BR112019021037A2 - PROCESSES AND SYSTEMS FOR THE CONVERSION OF ACYCLIC HYDROCARBONS - Google Patents

Abstract

the present invention relates to processes and systems for converting acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons, for example, converting acyclic c5 hydrocarbons to cyclopentadiene in a reactor system. the process includes contacting a raw material comprising acyclic hydrocarbons with a catalyst material in at least one reaction zone to convert at least a portion of the acyclic hydrocarbons into a first effluent comprising alkenes, cyclic and / or aromatic hydrocarbons. a coalimentation comprising h2, c1-c4 alkanes and / or c1-c4 alkenes can also be provided for at least one reaction zone.

Description

Descriptive Report of the Invention Patent for PROCESSES AND SYSTEMS FOR THE CONVERSION OF ACYCLIC HYDROCARBONS.

PRIORITY CLAIM

[0001] This order claims priority to Serial Provisional Order No. 62 / 500,898, filed on May 3, 2017, and European Order No. 17181734.9, filed on July 17, 2017, the disclosures of which are incorporated into this document as of reference.

FIELD OF THE INVENTION

[0002] The present invention relates to reactor processes and systems for the conversion of acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons.

BACKGROUND OF THE INVENTION

[0003] Cyclic, alkenic and aromatic hydrocarbons such as cyclopentadiene (CPD) and its dicyclopentadiene dimer (DCPD), ethylene, propylene and benzene, are highly desired raw materials, used throughout the chemical industry in a wide range of products, for example, polymeric materials, polyester resins, synthetic rubbers, solvents, fuels, fuel additives, etc. These compounds are typically derived from various streams produced during the processing of the oil refinery. In particular, CPD is currently a minor by-product of steam cracking in liquid feed (eg naphtha and heavier feed). As existing and new steam cracking plants move to lighter feeds, less CPD is produced while demand for CPD is increasing. The high cost due to supply limitations affects the potential use of CPD in the final product in polymers. More CPD-based polymer products can be produced if additional CPD can be produced at unrestricted rates

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2/67 and preferably at a lower cost than steam cracking recovery. When producing CPD, co-production of other cyclic Cs compounds is also desirable. Cyclopentane and cyclopentene can have high value as solvents, while cyclopentene can be used as a comonomer to produce polymers and as a starting material for other high-value chemicals.

[0004] It would be advantageous to be able to produce such alkenes, aromatics and cyclic hydrocarbons, including CPD, propylene, ethylene and benzene, as the primary product of an abundant hydrocarbon feedstock. Specifically, when producing CPD, it is also desirable to minimize the production of light by-products (C4-). Although a raw material composed of less hydrogen content (for example, cyclic, alkenes and dialkenes) may be preferred because the reaction endotherm is reduced and thermodynamic restrictions on conversion are improved, unsaturated raw material is more expensive than the saturated raw material. The linear skeletal hydrocarbon structure is preferred over branched hydrocarbon skeletal structures due to the reaction chemistry and the lower linear hydrocarbon value compared to the branched hydrocarbon (due to octane differences). In addition, an abundance of hydrocarbons, such as Cs hydrocarbons, are available from unconventional gas and shale oil, in addition to reduced use in motor fuels due to strict environmental regulations. Various hydrocarbon raw materials, such as the raw material Cs, can also be derived from bio-feeders.

[0005] Currently, several catalytic dehydrogenation technologies are used to produce mono- and di-olefins from Cse C4 alkanes, but not cyclic mono-olefins or cyclic di-olefins. A common process uses Pt / Sn compatible alumina as the active catalyst. Another useful process uses chromium in the alumina. See, B. V. Vora, Must

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3/67 lopment of Dehydrogenation Catalysts and Processes, Topics in Catalysis, vol. 55, pp. 1297-1308, 2012; and J. C. Bricker, Advanced Catalytic Dehydrogenation Technologies for Production of Olefins, Topics in Catalysis, vol. 55, pp. 1309-1314, 2012.

[0006] Yet another common process uses Pt / Sn compatible in Zn and / or Ca aluminate to dehydrogenate propane. Although these processes are successful in dehydrogenating alkanes, they do not carry out cyclization, which is essential for the production of CPD. The Pt-Sn / alumina and Pt-Sn / aluminate catalysts exhibit a moderate conversion of n-pentane, but this catalyst has low selectivity and yield for cyclic Cs products.

[0007] Pt compatible in chlorinated alumina catalysts is used to reform low-octane naphtha into aromatics such as benzene and toluene. See, US 3,953,368 (Sinfelt), Polymetallic Cluster Compositions Useful as Hydrocarbon Conversion Catalysts. Although these catalysts are effective in dehydrogenating and cyclizing Cs and higher alkanes to form aromatic Cs rings, they are less effective in converting acyclic Css to cyclic Css. These Pt compatible in chlorinated alumina catalysts exhibit low cyclic Cs yields and exhibit deactivation in the first two hours of time in the stream. The cyclization of Ce and C? it is aided by the formation of an aromatic ring, which does not occur in Cs cyclization. This effect may be due in part to the much higher formation heat for CPD, a cyclic Cs, compared to benzene, a cyclic Ce and toluene, a C? cyclic. This is also displayed by Pt / lr and Pt / Sn compatible on chlorinated alumina. Although these alumina catalysts perform dehydrogenation and cyclization of Ce + species to form Ce aromatic rings, a different catalyst will be needed to convert acyclic Cs to cyclic Cs.

[0008] ZSM-5 catalysts containing Ga are used in a

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4/67 process to produce aromatics from light paraffins. A study by Kanazirev et a /, showed that n-pentane is easily converted to GazOs / H-ZSM-õ. See Kanazirev Price et al., Conversion of Cs aromatics and n-pentane over Ga2O3 / H-ZSM-5 mechanically mixed catalysts, Catalysis Letters, vol. 9, pp. 35-42, 1991. No cyclic Cs production has been reported, while more than 6% by weight of aromatics were produced at 440 ° C and 1.8 h ~ ¹ WHSV. It has also been shown that Mo / ZSM-5 catalysts dehydrogenate and / or cyclize paraffins, especially methane. See, Y. Xu, S. Liu, X. Guo, L. Wang, and M. Xie, Methane activation without using oxidants over Mo / HZSM-5 zeolite catalysts, Catalysis Letters, vol. 30, pp. 135-149, 1994. High conversion of n-pentane has been demonstrated using Mo / ZSM-5, without cyclic Cs production and high yield for cracking products. This shows that catalysts based on ZSM-5 can convert paraffins into a Ce ring, but not necessarily to produce a C5 ring.

[0009] US Patent No. 5,254,787 (Dessau) introduced the NU-87 catalyst used in the dehydrogenation of paraffins. This catalyst has been shown to dehydrogenate C2-C6 + to produce its unsaturated analogs. A distinction between C2-5 θ Ce + alkanes was made explicit in this patent: the dehydrogenation of C2-5 alkanes produced linear or branched mono-olefins or di-olefins, while the dehydrogenation of Ce + alkanes produced aromatics. US Patent No. 5,192,728 (Dessau) involves similar chemistry, but with a microporous crystalline material containing tin. As with the NU-87 catalyst, C5 dehydrogenation has been shown to produce only linear or branched mono-olefins or di-olefins and not CPD.

[0010] US Patent No. 5,284,986 (Dessau) introduced a double step process for the production of cyclopentane and cyclopentene from n-pentane. An example was conducted in which the first eta

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5/67 pa involved dehydrogenation and dehydrocyclization of n-pentane in a mixture of paraffins, mono-olefins and di-olefins and naphthenes over a Pt / Sn-ZSM ~ 5 catalyst. This mixture was then introduced in a second stage reactor consisting of Pd / Sn-ZSM-5 catalyst, where dienes, especially CPD, were converted to olefins and saturated. Cyclopentene was the desired product in this process, while CPD was an unwanted by-product.

[0011] US Patent No. 2,438,398; 2,438,399; 2,438,400; 2,438,401; 2,438,402; 2,438,403; and 2,438,404 (Kennedy) reported the production of CPD from 1,3-pentadiene over various catalysts. Low operating pressures, low conversion per pass and low selectivity make this process undesirable. In addition, the

1,3-pentadiene is not a readily available raw material, unlike n-pentane. See also, Kennedy et al., Formation of Cyclopentadiene from 1,3-Pentadiene, Industrial & Engineering Chemistry, vol. 42, pp. 547-552, 1950.

[0012] Fel’dblyum et al. in Cyclization and dehydrocyclization of Cs hydrocarbons over platinum nanocatalysts and in the presence of hydrogen sulfide, Doklady Chemistry, vol. 424, pp. 27-30, 2009, reported the production of CPD from 1,3 ~ pentadiene, n-pentene, and an n ~ pentane. CPD yields were as high as 53%, 35% and 21% for the conversion of 1,3-pentadiene, n-pentene and n-pentane, respectively, at 600 ° C to 2% Pt / SiOz. While the initial production of CPD was observed, a drastic deactivation of the catalyst was observed in the first minutes of the reaction. Experiments carried out on silica containing Pt show moderate conversion of n-pentane over Pt-Sn / SiOz, but with low selectivity and yield for cyclic C5 products. The use of HzS as a promoter of 1,3-pentadiene cyclization was presented by Fel’dblyum, infra as well as in Marcinkowski, Isomerization and Dehydrogenation of 1,3-Pentadiene,

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M.S., University of Central Florida, 1977. Marcinkowski showed 80% conversion of 1,3-pententene with 80% selectivity for CPD with H2S at 700 ° C. The high temperature, the limited raw material and the potential of products containing sulfur that would later need to be washed make this process undesirable.

[0013] López et al. in n-Pentane Hydroisomerization on Pt Containing HZSM-5, HBEA, and SAPO-11, Catalysis Letters, vol. 122, pp. 267-273, 2008, studied reactions of n-pentane in zeolites containing Pt including H-ZSM-5. At intermediate temperatures (250 ° C-400 ° C), they reported efficient hydroisomerization of n-pentane in Pt zeolites without discussing the formation of cyclopentene. It is desirable to avoid this deleterious chemistry, since branched C5 does not produce cyclic C5 as efficiently as linear C5, as discussed above.

[0014] Li et al. in Catalytic dehydroisomerization of n-alkanes to isoalkenes, Journal of Catalysis, vol. 255, pp. 134-137, 2008, also studied the dehydrogenation of n-pentane in zeolites containing Pt in which Al had been isomorphically replaced by Fe. These Pt / [Fe] ZSM-5 catalysts were efficient in dehydrogenation and isomerization of n-pentane , but under the reaction conditions used, no cyclic Cs were produced and undesirable skeletal isomerization occurred.

[0015] US patent No. 5,633,421 describes a process for dehydrogenating C2-C5 paraffins to obtain corresponding olefins. Likewise, US Patent No. 2,982,798 describes a process for dehydrogenating an aliphatic hydrocarbon containing from 3 to 6 inclusive of carbon atoms. However, neither US Patent No. 5,633,421 nor US Patent No. 2,982,798 disclose the production of CPD from acyclic C5 hydrocarbons, which are desirable as a raw material because they are abundant and inexpensive.

[0016] In addition, the specific production of CPD, propylene, ethyl

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7/67 in and benzene is carried out through endothermic reactions. The engineering process and design of the reactor for endothermic reactions driven by catalysts presents many challenges. For example, maintaining the high temperatures required for reactions, including transferring a large amount of heat to a catalyst, can be difficult. CPD production is especially difficult between endothermic processes because it is favored by low pressure and high temperature, but competing reactions, such as cracking of n-pentane and other Cs hydrocarbons, can occur at relatively low temperatures (for example, 450 ^o C ™ 500 ^o C)

[0017] Additional challenges may include loss of catalyst activity due to coking during the process and additional processing required to remove the catalyst coke, and the inability to use oxygen-containing gas to directly provide the heat input necessary to combat the endothermic nature reaction without damaging the catalyst. In addition, non-uniform aging of the catalyst can also occur, which can affect the selectivity of the resulting product and the service life of the catalyst.

[0018] In addition, there are challenges in the design of the reactor, especially with regard to the selection of material, since the reactions are carried out at higher temperatures and high carb conditions. Metal alloys can potentially be carburized (resulting in loss of mechanical properties), as well as metal powder (resulting in loss of metal by metastable carbide formation) under the desired reaction conditions. Thus, given the need for large heat input to drive the reaction, the metal heat transfer surfaces exposed to the reaction mixture need to be able to resist attacks by carburizing / metal powder.

[0019] Therefore, there remains a need for a process for

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8/67 converting acidic hydrocarbons to alkenes, cyclic and aromatic hydrocarbons, particularly acidic Cs hydrocarbons to CPD, preferably at commercial rates and conditions. In addition, a catalytic process directed to the production of CPD is required, which generates high-yield CPD from abundant Cs raw materials, without excessive production of C4 cracked products and with acceptable catalyst aging properties. In addition, there is a need for processes and systems for specific production of CPD, propylene, ethylene and benzene from acidic hydrocarbons, which meet the challenges described above.

SUMMARY OF THE INVENTION

[0020] In one aspect, this invention relates to a process for converting acidic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons in a reactor system, wherein the process comprises: contacting a raw material comprising acidic hydrocarbons and optionally hydrogen with a catalyst material in at least one reaction zone under reaction conditions to convert at least a portion of the acidic hydrocarbons into a first effluent comprising alkenes, cyclic and / or aromatic hydrocarbons, where the raw material enters at least least one reaction zone at a temperature of 300 ° C to 700 ° C; and providing a coalimentation comprising hydrogen, alkanes (for example, CrC4 alkanes) and / or alkenes (for example, C1-C4 alkenes) at a temperature of 600 ° C to 1100 ° C to heat at least one reaction zone, in which the raw material and the coalimentation are supplied to at least one reaction zone in different locations through different inlets. The raw material and the coalimentation can be supplied to at least one reaction zone simultaneously or not. Preferably, the raw material and the coalimentation are supplied to at least one reaction zone simultaneously.

