TWI626991B - Processes and systems for converting hydrocarbons to cyclopentadiene - Google Patents

Abstract

The present invention relates to a non-cyclic C ₅ hydrocarbons in the reactor system of the process for converting cyclopentadiene, wherein the method comprises: providing a starting material of the reaction system comprises a non-cyclic hydrocarbons of C _5; provided that the reaction system comprises the particulate material of catalytic material; the material so that the particulate material is at least one contact in the reaction zone under reaction conditions to at least a portion of the non-cyclic C ₅ hydrocarbons to a first effluent comprising the cyclopentadienyl; wherein The feedstock flows countercurrent to the direction of flow of the particulate material.

Description

Method and system for converting hydrocarbons to cyclopentadiene Mutual reference to related applications

The present invention claims the priority and benefit of USSN 62/250,680, filed on Nov. 4, 2015, and EP Application No. 16153716.2, filed on Feb. 2, 2016.

The present invention may be used on the non-cyclic C ₅ feedstocks into the reactor process comprising cyclic C ₅ compounds of the product.

Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are used throughout the chemical industry in a wide range of products (such as polymeric materials, polyester resins, synthetic rubbers, solvents, fuels, fuel additives, etc.). Very needed raw materials. Cyclopentadiene is currently a small by-product of liquid feed steam cracking (eg, petroleum brain and heavier feedstock). While the demand for CPD is increasing, existing and new steam cracking facilities tend to be lighter feeds, producing less CPD. The high cost due to supply constraints affects the potential use of CPD in the final product in the polymer. More CPD-based polymer products can be produced if the additional CPD can be produced at unconstrained rates and preferably at a lower cost than recovered from steam cracking. It is also desirable to share the production of other cyclic C ₅ types. Cyclopentane and cyclopentene can be of high value as solvents, while cyclopentene can be used as a comonomer to make polymers and as a starting material for other high value chemicals.

Using the catalyst system from raw materials rich in C ₅ cyclic C ₅ compounds can be produced (including CPD) as the main product in the production CPD, while minimizing light (C _4-) by-product may be advantageous. Although lower hydrogen contents (e.g., cyclics, olefins, and diolefins) are preferred due to reduced heat absorption of the reaction and improved thermal constraints on conversion, the unsaturated material is more expensive than the saturated material. The linear C ₅ framework structure is superior to the branched C ₅ framework structure due to the reaction chemistry and the lower value of linear C ₅ relative to the branched chain C ₅ (due to octane difference). Fufeng's C _{5 is} available from non-traditional gases and shale oils, as well as reduced use of motor fuels due to strict emission regulations. The C ₅ starting material can also be derived from biological materials.

Currently we are using various techniques from the catalytic dehydrogenation of C ₃ and C ₄ alkanes and monoolefins producing dienes, but non-cyclic monoolefins or cyclic diolefins class. A typical method uses Pt/Sn supported on alumina as an active catalyst. Other useful methods use chromium oxide on alumina. See BVVora, "Development of Dehydrogenation Catalysts and Processes," Topics in Catalysis, Vol. 55, pp. 1297-1308, 2012; and JC Bricker, "Advanced Catalytic Dehydrogenation Technologies for Production of Olefins," Topics in Catalysis, Vol. 55 , pp. 1309-1314, 2012.

Still other common methods use Pt/Sn supported on Zn aluminate and/or aluminate Ca to dehydrogenate propane. Although these methods successfully dehydrogenate alkanes, they do not undergo cyclization, which is the key to producing CPD. Pt-Sn / alumina and Pt-Sn / n-pentane aluminosilicate catalyst exhibits a moderate rate of conversion, but this catalyst had poor selectivity and productivity to C ₅ cyclic product.

The Pt supported by the alumina chloride catalyst is used to reconstitute the low octane petroleum brain into aromatics such as benzene and toluene. See US 3,953,368 (Sinfelt), "Polymetallic Cluster Compositions Useful as Hydrocarbon Conversion Catalysts". Although such catalyst effective to C ₆ and higher carbon alkanes and dehydrogenation of C ₆ cyclized to form an aromatic ring, but their non-cyclic C ₅ C ₅ cyclic classes converted to less effective. These by Pt catalyst contained in the alumina exhibits a low chloride yields cyclic C ₅ stream and the presentation time within the first two hours (time on stream) is deactivated. The aromatic ring formation does not occur in the C ₅ cyclization by the formation of an aromatic ring to assist the cyclization of C ₆ and C ₇ alkanes. This effect may be due in part to the fact that CPD (cyclic C ₅ ) is much higher in heat than benzene (cyclic C ₆ ) and toluene (cyclic C ₇ ). This phenomenon is also exhibited by Pt/Ir and Pt/Sn supported on alumina chloride. While such alumina catalyst for both dehydrogenation and dehydrocyclization of C ₆₊ species cyclization to form aromatic C ₆ ring, but will require different catalysts in the conversion of non-cyclic C ₅ to C ₅ cyclic.

A ZSM-5 catalyst containing Ga is used for a method of producing an aromatic substance from light paraffin. A study by Kanazirev et al. showed that n-pentane was easily converted on Ga ₂ O ₃ /H-ZSM-5. Kanazirev Price et al., "Conversion of C ₈ aromatics and n-pentane over Ga ₂ O ₃ /H-ZSM-5 mechanically mixed catalysts," Catalysis Letters, Vol. 9, pp. 35-42, 1991. Not made to produce cyclic C _5, however, produce more than 6wt% of the aromatic was 1.8hr ^-1 WHSV and 440 ℃ lower. Mo/ZSM-5 catalysts have also been shown to dehydrogenate and/or cyclize paraffin waxes, 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. The high conversion of n-pentane using Mo/ZSM-5 was confirmed by the high yield in which no cyclic C ₅ and cleavage products were produced. This display ZSM-5 type catalyst can be converted to C ₆ paraffinic ring, but not necessarily produce C ₅ ring.

US 5,254,787 (Dessau) describes NU-87 catalyst for the dehydrogenation of paraffin waxes. The catalyst show that the C ₂ -C ₆₊ dehydrogenated to produce an unsaturated analogues thereof. The distinction between C _2-5 and C ₆₊ alkanes in this patent is clear: dehydrogenation of C _2-5 alkanes produces linear or branched monoolefins or diolefins, whereas C ₆₊ alkanes Dehydrogenation of the class produces aromatics. US 5,192,728 (Dessau) relates to similar chemical properties but has a tin-containing crystalline microporous material. The use of NU-87 catalyst, show only generate dehydrogenated to C ₅ straight or branched chain monoolefins or diolefins and no CPD.

US 5,284,986 (Dessau) describes a two-stage process for the manufacture of cyclopentane and cyclopentene from n-pentane. An example is carried out in which the first step involves dehydrogenating and dehydrocycling n-pentane to a mixture of paraffins, monoolefins and diolefins, and naphthenes on a Pt/Sn-ZSM-5 catalyst. The mixture is then introduced into a second stage reactor consisting of a Pd/Sn-ZSM-5 catalyst where the diolefins (especially CPD) are converted to olefins and saturates. ring Pentene is the desired product in this process, however CPD is an unwanted by-product.

US 2,438,398; US 2,438,399; US 2,438,400; US 2,438,401; US 2,438,402; US 2,438,403; and US 2,438,404 (Kennedy) disclose the manufacture of CPD from 1,3-pentadiene on various catalysts. Low operating pressures, low conversion per conversion, and low selectivity make this method unpopular. Further, unlike n-pentane, 1,3-pentadiene is a raw material that is not easily obtained. See also Kennedy et al., "Formation of Cyclopentadiene from 1,3-Pentadiene, "Industrial & Engineering Chemistry, Vol. 42, pp. 547-552, 1950.

Fel'dblyum et al., "Cyclization and dehydrocyclization of C ₅ hydrocarbons over platinum nanocatalysts and in the presence of hydrogen sulfide", (Doklady Chemistry, Vol. 424, pp. 27-30, 2009) CPD is produced from diene, n-pentene, and n-pentane. The yields of 1,3-pentadiene, n-pentene and n-pentane converted to CPD at 600 ° C on 2% Pt/SiO ₂ were as high as 53%, 35% and 21%, respectively. Although initial production of CPD was observed, the catalyst was observed to deactivate rapidly during the first few minutes of the reaction. Experiments conducted on Pt-containing vermiculite showed an appropriate conversion of n-pentane over Pt-Sn/SiO ₂ , but with poor selectivity and yield as a cyclic C ₅ product. The use of H ₂ S as a 1,3-pentadiene cyclization promoter is given by Fel'dblyum and Marcinkowski, "Isomerization and Dehydrogenation of 1,3-Pentadiene", (MS, University of Central Florida, 1977). Presented in. Marcinkowski showed an 80% conversion of 1,3,-pentadiene from H ₂ S at 700 ° C and a selectivity to CPD of 80%. High temperatures, limited raw materials, and potentially sulfur-containing products that would later require washing make this method undesirable.

López et al. studied n-pentane in H-ZSM in "n-Pentane Hydroisomerization on Pt Containing HZSM-5, HBEA, and SAPO-11", (Catalysis Letters, Vol. 122, pp. 267-273, 2008). -5 on the Pt-containing zeolite. The report indicates that n-pentane is efficiently hydroisomerized on Pt zeolite at intermediate temperatures (250 to 400 ° C), but cyclopentene formation is not discussed. Since the above-mentioned branched chain C _{5 is} less efficient than the linear C _{5 to} produce the cyclic C ₅ , it is desirable to avoid this harmful chemistry.

Li et al., "Catalytic dehydroisomerization of n-alkanes to isoalkenes" (Journal of Catalysis, Vol. 255, pp. 134-137, 2008) also studied the positive effect of Pt-containing zeolites in which Al has been Fe-like isomorphous substitution. Dehydrogenation of pentane. Such Pt / [Fe] ZSM-5 catalyst efficiency of dehydrogenation and isomerization of n-pentane, but under the reaction conditions employed, the C ₅ cyclic skeletons not generated and undesirable isomerization.

No. 5,633,421 discloses a process for the dehydrogenation of C ₂ -C ₅ paraffins to obtain corresponding olefins. No. 2,982,798 discloses a process for the dehydrogenation of aliphatic hydrocarbons having from 3 to 6 (inclusive) carbon atoms. However, US 5,633,421 or US 2,982,798 neither discloses CPD producing hydrocarbons from acyclic C _5, C ₅ acyclic hydrocarbons due to a sufficient quantity and at low cost, it is desirable for the raw material.

In addition, there are many challenges in the design of methods for deliberately making CPD. For example, the C ₅ hydrocarbons to the CPD is an endothermic reaction, and is facilitated by the low pressure and high temperature, but the n-pentane and other C ₅ hydrocarbons significant cracking occurs at relatively low temperatures (e.g. 450 deg.] C to 500 ℃). Other challenges include loss of catalyst activity due to coking during the process and the need for additional processing to remove coke from the catalyst, and the inability to use the oxygen containing gas to provide heat input directly to the reactor without damaging the catalyst.

Accordingly, there remains a need to acyclic C ₅ feedstocks into C ₅ cyclic non-aromatic hydrocarbon (in other words, cyclopentadiene) of the method, the preferred method to train the rate and conditions of the commercial. Further, the need-based catalytic process for producing certain of cyclopentadiene, which is produced in high yield without unduly C _4- C ₅ rich pyrolysis product is produced from raw materials, and has acceptable catalyst aging properties. Further, the above-described methods and systems to overcome the challenges of CPD deliberately created from non-cyclic C ₅ hydrocarbons.

In one aspect, the present invention relates to a reactor system for the non-cyclic C ₅ hydrocarbons to the cyclopentadiene method, wherein the method comprises: providing a non-cyclic C ₅ hydrocarbons in the reactor system comprising the raw material; providing particulate material comprises catalytic materials in the reactor system; the feedstock and the particulate material is at least one contact under reaction conditions of the reaction zone to convert at least a portion of the non-cyclic C ₅ hydrocarbons to comprise a ring a first effluent of pentadiene; wherein the feedstock flows countercurrent to the direction of flow of the particulate material.

In other aspects, the present invention also relates to the non-cyclic C ₅ hydrocarbons to the reaction system of cyclopentadiene, wherein the reaction system comprises: comprises C ₅ acyclic hydrocarbons of the feed stream; comprising of cyclopentadienyl a first effluent stream; catalyst stream comprising at least one catalytic material comprising the particulate material; and at least one spent catalyst stream comprising spent catalyst materials; at least one operating under reaction conditions to convert at least a portion of the non-cyclic C ₅ hydrocarbons a reactor for conversion to cyclopentadiene; and wherein the at least one reactor comprises: a feedstock inlet for providing the feedstream to the reaction system; at least one for providing the at least one catalyst stream to the reaction system a catalyst inlet; an effluent outlet for removing the first effluent stream; and a waste catalyst outlet for removing the at least one spent catalyst stream; wherein the feed stream in the reactor is in the reactor The flow of at least one of the catalyst streams flows countercurrently.

1‧‧‧Reaction system

2‧‧‧feedstream

3‧‧‧First outflow logistics

4‧‧‧catalyst flow

5‧‧‧Abuster flow

6‧‧‧Reactor

7,7a‧‧‧Hydrogen flow

8‧‧‧ internal structure

9,16‧‧ Cyclone

10‧‧‧Particulate materials

11‧‧‧Second effluent

12‧‧‧Reheating equipment

13‧‧‧ Tools

14‧‧‧Recovered catalytic material flow

15‧‧‧heated hydrogen flow

18‧‧‧Excessive hydrogen flow

4a‧‧‧Separated recovered catalytic material flow

19‧‧‧Regeneration equipment

20‧‧‧Steam flow

21‧‧‧First hydrogen lift gas flow

22‧‧‧Second hydrogen lift gas flow

23‧‧‧Compressor

24‧‧‧Separation equipment

25‧‧‧Less of light hydrocarbon flow

26‧‧‧Enriched in light hydrocarbon streams

27‧‧‧Supply hydrogen flow

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram of a reactor in accordance with an embodiment of the present invention.

2 is a diagram of a reactor having a reheating apparatus in accordance with another embodiment of the present invention.

Figure 3 is a diagram of a reactor having a reheating device and a regeneration device in accordance with another embodiment of the present invention.

Detailed description of the invention I. Definition

To facilitate the understanding of the present invention, some terms and phrases are defined below.

The singular forms "a", "the" and "the"

In this paper, the terms used in statements such as "A and / or B" "and / or "I want to include "A and B", "A or B", "A" and "B".

The term "about" as used herein refers to a range of values that are added or subtracted by a specified value by 10%. For example, the statement "about 200" includes 200 plus or minus 10%, or 180 to 220.

