WO2017078894A1 - Processus et systèmes de conversion d'hydrocarbures en cyclopentadiène - Google Patents
Processus et systèmes de conversion d'hydrocarbures en cyclopentadiène Download PDFInfo
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- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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- B01J2208/00106—Controlling the temperature by indirect heat exchange
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- B01J2208/00008—Controlling the process
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- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
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- B01J2208/00008—Controlling the process
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- B01J2208/00327—Controlling the temperature by direct heat exchange
- B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00884—Means for supporting the bed of particles, e.g. grids, bars, perforated plates
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- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Definitions
- This invention relates to reactors useful for processes for the conversion of acyclic Cs feedstock to a product comprising cyclic Cs compounds.
- Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are highly desired raw materials used throughout the chemical industry in a wide range of products such as polymeric materials, polyester resins, synthetic rubbers, solvents, fuels, fuel additives, etc. Cyclopentadiene is currently a minor byproduct of liquid fed steam cracking (for example, naphtha and heavier feed). As existing and new steam cracking facilities shift to lighter feeds, less CPD is produced while demand for CPD is rising. High cost due to supply limitations impacts the potential end product use of CPD in polymers. More CPD-based polymer product could be produced if additional CPD could be produced at unconstrained rates and preferably at a cost lower than recovery from steam cracking.
- Cyclopentane and cyclopentene can have high value as solvents, while cyclopentene may be used as a comonomer to produce polymers and as a starting material for other high value chemicals.
- C5 feedstock may also be derived from bio-feeds.
- Various catalytic dehydrogenation technologies are currently used to produce mono- and di-olefins from C3 and C4 alkanes, but not cyclic mono-olefins or cyclic di-olefins.
- a typical process uses Pt/Sn supported on alumina as the active catalyst.
- Another useful process uses chromia on alumina. See, B. V. Vora, "Development of Dehydrogenation Catalysts and Processes," Topics in Catalysis, vol. 55, pp. 1297-1308, 2012; and J. C. Bricker, “Advanced Catalytic Dehydrogenation Technologies for Production of Olefins,” Topics in Catalysis, vol. 55, pp. 1309-1314, 2012.
- Still another common process uses Pt/Sn supported on Zn and/or Ca aluminate to dehydrogenate propane. While these processes are successful in dehydrogenating alkanes, they do not perform cyclization, which is critical to producing CPD. Pt-Sn/alumina and Pt- Sn/ aluminate catalysts exhibit moderate conversion of n-pentane, but such catalyst have poor selectivity and yield to cyclic C5 products.
- Pt supported on chlorided alumina catalysts are used to reform low octane naphtha to aromatics, such as benzene and toluene. See, US 3,953,368 (Sinfelt), "Polymetallic Cluster Compositions Useful as Hydrocarbon Conversion Catalysts.” While these catalysts are effective in dehydrogenating and cyclizing Ce and higher alkanes to form Ce aromatic rings, they are less effective in converting acyclic Css to cyclic Css. These Pt supported on chlorided alumina catalysts exhibit low yields of cyclic C5 and exhibit deactivation within the first two hours of time on stream.
- Cyclization of Ce and Ci alkanes is aided by the formation of an aromatic ring, which does not occur in C5 cyclization. This effect may be due in part to the much higher heat of formation for CPD, a cyclic C5, as compared to benzene, a cyclic Ce, and toluene, a cyclic C7. This is also exhibited by Pt/Ir and Pt/Sn supported on chlorided alumina. Although these alumina catalysts perform both dehydrogenation and cyclization of C6+ species to form Ce aromatic rings, a different catalyst will be needed to convert acyclic C5 to cyclic C5.
- Ga-containing ZSM-5 catalysts are used in a process to produce aromatics from light paraffins.
- a study by Kanazirev et al. showed n-pentane is readily converted over Ga203/H- ZSM-5. See Kanazirev et al., "Conversion of Cs aromatics and n-pentane over GsaO ⁇ /H- ZSM-5 mechanically mixed catalysts," Catalysis Letters, vol. 9, pp. 35-42, 1991. No production of cyclic C5 was reported while upwards of 6 wt% aromatics were produced at 440°C and 1.8 hr 1 WHSV. Mo/ZSM-5 catalysts have also been shown to dehydrogenate and/or cyclize paraffins, especially methane.
- US 5,284,986 introduced a dual-stage process for the production of cyclopentane and cyclopentene from n-pentane.
- An example was conducted wherein the first stage involved dehydrogenation and dehydrocyclization of n-pentane to a mix of paraffins, mono-olefins and di-olefins, and naphthenes over a Pt/Sn-ZSM-5 catalyst.
- This mixture was then introduced to a second-stage reactor consisting of Pd/Sn-ZSM-5 catalyst where dienes, especially CPD, were converted to olefins and saturates. Cyclopentene wasthe desired product in this process, whereas CPD was an unwanted byproduct.
- US 5,633,421 discloses a process for dehydrogenating C2-C5 paraffins to obtain corresponding olefins.
- US 2,982,798 discloses a process for dehydrogenating an aliphatic hydrocarbon containing 3 to 6, inclusive, carbon atoms.
- neither US 5,633,421 nor US 2,982,798 disclose production of CPD from acyclic C5 hydrocarbons, which are desirable as feedstock because they are plentiful and low cost.
- this invention relates to a process for converting acyclic C5 hydrocarbons to cyclopentadiene in a reactor system, wherein the process comprises a reaction interval comprising: cyclically providing to the reactor system a feedstock comprising acyclic C5 hydrocarbons; contacting the feedstock with a particulate material comprising a catalyst material in a first reaction zone under reaction conditions to convert at least a portion of the acyclic C5 hydrocarbons to a first effluent comprising cyclopentadiene, and a reheating interval comprising: cyclically halting the feedstock to the first reaction zone; and providing a reheating gas to the first reaction zone to reheat the particulate material.
- this invention also relates to a reaction system for converting acyclic C5 hydrocarbons to cyclopentadiene, wherein the reaction system comprises: a feedstock stream comprising acyclic C5 hydrocarbons; a first effluent stream comprising cyclopentadiene; a reheating gas stream and at least one reactor operated under reaction conditions to convert at least a portion of the acyclic C5 hydrocarbons to cyclopentadiene; wherein the at least one reactor comprises: a particulate material comprising a catalyst material; a feedstock inlet for providing the feedstock stream and/or the reheating gas stream to the reaction system; and an effluent outlet for removal of the first effluent stream and/or the reheating gas stream.
- Figure 1 shows an example time sequence for the reaction zones according to one embodiment of the invention.
- Figure 2 shows an arrangement of reaction zones according to another embodiment of the invention.
- Figure 3 is a diagram of a reactor according to another embodiment of the invention.
- Figure 4 is a diagram of a reactor with a reheating apparatus according to another embodiment of the invention.
- Figure 5 is a diagram of a reactor with a reheating apparatus and a regenerating apparatus according to another embodiment of the invention.
- Figure 6 illustrates the site-time-yield (STY) of cyclic C5 hydrocarbons (i.e., the mols of cC5/mol of Pt/second) against T.O.S. in Example 2 under a continuously-on-oil reactor operating strategy and an intermittent H2 rejuvenation reactor operating strategy.
- STY site-time-yield
- the term "about” refers to a range of values of plus or minus 10% of a specified value.
- the phrase “about 200” includes plus or minus 10% of 200, or from 180 to 220.
- saturated includes, but is not limited to, alkanes and cycloalkanes.
- non-saturates includes, but is not limited to, alkenes, dialkenes, alkynes, cyclo-alkenes and cyclo-dialkenes.
- cyclics Cs or “cCs” includes, but is not limited to, cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more thereof.
- cyclic Cs or “cCs” also includes alkylated analogs of any of the foregoing, e.g., methyl cyclopentane, methyl cyclopentene, and methyl cyclopentadiene. It should be recognized for purposes of the invention that cyclopentadiene spontaneously dimerizes over time to form dicyclopentadiene via Diels-Alder condensation over a range of conditions, including ambient temperature and pressure.
- acyclics includes, but is not limited to, linear and branched saturates and non-saturates.
- aromatic means a planar cyclic hydrocarbyl with conjugated double bonds, such as benzene.
- aromatic encompasses compounds containing one or more aromatic rings, including, but not limited to, benzene, toluene, and xylene, and polynuclear aromatics (PNAs), which include naphthalene, anthracene, chrysene, and their alkylated versions.
- C6+ aromatics includes compounds based upon an aromatic ring having six or more ring atoms, including, but not limited to, benzene, toluene, and xylene, and polynuclear aromatics (PNAs), which include naphthalene, anthracene, chrysene, and their alkylated versions.
- PNAs polynuclear aromatics
- BTX includes, but is not limited to, a mixture of benzene, toluene, and xylene (ortho and/or meta and/or para).
- coke includes, but is not limited to, a low hydrogen content hydrocarbon that is adsorbed on the catalyst composition.
- Cn means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
- C n + means hydrocarbon(s) having at least n carbon atom(s) per molecule.
- Cn- means hydrocarbon(s) having no more than n carbon atom(s) per molecule.
- hydrocarbon means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.
- C5 feedstock includes a feedstock containing n-pentane, such as a feedstock which is predominately normal pentane and isopentane (also referred to as methylbutane), with smaller fractions of cyclopentane and neopentane (also referred to as 2,2-dimethylpropane).
- n-pentane such as a feedstock which is predominately normal pentane and isopentane (also referred to as methylbutane), with smaller fractions of cyclopentane and neopentane (also referred to as 2,2-dimethylpropane).
- Group 10 metal means an element in Group 10 of the Periodic Table and includes, but is not limited to, Ni, Pd, and Pt.
- Group 11 metal means an element in Group 11 of the Periodic Table and includes, but is not limited to, Cu, Ag, Au, and a mixture of two or more thereof.
- 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 a mixture of two or more thereof, and excludes hydrogen.
- Group 2 alkaline earth metal means an element in Group 2 of the Periodic Table and includes, but is not limited to, Be, Mg, Ca, Sr, Ba, and a mixture of two or more thereof.
- oxygen-containing or “oxygen-containing compound” means oxygen and compounds containing oxygen, including but not limited to, O2, CO2, CO, H2O, and oxygen-containing hydrocarbons such as alcohols, esters, ethers, etc.
- the term "constraint index” is defined in US 3,972,832 and US 4,016,218, both of which are incorporated herein by reference.
- the term "molecular sieve of the MCM-22 family" includes one or more of:
- molecular sieves made from a common first degree crystalline building block unit cell, which unit cell has the MWW framework topology.
- a unit cell is a spatial arrangement of atoms, which if tiled in three-dimensional space describes the crystal structure. Such crystal structures are discussed in the "Atlas of Zeolite Framework Types," Fifth edition, 2001, the entire content of which is incorporated herein by reference);
- molecular sieves made from a common second degree building block, being a 2- dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
- molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.
- the stacking of such second degree building blocks may be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof;
- molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
- the MCM-22 family includes those molecular sieves having an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07, and 3.42 ⁇ 0.07 Angstrom.
- the X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
- molecular sieve is used synonymously with the term
- microporous crystalline material or "zeolite.
- carbon selectivity means the moles of carbon in the respective cyclic Cs, CPD, Ci, and C2-4 formed divided by total moles of carbon in the pentane converted.
- a carbon selectivity to cyclic C5 of at least 30% means that 30 moles of carbon in the cyclic C5 is formed per 100 moles of carbon in the pentane converted.
- conversion means the moles of carbon in the acyclic C5 feedstock that is converted to a product.
- conversion of at least 70% of said acyclic C5 feedstock to said product means that at least 70% of the moles of said acyclic C5 feedstock was converted to a product.
- reactor system refers to a system including one or more reactors and all necessary and optional equipment used in the production of cyclopentadiene.
- reactor refers to any vessel(s) in which a chemical reaction occurs. Reactor includes both distinct reactors, as well as reaction zones within a single reactor apparatus and, as applicable, reactions zones across multiple reactors. In other words and as is common, a single reactor may have multiple reaction zones. Where the description refers to a first and second reactor, the person of ordinary skill in the art will readily recognize such reference includes two reactors, as well as a single reactor vessel having first and second reaction zones. Likewise, a first reactor effluent and a second reactor effluent will be recognized to include the effluent from the first reaction zone and the second reaction zone of a single reactor, respectively.
- the term "moving bed” reactor refers to a zone or vessel with contacting of solids (e.g. , catalyst particles) and gas flows such that the superficial gas velocity (U) is below the velocity required for dilute-phase pneumatic conveying of solid particles in order to maintain a solids bed with void fraction below 95%.
- the solids e.g., catalyst material
- the solids may slowly travel through the reactor and may be removed from the bottom of the reactor and added to the top of the reactor.
- a moving bed reactor may operate under several flow regimes including settling or moving packed-bed regime (U ⁇ Umf), bubbling regime (Umf ⁇ U ⁇ Umb), slugging regime (Umb ⁇ U ⁇ U c ), transition to and turbulent fluidization regime (U c ⁇ U ⁇ Utr), and fast-fluidization regime (U>Utr), where Umf is the minimum fluidizing velocity, Umb is the minimum bubbling velocity, Uc is the velocity at which fluctuation in pressure peaks and tr is transport velocity.
- These different fluidization regimes have been described in, for example, Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2 nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2 nd Edition, Butterworth- Heinemann, Boston, 2010, which are incorporated herein by reference.
- the term "settling bed” reactor refers to a zone or vessel wherein particulates contact with gas flows such that the superficial gas velocity (U) is below the minimum velocity required to fluidize the solid particles (e.g. , catalyst particles), the minimum fluidization velocity (Umf), U ⁇ Umf, in at least a portion of the reaction zone, and/or operating at a velocity higher than the minimum fluidization velocity while maintaining a gradient in gas and/or solid property (such as, temperature, gas, or solid composition, etc.) axially up the reactor bed by using reactor internals to minimize gas-solid back-mixing.
- U superficial gas velocity
- Umf minimum fluidization velocity
- U ⁇ Umf minimum fluidization velocity
- a settling bed reactor may be a "circulating settling bed reactor,” which refers to a settling bed with a movement of solids (e.g. , catalyst material) through the reactor and at least a partial recirculation of the solids (e.g. , catalyst material).