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[0021] In another aspect, this invention also relates to a reaction system for converting acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons, wherein the reaction system comprises a raw material stream comprising acyclic hydrocarbons and optionally hydrogen with a temperature of 300 ° C to 700 ° C; a coalimentation stream comprising hydrogen, alkanes (for example, C1-C4 alkanes) and / or alkenes (for example, C1-C4 alkenes) with a temperature of 600 ° C to 1100 ° C; an effluent stream comprising alkenes, cyclic and / or aromatic hydrocarbons; a separate stream of catalyst material; and an effluent stream substantially free of catalyst; at least one reactor operated under reaction conditions to convert at least a portion of the acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons, wherein at least one reactor comprises: a raw material current input; a coil current input; a current inlet of catalyst material; and an effluent current outlet; and a separator for separating the catalyst material from the effluent stream to produce the separate catalyst material stream and the second effluent stream, wherein the separator is fluidly connected to 0 at least one reactor and comprises an inlet current input. effluent, a separate catalyst material stream outlet and a substantially catalyst-free stream outlet.

BRIEF DESCRIPTION OF THE FIGURES

[0022] The figure is a diagram of a reactor system according to an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0023] All numerical values contained in the detailed description and the claims in this document are modified by

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10/67 about or approximately the indicated value, and take into account the experimental error and variations that would be expected by a person skilled in the art. Unless otherwise stated, the ambient temperature is 23 ° C.

I. Definitions

[0024] To facilitate the understanding of the present invention, a number of terms and phrases are defined below.

[0025] As used in the present disclosure and claims, the singular forms one, one and a / o include the plural forms, unless the context clearly dictates otherwise.

[0026] The term e / or, as used in a sentence such as A and / or B in this document, is intended to include both A and B, A or B, A, eB.

[0027] As used in this document, the term about refers to a range of values of plus or minus 10% of a specified value. For example, the phrase 200 includes about 10% of 200 or 180 to 220.

[0028] The term hydrocarbon means a class of compounds that contain carbon-bound hydrogen and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated) , including mixtures of hydrocarbon compounds with different values of η. The term C _n means hydrocarbon (s) with n carbon atom (s) per molecule, where n is a positive integer.

[0029] As used herein, the term light hydrocarbon means paraffinic and / or light olefinic hydrocarbons comprising substantially only hydrogen and carbon and having one to no more than 4 carbon atoms.

[0030] The term saturated includes, but is not limited to, alkanes

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11/67 and cycloalkanes,

[0031] The term unsaturated includes, but is not limited to, alkenes, dialkenes, alkines, cycloalkenes and cyclo-dialkenes.

[0032] The term cyclic hydrocarbon denotes groups such as cyclopropane, cyclopropene, cyclobutane, cyclobutadiene etc., and substituted analogues of these structures. These cyclic hydrocarbons can be structures of one or more rings. Preferably, the term cyclic hydrocarbon refers to non-aromatics.

[0033] The term "cyclic Cs" or cCs includes, but is not limited to, cyclopentane, cyclopentene, cyclopentadiene and mixtures of two or more thereof. The term cyclic Cs or cC also includes alkylated analogs of any of the foregoing, for example, methyl cyclopentane, methyl cyclopentene and methyl cyclopentadiene. It should be recognized for the purposes of the invention that cyclopentadiene spontaneously dimerizes over time to form dicyclopentadiene through Diels-Alder condensation under various conditions, including ambient temperature and pressure.

[0034] The term acyclic includes, but is not limited to, linear and branched and unsaturated saturated.

[0035] The term alkane refers to saturated non-aromatic hydrocarbons with the general formula C _n H (2n +2), where n is 1 or greater. An alkane can be straight or branched. Examples of alkanes include, but are not limited to, methane, ethane, propane, butane, pentane, hexane, heptane and octane. Alkane is intended to cover all structural isomeric forms of an alkane. For example, butane includes n-butane and isobutane: pentane includes n-pentane, isopentane and neopentane.

[0036] The term alkene, alternatively called olefin, refers to a branched or unbranched unsaturated hydrocarbon with one or more carbon-carbon double bonds. Alken yes

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12/67 pies comprises the general formula CnH2n, where n is 2 or greater. Examples of alkenes include, but are not limited to, ethylene, propylene, butylene, pentene, hexene and heptene. Alkene is intended to cover all structural isomeric forms of an alkene. For example, butllene encompasses but-1-ene, (Z) -but-2-ene, etc.

[0037] The term aromatic means a planar cyclic hydrocarbil with conjugated double bonds, such as benzene. As used herein, the term aromatic encompasses compounds containing one or more aromatic rings, including, but not limited to, benzene, toluene and xylene and polynuclear aromatics (PNAs), which include naphthalene, anthracene, chrysene and their alkylated versions. The term Ce * aromatics includes compounds based on an aromatic ring with six or more ring atoms, including, but not limited to, benzene, toluene and xylene and polynuclear aromatics (PNAs), which include naphthalene, anthracene, chrysene and their alkylated versions .

[0038] The term BTX includes, but is not limited to, a mixture of benzene, toluene and xylene (ortho and / or meta and / or para).

[0039] The term coke ”includes, but is not limited to, a hydrocarbon of low hydrogen content which is adsorbed on the catalyst composition.

[0040] The term C _n + means hydrocarbon (s) with at least n carbon atom (s) per molecule.

[0041] The term Cn · means hydrocarbon (s) with no more than n carbon atom (s) per molecule.

[0042] The term Cs raw material includes a raw material containing n-pentane, as a raw material that is predominantly pentane and normal isopentane (also known as methylbutane), with minor fractions of cyclopentane and neopentane (also known as 2,2-dimethylpropane)

[0043] All numbers and references to the Periodic Table of

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Elements are based on the new notation established in Chemical and Engineering News, 63 (5), 27 (1985), unless otherwise specified.

[0044] The term group 10 metal means an element in group 10 of the periodic table and includes, but is not limited to, Ni, Pd and Pt, and a mixture of two or more of them.

[0045] The term metal of Group 11 means an element of Group 11 of the Periodic Table and includes, among others, Cu, Ag, Au and a mixture of two or more of them.

[0046] The term alkali metal in group 1 means an element in group 1 of the periodic table and includes, but is not limited to, Li, Na, K, Rb, Cs and a mixture of two or more of them, and excludes hydrogen.

[0047] The term alkaline earth metal in group 2 means an element in group 2 of the periodic table and includes, among others, Be, Mg, Ca, Sr, Ba and a mixture of two or more of them.

[0048] The term rare earth metal means an element of the Lanthanide series of the Periodic Table, in addition to scandium and yttrium. The term rare earth metal includes, but is not limited to, lanthanum, praseodymium, neodymium, cerium, yttrium and a mixture of two or more of these.

[0049] The term oxygen includes air, O2, H2O, CO and CO2.

[0050] The term constraint index is defined in US 3,972,832 and US 4,016,218, both of which are incorporated herein by reference.

[0051] As used herein, the term molecular sieve of the MCM-22 family (or material of the MCM-22 family or material of the MCM-22 family or zeolite of the MCM-22 family) includes one or more of:

[0052] molecular sieves made from a unit cell of a first-grade crystalline building block, whose unit cell has the MVWV topology structure. (A unit cell is an arrangement

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14/67 space of the atoms, which if arranged in a three-dimensional space describe the structure of the crystal. Such crystalline structures are discussed in Atlas of Zeolite Framework Types, fifth edition, 2001, all of their content being incorporated into this document as a reference);

[0053] molecular sieves made from a common second degree building block, being a two-dimensional coating of such unit cells of structure of the MWW topology, forming a monolayer with the thickness of a unit cell, preferably the thickness of a cell unit c;

[0054] molecular sieves made of common second-degree building blocks, layers with thickness of one or more of a unit cell, in which the layer with thickness of more than one unit cell is made by stacking, packaging or bonding at least two monolayers with the thickness of a unit cell. These second degree building blocks can be stacked regularly, irregularly, randomly, or any combination thereof; and

[0055] molecular sieves made from a regular or random two or three dimensional combination of unit cells with the MWW structure topology.

[0056] The MCM-22 family includes those molecular sieves that have an X-ray diffraction pattern including maximum spacing d at 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07 and 3.42 ± 0.07 Angstrom. The X-ray diffraction data used to characterize the material are obtained by conventional techniques using the copper Kalfa doublet as the incident radiation and a diffractometer equipped with a scintillation counter and an associated computer as the collection system.

[0057] As used in this document, the term sieve

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Molecular 15/67 is used as a synonym for the term microporous crystalline material or zeolite.

[0058] As used in this document, the term selectivity means the carbon masses in the respective cyclic C5, CPD, Ci and C2-4 formed divided by the total carbon masses in the converted pentane. For example, the term carbon selectivity for cyclic C5 of at least 30% means that at least 30 volts of carbon in cyclic C5 are formed by 100 volts of carbon in the converted pentane.

[0059] As used herein, the term conversion means the carbon cores in the acyclic C5 raw material which is converted into a product. The phrase a conversion of at least 70% of said acyclic raw material into said product means that at least 70% of the cores of said acyclic raw material have been converted into a product.

[0060] As used herein, the Alpha value is a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 3,354,078 and in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966) and Vol. 61, p. 395 (1980), each incorporated by reference in this document. The experimental conditions of the test used in this document included a constant temperature of 538 ° C and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, p. 395 (1980).

[0061] As used herein, the term reactor system refers to a system that includes one or more reactors and all necessary and optional equipment used in the production of cyclopentadiene.

[0062] As used herein, the term reactor refers to any tank (s) in which a chemical reaction occurs. The reactor includes two distinct reactors, as well as reaction zones within

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16/67 a single reactor and, as applicable, reaction zones in several reactors. In other words, and as is common, a single reactor can have multiple reaction zones. Where the description refers to a first and a second reactor, the person skilled in the art will readily recognize that reference includes two reactors, as well as a single reactor tank having first and second reaction zones. Likewise, a first reactor effluent and a second reactor effluent will be recognized to include the effluent from the first reaction zone and the second reaction zone from a single reactor, respectively.

[0063] A reactor / reaction zone can be an adiabatic reactor / reaction zone (a) or a diabetic reactor / reaction zone (a). As used in this document, the term adiabatic refers to a reaction zone to which there is essentially no entry of heat into the system, except for a flowing process fluid. A reaction zone that has inevitable losses due to conduction and / or radiation can also be considered adiabatic for the purposes of this invention. As used herein, the term diabetic refers to a reactor / reaction zone to which heat is supplied by means other than that provided by the flowing process fluid.

[0064] As used herein, the term moving bed reactor refers to a zone or tank with contact of solids (eg, catalyst particles) and gas flows, so that the surface velocity of the gas (U ) is below the speed required for pneumatic transport in diluted solid particles to maintain a solid bed with a void fraction below 95%. In a moving bed reactor, solids (eg, catalyst material) can travel slowly through the reactor and can be removed from the bottom of the reactor and added to the top of the reactor. A movable bed reactor can operate under various flow regimes, including the one established in Petition 870190100185, of 10/07/2019, p. 34/91

17/67 cement or packaged bed regime (LJ <Umf), bubbly regime (Umf <U <Umb) _! aggregative fiuidization regime (Umb <U <U _c ), transition to turbulent e fiuidization regime (U _c <U <Utr), and rapid fluidization regime (U> Utr), where Umf is the minimum fiuidization speed, Umb is the minimum bubble speed, Uc is the speed at which the pressure fluctuation reaches its maximum, and tr is the transport speed. These different fluidizing regimes are described in, for example, Kunii, D. Levenspiel, O., Chapter 3 of Fluidization Engineering, 2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, SM, Chapter 6 Chemical Process Equipment 2 ^to Revised Edition, Butterworth-Heinemann, Boston, 2010, which are incorporated by reference.

[0065] As used in this document, the term sedimentation bed reactor refers to a zone or tank where the particles come into contact with the gas flows, so that the surface velocity of the gas (U) is below of the minimum speed required to fluidize the solid particles (eg, catalyst particles), the minimum fluidization speed (Umf), U <U _m f, is at least a portion of the reaction zone, and / or operating at a speed higher than the minimum flow rate while maintaining a gradient in the properties of the gas and / or solid (such as temperature, composition of the solid or gas, etc.) axially above the reactor bed using internal parts of the reactor to minimize mixing by gas and solids reflux description of the minimum fluidizing velocity is given, for example, Kunii, D. Levenspiel, O., Chapter 3 of Fluidization Engineering, 2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, SM, Chapter 6 of Chemical Process Equipment, 2nd Revised Edition, Butterworth-Heinemann, Boston, 2010. A settling bed reactor can be a circulating bed reactor settling, which refers to a settling bed with a motion

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18/67 solids (eg, catalyst material) through the reactor and at least a partial recirculation of the solids (eg, catalyst material). For example, solids (eg, catalyst material) may have been removed from the reactor, regenerated, reheated and / or separated from the product stream and then returned to the reactor.

[0066] As used herein, the term fluidized bed reactor refers to a zone or tank with contact of solids (eg, catalyst particles) and gas flows, so that the surface velocity of the gas (U ) is sufficient to fluidize solid particles (ie above the minimum fluidization speed Umf) and is below the speed required for pneumatic conveying in diluted solid particles in order to maintain a solid bed with a void fraction below 95%. As used herein, the term cascading fluid beds means a series arrangement of individual fluid beds, so that there may be a gradient in the property of gas and / or solid (such as temperature, composition of the solid or gas, pressure , etc.) like the solid or gas cascading from one fluid bed to another. The description of the minimum fluidization velocity is given, for example, in Kunii, D, Levenspiel, O., Chapter 3 of Fluidization Engineering, 2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, SM, Chapter 6 Chemical Process Equipment, 2nd Revised Edition, Butterworth-Heinemann, Boston, 2010. a fluidized bed reactor can be a fluidized bed reactor in motion, as a circulating fluidized bed reactor, which relates to a fluidized bed of solids movement (eg, catalyst material) through the reactor and at least a partial recirculation of the solids (eg, catalyst material). For example, solids (eg, catalyst material) may have been removed from the reactor, regenerated, reheated, and / or separated from the product stream.

