Processes for making EXO-dicyclopentadiene and tricyclopentadiene

Abstract

Processes for making exo-dicyclopentadiene and tricyclopentadiene. In some embodiments, the process can include introducing a hydrocarbon feed that can include cyclopentadiene and dicyclopentadiene into a reaction zone. The hydrocarbon feed can be subjected to reaction conditions sufficient to effect reaction between the cyclopentadiene and the dicyclopentadiene within the reaction zone to produce a reactor effluent that can include tricyclopentadiene, tetracyclopentadiene, cyclopentadiene, and dicyclopentadiene. A first product, a second product, and a purge stream can be separated from the reactor effluent. The first product can include dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. The second product can include cyclopentadiene and dicyclopentadiene. The purge stream can include cyclopentadiene, nitrogen, and oxygen. The second product can be separated into at least a first portion and a second portion. The first portion of the second product can be introduced into the reaction zone.

Description

PROCESSES FOR MAKING EXO-DICYCLOPENTADIENE AND TRICYCLOPENTADIENECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to US Provisional Application No. 63 / 649632 filed May 20, 2024 and US Provisional Application No. 63 / 650911 filed May 22, 2024 the disclosures of which are incorporated herein by reference.FIELD

[0002] Embodiments disclosed herein generally relate to processes for making exo- dicyclopentadiene and tricyclopentadiene.BACKGROUND

[0003] Commercially important olefin monomer resins include readily available and inexpensive cyclic olefins such as dicyclopentadiene (DCPD). There are two isomers of DCPD, z.e., exo-DCPD and endo-DCPD. The exo-DCPD isomer has significant benefits over the endo-DCPD isomer, both in physical and reactive properties. Due to reaction kinetics, the vast majority of commercially produced DCPD is endo-DCPD.

[0004] Upgrading endo-DCPD to exo-DCPD can be done at higher conversion rates, but the conventional upgrading processes also produce a significant amount of waste byproducts. Additionally, the conventional upgrading processes used to convert endo-DCPD to exo-DCPD typically use catalysts and / or solvents to obtain the higher rate of conversion.

[0005] There is a need, therefore, for improved processes for converting endo-DCPD to exo-DCPD that produce less waste byproducts and do not require solvents or catalysts. This disclosure satisfies this and other needs.SUMMARY

[0006] Processes for making exo-dicyclopentadiene and tricyclopentadiene are provided. In some embodiments, the process can include introducing a hydrocarbon feed that can include cyclopentadiene and dicyclopentadiene into a reaction zone. The hydrocarbon feed can be subjected to reaction conditions sufficient to effect reaction between the cyclopentadiene and the dicyclopentadiene within the reaction zone to produce a reactor effluent that can include tricyclopentadiene, tetracyclopentadiene, cyclopentadiene, and dicyclopentadiene. A first product, a second product, and a purge stream can be separated from the reactor effluent. The first product can include dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. The second product can include cyclopentadiene and dicyclopentadiene. The purge stream can include cyclopentadiene, nitrogen, and oxygen. The second product can be separated into atleast a first portion and a second portion. The first portion of the second product can be introduced into the reaction zone.BRIEF DESCRIPTION OF THE DRAWING

[0007] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

[0008] The Figure depicts an illustrative system for making a composition containing exo-DCPD and TCPD, according to one or more embodiments described.DETAILED DESCRIPTION

[0009] It is to be understood that the following disclosure describes several exemplary embodiments for implementing different features, structures, and / or functions of the invention. Exemplar}' embodiments of components, arrangements, and configurations are described below to simplify the present disclosure; however, these exemplary’ embodiments are provided merely as examples and are not intended to limit the scope of the invention. Moreover, the exemplary' embodiments presented below can be combined in any combination of ways, i.e., any element from one exemplary' embodiment can be used in any other exemplary' embodiment, without departing from the scope of the disclosure.

[0010] The indefinite article “a” or “an”, as used herein, means “at least one” unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments using “a separator” include embodiments where one or two or more separators are used, unless specified to the contrary or the context clearly indicates that only one separator is used. Likewise, embodiments using “a separation stage” include embodiments where one or two or more separation stages are used, unless specified to the contrary.

[0011] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and / or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0012] As used herein, the term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon. The term “Cn” hydrocarbon means hydrocarbon having n carbon atom(s) per molecule, where n is a positive integer. The term “Cn+” hydrocarbon means hydrocarbon having at least n carbon atom(s) per molecule, where n is a positive integer. The term “Cn” hydrocarbon means hydrocarbon having no more than n number of carbon atom(s) per molecule, where n is a positive integer. “Hydrocarbon” encompasses (i) saturated hydrocarbon, (ii) unsaturated hydrocarbon, and (iii) mixtures of hydrocarbons, including mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

[0013] In this disclosure, “cyclopentadiene” and “CPD” interchangeably mean cyclopenta-1.3-diene.

[0014] In this disclosure, “dicyclopentadiene” and “DCPD” interchangeably mean a molecule or a mixture of molecules each having a chemical formula C10H12 and obtainable via a Diels-Alder reaction between two CPD molecules. DCPD molecules in this disclosure). an endo-DCPD isomer (a mixture of both at any proportion.

[0015] In this disclosure, “tricyclopentadiene” and “TCPD” interchangeably mean a molecule or a mixture of molecules each having a chemical formula C15H18 and obtainable via a Diels-Alder reaction between a DCPD molecule and a CPD molecule. TCPD molecules in this disclosure include a single TCPD isomer or a mixture of any two or more TCPD isomers.TCPD molecules can include the 6,5,6-isomers (the 6,6,5-isomerseach of which can include multiple stereo isomers. TCPD molecules can include one or more of the following isomers TCPD-1. TCPD-2. TCPD-3, TCPD-4, TCPD-5, TCPD-6, TCPD-7, and TCPD-8, at various quantities thereof, which can be obtained via Diels-Alder reactions between a CPD molecule and an identified DCPD isomer at the identified DCPD reaction bond, shown in the Table below. A composition containingTCPD in this disclosure can include a single TCPD isomer, but typically includes a mixture of multiple TCPD isomers.TABLE

[0016] In this disclosure, “tetracyclopentadiene” or “TeCPD” interchangeably means a molecule or a mixture of molecules each having a chemical formula C20H24 and obtainable via a Diels-Alder reaction between a TCPD molecule and a CPD molecule. Thus, a TeCPD in this disclosure can be a single TeCPD isomer, or a mixture of any two or more TeCPD isomers.

[0017] The term “rich” when used in phrases such as “X-rich” or “rich in X” means, with respect to an outgoing product obtained from a device, e.g., a separation zone, that the product comprises material X at a concentration higher than in the feed material fed to the same device from which the product is derived. The term “lean” when used in phrases such as “X-lean” or “lean in X” means, with respect to an outgoing product obtained from a device, e.g., a separation zone, that the product comprises material X at a concentration lower than in the feed material fed to the same device from which the product is derived.