- the solids e.g. , catalyst material
- the solids may have been removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned back to the reactor.
- the term "fluidized bed” reactor refers to a zone or vessel with contacting of solids (e.g., catalyst particles) and gas flows such that the superficial gas velocity (U) is sufficient to fluidize solid particles (i.e., above the minimum fluidization velocity Umf) and is below the velocity required for dilute-phase pneumatic conveying of solid particles in order to maintain a solids bed with void fraction below 95%.
- solids e.g., catalyst particles
- Umf superficial gas velocity
- cascaded fluid-beds means a series arrangement of individual fluid-beds such that there can be a gradient in gas and/or solid property (such as, temperature, gas, or solid composition, pressure, etc.) as the solid or gas cascades from one fluid bed to another.
- a fluidized bed reactor may be a moving fluidized bed reactor, such as a "circulating fluidized bed reactor,” which refers to a fluidized bed with a movement of solids (e.g. , catalyst material) through the reactor and at least a partial recirculation of the solids (e.g. , catalyst material).
- the solids e.g. , catalyst material
- the solids may have been removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned back to the reactor.
- the term "riser” reactor also known as a transport reactor refers to a zone or vessel (such as, vertical cylindrical pipe) used for net upwards transport of solids (e.g. , catalyst particles) in fast-fluidization or pneumatic conveying fluidization regimes.
- Fast fluidization and pneumatic conveying fluidization regimes are characterized by superficial gas velocities (U) greater than the transport velocity (Utr).
- U superficial gas velocities
- Utr transport velocity
- Fast fluidization and pneumatic conveying fluidization regimes are also described in Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2 nd Edition, Butterworth-Heinemann, Boston, 1991, and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2 nd Edition, Butterworth-Heinemann, Boston, 2010.
- a fluidized bed reactor such as a circulating fluidized bed reactor, may be operated as a riser reactor.
- the term "fixed bed” or “packed bed” reactor refers to a zone or vessel (such as, vertical or horizontal, cylindrical pipe or a spherical vessel) and may include transverse (also known as cross flow), axial flow, and/or radial flow of the gas, where solids (e.g., catalyst particles) are substantially immobilized within the reactor and gas flows such that the superficial velocity (U) is below the velocity required to fluidize the solid particles (i.e., below the minimum fluidization velocity Umf) and/or the gas is moving in a downward direction so that solid particle fluidization is not possible.
- U superficial velocity
- Umf minimum fluidization velocity
- reactors may be cyclically operated to have a reaction interval, a reheat interval, and/or a regeneration interval. The duration and/or order of the interval steps may change over time.
- co-current refers to a flow of two streams (e.g. , stream (a), stream (b)) in substantially the same direction. For example, if stream (a) flows from a top portion to a bottom portion of at least one reaction zone and stream (b) flows from a top portion to a bottom portion of at least one reaction zone, the flow of stream (a) would be considered co-current to the flow of stream (b). On a smaller scale within the reaction zone, there may be regions where flow may not be co-current.
- counter-current refers to a flow of two streams (e.g., stream (a), stream (b)) in substantially opposing directions. For example, if stream (a) flows from a top portion to a bottom portion of the at least one reaction zone and stream (b) flows from a bottom portion to a top portion of the at least one reaction zone, the flow of stream (a) would be considered counter-current to the flow of stream (b). On a smaller scale within the reaction zone, there may be regions where flow may not be counter-current.
- 1 psi is equivalent to 6.895 kPa.
- 1 psia is equivalent to 1 kPa absolute (kPa-a).
- 1 psig is equivalent to 6.895 kPa gauge (kPa- g).
- the first aspect of the invention is a process for conversion of an acyclic Cs feedstock to a product comprising cyclic Cs compounds (e.g. , cyclopentadiene).
- the process comprises the steps of contacting said feedstock and, optionally, hydrogen under acyclic Cs conversion conditions in the presence of one or more catalyst compositions, including but not limited to the catalyst compositions described herein, to form said product.
- the C5 feedstock comprises cyclic C5 compounds.
- the cyclic C5 compounds comprise one or more of cyclopentane, cyclopentene, cyclopentadiene, and includes mixtures thereof.
- the cyclic C5 compounds comprise at least about 20 wt%, or 30 wt%, or 40 wt%, or 70 wt% cyclopentadiene, or in the range of from about 10 wt% to about 80 wt%, alternately 20 wt% to 70 wt%.
- the acyclic C5 conversion conditions include at least a temperature, an n-pentane partial pressure, and a weight hourly space velocity (WHSV).
- the temperature is in the range of about 400°C to about 700°C, or in the range from about 450°C to about 650°C, preferably, in the range from about 500°C to about 600°C.
- the n-pentane partial pressure is in the range of about 3 to about 100 psia at the reactor inlet, or in the range from about 3 to about 50 psia, preferably, in the range from about 3 psia to about 20 psia.
- the weight hourly space velocity is in the range from about 1 to about 50 hr "1 , or in the range from about 1 to about 20 hr "1 .
- Such conditions include a molar ratio of the optional hydrogen co-feed to the acyclic C5 feedstock in the range of about 0 to 3, or in the range from about 1 to about 2.
- Such conditions may also include co-feed C1-C4 hydrocarbons with the acyclic C5 feed.
- co-feed (if present), whether comprising hydrogen, C1-C4 hydrocarbons or both, is substantially free of oxygen-containing compounds.
- substantially free used in this context means the co-feed comprises less than about 1.0 wt%, based upon the weight of the co-feed, e.g., 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 wt% of oxygen-containing compounds.
- this invention relates to a process for conversion of n- pentane to cyclopentadiene comprising the steps of contacting n-pentane and, optionally, hydrogen (if present, typically H2 is present at a ratio to n-pentane of 0.01 to 3.0) with one or more catalyst compositions, including but not limited to, the catalyst compositions described herein, to form cyclopentadiene at a temperature of 400°C to 700°C, a partial pressure of n- pentane of 3 to about 100 psia at the reactor inlet, and a weight hourly space velocity of 1 to about 50 hr 1 .
- this invention relates to a process for converting Cs hydrocarbons to cyclopentadiene in a reactor system, wherein the process comprises a reaction interval comprising: cyclically providing to the reactor system a feedstock comprising Cs hydrocarbons; contacting the feedstock with a particulate material comprising a catalyst material in at least a first reaction zone under reaction conditions to convert at least a portion of the Cs hydrocarbons to a first effluent comprising cyclopentadiene.
- a feedstock comprising Cs hydrocarbons preferably an acyclic Cs feedstock is provided to a reaction system along with a particulate material comprising a catalyst material.
- An acyclic Cs feedstock useful herein is obtainable from crude oil or natural gas condensate, and can include cracked Cs (in various degrees of unsaturation: alkenes, dialkenes, alkynes) produced by refining and chemical processes, such as fluid catalytic cracking (FCC), reforming, hydrocracking, hydrotr eating, coking, and steam cracking.
- FCC fluid catalytic cracking
- the acyclic C5 feedstock useful in the process of this invention comprises pentane, pentene, pentadiene, and mixtures of two or more thereof.
- the acyclic C5 feedstock comprises at least about 50 wt%, or 60 wt%, or 75 wt%, or 90 wt% n-pentane, or in the range from about 50 wt% to about 100 wt% n-pentane.
- the acyclic C5 feedstock optionally, does not comprise Ce aromatic compounds, such as benzene, preferably Ce aromatic compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably present at less than 0.01 wt%, preferably at 0 wt%.
- the acyclic C5 feedstock optionally, does not comprise benzene, toluene, or xylene (ortho, meta, or para), preferably the benzene, toluene, or xylene (ortho, meta, or para) compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably present at less than 0.01 wt%, preferably at 0 wt%.
- the acyclic C5 feedstock optionally, does not comprise C6+ aromatic compounds, preferably C6+ aromatic compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably present at less than 0.01 wt%, preferably at 0 wt%.
- the acyclic C5 feedstock optionally, does not comprise C6+ compounds, preferably C6+ compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably present at less than 0.01 wt%, preferably at 0 wt%.
- the C5 feedstock is substantially free of oxygen-containing compounds.
- substantially free used in this context means the feedstock comprises less than about 1.0 wt%, based upon the weight of the feed, e.g., 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 wt% oxygen-containing compounds.
- an amount of the C5 hydrocarbons (e.g., acyclic C5 hydrocarbons) in the feedstock converted to cyclopentadiene is > about 5.0 wt%, > about 10.0 wt%, > about 20.0 wt%, > about 30.0 wt%, > about 40.0 wt%, > about 50.0 wt%, > about 60.0 wt%, > about 70.0 wt%, > about 80.0 wt%, or > about 90.0 wt%.
- at least about 30.0 wt% or at least about 60.0 wt% of the C5 hydrocarbons (e.g., acyclic C5 hydrocarbons) is converted to cyclopentadiene.
- Ranges expressly disclosed include combinations of any of the above-enumerated values; e.g., about 5.0 wt% to about 90.0 wt%, about 10.0 wt% to about 80.0 wt%, about 20.0 wt% to about 70.0 wt%, about 20.0 wt% to about 60.0 wt%, etc.
- about 20.0 wt% to about 90.0 wt% of the C5 hydrocarbons is converted to cyclopentadiene, more preferably about 30.0 wt% to about 85.0 wt%, more preferably about 40.0 wt% to about 80.0 wt%, about 45.0 wt% to about 75.0 wt%, or about 50.0 wt% to about 70.0 wt%.
- a hydrogen co-feedstock comprising hydrogen and, optionally, light hydrocarbons, such as C1-C4 hydrocarbons, is also fed into the first reactor.
- at least a portion of the hydrogen co-feedstock is admixed with the C5 feedstock prior to being fed into the first reactor.
- C1-C4 hydrocarbons may also be co-fed with the C5.
- the feedstock is fed into a reactor system and contacted with a particulate material comprising a catalyst material in a reaction zone under reaction conditions to convert at least a portion of the C5 hydrocarbons (e.g., acyclic C5 hydrocarbons) to a first effluent comprising cyclopentadiene.
- the reaction zone may be a fluidized bed reactor or a fixed bed reactor, preferably a fixed bed reactor.
- the fixed bed reactor may be a vertical fixed bed or a horizontal fixed bed.
- the vertical fixed bed is an axial flow vertical fixed bed or a radial flow fixed bed.
- the horizontal fixed bed is a transverse flow horizontal fixed bed.
- the reaction zone may include at least one internal structure to support the particulate material, to distribute feedstock uniformly, to collect hydrocarbon product, and/or reduce pressure drop within the reaction zone.
- one or more internal structures e.g. , permeable concentric shells, may be included in the reaction zone to contain and support the particulate material, and the feedstock may be fed into a substantially open, center axis portion of the reaction zone and radially flow over the particulate material.
- a reaction zone may include 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.). Examples of suitable internal structures include a plurality of support grids, hold down grids, baffles, sheds, trays, tubes, rods, and/or distributors.
- a reaction zone is operated under reaction conditions sufficient to convert the feedstock (e.g., acyclic Cs hydrocarbons) to cyclopentadiene.
- the feedstock e.g., acyclic Cs hydrocarbons
- the feedstock may be fed to the reaction system at a weight hourly space velocity (WHSV, mass of acyclic Cs hydrocarbons/mass of catalyst/hour) in the range of from about 1.0 to about 1000.0 hr 1 .
- the WHSV may be about 1.0 to about 900.0 hr 1 , about 1.0 to about 800.0 hr 1 , about 1.0 to about 700.0 hr 1 , about 1.0 to about 600.0 hr 1 , about 1.0 to about 500.0 hr 1 , about 1.0 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
- the WHSV is about 1.0 to about 100.0 hr 1 , more preferably about 1.0 to about 60.0 hr 1 , more preferably about 2.0 to about 40.0 hr 1 , more preferably about 2.0 to about 20.0 hr 1 .
- a substantially inverse temperature profile be maintained in a reaction zone.
- inverse temperature profile means that the reaction zone inlet temperature is lower than the reaction zone outlet temperature.
- centerline temperature at the reaction zone inlet is lower than the centerline temperature at the reaction zone outlet.
- Inverse temperature profile includes systems where the temperature varies in the reaction zone so long as the temperature at the reaction zone inlet is lower than the temperature at the reaction zone outlet.
- “Inverse temperature profile” further encompasses a reaction zone having a centerline temperature Tl ; at some length along the reaction zone, the centerline temperature decreases to temperature T2; at a further length along the reaction zone, the centerline temperature rises to temperature T3; finally, the centerline temperature at the reaction zone outlet decreases to temperature T4; wherein T3>T4>T1>T2.
- the temperature measured where feedstock first contacts catalyst composition near the reactor inlet may be between about 0°C to about 200°C, preferably, about 25°C to about 150°C, more preferably about 50°C to about 100°C, lower than the temperature measured where the effluent leaves contact with catalyst composition near the reactor outlet.
- the reaction zone centerline temperature measured where feedstock first contacts catalyst composition near the reactor inlet may be between about 0°C to about 200°C, preferably about 25°C to about 150°C, more preferably about 50°C to about 100°C, lower than the reaction zone centerline temperature measured where the effluent leaves contact with catalyst composition near the reactor outlet.
- the inverse temperature profile of a reaction zone means that temperature of the reaction zone increases from an inlet for the feedstock (e.g., acyclic C5 hydrocarbons) to an outlet for an effluent.
- the temperature of the reaction zone may increase from a substantially top portion to a substantially bottom portion of the reaction zone; conversely, temperature of the reaction may decrease from a substantially bottom portion to a substantially top portion of the reaction zone.
- Maintaining an inverse temperature profile in the reaction zone may advantageously minimize carbonaceous material formation at the inlet, which can contribute to coking of the catalyst material.
- the inverse temperature profile may also provide sufficient reaction time and length in the reaction zone to produce a sufficient amount of H2, at lower operating temperatures than outlet temperature, which can minimize carbonaceous material formation at the outlet for an effluent.