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19/67 duct and then returned to the reactor. In addition, a fluidized bed reactor can be a captive fluidized bed reactor in which solids (eg, catalyst material) can circulate between the reaction zones, but do not circulate, on a continuous flow basis, between the reactor and a separate tank (for example, for reheating and / or regeneration). Solids (eg, catalyst material) can be removed from the reactor and returned (along with any addition of fresh solids) to the reactor after batch regeneration carried out in a separate tank. In addition, the presence of an external cyclone (or any similar device to separate solids from the reactor effluent stream) and its vertical return tube is considered part of the captive fluidized bed reactor, that is, it does not constitute a separate tank with the purpose of defining a captive fluidized bed reactor.

[0067] As used in this document, the term “riser reactor” (also known as a transport reactor) refers to a zone or tank (as a vertical cylindrical tube) used for transporting upwards of solids (for example, catalyst particles) in rapid fluidization or pneumatic conveying fluidization regimes. The rapid fluidization and pneumatic transport fluidization regimes are characterized by surface gas velocities (U) greater than the transport speed (Utr). The fast fluidization regimes and pneumatic conveying fluidization are also described in Kunii, D, Levenspiel, O., Chapter 3 of Fluidization Engineering, 2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, SM, Chapter 6 Chemical Process Equipment, 2nd Revised Edition, Butterworth-Heinemann, Boston, 2010. a fluidized bed reactor as a circulating fluidized bed reactor can be operated as a riser reactor. The particle diameter for particles in the range 1 to 3500 pm is determined using a Mastersizer ™ 3000 available from Mal

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20/67 comes Instruments, Ltd., Worcestershire, England. Unless otherwise specified, the particle size is determined in D50. D50 is the value of the particle diameter at 50% in the cumulative distribution. For example, if 050 = 5.8 µm, then 50% of the particles in the sample are equal to or greater than 5.8 µm and 50% are less than 5.8 µm. (On the other hand, if D90-5.8 µm, 10% of the particles in the sample are greater than 5.8 µm and 90% are less than 5.8 µm.) The average diameter for particles in the range of 3 mm to 50 µm mm is determined using a micrometer on a representative sample of 100 particles.

[0068] For the purposes of the invention, 1 psi is equivalent to 6,895 kPa. In particular, 1 psia is equivalent to 1 kPa absolute (kPa-a). Likewise, 1 psig is equivalent to 6,895 kPa gauge (kPa-g).

II. Conversion process of acyclic hydrocarbons

[0069] In a first aspect, this invention relates to a process for converting acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons in a reactor system. The process may comprise contacting a raw material comprising acyclic hydrocarbons and optionally hydrogen with a catalyst material in at least one reaction zone under reaction conditions to convert at least a portion of the acyclic hydrocarbons into a first effluent comprising alkenes, hydrocarbons cyclic and / or aromatic and provide a coalimentation comprising hydrogen, alkanes (for example, C1-C4 alkanes) and / or alkenes (for example, C1-C4 alkenes) at a temperature of 600 ° C to 1100 ° C to heat the at least one reaction zone. In many respects, the raw material enters at least one reaction zone at a temperature of 300 ° C to 700 ° C. In addition, raw material and coalimentation can be supplied to at least one reaction zone at different locations, through different inlets.

[0070] In one or more embodiments, this invention refers to

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21/67 a process for converting an acyclic Cs raw material into a product comprising cyclic Cs compounds (e.g., cyclopentadiene). The process comprises contacting said raw material and, optionally, hydrogen under conditions of conversion of acyclic Cs in the presence of one or more catalyst compositions, including, but not limited to, the catalyst compositions described in this document, and providing a coalimentation as described in this document to form said product.

[0071] In one or more embodiments, the product of the process for converting an acyclic C5 raw material comprises cyclic C5 compounds. Cyclic C5 compounds comprise one or more of cyclopentane, cyclopentene, cyclopentadiene and include mixtures thereof. In one or more embodiments, the cyclic C5 compounds comprise at least 20% by weight, or 30% by weight, or 40% by weight, or 70% by weight of cyclopentadiene, or in the range of 10% by weight to 80% by weight. weight, alternatively 20% by weight to 70% by weight.

[0072] In one or more embodiments, the acyclic conversion conditions of C5 include at least one temperature, a partial pressure of n-pentane and an hourly space velocity by weight (WHSV). The temperature is in the range of 400 ° C to 700 ° C, or in the range of 450 ° C to 650 ° C, preferably in the range of 500 ° C to 600 ° C. The partial pressure of n-pentane is in the range of 3 to 100 psia at the reactor inlet, or in the range of 3 to 50 psia, preferably in the range of 3 psia to 20 psia. The hourly space speed in weight is in the range of 1 to 50 h ' ¹ , or in the range of 1 to 20 h ¹ . Such conditions include a molar ratio of the optional hydrogen coalimentation to the acyclic raw material C5 in the range 0 to 3 or in the range 1 to 2. Such conditions may also include the coalescence of Cr C4 hydrocarbons with the acyclic C5 feed.

[0073] In one or more embodiments, this invention refers to

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22/67 a process for converting n-pentane to cycopentadiene comprising the steps of contacting n-pentane and, optionally, hydrogen (if present, Hz is typically present in the npentane ratio of 0.01 to 3.0) with one or more catalyst compositions, including but not limited to the catalyst compositions described herein, and providing a coalimentation as described herein to form cytopopadiene at a temperature of 400 ° C to 700 ° C, a partial pressure of n-pentane of 3 to 100 psia at the reactor inlet and an hourly space speed of 1 to 50 It ¹ .

A. Raw material and coalimentation

[0074] In the process, a raw material comprising additive hydrocarbons, preferably C2-C10 acyclic hydrocarbons, is supplied to a reactor system comprising a catalyst material and an inert material. C2-C10 acyclic hydrocarbons include, but are not limited to, alkanes (e.g., ethane, propane, butane, pentane, hexane, etc.), alkenes (e.g., ethylene, propylene, butylene, etc.), alkanes ( e.g., ethino, propine, 1-butino, 2-butine, etc.), dialkenes (e.g., 1,2-propadiene, 1,3-butadiene,

1,3-pentadiene, etc.) and combinations thereof. A Cs-Cwaciclica hydrocarbon raw material, useful in this document, is obtained from crude oil or natural gas condensate. Optionally, hydrogen can also be present in the raw material. The molar ratio of optional hydrogen to acyclic hydrocarbon is preferably between 0 and 3, or in the range of 1 to 2. Hydrogen can be included in the raw material to minimize the production of coke material in the particulate material and / or to fluidize 0 particulate material in at least one reaction zone.

[0075] Preferably, in one or more embodiments, the acidic C5 raw material comprises at least 50% by weight, or 60% by weight.

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23/67 weight, or 75% by weight, or 90% by weight of acyclic hydrocarbons, or in the range of 50% by weight to 100% by weight of n-pentane. Preferably, an amount of acyclic hydrocarbons in the raw material converted to alkenes (eg, propylene), cyclic hydrocarbons (eg, cyclopentadiene) and / or aromatics (eg, benzene) is> 5.0% by weight,> 10 , 0% by weight,> 20.0% by weight,> 30.0% by weight,> 40.0% by weight,> 50.0% by weight,> 60.0% by weight,> 70.0 % by weight,> 80.0% by weight or> 90.0% by weight.

[0076] In several respects, the raw material may preferably be an acyclic Cs raw material and may include cracked Cs (in varying degrees of unsaturation: alkenes, dialcenes, alkines) produced by refining and chemical processes, such as fluid catalytic cracking ( FCC), reform, hydrocracking, hydrotreating, coking and steam cracking.

[0077] In one or more embodiments, the acyclic raw material useful in the process of this invention comprises pentane, pentene, pentadiene and mixtures of two or more thereof. Preferably, in one or more embodiments, the acyclic raw material Cs comprises at least 50% by weight, or 60% by weight, or 75% by weight, or 90% by weight of n-pentane, or in the range of 50% by weight to 100% by weight of n-pentane.

[0078] The acyclic hydrocarbon raw material optionally does not comprise aromatic Ce compounds, such as benzene. Preferably, the aromatic compounds Cs are present in less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight and preferably in 0% by weight. Alternatively, or even, the acyclic hydrocarbon raw material optionally does not comprise benzene, toluene or xylene (ortho, meta or para). Preferably, any benzene, toluene or xylene compounds (ortho, meta or para) are present in less than 5%

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24/67 by weight, preferably less than 1% by weight, preferably less than 0.01% by weight and preferably 0% by weight.

[0079] The acyclic hydrocarbon raw material optionally does not comprise aromatic compounds Ce +. Preferably, the Ce + aromatic compounds are present in less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight and preferably 0% by weight.

[0080] Preferably, an amount of Cs hydrocarbons (for example, Cs acyclic hydrocarbons) in the raw material converted to cyclopentadiene is> 5.0% by weight,> 10.0% by weight,> 20.0% by weight, > 30.0% by weight,> 40.0% by weight,> 50.0% by weight,> 60.0% by weight,> 70.0% by weight,> 80.0% by weight, or> 90 , 0% by weight. Preferably, at least 30.0% by weight or at least 60.0% by weight of the Cs hydrocarbons (e.g., Cs acyclic hydrocarbons) are converted to cyclopentadiene. The ranges expressly disclosed include combinations of any of the values listed above; for example, 5.0% to 90.0% by weight, 10.0% by weight to 80.0% by weight, 20.0% by weight to 70.0% by weight, 20.0% by weight to 60.0% by weight, etc. Preferably, 20.0% by weight to 90.0% by weight of the Cs hydrocarbons (e.g., acyclic Cs hydrocarbons) are converted to cyclopentadiene, more preferably 30.0% by weight to 85.0% by weight, more preferably 40.0% by weight to 80.0% by weight, more preferably 45.0% by weight to 75.0% by weight, and more preferably 50.0% by weight to 70.0% by weight.

[0081] In several aspects, a coalimentation comprising hydrogen and / or light hydrocarbons, such as CiCs hydrocarbons, preferably C1-C4 hydrocarbons, such as C1-C4 alkenes and / or C1-C4 alkanes, is fed into at least one reaction zone (discussed in this document). In one or more modalities, the coa

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The limitation comprises at least 50% by weight, or 60% by weight, or 75% by weight, or 90% by weight of hydrogen, or in the range of 50% by weight to 100% by weight of hydrogen. In one or more embodiments, the coalimentation comprises at least 50% by weight, or 60% by weight, or 75% by weight, or 90% by weight of light hydrocarbons, or in the range of 50% by weight to 100% by weight of light hydrocarbons. In a particular embodiment, the combined feed may comprise hydrogen, ethane, methane and / or a mixture of ethane and ethylene. Preferably, the raw material and coalimentation are substantially oxygen-free, for example, less than 1.0% by weight, less than 0.1% by weight, less than 0.01% by weight, less than 0.001% by weight, less than 0.0001% by weight, less than 0.00001% by weight, etc. The raw material and the coalimentation can also be supplied to at least one reaction zone simultaneously or not, preferably simultaneously. It is contemplated in this document that coalimentation and raw material are provided for at least one reaction zone in different horizontal and / or vertical planes. For example, coalimentation can be supplied to at least one reaction zone at a lower position in the at least one reaction zone in relation to the location where the raw material is supplied, that is, the raw material can be supplied to at least minus a zone reaction in a position above (or greater than) where coalimentation is provided. In such cases, the coalimentation and the raw material can be supplied for at least one reaction zone in different horizontal planes, preferably when the coalimentation is supplied in a horizontal plane in a lower position in the at least one reaction zone with in with respect to the horizontal plane in which the raw material is supplied and, optionally, the coalimentation and the raw material can be supplied along the same or a different vertical plane. Alternatively, coalimentation can be

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26/67 supplied to at least one reaction zone in a position above (or higher than) where the raw material is supplied in at least one reaction zone. In such cases, the coalimentation and the raw material can be supplied for at least one reaction zone in different horizontal planes, preferably when the coalimentation is provided in a horizontal plane above (or greater than) a horizontal plane in which the raw material is supplied and, optionally, coalimentation and raw material can be supplied along the same or a different vertical plane. In addition, it is contemplated in this document that raw material and coalimentation can be provided for at least one reaction zone at substantially the same locations through the same or different entrance. Hydrogen can be supplied to the reactor through raw material, coalimentation or a combination of both. Preferably, hydrogen is included both in the raw material and in the coalimentation. The presence of hydrogen in the feed mixture at or near the entry site, where the feed first comes into contact with the catalyst, can prevent or reduce the formation of coke in the catalyst particles. In addition, the presence of hydrogen in the coalimentation can prevent or reduce the formation of coke in the coalimentation preheating furnaces.

B. Reaction zone

[0082] The raw material is fed into a reactor system and brought into contact with a catalyst material in at least one reaction zone under reaction conditions to convert at least a portion of the acyclic hydrocarbons (eg, acyclic hydrocarbons Cs ) in a first effluent comprising alkenes (for example, propylene), cyclic hydrocarbons (for example, cyclopentadiene) and / or aromatics (for example, benzene). For example, the at least one reaction zone can be a cir fluidized bed reactor

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27/67 or a captive fluidized bed reactor. The circulating fluidized bed reactor can be operated in a bubbling or turbulent fluidization regime; and fast fluidization regime or transport, both as described in Kunii, D, Levenspiel, O., Fluidization Engineering Chapter 3, 2 ^to Edlção, Butterworth-Heinemann, Boston, 1991 and Walas, SM, Chapter 6 Chemical Process Equipment , 2nd Revised Edition, Butterworth-Heinemann, Boston, 2010. Alternatively, or in at least one reaction zone is not a radial flow reactor or a cross-flow reactor.