[0018] The Figure depicts an illustrative system 1000 for making a composition containing exo-DCPD and TCPD, according to one or more embodiments. The system 1000 can include, but is not limited to, a reaction zone 1030, a first separation zone 1040, a second separation zone 1052, an optional heat exchange zone 1046 located between the first and second separation zones 1040 and 1052, respectively, and an optional third separation zone 1070. In some embodiments, a hydrocarbon feed via line 1010 and a recycle stream via line 1058 can be combined or mixed within line 1023 and introduced into the reaction zone 1030. In other embodiments, the hydrocarbon feed in line 1010 and the recycle stream in line 1058 can be introduced into an optional mixing zone to produce the combined or mixed feed in line 1023 that can be introduced into the reaction zone 1030. In still other embodiments, the hydrocarbon feed via line 1010 and the recycle stream via line 1058 can be separately introduced into the reaction zone 1030. As described in more detail below, the recycle stream in line 1058 can be a first portion of a second product recovered via line 1054 from the second separation stage 1052.

[0019] The hydrocarbon feed in line 1010 and / or the recycle stream in line 1058 can be or can include, but is not limited to, DCPD or a mixture of DCPD and CPD. In some embodiments, a weight ratio of the recycle stream in line 1058 to the hydrocarbon feed in line 1010 introduced into the reaction zone 1030 can be in a range from 1.3, 1.5, 1.7, 2, 2.5, 3, 4, or 5 to 10, 11, 12, 13, 14, 15, 16, or 17.

[0020] The hydrocarbon feed in line 1010 can include at least 85 wt%, at least 87 wt%, at least 90 wt%, at least 93 wt%, at least 95 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt% of DCPD, based on the combined weight of CPD and DCPD in the hydrocarbon feed. The hydrocarbon feed in line 1010 can include endo-DCPD, exo-DCPD, or a mixture of endo-DCPD and exo-DCPD. In some embodiments, the hydrocarbon feed in line 1010 can include at least 95 wt%, at least 96 wt%, at least 97 wt%, or at least 97.5 wt% of endo-DCPD and less than 5 wt%. less than 4 wt%, less than 3 wt%, or less than 2.5 wt% of exo-DCPD, based on the combined weight of CPD and DCPD in the hydrocarbon feed. In other embodiments, the hydrocarbon feed in line 1010 can include 45 wt%, 47 wt%, 49 wt%, 50 wt%, 51 wt%, 55 wt%, 60 wt%, or 70 wt% to 80 wt%, 90 wt%, 95 wt%, 97 wt%, 99 wt%, or 100 wt% of endo-DCPD and 0 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 20 wt%, or 25 wt% to 30 wt%, 35 wt%, 40 wt%, 45 wt%. 47 wt%. 49 wt%, 50 wt%, 51 wt%. 53 wt%, or 55 wt% of exo-DCPD, based on the weight of DCPD in the hydrocarbon feed. In some embodiments, the hydrocarbon feed in line 1010 can also include one or more DCPD co-dimers, e.g., CPD-isoprene co-dimer, CPD- piperylene co-dimer, CPD-methylcyclopentadiene MCPD co-dimer, or any mixture thereof. In such embodiments, the hydrocarbon feed in line 1010 can include up to 0.3 wt%, 0.5 wt%, 0.9 wt%, 1.3 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt%, 7 wt%, or 10 wt% of a combined amount of any DCPD co-dimers, based on the total weight of the hydrocarbon feed.

[0021] In some embodiments, the recycle stream in line 1058 can include CPD and DCPD. In some embodiments, the recycle stream in line 1058 can include 0.1 wt%, 0.5 wt%, 1 wt%,3 wt%, 5 wt%, 7 wt%, or 10 wl% to 12 wt%, 15 wt%, 17 wt%, 20 wt%, or 22 wt% of CPD, based on the combined weight of CPD and DCPD in the recycle stream. In some embodiments, the recycle stream in line 1058 can include 78 wt%, 80 wt%, 83 wt%, 85 wt%, or 87 wt% to 90 wt%, 93 wt%, 95 wt%, 97 wt%, 99 wt%, 99.5 wt%, or 99.9 wt% of DCPD, based on the combined weight of CPD and DCPD in the recycle stream.

[0022] The recycle stream in line 1058 can include a mixture of endo-DCPD and exo-DCPD. In some embodiments, the recycle stream in line 1058 can include 3 wt%, 5 wt%, 6 wt%, 7 wt%, 10 wt%, 15 wt%, 20 wt%, or 25 wt% to 30 wt%, 35 wt%, 40 wt%, 45 wt%, 47 wt%, 48 wt%. 49 wt%, or 50 wt% of exo-DCPD, based on the weight of DCPD in the recycle stream. In some embodiments, the recycle stream in line 1058 can include at least 3 wt%, at least4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 47 wt%, or at least 49 wt% of exo-DCPD, based on the combined weight of CPD and DCPD in the recycle stream. In some embodiments, the recycle stream in line 1058 can include 3 wt%, 4 wt%, 5 wt%, or 6 wt% to 7 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 47 wt%, 48 wt%, 49 wt%, or 50 wt% of exo-DCPD, based on the combined weight of CPD and DCPD in the recycle stream. In some embodiments, the recycle stream in line 1058 can include a greater amount of exo-DCPD thanthe hydrocarbon feed in line 1010. In such embodiments, the recycle stream in line 1058 can contain 5%, 6%, or 7% to 13%, 14%, or 15% more exo-cyclopentadiene than the hydrocarbon feed in line 1010.

[0023] In some embodiments, the combination of the hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030, whether as a mixture or separately, can provide a combined reactor feed that can include 0.1 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, or 7 wt% to 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, or 22 wt% of CPD and 78 wt%. 80 wt%, or 82 wt%. 85 wt%, 88 wt%. or 90 wt% 90 wt%, 93 wt%. 95 wt%, 97 wt%, 99 wt%, 99.5 wt%, or 99.9 wt% of DCPD, based on the combined weight of CPD and DCPD in lines 1010 and 1058. In some embodiments, the hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030, whether as a mixture or separately, can provide a combined reactor feed that can include > 80 wt%, > 85 wt%, > 90 wt%, > 93 wt%, > 95 wt%, > 97 wt%, > 98 wt%, or > 99 wt% of DCPD and < 20 wt%, < 15 wt%, < 10 wt%, < 7 wt%, < 5 wt%, < 3 wt%, < 2 wt%, or < 1 wt % of CPD, based on the combined weight of CPD and DCPD in lines 1010 and 1058.

[0024] In some embodiments, the hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030, whether as a mixture or separately, can provide a combined reactor feed that has a weight ratio of endo-DCPD to exo-DCPD in a range from 1 , 2, 3, 4, 4.5, 5, 5.5, 6, or 7 to 8, 9, 9.5, 10, 12, 14, 16, 18, 20, 22, 24, 32, 40, 49, or 99. In some embodiments, the hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030, whether as a mixture or separately, can provide a combined reactor feed that includes 1 wt%, 3 wt%, 5 wt%, 7 wt%, or 10 wt% to 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% of exo-DCPD, based on the weight of DCPD in the combined reactor feed. In some embodiments, the hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030, whether as a mixture or separately, can provide a combined reactor feed that has a molar ratio of DCPD to CPD in a range from 0.5, 1, 5, 10, 25, 50, 75, or 100 to 150, 200, 250, 300, 350, 400, 450, or 499.5. In other embodiments, a molar ratio of DCPD to CPD introduced into the reaction zone 1030 can be in a range from 4.5, 5, 7, 9, 11, 13, 15, 17, or 20 to 23, 27, 29, 33, 37, 41, 45, 47. 48. 49, or 49.5.