The term "saturated" includes, but is not limited to, alkanes and naphthenes.

The term "unsaturated" includes, but is not limited to, olefins, diolefins, alkynes, cyclic olefins, and cyclic diolefins.

The term "cyclic C ₅ 'or including but not limited to cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more" ₅ cC. " The term "cyclic C _5" or "cC _5" also include alkylated analogs of any of the preceding one, such as methyl cyclopentane, methyl cyclopentene and methyl cyclopentadiene. For the purposes of the present invention, it will be appreciated that cyclopentadiene is simultaneously dimerized to form dicyclopentadiene via Dimes-Adel condensation at a range of conditions including ambient temperature and pressure.

The term "acyclic" includes, but is not limited to, linear and branched saturates and unsaturation.

The term "aromatic" means a planar cyclic hydrocarbon group having a conjugated double bond, 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 (PNA), including naphthalene, anthracene, And its alkylation variants. The term "C ₆₊ aromatics" includes compounds based on aromatic rings having six or more ring atoms, including but not limited to benzene, toluene, and xylene; and polynuclear aromatics (PNA), which include naphthalene, Oh, And its alkylation variants.

The term "BTX" includes, but is not limited to, a mixture of benzene, toluene and xylene (o- and/or meta- and/or p-).

The term "coke" includes, but is not limited to, low hydrogen content hydrocarbons adsorbed on a catalyst composition.

The term " _Cn " means a hydrocarbon (class) of n carbon atoms per molecule, where n is a positive integer.

The term " _Cn+ " means a hydrocarbon (class) having at least n carbon atoms per molecule.

The term " _Cn- " means a hydrocarbon (class) having no more than n carbon atoms per molecule.

The term "hydrocarbon" means a compound of a class containing hydrogen bonded to carbon and comprises (i) a saturated hydrocarbon compound, (ii) an unsaturated hydrocarbon compound, and (iii) a hydrocarbon compound (saturated and/or unsaturated). A mixture comprising a mixture of hydrocarbon compounds having different values of n.

The term "C ₅ raw material" includes raw materials containing n-pentane such as n-pentane and isopentane (also known as methylbutane) and having a smaller portion of cyclopentane and neopentane (also known as Raw material for 2,2-dimethylpropane).

Unless otherwise specified, all figures and references for the Periodic Table of Elements are based on the new representations described in Chemical and Engineering News, 63(5), 27 (1985).

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.

The term "Group 11 metal" means an element of Group 11 of the Periodic Table and includes, but is not limited to, Cu, Ag, Au, and a mixture of two or more thereof. Compound.

The term "Group 1 alkali metal" means an element in Group 1 of the Periodic Table and includes, but is not limited to, Li, Na, K, Rb, Cs, and mixtures of two or more thereof, and excludes hydrogen.

The term "Group 2 alkaline earth metal" means an element of Group 2 of the Periodic Table and includes, but is not limited to, Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof.

The term "oxygen" includes air, O ₂ , H ₂ O, CO and CO ₂ .

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

As used herein, the term "MCM-22 family molecular sieves" (or "MCM-22 family materials" or "MCM-22 family materials" or "MCM-22 family zeolites") includes one or more of the following: A molecular sieve made of a unit cell of a first-stage crystal building block, wherein the unit cell has a MWW architecture topology. (The spatial arrangement of atomic units of a unit cell, which is depicted when laid out in a three-dimensional space. This crystal structure is detailed in "Atlas of Zeolite Framework Types" (5th ed., 2001), the full text of which is Molecular sieves made from common second-stage building blocks are two-dimensionally laid out for such MWW architecture topographic unit cells to form a single layer of unit cell thickness, preferably Is a c-unit cell thickness; a molecular sieve made from a common second-stage constructed vertebra is a layer of one or more unit cell thicknesses, wherein the layer thickness greater than one unit cell thickness It is made by stacking, stacking, and bonding a single layer of at least two layers of unit cell thickness. The stack of such second-level building blocks can be in a regular manner, an irregular manner, a random manner, or any combination thereof; and can be made by any regular or random two-dimensional or three-dimensional combination of unit cells having a MWW architecture topology. Molecular sieves.

The MCM-22 family includes a molecular sieve having an X-ray diffraction pattern comprising a maximum interplanar spacing of 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07, and 3.42 ± 0.07 angstroms. The X-ray diffraction data used to characterize the material was obtained using a copper K-alpha double line as the standard technique for incident radiation and a diffractometer equipped with a scintillation counter and a combined computer as the collection system.

The term "molecular sieve" as used herein is used synonymously with "microporous crystalline material" or zeolite.

Individual cyclic C ₅ formed of, as used herein, the term "carbon selectivity" means, CPD, C ₁ pentane and the molar number of carbon atoms in C _2-4 divided by the total conversion of carbon molar number. Statement "become cyclic C ₅ carbon selectivity is at least 30%" means the conversion of pentane per 100 mole of carbon forming 30 mole cyclic C ₅ carbon.

As used herein, the term "conversion" means the conversion to carbon molar acyclic C ₅ feed of the product. Statement "the non-cyclic C ₅ conversion of starting material was the product of at least 70%" means the number of moles of acyclic C ₅ feed lines of at least 70% conversion to product.

As used herein, the term "reactor system" means all necessary and optional as used in the manufacture of one or more reactors and cyclopentadiene. Equipment system.

The term "reactor" as used herein refers to any container in which a chemical reaction occurs. The reactor comprises both different reactors and reaction zones in a single reactor apparatus, and, if applicable, the reaction zone spans multiple reactors. In other words, and often, a single reactor can have multiple reaction zones. When the description refers to the first and second reactors, it will be readily apparent to those of ordinary skill in the art that the reference includes two reactors, as well as a single reactor vessel having first and second reaction zones. Similarly, it will be appreciated that the first reactor effluent and the second reactor effluent comprise effluent from the first reaction zone and the second reaction zone, respectively.

As used herein, the term "moving bed" reactor means that a solid (eg, catalyst particles) is in contact with a gas stream such that the surface gas velocity (U) is less than the velocity required for pneumatic transport of the solid particulate diluent phase to maintain the void fraction. A zone or container of solid bed having a rate of less than 95%. In a moving bed reactor, a solid (e.g., catalyst material) can slowly travel through the reactor and can be removed from the bottom of the reactor and added to the top of the reactor. The moving bed reactor can be operated in several flow conditions, including sedimentation or moving packed bed conditions (U<U _mf ), foaming state (U _mf <U<U _mb ), agglomerated state (U _mb <U<U _c ), fluidized state of transition to turbulent flow (U _c <U<U _tr ), and rapid fluidization state (U>U _tr ), where U _mf is the minimum fluidization velocity and U _mb is the minimum foaming velocity , U _c is the speed of the spike that fluctuates in pressure and tr is the transport speed. These different fluidization states are described, for example, in Kunii, D., Levenspiel, O., Fluidization Engineering (Second Edition, Butterworth-Heinemann, Boston, 1991) Chapter 3 and Walas, SM, Chemical Process Equipment (Revised Chapter 6, Chapter 4 of Butterworth-Heinemann, Boston, 2010), which is incorporated by reference.

As used herein, the term "settling bed" reactor means that the particles are in contact with a gas stream such that the surface gas velocity (U) in at least a portion of the reaction zone is less than required to fluidize the solid particles (e.g., catalyst particles). Minimum speed (minimum fluidization velocity (U _mf )) (U < U _mf ), and/or operating at a speed above the minimum fluidization velocity while maintaining axially upward along the reactor bed by using reactor internal components A gradient of gas and/or solid properties (such as temperature, gas or solid composition, etc.) to minimize gas-solid reverse mixing zones or vessels. A description of the minimum fluidization velocity can be found, for example, in Kunii, D., Levenspiel, O., Fluidization Engineering (Second Edition, Butterworth-Heinemann, Boston, 1991) Chapter 3 and Walas, SM, Chemical Process Equipment (Revision 2). Edition, Butterworth-Heinemann, Boston, 2010) Chapter 6. A settled bed reactor can be a "circulating settled bed reactor" which refers to a settled bed in which solids (e.g., catalytic materials) move through the reactor and the solids (e.g., catalytic materials) are at least partially recycled. For example, the solids (e.g., catalyst materials) can be removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned to the reactor.

As used herein, the term "fluidized bed" reactor means that a solid (eg, catalyst particles) is in contact with a gas stream such that the surface gas velocity (U) is sufficient to fluidize the solid particles (ie, above the minimum fluidization velocity U _{mf )} And below the rate required for pneumatic transport of the solids diluent phase to maintain a zone or vessel of solid bed having a void fraction of less than 95%. As used herein, the term "cascade fluid bed" means a series of configurations of individual fluid beds to provide gas and/or solid properties (such as temperature, gas, or gas) as the solid or gas is reduced from one fluid bed to another. There is a gradient in the solid composition, pressure, etc.). The minimum fluidization velocity is found in, for example, Kunii, D., Levenspiel, O., Fluidization Engineering (Second Edition, Butterworth-Heinemann, Boston, 1991) Chapter 3 and Walas, SM, Chemical Process Equipment (Revision 2 Edition, Butterworth-Heinemann, Boston, 2010) Chapter 6. The fluidized bed reactor can be a mobile fluidized bed reactor, such as a "circulating fluidized bed reactor," which refers to the movement of solids (eg, catalytic materials) through the reactor and the solids (eg, catalytic materials). At least partially recycled fluidized bed. For example, the solids (e.g., catalyst materials) can be removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned to the reactor.

As used herein, the term "rising tube" reactor (also known as a transport reactor) refers to a zone used to transport solids (eg, catalyst particles) in a fluidized state that is rapidly fluidized or pneumatically transported, or A container (such as a vertical cylindrical tube). The fluidization state of rapid fluidization and pneumatic transport is characterized by a surface gas velocity (U) greater than the transport velocity ( _Utr ). The fluidization state of rapid fluidization and pneumatic transport is also described in Kunii, D., Levenspiel, O., Fluidization Engineering (Second Edition, Butterworth-Heinemann, Boston, 1991) Chapter 3 and Walas, SM, Chemical Process Equipment ( Revised Chapter 2, Butterworth-Heinemann, Boston, 2010) Chapter 6. Fluidized bed reactors, such as circulating fluidized bed reactors, can operate as riser reactors.

As used herein, the term "concurrent" means that the flow of two streams (eg, stream (a), stream (b)) is substantially the same direction. For example, if stream (a) flows from the top portion of the at least one reaction zone to the bottom portion and stream (b) flows from the top portion of the at least one reaction zone to the bottom portion, the flow of stream (a) is considered to be associated with the stream ( b) The flow is parallel. At smaller scales within the reaction zone, there may be areas where the flow may not be cocurrent.

As used herein, the term "countercurrent" means that the flow of two streams (eg, stream (a), stream (b)) is substantially opposite. For example, if stream (a) flows from the top portion of the at least one reaction zone to the bottom portion and stream (b) flows from the bottom portion of the at least one reaction zone to the top portion, the flow of stream (a) is considered to be associated with the stream ( b) The flow countercurrent. At smaller scales within the reaction zone, there may be regions where the flow may not be countercurrent.

Additionally, reactors having cocurrent or countercurrent flow (ie, cocurrent reactors, countercurrent reactors) are not intended to include where the first stream can be radially (eg, inward or outward) and the second stream can be along the axis A reactor (ie, a radial flow reactor) having a radial flow (eg, up or down).

Use available from Malvern Instruments, "average diameter" 3000 Determination of particle Ltd. (UK Worcestershire) of the Mastersizer ^TM in the range of 1 to 3500μm. The particle size is determined at D50 unless otherwise indicated. D50 is the value of the particle diameter at 50% in the cumulative distribution. For example, if D50 = 5.8 um, 50% of the particles in the sample are equal to or greater than 5.8 um and 50% less than 5.8 um. (Conversely, if D90 = 5.8um, 10% of the particles in the sample are larger than 5.8um and 90% is less than 5.8um.) The average diameter of the particles is measured from 3mm to 50mm on a representative sample of 100 particles using a micrometer. The scope.

For the purposes of the present invention, 1 psi is equivalent to 6.895 kPa. More specifically, 1 psia is equivalent to 1 kPa absolute pressure (kPa-a). Similarly, 1 psig is equivalent to 6.895 kPa gauge (kPa-g).

II. Acyclic C ₅ transformation method

The first aspect of the present invention is a kind of non-cyclic C ₅ feedstocks into C ₅ comprises a cyclic compound (e.g., cyclopentadiene) of the product of the method. The method comprises in one or more of the present catalyst composition and optional hydrogen feed step of contacting a non-cyclic C ₅ at conversion conditions (including but not limited to the catalyst composition described herein) to form said product.

In one or more aspects of the embodiments, the method of converting the product of acyclic C ₅ feed comprising C ₅ cyclic compound. The cyclic C ₅ compound comprises one or more of cyclopentane, cyclopentene, cyclopentadiene, and a mixture thereof. In one or more embodiments, the cyclic C ₅ compound comprises at least about 20 wt%, or 30 wt%, or 40 wt%, or 70 wt% cyclopentadiene, or from about 10 wt% to about 80 wt%, or 20 wt% Up to 70% by weight.

In one or more aspects of the embodiments, acyclic C ₅ conversion conditions include a temperature of at least, partial pressure of n-pentane, and the weight hourly space velocity (WHSV). The temperature is in the range of from about 400 ° C to about 700 ° C, or from about 450 ° C to about 650 ° C, preferably from about 500 ° C to about 600 ° C. The n-pentane partial pressure at the reactor inlet is in the range of from about 3 to about 100 psia, or in the range of from about 3 to about 50 psia, preferably from about 3 psia to about 20 psia. The weight-based hourly space velocity range from about 1 to about 50hr ^-1 of, or in the range of from about 1 to about 20hr ^-1 at the. Such conditions include optional hydrogen co-feed molar ratio range of C ₅ acyclic feedstock of from about 0 to 3, or in the range of from about 1 to about 2. Such conditions also include co-feed C ₁ -C ₄ hydrocarbons and C ₅ acyclic feed.

In one or more embodiments, the invention relates to a process for converting n-pentane to cyclopentadiene comprising a partial pentane partial pressure of 3 at a temperature of from 400 ° C to 700 ° C at the inlet of the reactor Up to about 100 psia and an hourly weight space velocity of from 1 to about 50 hr ^-1 to give n-pentane and optionally hydrogen (if present, usually has a ratio of n to pentane of from 0.01 to 3.0 H ₂ ) and one or The step of contacting a plurality of catalyst compositions, including but not limited to the catalyst compositions described herein.