[0083] In addition, or alternatively, at least one reaction zone may comprise at least one first reaction zone, a second reaction zone, a third reaction zone, a fourth reaction zone, a fifth reaction zone reaction zone, a sixth reaction zone, a seventh reaction zone, and / or an eighth reaction zone, etc. As understood in this document, each reaction zone can be an individual reactor or a reactor can comprise one or more of the reaction zones. Preferably, the reactor system includes from 1 to 20 reaction zones, more preferably 1 to 15 reaction zones, more preferably 2 to 10 reaction zones, most preferably 2 to 8 reaction zones. Where the at least one reaction zone includes a first and a second reaction zone, the reaction zones can be arranged in any suitable configuration, preferably in series. Each reaction zone can independently be a circulating fluidized bed or a captive fluidized bed, preferably each reaction zone is a captive fluidized bed. Alternatively, or even, the process described in this document may further comprise moving a mass of a raw material partially converted from the first reaction zone to the second reaction zone and / or moving a mass of particulate material (for example , catalyst material and / or material

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28/67 inert) from the second reaction zone to the first reaction zone. As used herein, mass refers to at least a majority portion of the partially converted raw material and particulate material, for example, portions of at least 50.0% by weight, at least 60.0% by weight, at least 70.0% by weight, at least 80.0% by weight, at least 90.0% by weight, at least 95.0% by weight, at least 99.0% by weight and 100.0% by weight Weight.

[0084] Preferably, the at least one reaction zone can include at least one internal structure, preferably a plurality of internal structures (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, etc.) to influence a velocity vector of the particulate material and / or gas flow. In addition, the internal structure (s) can guarantee the movement of the particulate material, minimizing the degree of gas reflux mixing. In particular, the at least one reaction zone can include a plurality of internal structures. Examples of suitable internal structures include a plurality of baffles, baffles, trays, tubes, tube bundles, tube coils, rods and / or dispensers.

[0085] At least one reaction zone is operated under reaction conditions sufficient to convert at least a portion of the raw material of acidic hydrocarbons, preferably acidic Cs hydrocarbons, into a first effluent comprising alkene, cyclic and aromatic hydrocarbons, preferably cyclopentadiene . Preferably, the raw material (for example, acidic hydrocarbons) and / or coalimentation can be fed to the reaction system at an hourly space weight speed (WHSV, mass of acyclic hydrocarbons / mass of catalyst / hour) in the range of 1 , 0 to 1000.0 h ' ¹ . WHSV can be 1.0 to 900.0 h ¹ , 1.0 to 800.0 h ' ¹ , 1.0 to 700.0 h' ¹ , 1.0 to 600.0 h ' ¹ , 1.0 at 500.0 h \ 1.0 to 400.0 h ' ¹ , 1.0 to 300.0 h' ¹ , 1.0 to 200.0 h ' ¹ , 1.0 to 100.0 It ¹ , 1 , 0 to 90.0 h ' ¹ , 1.0 to 80.0 h'

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29/67 ¹ , 1.0 to 70.0 It ¹ , 1.0 to 60.0 h ' ¹ , 1.0 to 50.0 h' ¹ , 1.0 to 40.0 It ¹ , 1.0 to 30.0 It ¹ , 1.0 to 20.0 It ¹ , 1.0 to 10.0 h ' ¹ , 1.0 to 5.0 It ¹ , 2.0 to 1000.0 h' ¹ , 2 , 0 to 900.0 h ' ¹ , 2.0 to 800.0 h' ¹ , 2.0 to 700.0 h ¹ , 2.0 to 600.0 h ' ¹ , 2.0 to 500.0 h '\ 2.0 to 400.0 h' ¹ , 2.0 to 300.0 h ' ¹ , 2.0 to 200.0 h' ¹ , 2.0 to 100.0 h ' ¹ , 2.0 to 90.0 h ¹ , 2.0 to 80.0 h ' ¹ , 2.0 to 70.0 h ¹ , 2.0 to 60.0 h' ¹ , 2.0 to 50.0 h ¹ , 2, 0 to 40.0 It ¹ , 2.0 to 30.0 h “ ¹ , 2.0 to 20.0 It ¹ , 2.0 to 10.0 h ¹ , and 2.0 to 5.0 h ¹ . Preferably, the WHSV is 1.0 to 100.0 h ^{_ 1} , more preferably 1.0 to 60.0 h ' ¹ , more preferably 2.0 to 40.0 h' ¹ , more preferably 2.0 to 20, 0 h ¹ .

[0086] As discussed above, the objective production of CPD, propylene, ethylene and benzene is carried out through endothermic reactions, which present several challenges, such as maintaining the high temperatures necessary for the reactions, including the transfer of a large amount heat to a catalyst. Advantageously, by preheating the coalimentation by any suitable means, for example, an oven, such as a driven tube oven, the heated coalimentation can provide the endothermic heat of the reaction for the conversion process within at least one reaction zone. In several respects, the coalimentation can come in contact with the catalyst present in at least one reaction zone and heat the catalyst, for example, where the coalimentation is supplied to the at least one reaction zone in a lower position than where the raw material is supplied. Thus, as the raw material is supplied to at least one reaction zone, the raw material can come in contact with the heated catalyst and at least a portion of the acyclic hydrocarbons can be converted into alkenes, cyclic and / or aromatic hydrocarbons . The direct mixing or contact of the heated coalimentation and the acyclic raw material, if both were fed using the same input from the reactor zone, would result in excessive thermal cracking of acyclic hydrocarbons and

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30/67 mation of non-selective light gases (C1-C4).

[0087] In particular, the coalimentation provided with at least one reaction can provide> 10%,> 20%,> 25%,> 30%,> 35%,> 40%> 45%,> 50%,> 55% ,> 60%,> 65%,> 70%,> 75%,> 80%,> 85%,> 90%,> 95% or 100% of the heat required to convert at least a portion of the acyclic hydrocarbons into the first effluent comprising alkenes, cyclic and / or aromatic hydrocarbons, particularly converting acyclic Cs hydrocarbons to cyclopentadiene. In particular, coalimentation can provide> 25% of the heat required to convert at least a portion of the acyclic Cs hydrocarbons into the first effluent comprising cyclopentadiene. The ranges expressly disclosed include combinations of any of the values listed above; for example, 20% to 100%, 40% to 95%, 50% to 90%, etc. Preferably, the coalimentation can provide 20% to 100% of the required heat, more preferably 40% to 100% of the required heat, or more preferably 50% to 100% of the required heat.

[0088] In several respects, after heating, coalimentation can enter at least one reaction zone at a temperature of> 450 ° C,> 500 ° C,> 550 ° C,> 600 ° C,> 650 ° C ,> 700 ° C,> 750 ° C,> 800 ° C,> 850 ° C,> 900 ° C,> 950 ° C,> 1000 ° C,> 1050 ° C,> 1100 ° C,> 1150 ° C , £ 1200 ° C,> 1250 ° C,> or 1300 ° C. Preferably, the coalimentation can enter at least one reaction zone at a temperature of> 600 ° C, more preferably> 750 ° C, or more preferably> 900 ° C. The temperature ranges expressly disclosed include combinations of any of the values listed above, for example, 450 ° C to 1500 ° C, 550 ° C to 1400 ° C, 600 ° C to 1250 ° C, 700 ° C to 1150 ° C , etc. Preferably, the temperature of the coaliment entering the reaction system is 550 ° C to 1150 ° C, more preferably 600 ° C to 1100 ° C, more preferably

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31/67

650 ° C to 1050 ° C, and more preferably 700 ° C to 1000 ° C.

[0089] Thus, the raw material can be heated to a lower temperature than coalification, to prevent cracking in the feed and coking of the catalyst. Thus, the temperature of the raw material (for example, acyclic hydrocarbons) entering the reactor system at a raw material inlet can be <750 ° C, <725 ° C, <700 ° C, <675 ° C, <650 ° C, <625 ° C, <600 ° C, <575 ° C, <550 ° C, <525 ° C, <500 ° C, <475 ° C, <450 ° C, <425 ° C, <400 ° C, <375 ° C, <350 ° C, <325 ° C, <or 300 ° C. Preferably, the temperature of the raw material (e.g., acyclic hydrocarbons) entering the reactor system is <700 ° C, more preferably <650 ° C, or more preferably <625 ° C. The temperature ranges expressly disclosed include combinations of any of the values listed above, for example, 300 ° C to 750 ° C, 350 ° C to 700 ° C, 450 ° C to 650 ° C, 475 ° C to 600 ° C , etc. Preferably, the temperature of the raw material (for example, acyclic hydrocarbons) entering the reaction system is 300 ° C to 750 ° C, more preferably 300 ° C to 700 ° C, more preferably 400 ° C to 700 ° C and more preferably 575 ° C to 675 ° C. Supplying the raw material (e.g., acyclic C hydrocarbons) at the temperatures described above can advantageously minimize the undesirable cracking of Cs hydrocarbons (e.g., acyclic C hydrocarbons) before they can react in the presence of the catalyst material. The raw material can be heated by any suitable means, for example, an oven, such as a tube driven oven and / or heat exchanger, before entering at least one reaction zone.

[0090] In addition, it may be preferable that an isothermal or substantially isothermal temperature profile is maintained in at least one reaction zone. A substantially isothermal temperature profile has the advantages of maximizing the efficient use of ca

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32/67 and minimize the production of undesirable C4 by-products. As used in this document, isothermal temperature profile means that the temperature at each point within the reaction zone between the reactor inlet and outlet, measured along the center line of the reactor tube, is kept essentially constant, for example, at the same temperature or within the same narrow temperature range where the difference between a higher temperature and a lower temperature is not more than 40 ° C; more preferably not more than 20 ° C. Preferably, the isothermal temperature profile is one where the temperature along the length of the reaction zone (s) inside the reactor does not vary by more than 40 ° C compared to the average temperature inside the reactor, alternately, not higher than 20 ° C, alternately, not exceeding 10 ° C, alternately, not exceeding 5 ° C. Alternatively, the isothermal temperature profile is one where the temperature along the length of the reaction zone (s) inside the reactor is within 20% of the average temperature inside the reactor, alternately within 10%, alternately within 5%, alternately within 1% of the average temperature inside the reactor.

[0091] In addition, the temperature of a first effluent leaving at least one reaction zone at an effluent outlet can be> 400 ° C,> 425 ° C,> 450 ° C,> 475 ° C,> 500 ° C,> 525 ° C,> 550 ° C,> 575 ° C,> 600 ° C,> 625 ° C,> 650 ° C,> 675 ° C or> 700 ° C. Preferably, the temperature of a first effluent leaving at least one reaction zone is> 550 ° C, more preferably> 575 ° C, more preferably> 600 ° C. The temperature ranges expressly disclosed include combinations of any of the values listed above, for example, 400 ° C to 700 ° C, 475 ° C to 675 ° C, 525 ° C to 650 ° C, 550 ° C to 600 ° C , etc. Preferably, the temperature of a first effluent that leaves the at least one reaction zone is

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33/67

475 ° C to 700 ° C, more preferably 500 ° C to 650 ° C, more preferably 550 ° C to 625 ° C.

[0092] In addition, or alternatively, the reaction conditions in at least one reaction zone may include a temperature of> 300 ° C,> 325 ° C,> 350 ° C,> 375 ° C,> 400 ° C,> 425 ° C,> 450 ° C,> 475 ° C,> 500 ° C,> 525 ° C,> 550 ° C,> 575 ° C,> 600 ° C> 625 ° C,> 650 ° C ,> 675 ° C or> 700 ° C. The temperature ranges expressly disclosed include combinations of any of the values listed above, for example, 300 ° C to 700 ° C, 350 ° C to 675 ° C and 400 ° C to 700 ° C, etc. Preferably, the temperature can be from 350 ° C to 700 ° C, more preferably 500 ° C to 700 ° C, or more preferably 500 ° C to 650 ° C. Optionally, the at least one reaction zone can include one or more means for heating at least one reaction zone in order to maintain a temperature therein. Examples of suitable heating means known in the art include, but are not limited to, a driven tube, heat transfer tubes, a coil heated with a high temperature heat transfer fluid, an electric heater and / or an emitter. microwave. As used in this document, coil refers to a structure placed inside a tank through which a heat transfer fluid flows to transfer heat to the contents of the tank. A coil can have any suitable cross-sectional shape and can be straight, include U-folds, include loops, etc.

[0093] In addition, or alternatively, the reaction conditions at the effluent outlet of at least one reaction zone may include a pressure of> 1.0 psia,> 2.0 psia,> 3.0 psia,> 4.0 psia,> 5.0 psia,> 10.0 psia,> 15.0 psia,> 20.0 psia,> 25.0 psia,> 30.0 psia,> 35.0 psia,> 40, 0 psia,> 45.0 psia,> 50.0 psia,> 55.0 psia,> 60.0 psia,> 65.0 psia,> 70.0 psia,> 75.0 psia,> 80.0 psia ,> 85.0 psia,> 90.0 psia,> 95.0 psia,> 100.0 psia,> 125.0 psia,> 150.0 psia,> 175.0

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34/67 psia or 200 psia. Temperature and pressure ranges and combinations disclosed expressly include combinations of any of the values listed above, for example, 1.0 psia to 200.0 psia, 2.0 psia to 175.0 psia, 5.0 psia to 95.0 psia, etc. Preferably, the pressure can be from 3.0 psia to 100.0 psia, more preferably 3.0 psia to 50.0 psia, more preferably 3.0 psia to 30.0 psia. In particular, the reaction conditions may comprise a temperature of 500 ° C to 700 ° C and a pressure of 3.0 psia to 100 psia.