[0025] In some embodiments, the hydrocarbon feed in line 1010 and / or the recycle stream in line 1058 fed into the reaction zone 1030 can include, in addition to CPD and DCPD, TCPD (preferably at a relatively low concentration, e.g., from 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, or 1 wt% to 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, or 5 wt%, based on the combined weight of the hydrocarbon feed and the recycle stream). In some embodiments, if the hydrocarbonfeed in line 1010 and / or the recycle stream in line 1058 fed into the reaction zone 1030 include, in addition to CPD and DCPD, TCPD, the amount of TCPD can be < 5 wt%, < 4 wt%, < 3 wt%, < 2 wt%, < 1 wt%, or < 0.5 wt%. based on the combined weight of the hydrocarbon feed and the recycle stream. The presence of TCPD can be particularly likely if the hydrocarbon feed in line 1010 and / or the recycle stream in line 1058 passes through an optional preheat zone (not shown) where it can be preheated to a temperature in the vicinity of the temperature within the reaction zone 1030.

[0026] The hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030 can be heated within the reaction zone 1030 to a temperature in a range from 100°C, 105°C, 110°C, 120°C, 130°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, or 170°C to 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, or 225°C. In some embodiments, the hydrocarbon feed in line 1010 and the recycle stream in line 1058 fed into the reaction zone 1030 can be heated within the reaction zone 1030 by heat generated from the reactions occurring therein. In some embodiments, the hydrocarbon feed in line 1010 and / or the recycle stream in line 1058 or the mixture thereof can be at a temperature in a range from 100°C, 105°C, 110°C, 120°C, 130°C. 135°C. 140°C. 145°C. 150°C. 155°C, or 160°C to 165°C, 170°C, 175°C, or 180°C when introduced into the reaction zone 1030. In some embodiments, the hydrocarbon feed in line 1010 and / or the recycle stream in line 1058 or the mixture thereof can be preheated in an optional preheat zone, if needed, to heat the feed(s) to a desired temperature for introduction into the reaction zone 1030. In other embodiments, the hydrocarbon feed in line 1010 can be obtained from an integrated upstream process that produces a suitable hydrocarbon feed having a sufficient elevated temperature such that the preheating step can be omitted.

[0027] The mixture of the hydrocarbon feed and the recycle stream can be subjected to reaction conditions within the reaction zone 1030 sufficient to effect reaction between the CPD and the DCPD to produce a reactor effluent that can include TCPD (e.g., a mixture of two or more TCPD isomers), TeCPD, optionally one or more oligomers heavier than TeCPD, e.g., pentacyclopentadiene, residual CPD, residual DCPD, or a mixture thereof. The reactor effluent can be recovered via line 1033 from the reaction zone 1030.

[0028] When the hydrocarbon feed in line 1010 and the recycle stream in line 1058 provide a mixture having a concentration of > 97 wt%, > 98 wt%, or > 99 wt% of DCPD, based on the combined amount of DCPD and any CPD, a portion of the DCPD can back crack via a retro Diels-Alder reaction to produce CPD, thereby increasing the concentration of CPD within the reaction zone 1030 available for reaction with the DCPD. For example, when the hydrocarbonfeed in line 1010 and the recycle stream in line 1058 provide a mixture that includes > 97.5 wt%, > 98 wt%, or > 99 wt% of DCPD, based on the combined amount of DCPD and CPD, and the reaction zone 1030 is at a temperature of 175°C an equilibrium amount of CPD in a range from 3 wt% to 4 wt%, e.g., 3.5 wt%, can be produced within the reaction zone 1030.

[0029] The reaction zone 1030 can be operated at a sufficient pressure to maintain a liquid phase of the contents therein. In some embodiments, the reaction zone 1030 can be operated at a pressure of > 138 kPa-absolute (kPa-a). > 206 kPa-a, or > 653 kPa-a and up to any pressure desired, e.g. , up to a pressure of 1.540 kPa-a or 4,485 kPa-a. In some embodiments, the reaction zone 1030 can be operated at a pressure > 255 kPa-absolute (kPa-a), > 351 kPa-a, or > 653 kPa-a and up to any pressure desired, e.g., up to a pressure of 1,420 kPa-a or 4,400 kPa-a.

[0030] In some embodiments, the reaction zone 1030 can be an isothermal reaction zone, an adiabatic reaction zone, or a combination thereof. For example, in some embodiments, the reaction zone 1030 can include one or more isothermal zones and one or more adiabatic zones serially arranged with respect to one another. In some embodiments, the reaction zone can include one or more internal structures configured to provide a desired hydrodynamic behavior of the reactants flowing therethrough. In other embodiments, the reaction zone can be free of any internal structure configured to provide a desired hydrodynamic behavior of the reactants flowing therethrough.

[0031] The reaction zone 1030 can be sized and the flowrate of the feed therethrough can be controlled to provide a relatively low conversion rate of DCPD per pass through the reaction zone 1030. In some embodiments, the residence time of the hydrocarbon feed and the recycle stream, whether introduced as a mixture or separately into the reaction zone 1030, can be in a range from 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, or 60 minutes to 65 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes. 150 minutes. 160 minutes, 175 minutes, 200 minutes, 225 minutes, 250 minutes, 275 minutes, or 300 minutes.

[0032] By maintaining a relatively low conversion rate of DCPD within the reaction zone 1030 the amount of higher oligomers of CPD, e.g., TeCPD and pentacy clopentadiene, can be reduced or minimized. In some embodiments, the amount of DCPD within the reaction zone 1030 converted to TCPD and TeCPD, and optionally one or more oligomers heavier than TeCPD can be < 15 wt%, < 12 wt%, < 10 wt%, < 9 wt%, < 8 wt%, or < 7.5 wt%, based on the weight of DCPD introduced into the reaction zone 1030.

[0033] In some embodiments, the reactor effluent in line 1033 can include, but is not limited to. CPD. DCPD. TCPD. TeCPD, one or more co-dimers, one or more oligomers heavierthan TeCPD, nitrogen (N2), oxygen (O2), or any mixture thereof. In some embodiments, the reactor effluent in line 1033 can include 0.5 wt%, 1 wt%, or 2 wt% to 3 wt%, 4 wt%, or 5 wt% of CPD. 60 wt%, 65 wt%, 70 wt%, 75 wt%, or 80 wt% to 85 wt%, 90 wt%, or 95 wt% of DCPD, 4 wt%, 5 wt%, 6 wt%, 7 wt%, or 10 wt% to 12 wt%, 15 wt%, 17 wt%, 20 wt%, 23 wt%, 25 wt%, 27 wt%, or 30 wt% of TCPD, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, or 3 wt% to 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% of TeCPD, and 0 wt% to 5 wt%, e.g., 0.1 wt%, 0.5 wt%, or 1 wt% to 2 wt%, 3 wt%, or 5 wt%, of one or more co-dimers, based on the combined weight of CPD, DCPD, TCPD, TeCPD. and any of the one or more co-dimers. The reactor effluent in line 1033 can include a mixture of endo-DCPD and exo-DCPD. In some embodiments, the reactor effluent in line 1033 can include 2 wt%, 5 wt%, 10 wt%, 15 wt%, or 20 wt% to 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% of exo-DCPD, based on the combined weight of endo-DCPD and exo-DCPD. In other embodiments, the reactor effluent in line 1033 can include 3 wt%, 4 wt%, 5 wt%, 6 wt%, or 7 wt% to 8 wt%, 9 wt%, 10 wt%, 12 wt%, or 15 wt% of exo-DCPD, based on the combined weight of endo-DCPD and exo-DCPD.