In one or more aspects of the embodiments, the present invention relates to a reactor system for the non-cyclic C ₅ hydrocarbons to the cyclopentadiene method, wherein the method comprises: providing a reactor system in the C ₅ the hydrocarbon feedstock; provide particulate material comprising the catalytic material in the reactor system; and contacting the feedstock with the particulate material to at least one reaction zone under reaction conditions to convert at least a portion of the C ₅ hydrocarbons to A first effluent comprising cyclopentadiene, wherein the feedstock flows countercurrent to the direction of flow of the particulate material.

A. Raw materials

In this process, the feedstock comprising hydrocarbons of the C ₅ (preferably acyclic C ₅ starting material) together with the particulate material comprises catalytic materials provided together to the reaction system. The acyclic C ₅ feedstock usable herein may be derived from crude oil or natural gas condensate and may include cracked C ₅ produced by refining and chemical processes (in varying degrees of unsaturation: olefins, diolefins, alkynes) These refining and chemical processes are such as fluid catalytic cracking (FCC), recombination, hydrocracking, hydrotreating, coking, and steam cracking.

In one or more aspects of the embodiments may be used in the methods of the present invention comprises a non-cyclic C ₅ feed pentane mixture pentene, pentadiene, and their two or more of. Preferably, in one or more embodiments, the acyclic C ₅ feedstock comprises at least about 50 wt%, or 60 wt%, or 75 wt%, or 90 wt% n-pentane, or from about 50 wt% to about 100 wt%. The range of pentane.

The acyclic C ₅ starting material optionally contains no C ₆ aromatic compound, such as benzene, preferably a C ₆ aromatic compound, less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight, It is preferably 0% by weight.

The acyclic C ₅ raw material optionally contains no benzene, toluene or xylene (o-, m-, or p-). Preferably, the benzene, toluene or xylene (o-, m-, or p-) compound is present in less than 5 wt%. Preferably, it is less than 1% by weight, preferably less than 0.01% by weight, preferably 0% by weight.

The acyclic C ₅ starting material optionally contains no C ₆₊ aromatic compound, preferably less than 5% by weight of the C ₆₊ aromatic compound, preferably less than 1% by weight, preferably less than 0.01% by weight, more preferably Good is 0wt%.

Acyclic C ₅ optionally does not comprise raw C ₆₊ compound, preferably C ₆₊ based compound there is less than 5wt%, preferably less than 1 wt.% Based, the preferred system there is less than 0.01wt%, preferably from 0wt% .

Preferably, the amount of C ₅ hydrocarbons (for example, acyclic C ₅ hydrocarbons) in the feed to cyclopentadiene is About 5.0% by weight, About 10.0% by weight, About 20.0% by weight, About 30.0% by weight, About 40.0% by weight, About 50.0% by weight, About 60.0% by weight, About 70.0% by weight, About 80.0% by weight, or About 90.0% by weight. Preferably, at least about, or at least about 30.0wt% 60.0wt% of C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbon) converted to cyclopentadiene-based. The range explicitly disclosed includes any combination of the foregoing recited values; for example from about 5.0% to about 90.0% by weight, from about 10.0% to about 80.0% by weight, from about 20.0% to about 70.0% by weight, from about 20.0% to about 60.0. Wt% and so on. Preferably, from about 20.0wt% to about 90.0wt% of C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbon) converted into cyclopentadiene-based, more preferably from about 30.0wt% to about based 85.0wt%, and more Preferably, from about 40.0 wt% to about 80.0 wt%, from about 45.0 wt% to about 75.0 wt%, from about 50.0 wt% to about 70.0 wt%.

Preferably, the hydrogen will also containing hydrogen and light hydrocarbons random (such as C ₁ -C ₄ hydrocarbons) of the co-feed is fed to the first reactor. Preferably, at least a portion of the co-feed of hydrogen and C ₅ feed blend prior to being fed to the first reactor. The presence of hydrogen in the feed mixture at the inlet location where the feed is initially contacted with the catalyst prevents or reduces the formation of coke on the catalyst particles. The C ₁ -C ₄ hydrocarbons can also be fed together with C ₅ .

B. Reaction zone

And the raw material fed to the at least one reaction zone in contact with the particulate material comprises catalytic materials under reaction conditions within the reactor system to convert at least a portion of the C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) into a ring comprising The first effluent of pentadiene. The at least one reaction zone can be a circulating fluidized bed reactor or a circulating settled bed reactor. In addition, the circulating fluidized bed reactor can be operated in a fluidized state of foaming or turbulence, as in Kunii, D., Levenspiel, O., Fluidization Engineering (2nd Edition, Butterworth-Heinemann, Boston, 1991). Chapter 3 is described in Chapter 6 of Walas, SM, Chemical Process Equipment (Revision 2nd Edition, Butterworth-Heinemann, Boston, 2010). Additionally or alternatively, the at least one reaction zone is not a radial flow reactor or a cross flow reactor.

Additionally or alternatively, the at least one reaction zone may comprise at least a first reaction zone, a second reaction zone, a third reaction zone, a fourth reaction zone, a fifth reaction zone, a sixth reaction zone, a seventh reaction zone, and/or Or the eighth reaction zone, etc. As understood herein, each reaction zone can be an individual reactor or the reactor can comprise one or more of such reaction zones. Preferably, the reactor system comprises from 1 to 20 reaction zones, more preferably from 1 to 15 reaction zones, more preferably from 2 to 10 reaction zones, more preferably from 2 to 8 reaction zones. When the at least one reaction zone comprises the first and second reaction zones, the reaction zones can be configured in any suitable configuration, preferably in series. Each reaction zone may independently be a circulating fluidized bed or a circulating settled bed, preferably each reaction zone being a circulating fluidized bed. Additionally or alternatively, the methods described herein can additionally comprise moving a substantial portion of the converted feedstock from the first reaction zone to the second reaction zone and/or moving a plurality of particulate material from the second reaction zone to the first reaction zone. . As used herein, the phrase "large amount" refers to at least a majority of partially converted starting materials and particulate materials, such as a portion of at least about 50.0 wt%, at least about 60.0 wt%, at least about 70.0 wt%, at least about 80.0 wt%, at least about 90.0 wt%, at least about 95.0 wt%, at least about 99.0 wt%, and 100.0 wt%.

Preferably, at least one reaction zone may comprise at least one internal structure, Preferably, a plurality of internal structures (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, etc.) are utilized to affect the velocity component of the particulate material. In addition, the internal structure ensures the movement of the particulate material while minimizing the degree of reverse mixing. More specifically, the at least one reaction zone may comprise a plurality of internal structures. Examples of suitable internal structures include a plurality of baffles, sheds, trays, tubes, rods, and/or distributors.

The at least one reaction zone sufficient to feed lines (e.g., non-cyclic C ₅ hydrocarbons) is converted to a cyclopentadienyl under reaction conditions of operation. Preferably, the raw material (e.g., non-cyclic C ₅ hydrocarbons) may be the weight hourly space velocity (WHSV, C ₅ mass of non-cyclic hydrocarbons / mass of catalyst / hour) from about 1.0 to about 1000.0hr ^-1 The range is fed to the reaction system. The WHSV can be from about 1.0 to about 900.0 hr ^-1 , from about 1.0 to about 800.0 hr ^-1 , from about 1.0 to about 700.0 hr ^-1 , from about 1.0 to about 600.0 hr ^-1 , from about 1.0 to about 500.0 hr ^-1 , about 1.0 Up to about 400.0 hr ^-1 , about 1.0 to about 300.0 hr ^-1 , about 1.0 to about 200.0 hr ^-1 , about 1.0 to about 100.0 hr ^-1 , about 1.0 to about 90.0 hr ^-1 , about 1.0 to about 80.0 hr ^{- 1} , about 1.0 to about 70.0 hr ^-1 , about 1.0 to about 60.0 hr ^-1 , about 1.0 to about 50.0 hr ^-1 , about 1.0 to about 40.0 hr ^-1 , about 1.0 to about 30.0 hr ^-1 , about 1.0 to About 20.0 hr ^-1 , about 1.0 to about 10.0 hr ^-1 , about 1.0 to about 5.0 hr ^-1 , about 2.0 to about 1000.0 hr ^-1 , about 2.0 to about 900.0 hr ^-1 , about 2.0 to about 800.0 hr ^-1 From about 2.0 to about 700.0 hr ^-1 , from about 2.0 to about 600.0 hr ^-1 , from about 2.0 to about 500.0 hr ^-1 , from about 2.0 to about 400.0 hr ^-1 , from about 2.0 to about 300.0 hr ^-1 , from about 2.0 to about 200.0 hr ^-1 , about 2.0 to about 100.0 hr ^-1 , about 2.0 to about 90.0 hr ^-1 , about 2.0 to about 80.0 hr ^-1 , about 2.0 to about 70.0 hr ^-1 , about 2.0 to about 60.0 hr ^-1 , From about 2.0 to about 50.0 hr ^-1 , from about 2.0 to about 40.0 hr ^-1 , from about 2.0 to about 30.0 hr ^-1 , from about 2.0 to about 20.0 hr ^-1 , from about 2.0 to about 10.0 hr ^-1 , and from about 2.0 to about 5.0hr ^-1 . Preferably, the WHSV is from about 1.0 to about 100.0 hr ^-1 , more preferably from about 1.0 to about 60.0 hr ^-1 , more preferably from about 2.0 to about 40.0 hr ^-1 , more preferably from about 2.0 to about 20.0 hr ^{-1 .} .

Additionally, it is preferred to maintain an inverted temperature profile in the at least one reaction zone. As used herein, the term "inverted temperature distribution" means that the reactor inlet temperature is below the reactor outlet temperature. Preferably, the reactor line temperature at the inlet of the tube is lower than the reactor line temperature at the outlet of the reactor. "Inverted temperature distribution" includes a system of temperature changes in the reactor as long as the temperature at the inlet of the reactor is lower than the temperature at the outlet of the reactor. The "inverted temperature profile" additionally comprises a reactor having a midline temperature T1; at some lengths along the reactor, the midline temperature drops to a temperature T2; at other lengths along the reactor, the midline temperature rises To temperature T3; finally, the line temperature drops to temperature T4 at the reactor outlet; where T3 > T4 > T1 > T2. The temperature measured at the earliest contact catalyst composition near the inlet of the reactor may be from about 0 ° C to about 200 ° C lower than the temperature measured at the point where the effluent exiting the reactor outlet is at contact with the catalyst composition, preferably. From 25 ° C to about 150 ° C, more preferably from about 50 ° C to about 100 ° C. Preferably, the reactor midline temperature measured at the earliest contact catalyst composition near the reactor inlet may be lower than the reactor neutral temperature measured at the point where the effluent exiting the reactor outlet is contacted with the catalyst composition. From about 0 ° C to about 200 ° C, preferably from about 25 ° C to about 150 ° C, more preferably from about 50 ° C to about 100 ° C. In the preferred embodiment aspect, the at least one reverse temperature profile of the reaction zone means that the temperature of the reaction zone at least one of the raw material (e.g., non-cyclic hydrocarbons, C ₅₎ of the inlet to the product outlet of the first effluent gradually increased . In other words, when the raw material flows upward, the temperature of the at least one reaction zone may gradually rise from the bottom portion to the top portion of the at least one reaction zone; conversely, the temperature of the at least one reaction may be from the top portion of the at least one reaction zone to The bottom part is reduced by chance. Maintaining the inverted temperature profile in the at least one reaction zone advantageously minimizes the formation of carbonaceous materials at the inlet that may result from coking of the catalytic material. Inverted temperature profile will also provide sufficient reaction time and the length of the at least one reaction zone to produce sufficient amounts of the H at a temperature below the operating temperature of the outlet _2, this can minimize the formation of carbonaceous material product outlet.

Additionally, it is preferred to maintain an isothermal or substantially isothermal temperature profile in the at least one reaction zone. Having a substantially isothermal temperature profile of the catalyst to maximize the efficient use of and minimize undesirable C ₄ - Formation of byproducts advantages. As used herein, the term "isothermal temperature distribution" means that the temperature at each point between the inlet of the reactor and the outlet of the reactor, measured along the tube centerline of the reactor, remains substantially constant, for example, at the same temperature or at The difference between high and low temperatures does not exceed about 40 ° C; more preferably, it does not exceed the same narrow temperature range of about 20 ° C. Preferably, the isothermal temperature profile is such that the reactor inlet temperature is within about 40 ° C of the reactor outlet temperature, or within about 20 ° C, or within about 10 ° C, or within about 5 ° C, or the reactor inlet temperature. Same as the reactor outlet temperature. Alternatively, the isothermal temperature profile is such that the reactor inlet temperature is within about 20% of the reactor outlet temperature, or within about 10%, or within about 5%, or within about 1%.

Preferably, the isothermal temperature profile is along the length of the reaction zone within the reactor. The temperature of the degree does not vary by more than about 40 ° C, or no more than about 20 ° C, or no more than about 10 ° C, or no more than about 5 ° C. Alternatively, the isothermal temperature profile is within about 20% of the reactor inlet temperature within the reactor along the length of the reaction zone, or between about 10%, or within about 5%, or at about 1%.

Thus, the feed inlet of the feed to the reactor system (e.g., a non-cyclic C ₅ hydrocarbons) may be temperature About 700 ° C, About 675 ° C, About 650 ° C, About 625 ° C, About 600 ° C, About 575 ° C, About 550 ° C, About 525 ° C, About 500 ° C, About 475 ° C, About 450 ° C, About 425 ° C, About 400 ° C, About 375 ° C, About 350 ° C, About 325 ° C, About 300 ° C, About 275 ° C, About 250 ° C, About 225 ° C or About 200 ° C. Preferably, the feed to reactor systems (e.g., non-cyclic C ₅ hydrocarbons) to a temperature About 575 ° C, more preferably About 550 ° C, more preferably About 525 ° C, more preferably About 500 ° C. The temperature range expressly disclosed includes any combination of the foregoing recited values, for example, from about 200 ° C to about 700 ° C, from about 250 ° C to about 600 ° C, from about 350 ° C to about 650 ° C, from about 375 ° C to about 500 ° C, and the like. Preferably, the temperature of the feed to the reaction system (e.g., a non-cyclic C ₅ hydrocarbons) is from about 700 to about 200 ℃ deg.] C, more preferably from about 300 deg.] C to about Department 600 ℃, more preferably from about 400 deg.] C to about Department 550 More preferably, the temperature is from about 475 ° C to about 525 ° C. Providing a raw material in the above temperature (e.g., non-cyclic C ₅ hydrocarbons) can be advantageously minimized in their catalytic material may be in the presence of the unwanted C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) before reacting Lysis.

