed and cracking feed can also be stripped using a stripping gas in a mixing tank. Passing the stripping gas through the combined feed can help remove the gas entrained in the combined feed.

[0060] According to certain embodiments, another option may be to mix the turf feed with the cracking feed after the preheat furnace of the coking unit. In these embodiments, the cracking feed may be heated to a higher temperature in the preheater, and then the turf feed may be added to the preheated cracking feed to heat the turf feed.

[0061] Artificial turf cracking

[0062] According to one or more embodiments, the turf feed is cracked to produce more valuable cracked products. Cracking is a process in which larger molecules are broken down to produce smaller, more useful molecules. For example, the cracking process includes thermal cracking of long chain hydrocarbons (or other long chain molecules) into shorter chain molecules. Examples of suitable cracking processes include coking, steam cracking, fluidized bed catalytic cracking and / or pyrolysis.

[0063] One example of turf feed cracking includes coking. Coking generally involves the thermal cracking of long chain molecules to produce shorter chain molecules, with excess carbon left behind in the form of petroleum coke. When the turf feed includes inorganic fillers, the inorganic fillers will be separated into the petroleum coke. The coking process in modern refineries can generally be divided into 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) produced by the fractionation of heavy oils, are converted into lighter, more useful products by thermal decomposition (coking) at high reaction temperatures, typically 480°C to 590°C, and in most cases 500°C to 550°C. Examples of heavy oils suitable for processing by fluidized bed coking processes include heavy atmospheric residues, petroleum vacuum distillation residues, aromatic hydrocarbon extracts, asphalt, and asphalt from tar sands, tar pitch, and asphalt lakes.

[0064] Flexicoking developed by Exxon Research and Engineering TM (FlexicokingTM ) process is a fluidized bed coking process that is operated in an apparatus that includes a reactor and a heater and a gasifier that is used to gasify the coke product by reacting with an air / steam mixture to form a low heating value fuel gas. The coke stream flows from the heater to the gasifier, where the coke except for a small portion of the coke is gasified into a low BTU gas (about 120 BTU / standard cubic foot) by adding steam and air to the fluidized bed in an oxygen-deficient environment to form a fuel gas that includes 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, while the balance of the reactor heat requirement is provided by combustion in the heater. A small amount of clean coke (1% of the feed) is removed from the heater to remove metals and ash from the system. The liquid yield and properties are comparable to those of fluidized bed coking. The fuel gas product is removed from the heater after separation in an internal cyclone separator, which returns the coke particles through its dipleg.

[0065] In this specification, the term "flexicoking" (a trademark of ExxonMobil Research and Engineering Company) is used to refer to a fluidized bed coking process in which a heavy petroleum feed undergoes thermal cracking in a fluidized bed of heated solid particles to produce lower molecular weight and boiling point hydrocarbons and coke deposited on the solid particles in the fluidized bed as a byproduct. References to fluidized cokers are intended to include conventional fluidized cokers as well as flexicokers. The resulting coke can then be converted into fuel gas in a gasification reactor (gasifier) ​​by contact with steam and an oxygen-containing gas at high temperature. This configuration may more generally be referred to as the integration of fluidized bed coking and gasification. Figure 4 and Figure 5 Examples of fluid coking reactors including gasifiers are provided.

[0066] Figure 4 An example of a flexcoking unit (i.e., a system including a gasifier thermally integrated with a fluidized bed coker) is shown having three reaction vessels: a reactor, a heater, and a gasifier. Coking system 400 includes a reactor section 402 having a coking zone and its associated stripping and scrubbing sections (not separately indicated), a heater 404, and a gasifier 406. A cracking feedstock, which may be a turf feed (or a combination of a turf feed and a conventional cracking feedstock), is introduced into coking system 400 via line 408, and cracked hydrocarbon products are removed via line 410. Although Figure 4Combination feedstocks are shown, but the exemplary embodiment also includes introducing conventional cracking feedstocks and turf feed separately into the reactor section 402. Fluidizing and stripping steam are supplied by line 412. Cold coke is taken out of the stripping section at the bottom of the reactor section 402 through line 414 and conveyed to the heater 404. Of course, the term "cold" used to describe the temperature of the taken coke is certainly relative, because it is under the operating conditions of the stripping section and is much higher than the ambient temperature. Hot coke is circulated from the heater 404 to the reactor section 402 through line 416. The coke from the heater 404 is transported to the gasifier 406 through line 418, and the hot, partially gasified coke particles are circulated from the gasifier to the heater 404 through line 420. Excess coke is taken out of the heater 404 through line 422. In a conventional configuration, a steam and air supply is provided to the gasifier 406 via line 424, and hot fuel gas is removed from the gasifier 406 and sent to the heater 404 via line 426. In some alternative embodiments, rather than supplying air to the gasifier 406 via line 424, an oxygen stream having a purity of 95 vol% or higher, such as an oxygen stream from an air separation unit, may be provided. In such embodiments, in addition to supplying the oxygen stream, a stream of additional dilution gas may be supplied via line 428. The additional dilution gas may correspond to, for example, CO separated from the fuel gas produced during the gasification process. 2 The fuel gas is removed from the unit via line 430 on heater 404; coke fines are removed from the fuel gas in a heater cyclone system 432, which includes primary and secondary cyclones in series with diplegs that return the separated fines to the fluidized bed in heater 404. The fuel gas from line 430 may then be further processed. For example, in some embodiments, the fuel gas from line 430 may be sent to a separation stage to separate CO 2 (and / or H 2 S). This may result in a stream with an increased synthesis gas concentration, which stream may then be sent to a conversion stage to convert the synthesis gas into methanol.