[0034] The TCPD in the reactor effluent in line 1033 can be or can include, but is not limited to. TCPD-1. TCPD-2. TCPD-3, TCPD-4, TCPD-5, TCPD-6, TCPD-7, TCPD-8, or any mixture thereof. In some embodiments, the TCPD in the reactor effluent in line 1033 can include, but is not limited to, a mixture of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In other embodiments, the TCPD in the reactor effluent in line 1033 can include, but is not limited to, a mixture of TCPD-7. TCPD-3. TCPD-5, TCPD-1, TCPD-8, and TCPD-6.

[0035] In some embodiments, the reactor effluent in line 1033 can include 0. 1 wt%, 1 wt%, 1.5 wt%, 2 wt%, or 3 wt% to 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, or 6 wt% of TCPD-7, based on the combined weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can include 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt% to 10 wt%, 13 wt%. 15 wt%, 20 wt%, or 25 wt% of TCPD-3, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can include 10 wt%, 12 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, or 25 wt% to 27 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, or 75 wt% of TCPD-5, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can include 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 30 wt% to 40 wt%, 50 wt%, 60 wt%, 65 wt%, 70 wt%, 72 wt%, or 75 wt% of TCPD-1, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can be free of or can include < 1 wt%, < 0.5 wt%, or < 0. 1 wt% of TCPD-8. based on the combined weightof TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-6, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can be free of or can include < 1 wt%, < 0.5 wt%, or < 0. 1 wt% of TCPD-2, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can be free of or can include < 1 wt%,< 0.5 wt%, or < 0.1 wt% of TCPD-4, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1.

[0036] In some embodiments, the reactor effluent in line 1033 can include > 10 wt%,> 12 wt%, > 14 wt%, > 16 wt%, > 18 wt%, > 20 wt%, > 25 wt%, > 30 wt%, > 35 wt%,> 40 wt%, > 45 wt%, > 50 wt%, > 55 wt%, or > 60 wt% of TCPD-5, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can include < 75 wt%, < 73 wt%, < 70 wt%, < 68 wt%, < 67 wt%,< 66 wt%, < 65 wt%, < 60 wt%, < 55 wt%, < 50 wt%, < 45 wt%, < 40 wt%, < 35 wt%,< 30 wt%, < 25 wt%, or < 20 wt% of TCPD-1, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the reactor effluent in line 1033 can include 0.1 wt%, 1 wt%, 1.5 wt%, 2 wt%, or 3 wt% to 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, or 6 wt% of TCPD-7, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt% to 10 wt%, 13 wt%, 15 wt%, 20 wt%, or 25 wt% of TCPD-3, > 10 wt%, > 12 wt%, > 14 wt%, > 16 wt%, > 18 wt%,> 20 wt%, > 25 wt%, > 30 wt%, > 35 wt%, > 40 wt%, > 45 wt%, > 50 wt%, > 55 wt%, or> 60 wt% of TCPD-5, < 75 wt%, < 73 wt%, < 70 wt%, < 68 wt%, < 67 wt%, < 66 wt%,< 65 wt%, < 60 wt%, < 55 wt%, < 50 wt%, < 45 wt%, < 40 wt%, < 35 wt%, < 30 wt%,< 25 wt%, or < 20 wt% of TCPD-1, can be free of or can include < 1 wt%, < 0.5 wt%, or< 0.1 wt% of TCPD-8, can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-6, can be free of or can include < 1 wt%, < 0.5 wt%, or < 0. 1 wt% of TCPD-2, and can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-4, where all weight percent values are based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 can constitute at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, or at least 99.5 wt% of all TCPD in the reactor effluent in line 1033.

[0037] In some embodiments, the reactor effluent in line 1033 can further include one or more light compounds present in the hydrocarbon feed in line 1010 and / or the recycle stream in line 1058 and / or produced within the reaction zone 1030, or a mixture thereof. The one or more light compounds that can be present in the hydrocarbon feed in line 1010 and / or therecycle stream 1058 and / or produced within the reaction zone 1030 can be or can include, but are not limited to, isoprene, piperylene, benzene, butadiene, pentene, or any mixture thereof.

[0038] In some embodiments, the reactor effluent in line 1033 can be introduced into the first separation zone 1040. As shown, a bottoms or first product via line 1042 and an overhead via line 1044 can be recovered from the first separation zone 1040. The first product in line 1042 can include, but is not limited to, DCPD, TCPD, TeCPD, one or more oligomers heavier than TeCPD, or any mixture thereof. The overhead in line 1044 can include, but is not limited to, CPD, DCPD, nitrogen (N2), oxygen (O2), isoprene, piperylene, benzene, butadiene, pentene, or any mixture thereof.

[0039] In some embodiments, the first separation zone 1040, e.g., a distillation column, can operate under a vacuum to reduce or avoid fouling and / or to reduce or avoid cracking of TCPD that may occur at a high bottom temperature. In some embodiments, the separation zone 1040, e.g., a distillation column, can be operated at a pressure < 100 kPa-a, < 80 kPa-a, < 60 kPa-a, < 40 kPa-a, < 30 kPa-a, or < 20 kPa-a. In other embodiments, however, the separation zone 1040, e.g., a distillation column, can be operated at ambient pressure. In some embodiments, the first separation zone 1040, e.g., a distillation column, can be equipped with one or more reboilers that can operate at a temperature in a range from 110°C, 120°C, 130°C, 140°C, 145°C, 150°C, or 160°C to 170°C, 180°C, or 190°C.

[0040] In some embodiments, the first product in line 1042 can include 8 wt%, 10 wt%, 15 wt%, or 20 wt% to 30 wt%, 35 wt%, 40 wt%, or 45 wt% of DCPD, based on the combined weight of DCPD, TCPD, and TeCPD. In some embodiments, the first product in line 1042 can include 45 wt%, 50 wt%, 55 wt%, or 60 wt% to 70 wt%, 75 wt%, 80 wt%, or 85 wt% of TCPD, based on the combined weight of DCPD, TCPD, and TeCPD. In some embodiments, the first product in line 1042 can include 0.5 wt%, 1 wt, 2 wt%, or 3 wt% to 5 wt%, 7 wt%, 10 wt%, or 12 wt% of TeCPD, based on the combined weight of DCPD, TCPD, and TeCPD. In some embodiments the first product in line 1042 can include 0. 1 wt%, 0.5 wt%, or 1 wt% to 1.5 wt%, 2 wt%, 2.5 wt%, or 3 wt% of one or more oligomers heavier than TeCPD, based on the combined weight of DCPD, TCPD, and TeCPD. In some embodiments, the first product in line 1042 can include 10 wt% to 40 wt% of DCPD, 50 wt% to 80 wt% of TCPD, and 1 wt% to 10 wt% of TeCPD, based on the combined weight of DCPD, TCPD, and TeCPD.