- an isothermal or substantially isothermal temperature profile be maintained in the reaction zone (e.g., in the reactor tubes).
- An advantage of maintaining an isothermal temperature may be increased catalyst efficiency and improved product yield by reducing the amount of low value, cracked (i.e., C4-) byproduct.
- isothermal temperature profile means that the temperature at each point between the reactor inlet and reactor outlet as measured along the tube centerline of the reactor is kept essentially constant, e.g., at the same temperature or within the same narrow temperature range wherein the difference between an upper temperature and a lower temperature is no more than about 40°C; more preferably no more than about 20°C.
- the isothermal temperature profile is one where the reactor inlet temperature is within about 40°C of the reactor outlet temperature, alternately within about 20°C, alternately within about 10°C, alternately within about 5°C, alternately the reactor inlet temperature is the same as the reactor outlet temperature.
- the isothermal temperature profile is one where the reactor inlet temperature is within about 20% of the reactor outlet temperature, alternately within about 10%, alternately within about 5%, alternately within about 1%.
- the isothermal temperature profile is one where the temperature along the length of the reaction zone(s) within the reactor does not vary by more than about 40°C as compared to reactor inlet temperature, alternately not more than about 20°C, alternately not more than about 10°C, alternately not more than about 5°C.
- the isothermal temperature profile is one where the temperature along the length of the reaction zone(s) within the reactor is within about 20% of the reactor inlet temperature, alternately within about 10%, alternately within about 5%, alternately within about 1% of the reactor inlet temperature.
- the temperature of the feedstock (e.g., acyclic C5 hydrocarbons) entering the reactor system at a feedstock inlet may be ⁇ 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.
- the feedstock e.g., acyclic C5 hydrocarbons
- the temperature of the feedstock (e.g., acyclic C5 hydrocarbons) entering the reactor system is ⁇ about 550°C, more preferably ⁇ about 525°C, more preferably ⁇ about 500°C.
- Ranges of temperatures expressly disclosed include combinations of any of the above-enumerated values, e.g. , about 200°C to about 700°C, about 250°C to about 600°C, about 350°C to about 650°C, about 375°C to about 500°C, etc.
- the temperature of the feedstock (e.g., acyclic C5 hydrocarbons) entering the reaction system is about 200°C to about 700°C, more preferably about 300°C to about 600°C, more preferably about 350°C to about 550°C, more preferably about 375°C to about 500°C.
- Providing the feedstock (e.g., acyclic C5 hydrocarbons) at the above-described temperatures may advantageously minimize undesirable cracking of the C5 hydrocarbons (e.g. , acyclic C5 hydrocarbons) before they can react in the presence of the catalyst material.
- the temperature of a first effluent exiting a reaction zone at an 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.
- the temperature of a first effluent exiting a reaction zone is > about 550°C, more preferably > about 575°C, more preferably > about 600°C. Ranges of temperatures expressly disclosed include combinations of any of the above-enumerated values, e.g.
- the temperature of a first effluent exiting the at least one first reaction zone is about 475°C to about 700°C, more preferably about 500°C to about 650°C, more preferably about 550°C to about 625°C.
- reaction conditions in a reaction zone may include a temperature (such as at the reactor centerline) 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.
- the temperature may 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.
- Ranges of temperatures expressly disclosed include combinations of any of the above-enumerated values, e.g. , about 300°C to about 1,000°C, about 350°C to about 875°C, and about 400°C to about 700°C, etc.
- the temperature may be about 325°C to about 700°C, more preferably about 400°C to about 675°C, more preferably about 350°C to about 650°C, more preferably about 450°C to about 625°C.
- a reaction zone may include one or more heating devices in order to maintain a temperature therein. Examples of suitable heating devices known in the art include, but are not limited to a fired tube, a heated coil with a high temperature heat transfer fluid, an electrical heater, and/or a microwave emitter.
- reaction conditions in a reaction zone may include a pressure (e.g. , outlet pressure) of ⁇ about 1.0 psia, ⁇ about 2.0 psia, ⁇ about 3.0 psia, ⁇ about 4.0, ⁇ 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, or ⁇ about 60.0 psia.
- a pressure e.g. , outlet pressure
- the pressure may 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, or
- Ranges and combinations of temperatures and pressures expressly disclosed include combinations of any of the above-enumerated values, e.g., about 1.0 psia to about 60.0 psia, about 2.0 psia to about 50.0 psia, about 5.0 psia to about 35.0 psia, etc.
- the pressure may be about 1.0 psia to about 60.0 psia, more preferably about 2.0 psia to about 40.0 psia, more preferably about 3.0 psia to about 30.0 psia, more preferably about 4.0 psia to about 15.0 psia, more preferably about 4.0 psia to about 10.0 psia.
- a pressure substantially at a feedstock inlet and/or substantially at an effluent outlet may be > about 0.5 psia, > about 1.0 psia, > about 2.0 psia,
- a pressure substantially at an inlet of a feedstock e.g., acyclic Cs hydrocarbons
- substantially at an outlet of at least a first effluent may be ⁇ about 0.5 psia, ⁇ about 1.0 psia
- Ranges of pressures expressly disclosed include combinations of any of the above- enumerated values, e.g., about 0.5 psia to about 50.0 psia, about 5.0 psia to about 35.0 psia, about 1.0 psia to about 15.0 psia, etc.
- the pressure substantially at an inlet of a feedstock may be about 1.0 psia to about 20.0 psia, preferably about 4.0 psia to about 14.0 psia, more preferably about 4.0 psia to about 10.0 psia.
- the pressure substantially at an outlet of an effluent may be about 1.0 psia to about 50.0 psia, more preferably about 2.0 psia to about 40.0 psia, more preferably about 3.0 psia to about 30.0 psia, more preferably about 4.0 psia to about 14.0 psia, more preferably about 4.0 psia to about 10.0 psia.
- the pressure drop across the at least first reaction zone is low, e.g. , at least about 0.1 psi, at least about 0.2 psi, at least about 0.3 psi, at least about 0.4 psi, at least about 0.5 psi, at least about 0.6 psi, at least about 0.7 psi, at least about 0.8 psi, at least about 0.9 psi, at least about 1.0 psi, at least about 1.5 psi, at least about 2.0 psi, at least about 4.0 psi, at least about 6.0 psi, at least about 8.0 psi, at least about 10.0 psi, at least about 12.0 psi, at least about 15.0 psi, at least about 20.0 psi, at least about 25 psi, or at least about 30 psi.
- the pressure drop across the at least first reaction zone is between about 0.3 to about 30.0 psi, more preferably about 0.4 to about 25.0 psi, more preferably about 0.5 to about 20.0 psi.
- the pressure drop across the at least first reaction zone is between about 0.1 to about 10.0 psi, more preferably about 0.1 to about 5.0 psi, more preferably about 0.2 to about 1.0 psi.
- a stream comprising hydrogen may be fed to a reaction zone.
- a stream comprising hydrogen may be introduced into the reaction zone in order to minimize production of coke material on the particulate material and/or to fluidize the particulate material in the reaction zone.
- Such a stream comprising hydrogen may contain light hydrocarbons (e.g., C1-C4); preferably the content of light hydrocarbons is less than about 50 mol%, less than about 40 mol%, less than about 30 mol%, less than about 20 mol%, less than about 10 mol%, less than about 5 mol%, less than about 1 mol%.
- the stream comprising hydrogen is substantially free of oxygen, e.g., 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 wt%, etc.
- the reaction zone comprises a particulate material comprising a catalyst material
- C5 hydrocarbons e.g., acyclic C5 hydrocarbons
- Catalyst compositions useful herein include microporous crystalline metallosilicates, such as crystalline aluminosilicates, crystalline ferrosilicates, or other metal-containing crystalline silicates (such as those where the metal or metal-containing compound is dispersed within the crystalline silicate structure and may or may not be a part of the crystalline framework.
- microporous crystalline metallosilicate framework types useful as catalyst compositions herein include, but are not limited to, MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU.
- microporous metallosilicates for use herein include those of framework type MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU (such as zeolite beta, 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 family materials), where one or more metals from Groups 8, 11, and 13 of the Periodic Table of the Elements (preferably one or more of Fe, Cu, Ag, Au, B, Al, Ga, and/or In) are incorporated in the crystal structure during synthesis or impregnated post crystallization.
- a metallosilicate may have one or more metals present and, for example, a material may be referred to as a ferrosilicate, but it will most likely still contain small
- the microporous crystalline metallosilicates preferably have a constraint index of less than 12, altemately from 1 to 12, altemately from 3 to 12.
- Aluminosilicates useful herein have a constraint index of less than 12, such as 1 to 12, altemately 3 to 12, and include, but are 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.
- the crystalline aluminosilicate has a constraint index of about 3 to about 12 and is ZSM-5.
- ZSM-5 is described in US 3,702,886.
- ZSM-11 is described in US 3,709,979.
- ZSM- 22 is described in US 5,336,478.
- ZSM-23 is described in US 4,076,842.
- ZSM-35 is described in US 4,016,245.
- ZSM-48 is described in US 4,375,573.
- ZSM-50 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. Constraint index and a method for its determination are described in US 4,016,218. The entire contents of each of the aforementioned 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.
- 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 mixtures of two or more thereof.
- zeolites to be included in the MCM-22 family are UZM-8 (described in US 6,756,030) and UZM-8HS (described in US 7,713,513), both of which are also suitable for use as the molecular sieve of the MCM-22 family.
- the crystalline metallosilicate has an Si/M molar ratio (where 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 about 400, or in the range from about 100 to about 2,000, or from about 100 to about 1,500, or from about 50 to about 2,000, or from about 50 to about 1,200.
- the crystalline aluminosilicate has an S1O2/AI2O3 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 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 1,200, or from about 100 to about 1,000.
- the microporous crystalline metallosilicate (such as an aluminosilicate) is combined with a Group 10 metal or metal compound, and, optionally, one, two, three, or more Group 1, 2, or 11 metals or metal compounds.
- the Group 10 metal includes, or is selected from the group consisting of, Ni, Pd, and Pt, preferably Pt.
- the Group 10 metal content of said catalyst composition is at least 0.005 wt%, based on the weight of the catalyst composition. In one or more embodiments, the Group 10 content is in the range 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.
- the Group 1 alkali metal includes, or is selected from the group consisting of, Li, Na, K, Rb, Cs, and mixtures of two or more thereof, preferably Na.
- 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.
- the Group 1 alkali metal is present as an oxide and the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof.
- the Group 2 alkaline earth metal is present as an oxide and the metal is selected from the group consisting of Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof.
- the Group 1 alkali metal is present as an oxide and the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof; and the Group 2 alkaline earth metal is present as an oxide and the metal is selected from the group consisting of Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof.
- the Group 11 metal includes, or is selected from the group consisting of, silver, gold, copper, preferably silver or copper.
- the Group 11 metal content of said catalyst composition is at least 0.005 wt%, based on the weight of the catalyst composition. In one or more embodiments, the Group 11 content is in the range 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.
- the catalyst composition has an Alpha Value (as measured prior to the addition of the Group 10 metal, preferably platinum) of less than 25, alternately less than 15, alternately from 1 to 25, alternately from 1.1 to 15.
- Alpha Value is determined as described in US 3,354,078; The Journal of Catalysis, v. 4, p. 527, (1965); v. 6, p. 278 (1966); and v, 61 , p. 395 (1980) using a constant temperature of 538°C and a variable flow rate, as described in detail in The Journal of Catalysis, v. 61 , p. 395, (1980).
- the molar ratio of said Group 1 alkali metal to Al is at least about 0.5, or from at least about 0.5 up to about 3, preferably at least about 1, more preferably at least about 2.
- the molar ratio of said Group 2 alkaline earth metal to Al is at least about 0.5, or from at least about 0.5 up to about 3, preferably at least about 1, more preferably at least about 2.
- the molar ratio of said Group 11 metal to Group 10 metal is at least about 0.1, or from at least about 0.1 up to about 10, preferably at least about 0.5, more preferably at least about 1.
- the Group 11 alkaline earth metal is present as an oxide and the metal is selected from the group consisting of gold, silver, and copper, and mixtures of two or more thereof.
- any one of the catalyst compositions of this invention provides a conversion of at least about 70%, or at least about 75%, or at least about 80%, or in the range from about 60% to about 80%, of said acyclic Cs feedstock under acyclic Cs conversion conditions of an n-pentane containing feedstock with equimolar H 2 , a temperature in the range of about 550°C to about 600°C, an n-pentane partial pressure between 3 and 10 psia, and an n-pentane weight hourly space velocity of 10 to 20 hr 1 .
- any one of the catalyst compositions of this invention provides a carbon selectivity to cyclic Cs compounds of at least about 30%, or at least about 40%, or at least about 50%, or in the range from about 30% to about 80%, under acyclic Cs conversion conditions including an n-pentane feedstock with equimolar H 2 , a temperature in the range of about 550°C to about 600°C, an n-pentane partial pressure between 3 and 10 psia, and an n-pentane weight hourly space velocity between 10 and 20 hr 1 .
- any one of the catalyst compositions of this invention provides a carbon selectivity to cyclopentadiene of at least about 30%, or at least about 40%, or at least about 50%, or in the range from about 30% to about 80%, under acyclic C5 conversion conditions including an n-pentane feedstock with equimolar H2, a temperature in the range of about 550°C to about 600°C, an n-pentane partial pressure between 3 and 10 psia, and an n-pentane weight hourly space velocity between 10 and 20 hr 1 .
- the catalyst compositions of this invention can be combined with a matrix or binder material to render them attrition resistant and more resistant to the severity of the conditions to which they will be exposed during use in hydrocarbon conversion applications.
- the combined compositions can contain 1 to 99 wt% of the materials of the invention based on the combined weight of the matrix (binder) and material of the invention.
- the relative proportions of microcrystalline material and matrix may vary widely, with the crystal content ranging from about 1 to about 90 wt% and, more usually, particularly when the composite is prepared in the form of beads, extrudates, pills, oil drop formed particles, spray dried particles, etc., in the range of about 2 to about 80 wt% of the composite.