[0094] Alternatively, or even, a delta pressure (or pressure drop) through at least one reaction zone (pressure at the input of the raw material less pressure at the outlet of the effluent) can be> 0.5 psia, > 1.0 psia,> 2.0 psia,> 3.0 psia,> 4.0 psia,> 5.0 psia,> 10.0 psia,> 14.0 psia,> 15.0, psia,> 20.0 psia,> 24.0 psia,> 25.0 psia,> 30.0 psia,> 35.0 psia,> 40.0 psia,> 45.0 psia,> 50.0 psia,> 55, 0 psia,> 60.0 psia,> 65.0 psia,> 70.0 psia,> 75.0 psia,> 80.0 psia,> 85.0 psia,> 90.0 psia,> 95.0 psia ,> 100.0 psia,> 125.0 psia or> 150.0 psia. As understood in this document, in a raw material inlet, inlet, effluent outlet and outlet include space and substantially around the inlet and / or outlet. Alternatively, or even, a delta pressure (or pressure drop) through at least one reaction zone (pressure at the input of the raw material less pressure at the outlet of the effluent) can be <2.0 psia, <3, 0 psia, <4.0 psia, <5.0 psia, <10.0 psia, <14.0 psia, <15.0 psia, <20.0 psia, <24.0 psia, <25.0 psia , <30.0 psia, <35.0 psia, <40.0 psia, <45.0 psia, <50.0 psia, <55.0 psia, <60.0 psia, <65.0 psia, < 70.0 psia, <75.0 psia, <80.0 psia, <85.0 psia, <90.0 psia, <95.0 psia, <100.0 psia, <125.0 psia, <150, 0 psia, <175.0 psia or <200.0 psia. The delta pressure ranges expressly disclosed include combinations of any of the values listed above, for example, 10 psia at 70.0 psia, 20.0 psia at 60.0

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35/67 psia, 30.0 psia to 50.0 psia, etc. In particular, the pressure substantially at an inlet of a raw material (for example, acyclic Cs hydrocarbons) can be from 10.0 psia to 70.0 psia, preferably 10.0 psia to 60.0 psia, more preferably 10, 0 psia to 40.0 psia. The pressure substantially at an outlet of at least one first effluent can still be from 1.0 psia to 60.0 psia, preferably 5 psia to 40.0 psia, more preferably 10.0 psia to 30.0 psia.

C. Catalyst material and inert material

[0095] The at least one reaction zone comprises particulate material, including a catalyst material. The catalyst material, also referred to as the catalyst composition, is present in the reaction system to promote the conversion of at least a portion of the acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons, in particular, the conversion of acyclic Cs hydrocarbons to cyclopentadiene.

[0096] The catalyst compositions useful herein include microporous crystalline metallosilicates, such as crystalline aluminosilicates, crystalline ferrosilicates or other crystalline silicates containing metals (such as those where the metal or metal-containing compound is dispersed in the crystalline silicate structure and can or not be a part of the crystalline structure). The types of microporous crystalline metallosilicate structure useful as catalyst compositions herein include, but are not limited to, MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU.

[0097] Microporous metallosilicates particularly suitable for use in this document include those of the MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU structure type (such like beta zeolite, mordenite, faujasita,

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Zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM50, ZSM-57, ZSM-58 and materials from the MCM-22 family), where one or more metals groups 8, 11 and 13 of the Periodic Table of the Elements (preferably one or more of Fe, Cu, Ag, Au, B, Al, Ga and / or In) are incorporated into the crystal structure during synthesis or impregnated post-crystallization. It is recognized that a metallosilicate can have one or more metals present and, for example, a material can be referred to as ferrosilicate, but it will probably still contain small amounts of aluminum.

[0098] The microporous crystalline metallosilicates preferably have a restriction index less than 12, alternatively from 1 to 12, alternatively from 3 to 12. The aluminosilicates useful in this document have a restriction index less than 12, such as 1 to 12, alternatively 3 to 12, and include, but are not limited to, Zeolite beta, mordenite, faujasita, Zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-50, ZSM-50 , ZSM-57, ZSM-58, materials from the MCM-22 family and mixtures of two or more of them. In a preferred embodiment, crystalline aluminosilicate has a restriction index of 3 to 12 and is ZSM-5.

[0099] ZSM-5 is described in U.S. Patent No. 3,702,886. ZSM-11 is described in U.S. Patent No. 3,709,979. ZSM-22 is described in U.S. Patent No. 5,336,478. ZSM-23 is described in U.S. Patent No. 4,076,842. ZSM-35 is described in U.S. Patent No. 4,016,245. ZSM-48 is described in U.S. Patent No. 4,375,573. The ZSM-50 is described in U.S. Patent No. 4,640,829. ZSM-57 is described in U.S. Patent No. 4,873,067. ZSM-58 is described in U.S. Patent No. 4,698,217.

[00100] The material of the MCM-22 family is selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM -10-P, EMM-12, EMM-13, UZM-8, UZM-8HS,

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ITQ-1, ITQ-2, ITQ-30, and mixtures of two or more of the same.

[00101] Materials from the MCM-22 family include MCM-22 (described in US Patent No. 4,954,325), PSH-3 (described in US Patent No. 4,439,409), SSZ-25 (described in US Patent No. No. 4,826,667), ERB-1 (described in EP 0 293 032), ITQ-1 (described in US Patent No. 6,077,498), and ITQ-2 (described in WO 97/17290), MCM-36 ( described in US Patent No. 5,250,277), MCM-49 (described in US Patent No. 5,236,575), MCM-56 (described in US Patent No. 5,362,697), and mixtures of two or more of the same. The related zeolites to be included in the MCM-22 family are UZM-8 (described in US Patent No. 6,756,030) and UZM-8HS (described in US Patent No. 7,713,513), both also suitable for use as a molecular sieve of the MCM-22 family.

[00102] In one or more modalities, the crystalline metallosilicate has a molar ratio of Si / M (where M is a group 8, 11 or 13 metal) greater than 3, or greater than 25, or greater than 50, or greater than 100, or greater than 400, or in the range of 100 to 2,000, or from 100 to 1,500, or from 50 to 2,000, or from 50 to 1,200.

[00103] In one or more embodiments, the crystalline aluminosilicate has a molar ratio of SiO2 / AI2O3 greater than 3, or greater than 25, or greater than 50, or greater than 100, or greater than 400, or greater than 1,000, or in the range of 100 to 400, or from 100 to 500, or from 25 to 2,000, or from 50 to 1,500, or from 100 to 1,200, or from 50 to 1,000.

[00104] Normally, the microporous crystalline metallosilicate (such as an aluminosilicate) is combined with a Group 10 metal or metal compound and, optionally, one, two, three or more additional metals selected from Groups 8, 9, 11 and 13 of the Periodic Table of Elements and rare earth metals, such as Ga, In, Zn, Cu, Re, Mo, W, La, Fe, Ag, Rh, Pr, La and / or oxides, sulfides, nitrides and / or carbides of these metals. Alternatively, or 0

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38/67 Group 10 metal is present in combination with a Group I alkali metal and / or a Group 2 alkaline earth metal.

[00105] In one or more embodiments, the Group 10 metal includes, or is selected from the group consisting of Ni, Pd and Pt, preferably Pt. The Group 10 metal content of said catalyst composition is at least minus 0.005% by weight, based on the weight of the catalyst composition. In one or more embodiments, the Group 10 content is in the range of 0.005% by weight to 10% by weight, or from 0.005% by weight to 1.5% by weight, based on the weight of the catalyst composition.

[00106] The alkaline metal of Group 1 is generally present as oxide and the metal is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and mixtures of two or more of them. The alkaline earth metal of Group 2 is generally present as oxide and the metal is selected from the group consisting of beryllium, magnesium, calcium, strontium, barium and mixtures of two or more of them.

[00107] In one or more modalities, the Group 11 metal includes, or is selected from, the group consisting of silver, gold, copper, preferably silver or copper. The Group 11 metal content of said catalyst composition is at least 0.005% by weight, based on the weight of the catalyst composition. In one or more embodiments, the Group 11 content is in the range of 0.005% by weight to 10% by weight, or from 0.005% by weight to 1.5% by weight, based on the weight of the catalyst composition. In one or more embodiments, the molar ratio of said Group 11 metal to Group 10 metal is at least 0.1 or at least 0.1 to 10, preferably at least 0.5, more preferably at least 1 In one or more modalities, Group 11 metal is present as an oxide.

[00108] A preferred Group 9 metal is Rh, which can form

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39/67 an alloy with the Group 10 metal. Preferably, the molar ratio of the Rh metal to Group 10 is in the range of 0.1 to 5.

[00109] Typically, rare earth metal is selected from the group consisting of yttrium, lanthanum, cerium, praseodymium and mixtures or combinations thereof. Preferably, the molar ratio of rare earth metal to Group 10 metal is in the range 1 to 10. The rare earth metal can be added to the catalyst composition during or after synthesis of the microporous crystalline molecular sieve like any metal compound. suitable rare earth.

[00110] In one or more modalities of aluminosilicates, the molar ratio of said alkali metal from Group 1 to Al is at least 0.5 or at least 0.5 to 3, preferably at least 1, more preferably at least 2 .

[00111] In one or more modalities of aluminosilicates, the molar ratio of said alkaline earth metal from Group 2 to Al is at least 0.5 or at least 0.5 to 3, preferably at least 1, more preferably at least 2 .

[00112] In one or more embodiments, the catalyst composition has an Alpha Value (as measured before the addition of Group 10 metal, preferably platinum) less than 25, alternatively less than 15, alternatively from 1 to 25, alternatively from 1 , 1 to 15. The Alpha Value is determined as described in US 3,354,078; The Journal of Catalysis, v. 4, p. 527 (1965); v. 6, p. 278 (1966); and v. 61, p. 395 (1980) using a constant temperature of 538 ° C and a variable flow rate, as described in detail in The Journal of Catalysis, vol. 61, p. 395, (1980).

[00113] In one or more embodiments, the use of any of the catalyst compositions of this invention provides a conversion of at least 70%, or at least 75%, or at least 80%, or in the range of 60% to 80% , of said acyclic raw material Cs in conditions of

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40/67 acyclic Cs conversion. This includes a raw material containing n-pentane with equimolar H2, a temperature in the range of 550 ° C to 600 ° C, a partial pressure of n-pentane between 3 and 10 psia, and an hourly space speed in weight of n-pentane of 10 to 20 hours' ¹ . [00114] In one or more embodiments, the use of any of the catalyst compositions of this invention provides a carbon selectivity to cyclic Cs compounds of at least 30%, or at least 40%, or at least 50%, or in the range from 30% to 80%, under conditions of acyclic Cs conversion. This includes an equimolar H2 npentane raw material, a temperature in the range of 550 ° C to 600 ° C, a partial pressure of n-pentane between 3 and 10 psia, and an hourly space speed in weight of n-pentane between 10 and 20 hours ¹ . [00115] In one or more embodiments, the use of any of the catalyst compositions of this invention provides a carbon selectivity for cyclopentadiene of at least 30%, or at least 40%, or at least 50%, or in the range of 30 % to 80%, under conditions of acyclic Cs conversion. This includes a n-pentane raw material with equimolar H2, a temperature in the range of 550 ° C to 600 ° C, a partial pressure of n-pentane between 3 and 10 psia, and an hourly space speed in weight of n- pentane between 10 and 20 hours ¹ .

[00116] The catalyst compositions of this invention can be combined with a matrix or binder material to make them resistant to friction and more resistant to the severity of the conditions to which they will be exposed during use in hydrocarbon conversion applications. The combined compositions can contain 1 to 99% by weight of the materials of the invention based on the combined weight of the matrix (binder) and material of the invention. The relative proportions of matrix and microcrystalline material can vary widely, with the crystal content ranging from 1 to 90% by weight and, more generally, particularly when the composite is prepared in the form of grain.

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41/67 null, extruded, pills, particles formed by drop of oil, spray dried particles, etc., in the range of 2 to 80% by weight of the composite. Preferred binder materials comprise one or more of silica, titania, zirconia, Group 1 or Group 13 metal silicates in the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, passivated alumina on the surface and mixtures thereof. . Preferably, suitable binder materials have a lower affinity for Group 10 metal particles, for example, Pt, compared to crystalline metallosilicate, for example, aluminosilicate.

[00117] Useful catalyst compositions comprise a crystalline aluminosilicate or ferrous silicate, which is optionally combined with one, two or more additional metals or metal compounds. Preferred combinations include:

1) a crystalline aiuminosilicate (such as ZSM-5 or Zeolite L) combined with a Group 10 metal (such as Pt), a Group 1 alkali metal (such as sodium or potassium) and / or a Group 2 alkaline earth metal ;

2) a crystalline aluminosilicate (such as ZSM-5 or Zeolite L) combined with a Group 10 metal (such as Pt), and a Group 1 alkali metal (such as sodium or potassium);

3) a crystalline aluminosilicate (such as a ferrous silicate or iron treated with ZSM-5) combined with a Group 10 metal (such as Pt), and a Group 1 alkali metal (such as sodium or potassium);

4) a crystalline aluminum silicate (Zeolite L) combined with a Group 10 metal (such as Pt) and an alkaline Group 1 metal (such as potassium); and

5) a crystalline aluminosilicate (such as ZSM-5) combined with a Group 10 metal (such as Pt), an alkali metal from

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Group 1 (such as sodium), and a Group 11 metal (such as silver or copper).