[0041] In some embodiments, the first product in line 1042 can include 0.1 wt%, 1 wt%, 1.5 wt%, 2 wt%, or 3 wt% to 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, or 6 wt% of TCPD-7, based on the combined weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can include 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt%to 10 wt%, 13 wt%, 15 wt%, 20 wt%, or 25 wt% of TCPD-3, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD- 1. In some embodiments, the first product in line 1042 can include 10 wt%, 12 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, or 25 wt% to 27 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, or 75 wt% of TCPD-5, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can include 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 30 wt% to 40 wt%, 50 wt%, 60 wt%, 65 wt%, 70 wt%, 72 wt%, or 75 wt% of TCPD-1, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-8, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can be free of or can include < 1 wt%,< 0.5 wt%, or < 0.1 wt% of TCPD-6, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-2, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-4, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1.

[0042] In some embodiments, a weight ratio of TCPD to TeCPD and, if present, the one or more oligomers heavier than TeCPD in the first product in line 1042 can be > 5, > 10, > 15,> 20, > 25, > 30, > 35, > 40, > 45, > 50, > 55, or > 60. In some embodiments, the first product in line 1042 can include > 95 wt%, > 96 wt%, > 97 wt%, > 98 wt%, or > 99 wt% of a combined amount of TCPD, DCPD, TeCPD, and, if present, the one or more oligomers heavier than TeCPD, based on the total weight of the first product in line 1044. In some embodiments, a weight ratio of TCPD to DCPD in the first product in line 1042 can be > 1, > 2, or > 2.5.

[0043] In some embodiments, the first product in line 1042 can include > 10 wt%,> 12 wt%, > 14 wt%, > 16 wt%, > 18 wt%, > 20 wt%, > 25 wt%, > 30 wt%, > 35 wt%,> 40 wt%, > 45 wt%, > 50 wt%, > 55 wt%, or > 60 wt% of TCPD-5, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can include < 75 wt%, < 73 wt%, < 70 wt%, < 68 wt%, < 67 wt%,< 66 wt%, < 65 wt%, < 60 wt%, < 55 wt%, < 50 wt%, < 45 wt%, < 40 wt%, < 35 wt%,< 30 wt%, < 25 wt%, or < 20 wt% of TCPD-1, based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the first product in line 1042 can include 0.1 wt%, 1 wt%, 1.5 wt%, 2 wt%, or 3 wt% to 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, or 6 wt% of TCPD-7, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt% to 10 wt%, 13 wt%, 15 wt%,20 wt%, or 25 wt% of TCPD-3, > 10 wt%, > 12 wt%, > 14 wt%, > 16 wt%, > 18 wt%,> 20 wt%, > 25 wt%, > 30 wt%, > 35 wt%, > 40 wt%, > 45 wt%, > 50 wt%, > 55 wt%, or> 60 wt% of TCPD-5, < 75 wt%, < 73 wt%, < 70 wt%, < 68 wt%, < 67 wt%, < 66 wt%,< 65 wt%, < 60 wt%, < 55 wt%, < 50 wt%, < 45 wt%, < 40 wt%, < 35 wt%, < 30 wt%,< 25 wt%, or < 20 wt% of TCPD-1, can be free of or can include < 1 wt%, < 0.5 wt%, or< 0.1 wt% of TCPD-8, can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-6, can be free of or can include < 1 wt%, < 0.5 wt%, or < 0. 1 wt% of TCPD-2, and can be free of or can include < 1 wt%, < 0.5 wt%, or < 0.1 wt% of TCPD-4, where all weight percent values are based on the combined weight of TCPD-7, TCPD-3, TCPD-5, and TCPD-1. In some embodiments, the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 can constitute at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, or at least 99.5 wt% of all TCPD in the first product in line 1042.

[0044] The overhead in line 1044 can include CPD, DCPD, nitrogen (N2), oxygen (O2), isoprene, piperylene, benzene, butadiene, pentene, or any mixture thereof. In some embodiments, the nitrogen and oxygen can be present in the hydrocarbon feed and / or introduced via the separation zone 1040. In some embodiments, the overhead in line 1044 can include 0.3 wt%, 0.5 wt%, 1 wt%, or 2 wt% to 3 wt%, 5 wt%, or 6 wt% of CPD, based on the combined weight of CPD, DCPD, nitrogen, and oxygen. In some embodiments, the overhead in line 1044 can include 75 wt%, 80 wt%, or 85 wt% to 90 wt%, 93 wt%, 95 wt%, or 97 wt% of DCPD, based on the combined weight of CPD, DCPD, nitrogen, and oxygen. In some embodiments, the overhead in line 1044 can include 0.001 wt%, 0.01 wt%, or 0.1 wt% to 0.3 wt%, 0.5 wt%, 1 wt%, or 1.2 wt% of nitrogen, based on the combined weight of CPD, DCPD, nitrogen, and oxygen. In some embodiments, the overhead in line 1044 can include 0.001 wt%, 0.01 wt%, or 0.1 wt% to 0.3 wt%, 0.5 wt%, 1 wt%, or 1.2 wt% of oxygen, based on the combined weight of CPD, DCPD, nitrogen, and oxygen.

[0045] In some embodiments, the overhead via line 1044 can be introduced into the second separation zone 1052. The second product via line 1054 and a purge stream via line 1062 can be recovered from the second separation zone 1052. The second product in line 1054 can be or can include, but is not limited to, CPD and DCPD. In some embodiments, the second product in line 1054 can include 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, or 7 wt% to 12 wt%, 15 w% 17 wt%, 20 wt% or 22 wt% of CPD, based on the combined weight of CPD and DCPD. In some embodiments, the second product in line 1054 can include 78 wt%, 80 wt%, 83 wt%, 85 wt%, or 88 wt% to 93 wt%, 95 wt%, 97 wt%, 99 wt%, 99.5 wt%, or 99.7 wt% of DCPD, based on the combined weight of CPD and DCPD.

[0046] The second product in line 1054 can have the same composition as the recycle stream in line 1058. As such, the second product in line 1054 can include a mixture of endo- DCPD and exo-DCPD. In some embodiments, the second product in line 1054 can include3 wt%, 5 wt%, 6 wt%, 7 wt%, 10 wt%, 15 wt%, 20 wt%, or 25 wt% to 30 wt%, 35 wt%, 40 wt%, 45 wt%, 47 wt%, 48 wt%, 49 wt%, or 50 wt% of exo-DCPD, based on the weight of DCPD in the recycle stream. In some embodiments, the second product in line 1054 can include 0.1 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 7 wt%, or 10 wt% to 12 wt%, 15 wt%, 17 wt%, 20 wt%, or 22 wt% of CPD, based on the combined weight of CPD and DCPD in the second product. In some embodiments, the second product in line 1054 can include 78 wt%, 80 wt%, 83 wt%, 85 wt%, or 87 wt% to 90 wt%, 93 wt%, 95 wt%, 97 wt%, 99 wt%, 99.5 wt%, or 99.9 wt% of DCPD, based on the combined weight of CPD and DCPD in the second product. In some embodiments, the second product in line 1054 can include at least 3 wt%, at least4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 47 wt%, or at least 49 wt% of exo-DCPD, based on the combined weight of CPD and DCPD in the second product. In some embodiments, the second product in line 1054 can include 3 wt%, 4 wt%, 5 wt%, or 6 wt% to 7 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 47 wt%, 48 wt%, 49 wt%, or 50 wt% of exo-DCPD, based on the combined weight of CPD and DCPD in the second product.