- coke may be deposited on the catalyst compositions, whereby such catalyst compositions lose a portion of its catalytic activity and become deactivated.
- the deactivated catalyst compositions may be regenerated by conventional techniques, including high pressure hydrogen treatment and combustion of coke on the catalyst compositions with an oxygen- containing gas, such as air or O2.
- Useful catalyst compositions comprise a crystalline aluminosilicate or ferrosilicate, which is optionally combined with one, two, or more additional metals or metal compounds. Preferred combinations include:
- a crystalline aluminosilicate such as ZSM-5 or Zeolite L
- a Group 10 metal such as Pt
- a Group 1 alkali metal such as sodium or potassium
- a crystalline aluminosilicate such as ZSM-5 or Zeolite L
- a Group 10 metal such as Pt
- a Group 1 alkali metal such as sodium or potassium
- a crystalline aluminosilicate such as a ferrosilicate or an iron treated ZSM-5 combined with a Group 10 metal (such as Pt), and a Group 1 alkali metal (such as sodium or potassium);
- a crystalline aluminosilicate (Zeolite L) combined with a Group 10 metal (such as Pt) and a Group 1 alkali metal (such as potassium); and
- a crystalline aluminosilicate such as ZSM-5 combined with a Group 10 metal (such as Pt), a Group 1 alkali metal (such as sodium), and a Group 11 metal (such as silver or copper).
- Another useful catalyst composition is a Group 10 metal (such as Ni, Pd, and Pt, preferably Pt) supported on silica (e.g., silicon dioxide) modified by a Group 1 alkali metal silicate (such as Li, Na, K, Rb, and/or Cs silicates) and/or a Group 2 alkaline earth metal silicate (such as Mg, Ca, Sr, and/or Ba silicates), preferably potassium silicate, sodium silicate, calcium silicate, and/or magnesium silicate, preferably potassium silicate and/or sodium silicate.
- a Group 1 alkali metal silicate such as Li, Na, K, Rb, and/or Cs silicates
- a Group 2 alkaline earth metal silicate such as Mg, Ca, Sr, and/or Ba silicates
- the Group 10 metal content of the catalyst composition is at least 0.005 wt%, based on the weight of the catalyst composition, preferably, in the range 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.
- the silica (SiC ) may be any silica typically used as catalyst support such as those marketed under the tradenames of DAVISIL 646 (Sigma Aldrich), DAVISON 952, DAVISON 948, or DAVISON 955 (Davison Chemical Division of W.R. Grace and Company).
- Catalyst composition shape and design are preferably configured to minimize pressure drop, increase heat transfer, and minimize mass transport phenomena. Suitable catalyst shape and design are described in WO 2014/053553, which is incorporated by reference in its entirety.
- the catalyst composition may be an extrudate with a diameter of 2 mm to 20 mm.
- the catalyst composition cross section may be shaped with one or more lobes and/or concave sections. Additionally, the catalyst composition lobes and/or concave sections may be spiraled.
- the catalyst composition may be an extrudate with a diameter of 2 mm to 20 mm; and the catalyst composition cross section may be shaped with one or more lobes and/or concave sections; and the catalyst composition lobes and/or concave sections may be spiraled.
- particle shapes are particularly useful and for fluid bed reactors spherical particle shapes are particularly useful.
- particles for a fixed bed e.g.
- cyclic fixed bed reactor, fired tubes reactor, convectively heated tubes reactor, etc. are typically an extrudate with a diameter of 2 mm to 20 mm; and the catalyst composition cross section may be shaped with one or more lobes and/or concave sections; and the catalyst composition lobes and/or concave sections may be spiraled.
- the catalyst material comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on silica.
- Suitable amounts of catalyst material in the particulate material may be ⁇ about 1.0 wt%, ⁇ about 5.0 wt%, ⁇ about 10.0 wt%, ⁇ about 15.0 wt%, ⁇ about 20.0 wt%, ⁇ about 25.0 wt%, ⁇ about 30.0 wt%, ⁇ about 35.0 wt%, ⁇ about 40.0 wt%, ⁇ about 45.0 wt%, ⁇ about 50.0 wt%, ⁇ about 55.0 wt%, ⁇ about 60.0 wt%, ⁇ about 65.0 wt%, ⁇ about 70.0 wt%, ⁇ about75.0 wt%, ⁇ about 80.0 wt%, ⁇ about 85.0 wt%, ⁇ about 90.0 wt%, ⁇ about 95.0 wt%, ⁇ about 99.0 wt% or about 100.0 wt%.
- the particulate material may comprise ⁇ about 25.0 wt% catalyst material. Additionally or alternatively, the particulate material (e.g., first particulate material, second particulate material) may comprise the catalyst material in an amount of > about 1.0 wt%,
- Ranges expressly disclosed include combinations of any of the above-enumerated values; e.g., about 1.0 wt% to about 100.0 wt%, about 5.0 wt% to about 100.0 wt%, about 10.0 wt% to about 90.0 wt%, about 20.0 wt% to about 80.0 wt%, e/c.
- the particulate material e.g.
- first particulate material, second particulate material may comprise the catalyst material in an amount of about 1.0 wt% to about 100.0 wt%, more preferably about 5.0 wt% to about 100.0 wt%, more preferably about 25.0 wt% to about 100.0 wt%, more preferably about 50.0 wt% to about 100.0 wt%, more preferably about 10.0 wt% to about 75.0 wt%, more preferably about 20.0 wt% to about 70.0 wt, more preferably about 70.0 wt% to about 100.0 wt%.
- the particulate material may further comprise one or more inert materials.
- the inert material is understood to include materials which promote a negligible amount (e.g., ⁇ about 3%, ⁇ about 2%, ⁇ about 1%, etc.) of conversion of the feedstock intermediate products, or final products under the reaction conditions described herein.
- the catalyst material and the inert material may be combined as portions of the same particles and/or may be separate particles.
- Catalyst composition shape and design are preferably configured to minimize pressure drop, increase heat transfer, and minimize mass transport phenomena.
- Catalyst composition may be formed into particles that are randomly loaded into the reactor or may be structured catalyst shapes within the reactor.
- the catalyst composition may be an extrudate with a diameter of 2 mm to 20 mm, for example, 2 mm to 10 mm, or 5 mm to 15 mm.
- the catalyst composition cross section may be shaped with one or more lobes and/or concave sections. Additionally, the catalyst composition lobes and/or concave sections may be spiraled. Shapes may also include holes or perforations in the shapes to increase voidage and improve mass transfer.
- Structured catalyst shape examples are coating of catalyst onto the inner wall of the reactor and onto formed inorganic support structures (metallic and ceramic preferred ceramics are those with high thermal conductivity, such as silicon carbide, aluminum nitride, boron carbide, and silicon nitride).
- Formed inorganic support structures may be ordered structures, such as extruded ceramic monoliths and extruded or rolled metal monoliths.
- Formed inorganic support structures may also include ceramic or metal foams and 3D printed structures.
- the catalyst material and/or inert material may be essentially spherical (i.e., ⁇ about 20%, ⁇ about 30%, ⁇ about 40%, ⁇ about 50% aberration in diameter), cylindrical or lobed shaped.
- Suitable amounts of inert material in the particulate material may be about 0.0 wt%
- the particulate material may comprise > about 25.0 wt% inert material.
- the particulate material may comprise an inert material in an amount of ⁇ about 1.0 wt%, ⁇ about 5.0 wt%, ⁇ about 10.0 wt%, ⁇ about 15.0 wt%, ⁇ about 20.0 wt%, ⁇ about 25.0 wt%, ⁇ about 30.0 wt%, ⁇ about 35.0 wt%, ⁇ about 40.0 wt%, ⁇ about 45.0 wt%, ⁇ about 50.0 wt%, ⁇ about 55.0 wt%, ⁇ about 60.0 wt%, ⁇ about 65.0 wt%, ⁇ about 70.0 wt%, ⁇ about 75.0 wt%, ⁇ about 80.0 wt%, ⁇ about 85.0 wt%, ⁇ about 90.0 wt%, ⁇ about 95.0 wt%, or ⁇ about 99.0 wt%.
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g. , about 0.0 wt% to about 99.0 wt%, about 0.0 wt% to about 95.0 wt%, about 10.0 wt% to about 90.0 wt%, about 20.0 wt% to about 80.0 wt%, etc.
- the particulate material may comprise an inert material in an amount of about 0.0 wt% to about 95.0 wt%, more preferably about 25.0 wt% to about 90.0 wt%, more preferably about 30.0 wt% to about 80.0 wt%.
- the catalyst material and/or the inert material may have an average diameter of > about 0.1 mm, > about 0.5 mm, > about 1 mm, > about 2 mm,
- the catalyst material and/or the inert material may have an average diameter of ⁇ about 0.1 mm, ⁇ about 0.5 mm, ⁇ about 1 mm, ⁇ about 2 mm, ⁇ about 3 mm, ⁇ about 4 mm, ⁇ about 5 mm, ⁇ about 6 mm, ⁇ about 7 mm, ⁇ about 8 mm, ⁇ about 9 mm, ⁇ about 10 mm, ⁇ about 12 mm, ⁇ about 14 mm, ⁇ about 16 mm, ⁇ about 18 mm, ⁇ about 20 mm, ⁇ about 22 mm, ⁇ about 24 mm, ⁇ about 26 mm, ⁇ about 28 mm, ⁇ about 30 mm, ⁇ about 35 mm, ⁇ about 40 mm, ⁇ about 45 mm, or ⁇ about 50 mm.
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g. , about 0.1 mm to about 50 mm, about 1 mm to about 35 mm, about 2 mm to about 30 mm, about 3 mm to about 40 mm, etc.
- the catalyst material and/or the inert material may have an average diameter of about 0.5 mm to about 30 mm, more preferably about 1 mm to about 20 mm, more preferably about 2 mm to about 10 mm, more preferably about 3 mm to about 8 mm.
- the catalyst material and/or the inert material may have an average diameter of > about 50 ⁇ , > about 100 ⁇ , > about 200 ⁇ , > about 300 ⁇ % > about 400 ⁇ , > about 500 ⁇ , > about 600 ⁇ , > about 700 ⁇ , > about 800 ⁇ , > about 900 ⁇ , > about 1000 ⁇ , > about 1100 ⁇ , > about 1200 ⁇ , > about 1300 ⁇ , > about 1400 ⁇ , > about 1500 ⁇ , > about 1600 ⁇ , > about 1700 ⁇ ,
- the catalyst material and/or the inert material may have an average diameter of ⁇ about 50 ⁇ , ⁇ about 100 ⁇ , ⁇ about 200 ⁇ , ⁇ about 300 ⁇ , ⁇ about 400 ⁇ , ⁇ about 500 ⁇ m, ⁇ about 600 ⁇ , ⁇ about 700 ⁇ , ⁇ about 800 ⁇ , ⁇ about 900 ⁇ m, ⁇ about 1000 ⁇ , ⁇ about 1 100 ⁇ , ⁇ about 1200 ⁇ , ⁇ about 1300 ⁇ , ⁇ about 1400 ⁇ m, ⁇ about 1500 ⁇ m, ⁇ about 1600 ⁇ , ⁇ about 1700 ⁇ , ⁇ about 1800 ⁇ , ⁇ about 1900 ⁇ m, ⁇ about 2000 ⁇ m, ⁇ about 2100 ⁇ , ⁇ about 2200 ⁇ , ⁇ about 2300 ⁇ , ⁇ about 2400 ⁇ , ⁇ about 2500 ⁇ m, ⁇ about 2600 ⁇ m,
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 50 ⁇ to about 10,000 ⁇ , about 100 ⁇ to about 9000 ⁇ , about 200 ⁇ to about 7500 ⁇ , about 200 ⁇ to about 5500 ⁇ , about 100 ⁇ m to about 4000 ⁇ , about 100 ⁇ to about 700 ⁇ , etc.
- the catalyst material and/or the inert material may have an average diameter of about 100 ⁇ to about 4000 ⁇ , more preferably about 100 ⁇ to about 700 ⁇ , more preferably about 100 ⁇ to about 600 ⁇ , more preferably about 100 ⁇ to about 500 ⁇ .
- the catalyst material and/or the inert material may have an average diameter of about 1000 ⁇ to about 10,000 ⁇ , more preferably about 2000 ⁇ to about 8000 ⁇ , more preferably about 3000 ⁇ to about 6000 ⁇ , more preferably about 3500 ⁇ to about 4500 ⁇ .
- the particulate material (e.g. , thermal energy stored in the particulate material) provides at least a portion of the heat required for increasing sensible heat of the feedstock and/or converting at least a portion of the acyclic Cs hydrocarbons to the first effluent comprising cyclopentadiene.
- the particulate material may provide
- the particulate material may provide > about 50% of the heat required for converting at least a portion of the acyclic Cs hydrocarbons to the first effluent comprising cyclopentadiene. Ranges expressly disclosed include combinations of any of the above-enumerated values; e.g. , about 30% to about 100%, about 40% to about 95%, about 50% to about 90%, etc.
- the particulate material may provide about 30% to about 100% of the heat required, more preferably 50% to about 100% of the heat required, more preferably 70% to about 100% of the heat required.
- fresh particulate material may be provided directly to a reaction zone on an as needed basis to make up for catalyst losses due to physical degradation (i.e., attrition and loss of fines from the reactor) or catalyst performance deterioration due to aging.
- An effluent (e.g., first effluent, second effluent) exiting a reaction zone during the reaction interval may comprise a variety of hydrocarbon compositions produced from the reaction of the Cs hydrocarbons (e.g., acyclic Cs hydrocarbons) in the reaction zone.
- Cs hydrocarbons e.g., acyclic Cs hydrocarbons
- the hydrocarbon compositions typically have mixtures of hydrocarbon compounds having from 1 to 30 carbon atoms (C1-C30 hydrocarbons), from 1 to 24 carbon atoms (C1-C24 hydrocarbons), from 1 to 18 carbon atoms (C1-C18 hydrocarbons), from 1 to 10 carbon atoms (C1-C10 hydrocarbons), from 1 to 8 carbon atoms (Ci-Ce hydrocarbons), and from 1 to 6 carbon atoms (Ci-C 6 hydrocarbons).