[0067] It should be noted that in some optional embodiments, the heater cyclone system 432 can be located in a separate container (not shown) rather than in the heater 404. In such aspects, the pipeline 430 can take out the fuel gas from the separate container, and the pipeline 422 for removing excess coke can correspond to the pipeline for conveying coke fines from the separate container. Relative to the raw material, these coke fines and / or other partially gasified coke particles discharged from the heater 404 (or gasifier 406) can have an increased metal content. For example, the metal weight percentage (relative to the weight of the discharged particles) in the coke particles discharged from the system can be greater than the metal weight percentage (relative to the weight of the raw material) in 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 the mechanism of removing metals from the coker / gasifier environment. In some embodiments, the metal can 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 gasifier interior walls, such as deposition in an amount less than 0.1 wt %, or less than 0.01 wt %, of the metals present in the feedstock introduced into the coker / gasifier system.

[0068] In e.g. Figure 4 In the configuration of FIG. 4 , the system elements shown in the figure can be described according to the fluid communication between the elements. For example, the reactor section 402 is directly in fluid communication with the heater 404. The reactor section 402 is also indirectly in fluid communication with the gasifier 406 through the heater 404.

[0069] As an alternative, it is also possible to integrate the fluidized bed coker with the gasifier without the use of an intermediate heater. In such an alternative aspect, the cold coke from the reactor can be transferred directly to the gasifier. In almost all cases, this transfer is clear and direct, with one end of a tubular transfer line connected to the coke outlet of the reactor and the other end connected to the coke inlet of the gasifier, without an intermediate reaction vessel, i.e., a heater. However, the presence of equipment other than a heater, such as a gas lift inlet, etc., is not excluded. Similarly, although the hot, partially gasified coke particles from the gasifier are returned directly from the gasifier to the reactor, this only means that they should not be transported to the reactor as in a conventional three-vessel Flexicoker. TM An intermediate heater is used as in the process, but other equipment such as a gas lift inlet and outlet may be present between the gasifier and the reactor.

[0070] Figure 5 An example of a fluidized bed coker integrated with a gasifier but without a separate heater vessel is shown. Figure 5In 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 504.

[0071] exist Figure 5 In the configuration shown in FIG. 5 , the coking system 500 includes a reactor 502, a main gasifier vessel 504, and a separation vessel 506. A cracking feedstock (e.g., a combination of a cracking feedstock (e.g., a heavy oil feedstock) and a turf feedstock) is introduced into the reactor 502 via line 508, a fluidizing / stripping gas is introduced via line 510, and cracked hydrocarbon products are removed via line 512. The cracking feedstock includes a turf feedstock optionally combined with a conventional cracking feedstock. The turf feedstock may be introduced into the reactor 502 alone or, for example, in combination with a conventional cracking feedstock. The cold, extracted coke is transported directly from the reactor 502 to the main gasifier vessel 504 via line 514, while the hot coke is returned to the reactor via line 516. Steam and oxygen are supplied via line 518. A gas stream containing coke fines is sent to the separation vessel 506 via line 520 connected to the gas outlet of the main gasifier vessel 504. The fines are separated from the gas stream in a cyclone system 522, which includes primary and secondary cyclones in series with a dipleg that returns the separated fines to the separation vessel. The separated fines are then returned to the main gasifier vessel 504 via return line 524, and a fuel gas product is removed via line 526. Coke is removed from the separator via line 528. The fuel gas from line 526 may then undergo further processing to separate CO. 2 (and / or H 2 S) and converts the synthesis gas into methanol.