[0047] As noted above, the recycle stream in line 1058 can include a first portion of the second product in line 1054 and a second portion via line 1056 of the second product in line 1054 can be recovered from the system 1000 as a product. As shown in the Figure, in some embodiments, the first portion, the second portion, and a third portion of the second product in line 1054 can be recycled via line 1058, recovered as a product via line 1056, and recycled via line 1060 to the first separation zone 1040 as a reflux, respectively. In some embodiments, a weight ratio of the first portion of the second product in line 1054 to the second portion of the second product in line 1056 can be in a range from 3, 5, 7, 10, or 15 to 25, 30, 35, 40, 45, or 50. In some embodiments, a weight ratio of the second portion of the second product in line 1056 to the third portion of the second product in line 1060 can be in a range from 6: 1, 5: 1, 4:, 3: 1, 2: 1, or 1 : 1 to 1 :2, 1:3, 1:4, 1:5, or 1:6. In some embodiments, a weight ratio of the first portion of the second product in line 1054 to the third portion of the second product in line 1060 can be in a range from 1: 1, 2:1, 4: 1, or 6: 1 to 15: 1, 25: 1, 30: 1, or 35:1.

[0048] The purge stream in line 1062 can include, but is not limited to, CPD, DCPD, one or more light compounds such as isoprene, piperylene, butadiene, pentene, and / or benzene,nitrogen, oxygen, or any mixture thereof. In some embodiments, the purge stream in line 1062 can include 17 wt%, 20 wt%, 25 wt%, 30 wt%, or 35 wt% to 50 wt%, 55 wt%, 60 wt% or 63 wt% of CPD, 13 wt%, 15 wt%, 20 wt%, 30 wt%, or 40 wt% to 60 wt%, 70 wt%, 75 wt%, or 77 wt% of nitrogen, and 3 wt%, 5 wt%, 7 wt%, or 10 wt% to 15 wt%, 17 wt%, 20 wt%, or 22 wt% of oxygen, based on the combined weight of CPD, nitrogen, and oxygen. In other embodiments, the purge stream in line 1062 can include 45 wt%, 50 wt%, 55 wt%, 60 wt%, or 65 wt% to 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of CPD, 8 wt%, 10 wt%, 15 wt%, or 20 wt% to 25 wt%, 30 wt%, 35 wt%, 45 wt% of DCPD, 0.0001 wt%, 0.001 wt%, 0.01 wt%, or 0.1 wt% to 1 wt%, 3 wt%, or 5 wt% of nitrogen, and 0.00001 wt%, 0.0001 wt%, 0.001 wt%, 0.01 wt%, or 0.1 wt% to 0.5 wt%, 1 wt%, 1.5 wt%, or 2 wt% of oxygen, based on the combined weight of CPD, DCPD, nitrogen, and oxygen.

[0049] In some embodiments, the first product in line 1042 can be cooled to a temperature in a range from 30°C, 35°C, 40°C, or 45°C to 50°C, 60°C, or 70°C. In some embodiments, the cooled first product in line 1042 can be sent to storage. In some embodiments, the first product via line 1042 can be introduced into the optional third separation zone 1070. In such embodiments, a third product rich in TCPD and lean in TeCPD via line 1072 and a fourth product rich in TeCPD and lean in TCPD via line 1074 can be recovered from the third separation zone 1070. In some embodiments, the third product rich in TCPD and lean in TeCPD in line 1072 can include > 95 wt%, > 98 wt%, or > 99 wt% of a combined amount of DCPD and TCPD. In some embodiments, a weight ratio of TCPD to DCPD in the second product can be > 1, > 2, or > 2.5.

[0050] In some embodiments, an optional diluent can be combined with the reactor effluent in line 1033, introduced into the first separation zone 1040, combined with the first product in line 1042, and / or introduced into the optional third separation zone 1070. The diluent, if used, can reduce or suppress the melting point of TeCPD and reduce or suppress the melting point of the one or more oligomers heavier than TeCPD within the first separation zone 1040 and / or the third separation zone 1070. In some embodiments, the diluent can be or can include, but is not limited to, one or more C9+ paraffins, C9+ iso-paraffms, C9+ aromatics, C9+ naphthenes, C9+ alpha-olefms, or a mixture thereof.

[0051] The first, second, and third separation zones 1040, 1052, 1070, respectively, can be or can include any suitable separation apparatus or combination of separation apparatus. In some embodiments, suitable separation apparatus can be or can include, but are not limited to, distillation columns, evaporators, crystallizers, vapor / liquid separation drums, drumless condensers, or a combination thereof. In some embodiments, the first separation zone 1040and / or the third separation zone 1070 can be or can include one or more distillation columns, one or more divided wall distillation columns, or a combination thereof. In some embodiments, the second separation zone can be a vapor / liquid separation drum and / or a drumless condenser. In some embodiments, the first separation zone 1040 can be a divided wall distillation column such that the overhead in line 1044, the third product in line 1072, and the fourth product in line 1074 can be obtained from the divided wall distillation column. In other words, if the first separation zone 1040 includes a divided wall distillation column, such divided wall distillation column can carry out the separation of both the first and third separation zones 1040, 1070, respectively.

[0052] In some embodiments, the first separation zone 1040, the second separation zone 1052, and / or the third separation zone 1070 can include one or more internal structures to facilitate separation of the products recovered therefrom. The internal structure(s) can facilitate vapor / liquid separation and / or liquid collection. Illustrative internal structures can be or can include, but are not limited to, trays, grids, packing, or any combination thereof. Illustrative trays can include, but are not limited to, fixed valve trays, jet tab trays, sieve trays, dual flow trays, baffle trays, angle iron trays, draw off trays, shed deck trays, disk trays, donut trays, side by side-splash trays, or any combination thereof. Suitable fixed valve trays, sieve trays, dual flow trays, and grids can include those disclosed in Distillation Design, Henry Z. Kister, McGraw-Hill Inc., 1992, pages 262 to 265 and pages 464-466. Suitable jet tab trays can include those disclosed in WO Publication No. WO2011 / 014345.