- an effluent comprises cyclopentadiene.
- the cyclopentadiene may be present in a hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in an amount of > about 20.0 wt%, > about 25.0 wt%,
- the cyclopentadiene may be present in a hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in an amount of ⁇ about 20.0 wt%, ⁇ about 25.0 wt%, ⁇ about 30.0 wt%, ⁇ about 35.0 wt%, ⁇ about 40.0 wt%, ⁇ about 45.0 wt%, ⁇ about 50.0 wt%, ⁇ about 55.0 wt%, ⁇ about 60.0 wt%, ⁇ about 65.0 wt%, ⁇ about 70.0 wt%, ⁇ about 75.0 wt%, ⁇ about 80.0 wt%, or ⁇ about 85.0 wt%.
- an effluent e.g., first effluent, second effluent
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 20.0 wt% to about 85.0 wt%, about 30.0 wt% to about 75.0 wt%, about 40.0 wt% to about 85.0 wt%, about 50.0 wt% to about 90.0 wt%, etc.
- the cyclopentadiene may be present in a hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in an amount of about 10.0 wt% to about 85.0 wt%, more preferably about 25.0 wt% to about 80.0 wt%, more preferably about 40.0 wt% to about 75.0 wt%.
- an effluent e.g., first effluent, second effluent
- an effluent may comprise one or more other Cs hydrocarbons in addition to cyclopentadiene.
- examples of other Cs hydrocarbons include, but are not limited to, cyclopentane and cyclopentene.
- the one or more other Cs hydrocarbons may be present in a hydrocarbon portion of an effluent (e.g. , first effluent, second effluent) in an amount of > about 10.0 wt%, > about 15.0 wt%,
- the one or more other Cs hydrocarbons may be present in a hydrocarbon portion of an effluent (e.g.
- first effluent, second effluent in an amount of ⁇ about 15.0 wt%, ⁇ about 20.0 wt%, ⁇ about 25.0 wt%, ⁇ about 30.0 wt%, ⁇ about 35.0 wt%, ⁇ about 40.0 wt%, ⁇ about 45.0 wt%, ⁇ about 50.0 wt%, ⁇ about 55.0 wt%, ⁇ about 60.0 wt%, ⁇ about 65.0 wt%, or ⁇ about 70.0 wt%.
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 10.0 wt% to about 70.0 wt%, about 10.0 wt% to about 55.0 wt%, about 15.0 wt% to about 60.0 wt%, about 25.0 wt% to about 65.0 wt%, efc.
- the one or more other Cs hydrocarbons may be present in a hydrocarbon portion of an effluent (e.g.
- first effluent, second effluent in an amount of about 30.0 wt% to about 65.0 wt%, more preferably about 20.0 wt% to about 40.0 wt%, more preferably about 10.0 wt% to about 25.0 wt%.
- an effluent (e.g. , first effluent, second effluent) may also comprise one or more aromatics, e.g. , having 6 to 30 carbon atoms, particularly 6 to 18 carbon atoms.
- the one or more aromatics may be present in a hydrocarbon portion of an effluent (e.g. , first effluent, second effluent) in an amount of about > about 1.0 wt%, > about 5.0 wt%,
- the one or more aromatics may be present in a hydrocarbon portion of an effluent (e.g.
- first effluent, second effluent in an amount of ⁇ about 1.0 wt%, ⁇ about 5.0 wt%, ⁇ about 10.0 wt%, ⁇ about 15.0 wt%, ⁇ about 20.0 wt%, ⁇ about 25.0 wt%, ⁇ about 30.0 wt%, ⁇ about 35.0 wt%, ⁇ about 40.0 wt%, ⁇ about 45.0 wt%, ⁇ about 50.0 wt%, ⁇ about 55.0 wt%, ⁇ about 60.0 wt%, or ⁇ about 65.0 wt%.
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 1.0 wt% to about 65.0 wt%, about 10.0 wt% to about 50.0 wt%, about 15.0 wt% to about 60.0 wt%, about 25.0 wt% to about 40.0 wt%, efc.
- the one or more aromatics may be present in a hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in an amount of about 1.0 wt% to about 15.0 wt%, more preferably about 1.0 wt% to about 14.0 wt%, more preferably about 1.0 wt% to about 5.0 wt%.
- an effluent e.g., first effluent, second effluent
- the reaction interval may have a duration of > about 1 min, > about 2 min, > about 3 min, > about 4 min, > about 5 min, > about 6 min, > about 7 min, > about 8 min, > about 9 min, > about 10 min, > about 15 min, > about 20 min, > about 25 min, > about 30 min, > about 35 min, > about 40 min, > about 45 min, > about 50 min, > about 55 min, > about 60 min, > about 65 min, > about 70 min, > about 75 min, > about 80 min, > about 85 min, > about 90 min, > about 95 min, > about 100 min, > about 110 min, or > about 120 min.
- the reaction interval may have a duration of ⁇ about 1 min, ⁇ about 2 min, ⁇ about 3 min, ⁇ about 4 min, ⁇ about 5 min, ⁇ about 6 min, ⁇ about 7 min, ⁇ about 8 min, ⁇ about 9 min, ⁇ about 10 min, ⁇ about 15 min, ⁇ about 20 min, ⁇ about 25 min,
- ⁇ about 30 min ⁇ about 35 min, ⁇ about 40 min, ⁇ about 45 min, ⁇ about 50 min, ⁇ about 55 min, ⁇ about 60 min, ⁇ about 65 min, ⁇ about 70 min, ⁇ about 75 min, ⁇ about 80 min, ⁇ about 85 min, ⁇ about 90 min, ⁇ about 95 min, ⁇ about 100 min,
- the reaction interval may have a duration of about 1 to about 120 min, more preferably about 1 to about 90 min, more preferably about 1 to about 60 min, more preferably about 1 to about 40 min, more preferably about 1 to about 15 min, more preferably about 1 to about 10 min, more preferably about 2 to about 8 min.
- the reaction interval may be performed until the temperature in a reaction zone is ⁇ 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 650°C or ⁇ about 675°C. Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 300°C to about 675°C, about 400°C to about 600°C, about 425°C to about 575°C, etc.
- the reaction interval may be performed until the temperature in a reaction zone falls below about 400°C, below about 450°C, below about 475°C, below about 500°C, below about 550°C, below about 575°C, or below about 600°C.
- the particulate material may become entrained with hydrocarbons (e.g., cyclopentadiene) in the effluent (e.g., first effluent, second effluent) as the effluent travels through and/or exits a reaction zone.
- the process may further comprise separating particulate material, which may be entrained with hydrocarbons (e.g., cyclopentadiene) in the effluent (e.g., first effluent, second effluent).
- This separating may comprise removal of the particulate material from the hydrocarbons (e.g., cyclopentadiene) by any suitable means, such as, but not limited to cyclones, filter, electrostatic precipitators, heavy liquid contacting, and/or other gas solid separation equipment, which may be inside and/or outside the at least one reaction zone.
- the effluent free of particulate material may then travel to a product recovery system. Additionally, the removed particulate material may then be fed back into the at least one reaction zone, for example, in a substantially top portion of the at least one reaction zone using known methods.
- the particulate material may cool, i.e., reduce temperature. Further, coke material may form on the particulate material, particularly on the catalyst material, which may reduce the activity of the catalyst material.
- This catalyst material at the end of a reaction interval with coke formation and/or having a reduced temperature is referred to as a "spent catalyst material.”
- the process may further comprise a reheating interval where the feedstock at a reaction zone may be cyclically halted and a reheating gas may be provided to the reaction zone to the reactor system to reheat the particulate material.
- the reheating gas may comprise an inert substance (e.g., N 2 , CO), methane, and/or hydrogen.
- the reheating gas may comprise an inert substance and may be fed a reaction zone to reheat the particulate material.
- the reheating gas may comprise hydrogen and the reheating gas may contact the particulate material (e.g.
- the term "incrementally deposited" coke material refers to an amount of coke material that is deposited on the catalyst material during each reaction interval as opposed to a cumulative amount of coke material deposited on the catalyst material during multiple reaction intervals.
- the reheating gas comprising hydrogen is substantially free of oxygen, which can damage and/or reduce activity of the catalyst material.
- the reheating gas comprises hydrogen and is substantially free of reactive oxygen-containing compounds.
- substantially free used in this context means the reheating gas comprises less than about 1.0 wt%, based upon the weight of the rejuvenation stream, e.g., 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 wt% oxygen-containing compounds.
- “Reactive oxygen-containing compounds” are compounds where the oxygen is available to react with the catalyst as compared to inert compounds containing oxygen (such as CO), which do not react with the catalyst.
- the reheating gas comprises > 50 wt% H2, such as > 60 wt%, > 70 wt%, preferably > 90 wt% H2 and may further comprise an inert substance (e.g., N 2 , CO), and/or methane.
- an inert substance e.g., N 2 , CO
- methane methane
- the reheating gas may flow in a direction co-current or counter- current to a direction of a flow of the feedstock.
- the reheating gas may also enter at a top portion of a reaction zone and thereby flow in a direction co-current to a direction of flow of the feedstock.
- the reheating gas may enter at a bottom portion of a reaction zone and thereby flow in a direction counter-current to a direction of flow of the feedstock.
- the reheating gas flows in a direction counter-current to a direction of flow of the feedstock and/or an inverse temperature profile in the reaction zone may be achieved.
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a temperature of > about 400°C, > about 450°C, > about 500°C, > about 550°C, > about 600°C, > 650°C, > about 700°C, > 750°C, > about 800°C, > 850°C, or > about 900°C.
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a temperature of > about 600°C.
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a temperature of ⁇ about 400°C, ⁇ about 450°C, ⁇ about 500°C, ⁇ about 550°C, ⁇ about 600°C, ⁇ 650°C, ⁇ about 700°C, ⁇ about 750°C, ⁇ about 800°C, ⁇ about 850°C, or ⁇ about 900°C.
- Ranges of temperatures expressly disclosed include combinations of any of the above-enumerated values, e.g., about 400°C to about 900°C, about 450°C to about 850°C, about 500°C to about 800°C, etc.
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a temperature of about 400°C to about 800°C, more preferably about 600°C to about 800°C, more preferably about 625°C to about 700°C, more preferably about 550°C to about 750°C.
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a pressure of > about 1.0 psia, > about 5.0 psia, > about 25.0 psia, > about 50.0 psia, > about 75.0 psia, > about 100.0 psia, > about 125.0 psia,
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a pressure of > about 100.0 psia. Additionally or alternatively, the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a pressure of
- Ranges of pressures expressly disclosed include combinations of any of the above-enumerated values, e.g., about 1.0 psia to about 350.0 psia, about 5.0 psia to about 275.0 psia, about 25.0 psia to about 250.0 psia, etc.
- the reheating gas may enter a reaction zone and/or the reheating interval may be operated at a pressure of about 1 psia to about 300 psia, more preferably about 5 psia to about 250 psia, more preferably about 25 psia to about 250 psia.
- the incrementally deposited coke material is removed from the catalyst material in an amount of > about 1.0 wt%, > about 5.0 wt%, > about 10.0 wt%, > about 15.0 wt%, > about 20.0 wt%, > about 25.0 wt%, > about
- At least about 10.0 wt% of the incrementally deposited coke material is removed from the catalyst material, more preferably at least about 90.0 wt%, more preferably at least about 95.0 wt%, more preferably at least about 99.0 wt%.
- the incrementally deposited coke material is removed from the catalyst material in an amount of ⁇ about 1.0 wt%, ⁇ about 5.0 wt%, ⁇ about 10.0 wt%, ⁇ about 15.0 wt%, ⁇ about 20.0 wt%, ⁇ about 25.0 wt%, ⁇ about 30.0 wt%, ⁇ about 35.0 wt%, ⁇ about 40.0 wt%, ⁇ about 45.0 wt%, ⁇ about 50.0 wt%, ⁇ about 55.0 wt%, ⁇ about 60.0 wt%, ⁇ about 65.0 wt%, ⁇ about 70.0 wt%, ⁇ about 75.0 wt%, ⁇ about 80.0 wt%, ⁇ about 85.0 wt%, ⁇ about 90.0 wt%, ⁇ about 95.0 wt%, ⁇ about 99.0 wt%, or about 100.0 wt%.
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 1.0 wt% to about 100.0 wt%, about 5.0 wt% to about 95.0 wt%, about 10.0 wt% to about 90.0 wt%, about 30.0 wt% to about 90.0 wt%, efc.
- the incrementally deposited coke material is removed from the catalyst material in an amount of about 1.0 wt% to about 100.0 wt%, more preferably about 10.0 wt% to about 100.0 wt%, more preferably about 90.0 wt% to about 100.0 wt%, more preferably about 95.0 wt% to about 100.0 wt%.
- the temperature of the rejuvenated 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, > about 850°C, or > about 900°C. Additionally or alternatively, the temperature of the rejuvenated 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, ⁇ about 850°C, or ⁇ about 900°C.
- Ranges of temperatures expressly disclosed include combinations of any of the above-enumerated values, e.g., about 400°C to about 900°C, about 450°C to about 850°C, about 500°C to about 800°C, etc.
- the temperature of the rejuvenated catalyst material may be about 400°C to about 800°C, more preferably about 600°C to about 800°C, more preferably about 550°C to about 750°C.
- the reheating interval may have a duration of > about 1 min, > about 5 min, > about 10 min, > about 15 min, > about 20 min, > about 25 min, > about 30 min, > about 35 min, > about 40 min, > about 45 min, > about 50 min, > about 55 min, > about 60 min, > about 65 min, > about 70 min, > about 75 min, > about 80 min, > about 85 min, > about 90 min, > about 95 min, > about 100 min, > about 110 min or > about 120 min.