[0072] The coker and gasifier can be operated according to the parameters required for the desired coking process. Therefore, the heavy oil feed in the cracking feed is usually a heavy (high boiling point) topped crude oil; petroleum atmospheric distillation residue; petroleum vacuum distillation residue or residual oil; asphalt; tar; bitumen; other heavy hydrocarbon residues; tar sand oil; shale oil; or even coal slurry or coal liquefaction products, such as coal liquefaction residue. Such feeds usually have a Conradson carbon residue value (ASTM D189-165) of at least 5wt%, generally 5wt% to 50wt%. In some embodiments, the cracking feed is a petroleum vacuum residue.

[0073] Fluidized bed coking is carried out in an apparatus having a large reactor containing hot coke particles maintained in a fluidized state at the desired reaction temperature, with steam injected from the bottom of the vessel, and the average direction of movement of the coke particles being downward through the bed. In some specific embodiments, the combined feedstock is heated to a pumpable temperature (usually in the range of 350°C to 400°C), mixed with atomized steam, and fed through a plurality of feed nozzles arranged at several consecutive levels in the reactor. Steam is injected into the stripping section at the bottom of the reactor and passes upward through the coke particles that descend through the fluidized bed dense phase in the main part of the reactor above the stripping section. A portion of the feed liquid covers the coke particles in the fluidized bed and is subsequently cracked into a solid coke layer and lighter products, which are released in the form of 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 to facilitate the evaporation of hydrocarbon vapors, which pass 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, 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 phase fluidized bed under gravity through the cyclone legs. The mixture of steam and hydrocarbon vapor from the reactor is then discharged from the cyclone separator gas outlet to the scrubber section in a gas chamber located above the coking zone and separated from the coking zone by a partition. The mixture is quenched in the scrubber section by contact with liquid falling from the ceiling. A pump circulation loop circulates the condensed liquid to an external cooler and back to the ceiling row of the scrubber section to provide cooling for quenching and condensing the heaviest fraction of the liquid product. This heavy fraction is usually fully recycled by feeding back to the coking zone in the reactor.

[0074] During the fluidized bed coking process, the mixed feedstock, which is preheated to a flowable and pumpable temperature, is introduced into the top of the reactor vessel in the coking reactor through an injection nozzle, which is constructed to produce a feed spray to the fluidized bed of coke particles in the reactor vessel. The temperature in the coking zone of the reactor is generally in the range of 450°C to 650°C, and the pressure is maintained at a relatively low level, generally in the range of 0kPag to 700kPag, most commonly in the range of 35kPag to 320kPag, to facilitate rapid drying of the coke particles and prevent the formation of sticky, adherent high molecular weight hydrocarbon deposits on the particles that can cause 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 the desired amount of feedstock conversion occurs in the fluidized bed reactor. For example, conditions may be selected to achieve a conversion of at least 10 wt% about 343°C (or 371°C), or at least 20 wt% about 343°C (or 371°C), or at least 40 wt% about 343°C (or 371°C), such as up to 80 wt% or possibly higher. The light hydrocarbon products of the coking (thermal cracking) reaction evaporate, mix with the fluidizing steam, and pass upward through the dense phase of the fluidized bed into the dilute phase region above the dense fluidized bed of coke particles. This mixture of evaporated hydrocarbon products formed in the coking reaction flows upward through the dilute phase with the steam at a superficial velocity of about 1 to 2 m / sec (about 3 to 6 ft / sec), entraining some fine solid particles of coke, which are separated from the cracking vapor in the reactor cyclone separator as described above. In embodiments where steam is used as a fluidizing agent, the weight of steam introduced into the reactor may be selected relative to the weight of feedstock introduced into the reactor. For example, the mass flow rate of steam entering the reactor can correspond to 6.0% of the mass flow rate of the feedstock, or 8.0% or more, such as up to 10% or possibly higher. If an active light hydrocarbon stream is used as part of the stripping and / or fluidizing gas in the reactor, the amount of steam can potentially be reduced. In such an embodiment, the mass flow rate of steam can correspond to 6.0% or less of the mass flow rate of the feedstock, 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 lower, such as corresponding to 1.0% or less of the mass flow rate of the feedstock, or 0.8% or less, or 0.6% or less, such as as low as substantially all of the steam is replaced by the active light hydrocarbon stream. The cracked hydrocarbon vapor comes out of the cyclone separator and enters the washing section of the reactor, and then the product is fractionated and recovered.

[0075] In a typical fluidized bed coking process, the coke particles formed in the coking zone move downward in the reactor and leave the bottom of the reactor vessel through the stripper section, where they are exposed to steam to remove absorbed hydrocarbons. The solid coke from the reactor, consisting mainly of carbon and small amounts of hydrogen, sulfur, nitrogen and trace amounts of vanadium, nickel, iron and other elements derived from the feed, passes through the stripper and flows out of the reactor vessel to a burner or heater, where it is partially combusted with air in the fluidized bed, thereby raising its temperature from 480°C to 700°C to provide the heat required for the endothermic coking reaction, after which a portion of the hot coke particles are recycled to the fluidized bed reaction zone to transfer heat to the reactor and serve as the core of coke formation. The remaining coke particles are taken out as coke product. The net coke production is only 65% ​​of the delayed coking production.