[0053] In some embodiments, divided wall distillation columns can include those disclosed in I. J. Halvorsen, I. Dejanovic, S. Skogestad, Z. Olujic, Internal Configurations for a Multiproduct Dividing Wall Column, Chemical Engineering Research and Design, v. 91(10), 2013, Pages 1954-1965; I. J. Halvorsen, S. Skogestad, I. Dejanovic, L. Matijasevic, Z. Olujic, MultiProduct Dividing Wall Columns: A Simple and Effective Assessment and Conceptual Design Procedure; S. Tututi-Avila, L.A. Dominguez-Diaz, N. Medina-Herrera, A. Jimenez-Gutierrez, J. Hahn, Dividing-wall Columns: Design and Control of a Kaibel and a Satellite Distillation Column for BTX Separation, Chemical Engineering and Processing: Process Intensification, v. 114, 2017, Pages 1-15; Z. Olujic, M. Jbdecke, A. Shilkin, G. Schuch, B. Kaibel, Equipment Improvement Trends in Distillation, Chemical Engineering and Processing: Process Intensification, v. 48(6), 2009, Pages 1089-1 104; and I. Dejanovic, Lj. Matijasevic, Z. Olujic, Dividing Wall Column — A Breakthrough Towards Sustainable Distilling, Chemical Engineering and Processing: Process Intensification, v. 49(6), 2010, Pages 559-580; U.S. Patent Nos.: 1,915,681; 2,134,882; 2,295,256; 2,471,134; 3,058,893; 3,314,879;3,412,016; 4,230,533; 4,994,152; 5,339,648; 5,580,425; 5,585,046; 5,709,780; 5,755,993;5,785,819; 5,836,174; 5,897,748; 5,902,460; 5,914,012; 5,946,942; 6,077,985; 6,166,279;6,250,106; 6,347,533; 6,395,950; 6,395,951; 6,407,303; 6,479,720; 6,483,002; 6,540,907;6,551,465; 6,558,515; 6,628,468; 6,645,350; 6,726,835; 6,770,173; 6,846,389; 6,884,324;6,927,314; 6,930,206; 6,958,111; 7,001,490; 7,005,057; 7,090,748; 7,108,770; 7,112,707;7,118,653; 7,132,038; 7,169,267; 7,234,691; 7,264,696; 7,267,746; 7,287,747; 7,342,134;7,357,378; 7,527,712; 7,528,290; 7,547,378; 7,556,717; U.S. Patent Application Publication Nos.: 2001 / 0010286; 2001 / 0052453; 2003 / 0230476; 2004 / 0204614; 2006 / 0005574;2006 / 0137967; 2007 / 0293688; 2008 / 0081937; 2008 / 0289946; and 2009 / 0139852; EP Patent Application Publication Nos. : EP0122367A2; EP0126288A2; EP0780147A2; EP0806406A1; German Patent Application Publication and Patent Nos.: DE3522234C3; DE4336983A1; DE3510365C2; DE4336984C2; DE4336986C2; DE10135585C1; DE102004024688(Al); and WO Publication Nos.: WO 2003 / 051799; WO 2004 / 071618; WO 2005 / 046831; and WO 2009 / 092682.

[0054] Suitable evaporation systems can be or can include one or more wiped film evaporators such as those described in Boung Wook Lee et al., Thin-Film Evaporator Model for Continuous Active Pharmaceutical Ingredient Manufacturing, Ind. Egn. Chem. Res. 2020, v. 57(7), pp. 3252-3260; Leonard E. Najder, Thin Film Evaporation, Ind. Eng. Chem. 1964, v. 56(2), pp. 26-30; and Jacinto Lopez-Toledo, Heat and Mass Transfer Characteristics of a Wiped Film Evaporator, Dissertation, The University of Texas at Austin, August 2006. Suitable crystallization systems can be or can include those described in H.J.M. Kramer, G.M. van Rosmalen, CRYSTALLIZATION, Encyclopedia of Separation Science, Academic Press, 2000, Pages 64-84.

[0055] In some embodiments, the overhead via line 1044 can be introduced into the optional heat exchange zone 1046 located between the first and second separation zones 1040 and 1052, respectively. In such embodiments, a heat transfer medium via line 1048 can also be introduced into the heat exchange zone 1046 and heat can be indirectly transferred from the overhead to the heat transfer medium. A heated heat transfer medium via line 1049 and a cooled overhead via line 1050 can be recovered from the heat exchange zone 1046. The cooled overhead via line 1050 can be introduced into the second separation zone 1052 and the second product via line 1054 and the purge stream via line 1062 can be recovered therefrom. The heat transfer medium in line 1048 can be or can include, but is not limited to, water, air, glycol, or any mixture or combination thereof. In some embodiments, the cooled overhead in line 1050can be at a temperature in a range from 32°C, 35°C, or 40°C to 45°C, 47°C, or 50°C when introduced into the second separation zone 1052.

[0056] As noted above, in some embodiments nitrogen and / or oxygen can contaminate the hydrocarbon feed in line 1010 and and / or enter the system via the separation zone 1040 and it can be desirable to remove at least a portion of the oxygen therefrom. In some embodiments, the hydrocarbon feed via line 1010 and a stripping gas deficient in molecular oxygen can be introduced into an optional oxygen separation zone and can flow counter currently through the oxygen separation zone. The oxygen separation zone can include one or more internal components such as packing, trays, or a combination thereof, to promote mass transfer of the molecular oxygen from the hydrocarbon feed to the stripping gas. A molecular oxygen rich gas and a molecular oxygen lean hydrocarbon feed can be recovered from the oxygen separation zone. In some embodiments, the amount of molecular oxygen removed from the hydrocarbon feed in line 1010 can be > 90%, > 93%, > 95%, > 97%, > 98%, or > 99% of any molecular oxygen present in the hydrocarbon feed in line 1010.

[0057] In other embodiments, the second product in line 1054 and / or the recycle stream in line 1058 and / or the combined or mixed feed in line 1023 and a stripping gas deficient in molecular oxygen can be introduced into an optional oxygen separation zone and can counter currently flow through the oxygen separation zone. It should be understood that the second product in line 1054 and / or the recycle stream in line 1058 and / or the combined or mixed feed in line 1023 can be in the liquid phase when introduced into the optional oxygen separation zone. The optional oxygen separation zone can include one or more internal components such as packing, trays, or a combination thereof, to promote mass transfer of the molecular oxygen from the second product and / or the recycle stream to the stripping gas. A molecular oxygen rich gas and a molecular oxygen lean product can be recovered from the optional oxygen separation zone. In some embodiments, the amount of molecular oxygen removed from the second product in line 1054 and / or the recycle stream in line 1058 can be > 90%, > 93%, > 95%, > 97%, > 98%, or > 99% of any molecular oxygen present in the second product in line 1054 and / or the recycle stream in line 1058.

[0058] In some embodiments, an optional antioxidant can be combined with the hydrocarbon feed in line 1010, the reactor effluent in line 1033, the first product in line 1042, the second product in line 1054, and / or the recycle stream in line 1058. The optional antioxidant can be or can include, but is not limited to, butylated hydroxytoluene, triphenyl phosphine, 4-tert-butylcatechol, phenylenediamine, or a mixture thereof.