Additionally, the temperature at which the first effluent of the at least one reaction zone exits the effluent outlet may be About 400 ° C, About 425 ° C, About 450 ° C, About 475 ° C, About 500 ° C, About 525 ° C, About 550 ° C, About 575 ° C, About 600 ° C, About 625 ° C, About 650 ° C, About 675 ° C, or About 700 ° C. Preferably, the temperature of the first effluent exiting the at least one reaction zone is About 550 ° C, more preferably About 575 ° C, more preferably About 600 ° C. The temperature range expressly disclosed includes any combination of the foregoing recited values, for example, from about 400 ° C to about 700 ° C, from about 475 ° C to about 675 ° C, from about 525 ° C to about 650 ° C, from about 550 ° C to about 600 ° C, and the like. Preferably, the temperature of the first effluent exiting the at least one reaction zone is from about 475 ° C to about 700 ° C, more preferably from about 500 ° C to about 650 ° C, more preferably from about 550 ° C to about 625 ° C.

Additionally or alternatively, the reaction conditions in the at least one reaction zone may include a temperature of About 300 ° C, About 325 ° C, About 350 ° C, About 375 ° C, About 400 ° C, About 425 ° C, About 450 ° C, About 475 ° C, About 500 ° C, About 525 ° C, About 550 ° C, About 575 ° C, About 600 ° C, About 625 ° C, About 650 ° C, About 675 ° C, or About 700 ° C. Alternatively or alternatively, the temperature can be About 300 ° C, about 325 ° C, About 350 ° C, About 375 ° C, About 400 ° C, About 425 ° C, About 450 ° C, About 475 ° C, About 500 ° C, About 525 ° C, About 550 ° C, About 575 ° C, About 600 ° C, About 625 ° C, About 650 ° C, About 675 ° C, or About 700 ° C. The temperature range expressly disclosed includes any combination of the foregoing recited values, for example, from about 300 ° C to about 700 ° C, from about 350 ° C to about 675 ° C, and from about 400 ° C to about 600 ° C, and the like. Preferably, the temperature may range from about 350 ° C to about 700 ° C, more preferably from about 400 ° C to about 650 ° C, more preferably from about 450 ° C to about 625 ° C. Optionally, the at least one reaction zone may include one or more heating devices to maintain the temperature therein. Examples of suitable heating devices known in the art include, but are not limited to, fired tubes, heated coils with high temperature heat transfer fluids, electric heaters, and/or microwave emitters. As used herein, the term "coil" refers to a structure that is placed within a container and through which a heat transfer fluid flows to transfer heat to the contents of the container. The coil can have any suitable cross-sectional shape and can be straight, including U-tubes, including rings, and the like.

Additionally or alternatively, the reaction conditions at the effluent outlet of the at least one reaction zone may include a pressure of About 1.0 psia, About 2.0 psia, About 3.0 psia, About 4.0 psia, About 5.0 psia, About 10.0 psia, About 15.0 psia, About 20.0 psia, About 25.0 psia, About 30.0 psia, About 35.0 psia, About 40.0 psia, About 45.0 psia, About 50.0 psia, About 55.0 psia, About 60.0 psia, About 65.0 psia, About 70.0 psia, About 75.0 psia, About 80.0 psia, About 85.0 psia, About 90.0 psia, About 95.0 psia, About 100.0psia, About 125.0 psia, About 150.0psia, About 175.0 psia, or About 200.0 psia. Alternatively or alternatively, the pressure can be About 1.0 psia, About 2.0 psia, About 3.0 psia, About 4.0 psia, About 5.0 psia, About 10.0 psia, About 15.0 psia, About 20.0 psia, About 25.0 psia, About 30.0 psia, About 35.0 psia, About 40.0 psia, About 45.0 psia, About 50.0 psia, About 55.0 psia, About 60.0 psia, About 65.0 psia, About 70.0 psia, About 75.0 psia, About 80.0 psia, About 85.0 psia, About 90.0 psia, About 95.0 psia, About 100.0psia, About 125.0 psia, or About 150.0 psia. The ranges and combinations of temperatures and pressures expressly disclosed include any combination of the foregoing recited values, for example, from about 1.0 psia to about 200.0 psia, from about 2.0 psia to about 175.0 psia, from about 5.0 psia to about 95.0 psia, and the like. Preferably, the pressure can range from about 1.0 psia to about 100.0 psia, more preferably from about 2.0 psia to about 50.0 psia, more preferably from about 3.0 psia to about 20.0 psia.

Additionally or alternatively, the pressure differential across the at least one reaction zone (the pressure at the feed inlet minus the pressure at the effluent outlet) may be About 0.5 psia, About 1.0 psia, About 2.0 psia, About 3.0 psia, About 4.0 psia, About 5.0 psia, About 10.0 psia, About 14.0 psia, About 15.0, psia, About 20.0 psia, About 24.0 psia, About 25.0 psia, About 30.0 psia, About 35.0 psia, About 40.0 psia, About 45.0 psia, About 50.0 psia, About 55.0 psia, About 60.0 psia, About 65.0 psia, About 70.0 psia, About 75.0 psia, About 80.0 psia, About 85.0 psia, About 90.0 psia, About 95.0 psia, About 100.0psia, About 125.0 psia, or About 150.0 psia. As understood herein, "at the raw material inlet", "at the inlet", "at the effluent outlet" and "at the outlet" include spaces in and substantially around the inlet and/or outlet. Alternatively or alternatively, the differential pressure differential (or pressure drop) across the at least one reaction zone (the pressure at the feed inlet minus the pressure at the effluent outlet) may be About 2.0 psia, About 3.0 psia, About 4.0 psia, About 5.0 psia, About 10.0 psia, About 14.0 psia, About 15.0 psia, About 20.0 psia, About 24.0 psia, About 25.0 psia, About 30.0 psia, About 35.0 psia, About 40.0 psia, About 45.0 psia, About 50.0 psia, About 55.0 psia, About 60.0 psia, About 65.0 psia, About 70.0 psia, About 75.0 psia, About 80.0 psia, About 85.0 psia, About 90.0 psia, About 95.0 psia, About 100.0psia, About 125.0 psia, About 150.0psia, About 175.0 psia, or About 200.0 psia. The range of differential pressures expressly disclosed includes any combination of the foregoing recited values, for example, from about 10 psia to about 70.0 psia, from about 20.0 psia to about 60.0 psia, from about 30.0 psia to about 50.0 psia, and the like. In particular, the raw material substantially (e.g., non-cyclic hydrocarbons, C ₅₎ of the inlet pressure may be from about to about 10.0psia 70.0psia, preferably from about to about 20.0psia 60.0psia, more preferably from about 30.0psia about Department 50.0 psia. Additionally, substantially at least the outlet of the first effluent may have a pressure of from about 1.0 psia to about 20.0 psia, preferably from about 4.0 psia to about 15.0 psia, more preferably from about 4.0 psia to about 10.0 psia.

Additionally or alternatively, a stream comprising hydrogen may be fed to the at least one reaction zone. Such a hydrogen-containing stream can be introduced into the at least one reaction zone to minimize coke formation on the particulate material and/or to fluidize the particulate material in the at least one reaction zone. Of this stream may contain hydrogen contains light hydrocarbons (e.g., C ₁ -C _4); a light hydrocarbon content of the preferred system is less than about 50mol%, less than about 40mol%, less than about 30mol%, less About 20 mol%, less than about 10 mol%, less than about 5 mol%, less than about 1 mol%. Preferably, the hydrogen-containing stream is substantially free of oxygen, such as less than about 1.0 wt%, less than about 0.1 wt%, less than about 0.01 wt%, less than about 0.001 wt%, less than about 0.0001 wt%. , less than about 0.00001% by weight, and the like.

C. particulate material

Comprising the catalytic material (e.g., catalyst composition) of particulate material supplied to the reaction system to promote the C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) is converted to cyclopentadiene. Preferably, the material flows countercurrently in a direction to the flow of the particulate material.

Catalyst compositions useful herein include microporous crystalline metal ruthenates, such as crystalline aluminosilicates, crystalline ferric silicates, or other metal-containing crystalline silicates such as metals or metal-containing compounds dispersed in crystals. Within the citrate structure and may or may not be part of the crystallisation structure). The types of microporous crystalline metal ruthenate structures that can be used 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.

Particularly suitable microporous metal ruthenates for use herein include those of the MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU architecture types (such as zeolites). β, mordenite, faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58 and MCM- 22 mirror material), one or more of which are from the metals of 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) It is incorporated into the crystal structure during the synthesis or after the crystallization. It is known that metal citrate may be present in one or more metals, and for example a material may be referred to, but it is most likely still containing a small amount of aluminum.

The microporous crystalline metal phthalate preferably has a confinement index of less than 12, or 1 to 12, or 3 to 12. Aluminosilicates useful herein have a constraint index of less than 12, such as 1 to 12, or 3 to 12, and Including but not limited to zeolite beta, mordenite, faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, MCM-22 family materials, and mixtures of two or more thereof. In a preferred embodiment, the crystalline aluminosilicate has a Constraint Index of from about 3 to about 12 and is ZSM-5.

The ZSM-5 series is described in US 3,702,886. ZSM-11 is described in US 3,709,979. The ZSM-22 series is described in US 5,336,478. The ZSM-23 series is described in US 4,076,842. The ZSM-35 series is described in US 4,016,245. The ZSM-48 series is described in US 4,375,573. The ZSM-50 series is described in US 4,640,829. ZSM-57 is described in US 4,873,067. ZSM-58 is described in US 4,698,217. The constraint index and its method of determination are described in US 4,016,218. The entire contents of each of the above patents are incorporated herein by reference.

The MCM-22 family material 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, ITQ-1, ITQ-2, ITQ-30, and mixtures of two or more thereof.

Materials of the MCM-22 family include MCM-22 (described in US 4,954,325), PSH-3 (described in US 4,439,409), SSZ-25 (described in US 4,826,667), ERB-1 (described in EP 0 293 032), ITQ -1 (described in US 6,077,498) and ITQ-2 (described in WO 97/17290), MCM-36 (described in US 5,250,277), MCM-49 (described in US 5,236,575), MCM-56 (described in US 5,362,697) And two or more a mixture. The related zeolites UZM-8 (described in US 6,756,030) and UZM-8HS (described in US 7,713,513) included in the MCM-22 family are also suitable for use as molecular sieves of the MCM-22 family.

In one or more embodiments, the crystalline metal citrate has a Si/M molar ratio (wherein M is a Group 8, 11 or 13 metal) greater than about 3, or greater than about 25, or greater than about 50, or Greater than about 100, or greater than 400, or in the range of from about 100 to about 2,000, or from about 100 to about 1,500, or from about 50 to 2,000, or from about 50 to 1,200.

In one or more embodiments, the crystalline aluminosilicate has a SiO ₂ /Al ₂ O ₃ molar ratio greater than about 3, or greater than about 25, or greater than about 50, or greater than about 100, or greater than about 400, Or in the range of from about 100 to about 400, or from about 100 to about 500, or from about 25 to about 2,000, or from about 50 to about 1,500, or from about 100 to about 1,200, or from about 100 to about 1,000.

In another embodiment of the present invention, a microporous crystalline metal ruthenate (such as an aluminosilicate) and a Group 10 metal or metal compound, and optionally one, two, three or more first, two or Group 11 metals or metal compounds are combined.

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 the catalyst composition is at least 0.005 wt% based on the weight of the catalyst composition. In one or more embodiments, the Group 10 content ranges from about 0.005 wt% to about 10 wt%, or from about 0.005 wt% up to about 1.5 wt%, based on the weight of the catalyst composition.

In one or more embodiments, the Group 1 alkali metal comprises or is selected from the group consisting of Li, Na, K, Rb, Cs, and two or more thereof. The mixture is preferably Na.

In one or more embodiments, the Group 2 alkaline earth metal is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof.

In one or more embodiments, the Group 1 alkali metal is present in the form of an oxide, and the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and two or more thereof. a mixture. In one or more embodiments, the Group 2 alkaline earth metal is present in the form of an oxide, and the metal is selected from the group consisting of Be, magnesium, calcium, Sr, Ba, and two or more thereof. a mixture. In one or more embodiments, the Group 1 alkali metal is present in the form of an oxide, and the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and two or more thereof. a mixture; and the Group 2 alkaline earth metal is present in the form of an oxide, and the metal is selected from the group consisting of Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof.

In one or more embodiments, 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 the catalyst composition is at least 0.005 wt% based on the weight of the catalyst composition. In one or more embodiments, the Group 11 content ranges from about 0.005 wt% to about 10 wt%, or from about 0.005 wt% up to about 1.5 wt%, based on the weight of the catalyst composition.

In one or more embodiments, the alpha value of the catalyst composition (measured prior to the addition of the Group 10 metal, preferably platinum) is less than 25, or less than 15, either 1 to 25, or 1.1 to 15. The alpha value is as described in US 3,354,078; The Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), used. A constant temperature of 538 ° C and a variable flow rate are described in detail in The Journal of Catalysis, Vol. 61, p. 395 (1980).

In one or more embodiments of the aluminosilicate, the ratio of the Group 1 alkali metal to Al is at least about 0.5, or at least about 0.5 up to about 3, preferably at least about 1, more preferably At least about 2.

In one or more embodiments of the aluminosilicate, the ratio of the Group 2 alkaline earth metal to Al is at least about 0.5, or at least about 0.5 up to about 3, preferably at least about 1, more preferably At least about 2.

In one or more embodiments, the Group 11 metal to Group 10 metal molar ratio is at least about 0.1, or at least about 0.1 up to about 10, preferably at least about 0.5, more preferably at least About 1. In one or more embodiments, the Group 11 alkaline earth metal is present in the form of an oxide, and the metal is selected from the group consisting of gold, silver, and copper, and mixtures of two or more thereof.

In one or more aspects of the embodiments, the use of the catalyst composition of the present invention, there is provided a non-cyclic C ₅ feed of at least about 70% in the following non-cyclic C ₅ conversion conditions, or at least about 75%, or at least Conversion of about 80%, or in the range of from about 60% to about 80%: the n-pentane-containing feedstock has a molar H ₂ , the temperature ranges from about 550 ° C to about 600 ° C, and the n-pentane partial pressure is between The weight space velocity between 3 and 10 psia and n-pentane per hour is 10 to 20 hr ^-1 .

In one or more aspects of the embodiments, the present invention using the catalyst composition according to any one of the composition, at least about 30% C ₅ at conversion conditions include the following acyclic, or at least about 40%, or at least about 50%, or in the range from about 30% to about 80% of the carbon becomes the selective cyclic C ₅ compounds: n-pentane having equimolar H ₂ of the raw material, at a temperature range of from about 550 deg.] C to about 600 deg.] C, the n-pentane The partial pressure is between 3 and 10 psia, and the weight space velocity of n-pentane per hour is between 10 and 20 hr ^-1 .