[00118] Another useful catalyst composition is a Group 10 metal (such as Ni, Pd and Pt, preferably Pt) supported on silica (eg silicon dioxide) modified by a Group 1 alkali metal silicate (such as Li, Na, K, Rb, and / or Cs silicates) and / or a Group 2 alkaline earth metal silicate (such as Mg, Ca, Sr and / or Ba silicates), preferably potassium silicate, sodium silicate , calcium silicate and / or magnesium silicate, preferably potassium silicate and / or sodium silicate. The Group 10 metal content of the catalyst composition is at least 0.005% by weight, based on the weight of the catalyst composition, preferably in the range of 0.005% by weight to 10% by weight, or 0.005% by weight to 1.5% by weight, based on the weight of the catalyst composition. Silica (SiOz) can be any silica normally used as a catalyst support, such as those marketed under the trade names DAVISIL 646 (Sigma Aldrich), DAVISON 952, DAVISON 948 or DAVISON 955 (Davison Chemical Division of WR Grace and Company) .

[00119] The format and design of the catalyst composition are preferably configured to minimize pressure drop, increase heat transfer and minimize mass transport phenomena. The appropriate catalyst shape and design are described in WO 2014/053553, which is incorporated by reference in its entirety. The catalyst composition can be an extrudate with a diameter of 2 mm to 20 mm. Optionally, the cross section of the catalyst composition can be modeled with one or more lobes and / or concave sections. In addition, the lobes and / or concave sections of the catalyst composition can be coiled. The catalyst composition can be an extrudate with a diameter

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43/67 from 2 mm to 20 mm; and the cross-section of the catalyst composition can be molded with one or more lobes and / or concave sections; and the lobes and / or concave sections of the catalyst composition can be coiled. In addition, the formulated catalyst composition can be transformed into a particle, such as, for example, a spray dried particle, an oil drop particle, a hot particle, or a spherical particle. The formulated catalyst composition can be made into a slurry. Such paste materials typically contain microporous crystalline metallosilicate, such as zeolite, and a filler material, such as a silicate. For fluidized bed reactors, spherical particle shapes are particularly useful.

[00120] For more information on useful catalyst compositions, see the orders: USSN 62 / 250.675, deposited on November 4, 2015; USSN 62 / 250,681, deposited on November 4, 2015; USSN 62 / 250,688, deposited on November 4, 2015; USSN 62 / 250,695, deposited on November 4, 2015; and USSN 62 / 250,689, deposited on November 4, 2015; which are incorporated into this document by reference.

[00121] Preferably, the catalyst material comprises platinum in ZSM-5, platinum in L zeolite and / or platinum in silica.

[00122] In addition to the catalyst material, the inert material can also be present in at least one reaction zone. As mentioned in this document, it is understood that the inert material includes materials that promote an insignificant amount (for example, <3%, <2%, <1%, etc.) of conversion of the raw material, intermediate products or products final under the reaction conditions described in this document. In many respects, the catalyst material and / or the inert material can have an average diameter of> 10 pm> 25 pm,> 50 pm,> 100 pm,> 200 pm,> 300 pm,> 400 pm,> 500 pm, > 600 pm,>

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700 pm,> 800 pm,> 900 pm,> 1000 pm. Alternatively or even, the catalyst material and / or the inert material can have an average diameter of <50 pm, <100 pm, <200 pm, <300 pm, <400 pm, <500 pm, <600 pm, < 700 pm, <800 pm, <900 pm, <1000 pm. The ranges expressly disclosed include combinations of any of the values listed above, for example, 10 pm to 1,000 pm, 50 pm to 500 pm, 100 pm to 750 pm, 200 pm to 500 pm, etc. Preferably, in a circulating fluidized bed or in a captive fluidized bed reactor, the catalyst material and / or the inert material can have an average diameter of 20 pm to 300 pm, more preferably 20 pm to 100 pm, more preferably 40 pm to 90 pm, more preferably 50 pm to 80 pm.

[00123] The catalyst material and the inert material can be combined as portions of the same particles and / or they can be separate particles. Preferably, the catalyst material and the inert material are separate particles. The catalyst material and / or inert material can also be essentially spherical (ie, <20%, <30%, <40% or <50% in diameter aberration). Examples of suitable inert materials include, without limitation, metal carbides (eg, silicon carbide, tungsten carbide, etc.), metal oxides (eg, silica, zirconia, titania, alumina, etc.), clays, phosphates metallic (eg aluminum phosphates, nickel phosphates, zirconium phosphates, etc.) and combinations thereof. In particular, the inert material can comprise silicon carbide, silica and a combination thereof.

D. Effluents

[00124] An effluent (for example, first effluent, second effluent) that leaves the at least one reaction zone can comprise a variety of hydrocarbon compositions produced from the reaction of acyclic hydrocarbons (for example, hydrocarbon

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45/67 acidic Cs) in at least one reaction zone. Hydrocarbon compositions typically have mixtures of hydrocarbon compounds, such as alkenes, cyclic and aromatic hydrocarbons, with 1 to 30 carbon atoms (C1-C30 hydrocarbons), 1 to 24 carbon atoms (C1-C24 hydrocarbons), 1 to 18 carbon atoms (Ci-Cis hydrocarbons), 1 to 10 carbon atoms (C1-C10 hydrocarbons), 1 to 8 carbon atoms (Ci-Ca hydrocarbons) and 1 to 6 carbon atoms (Ci-Ce hydrocarbons). In particular, the first effluent comprises cyclopentadiene. Cyclopentadiene may be present in a hydrocarbon portion of an effluent (for example, first effluent, second effluent) in an amount of> 20.0% by weight,> 25.0% by weight,> 30.0% by weight ,> 35.0% by weight,> 40.0% by weight,> 45.0% by weight,> 50.0% by weight,> 55.0% by weight,> 60.0% by weight,> 65.0% by weight,> 70.0% by weight,> 75.0% by weight or> 80.0% by weight. Alternatively or even, the cyclopentadiene may be present in a hydrocarbon portion of an effluent (for example, first effluent, second effluent) in an amount of <20.0% by weight, <25.0% by weight, < 30.0% by weight, <35.0% by weight, <40.0% by weight, <45.0% by weight, <50.0% by weight, <55.0% by weight, <60, 0% by weight, <65.0% by weight, <70.0% by weight, <75.0% by weight, <80.0% by weight or <85.0% by weight. The ranges expressly disclosed include combinations of any of the values listed above, for example, 20.0% to 85.0% by weight, 30.0% by weight to 75.0% by weight, 40.0% by weight to 85.0% by weight, 50.0% by weight to 85.0% by weight, etc. Preferably, the cyclopentadiene may be present in a hydrocarbon portion of an effluent (for example, first effluent, second effluent) in an amount of 10.0% by weight to 85.0% by weight, more preferably 25.0% by weight weight at 80.0% by weight, more preferably 40.0% by weight at 75.0% by weight.

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[00125] In other respects, an effluent (for example, first effluent, second effluent) may comprise one or more other Cs hydrocarbons in addition to cyclopentadiene. Examples of other Cs hydrocarbons include, but are not limited to, cyclopentane and cyclopentene. The one or more hydrocarbons Cs may be present in a hydrocarbon portion of an effluent (for example, first effluent, second effluent) in an amount of> 10.0% by weight,> 15.0% by weight,> 20, 0% by weight,> 25.0% by weight,> 30.0% by weight,> 35.0% by weight,> 40.0% by weight,> 45.0% by weight,> 50.0% by weight> 55.0% by weight> 60.0% by weight> 65.0% by weight or> 70.0% by weight. Alternatively or even, the one or more hydrocarbons Cs may be present in a hydrocarbon portion of an effluent (eg first effluent, second effluent) in an amount of <15.0% by weight, <20.0% by weight, <25.0% by weight, <30.0% by weight, <35.0% by weight, <40.0% by weight, <45.0% by weight, <50.0% by weight , <55.0% by weight, <60.0% by weight, <65.0% by weight or <70.0% by weight. The ranges expressly disclosed include combinations of any of the values listed above, for example, 10.0% to 70.0% by weight, 10.0% by weight to 55.0% by weight, 15.0% by weight to 60.0% by weight, 25.0% by weight to 65.0% by weight, etc. Preferably, the one or more C hydrocarbons may be present in a hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in an amount of 30.0% by weight to 65.0% by weight, more preferably 20 , 0% by weight to 40.0% by weight, more preferably 10.0% by weight to 25.0% by weight.

[00126] In other respects, an effluent (for example, first effluent, second effluent) can also comprise one or more aromatics, for example, with 6 to 30 carbon atoms, particularly 6 to 18 carbon atoms. The one or more aromatics can be

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47/67 tar present in a hydrocarbon portion of an effluent (eg first effluent, second effluent) in an amount of> 1.0% by weight,> 5.0% by weight,> 10.0% by weight ,> 15.0% by weight,> 20.0% by weight,> 25.0% by weight,> 30.0% by weight,> 35.0% by weight,> 40.0% by weight,> 45.0% by weight,> 50.0% by weight,> 55.0% by weight,> 60.0% by weight or> 65.0% by weight. Alternatively or even, the one or more aromatics may be present in a hydrocarbon portion of an effluent (eg first effluent, second effluent) in an amount of <1.0% by weight, <5.0% by weight weight, <10.0% by weight, <15.0% by weight, <20.0% by weight, <25.0% by weight, <30.0% by weight, <35.0% by weight, <40.0% by weight, <45.0% by weight, <50.0% by weight, <55.0% by weight, <60.0% by weight or <65.0% by weight. The ranges expressly disclosed include combinations of any of the values listed above, for example, 1.0% to 65.0% by weight, 10.0% by weight to 50.0% by weight, 15.0% by weight to 60.0% by weight, 25.0% by weight to 40.0% by weight, etc. Preferably, the one or more aromatics may be present in a hydrocarbon portion of an effluent (for example, first effluent, second effluent) in an amount of 1.0% by weight to 15.0% by weight, more preferably 1, 0 wt% to 10 wt%, more preferably 1.0 wt% to 5.0 wt%.

[00127] For information on possible effluent dispositions, see the orders: USSN 62 / 250,678, deposited on November 4, 2015; USSN 62 / 250,692, deposited on November 4, 2015; USSN 62 / 250,702, deposited on November 4, 2015; and USSN 62 / 250,708, deposited on November 4, 2015; which are incorporated into this document by reference.

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E. Effluent Extraction / Separation

[00128] In several respects, the catalyst material and / or inert material can be entrained with hydrocarbons (eg cyclopentadiene) in the effluent (eg first effluent, second effluent) as the effluent travels through and / or leaves at least a reaction zone. Thus, the process can further comprise separating the catalyst material and / or inert material, which can be entrained with hydrocarbons (for example, cyclopentadiene) in the effluent (for example, first effluent, second effluent). This separation may include the removal of the catalyst material and / or inert material from the hydrocarbons (for example, cyclopentadiene) by any suitable means, such as, but not limited to, cyclones, filters, electrostatic precipitators, contact with heavy liquids and / or other equipment separation of solids and gases, which can be inside and / or outside at least one reaction zone. The effluent substantially free of particulate matter can then move to a product recovery system. The catalyst material and / or the separated inert material can then be further fed back to at least one reaction zone at any desirable location. In a specific embodiment, a stream of separate catalyst material can be introduced into at least one reaction zone at a position above where the raw material and coalimentation are supplied to at least one reaction.

[00129] Alternatively or even, the coalimentation can also be separated from the effluent (for example, first effluent, second effluent) by any suitable means or combinations, such as distillation, adsorption (pressure or temperature oscillation), separation by membrane, liquid / solvent absorption, condensation, etc. and the separate coalimentation can be recycled back to at least one reaction zone. Preferably, coalition sePetição 870190100185, of 10/07/2019, p. 66/91

49/67 stop is heated As described above before being reintroduced into at least one reaction zone.

[00130] Alternatively or even, the separated material with reduced level of hydrocarbons can then move to a rejuvenation zone and / or regeneration zone, and the hydrocarbons extracted from the particulate material can be directed to the product recovery system or for the reactor system.

F. Rejuvenation

[00131] As the reaction occurs in at least one reaction zone, the coke material can form in the particulate material, particularly in the catalyst material, which can reduce the activity of the catalyst material. Alternatively or even, the particulate material can cool as the reaction occurs. The catalyst material that leaves the at least one reaction zone is referred to as spent catalyst material. Thus, the effluent and the separate catalyst material can comprise the spent catalyst material. This spent catalyst material may not necessarily be a homogeneous mixture of particles, since the individual particles may have a distribution of total aging in the system, the time since the last regeneration and / or rejuvenation, and / or the ratio of time spent in reaction in relation to regeneration and / or rejuvenation zones.

[00132] Thus, at least a portion of the particulate material (e.g. spent catalyst material) can be transferred from at least one reaction zone to a rejuvenation zone to produce rejuvenated catalyst material. The transfer of particulate material (eg spent catalyst material) from at least one reaction zone to a reheating zone can occur after the catalyst material has been extracted and / or separated from the hydrocarbons after leaving at least one reaction zone.

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Alternatively or even, the catalyst material (for example, spent catalyst material) can be transferred directly from at least one reaction zone to a reheating zone. The reheat zone may include an additional heating device, such as, but not limited to, direct contact, a heating coil and / or a driven tube.