- the reheating interval may have a duration of ⁇ about 1 min, ⁇ about 5 min, ⁇ about 10 min, ⁇ about 15 min, ⁇ about 20 min, ⁇ about 25 min, ⁇ about 30 min, ⁇ about 35 min, ⁇ about 40 min, ⁇ about 45 min, ⁇ about 50 min, ⁇ about 55 min, ⁇ about 60 min, ⁇ about 65 min, ⁇ about 70 min, ⁇ about 75 min, ⁇ about 80 min, ⁇ about 85 min, ⁇ about 90 min, ⁇ about 95 min, ⁇ about 100 min, ⁇ about 110 min or ⁇ about 120 min.
- Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 1 to about 120 min, about 1 to about 90 min, about 4 to about 80 min, about 10 to about 75 min, etc.
- the reaction interval may have a duration of about 1 to about 120 min, more preferably about 1 to about 90 min, more preferably about 1 to about 60 min, more preferably about 5 to about 40 min.
- the duration of the reheating interval is less than the duration of the reaction interval; more preferably, the duration of the reheating interval is less than one half the duration of the reaction interval.
- the reheating gas is provided by a suitable reheating apparatus, such as, but not limited to a fire heater.
- the reheating gas may be heated to a suitable temperature as described above prior to providing the reheating gas to a reaction zone.
- the reheating gas exiting a reaction zone may also be returned to the reheating apparatus to be reheated to a suitable temperature as described above and then provided to a reaction zone.
- the reheating apparatus may also make steam and/or heat the feedstock prior to the feedstock entering a reaction zone.
- rejuvenated catalyst material may be separated from the reheating gas and/or volatile hydrocarbon in one or multiple separation steps inside or outside the reheating zone by any suitable means, such as, but not limited to cyclones. Additionally, the hydrogen gas may be used in the separation step.
- the process may further comprise a regeneration interval to recapture catalyst activity lost due to the accumulation of coke material and/or agglomeration of metal on the catalyst material during the reaction.
- This regeneration interval may be carried out when there has not been sufficient removal of the coke material from the particulate material (e.g. , spent catalyst material) during the reheating intervals.
- catalyst activity in a reaction zone may be restored to above about 50% of the fresh catalyst activity, preferably above about 80% of the fresh catalyst activity, and most preferably above about 95% and below about 99.9% of the fresh catalyst activity.
- the feedstock may be cyclically halted to a reaction zone.
- purging of any combustible gas to below an explosive limit may be performed.
- feedstock and/or reactor product e.g. , cyclopentadiene
- reactor product e.g. , cyclopentadiene
- below an explosive limit means that sufficient purging of any combustible gas has occurred such that when the gas flow is changed to a next composition (e.g. , a regeneration gas), a hazardous mixture is not formed, which could result in an explosion.
- a regeneration gas may then be supplied to the reaction zone, where the particulate material is contacted with the regeneration gas under regenerating conditions to oxidatively remove at least a portion of cumulatively deposited coke material on the catalyst material thereby forming a regenerated catalyst material.
- Suitable regeneration gases include, but are not limited to oxygen.
- the regeneration gas may flow in a direction counter-current or co- current to a direction of flow of the feedstock as described above for the reheating gas.
- the regeneration gas may further comprise an inert substance (e.g., N 2 ) as well.
- an inert substance e.g., N 2
- purging of the regeneration gas to below an explosive limit may be performed. Once purging of the regeneration gas is complete, feedstock may then be provided to the reaction zone.
- the regeneration interval may have a duration of > about 0.5 day, > about 1 day, > about 1.5 days, > about 2 days, > about 3 days, > about 4 days, > about 5 days, > about 6 days, > about 7 days, > about 8 days, > about 9 days, > about 10 days, > about 11 days, > about 12 days, > about 13 days, > about 14 days, or > about 15 days.
- day refers to an about 24 hour period
- 0.5 day refers to an about 12 hour period.
- the regeneration interval may have a duration of ⁇ about 0.5 day, ⁇ about 1 day, ⁇ about 1.5 days, ⁇ about 2 days, ⁇ about 3 days, ⁇ about 4 days, ⁇ about 5 days, ⁇ about 6 days, ⁇ about 7 days, ⁇ about 8 days, ⁇ about 9 days, ⁇ about 10 days, ⁇ about 11 days, ⁇ about 12 days, ⁇ about 13 days, ⁇ about 14 days, or ⁇ about 15 days. Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 0.5 to about 15 days, about 1 to about 12 days, about 2 to about 11 days, etc.
- the regeneration interval may have a duration of about 1 to about 15 days, more preferably about 1 to about 10 days, more preferably about 1.5 to about 5 days.
- the regeneration interval may be performed at a frequency of about every 1 day, about every 2 days, about every 4 days, about every 6 days, about every 8 days, about every 10 days, about every 12 days, about every 14 days, about every 16 days, about every 18 days, about every 20 days, about every 22 days, about every 24 days, about every 26 days, about every 28 days, about every 30 days, about every 35 days, about every 40 days, about every 45 days, or about every 50 days. Ranges expressly disclosed include combinations of any of the above-enumerated values, e.g., about 1 to about 50 days, about 1 to about 45 days, about 2 to about 35 days, etc.
- the regeneration interval may be performed at a frequency of every 1 to 50 days, more preferably every 10 to 45 days, more preferably every 20 to 40 days, more preferably every 30 to 35 days.
- the regeneration interval may be performed at a frequency of 1 to 50 days, more preferably 10 to 45 days, more preferably 20 to 40 days, more preferably 30 to 35 days.
- the reactor system may further comprise additional reaction zones, which may be operated in parallel, where the reaction zones alternate operating in a reaction interval, a reheating interval, and/or a regeneration interval.
- the reactor system may comprise 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 an eighth reaction zone, etc.
- the reactor system includes 1 to 20 reaction zones, more preferably 3 to 15 reaction zones, more preferably 5 to 10 reaction zones.
- Each reaction zone independently may be a fixed bed reactor or a fluidized bed reactor as described above.
- Figure 1 One cyclic arrangement of various reaction zones is shown in Figure 1 , where a first, second, third, and fourth reaction zone alternate between reaction intervals and reheating intervals, while a fifth reaction zone undergoes a regeneration interval.
- the process described herein may further comprise a second reaction zone, and a third reaction zone operated in parallel with a first reaction zone.
- a reheating interval may be performed in the second reaction zone, wherein a second feedstock comprising acyclic Cs hydrocarbons fed to the second reaction zone may be cyclically halted; a second reheating gas may be supplied to the second reaction zone and contacts a particulate material comprising a catalyst material to reheat the particulate material, and/or to remove at least a portion of incrementally deposited coke material on the catalyst material thereby forming a reheated particulate material and/or a rejuvenated catalyst material and a volatile hydrocarbon.
- a regeneration interval may be performed in the third reaction zone, wherein a third feedstock comprising acyclic Cs hydrocarbons fed to the third reaction zone may be cyclically halted; a regeneration gas may be supplied to the third reaction zone and contact a particulate material comprising a catalyst material under regenerating conditions to remove at least a portion of coke material deposited on the catalyst material thereby forming a regenerated catalyst material.
- a reaction interval in the second reaction zone and a reaction interval in the third reaction zone may be performed, wherein the reaction interval in the first reaction zone, the reaction interval in the second reaction zone, and the reaction interval in the third reaction zone may be performed in a staggered fashion (i.e. , be performed at different times).
- Feedstock comprising Cs hydrocarbons may be distributed to all the reactors from one feedstock header 201 (not all conduits from every header to every reactor are shown in Figure 2).
- Product may be collected from all the reactors via one product header 204.
- there may be one reheating gas supply header 202 for the reheating gas and/or one regeneration gas supply header 200 for regeneration gas that is distributed to all the reactors.
- a regeneration effluent gas header 203 may collect regeneration gas effluent from all the reactors.
- a reheating gas effluent header 205 may collect reheating gas effluent from all the reactors.
- Feedstock comprising acyclic Cs may be provided from feedstock header 201 to at least one reactor, e.g., via conduit 206 to reactor 211 and/or via conduit 208 to reactor 213, as part of a reaction cycle or an "on-oil" conversion cycle.
- Reactor effluent comprising cyclic C5 product exiting the "on-oil" reactors (e.g., via conduits 216 and/or 218) may be combined and conducted away via common product header 204.
- reheating gas may be provided to one or more reactors, e.g., via conduit 207 to reactor 212 and/or via conduit 209 to reactor 214.
- regeneration gas and purge gas may be provided concurrently to one or more reactors through regeneration gas supply header 200, e.g., via conduit 210 to reactor 215.
- Regeneration gas effluent may be collected from the one or more reactors, which were provided regeneration gas and purge gas.
- regeneration gas effluent may be collected from reactor 215 via conduit 220 to regeneration gas effluent header 203.
- Reheating gas effluent may be collected from the one or more reactors, which were provided reheating gas.
- reheating gas effluent may be collected from reactor 212 via conduit 217 and/or reactor 214 via conduit 219 to reheating gas effluent header 205.
- Each reactor is designed with valving systems not shown to enable isolation from various headers when not in use between on-oil feedstock conversion, reheat, and/or regeneration cycles.
- Any valving system and control system known in the art may be used; e.g., double block and bleed to prevent contacting of flammable gases and oxidant gases.
- the conversion process can comprise a cyclic arrangement for concurrent "on-oil" feedstock conversion, reheating, and/or regeneration in a multiple reactor conversion system.
- "On-oil" conversion time is typically greater than 1 minute, typically greater than 5 minutes, often from about 1 minute to about 120 minutes.
- Reheating time is typically from about 1 minute to about 120 minutes.
- the arrangement 220 in Figure 2 allows for multiple reactors, e.g., reactors 211, 212, 213, and 215, to repeat a rotating cycle of "on- oil" conversion and reheating, while at least one other reactor, e.g., reactor 215, completes regeneration.
- reactor 215 When regeneration of a reactor, e.g., reactor 215, is complete, it may be returned to "on-oil" conversion/reheat cycle while another reactor, e.g., reactor 211, may be cycled out for regeneration as required.
- another reactor e.g., reactor 211
- Such an arrangement provides more consistent product composition while reducing the amount of equipment needed.
- a reaction system 1 for converting Cs hydrocarbons (e.g. , acyclic Cs hydrocarbons) to cyclopentadiene is provided, as shown in Figure 3.
- the reaction system 1 may comprise a feedstock stream 2 comprising Cs hydrocarbons (e.g. , acyclic Cs hydrocarbons) as described above, an effluent stream 3 comprising cyclopentadiene; and at least one reactor 4 as described above.
- the at least one reactor 4 may comprise a particulate material 5 comprising a catalyst material as described above, a feedstock inlet 6 for providing the feedstock stream 2 to the reaction system 1, and an effluent outlet 7 for removal of the first effluent stream 3.
- the at least one reactor 4 may be a fixed bed reactor (e.g. , horizontal or vertical fixed bed reactor) or a fluidized bed reactor as described above.
- the at least one reactor 4 may include at least one internal structure (not shown) as described above.
- the at least one reactor 4 may include a support 8 for the particulate material and/or a distributer 9.
- the at least one reactor 4 is operated under reaction conditions as described above to convert at least a portion of the Cs hydrocarbons (e.g. , acyclic Cs hydrocarbons) to cyclopentadiene. Additionally, it is preferable that the at least one reactor 4 has an inverse temperature profile as described above.
- the feedstock stream 2 at the feedstock inlet may have a temperature of less than about 525°C and/or the effluent stream 3 at the effluent outlet has a temperature of at least about 575°C.
- the reaction conditions may comprise a temperature of about 400°C to about 700°C and/or a pressure of about 3 psia to about 30 psia.
- the at least one reactor 4 may include one or more heating devices (e.g. , fired tube, heated coil) (not shown) in order to maintain temperature therein.
- heating devices e.g. , fired tube, heated coil
- the particulate material comprises less than about 25.0 wt% catalyst material as described above and further comprises an inert material as described above (e.g. , at least about 25.0 wt%).
- the catalyst material and/or the inert material may have an average diameter as described above, e.g. , about 1.0 mm to about 20 mm and about 3.0 mm to about 20 mm, respectively.
- the catalyst material comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on silica, preferably platinum on ZSM-5.
- the particulate material may provide at least a portion of (e.g., at least about 50%) the heat required for converting the C5 hydrocarbons (e.g. , acyclic C5 hydrocarbons) to cyclopentadiene.
- reaction system 1 may further comprise a cyclone (not shown) for separating the particulate material, which may be entrained with hydrocarbons (e.g. cyclopentadiene) in the effluent stream 3.
- a cyclone for separating the particulate material, which may be entrained with hydrocarbons (e.g. cyclopentadiene) in the effluent stream 3.
- Another effluent stream (not shown) substantially free of particulate material may then travel to a product recovery system.
- the reaction system 1 may further comprise a reheating gas stream 10 for reheating the particulate material and/or restoring activity of the spent catalyst material, as shown in Figure 4.
- the reheating gas stream 10 may enter via feedstock inlet 6 or via a different inlet (not shown).
- the reheating gas stream 10 may comprise an inert substance (e.g. , CO, N 2 ) and/or hydrogen for removal of at least a portion of incrementally deposited coke material on spent catalyst material thereby forming a rejuvenated catalyst material, and a volatile hydrocarbon.
- the rejuvenated catalyst material comprises less of the incrementally deposited coke material than the spent catalyst material as described above, preferably at least about 10 wt% less of the incrementally deposited coke material than the spent catalyst material.
- the reheating gas and, optionally, the volatile hydrocarbon may exit the at least one reactor 4 via the effluent outlet 7 or a different outlet (not shown) as an effluent reheating gas stream 11.
- the reheating gas stream 10 has an inlet temperature and pressure as described above, preferably an inlet temperature of at least about 600°C and/or an inlet pressure of about 100 psia.
- the rejuvenated catalyst material comprises less of the incrementally deposited coke material than the spent catalyst material as described above, preferably at least about 10 wt% less of the incrementally deposited coke material than the spent catalyst material.
- the reheating gas stream 10 may flow in a co-current or counter-current direction to a direction of flow of the feedstock stream 2, preferably in counter-current direction.
- the reheating gas stream 10 may be provided by a reheating apparatus 12 as described above in fluid connection with the at least one reactor 4.