In one or more aspects of the embodiments, the present invention using the catalyst composition according to any one of the composition, at least about 30% C ₅ at conversion conditions include the following acyclic, or at least about 40%, or at least about 50%, Or carbon selectivity to cyclopentadiene in the range of from about 30% to about 80%: n-pentane starting material with equal molar H ₂ , temperature in the range of from about 550 ° C to about 600 ° C, n-pentane The pressure is between 3 and 10 psia, and the weight space velocity of n-pentane per hour is between 10 and 20 hr ^-1 .

The catalyst composition of the present invention can be combined with a matrix or binder material to render it resistant to agitation and to the severity of the conditions exposed during use in hydrocarbon conversion applications. The combined composition may contain from 1 to 99% by weight of the material of the invention, based on the combined weight of the substrate (adhesive) and the material of the invention. The relative proportions of the positive crystalline material and the matrix can vary widely, from about 1 to about 90% by weight of the crystalline material, and more commonly, especially when the composite is prepared into beads, extrudates, pellets, particles formed by oil droplets, When spray dried particles or the like, it is in the range of from about 2 to about 80% by weight of the composite.

During the use of the catalyst composition in the process of the invention, coke is deposited on the catalyst composition, thereby causing such catalyst compositions to lose some of their catalytic activity. Sex and become deactivated. The deactivated catalyst composition can be regenerated by conventional techniques, including high pressure hydrogen treatment and coke on the oxygen-containing gas combustion catalyst composition.

Useful catalyst compositions comprise crystalline aluminosilicate or ferrite, optionally in combination with one, two or more additional metals or metal compounds. Preferred combinations include: 1) a crystalline aluminosilicate (such as ZSM-5 or zeolite) in combination 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. L); 2) 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) with Group 10 metals (such as Pt) and a group of alkali metal (such as sodium or potassium) combined with crystalline aluminosilicate (such as ferric or iron-treated ZSM-5); 4) with a Group 10 metal (such as Pt) a crystalline aluminosilicate (zeolite L) combined with a Group 1 alkali metal (such as potassium); and 5) with a Group 10 metal (such as Pt), a Group 1 alkali metal (such as sodium), and a Group 11 metal A crystalline aluminosilicate (such as ZSM-5) combined with (such as silver or copper).

Other useful catalyst compositions are Group 10 metals (such as Ni, Pd, and Pt, preferably Pt) supported on vermiculite (e.g., cerium oxide), which are based on Group 1 alkali metals. A citrate such as Li, Na, K, Rb and/or Cs citrate and/or a Group 2 alkaline earth metal citrate such as Mg, Ca, Sr and/or ba citrate, preferably Potassium citrate, sodium citrate, calcium citrate and/or magnesium citrate are preferably modified with potassium citrate and/or sodium citrate. The Group 10 metal content of the catalyst composition is at least 0.005 wt%, based on the weight of the catalyst composition, preferably from about 0.005 wt% to about 10 wt%, or about, based on the weight of the catalyst composition. From 0.005 wt% up to about 1.5 wt%. Vermiculite (SiO ₂ ) can be any vermiculite commonly used as a catalyst carrier, such as those commercially available under the trade designations DAVISIL 646 (Sigma Aldrich), DAVISON 952, DAVISON 948 or DAVISON 955 (Davison Chemical Division of WR Grace and Company).

The catalyst composition shape and design are preferably configured to minimize pressure drop, improve heat transfer, and minimize mass transfer phenomena. Suitable catalyst shapes and designs are described in WO 2014/053553, which is incorporated by reference in its entirety. The catalyst composition can be an extrudate having a diameter of from 2 mm to 20 mm. Optionally, the cross-section of the catalyst composition can be shaped to have one or more raised and/or recessed portions. Additionally, the raised and/or recessed portions of the catalyst composition may be helical. The catalyst composition may be an extrudate having a diameter of from 2 mm to 20 mm; the catalyst composition may be shaped to have one or more raised and/or recessed portions in cross section; and the catalyst composition is raised and/or The concave portion may be spiral. In the case of fixed bed reactors (flammable tubes, convection tubes, and rings), the shape of the particles such as protrusions, recesses, and spirals is particularly useful, and in the case of fluid bed reactors, the shape of the sphere particles is particularly useful. Preferably, the particles used in the fixed bed (for example, an annular fixed bed, a gas tube reactor, a convection heating tube reactor, etc.) are generally extrudates having a diameter of 2 mm to 20 mm; and the catalyst composition is traversed The face may be shaped to have one or more raised and/or recessed portions; and the catalyst composition raised and/or recessed portions may be helical.

For more information on available catalyst compositions, please see the following applications: 1) USSN 62/250,675, filed on November 4, 2015; 2) USSN 62/250,681, filed on November 4, 2015; USSN 62/250,688, filed on November 4, 2015; 4) USSN 62/250,695, filed on November 4, 2015; and 5) USSN 62/250,689, filed on November 4, 2015; The application is incorporated herein by reference.

Preferably, the catalyst material comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on vermiculite.

The appropriate amount of catalyst material in the particulate material can be About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, About 85.0wt%, About 90.0% by weight, About 95.0wt%, About 99.0 wt% or about 100.0 wt%. Preferably, the particulate material can comprise About 30.0% by weight of the catalyst material. Additionally or alternatively, the particulate material may comprise the following amounts of catalyst material: About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, About 85.0wt%, About 90.0% by weight, or About 95.0% by weight. The range explicitly disclosed includes any combination of the foregoing recited values; for example from about 1.0 wt% to about 100.0 wt%, from about 5.0 wt% to about 100.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 20.0 wt% to about 80.0 wt%, etc. Preferably, the particulate material may comprise the following amount of catalyst material: from about 5.0 wt% to about 90.0 wt%, more preferably from about 10.0 wt% to about 80.0 wt%, more preferably from about 20.0 wt% to about 70.0 wt%. More preferably, it is from about 25.0% by weight to about 60.0% by weight, more preferably from about 30.0% by weight to about 50.0% by weight.

In various aspects, the particulate material may additionally comprise one or more inert materials. As referred to herein, it is understood that inert materials include promoting negligible amounts under the reaction conditions described herein (eg, About 3%, About 2%, About 1%, etc.) of the material, intermediate product, or material converted from the final product. The catalytic material and the inert material may be combined as parts of the same particle and/or may be separate particles. Additionally, the catalyst material and/or inert material can be substantially spherical (ie, < about 20%, < about 30%, < about 40%, or < about 50% of the diameter variation).

A suitable amount of the inert material in the particulate material may be about 0.0 wt%, About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, About 85.0wt%, About 90.0% by weight, About 95.0% by weight, or About 99.0% by weight. Preferably, the particulate material can comprise About 30.0% by weight of inert material. Additionally or alternatively, the particulate material may comprise the following amounts of inert material: About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, About 85.0wt%, About 90.0% by weight, About 95.0% by weight, or About 99.0% by weight. The range explicitly disclosed includes any combination of the foregoing recited values, for example, from about 0.0 wt% to about 99.0 wt%, from about 0.0 wt% to about 95.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 20.0 wt% to About 80.0% by weight and the like. Preferably, the particulate material may comprise an inert material in an amount of from about 0.0 wt% to about 95.0 wt%, more preferably from about 0.0 wt% to about 90.0 wt%, more preferably from about 30.0 wt% to about 85.0 wt%.

In various aspects, the catalytic material and/or the inert material (either as separate particles or as part of a combination of the same particles) may have the following average diameter: About 50μm, About 100μm, About 200μm, About 300μm, About 400μm, About 500μm, About 600μm, About 700μm, About 800μm, About 900μm, About 1000μm, About 1100μm, About 1200μm, About 1300μm, About 1400μm, About 1500μm, About 1600μm, About 1700μm, About 1800μm, About 1900μm, About 2000μm, About 2100μm, About 2200μm, About 2300μm, About 2400μm, About 2500μm, About 2600μm, About 2700μm, About 2800μm, About 2900μm, About 3000μm, About 3100μm, About 3200μm, About 3300μm, About 3400μm, About 3500μm, About 3600μm, About 3700μm, About 3800μm, About 3900μm, About 4000μm, About 4100μm, About 4200μm, About 4300μm, About 4400μm, About 4,500 μm, About 5000μm, About 5500 μm, About 6000μm, About 6500μm, About 7000μm, About 7500μm, About 8000μm, About 8500μm, About 9000μm, About 9500μm, or About 10,000 μm. Additionally or alternatively, the catalyst material and/or the inert material (either as separate particles or as part of a combination of the same particles) may have the following average diameter: may have the following average diameter: About 50μm, About 100μm, About 200μm, About 300μm, About 400μm, About 500μm, About 600μm, About 700μm, About 800μm, About 900μm, About 1000μm, About 1100μm, About 1200μm, About 1300μm, About 1400μm, About 1500μm, About 1600μm, About 1700μm, About 1800μm, About 1900μm, About 2000μm, About 2100μm, About 2200μm, About 2300μm, About 2400μm, About 2500μm, About 2600μm, About 2700μm, About 2800μm, About 2900μm, About 3000μm, About 3100μm, About 3200μm, About 3300μm, About 3400μm, About 3500μm, About 3600μm, About 3700μm, About 3800μm, About 3900μm, About 4000μm, About 4100μm, About 4200μm, About 4300μm, About 4400μm, About 4,500 μm, About 5000μm, About 5500μm, About 6000μm, About 6500μm, About 7000μm, About 7500μm, About 8000μm, About 8500μm, About 9000μm, About 9500μm, or About 10,000 μm. The range explicitly disclosed includes any combination of the foregoing recited values, for example, from about 50 μm to about 10,000 μm, from about 100 μm to about 9000 μm, from about 200 μm to about 7500 μm, from about 200 μm to about 5500 μm, from about 100 μm to about 4000 μm, from about 100 μm to about 700 μm, etc. Preferably, in a circulating fluidized bed, the catalytic material and/or the inert material (either as separate particles or as part of a combination of the same particles) may have an average diameter of from about 100 μm to about 4000 μm, more preferably about From 100 μm to about 700 μm, more preferably from about 100 μm to about 600 μm, more preferably from about 100 μm to about 500 μm. Preferably, in the circulating settled bed, the catalytic material and/or the inert material (in the form of separated particles or portions joined as the same particles) may have an average diameter of from about 1000 μm to about 10,000 μm, more preferably about From 2000 μm to about 8000 μm, more preferably from about 3000 μm to about 6000 μm, more preferably from about 3500 μm to about 4500 μm.

Preferably, the particulate material is provided to improve at least a portion of the sensible heat of the raw material, and / or at least a portion of the non-cyclic C ₅ hydrocarbons to the desired hot effluent comprising a first sum of cyclopentadiene. For example, particulate materials are available About 30%, About 35%, About 40%, About 45%, About 50%, About 55%, About 60%, About 65%, About 70%, About 75%, About 80%, About 85%, About 90%, About 95%, or 100% of the heat required. The scope of the explicit disclosure includes any combination of the foregoing recited values; for example, from about 30% to about 100%, from about 40% to about 95%, from about 50% to about 90%, and the like. Preferably, the particulate material provides from about 30% to about 100% of the desired heat, more preferably from 50% to about 100% of the desired heat, more preferably from 70% to about 100% of the desired heat. .

D. Effluent

Discharging the at least one reaction zone effluent (e.g., a first effluent, second effluent) can comprise a wide range from the at least one reaction zone of C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) The hydrocarbon composition produced by the reaction. The hydrocarbon compositions typically have from 1 to 30 carbon atoms (C ₁ -C ₃₀ hydrocarbons), from 1 to 24 carbon atoms (C ₁ -C ₂₄ hydrocarbons), from 1 to 18 carbon atoms (C ₁ -C) ₁₈ hydrocarbons), 1 to 10 carbon atoms (C ₁ -C ₁₀ hydrocarbons), 1 to 8 carbon atoms (C ₁ -C ₈ hydrocarbons), and 1 to 6 carbon atoms (C ₁ -C _{6 )} a mixture of hydrocarbon compounds of hydrocarbons. More specifically, the first effluent comprises cyclopentadiene. Cyclopentadiene may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0% by weight, or About 80.0% by weight. Additionally or alternatively, cyclopentadiene may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount of About 20.0% by weight, about 25.0% by weight, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, or About 85.0% by weight. The range explicitly disclosed includes any combination of the foregoing recited values, for example, from about 20.0 wt% to about 85.0 wt%, from about 30.0 wt% to about 75.0 wt%, from about 40.0 wt% to about 85.0 wt%, from about 50.0 wt% to About 85.0% by weight and the like. Preferably, the cyclopentadiene may be present in the hydrocarbon portion of the effluent (e.g., the first effluent, the second effluent) in an amount from about 10.0% to about 85.0% by weight, more preferably about 25.0% by weight. To about 80.0% by weight, more preferably from about 40.0% by weight to about 75.0% by weight.

In other aspects, in addition to the cyclopentadiene, the effluent (e.g., a first effluent, second effluent) may further comprise one or more other C ₅ hydrocarbons. Examples of other C ₅ hydrocarbons include, but are not limited to, cyclopentane and cyclopentene. The one or more other C ₅ hydrocarbons may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount of About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0% by weight, or About 70.0% by weight. Additionally or alternatively, the one or more other C ₅ hydrocarbons may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount of About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, about 35.0% by weight, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0 wt%, or about 70.0 wt%. The range explicitly disclosed includes any combination of the foregoing recited values, for example, from about 10.0 wt% to about 70.0 wt%, from about 10.0 wt% to about 55.0 wt%, from about 15.0 wt% to about 60.0 wt%, from about 25.0 wt% to About 65.0% by weight and the like. Preferably, the one or more other C ₅ hydrocarbons may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount from about 30.0 wt% to about 65.0 wt%, more preferably It is from about 20.0% by weight to about 40.0% by weight, more preferably from about 10.0% by weight to about 25.0% by weight.

In other aspects, the effluent (eg, the first effluent, the second effluent) may also comprise one or more aromatics, for example, having from 6 to 30 carbon atoms, particularly from 6 to 18 carbon atoms. The one or more aromatics may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount of about About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, or About 65.0% by weight. Additionally or alternatively, the one or more aromatics may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount of About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, or About 65.0% by weight. The range explicitly disclosed includes any combination of the foregoing recited values, for example, from about 1.0 wt% to about 65.0 wt%, from about 10.0 wt% to about 50.0 wt%, from about 15.0 wt% to about 60.0 wt%, from about 25.0 wt% to About 40.0% by weight, and the like. Preferably, the one or more aromatics may be present in the hydrocarbon portion of the effluent (eg, the first effluent, the second effluent) in an amount from about 1.0% to about 15.0% by weight, more preferably about From 1.0 wt% to about 10 wt%, more preferably from about 1.0 wt% to about 5.0 wt%.