[00133] In several respects, in the rejuvenation zone, the particulate material (e.g. spent catalyst material) can be contacted with a gas stream comprising hydrogen and substantially free of reactive compounds containing oxygen to remove at least a portion of coke material gradually deposited in the catalyst material, thus forming a rejuvenated catalyst material and a volatile hydrocarbon, such as, but not limited to, methane. As used herein, the term gradually deposited coke material refers to an amount of coke material that is deposited in the catalyst material during each passage of the catalyst material through at least one reaction zone, as opposed to a cumulative amount of coke material deposited on the catalyst material during multiple passes through at least one reaction zone. Substantially free used in this context means that the rejuvenation gas comprises less than 1.0% by weight, based on the weight of the gas stream, for example, less than 0.1% by weight, less than 0.01% by weight, less than 0.001% by weight, less than 0.0001% by weight, less than 0.00001% by weight of compounds containing oxygen. The gas stream may comprise> 50% by weight of H2, such as> 60% by weight,> 70% by weight, preferably> 90% by weight of H2. The gas stream may further comprise an inert substance (for example, N2) and / or methane. The contact of the spent catalyst material with the gas stream can occur at a temperature of 500 ° C to

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900 ° C, preferably 575 ° C to 750 ° C and / or at a pressure between 5.0 psia to 250 psia, preferably 25 psia to 250 psia.

[00134] In alternative aspects, in the rejuvenation zone, ο particulate material (for example, spent catalyst material) can be rejuvenated by means of a moderate oxidation procedure that comprises the contact of the particulate material with a gas stream containing oxygen under effective conditions to remove at least a portion of coke material deposited gradually on the catalyst material, thereby forming a rejuvenated catalyst material. Typically, these conditions include a temperature range of 250 ° C to 500 ° C and a total pressure of 0.1 bar to 100 bar, preferably at atmospheric pressure. In addition, the oxygen-containing gas stream is typically supplied to the rejuvenation zone for a total of WHSV in the range of 1 to 10,000. After moderate oxidation, the purge gas is generally reintroduced to purge oxidants from the catalyst composition using a purge gas, for example, N2. This purge step can be omitted if the CO2 is the oxidizer, since it will not produce a flammable mixture. Optionally, rejuvenation through moderate oxidation also comprises one or more hydrogen treatment steps.

[00135] In any mode, the rejuvenated catalyst material can then be returned to at least one reaction zone.

[00136] In any embodiment, rejuvenation is generally effective in removing at least 10% by weight (> 10% by weight) of coke material deposited gradually. Between 10% by weight and 100% by weight, preferably between 60% by weight and 100% by weight, more preferably between 90% by weight and 100% by weight of the deposited coke material is gradually removed.

[00137] Rejuvenation can advantageously last <90 minutes, for example, <60 minutes, <30 minutes, <

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52/67 minutes, such as <1 minute or <10 seconds. Rejuvenation can be advantageously performed in> 10 minutes, for example,> 30 minutes,> 2 hours,> 5 hours,> 24 hours,> 2 days,> 5 days,> 20 days after the start of the specified conversion process.

[00138] The rejuvenation effluent that leaves the rejuvenation zone and comprises unreacted hydrogen, coke particles and, optionally, light hydrocarbon, can still be processed. For example, in aspects where rejuvenation is achieved through contact with a gas stream rich in hydrogen, the rejuvenation effluent can be sent to a compression device and then sent to a separation device in which a gas enriched with light hydrocarbon and a gas depleted in light hydrocarbon. Light hydrocarbon can be taken, for example, for use as a fuel gas. The stream depleted in light hydrocarbon can be combined with replacement hydrogen and form at least a portion of the gas stream supplied to the rejuvenation zone. The separation apparatus can be a membrane system, adsorption system (for example, pressure oscillation or temperature oscillation) or another known system for separating hydrogen from light hydrocarbons. A particle separation device, for example, a cyclonic separation drum, can be provided in which coke particles are separated from the rejuvenation effluent.

G. Regeneration

[00139] The process may also comprise a regeneration step to recover the catalyst activity lost due to the accumulation of coke material and / or metal agglomeration in the catalyst material during the reaction. This regeneration step can be performed when there is not enough removal of the coke material from the particulate material (for example, spent catalyst material) in the

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53/67 rejuvenation zone.

[00140] Preferably, in the regeneration step, at least a portion of the spent catalyst material from at least one reaction zone, the separate catalyst material after the extraction of the effluent and / or the rejuvenation zone can be transferred to a zone regeneration and regenerated by methods known in the art. For example, oxidative regeneration can be used to remove at least a portion of coke material from the spent catalyst material. In many respects, a regeneration gas comprising an oxidizing material, such as oxygen, for example, air, can come in contact with the spent catalyst material. The regeneration gas can oxidatively remove at least 10% by weight (> 10% by weight) of the total amount of coke material deposited in the catalyst composition at the beginning of the regeneration. Typically, an oxychlorination step is carried out after removing coke, comprising contacting the catalyst composition with a gas stream comprising a chlorine source and an oxygen source under conditions effective to disperse at least a portion of metal, for example, Group 10 metal, particles on the surface of the catalyst and to produce a metal hydrochloride, for example, a Group 10 metal hydrochloride. A chlorine extraction step is still typically carried out after oxychlorination, comprising contacting the catalyst composition with a gas stream comprising an oxygen source and, optionally, a chlorine source, under conditions effective to increase the metal hydrochloride O / CI ratio. Generally, a reduction step and, optionally, a sulphide step can also be carried out in the regeneration step. Typically, regeneration is effective in removing between 10% by weight and 100% by weight, preferably between 90% by weight and 100% by weight, of the coke material that is removed. Optionally, before or after the

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54/67 contact of the catalyst material spent with the regeneration gas, the catalyst material can also be contacted with a purge gas, for example, N2. Regeneration, including purging before and after oxidation of the coke, requires less than 10 days, preferably less than 3 days to complete.

[00141] The catalyst can be continuously removed and returned to the reaction zone and / or rejuvenation zone or it can be periodically removed and returned to the reaction zone and / or regeneration zone. For a periodic method, typically, the regeneration times between when withdrawals are made for burning coke, oxychlorination, chlorine extraction, purging, reduction and optional sulphide occur between 24 hours (1 day) and 240 hours (10 days), preferably between 36 hours (1.5 days) and 120 hours (5 days). Alternatively for the continuous mode, the removal / addition of the particulate material rate can vary between 0.0% by weight and 100% by weight (for example, 0.01% by weight to 100% by weight) per day from the inventory of particulate material and, preferably, between 0.25% by weight and 30.0% by weight per day of the particulate material inventory, where there is a balanced addition / removal of particulate material. The regeneration of the catalyst material can occur as a continuous process or can be done in batches, in both cases, intermediate tanks for accumulation of inventory and / or discharge of inventory may be required.

[00142] The removal and addition of particulate material (for example, spent catalyst material, fresh catalyst material, fresh inert material, rejuvenated catalyst material, regenerated catalyst material) can occur at the same or a different location in the reactor system. Particulate material (eg fresh catalyst material, fresh inert material, rejuvenated catalyst material, regenerated catalyst material) can be added after or before the rejuvenation zone, while removing the particulate material

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55/67 (for example, spent catalyst material) can be made before or after the particulate material (for example, spent catalyst material) passes through the rejuvenation zone. At least a portion of the regenerated catalyst material can be recycled to at least one reaction zone or at least one rejuvenation zone. Preferably, the regenerated catalyst material and / or fresh particulate material are supplied to the rejuvenation zone to minimize any loss of heat input and to remove any remaining species that may be transported by the regenerated catalyst material from the regeneration zone. Alternatively or further, separators inside or outside the regeneration zone can be used to separate the inert material from the catalyst material before regeneration, so that only the catalyst material is regenerated. This separation can be carried out based on differences in size, magnetic and / or density properties between the inert material and the regenerated catalyst material using any suitable means.

[00143] For the processes described above, cane tubes, well known to those skilled in the art, with the particle size and operating conditions described above, can be used to provide the means of transporting particulate material between at least one zone reaction zone, rejuvenation zone, and / or regeneration zone. Sliding valves and lifting gas, known to those skilled in the art, can also be used to help circulate particulate material and / or build the necessary pressure profile within the regeneration zone. The lifting gas can be the same as the fluidizing gas used in the rejuvenation zone, for example, a hydrogen stream that can contribute to minimizing the use of hydrogen in the reaction system, while also reducing the formation of coke material.

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III · Reaction Systems for Conversion of Acyclic Hydrocarbons [00144] In another embodiment, a reaction system 1 for converting acyclic hydrocarbons (for example, acyclic hydrocarbons Cs) into aicynes, cyclic hydrocarbons (for example, cyclopentadiene) and / or aromatics is provided, as shown in Figure. Reaction system 1 may comprise a raw material stream 2, a coalification stream 3, at least one reactor 10, and an effluent stream 11. Feed stream 2 may comprise an acyclic hydrocarbon stream (for example, acyclic hydrocarbons Cs, such as pentane) 2a as described above and, optionally, a first stream of hydrogen 2b. The coalimentation stream 3 can comprise a light hydrocarbon stream (for example, C1-C4 alkanes and / or C1-C4 alkene) 3a as described above, and a second hydrogen stream 3b. In particular, the coalimentation stream 3 may comprise hydrogen, ethane, methane and / or a mixture of ethane and ethylene. The reaction system 1 may further comprise a first furnace 4 for heating the raw material stream 2 to produce a heated raw material stream 5, which can be supplied to at least one reactor 10 at the raw material temperatures, as described in this document (for example, 300 ° C to 700 ° C). For example, a first stream of combustible gas 6 can be supplied to the first furnace 4 to heat the stream of raw material 2. In addition, the reaction system 1 can further comprise a second furnace 7 to heat the coalification stream 3 to produce a heated coalification stream 8, which can be supplied to at least one reactor 10 at coaliment temperatures, as described in this document (for example, 600 ° C to 1100 ° C) and which can heat the catalyst material present in the hair least one reactor 10. For example, a second stream of combustible gas 9 can be supplied to the second furnace 7 for heating

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57/67 cease the coaliment current 3. The at least one reactor 10 may comprise a raw material current input (not shown) to supply the heated reaction material 5 to the reaction system, a current input of coalimentation (not shown) to provide the heated coalimentation stream 8, and an effluent stream outlet (not shown) for the removal of the effluent stream 11. In a particular embodiment, the raw material stream input (not shown) ) is a position in at least one reactor 10 above the inlet of the coil current (not shown). [00145] The at least one reactor 10 can be a circulating fluidized bed reactor or a captive fluidized bed reactor, preferably a captive fluidized bed reactor. Alternatively, or even, the at least one reactor is not a radial flow reactor or a cross flow reactor.

[00146] Alternatively or even, reaction system 1 may comprise at least one first reactor, a second reactor, a third reactor, a fourth reactor, a fifth reactor, a sixth reactor, a seventh reactor, etc. As used herein, each reactor ”can be individual tanks or individual reaction zones within a single tank. Preferably, the reactor system includes from 1 to 20 reactors, more preferably 1 to 15 reactors, more preferably 2 to 10 reactors, more preferably 3 to 8 reactors. A circulating fluidized bed reactor can include multiple reaction zones (for example, 3-8) within a single tank or multiple tanks (for example, 3-8). Where the reaction system includes more than one reactor, the reactors can be arranged in any suitable configuration, preferably in series, in which a mass of the raw material moves from the first reactor to the second reactor and / or a mass of the material particulate moves from the second reactor to the first reactor, and so on. Each reactor, independently

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58/67 te, can be a circulating fluidized bed reactor or a captive fluidized bed reactor.

[00147] Preferably, the at least one reactor 10 can include at least one or more internal structures 8, as described above. In particular, the at least one reactor 10 can include a plurality of internal structures (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, etc.) , such as deflectors, baffles, trays, tubes, tube bundles, tube reels, rods and / or dispensers.

[00148] The at least one reactor 10 is operated under reaction conditions as described above to convert at least a portion of the acyclic hydrocarbons (for example, Cs acyclic hydrocarbons) into alkenes, cyclic hydrocarbons (for example, cyclopentadiene) and / or aromatics . For example, the reaction conditions can comprise a temperature of 500 ° C to 700 ° C and / or a pressure of 3.0 psia to 100 psia. Preferably, at least 30% by weight of the Cs hydrocarbons is converted to cyclopentadiene. Optionally, the at least one reactor 10 can include one or more heating means (for example, driven pipe, heated coil, heat transfer pipes) (not shown), as described in this document, in order to maintain the temperature in the same.

[00149] In addition, reaction system 1 may further comprise a separator 12, such as a cyclone, (one is shown, but two or more operating in series may be present with one or more operating in parallel) in fluid connection with the at least one reactor 10. Separator 12 may be located externally (as shown) or internally (not shown) within the reactor. The separator 12 can separate the catalyst material, which can be entrained with hydrocarbons (for example, cyclopentadiene) in the effluent stream 11 to produce a separate catalyst material stream 14 and a substantially catalyst-free effluent stream 13. The color

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59/67 stream of substantially catalyst-free effluent 13 may comprise a smaller amount of catalyst material than effluent stream 11, preferably, the substantially catalyst-free effluent stream 13 comprises an insignificant amount (for example, <5.0% by weight, <2.0% by weight, <1.0% by weight) of catalyst material or no catalyst material. The substantially catalyst-free effluent stream 13 can optionally shift to a product recovery system. The separate catalyst material stream 14 can then be further fed back to the at least one reactor 10 (the material can be returned to a position above where the heated raw material stream 5 enters) through a catalyst material inlet separate (not shown) in at least one reactor 10. The separator 12 may comprise an effluent current inlet (not shown), a separate catalyst material current outlet (not shown) and an effluent current outlet substantially free of catalyst (not shown). Optionally, a third hydrogen stream 15 can be present in reaction system 1, which can be fed to the first separator 12 and / or combined with the separate catalyst material stream 14.

[00150] Alternatively or even, the reaction system 1 may further comprise a rejuvenation and / or regeneration device 16 to restore the spent catalyst material activity, in which the rejuvenation and / or regeneration device 16 is in fluid connection with at least one reactor 10. For example, a spent catalyst stream 17 comprising at least a portion of the separate catalyst material stream 14 can be supplied to the rejuvenation and / or regeneration apparatus 16 to produce a rejuvenated and / or catalyst stream. or regenerated 18 that can be combined with the separate catalyst material stream 14 or,

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60/67 alternatively, enter the reactor via a separate outlet (not shown).