[0076] For a coking process including a gasification zone, the cracking process is carried out in a reactor, and the coke particles pass downward through the coking zone, through a stripping zone, where the absorbed hydrocarbons are stripped off by an upward flow of a fluidizing gas (steam). They then leave the coking reactor and enter a gasification reactor (gasifier), which contains a fluidized bed of solid particles and which operates at a temperature higher than that of the coking zone of the reactor. In the gasifier, the coke particles are converted into a fuel gas comprising carbon monoxide and hydrogen by reacting with steam and an oxygen-containing gas at high temperatures.

[0077] The gasification zone is typically maintained at a high temperature in the range of 850°C to 1,000°C and a pressure in the range of 0 kPag to 1000 kPag, preferably 200 kPag to 400 kPag. Steam and an oxygen-containing gas are introduced to provide fluidization and an oxygen source for the gasification reaction. 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 comprising 95 vol% or more oxygen, or 98 vol% or more oxygen, is passed into the gasifier for reaction with solid particles including coke deposited thereon in the coking zone. In embodiments in which the oxygen-containing gas has a low nitrogen content, a separate diluent stream such as recycled CO 2 from the fuel gas produced by the gasifier may be used. 2 or H 2 The S stream may also be passed to the gasifier.

[0078] In the gasification zone, the reaction between coke and steam and oxygen-containing gas produces fuel gas containing hydrogen and carbon monoxide and partially gasified residual coke product. The gasifier conditions are selected accordingly to generate these products. The steam and oxygen flow rates (and any optional carbon dioxide flow rates) will depend on the flow rate of cold coke entering from the reactor, and to a lesser extent on the composition of coke, which will vary according to the composition of the heavy oil feed and the severity of the cracking conditions in the reactor, and these parameters 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 these entrained coke solids are removed by a cyclone separator or other separation technology in the gasifier section of the device. Suitable cyclone separators include internal cyclone separators in the main gasifier container itself, or external cyclone separators located in separate smaller containers as described below. The fuel gas product is taken out from the gasifier cyclone separator as an overhead product. The resulting partially gasified solids are removed from the gasifier and introduced directly into the coking zone of the coking reactor with the feed level being in the dilute phase above the lower dense phase.

[0079] In some embodiments, coking conditions may be selected to provide a desired conversion amount about 343° C. Typically, the desired conversion amount about 343° C. may be 10 wt % or more, or 50 wt % or more, or 80 wt % or more, such as up to substantially complete conversion of the feedstock.

[0080] Volatile products from the coker drum are directed out of the process for further processing. For example, volatiles may be directed to a coker fractionator for distillation and recovery of coker gas, coker naphtha, light gas oil, and heavy gas oil. Such fractions may typically (but not always) be used for blending fuel and lubricant products such as motor gasoline, motor diesel, fuel oil, and lubricant oil after upgrading. Upgrading may include separation, removal of heteroatoms by hydrotreating and non-hydrotreating processes, dearomatization, solvent extraction, and the like. The process is compatible with the following process: 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 component) to form a coker heater or coke oven feed. The mixed feed ratio ("CFR") is the volume ratio of the furnace charge (fresh feed plus circulating oil) to the fresh feed of a continuous fluidized bed coking operation. Fluidized bed coking operations typically use 5 vol% to 35 vol% recycle (CFR of 1.05 to 1.35). In some embodiments, there may be no recycle, but sometimes recycle rates as high as 200% can be used in special applications.

[0081] Delayed coking is another coking process for thermally converting heavy oils such as petroleum residue (also referred to as "residue") to produce liquid and vapor hydrocarbon products and coke. In some specific embodiments, delayed coking is performed on a feedstock consisting of a turf feed optionally combined with a conventional cracking feedstock to produce liquid and vapor hydrocarbon products and coke. In some embodiments, the conventional hydrocarbon feedstock comprises a residue from heavy and / or sour (high sulfur) crude oil. Delayed coking of the feedstock is performed by converting part of the feedstock into more valuable hydrocarbon products. The resulting coke is valuable and can be used as a fuel (fuel grade coke), an electrode for aluminum manufacturing (anode grade coke), etc., depending on its grade.