[0059] In some embodiments, the recycle stream in line 1058 can be introduced into an optional dimerization zone. In some embodiments, the optional dimerization zone can be operated at a temperature in a range from 70°C, 75°C, 80°C, 85°C, 90°C, 100°C, or 105°C to 110°C, 120°C, 125°C, 130°C, or 135°C. The dimerization zone can be operated at a pressure sufficient to maintain the contents therein in a liquid phase. In some embodiments, the dimerization zone can be operated at a temperature of > 15 kPa- a, > 44 kPa-a, or > 790 kPa-a and up to any pressure desired, e.g., up to a pressure of 1,800 kPa-a or 4,730 kPa-a. In some embodiments, the residence time of the recycle stream introduced into the optional dimerization zone can be in a range from 10 minutes, 20 minutes, 30 minutes, 45 minutes, 60 minutes, or 70 minutes to 100 minutes, 150 minutes, 200 minutes, 250 minutes, or 300 minutes. Within the optional dimerization zone at least a portion of any CPD therein can dimerize to produce a dimerized product or dimerized recycle stream that can include less CPD than the recycle stream introduced into the optional dimerization zone. In some embodiments, when the recycle stream in line 1058 is introduced into the optional dimerization zone, the dimerization zone can be operated at a temperature in a range from 75°C to 85°C, 85°C to 95°C, or 115°C to 125°C, a residence time within the dimerization zone can be in a range from 3 minutes, 10 minutes, or 20 minutes to 35 minutes, 45 minute, or 60 minutes to produce the dimerized recycle stream.

[0060] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0061] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

CLAIMS: hat is claimed is:

1. A process, comprising: introducing a hydrocarbon feed comprising cyclopentadiene and dicyclopentadiene into a reaction zone; subjecting the hydrocarbon feed to reaction conditions sufficient to effect reaction between the cyclopentadiene and the dicyclopentadiene within the reaction zone to produce a reactor effluent comprising tricyclopentadiene, tetracyclopentadiene, cyclopentadiene, and di cyclopentadiene; separating from the reactor effluent a first product, a second product, and a purge stream, wherein: the first product comprises dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, the second product comprises cyclopentadiene and dicyclopentadiene, and the purge stream comprises cyclopentadiene, nitrogen, and oxygen; separating the second product into at least a first portion and a second portion; and introducing the first portion of the second product into the reaction zone.

2. The process of claim 1, wherein introducing the hydrocarbon feed and the first portion of the second product into the reaction zone provides a combined reactor feed containing 0.5 wt% to 20 wt% of cyclopentadiene and 80 wt% to 99.5 wt% of dicyclopentadiene, based on the combined weight of cyclopentadiene and di cyclopentadiene.

3. The process of claim 2, wherein the dicyclopentadiene in the combined reactor feed comprises 1 wt% to 50 wt% of exo-dicyclopentadiene, based on the weight of the dicyclopentadiene in the combined reactor feed.

4. The process of claim 2, wherein the hydrocarbon feed and the second product each comprise a mixture of endo-dicyclopentadiene and exo-dicyclopentadiene, and wherein the combined reactor feed has a weight ratio of endo-dicyclopentadiene to exo-dicyclopentadiene in a range from 4.5 to 20.

5. The process of any one of claims 1 to 4, wherein the reactor effluent comprises 0.5 wt% to 5 wt% of cyclopentadiene, 60 wt% to 95 wt% of dicyclopentadiene, 4 wt% to 30 wt% of tricyclopentadiene, 0.1 wt% to 10 wt% of tetracyclopentadiene, and 0 wt% to 5 wt% of one ormore co-dimers, based on the combined weight of cyclopentadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, and any of the one or more co-dimers.

6. The process of any one of claims 1 to 5, wherein the first product comprises 10 wt% to 40 wt% of dicyclopentadiene, 50 wt% to 80 wt% of tricyclopentadiene, and 1 wt% to 10 wt% of tetracyclopentadiene, based on the combined weight of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene.

7. The process of any one of claims 1 to 6, wherein the second product comprises 0.5 wt% to 20 wt% of cyclopentadiene and 80 wt% to 99.5 wt% of di cyclopentadiene, based on the combined weight of cyclopentadiene and dicyclopentadiene.

8. The process of any one of claims 1 to 7. wherein the second product comprises a mixture of endo-dicyclopentadiene and exo-dicyclopentadiene, and wherein the second product comprises at least 3 wt% of exo-dicyclopentadiene, based on the combined weight of cyclopentadiene and di cyclopentadiene.

9. The process of any one of claims 1 to 8, wherein the second product comprises a mixture of endo-dicyclopentadiene and exo-dicyclopentadiene, and wherein the second product comprises at least 6 wt% of exo-dicyclopentadiene, based on the combined weight of cyclopentadiene and di cyclopentadiene.

10. The process of any one of claims 1 to 9, wherein the purge stream comprises 20 wt% to 60 wt% of cyclopentadiene, 15 wt% to 75 wt% of nitrogen, and 5 wt% to 20 wt% of oxygen, based on the combined weight of cyclopentadiene, nitrogen, and oxygen.

11. The process of any one of claims 1 to 9. wherein the purge stream further comprises dicyclopentadiene, and wherein the purge stream comprises 50 wt% to 90 wt% of cyclopentadiene, 10 wt% to 45 wt% of di cyclopentadiene, up to 5 wt% of nitrogen, and up to 2 wt% of oxygen, based on the combined weight of cyclopentadiene, dicyclopentadiene, nitrogen, and oxygen.

12. The process of any one of claims 1 to 11, wherein a weight ratio of the first portion of the second product recycled into the reaction zone and the hydrocarbon feed introduced into the reaction zone is in a range from 1.5 to 15.

13. The process of any one of claims 1 to 12, wherein a weight ratio of the first portion of the second product to the second portion of the second product is in a range from 3 to 45.

14. The process of any one of claims 1 to 13, wherein the reaction conditions comprise a residence time within the reaction zone in a range from 10 minutes to 300 minutes.

15. The process of any one of claims 1 to 14, wherein the reaction zone is adiabatic, isothermal, or a combination of adiabatic and isothermal.

16. The process of any one of claims 1 to 15, wherein the reaction conditions comprise a temperature in a range from 150°C to 220°C and a pressure sufficient to maintain the compounds within the reaction zone in a liquid phase.

17. The process of any one of claims 1 to 16, wherein the first product and the second product are separated from the reactor effluent by distillation, evaporation, crystallization, or a combination thereof.

18. The process of any one of claims 1 to 17, wherein the tricyclopentadiene in the first product comprises:

0. 1 wt% to 6 wt% of TCPD-7 having a structure5 wt% to 25 wt% of TCPD-3 having a structure15 wt% to 75 wt% of TCPD-5 having a structure5 wt% to 75 wt% of TCPD-1 having a structure ofwherein all wt% values are based on the combined weight of TCPD-7, TCPD-3, TCPD-5, andTCPD-1 in the first product.

19. The process of any one of claims 1 to 18, further comprising combining an anti-oxidant with at least one of: the hydrocarbon feed, the first product, the second product, and the first portion of the second product recycled into the reaction zone.

20. The process of claim 19, wherein the antioxidant comprises butylated hydroxy toluene, triphenyl phosphine, 4-tert-butyIcatechol, phenylenediamine, or a mixture thereof.

21. The process of any one of claims 1 to 20, further comprising separating from the first product a third product that is rich in tricyclopentadiene and lean in tetracyclopentadiene and a fourth product that is rich in tetracyclopentadiene and lean in tricyclopentadiene.

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