For information on possible disposal of effluents, please see the following applications: 1) USSN 62/250,678, filed on November 4, 2015; 2) USSN 62/250,692, filed on November 4, 2015; 3) USSN 62/250, 702, filed on November 4, 2015; and 4) USSN 62/250, 708, filed on Nov. 4, 2015, the disclosure of which is hereby incorporated by reference.

E. Stripping/separating effluent

In various aspects, as the effluent travels through and/or exits to When one reaction zone is less, the particulate material is entrained by hydrocarbons (e.g., cyclopentadiene) in the effluent (e.g., the first effluent, the second effluent). As such, the method additionally includes separating particulate material entrained by hydrocarbons (eg, cyclopentadiene) in the effluent (eg, the first effluent, the second effluent). The separation may comprise the removal of particulate material from a hydrocarbon (eg, cyclopentadiene) by any suitable means such as, but not limited to, a cyclone, a filter, an electrostatic precipitator, heavy liquid contact, And/or other gas-solid separation equipment, which may be internal and/or external to the at least one reaction zone. The effluent without particulate material can then travel to the product recovery system. Additionally, the removed particulate material can then be fed back into the at least one reaction zone using known methods, for example, a substantially top portion of the at least one reaction zone.

In various aspects, a hydrocarbon (e.g., cyclopentadiene) is entrained by the particulate material as it travels through and/or exits at least one of the reaction zones. Hydrocarbons can be adsorbed onto and/or within the particles and in the interstitial regions between the particles. As such, the method additionally includes the reference to/or separation of hydrocarbons from the particulate material vapor in the effluent. The mentioned vapor / or isolated by any suitable means may comprise removing hydrocarbons (e.g., cyclopentadiene and / or non-cyclic C ₅ classes) from the particulate material, such as but not limited to such means with a gas (such as H ₂ or methane) stripping, and / or other gas-solid separation equipment, their may be a reaction zone at least the internal and / or external. The particulate material having a reduced hydrocarbon content can then travel to a reheat zone, a rejuvenation zone, and/or a regeneration zone, and the hydrocarbons stripped from the particulate material can be passed to product recovery. System or lead to the reactor system.

F. Reheat/recovery zone

When the reaction occurs in the at least one reaction zone, the coke material is formed on the particulate material, particularly on the catalyst material, which reduces the activity of the catalyst material. Alternatively or alternatively, the particulate material will cool as the reaction occurs. The catalyst material that discharges the at least one reaction zone is referred to as "a waste catalyst material." Since the individual particles have a total aging distribution in the system, the time of the last regeneration, and/or the time spent in the reaction zone relative to the reheat/recovery zone, the spent catalyst material may not necessarily be microparticles. A homogeneous mixture.

As such, at least a portion of the particulate material (eg, spent catalyst material) can be transferred from the at least one reaction zone to the reheat zone. Transfer of the particulate material (e.g., spent catalyst material) from the at least one reaction zone to the reheat zone can occur after the particulate material has been stripped of the at least one reaction zone and/or separated from the hydrocarbon. The reheat zone may include one or more heating devices such as, but not limited to, direct contact, heating coils, and/or fuel tubes.

In various aspects, in the reheat zone, particulate material (eg, spent catalyst material) can be contacted with a stream of hydrogen to remove at least a portion of the coke material incrementally deposited on the catalyst material to form a recovery catalyst. Materials and volatile hydrocarbons such as, but not limited to, methane. As used herein, the term "incremental deposition" of coke material refers to the amount of coke deposited on the catalyst material during each passage of at least one reaction zone of the catalyst material during a plurality of passes through at least one reaction zone. The cumulative amount of coke material deposited on the catalyst material. Preferably, the hydrogen flow is substantially free of damage and/or catalyst loss. The active oxygen of the material. The recovered catalytic material can then be returned to the at least one reaction zone.

The reheat zone (ie, the temperature at which the particulate material is exposed) can be operated at the following temperatures: About 400 ° C, About 450 ° C, About 500 ° C, About 550 ° C, About 600 ° C, About 650 ° C, About 700 ° C, About 750 ° C, or About 800 ° C. Alternatively or alternatively, the reheat zone can be operated at the following temperatures: About 400 ° C, About 450 ° C, About 500 ° C, About 550 ° C, About 600 ° C, About 650 ° C, About 700 ° C, About 750 ° C, About 800 ° C, or About 850 ° C. The temperature range expressly disclosed includes any combination of the foregoing recited values, for example, from about 400 ° C to about 600 ° C, from about 450 ° C to about 850 ° C, from about 500 ° C to about 800 ° C, and the like. Preferably, the reheat zone is operable at a temperature of from about 400 ° C to about 800 ° C, more preferably from about 600 ° C to about 750 ° C, more preferably from about 550 ° C to about 700 ° C.

Alternatively or alternatively, the reheat zone can be operated at the following pressures: About 1.0 psia, About 5.0 psia, About 25.0 psia, About 50.0 psia, About 75.0 psia, About 100.0psia, About 125.0 psia, About 150.0psia, About 175.0, psia About 200.0psia, About 225.0 psia, About 250.0psia, About 275.0 psia, or About 300.0 psia. Alternatively or alternatively, the reheat zone can be operated at the following pressures About 1.0 psia, About 5.0 psia, About 25.0 psia, About 50.0 psia, About 75.0 psia, About 100.0psia, About 125.0 psia, About 150.0psia, About 175.0 psia, About 200.0psia, About 225.0 psia, About 250.0psia, About 275.0 psia, or About 300.0 psia. The range of pressures expressly disclosed includes any combination of the foregoing recited values, for example, from about 1.0 psia to about 300.0 psia, from about 5.0 psia to about 275.0 psia, from about 25.0 psia to about 250.0 psia, and the like. In particular, the reheat zone can be operated at a pressure of from about 1 psia to about 300 psia, more preferably from about 5 psia to about 250 psia, more preferably from about 25 psia to about 250 psia.

Preferably, in the reheat zone, the amount of incrementally deposited coke material removed from the catalyst material is About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, About 85.0wt%, About 90.0% by weight, About 95.0 wt%, or about 100.0 wt%. Preferably, the coke material deposited in increments of at least about 10 wt%, at least about 20 wt%, at least about 50 wt%, at least about 70 wt%, or at least about 90 wt% is removed from the catalyst material. Additionally or alternatively, the amount of incrementally deposited coke material removed from the catalyst material is About 1.0% by weight, About 5.0% by weight, About 10.0% by weight, About 15.0wt%, About 20.0% by weight, About 25.0wt%, About 30.0% by weight, About 35.0wt%, About 40.0% by weight, About 45.0wt%, About 50.0% by weight, About 55.0wt%, About 60.0% by weight, About 65.0wt%, About 70.0% by weight, About 75.0wt%, About 80.0% by weight, About 85.0wt%, About 90.0% by weight, About 95.0 wt%, or about 100.0 wt%. The range explicitly disclosed includes any combination of the foregoing recited values, for example, from about 1.0 wt% to about 100.0 wt%, from about 5.0 wt% to about 95.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 30.0 wt% to About 90.0% by weight and the like. Preferably, the amount of incrementally deposited coke material removed from the catalyst material is from about 1.0 wt% to about 100.0 wt%, more preferably from about 10.0 wt% to about 100.0 wt%, more preferably about 60.0 wt%. To about 100.0% by weight, more preferably from about 90.0% by weight to about 100.0% by weight.

In various aspects, the temperature of the recovered catalyst material can be About 400 ° C, About 450 ° C, About 500 ° C, About 550 ° C, About 600 ° C, About 650 ° C, About 700 ° C, About 750 ° C, or About 800 ° C. Alternatively or alternatively, the temperature of the recovered catalyst material may be About 400 ° C, About 450 ° C, About 500 ° C, About 550 ° C, About 600 ° C, About 650 ° C, About 700 ° C, About 750 ° C, About 800 ° C, or About 850 ° C. The temperature range expressly disclosed includes any combination of the foregoing recited values, for example, from about 400 ° C to about 800 ° C, from about 450 ° C to about 850 ° C, from about 500 ° C to about 800 ° C, and the like. Preferably, the temperature of the recovered catalyst material can range from about 400 ° C to about 700 ° C, more preferably from about 500 ° C to about 750 ° C, more preferably from about 550 ° C to about 700 ° C.

In one embodiment, the reheat zone can include a plurality of fluid bed tubes disposed within the firebox (or furnace). The firebox can include a radiating portion, a shield, and a convection portion. Introduction of fuels which may contain H ₂ , CO, light hydrocarbons (C ₁ -C ₄ ), liquid hydrocarbons (C ₅ -C ₂₅ ), and/or heavy liquid hydrocarbons (C ₂₅₊ ) and air One or more burners and burn it. The radiant heat generated in the fire box can then be transferred to the tube wall to provide the heat required to heat the circulating particulate material (eg, waste catalyst material). The convection section can be used for feed preheating, gas preheating, and/or for steam production. The fire box can be burned from the top or bottom. The flue gas may flow in a direction of cross flow, cocurrent flow, or countercurrent flow in a direction in which particulate material (eg, waste catalyst material) circulating inside the plurality of fluid bed tubes flows. Additionally, hydrogen can be used to raise and fluidize particulate material (eg, spent catalyst material) that circulates within the plurality of fluid bed tubes. Hydrogen may flow in a direction of cocurrent or countercurrent to the direction of the particulate material (eg, spent catalyst material).

In other embodiments, the reheat zone can include a plurality of fluid bed tubes disposed within the outer casing, wherein the tubes can be in contact with the hot combustion gases such that the tubes can be combusted from a furnace, gas turbine, or catalytic combustion The hot gas of the product is convectively heated. The use of convection heating reduces the temperature of the membrane exposed by the particulate material, thereby reducing the likelihood of catalyst damage due to overheating. The hot combustion gases may flow in a direction of cross flow, cocurrent flow, or countercurrent flow in a direction in which particulate material (eg, waste catalyst material) circulating inside the plurality of fluid bed tubes flows. Additionally, hydrogen can be used to raise and fluidize particulate material (eg, spent catalyst material) that circulates within the plurality of fluid bed tubes. Hydrogen may flow in a direction of cocurrent or countercurrent to the direction of the particulate material (eg, spent catalyst material).

In other embodiments, the reheat zone can include a fluid bed equipped with a plurality of burner tubes or coils. Each coil or burner may be combusted individually or collectively by fuel and air to provide radiant heat that may be transferred to the fluid bed via the wall. As such, particulate material (eg, spent catalyst material) circulating within the fluid bed can be reheated via the heat transfer properties of the fluid bed. The particulate material (e.g., waste catalyst material) circulating inside the fluid bed may flow in a direction of cross flow, cocurrent flow, or countercurrent flow with the gas flow direction in the combustion tube. In addition, the flue gas in each of the burner tubes can be discharged to the reheating zone and connected to a common heater that can be led to the convection tank, which can be used to heat the feedstock, preheat the reheat zone (eg, preheat the hydrogen) Flow), and manufacturing steam. The coil may contain hot combustion gases such that the tubes are heated by convection of hot gases from the combustion products of the furnace, gas turbine or catalytic combustion; or the coils contain heat that has been heated elsewhere (such as in a furnace) Transfer the medium (for example, melt or vaporize the metal or salt).

The state inside the reheating zone may be: 1. a foaming state in which the surface gas velocity is greater than the minimum foaming velocity but lower than the minimum agglomeration velocity; 2. the agglomerated state in which the standard at the beginning of the agglomeration (for example, Stewart Standard, Kunii, D., Levenspiel, O., Fluidization Engineering (Second Edition, Butterworth-Heinemann, Boston, 1991) Chapter 3 and Walas, SM, Chemical Process Equipment (Revision 2nd Edition, Butterworth-Heinemann, In Boston, 2010), in the diameter and length of the tube, the surface gas velocity is greater than the minimum agglomeration velocity, but lower than the transition to turbulent fluidization velocity; 3. Transition to turbulent fluidization state, where the surface The gas velocity is greater than the transition to turbulent fluidization velocity, but lower than the rapid fluidization velocity; or 4. The fast fluidization state, wherein the surface gas velocity is greater than the rapid fluidization velocity.

Preferably, the reheat zone operates in state 1 or 2 which minimizes the amount of hydrogen in the fluid bed, maximizes the residence time of the catalyst material for coke removal, and/or improves heat transfer properties.

In other embodiments, the particulate material (eg, spent catalyst material) may be heated by heat with other devices (such as furnaces) that facilitate coke removal or at least do not cause additional coke deposition (eg, methane). The stream (i.e., H ₂ ) is directly contacted and reheated.

Additionally or alternatively, the recovered catalytic material may be separated from the hydrogen and/or volatile hydrocarbons by any suitable means such as, but not limited to, a cyclone, either inside or outside the reheat zone.

Additionally or alternatively, the fresh particulate material may be provided directly to at least one reaction zone and/or to the reheat zone prior to entering the at least one reaction zone.

G. Regeneration area

The method may also include a regeneration step to retrieve the catalyst activity lost to the catalyst material during the reaction due to accumulation of coke material and/or metal agglomeration. The regeneration step can be performed when the coke material of the particulate material (e.g., waste catalyst material) in the reheat zone is not sufficiently removed. Advantageously, the regeneration step enables substantially continuous removal and addition of particulate material to the at least one reaction zone to maintain continuous operation of high catalyst activity. For example, the activity of the catalyst in the at least one reaction zone can be maintained above about 10% of the activity of the fresh catalyst, preferably above about 30% of the activity of the fresh catalyst, and the optimum is higher than the activity of the fresh catalyst. About 60%, and about 99.9% below the activity of the fresh catalyst.

Preferably, in the regeneration step, at least a portion of the particulate material from the at least one reaction zone or reheat zone is transferred to the reheat zone and regenerated by methods known in the art.

The catalyst may be continuously withdrawn from the reaction zone and/or the reheat/recovery zone and returned to the reaction zone and/or the reheat/recovery zone, or may be periodically withdrawn from the reaction zone and/or the reheat/recovery zone and returned to the reaction zone. And / or reheat / recovery zone. Set The method, usually, the regeneration time between the extraction for coke combustion, washing and reduction is from about 24 hours (about 1 day) to about 240 hours (about 10 days), preferably about 36 hours ( About 1.5 days) to about 120 hours (about 5 days). Alternatively, in the continuous mode, when the particulate material is balanced addition/removal, the removal/addition rate of the particulate material can range from about 0.0 wt% to about 100 wt% of the particulate material inventory per day (eg, from about 0.01 wt% to about 100 wt%), preferably from about 0.25 wt% to about 30.0 wt% of the inventory of particulate material per day. Regeneration of the catalytic material can be carried out as a continuous process, or it can be done in batches, both of which would require intermediate containers for inventory accumulation and/or inventory discharge.