[0082] Typically, the feedstock is pumped to a preheater where it is preheated, for example, to a temperature in the range of 480°C to 520°C. The preheated feed is directed to a coking zone, typically an upright, insulated coker vessel such as a coke drum, through an inlet at the bottom of the drum. The pressure within the drum is typically relatively low, for example, in the range of 100 kPa-g to 550 kPa-g or 100 kPa-g to 240 kPa-g, to allow volatiles to be removed from the top. Typical operating temperatures for coke drums are in the range of about 400°C to 445°C, but can be as high as 475°C. The hot feed is thermally cracked within the coke drum for a period of time ("coking time"), releasing volatile materials consisting primarily of hydrocarbon products, which continuously rise through a coke bed consisting of channels, pores and passages and are collected at the top. The volatile products are directed to a coker fractionator for distillation and recovery of coking gases, gasoline boiling range materials such as coker naphtha, light gas oil, and heavy gas oil. In one embodiment, a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator can be captured for recycling and combined with fresh feed (coker feed component) to form a coker heater or coker furnace feed. In addition to the volatile products, the process also causes coke to accumulate in the coke drum. When the coke drum is full of coke, the heated feed is switched to another coke drum, and hydrocarbon vapors are purged from the coke drum with steam. The coke drum is then quenched with water to reduce the temperature to 95°C to 150°C, after which the water is drained. When the drainage step is completed, the drum is opened and the coke is removed by drilling and / or cutting using high-speed water jets ("hydraulic decoking").

[0083] Figure 6An exemplary delayed coking system 600 is illustrated. In the illustrated embodiment, a feedstock 602 including a turf feedstock (which may be preheated) is fed to a coker fractionator 604. In some embodiments, the feedstock 602 also includes a conventional cracking feedstock, which may also be fed separately to the coker fractionator 604. In the illustrated embodiment, a fractionator effluent 606 including at least a portion of the turf feedstock and / or the conventional cracking feedstock is removed from the coker fractionator 604 and fed to a coker furnace 608. The preheated effluent 610 from the coker furnace 608 (which includes the preheated turf feedstock and / or the preheated conventional cracking feedstock) is conveyed to a coking zone 612, which includes, for example, a coking vessel or a coking drum. The preheated effluent 610 also includes, for example, a bottoms (or recycle). The coking zone 612 is operated under coking conditions such that the preheated turf feed / conventional cracking feedstock is thermally cracked in the coking zone for a period of time ("coking time"), releasing volatile materials consisting primarily of hydrocarbon products, which continuously rise through a coke bed consisting of channels, pores and passages and are collected at the top as a coker effluent 614, which is conveyed to a coker fractionator 604. In the illustrated embodiment, the coker effluent 614 is separated into various fractions in the coker fractionator 604, including but not limited to one or more of a coking gas fraction 618, a coking naphtha fraction 620, a coking distillate fraction 622, and a coking gas oil fraction 624. As previously described, coke accumulates in the coking zone 612 (e.g., a coking vessel). The coke also includes inorganic fillers from the turf feed. A coke product 616 including coke and inorganic fillers is removed from the coking zone 612.

[0084] Cleavage products

[0085] The turf feed is cracked alone or in combination with conventional cracking feedstock to produce cracking products. In some embodiments, the cracking products include cracking effluents, which may include gases, liquids, or mixtures thereof. As discussed above, the cracking effluents may be fractionated or otherwise separated to form desired product streams, such as fuel gas (e.g., C 4 and lighter hydrocarbons), naphtha, diesel, gasoline, light cycle oil and / or heavy cycle oil. In some embodiments, the cracking product also includes coke.

[0086] The coke produced in the coking process is generally a carbonaceous solid material, most of which is carbon. According to one or more embodiments, since coke is produced by the petroleum cracking process of conventional cracking raw materials in a coker, it may also be referred to as petroleum coke or petroleum coke. The specific composition of coke depends on many factors, including specific coking process such as delayed coker, or in some embodiments, coke comprises 80 wt % to 95 wt % carbon based on the gross weight of coke. Other 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.

[0087] In some embodiments, the coke produced is derived at least in part from turf feed that can include inorganic fillers. Examples of suitable inorganic fillers include sand and gravel. In these embodiments, the inorganic filler is transferred to the coke, causing the coke to contain inorganic residues, such as oxides composed of silicon dioxide, etc. For example, conventional coke can include oxides of silicon dioxide with a content of up to 600wppm. However, in exemplary embodiments, the coke produced at least in part by turf feed includes an amount of 1000wppm or more of silicon dioxide oxides. In some embodiments, the coke includes an oxide of silicon dioxide in an amount of 1000wppm to 2wt%, 1000wppm to 1wt%, 5000wppm to 2wt% or 1wt% to 2wt%. However, although fillers and reinforcing materials exist in sufficient amounts to be discharged from the process to achieve steady-state operation, according to one or more embodiments, the coke should meet the specifications of petroleum coke.