- the effluent reheating gas stream 11 may be sent to a compression device 22 and then sent to a separation apparatus 18 wherein a light hydrocarbon enriched gas stream 19 and a light hydrocarbon depleted gas stream 20 may be produced.
- the light hydrocarbon enriched gas stream 19 may be used, inter alia, as a fuel.
- the light hydrocarbon depleted gas stream 20 may be combined with a make-up hydrogen stream 21 and heated in reheating apparatus 12.
- the reheating apparatus 12 may comprise one or more heating devices as described above, a reheating inlet for the light hydrocarbon depleted gas stream 20, a means 13 for heating the light hydrocarbon depleted gas stream 20 to produce the reheating gas stream 10, and a reheating outlet (not shown) for returning the reheating gas stream 10 to the at least one reactor 4.
- the means 13 for heating the recycled reheating gas stream 11 may include any suitable means known in the art, for example, a fired heater as described above.
- the separation apparatus 18 may be a membrane system, adsorption system, or other known system for separation of H2 from light hydrocarbons.
- the reheating apparatus 12 operates under conditions described above, preferably reheating apparatus 12 has a temperature of about 550°C to about 800°C. Additionally, the reheating apparatus 12 may produce a steam stream 14, typically from water, but steam is also possible. Also, the reheating apparatus 12 may heat feedstock stream 2 prior to feedstock stream 2 entering the at least one reactor 4.
- the reaction system 1 may further comprise a regeneration gas stream 15, as shown in Figure 5.
- the regeneration gas stream 15 may enter via feedstock inlet 6 or via a different inlet (not shown), under regeneration conditions as described above for removing at least a portion of coke material deposited on the catalyst material (e.g., spent catalyst material) thereby forming a regenerated catalyst material.
- the regeneration gas may exit the at least one reactor 4 via the effluent outlet 7 or a different outlet (not shown) as a recycled regeneration gas stream 16.
- the regeneration gas stream 15 may be provided by a regeneration apparatus 17 as described above in fluid connection with the at least one reactor 4.
- reaction system 1 may further comprise a fresh particulate material stream (not shown) in fluid connection with the at least one reactor 6.
- the at least one reactor 4 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, an eighth reactor, etc.
- the reaction system includes 1 to 20 reactors, more preferably 3 to 15 reactors, more preferably 5 to 10 reactors.
- the reactors may be operated in parallel, wherein the first reactor, the second reactor, and third reactor independently, cyclically operate under a reaction interval, a rejuvenation interval, and/or a regeneration interval.
- Each reactor independently may be a fixed bed or a fluidized bed reactor. IV.
- This invention further relates to:
- Embodiment 1 A process for converting acyclic C5 hydrocarbons to cyclopentadiene in a reactor system, wherein the process comprises: a reaction interval comprising: cyclically providing to the reactor system a feedstock comprising acyclic C5 hydrocarbons; contacting the feedstock with a particulate material comprising a catalyst material (e.g., platinum on ZSM-5, platinum on zeolite L, and/or platinum on silica) in a first reaction zone (e.g.
- a catalyst material e.g., platinum on ZSM-5, platinum on zeolite L, and/or platinum on silica
- fixed bed reactor fluidized bed reactor, horizontal fixed bed reactor, vertical fixed bed reactor
- a reheating interval comprising: cyclically halting the feedstock to the first reaction zone; and providing a reheating gas to the first reaction zone to reheat the particulate material.
- Embodiment 2 The process of embodiment 1, wherein an inverse temperature profile is maintained in the first reaction zone.
- Embodiment 3 The process of embodiment 1 or 2, wherein the feedstock flows co-current or counter-current to a direction of a flow of the reheating gas.
- Embodiment 4 The process of any one of the previous embodiments, wherein the feedstock is provided at a temperature of less than or equal to about 525°C and/or the first effluent exiting the first reaction zone has a temperature of at least about 575°C.
- Embodiment 5 The process of any one of the previous embodiments, wherein the reaction interval has a duration of about 1 min to about 90 min and/or the reaction interval is performed until the temperature in the first reaction zone falls below about 450°C to about 550°C.
- Embodiment 6 The process of any one of the previous embodiments, wherein the reheating gas comprises hydrogen and the reheating gas contacts the particulate material to remove at least a portion of incrementally deposited coke material (e.g., at least about
- Embodiment 7 The process of any one of the previous embodiments, wherein the reheating gas enters the first reaction zone at a temperature of at least about 600°C and a pressure of about 100 psia.
- Embodiment 8 The process of any one of the previous embodiments, wherein the reheating interval has a duration of about 1 min to about 90 min.
- Embodiment 9. The process of any one of the previous embodiments, wherein the reaction conditions comprise a temperature of about 400°C to about 700°C and an outlet pressure of about 3 psia to about 30 psia and/or at least about 30 wt% of the acyclic Cs hydrocarbons is converted to cyclopentadiene.
- Embodiment 10 The process of any one of the previous embodiments, wherein the particulate material further comprises an inert material (e.g. , at least about 25.0 wt%) and/or at less than about 25.0 wt% catalyst material.
- an inert material e.g. , at least about 25.0 wt% and/or at less than about 25.0 wt% catalyst material.
- Embodiment 11 The process of any one of the previous embodiments, wherein the catalyst material has an average diameter of about 1.0 mm to about 20.0 mm ⁇ and/or the inert material has an average diameter of about 3.0 mm to about 20.0 mm.
- Embodiment 12 The process of any one of the previous embodiments, wherein the particulate material provides at least about 50% of heat required for converting at least a portion of the acyclic Cs hydrocarbons to the first effluent comprising cyclopentadiene.
- Embodiment 13 The process of any one of the previous embodiments, wherein the first reaction zone comprises at least one heating device.
- Embodiment 14 The process of any one of the previous embodiments further comprising cyclically halting the feedstock to the first reaction zone; supplying a regeneration gas to the first reaction zone; and contacting the particulate material with the regeneration gas under regenerating conditions to remove at least a portion of coke material deposited on the catalyst material thereby forming a regenerated catalyst material.
- Embodiment 15 The process of embodiment 14, wherein the regeneration interval occurs at an interval of every about 1 day to about 30 days.
- Embodiment 16 The process of any one of the previous embodiments further comprising a second reaction zone (e.g. , fixed bed reactor or fluidized bed reactor), and a third reaction zone (e.g. , fixed bed reactor or fluidized bed reactor) operated in parallel with the first reaction zone; wherein during the reaction interval in the first reaction zone: a reheating interval is performed in the second reaction zone, wherein a second feedstock comprising acyclic Cs hydrocarbons fed to the second reaction zone is cyclically halted; a second reheating gas is supplied to the second reaction zone and contacts a particulate material comprising a catalyst material to reheat the particulate material and/or remove at least a portion of incrementally deposited coke material on the catalyst material thereby forming a reheated and/or rejuvenated catalyst material and a volatile hydrocarbon; and a regeneration interval is performed in the third reaction zone, wherein a third feedstock comprising acyclic C5 hydrocarbons fed to the third reaction zone is cyclically halted
- Embodiment 17 The process of any one of the previous embodiments further comprising providing fresh particulate material to the first reaction zone.
- Embodiment 18 A reaction system for converting acyclic Cs hydrocarbons to cyclopentadiene, wherein the reaction system comprises: a feedstock stream comprising acyclic Cs hydrocarbons; a first effluent stream comprising cyclopentadiene; a reheating gas stream and at least one reactor (e.g. , fixed bed reactor, fluidized bed reactor, horizontal fixed bed reactor, vertical fixed bed reactor) operated under reaction conditions to convert at least a portion of the acyclic Cs hydrocarbons to cyclopentadiene; wherein the at least one reactor comprises: a particulate material comprising a catalyst material (e.g.
- a feedstock inlet for providing the feedstock stream and/or the reheating gas stream to the reaction system; and an effluent outlet for removal of the first effluent stream and/or the reheating gas stream.
- Embodiment 19 The reaction system of embodiment 18, wherein the at least one reactor has an inverse temperature profile and/or the feedstock stream has a flow in a co-current or a counter-current direction to a flow of the reheating gas stream.
- Embodiment 20 The reaction system of embodiment 18 or 19, wherein the feedstock stream at the feedstock inlet has a temperature of less than about 525°C and/or the first effluent stream at the effluent outlet has a temperature of at least about 575°C.
- Embodiment 21 The reaction system of any one of embodiments 18, 19, or 20, wherein the at least one reactor further comprises at least one heating device.
- Embodiment 22 The reaction system of any one of embodiments 18, 19, 20, or 21 , wherein the reaction conditions comprise a temperature of about 400°C to about 700°C and a pressure of about 3 psia to about 30 psia and/or at least about 30 wt% of the acyclic Cs hydrocarbons is converted to cyclopentadiene.
- Embodiment 23 The reaction system of any one of embodiments 18, 19, 20, 21, or 22, wherein the particulate material further comprises an inert material (at least about 25.0 wt%) and/or less than about 25.0 wt% catalyst material.
- Embodiment 24 The reaction system of any one of embodiments 18, 19, 20, 21 , 22, or 23, wherein the catalyst material has an average diameter of about 1.0 mm to about 20.0 mm ⁇ and/or the inert material has an average diameter of about 3.0 mm to about 20.0 mm.
- Embodiment 25 The reaction system of any one of embodiments 18, 19, 20, 21 , 22, 23, or
- the particulate material provides at least about 50% of heat required for converting at least a portion of the acyclic Cs hydrocarbons to the first effluent comprising cyclopentadiene.
- Embodiment 26 The reaction system of any one of embodiments 18, 19, 20, 21 , 22, 23, 24, or 25, wherein the reheating gas stream comprises hydrogen for removal of at least a portion of incrementally deposited coke material on spent catalyst material thereby forming a rejuvenated catalyst material and a volatile hydrocarbon.
- Embodiment 27 The reaction system of embodiment 26, wherein the reheating gas stream has an inlet temperature of at least about 600°C and an inlet pressure of about 100 psia and/or the rejuvenated catalyst material comprises at least about 10 wt% less of the incrementally deposited coke material than the spent catalyst material.
- Embodiment 28 The reaction system of any one of embodiments 18, 19, 20, 21 , 22, 23, 24,
- 25, 26, or 27 further comprising a regeneration gas stream, wherein the inlet provides the regeneration gas stream to the at least one reactor under regenerating conditions to remove at least a portion of coke material deposited on the catalyst material thereby forming a regenerated catalyst material.
- Embodiment 29 The reaction system of any one of embodiments 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, or 28 further comprising a fresh particulate material stream in fluid connection with the at least one reactor.
- Embodiment 30 The reaction system of any one of embodiments 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, or 29, wherein the at least one reactor comprises at least a first reactor (e.g., fixed bed reactor, fluidized bed reactor), a second reactor (e.g. , fixed bed reactor, fluidized bed reactor) and a third reactor (e.g. , fixed bed reactor, fluidized bed reactor) operated in parallel, wherein the first reactor, the second reactor, and third reactor, independently, cyclically operate under a reaction interval, a rejuvenation interval, and/or a regeneration interval.
- a first reactor e.g., fixed bed reactor, fluidized bed reactor
- a second reactor e.g. , fixed bed reactor, fluidized bed reactor
- a third reactor e.g. , fixed bed reactor, fluidized bed reactor
- This invention further relates to the following embodiments 31 to 52:
- Embodiment 31 A reaction system for converting acyclic Cs hydrocarbons to cyclopentadiene, wherein the reaction system comprises: a feedstock stream comprising acyclic C5 hydrocarbons;
- At least one reactor operated under reaction conditions to convert at least a portion of the acyclic C5 hydrocarbons to cyclopentadiene; wherein the at least one reactor comprises:
- a particulate material comprising a catalyst material
- a feedstock inlet for providing the feedstock stream and/or the reheating gas stream to the reaction system
- Embodiment 32 The reaction system of embodiment 31 , wherein the at least one reactor has an inverse temperature profile.
- Embodiment 33 The reaction system of embodiment 31, wherein the at least one reactor is a fixed bed reactor or a fluidized bed reactor.
- Embodiment 34 The reaction system of embodiment 31 , wherein at least one reactor is a horizontal fixed bed reactor or a vertical fixed bed reactor.
- Embodiment 35 The reaction system of embodiment 31 , wherein the feedstock stream has a flow in a co-current direction or a counter-current direction to a flow of the reheating gas stream.
- Embodiment 36 The reaction system of embodiment 31 , wherein the feedstock stream at the feedstock inlet has a temperature of less than about 525°C.
- Embodiment 37 The reaction system of embodiment 31 , wherein the first effluent stream at the effluent outlet has a temperature of at least about 575°C.
- Embodiment 38 The reaction system of embodiment 31, wherein the reheating gas stream comprises hydrogen for removal of the at least a portion of incrementally deposited coke material on spent catalyst material thereby forming a rejuvenated catalyst material and a volatile hydrocarbon.
- Embodiment 39 The reaction system of embodiment 31, wherein the reheating gas stream has an inlet temperature of at least about 600°C and an inlet pressure of about 100 psia.
- Embodiment 40 The reaction system of embodiment 38, wherein the rejuvenated catalyst material comprises at least about 10 wt% less of the incrementally deposited coke material than the spent catalyst material.
- Embodiment 41 The reaction system of embodiment 31 further comprising: a regeneration gas stream, wherein the feedstock inlet provides the regeneration gas stream to the at least one reactor under regenerating conditions to remove at least a portion of coke material deposited on the catalyst material thereby forming a regenerated catalyst material.
- Embodiment 42 The reaction system of embodiment 31, wherein the at least one reactor further comprises at least one heating device.
- Embodiment 43 The reaction system of embodiment 31 , wherein the reaction conditions comprise a temperature of about 400°C to about 700°C and an outlet pressure of about 3 psia to about 30 psia.
- Embodiment 44 The reaction system of embodiment 31, wherein at least about 30 wt% of the acyclic Cs hydrocarbons is converted to cyclopentadiene.
- Embodiment 45 The reaction system of embodiment 31, wherein the particulate material further comprises an inert material.