The removal and addition of particulate material (waste catalyst, fresh particulate material, recycled catalytic material) can be carried out at the same or different locations in the reactor system. The particulate material (eg, fresh particulate material, recycled catalytic material) may be added after or before the reheat zone, and the particulate material (eg, waste catalyst material) may be removed from the particulate material (eg, spent catalyst) Material) is completed before or after the reheat zone. At least a portion of the regenerated catalyst material can be recycled to the at least one reaction zone or the at least one reheat zone. Preferably, the regenerated catalyst material and/or fresh particulate material is provided to the reheat zone to minimize any loss of heat input and to remove any residual species that would be carried by the regenerated catalyst material from the regeneration zone. Additionally or alternatively, a separator internal or external to the regeneration zone can be used to separate the inert material from the catalytic material prior to regeneration, thus regenerating only the catalytic material. The separation can be carried out using any suitable means depending on the size, magnetic and/or density properties between the inert material and the regenerated catalyst material.

For the above methods, a standpipe known to those skilled in the art can be used to provide particulate material transport between the at least one reaction zone, the reheat zone, and/or the regeneration zone under the above-described particle size and operating conditions. Tool of. Spool valves and lift gases known to those skilled in the art can also be used to assist in circulating particulate material and/or establishing the necessary pressure distribution within the regeneration zone. The lift gas is the same as the fluidizing gas used in the reheat zone, for example, to minimize hydrogen use in the reaction system while also reducing the hydrogen flow formed by the coke material.

III. Reaction system for acyclic C ₅ conversion

In other embodiments aspects, there is provided the C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) is converted to cyclopentadiene of the reaction system, as shown in FIG. The reaction system may contain as the raw material contains C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbon) stream 2, a first effluent stream comprising cyclopentadiene of 3, as described above comprising at least one catalytic material comprising the particulate material The catalyst stream 4, at least one spent catalyst stream 5 comprising spent catalyst material as described above, and at least one reactor 6 as described above. At least one reactor 6 may comprise a feedstock inlet (not shown) for providing a feed stream 2 to the reaction system; at least one catalyst inlet for providing at least one catalyst stream 4 to the reaction system (not shown) An effluent outlet (not shown) for removing the first effluent stream 3; and a spent catalyst outlet (not shown) for removing at least one spent catalyst stream 5. Additionally or alternatively, the reaction system may also include a hydrogen stream 7 fed to a catalyst stripping zone (not shown), a gas effluent (eg, hydrogen and/or hydrocarbons that have stripped off the catalyst material) Flow to the at least one reactor 6.

The at least one reactor 6 can be a circulating fluidized bed or a circulating settled bed reactor, preferably a circulating fluidized bed reactor. Additionally or alternatively, the at least one reactor is not a radial flow reactor or a cross flow reactor.

Additionally or alternatively, the at least one reactor 6 may comprise at least a first reactor, a second reactor, a third reactor, a fourth reactor, a fifth reactor, a sixth reactor, a seventh reactor, and the like. As used herein, each "reactor" can be an individual vessel or an individual reaction zone within a single vessel. Preferably, the reaction system comprises from 1 to 20 reactors, more preferably from 1 to 15 reactors, more preferably from 2 to 10 reactors, still more preferably from 3 to 8 reactors. More specifically, the circulating settled bed reactor can be a vessel having a bed height to diameter ratio of at least about 2:1. The fluidized bed reactor may comprise a plurality of reaction zones (e.g., 3 to 8) or a plurality of vessels (e.g., 3 to 8) in a single vessel. When the at least one reactor 6 comprises first and second reactors, the reactors may be configured in any suitable configuration, preferably in series, wherein a plurality of feedstocks are moved from the first reactor to the second reactor, and / or a large amount of particulate material is moved from the second reactor to the first reactor. Each reactor can independently be a circulating fluidized bed reactor or a circulating settled bed reactor.

Preferably, the at least one reactor 6 can comprise at least one or more internal structures 8 as described above. More specifically, the at least one reactor 6 may comprise a plurality of internal structures (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, etc.), Such as baffles, sheds, trays, tubes, rods and/or distributors.

The at least one reactor system to convert at least a portion of the 6 C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) is converted into cyclopentadiene at reaction conditions of operation as described above. Preferably, the feed stream 2 in the reactor 6 flows countercurrently to the flow direction of at least one of the catalyst streams 4 in the reactor. Further, it is preferred that the at least one reactor 6 has an inverted temperature distribution as described above. In particular, feed stream 2 at the feedstock inlet has a temperature of less than about 500 °C, and/or first effluent stream 3 at the outlet of the effluent has a temperature of at least about 550 °C. Additionally, the reaction conditions can include a temperature of from about 400 ° C to about 700 ° C and/or a pressure of from about 3 psia to about 100 psia. Preferably, at least about 30wt% based conversion C ₅ acyclic hydrocarbons into cyclopentadiene. Optionally, the at least one reactor 6 can include one or more heating devices (e.g., a burner, a heated coil) (not shown) to maintain the temperature therein.

More specifically, the particulate material comprises less than about 30.0% by weight of the above-described catalyst material and comprises an inert material as described above (e.g., at least about 30.0% by weight). The catalyst material and/or the inert material may have an average diameter as described above (e.g., from about 100 μm to about 4,000 μm). Preferably, the catalyst material comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on vermiculite, preferably platinum on ZSM-5. Further, the particulate material may provide at least a portion (e.g., at least about 50%) for increasing the temperature of the raw material 2 and / or C ₅ hydrocarbons (e.g., C ₅ acyclic hydrocarbons) is converted to the desired flow cyclopentadiene hot.

Additionally, the reaction system may also include a cyclone 9 (showing one, but there may be two or more series operators operating in parallel with one or more) to separate hydrocarbons entrained in the first effluent stream 3 (eg, , cyclopentadiene) particulate material. The second effluent stream 11 which is substantially free of particulate material can then travel to the product recovery system. In addition, the removed particulate material 10 is then The at least one reactor 6 can be fed back (the material can be returned to the top of the reactor, but more preferably, it can be returned to the bottom of the reactor).

In other embodiments, as shown in FIG. 2, the reaction system may further comprise a reheating device 12 for reheating and/or regenerating the activity of the spent catalyst material, wherein the reheating device 12 is reactive with the at least one The device 6 is fluidly connected. The reheating device 12 can include one or more heating devices as described above, a reheat inlet (not shown) for the at least one spent catalyst stream 5, for causing the at least one spent catalyst stream 5 to be hydrogen Contacting to remove the tool 13 that incrementally deposits at least a portion of the coke material on the spent catalyst material to form a recovered catalytic material as described above and a volatile hydrocarbon (eg, methane), and a catalyst for recovery Material stream 14 is returned to the recovery outlet (not shown) of the at least one reactor 6. The tool 13 for contacting the at least one spent catalyst stream 5 with the heated hydrogen stream 15 may comprise any suitable tool known in the art, such as the plurality of fluid bed tubes disposed above the firebox or furnace, A fluid bed equipped with a plurality of burner tubes or coils, or a plurality of fluid bed tubes disposed within the outer casing as described above, wherein the tubes are in contact with hot combustion gases.

Additionally or alternatively, the recovered catalyst material stream 14 can be fed to a separator, such as cyclone 16, to separate the recovered catalytic material from hydrogen and/or volatile hydrocarbons to form a separate recovery touch. The media stream 4a, another hydrogen stream 7a, and/or excess hydrogen stream 18. The separated recovered catalytic material stream 4a and/or another hydrogen stream 7a may be provided to the at least one reactor 6. This further hydrogen stream 7a can be the same as or different from the hydrogen stream 7. The excess hydrogen stream 18 can be compressed in compressor 23 and sent to separation unit 24 to separate a portion of the light hydrocarbons (C ₁ -C ₄ ) from the excess hydrogen stream 18 to produce a light hydrocarbon-rich stream 26 and A light hydrocarbon stream 25 is consumed which can be recycled back to the reheating unit 12. Additionally, supplemental hydrogen stream 27 can be combined with stream 25 to supplement the hydrogen consumed to remove coke from the catalyst. System 24 may be a membrane, adsorption separation system device, or other known systems for separating H ₂ from light hydrocarbons.

In particular, the reheating device 12 operates under the described conditions, preferably the reheating device 12 has a temperature of from about 600 °C to about 800 °C. In addition, the recovered catalyst material comprises less incremental deposited coke material than the waste catalyst material described above, preferably at least about 10% by weight less than the waste catalyst material.

Additionally, reheating device 12 can generate steam stream 20. The feed stream 2 can also be heated in a convection section (not shown) or in a separation furnace (not shown). Again, a first hydrogen-up gas stream 21 and/or a second hydrogen-up gas stream 22 may be provided to the reaction system 1 to assist in transporting the spent catalyst stream 5 to the reheating unit 12 and/or to recover the separated unit. The catalyst material stream 4a is transported to the at least one reactor 6. Hydrogen lift gas stream 21 and/or second hydrogen lift gas stream 22 may originate from a portion of heated hydrogen stream 15.

In other embodiments, as is known in the art, the reaction system can also include a regeneration device 19 fluidly coupled to the at least one reactor 6, as shown in Figure 3, to produce a regenerated catalyst material.

Additionally or alternatively, the reaction system may further comprise a stream of fresh particulate material (not shown) fluidly coupled to the at least one reactor 6 and/or fluidly coupled to the reheating device 12.

IV. Other implementation aspects

An aspect of embodiment a reactor system for the non-cyclic C ₅ hydrocarbons to the cyclopentadiene method, wherein the method comprises: providing to the reactor system comprises a non-cyclic starting material of C ₅ hydrocarbons; Providing a particulate material comprising a catalytic material (e.g., platinum on ZSM-5, platinum on zeolite L, and/or platinum on vermiculite) in the reactor system; making the material and the particulate material the at least one reaction zone under reaction conditions (e.g., circulating fluidized bed, circulating bed settling) contacting at least a portion of the non-cyclic C ₅ hydrocarbons to the effluent comprises a first of cyclopentadiene, wherein the feedstock with the The flow of particulate material flows countercurrently.

Embodiment 2. The method of Embodiment 1, wherein the inverted temperature distribution is maintained in the at least one reaction zone.

The method of embodiment 1 or 2, wherein the feedstock provides and/or discharges the at least one reaction zone at a temperature of less than or equal to about 500 ° C. the first effluent has a flow of at least about 550 ° C. The temperature.

The method of any of the preceding embodiments, wherein the at least one reaction zone further comprises a plurality of internal structures and/or at least one heating device.

The method of any of the preceding embodiments, wherein the reaction conditions comprise acyclic C _{5 having a} temperature of from about 400 ° C to about 700 ° C and a pressure of from about 3 psia to about 100 psia and/or at least about 30 wt % The hydrocarbons are converted to cyclopentadiene.

Embodiment 6. The method of any of the preceding embodiments, wherein the particle The material also includes an inert material (e.g., at least about 30% by weight) and/or less than about 30% by weight of the catalyst material.

The method of any of the preceding embodiments, wherein the catalyst material and/or the inert material has an average diameter of from about 100 μm to about 10,000 μm.

8. The preceding embodiment aspect of embodiment a method according to any one of the aspects of, wherein the particulate material provides at least a portion of the non-cyclic C ₅ hydrocarbons to the heat required to include a cyclopentadienyl first effluent is at least about 50 %.

The method of any of the preceding embodiments, wherein the at least one reaction zone comprises at least a first reaction zone (eg, a circulating fluidized bed) and a second reaction zone (eg, a circulating fluidized bed) And/or further comprising moving a plurality of materials from the first reaction zone to the second reaction zone; and moving a plurality of the particulate material from the second reaction zone to the first reaction zone.

The method of any of the preceding embodiments, further comprising any one or more of: transferring at least a portion of the particulate material from the at least one reaction zone to a reheat zone (eg, in a furnace) a plurality of fluid bed tubes and/or a fluidized bed having one or more heating devices, wherein the reheating zone comprises one or more heating devices; contacting the particulate material with hydrogen to remove the catalytic material At least a portion of the deposited coke material is incrementally formed to form the recovered catalytic material and volatile hydrocarbons; and the recovered catalytic material is returned to the at least one reaction zone.

The method of embodiment 10, wherein the reheating zone operates at a temperature of from about 600 ° C to about 800 ° C and/or removes at least 10 wt % of the incrementally deposited coke material from the catalyst material. .

The method of any of the preceding embodiments, further comprising any one or more of: transferring at least a portion of the particulate material from the at least one reaction zone to a regeneration zone; wherein the particulate material is being regenerated Contacting the regeneration gas to remove at least a portion of the coke material deposited on the catalyst material to form a regenerated catalyst material; and recycling at least a portion of the regenerated catalyst material to the at least one reaction Zone or at least one reheat zone.

The method of any of the preceding embodiments, further comprising feeding hydrogen to the at least one reaction zone and/or providing the fresh particulate material (i) directly to the at least one reaction zone, and/ Or (ii) supplied to the reheat zone prior to entering the at least one reaction zone.

Embodiment 14. A reaction system for converting acyclic C ₅ hydrocarbons to cyclopentadiene, wherein the reaction system comprises: a feed stream comprising acyclic C ₅ hydrocarbons; and a first effluent stream comprising cyclopentadiene At least one catalyst stream comprising particulate material comprising a catalytic material (eg, platinum on ZSM-5, platinum on zeolite L, and/or platinum on vermiculite); at least one comprising a spent catalyst material the spent catalyst stream; at least one operation to at least a portion of non-cyclic C ₅ hydrocarbons to the reactor cyclopentadienyl under reaction conditions (e.g., circulating fluidized bed reactor, a circulating bed reactor settling); and Wherein the at least one reactor comprises: a feed inlet for providing the feed stream to the reaction system; at least one catalyst inlet for providing the at least one catalyst stream to the reaction system; for removing the first An effluent outlet of the effluent stream; and a spent catalyst outlet for removing the at least one spent catalyst stream; wherein the feed stream in the reactor flows countercurrently to the direction of at least one of the catalyst streams in the reactor.

Embodiment 15. The reaction system of Embodiment 14, wherein the at least one reactor has an inverted temperature distribution.

The reaction system of any one of embodiments 14 or 15, wherein the feed stream at the feed inlet has a temperature of less than about 500 ° C and/or the first effluent stream at the effluent outlet has at least about 550 ° C temperature.

The reaction system of any one of embodiments 14, 15 or 16, wherein the at least one reactor further comprises a plurality of internal structures and/or at least one heating device.