[00151] Alternatively or even, the reaction system 1 may further comprise a stream of fresh catalyst material (not shown) in fluid connection with at least one reactor 10.

IV. Industrial Applicability

[00152] A first hydrocarbon reactor effluent obtained during the acyclic Cs conversion process containing cyclic, branched and linear Cs hydrocarbons and, optionally, containing any combination of hydrogen, C4 and lighter by-products, or heavier Cs and by-products, it is a valuable product in its own right. Preferably, the CPD and / or DCPD can be separated from the reactor effluent to obtain streams of purified products that are useful in the production of a variety of high value products.

[00153] For example, a purified product stream containing 50% by weight or more, or preferably 60% by weight or more of DCPD is useful for the production of hydrocarbon resins, unsaturated polyester resins and epoxy materials. A purified product stream containing 80% by weight or more, or preferably 90% by weight or more of CPD is useful for producing Diels-Alder reaction products formed according to the following Reaction Scheme (I):

Scheme I

4 + 2 yt cidoadjção

K J 'V-— »** ps Reaction product of

Djeis-Âtoer.

where R is a substituted heteroatom or heteroatom, substituted or unsubstituted C1-C50 hydrocarbyl radical (usually a hydrocarbyl radical containing double bonds), an aromatic radical or any

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61/67 combination thereof. Preferably, radicals or substituted groups contain one or more elements from Groups 13-17, preferably from Groups 15 or 16, more preferably nitrogen, oxygen or sulfur. In addition to the mono-olefin Dieis-Alder reaction product depicted in Scheme (I), a purified product stream containing 80% by weight or more, or preferably 90% by weight or more of CPD can be used to form products of Diels-Alder CPD reaction with one or more of the following items: another CPD molecule, conjugated dienes, acetylenes, alenes, disubstituted olefins, tri-substituted olefins, cyclic olefins and substituted versions of the preceding ones. Preferred Dieis-Alder reaction products include norbornene, ethylidene norbornene, substituted norbornenes (including oxygen-containing norbornenes), norbornadienes and tetracyclododecene, as illustrated in the following structures:

norbornene ethylidene

tetracidododecene

norbomadieno

noríxsmeno subsíitisidü by eugenia.

[00154] The preceding Dieis-Alder reaction products are useful for producing polymers and copolymers of cyclic olefins copolymerized with olefins, such as ethylene. The resulting cyclic olefin copolymer and cyclic olefin polymer products are useful in a variety of applications, for example, packaging film.

[00155] A purified product stream containing 99% by weight or more of DCPD is useful for producing DCPD polymers using, for example, ring opening metathesis polymerization catalysts (ROMP). DCPD polymer products are useful in forming articles, particularly molded parts, for example, wind turbine blades and auto parts.

[00156] Additional components can also be separated

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62/67 of the reactor effluent and used in the formation of high value products. For example, the separate cyclopentene is useful for producing polycyclopentene, also known as polypentenamer, as depicted in Scheme (II).

Scheme II

ROMP catalyst

[00157] The separated cyclopentane is useful as a blowing agent and as a solvent. Linear and branched Cs products are useful for conversion to olefins and higher alcohols. Cyclic and non-cyclic Cs products, optionally after hydrogenation, are useful as octane enhancers and transport fuel mixture components.

[00158] All documents described in this document are incorporated by reference in this document, including any priority documents and / or testing procedures, insofar as they are not inconsistent with this text. As is evident from the previous general description and specific modalities, although the forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. In that sense, the invention is not intended to be limited in this way. Likewise, the term comprising is considered synonymous with the term including. Likewise, whenever a composition, an element or a group of elements is preceded with the transition phrase comprising, it is understood that we also contemplate the same composition or group of elements with transition phrases consisting essentially of consisting of / 'selected a from the group consisting of or is, preceding the recitation of the composition, the element or elements and vice versa.

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PROPHETIC EXAMPLES

[00159] The following examples are derived from modeling techniques and, although the work has actually been done, the inventors have not presented these examples in the past to comply with M.P.E.P. § 608.01 (p), if necessary.

Example 1 - Reactor Performance Modeling

[00160] The reactor modeling was performed using Invensys Systems Inc. PRO / II 9.3.4 with the objective of estimating performance under various commercially relevant operating conditions. Depending on the specifics of the modeling, variation in the results will occur, but the models will still demonstrate the relative benefits of the present invention. Numerous modifications and variations are possible and it is to be understood that within the scope of the claims, the invention may be practiced in a manner different from that described specifically in this document.

Example 1A - Methane thinner, 20 psia outlet pressure, 10 psia HC partial pressure

[00161] A 20 psia outlet pressure fluid bed reactor and an output temperature of 575 ° C is simulated with a feed comprising n-pentane, which is preheated to 621 ° C before feeding into the fluid bed and a coalimentation comprising methane and hydrogen, which is preheated separately to the temperature required to provide 100% of the reaction heat. Under these conditions, the catalyst is assumed to have a selectivity of lights (C4 products) of ~ 18%. It is assumed that the residence time in the catalyst bed will provide the CPD concentration to reach its thermodynamic concentration in the reactor outlet conditions. The molar ratio of hydrogen in the reactor coalimentation is set to provide a molar ratio of hydrogen: n-pentane in the feed of 1: 1. The molar rate of methane in the reactor supply is defined

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64/67 defined to provide a partial pressure of methane at the 10 psia reactor outlet (ie the combined partial pressure of all other hydrocarbons, including 10 psia hydrogen). Based on the reactor's performance, this corresponds to a 4: 1 molar ratio of methanomentan in the feed. To generate 1 lb-mol of CPD in the effluent of the fluidized reactor, it is determined from the simulation that 2,195 Ib-moles of n-Pentane, 8,741 Ib-moles of methane and a preheating temperature of coalimentation of 1098 ° C. Example 1B - Methane thinner, 950 ° C coalimentation preheating, 10 psia outlet HC partial pressure

[00162] As a comparison to Example 1A, a fluidized bed reactor at an outlet temperature of 575 ° C is simulated with a feed comprising n-pentane, which is preheated to 621 ° C before feeding into the fluidized bed and a coalimentation comprising methane and hydrogen, which is preheated separately to 950 ° C. Under these conditions, the catalyst is assumed to have a selectivity of lights (C4 products) of - 18%. It is assumed that the residence time in the catalyst bed will provide the CPD concentration to reach its thermodynamic concentration in the reactor outlet conditions. The molar ratio of hydrogen in the reactor coalimentation is set to provide a molar ratio of hydrogen: n-pentane in the feed of 1: 1. The molar rate of methane in the reactor coalimentation is set to provide 100% of the reaction heat. The combined outlet pressure of all components, including hydrogen, with the exception of methane, is set at 10 psia, adjusting the total outlet pressure. To generate 1 lb-mol of CPD in the effluent from the fluidized bed reactor, it is determined from the simulation that 2,195 Ib-moles of n-Pentane and 13.0 Ib-moles of methane are required. The pressure of the output reactor is further determined at 25 psia. As can be seen by comparing the simulation results of Example 1A and Exem

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65/67 pio 1Β, reducing the methane preheating temperature from 1098 to 950 ° C results in a higher methane feed rate (increase from 8.7 to 13.0 Ib-mol per Ib-mol of CPD produced) in order to provide the same reaction heat.

Example 1C - Ethane thinner, 20 psia outlet pressure, 10 psia HC partial pressure

[00163] A 20 psia outlet pressure fluid bed reactor and 575 ° C outlet temperature is simulated with a feed comprising n-pentane, which is preheated to 621 ° C prior to the feed in the fluid bed and a coalimentation comprising methane and hydrogen, which is preheated separately to the temperature required to provide 100% of the reaction heat. Under these conditions, the catalyst is assumed to have a selectivity of lights (C4 products) of ~ 18%. It is assumed that the residence time in the catalyst bed will provide the CPD concentration to reach its thermodynamic concentration in the reactor outlet conditions. The molar ratio of hydrogen in the reactor coalimentation is set to provide a molar ratio of hydrogen to pentane in the feed of 1: 1. The molar rate of ethane in the reactor supply is set to provide a partial pressure of ethane at the outlet of the 10 psia reactor (ie the combined partial pressure of all other hydrocarbons, including 10 psia hydrogen). Based on the reactor's performance, this corresponds to a molar ratio of ethane: npentane in the feed of 4: 1. To generate 1 Ib-mol of CPD in the effluent from the fluidized bed reactor, it is determined that 2,195 lb-moles of n-Pentane, 8,741 lb-moles of ethane and a preheating temperature of 911 ° C are required. As can be seen by comparing the results of the simulation of Example 1A and Example 1B, the use of ethane as coalimentation allows for a lower preheating temperature due to its greater capacity for heating

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66/67 lor in relation to methane.

Example 1D - Ethane Diluent, 732 ° C coalimentation preheating, 10 psia outlet HC partial pressure

[00164] As a comparison to Example 1C, a fluidized bed reactor at an outlet temperature of 575 ° C is simulated with a feed comprising n-pentane, which is preheated to 621 ° C before feeding into the fluidized bed and a coalimentation comprising ethane and hydrogen, which is preheated separately to 732 ° C. Under these conditions, the catalyst is assumed to have a selectivity of lights (C4 products) of ~ 18%. It is assumed that the residence time in the catalyst bed will provide the CPD concentration to reach its thermodynamic concentration in the reactor outlet conditions. The molar ratio of hydrogen in the reactor coalimentation is set to provide a molar ratio of hydrogen: n-pentane in the feed of 1: 1. The molar rate of ethane in the reactor coalimentation is set to provide 100% of the reaction heat. The combined outlet pressure of all components, including hydrogen, with the exception of ethane, is set at 10 psia, adjusting the total outlet pressure. To generate 1 lb-mol of CPD in the effluent from the fluidized bed reactor, it is determined from the simulation that 2,195 lb-moles of n-Pentane and 19,35 lb-moles of methane are required. The output reactor pressure is further determined at 33 psia. As can be seen by comparing the simulation results for Example 1D and Example 1C, reducing the preheat temperature of ethane from 911 to 732 ° C results in a higher ethane feed rate (increase from 8.7 to 19, 4 lb-mol per lb-mol of CPD produced) to provide the same reaction heat.

[00165] All documents described in this document are incorporated by reference into this document for the purposes of all jurisdictions where such practice is permitted, including any

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67/67 priority documents and / or testing procedures insofar as they are not incompatible with this text, as is evident from the previous general description and specific modalities, although the forms of the invention have been illustrated and described, several modifications can be made without deviating from the spirit and scope of the invention. In that sense, it is not intended that the invention be so limited. For example, the compositions described in this document may be free of any component, or composition not expressly recited or disclosed in this document. Any method may not have any steps not recited or disclosed in this document. Likewise, the term comprising is considered synonymous with the term including. And whenever a method, composition, element or group of elements is preceded with the transition phrase comprising, it is understood that we also contemplate the same composition or group of elements with transition phrases consisting essentially of consisting of / 'selected a from the group consisting of or is, preceding the recitation of the composition, the element or elements and vice versa.

Claims (10)

1. Process for converting acyclic hydrocarbons to alkenes, cyclic and / or aromatic hydrocarbons in a reactor system, characterized by the fact that the process comprises: placing a raw material comprising acyclic hydrocarbons and optionally H2 in contact with a catalyst material in at least one reaction zone under reaction conditions to convert at least a portion of the acyclic hydrocarbons into a first effluent comprising alkenes, cyclic and / or aromatic hydrocarbons , in which the raw material enters at least one reaction zone at a temperature of 300 ° C to 700 ° C; and providing a coalification comprising H2, C1-C4 alkanes and / or C1-C4 alkenes at a temperature of 600 ° C to 1100 ° C to heat at least one reaction zone, where the raw material and the coalimentation are supplied to at least one reaction zone at different locations through different inputs, where the raw material and coalimentation can be supplied to at least one reaction zone simultaneously or not. 2. Process according to claim 1, characterized by the fact that at least one reaction zone is a circulating or captive fluidized bed reactor. Process according to claim 1 or 2, characterized in that the first effluent that leaves at least one reaction zone has a temperature of at least 550 ° C. Process according to any one of the preceding claims, characterized in that the reaction conditions comprise a temperature of 500 ° C to 700 ° C and a pressure of 3 psia to 100 psia. 5. Process according to any one of the claims Petition 870190100185, of 10/07/2019, p. 86/91 2/3 previous sections, characterized by the fact that the catalyst material comprises platinum in ZSM-5, platinum in zeolite L and / or platinum in silica. 6. Process according to any one of the preceding claims, characterized by the fact that the catalyst material further comprises a binder comprising one or more of silica, titania, zirconia, Group 1 or Group 13 metal silicates in the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, passivated alumina on the surface and mixtures thereof. 7. Process according to any one of the preceding claims, characterized by the fact that the raw material is supplied to at least one reaction zone in a position above where the coalimentation is supplied. Process according to any one of the preceding claims, characterized in that it further comprises separating the catalyst material from the first effluent to produce separate catalyst material and introducing the separate catalyst material into at least one reaction zone. Process according to any one of the preceding claims, characterized in that it further comprises transferring at least a portion of the catalyst material to a rejuvenation zone and / or a regeneration zone to produce a rejuvenated catalyst material and / or a material regenerated catalyst; and returning the rejuvenated catalyst material and / or the regenerated catalyst material to at least one reaction zone. 10. Process according to claim 8, characterized in that it further comprises transferring at least a portion of the separate catalyst material to a rejuvenation zone and / or a regeneration zone to produce a ca Petition 870190100185, of 10/07/2019, p. 87/91 3/3 rejuvenated thais and / or regenerated catalyst material; and returning the rejuvenated catalyst material and / or the regenerated catalyst material to at least one reaction zone.