[0088] In some embodiments, the cracking unit effluent is at least partially derived from the polymer material in the turf feed, such as thermoplastic resin and thermosetting resin. In some embodiments, the processing of turf feed can cause the generation or recovery of olefins, or turf feed is converted into olefins. In some embodiments, polymers can be produced by the olefins. For example, olefins for the manufacture of polymers can be directly produced or recovered by cracking turf feed. At least a portion of these olefins can be the circulating olefins attributable to turf feed, such as by attributing to, distributing and / or offsetting or replacing the circulating olefins determined by other hydrocarbons in system mass or energy balance, such as according to the third party certification related to circularity. At least a portion of these chemical products can be certified circulating chemical products, and their circularity is certified by a third party certification body, and can be referred to as certified circulating products. An example of such certification is the mass balance custody chain method specified by international sustainability and carbon certification bodies (the International Sustainability and Carbon Certification).

[0089] Additional Implementations

[0090] Thus, the present disclosure may provide for chemical recycling of artificial turf, which includes pyrolysis of a turf feed to produce hydrocarbons.The methods and systems may include any of the various features disclosed herein, including one or more of the following statements.

[0091] Embodiment 1. A method of chemically recycling artificial turf, the method comprising: providing a turf feed comprising a size-adjusted turf composition; and cracking at least the turf feed to produce at least a cracking product comprising hydrocarbons.

[0092] Embodiment 2. The method of embodiment 1, wherein the turf feed further comprises an inorganic filler from the artificial turf in an amount of about 0.1 wt % to about 50 wt % of the turf feed.

[0093] Embodiment 3. The method of Embodiment 1, wherein the first fill material is present in the turf feed in an amount of about 0.1% to about 5% by weight of the turf feed.

[0094] Embodiment 4. The method of any preceding embodiment, wherein the turf feed further comprises a second infill material from the artificial turf, wherein the second infill material comprises a polymer material.

[0095] Embodiment 5. The method of any preceding embodiment, wherein the sized carpet composition comprises turf fibers.

[0096] Embodiment 6. The method of Embodiment 5, wherein the turf fibers have a median particle size of 0.1 mm to 5 mm.

[0097] Embodiment 7. The method of Embodiment 5 or Embodiment 6, wherein the turf fibers comprise a thermoplastic material.

[0098] Embodiment 8. The method of any preceding embodiment, wherein the sized carpet composition comprises turf fibers, a primary backing material, and a secondary backing material.

[0099] Embodiment 9. The method of any preceding embodiment, further comprising sizing the artificial turf to reduce particle size, wherein the sized artificial turf is used as the sized carpet composition in the turf feed without further separation.

[0100] Embodiment 10. The method of any one of Embodiments 1-8, further comprising adjusting the size of the artificial turf to reduce the particle size and then separating at least a portion of the filling material from the artificial turf to form the carpet composition, wherein the carpet composition comprises turf fibers, a primary backing material, and a secondary backing material.

[0101] Embodiment 11. The method of any one of Embodiments 1-8, further comprising resizing the artificial turf to reduce particle size, then separating filler material from the resized artificial turf, then subjecting the resized artificial turf to a second resizing step after separation, and then separating additional filler material from the resized artificial turf to obtain the carpet composition.

[0102] Embodiment 12. The method of any preceding embodiment, further comprising separating at least a naphtha fraction and a gas fraction from the cracked product.

[0103] Embodiment 13. The method of any of the preceding embodiments, wherein the cracking comprises exposing at least a portion of the coking feedstock comprising the turf feed to coking conditions in a coking reactor, wherein the coking conditions comprise exposing the coking feedstock to a fluidized bed of coke particles at a temperature of about 450°C to about 650°C.

[0104] Embodiment 14. The method of Embodiment 13, wherein the coking feedstock comprises a petroleum feedstock having a T10 distillation point of about 343°C to about 650°C.

[0105] Embodiment 15. The method of any of the preceding embodiments, wherein the cracking also produces a coke product, wherein the coke product comprises coke and recycled filler material, wherein at least 99 weight percent of the inorganic filler from the artificial turf in the turf feed is recovered in the coke product as recycled filler material.

[0106] Embodiment 16. The method of any preceding embodiment, wherein cracking at least the turf feed comprises preheating a coking feed comprising the turf feed and a petroleum feed, feeding the coking feed into a coking zone of a coking drum, where the coking feed is thermally cracked.

[0107] Embodiment 17. The method of any preceding embodiment, wherein the cracking product comprises olefins.

[0108] Embodiment 18. The method of Embodiment 17, further comprising producing at least a recycled polyolefin from the olefin.