The reaction system of any one of embodiments 14, 15, 16 or 17, wherein the reaction conditions comprise a temperature of from about 400 ° C to about 700 ° C, a pressure of from about 3 psia to about 100 psia, and/or at least about 30wt% of the C ₅ acyclic hydrocarbons converted to cyclopentadiene-based.

The reaction system of any one of embodiments 14, 15, 16, 17, or 18, wherein the particulate material further comprises an inert material (at least about 30% by weight) and/or less than about 30% by weight of the touch Media material.

The reaction system of any one of embodiments 14, 15, 16, 17, 18 or 19, wherein the catalytic material and/or the inert material has an average diameter of from about 100 μm to about 10,000 μm.

21. The embodiment aspect of embodiment a reaction system according to any one aspect of 14,15,16,17,18,19 or 20, wherein the particulate material is provided wherein at least part of the non-cyclic C ₅ hydrocarbons to comprise a cyclopentyl At least about 50% of the heat required for the first effluent of the diene.

Embodiments 22. As in the embodiment 14, 15, 16, 17, 18, 19, 20 Or a reaction system according to any one of the preceding claims, wherein the at least one reactor comprises at least a first reactor (e.g., a circulating fluidized bed) and a second reactor (e.g., a circulating fluidized bed) connected in series, wherein a large amount of raw materials are The first reactor is moved to the second reactor; and a plurality of particulate material is moved from the second reactor to the first reactor.

Embodiment 2. The reaction system of any one of embodiments 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23, further comprising reheating fluidly coupled to the at least one reactor a device (eg, a plurality of fluid bed tubes in a furnace and/or a fluidized bed having one or more devices), wherein the reheating device comprises: one or more heating devices; for the at least one spent catalyst a reheating inlet; a means for contacting the at least one spent catalyst stream with hydrogen to remove at least a portion of the spent catalyst material by incrementally depositing coke material to form a recovered catalytic material and a volatile hydrocarbon And a recovery outlet for returning the recovered catalyst material stream to the at least one reactor.

Embodiment 24. The reaction system of embodiment 23, wherein the reheating device has a temperature of from about 600 ° C to about 800 ° C and/or the recovered catalytic material comprises at least about 10 wt% less than the spent catalyst material The incremental deposition of coke material.

The reaction system of any one of embodiments 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24, further comprising: fluidly connecting to the at least one reactor Regeneration equipment to form a regenerated catalyst material.

Embodiment 26. A reaction system according to any one of embodiments 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25, further comprising A stream of fresh particulate material fluidly coupled to at least one reactor and/or fluidly coupled to the at least one reactor and/or fluidly coupled to the reheating apparatus.

The invention also relates to:

Embodiment 27. A reaction system for converting acyclic C ₅ hydrocarbons to cyclopentadiene, wherein the reaction system comprises: a feed stream comprising acyclic C ₅ hydrocarbons; and a first effluent stream comprising cyclopentadiene; catalyst stream comprising at least one catalytic material comprising the particulate material; and at least one spent catalyst stream comprising spent catalyst materials; at least one operating under reaction conditions to convert at least a portion of the non-cyclic C ₅ hydrocarbons to cyclopentadiene a reactor of olefin; and wherein the at least one reactor comprises: a feed inlet for providing the feed stream to the reaction system; at least one catalyst inlet for providing the at least one catalyst stream to the reaction system; And a waste catalyst outlet for removing the at least one waste catalyst stream; wherein the feed stream in the reactor and at least one catalyst stream in the reactor The direction of the flow is countercurrent.

Embodiment 28. The reaction system of Embodiment 27, wherein the at least one reactor has an inverted temperature distribution.

Embodiment 29. The reaction system of Embodiment 27, wherein the at least one reactor or a fluidized bed reactor or a circulating settled bed reactor.

Embodiment 30. The reaction system of embodiment 27, wherein the feed stream at the feedstock inlet has a temperature of less than about 500 °C.

Embodiment 31. The reaction system of embodiment 27, wherein the first effluent stream at the effluent outlet has a temperature of at least about 550 °C.

Embodiment 32. The reaction system of embodiment 27, further comprising: the at least one reactor fluidly coupled to the reheating device, wherein the reheating device comprises: one or more heating devices; for the at least one waste contact a reheating inlet of the media stream; means for contacting the at least one spent catalyst stream with hydrogen to remove at least a portion of the spent catalyst material for incremental deposition of the coke material to form a recovered catalyst material and volatility a hydrocarbon; and a recovery outlet for returning the recovered catalyst material stream to the at least one reactor.

Embodiment 33. The reaction system of embodiment 32, wherein the reheating device has a temperature of from about 600 °C to about 800 °C.

Embodiment 34. The reaction system of embodiment 32, wherein the recovered catalytic material comprises at least about 10 wt% less deposition of coke material than the spent catalyst material.

Embodiment 35. The reaction system of embodiment 32, wherein the reheating device comprises a plurality of fluid bed tubes in the furnace and/or a fluidized bed having one or more heating devices.

Embodiment 36. The reaction system of embodiment 27, further comprising: a regeneration device fluidly coupled to the at least one reactor to form a regenerated catalyst material.

Embodiment 37. The reaction system of embodiment 27, further comprising a hydrogen stream fluidly coupled to the at least one reactor.

Embodiment 38. The reaction system of Embodiment 27, wherein the at least one reactor further comprises a plurality of internal structures.

Embodiment 39. The reaction system of Embodiment 27, wherein the at least one reactor further comprises at least one heating device.

Embodiment 40. The reaction system of Embodiment 27, wherein the reaction conditions comprise a temperature of from about 400 ° C to about 700 ° C and a pressure of from about 3 psia to about 100 psia.

41. The embodiment aspect of embodiments of the aspect of the reaction system 27, wherein at least about 30wt% of the C ₅ acyclic hydrocarbons converted to cyclopentadiene-based.

Embodiment 42. The reaction system of Embodiment 27, wherein the particulate material further comprises an inert material.

Embodiment 43. The reaction system of Embodiment 42 wherein the catalyst material has an average diameter of from about 100 μm to about 10,000 μm and the inert material has an average diameter of from about 100 μm to about 10,000 μm.

Embodiment 44. The reaction system of Embodiment 42 wherein the particulate material comprises at least about 30% by weight inert material.

Embodiment 45. The reaction system of embodiment 27, wherein the particulate material comprises less than about 30% by weight of the catalytic material.

Embodiment 46. The reaction system of Embodiment 27, wherein the catalyst medium The material contained platinum on the ZSM-5.

Embodiment 47. The embodiment aspect aspect of the reaction system of 27, wherein the particulate material provides the non-cyclic C ₅ hydrocarbons to the desired heat of cyclopentadiene at least about 50%.

The reaction system of embodiment 27, wherein the at least one reactor comprises at least a first reactor and a second reactor in series, wherein: a plurality of raw materials are moved from the first reactor to the second reaction And a large amount of particulate material is moved from the second reactor to the first reactor.

Embodiment 49. The reaction system of Embodiment 48, wherein the first reactor and the second reactor are each a fluidized bed reactor.

Embodiment 50. The reaction system of embodiment 32, further comprising a hydrogen stream fluidly coupled to the at least one reactor and/or fluidly coupled to the at least one reactor and/or fluidly coupled to the reheating apparatus Flow of particulate material.

Industrial applicability

The cyclic, branched and linear C ₅ hydrocarbons obtained during the acyclic C ₅ conversion process, as well as optionally containing hydrogen, C ₄ and lighter by-products, or C ₆ and heavier by-products The first hydrocarbon reactor effluent of any combination is itself a valuable product. Preferably, the CPD and/or DCPD can be separated from the reactor effluent to obtain a purified product stream that can be used to make a wide variety of high cost products.

For example, a purified product stream containing 50 wt% or more, or preferably 60 wt% or more, of DCPD can be used to make hydrocarbon resins, unsaturated polyester resins, and epoxy materials. The purified product containing 80% by weight or more, or preferably 90% by weight or more, of CPD can be used to produce the Diles-Alder reaction product formed according to the following reaction formula (I): Wherein R is a heteroatom or substituted hetero atom, a substituted or unsubstituted C ₁ -C ₅₀ hydrocarbyl group (often a hydrocarbyl group containing a double bond), an aromatic group, or any combination thereof. Preferably, the substituent or group contains one or more elements from Groups 13 to 17, preferably selected from Groups 15 or 16, more preferably nitrogen, oxygen or sulfur. In addition to the monoolefin Dier-Alder reaction product described in formula (I), a purified product stream containing 80 wt% or more, or preferably 90 wt% or more, of CPD can be used to form CPD. Diles-Alder reaction product having one or more of the following: other CPD molecules, conjugated dienes, acetylenes, heavy olefins, disubstituted olefins, trisubstituted olefins, cyclic olefins, And the substitutions of the foregoing. Preferred Dier-Adel reaction products include, ethylene norbornene, substituted norbornenes (including oxygenated norbornenes), norbornadienes, and tetracyclododecene, such as the following The structure shows:

The aforementioned Diles-Alder reaction product can be used to produce copolymers of polymers and cyclic olefins copolymerized with olefins such as ethylene. The resulting cyclic olefin copolymer and cyclic olefin polymer product can be used in a variety of applications, such as packaging films.

A purified product stream containing 99 wt% or more of DCPD can be used to make DCPD polymers using, for example, ring opening displacement polymerization (ROMP) catalysts. The DCPD polymer product can be used to form articles, particularly molded parts, such as wind turbine blades and automotive parts.

Additional components can also be separated from the reactor effluent and used to form high value products. For example, the isolated cyclopentene can be used to make polycyclopentene (also known as polypentene rubber) as described for formula (II).

The isolated cyclopentane can be used as a blowing agent and as a solvent. Linear and branched C ₅ products available for conversion to higher carbon olefins and alcohols. Cyclic and non-cyclic C ₅ product (optionally after hydrogenation) can be used as octane enhancers and transport fuel blend component.

All documents described herein are incorporated herein by reference to the extent that they do not contradict the present disclosure, including any priority document and/or testing Cheng. Various modifications may be made without departing from the spirit and scope of the inventions. Therefore, the invention is not intended to be limited thereby. Similarly, the term "comprising" is used as a synonym for the term "including". Similarly, when a composition, element, or group of elements has a transitional phrase "contains" before, it should be understood that we also consider having a transitional conjunction before the composition, element, or elements are detailed. .. consists of the same composition or group of elements consisting of "composed of", "consisting of" or "as", and vice versa.

Claims (25)

A method for transforming into a cyclopentadiene method comprising the class of cyclic C ₅ C ₅ acyclic hydrocarbons in the reactor system, wherein the method comprises: providing a reactor system comprising the non-cyclic C ₅ hydrocarbons of material; providing particulate material comprising the catalytic material of the reactor system; the feedstock and the particulate material is at least one contact in the reaction zone under reaction conditions to at least a portion of the non-cyclic C ₅ hydrocarbons to comprise a cyclopentyl a first effluent of the diene; wherein the feedstock flows countercurrent to the direction of flow of the particulate material, and wherein an inverse temperature profile or an isothermal temperature profile is maintained in the at least one reaction zone. The method of claim 1, wherein the at least one reaction zone is a circulating fluidized bed or a circulating settling bed. The method of claim 1, wherein the material is provided at a temperature of less than or equal to about 500 °C. The method of claim 1, wherein the first effluent exiting the at least one reaction zone has a temperature of at least about 550 °C. The method of claim 1, further comprising: transferring at least a portion of the particulate material from the at least one reaction zone to a reheat zone, wherein the reheat zone comprises one or more heating devices. The method of claim 1, further comprising: contacting the particulate material with hydrogen to remove at least a portion of the incrementally deposited coke material on the catalyst material to form a recovered catalytic material and a hydrocarbon; and returning the recovered catalyst material to the at least one reaction zone. The method of claim 5, wherein the reheating zone is operated at a temperature of from about 600 °C to about 800 °C. The method of claim 5, wherein at least 10% by weight of the incrementally deposited coke material is removed from the catalyst material. The method of claim 5, wherein the reheat zone comprises a plurality of fluid bed tubes in the furnace and/or a fluidized bed having one or more heating devices. The method of claim 1, further comprising: transferring at least a portion of the particulate material from the at least one reaction zone to a regeneration zone; wherein the particulate material is contacted with the regeneration gas under regeneration conditions to be oxidatively removed At least a portion of the coke material deposited on the catalyst material to form a regenerated catalyst material; and recycling at least a portion of the regenerated catalyst material to the at least one reaction zone or the at least one reheat zone. The method of claim 1, further comprising feeding hydrogen to the at least one reaction zone. The method of claim 1, wherein the at least one reaction zone comprises a plurality of internal structures. The method of claim 1, wherein the at least one reaction zone comprises at least one heating device. The method of claim 1, wherein the reaction conditions comprise a temperature of from about 400 ° C to about 700 ° C and a pressure of from about 3 psia to about 100 Psia. The method according to Claim 1 patentable scope, wherein at least about 30wt% of the C ₅ acyclic hydrocarbons converted to cyclopentadiene. The method of claim 1, wherein the particulate material further comprises an inert material. The method of claim 16, wherein the catalyst material has an average diameter of from about 100 μm to about 10,000 μm, and the inert material has an average diameter of from about 100 μm to about 10,000 μm. The method of claim 16, wherein the particulate material comprises at least about 30% by weight of an inert material. The method of claim 1, wherein the catalyst material comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on vermiculite. The method of claim 1, wherein the at least one reaction zone comprises at least a first reaction zone and a second reaction zone connected in series. The method of claim 20, further comprising: moving a plurality of raw materials from the first reaction zone to the second reaction zone; and moving a plurality of the particulate material from the second reaction zone to the first reaction zone . The method of claim 20, wherein the first reaction zone and the second reaction zone are each a circulating fluidized bed. The method of claim 5, further comprising providing fresh particulate material (i) directly to the at least one reaction zone, and/or (ii) providing to the reheat zone prior to entering the at least one reaction zone. An article derived from a product produced by the method of any one of claims 1 to 23, wherein the article is selected from the group consisting of cyclopentadiene, dicyclopentane Diene, cyclopentene, cyclopentane, pentene, pentadiene, norbornene, tetracyclodocene, substituted decene, cyclopentadiene , cyclic olefin copolymer, cyclic olefin polymer, polycyclopentene, unsaturated polyester resin, hydrocarbon resin adhesive, formulated epoxy resin, polydicyclopentadiene, norbornene or substituted Displacement polymer of terpene or dicyclopentadiene or any combination thereof, wind turbine blade, composite containing glass or carbon fiber, formulated adhesive, ethylene norbornene, EPDM rubber, alcohol, plasticizer , blowing agents, solvents, octane enhancers, gasoline, and mixtures thereof. An article of claim 24, wherein the article is derived from a material derived from the product and a Diels-Alder reaction of a substrate comprising a double bond.