- Embodiment 46 The reaction system of embodiment 45, wherein the catalyst material has an average diameter of about 1.0 mm to about 20.0 mm and the inert material has an average diameter of about 3.0 mm to about 20.0 mm.
- Embodiment 47 The reaction system of embodiment 45, wherein the particulate material comprises at least about 25 wt% inert material.
- Embodiment 48 The reaction system of embodiment 31, wherein the particulate material comprises less than about 25 wt% catalyst material.
- Embodiment 49 The reaction system of embodiment 31, wherein the catalyst material comprises platinum on ZSM-5.
- Embodiment 50 The reaction system of embodiment 31 , wherein the particulate material provides a portion of (such as, at least about 50%) of heat required for converting the acyclic C5 hydrocarbons to cyclopentadiene.
- Embodiment 51 The reaction system of embodiment 31, wherein the at least one reactor comprises at least a first reactor, a second reactor, and a third reactor operated in parallel, wherein the first reactor, the second reactor, and third reactor, independently, and cyclically operate under a reaction interval, a rejuvenation interval, and/or a regeneration interval.
- Embodiment 52 The reaction system of embodiment 50, wherein the first reactor, the second reactor, and third reactor are each, independently, a fixed bed reactor or a fluidized bed reactor.
- Embodiment 53 The reaction system of embodiment 51 further comprising a fresh particulate material stream in fluid connection with the at least one reactor.
- This invention further relates to the following embodiments 54 to 56:
- Embodiment 54 A process for converting acyclic Cs hydrocarbons to cyclopentadiene in a reactor system, wherein the process comprises:
- a reaction interval comprising:
- a reheating interval is performed in the second reaction zone, wherein a second feedstock comprising acyclic Cs hydrocarbons fed to the second reaction zone is cyclically halted; a second reheating gas is supplied to the second reaction zone and contacts a particulate material comprising a catalyst material to reheat the particulate material and/or remove at least a portion of incrementally deposited coke material on the catalyst material thereby forming a reheated and/or rejuvenated catalyst material and a volatile hydrocarbon; and
- a regeneration interval is performed in the third reaction zone, wherein a third feedstock comprising acyclic Cs hydrocarbons fed to the third reaction zone is cyclically halted; a regeneration gas is supplied to the third reaction zone and contacts a particulate material comprising a catalyst material under regenerating conditions to remove at least a portion of coke material deposited on the catalyst material thereby forming a regenerated catalyst material.
- Embodiment 55 The process of embodiment 54 further comprising performing a reaction interval in the second reaction zone and a reaction interval in the third reaction zone, wherein the reaction interval in the first reaction zone, the reaction interval in the second reaction zone, and the reaction interval in the third reaction zone are performed in a staggered fashion.
- Embodiment 56 The process of embodiment 54, wherein the first reaction zone, the second reaction zone, and the third reaction zone are each independently a fixed bed reactor or a fluidized bed reactor.
- This invention further relates to a process for converting acyclic Cs hydrocarbons to cyclopentadiene in a reactor system, wherein the process comprises:
- a reaction interval comprising:
- the first hydrocarbon reactor effluent obtained during the acyclic Cs conversion process containing cyclic, branched and linear Cs hydrocarbons and, optionally, containing any combination of hydrogen, C4 and lighter byproducts, or Ce and heavier byproducts is a valuable product in and of itself.
- CPD and/or DCPD may be separated from the reactor effluent to obtain purified product streams, which are useful in the production of a variety of high value products.
- a purified product stream containing 50 wt% or greater, or preferably 60 wt% or greater of DCPD is useful for producing hydrocarbon resins, unsaturated polyester resins, and epoxy materials.
- a purified product stream containing 80 wt% or greater, or preferably 90 wt% or greater of CPD is useful for producing Diels-Alder reaction products formed in accordance with the following reaction Scheme (I):
- R is a heteroatom or substituted heteroatom, substituted or unsubstituted C1-C50 hydrocarbyl radical (often a hydrocarbyl radical containing double bonds), an aromatic radical, or any combination thereof.
- substituted radicals or groups contain one or more elements from Groups 13-17, preferably from Groups 15 or 16, more preferably nitrogen, oxygen, or sulfur.
- a purified product stream containing 80 wt% or greater, or preferably 90 wt% or greater of CPD can be used to form Diels-Alder reaction products of CPD with one or more of the following: another CPD molecule, conjugated dienes, acetylenes, allenes, disubstituted olefins, trisubstituted olefins, cyclic olefins, and substituted versions of the foregoing.
- Preferred Diels-Alder reaction products include norbomene, ethylidene norbornene, substituted norbomenes (including oxygen-containing norbornenes), norbornadienes, and tetracyclododecene, as illustrated in the following structures:
- norbornene ethylidene norbornene tetracyclododecene norbornadiene oxygen substituted norbornene norbornene ethylidene norbornene tetracyclododecene norbornadiene oxygen substituted norbornene.
- the foregoing Diels-Alder reaction products are useful for producing polymers and copolymers of cyclic olefins copolymerized with olefins such as ethylene.
- the resulting cyclic olefin copolymer and cyclic olefin polymer products are useful in a variety of applications, e.g., packaging film.
- a purified product stream containing 99 wt% or greater of DCPD is useful for producing DCPD polymers using, for example, ring opening metathesis polymerization (ROMP) catalysts.
- the DCPD polymer products are useful in forming articles, particularly molded parts, e.g., wind turbine blades and automobile parts.
- Additional components may also be separated from the reactor effluent and used in the formation of high value products.
- separated cyclopentene is useful for producing poly cyclopentene, also known as polypentenamer, as depicted in Scheme (II).
- cyclopentane is useful as a blowing agent and as a solvent.
- Linear and branched Cs products are useful for conversion to higher olefins and alcohols.
- Cyclic and non-cyclic Cs products, optionally after hydrogenation, are useful as octane enhancers and transportation fuel blend components. Examples
- a mixture with - 22 % solids was prepared by mixing 950 g of DI water, 53.5 g of 50% NaOH solution, 76.8 g of n-propyl amine 100% solution, 10 g of ZSM-5 seed crystals, and 336 g of Ultrasil PMTM Modified silica, and 4.4 g of Silver Nitrate in a 2-liter container. The mixture was then charged into a 2-liter autoclave. The mixture had the following molar composition:
- the mixture was mixed at 250 rpm and reacted at 230°F (110°C) for 72 hours.
- the resulting products were filtered and washed with deionized water then dried overnight at 250°F (120°C).
- the XRD pattern (not shown) of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
- the SEM (not shown) of the as- synthesized material showed that the material was composed of a mixture of large crystals with a size of ⁇ 1 micron.
- the resulting ZSM-5 crystals had a Si02/A1203 molar ratio of > 800, Na of - 0.28 % , and Ag of 0.9 wt%
- This material was calcined for 6 hours in nitrogen at 900°F (482°C). After cooling, the sample was re-heated to 900°F (482°C) in nitrogen and held for three hours. The atmosphere was then gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise increments. Each step was followed by a thirty minute hold. The temperature was increased to 1000°F, the oxygen content was increased to 16.8%, and the material was held at 1000°F for 6 hours. After cooling, 0.45 wt% Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide. The catalyst was then dried in air at room temperature at 250°F (120°C), and calcined in air for three hours at 660°F (350°C). The catalyst powder was pressed (15 ton), crushed, and sieved to obtain 40-60 mesh particle size.
- the catalyst of Example 1 was tested under two reactor operating strategies: a continuously on-oil strategy and an intermittent H2 rejuvenation strategy.
- the catalyst (0.5 g) was physically mixed with quartz (1.5 g, 60-80 mesh) and loaded into a 3/8" OD, 18" long stainless steel reactor.
- the catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse quartz particles.
- the catalyst was dried for 1 hour under He (100 mL/min, 30 psig, 250°C) then reduced for 1 hour under H2 (200 mL/min, 30 psig, 500°C).
- the catalyst was then tested for performance with a feed containing n-pentane, H2, and balance He.
- test conditions for a continuously on-oil operating strategy were the following: 0.5 g [0.96%Ag]-ZSM-5/0.5%Pt, 5.0 psia C5H12, 1 : 1 molar H2:C5, 14.7 WHSV, 45 psia total during the on-oil period.
- the test conditions for an intermittent H2 rejuvenation strategy were the following: the reactor was cycled for one hour on-oil and one hour on H2 rejuvenation at the conditions of 200 cm3 min-1 H2 at 600°C and 45 psia of all H2; i.e., with no additional He.
- FIG. 6 Performance results for both operating strategies are shown in Figure 6 as the site-time-yield of cyclic C5's (i.e., the mols of cC5/mol of Pt/second).
- Figure 6 demonstrates that the H2 rejuvenation is capable of improving catalyst capability over time to catalyze C5 hydrocarbon cyclization.
- compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.
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Abstract
La présente invention concerne un procédé pour convertir des hydrocarbures en C5 acycliques en cyclopentadiène dans un système de réacteur, le procédé comprenant un intervalle de réaction consistant à : introduire cycliquement dans le système de réacteur une charge comprenant des hydrocarbures en C5 acycliques ; mettre en contact la charge avec un matériau particulaire comprenant un matériau catalyseur dans une première zone de réaction dans des conditions réactionnelles permettant de convertir au moins une partie des hydrocarbures en C5 acycliques en un premier effluent comprenant du cyclopentadiène ; et un intervalle de réchauffage consistant à interrompre cycliquement la charge dans la première zone de réaction ; et introduire un gaz de réchauffage dans la première zone de réaction pour réchauffer le matériau particulaire.
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Cited By (10)
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WO2017078896A2 (fr) | 2015-11-04 | 2017-05-11 | Exxonmobil Chemical Patents Inc. | Procédé de conversion de composés c5 acycliques en composés c5 cycliques et composition catalytique à utiliser dans celui-ci |
WO2019055076A1 (fr) * | 2017-09-14 | 2019-03-21 | Exxonmobil Chemical Patents Inc. | Procédés et systèmes permettant de convertir des hydrocarbures acycliques en cyclopentadiène |
CN110437571A (zh) * | 2019-08-19 | 2019-11-12 | 山东科荣化工有限公司 | 用于制备防弹盾牌的聚双环戊二烯复合材料及其制备方法 |
WO2021178088A1 (fr) | 2020-03-06 | 2021-09-10 | Exxonmobil Chemical Patents Inc. | Procédés de valorisation d'alcanes et d'hydrocarbures aromatiques alkyliques |
WO2022031423A1 (fr) | 2020-08-06 | 2022-02-10 | Exxonmobil Chemical Patents Inc. | Procédés de valorisation d'alcanes et d'hydrocarbures aromatiques alkyliques |
WO2022256132A1 (fr) | 2021-06-02 | 2022-12-08 | Exxonmobil Chemical Patents Inc. | Procédés pour la régénération de catalyseurs et pour la revalorisation d'hydrocarbures d'alcanes et/ou aromatiques alkyliques |
WO2023009259A1 (fr) | 2021-07-28 | 2023-02-02 | Exxonmobil Chemical Patents Inc. | Compositions de catalyseur et leurs procédés de fabrication et d'utilisation |
WO2023018538A1 (fr) | 2021-08-11 | 2023-02-16 | Exxonmobil Chemical Patents Inc. | Procédés pour la régénération de catalyseurs et pour la revalorisation d'hydrocarbures alcanes et/ou aromatiques alkyliques |
WO2023107797A1 (fr) | 2021-12-06 | 2023-06-15 | Exxonmobil Chemical Patents Inc. | Compositions de catalyseur et leurs procédés de fabrication et d'utilisation |
US11859136B2 (en) | 2020-03-06 | 2024-01-02 | Exxonmobil Chemical Patents Inc. | Processes for upgrading alkanes and alkyl aromatic hydrocarbons |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017078896A2 (fr) | 2015-11-04 | 2017-05-11 | Exxonmobil Chemical Patents Inc. | Procédé de conversion de composés c5 acycliques en composés c5 cycliques et composition catalytique à utiliser dans celui-ci |
WO2019055076A1 (fr) * | 2017-09-14 | 2019-03-21 | Exxonmobil Chemical Patents Inc. | Procédés et systèmes permettant de convertir des hydrocarbures acycliques en cyclopentadiène |
US11261140B2 (en) | 2017-09-14 | 2022-03-01 | Exxonmobil Chemical Patents Inc. | Processes and systems for the conversion of acyclic hydrocarbons to cyclopentadiene |
CN110437571A (zh) * | 2019-08-19 | 2019-11-12 | 山东科荣化工有限公司 | 用于制备防弹盾牌的聚双环戊二烯复合材料及其制备方法 |
WO2021178088A1 (fr) | 2020-03-06 | 2021-09-10 | Exxonmobil Chemical Patents Inc. | Procédés de valorisation d'alcanes et d'hydrocarbures aromatiques alkyliques |
US11859136B2 (en) | 2020-03-06 | 2024-01-02 | Exxonmobil Chemical Patents Inc. | Processes for upgrading alkanes and alkyl aromatic hydrocarbons |
WO2022031423A1 (fr) | 2020-08-06 | 2022-02-10 | Exxonmobil Chemical Patents Inc. | Procédés de valorisation d'alcanes et d'hydrocarbures aromatiques alkyliques |
WO2022256132A1 (fr) | 2021-06-02 | 2022-12-08 | Exxonmobil Chemical Patents Inc. | Procédés pour la régénération de catalyseurs et pour la revalorisation d'hydrocarbures d'alcanes et/ou aromatiques alkyliques |
WO2023009259A1 (fr) | 2021-07-28 | 2023-02-02 | Exxonmobil Chemical Patents Inc. | Compositions de catalyseur et leurs procédés de fabrication et d'utilisation |
WO2023018538A1 (fr) | 2021-08-11 | 2023-02-16 | Exxonmobil Chemical Patents Inc. | Procédés pour la régénération de catalyseurs et pour la revalorisation d'hydrocarbures alcanes et/ou aromatiques alkyliques |
WO2023107797A1 (fr) | 2021-12-06 | 2023-06-15 | Exxonmobil Chemical Patents Inc. | Compositions de catalyseur et leurs procédés de fabrication et d'utilisation |
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