[0109] Embodiment 19. A method of chemically recycling artificial turf, the method comprising: providing a turf feed comprising infill material from artificial turf, wherein the infill material comprises a polymeric material; and cracking the turf feed to produce at least a cracking product comprising hydrocarbons.

[0110] Embodiment 20. The method of Embodiment 18, wherein the turf feed further comprises an inorganic filler from the artificial turf, wherein the inorganic filler is present in the turf feed in an amount of about 0.1 wt % to about 50 wt % of the turf feed.

[0111] Embodiment 21. The method of Embodiment 18, wherein the turf feed further comprises an inorganic filler from the artificial turf, wherein the inorganic filler is present in the turf feed in an amount of about 1 wt % to about 5 wt % of the turf feed.

[0112] Embodiment 22. The method of any one of Embodiments 19-21, further comprising adjusting the size of the artificial turf to reduce particle size, and then separating the infill material from the adjusted size artificial turf.

[0113] Embodiment 23. The method of any one of Embodiments 19-22, wherein the cracking also produces a coke product, wherein the coke product comprises coke and recycled filling material, wherein at least 99 weight percent of the inorganic filler from the artificial turf in the turf feed is recovered in the coke product as recycled filling material.

[0114] Embodiment 24. The method of any of Embodiments 19-23, wherein the polymeric material comprises a thermoplastic elastomer.

[0115] Embodiment 25. The method of any of Embodiments 19-23, wherein the polymeric material comprises ground tire rubber.

[0116] Embodiment 26. The method of any of Embodiments 19-23, wherein the polymeric material comprises a thermoset rubber.

[0117] To facilitate a better understanding of the present invention, the present disclosure gives the following examples of certain aspects of some embodiments. The following examples should in no way be construed as limiting or defining the entire scope of the present disclosure.

[0118] Example 1

[0119] Various artificial turf samples were obtained from scrapped sports fields using the recycling method described herein. Primary filling material and secondary filling material were separated from the turf samples to provide carpet compositions. The secondary filling material (rubber) was then separated from the primary filling material (sand).

[0120] Table 2 below shows the chemical composition of various turf samples. Sample 1 is a carpet composition separated from a first artificial turf. Sample 2 is a secondary fill material separated from a first artificial turf. Sample 3 is a carpet composition in particle form separated from a second artificial turf. Sample 4 is a carpet composition in particle form separated from a third artificial turf. The separated carpet composition of sample 4 was extruded into pellets. Sample 5 is a carpet composition separated from a fourth artificial turf. Sample 5 was prepared by cutting the artificial turf and then separating the carpet composition. The chemical composition of the samples was determined by a variety of different characterization techniques. For example, ash content was measured using ICP-AES (Perkin Elmer 8300) according to ASTM D5185 method. Halide content (Cl, F) was measured using X-ray fluorescence technology (Malvern P analytical instrument). CHNOS analysis was performed using a combustion element analyzer according to ASTM D5291 method. Mercury measurement was performed using CVAAS spectroscopy according to UOP938 method. Ti, Ca, Na, Fe analysis was performed using ICP.

[0121] Table 2

[0122]

[0123] Table 2 (Continued)

[0124]

[0125] Comparison of the chemical compositions of the separated carpet composition samples 1 and 3-5 and the separated secondary filler portion sample 2 shows that these can be pyrolyzed at any suitable combination, such as 0-100% by weight of carpet composition / secondary filler. The samples have high carbon and hydrogen contents, and thermal cracking by cracking will produce the desired products for further processing. These hydrogen-to-carbon ratios are consistent with carpet compositions containing polyolefin fibers and general purpose rubber as secondary filler materials. In addition, the samples have low chloride contents, so no dechlorination step is required. The ash content of each sample is above 10 wt%. Therefore, in chemical recycling, it is necessary to remove the inorganic filler from the process, such as removing it with the coke in the coking process, to prevent the accumulation of inert inorganic fillers in the process.

[0126] Example 2

[0127] This example was conducted to illustrate the pyrolysis of turf feed on a laboratory scale. The pyrolysis of Sample 1, consisting of an isolated carpet composition, was analyzed using thermogravimetric analysis (TGA). In the TGA, the sample was pyrolyzed by controlled heating under an inert nitrogen atmosphere. The temperature was increased from room temperature to 700°C at a ramp rate of 20°C / min and then held at 700°C for 1 hour. Figure 6The mass loss curve of TGA is shown in . As shown in this figure, more than 88 wt % of the turf feed of Sample 1 was converted to volatiles at 530°C.

[0128] Example 3

[0129] This example was conducted to determine the pyrolysis product distribution of a turf feed on a laboratory scale. Approximately 0.5 mg of turf feed of Sample 1, consisting of an isolated carpet composition, was charged to a CDS5150 micro-pyrolyzer and the temperature program was set to rapidly heat it to the pyrolysis temperature associated with a coking operation. The resin sample was pyrolyzed at 530°C for 20 seconds. The micro-pyrolyzer was connected to the inlet of a GC / MS via a transfer line that was heated to 250°C to avoid condensation. The pyrolysis products formed were identified using electron impact mass spectrometry. The major pyrolysis products are provided in Table 3 below. The % area given in Table 3 represents the relative concentration of the products.

[0130] Table 3

[0131]

[0132] As shown in Table 3, cleavage of Sample 1 consisting of the isolated carpet composition resulted in the production of various monomers that were useful for further processing.

[0133] Although the invention has been described with reference to many embodiments and examples, those skilled in the art who have benefited from this disclosure will appreciate that other embodiments that do not depart from the spirit and scope of the invention disclosed herein may be suggested. Although various embodiments have been discussed, this disclosure encompasses all combinations of all such embodiments.

[0134] Although compositions, methods and processes are described herein as "comprising," "containing," "having," or "including" various components or steps, the compositions and methods may also be "consisting essentially of" or "consisting of" the various components and steps. Unless otherwise indicated, the phrase "consisting essentially of" does not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in the specification, as long as such steps, elements, or materials do not affect the basic and novel characteristics of the invention. In addition, the above phrase does not exclude impurities and variants that are normally associated with the elements and materials used.

[0135] All numerical values ​​in the detailed description are "about" the indicated value, and take into account experimental error and variations that would be expected by a person of ordinary skill in the art.

[0136] Numerous modifications, changes and variations will be apparent to those skilled in the art in view of the above description without departing from the spirit or scope of the 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 chemically recycling artificial turf, the method comprising: providing a turf feed comprising a size-adjusted carpet composition; and At least the turf feed is cracked to produce at least a cracking product comprising hydrocarbons.

2. The method of claim 1, wherein the turf feed further comprises infill material from the artificial turf, wherein the infill material comprises a polymer material.

3. The method of claim 1 or claim 2, wherein the sized carpet composition comprises turf fibers, and wherein the turf fibers have a median particle size of 0.1 mm to 5 mm, optionally wherein the turf fibers comprise a thermoplastic material.

4. The method of any preceding claim, wherein the sized turf composition comprises turf fibers, a primary backing material and a secondary backing material.

5. The method of any preceding claim, further comprising sizing the artificial turf to reduce particle size, wherein the sized artificial turf is used as the sized carpet composition in the turf feed without further separation.

6. The method of any one of claims 1-4, further comprising sizing the artificial turf to reduce particle size and then separating at least a portion of the fill material from the artificial turf to form the carpet composition, wherein the carpet composition comprises turf fibers, a primary backing material, and a secondary backing material.

7. The method of any one of claims 1-4, further comprising sizing the artificial turf to reduce particle size, then separating filler material from the sized artificial turf, then subjecting the sized artificial turf to a second sizing step after separation, and then separating additional filler material from the sized artificial turf to obtain the carpet composition.

8. The method of any preceding claim, further comprising separating at least a naphtha fraction and a gas fraction from the cracked product.

9. The method of any preceding claim, wherein the cracking comprises exposing at least a portion of a coking feedstock comprising the turf feed to coking conditions in a coking reactor, wherein the coking conditions comprise exposing the coking feedstock to a fluidized bed of coke particles at a temperature of about 450° C. to about 650° C., wherein the coking feedstock comprises a petroleum feedstock having a T10 distillation point of about 343° C. to about 650° C.

10. The process of any preceding claim, wherein the cracked products comprise olefins, wherein the process further comprises producing at least recycled polyolefins from the olefins.

11. A method for chemically recycling artificial turf, the method comprising: providing a turf feed comprising infill material from said artificial turf, wherein said infill material comprises a polymeric material; and The turf feed is cracked to produce at least a cracking product comprising hydrocarbons.

12. The method of claim 11, further comprising resizing the artificial turf to reduce particle size and then separating the infill material from the resized artificial turf.

13. The method of claim 11 or claim 12, wherein the polymeric material comprises at least one of a thermoplastic elastomer, ground tire rubber, or a thermoset rubber.

14. The method of any preceding claim, wherein the turf feed further comprises an inorganic filler from the artificial turf, wherein the inorganic filler is present in the turf feed in an amount of about 0.1% to about 50% by weight of the turf feed.

15. The method of any preceding claim, wherein the cracking also produces a char product, wherein the char product comprises char and recovered filler material, wherein at least 99 weight percent of the inorganic filler from the artificial turf in the turf feed is recovered in the char product as recovered filler material.

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