Production of cyclic C5 compounds
09994499 ยท 2018-06-12
Assignee
Inventors
Cpc classification
International classification
C07C5/327
CHEMISTRY; METALLURGY
C07C5/32
CHEMISTRY; METALLURGY
Abstract
Disclosed is a process for the conversion of acyclic C.sub.5 feedstock to a product comprising cyclic C.sub.5 compounds, including cyclopentadiene, and catalyst compositions for use in such process. The process comprises contacting the feedstock and, optionally, hydrogen under acyclic C.sub.5 conversion conditions in the presence of a catalyst composition to form said product. The catalyst composition comprises a microporous crystalline metallosilicate, a Group 10 metal or compound thereof, and a Group 11 metal or compound thereof.
Claims
1. A process for producing cyclic C.sub.5 compounds including cyclopentadiene, the process comprising: (a) contacting a feed containing acyclic C.sub.5 hydrocarbons with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index less than or equal to 12, (ii) a Group 10 metal or a compound thereof, and (iii) a Group 11 metal or a compound thereof under conditions effective to convert at least part of the acyclic C.sub.5 hydrocarbons in the feed to produce an effluent comprising cyclopentadiene, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU; and (b) recovering cyclopentadiene from the effluent.
2. The process of claim 1, wherein the microporous crystalline metallosilicate has a constraint index from 1 to 12.
3. The process of claim 1, wherein the Group 10 metal is selected from the group consisting of Ni, Pd, Pt, and mixtures thereof.
4. The process of claim 1, wherein the Group 10 metal is present in an amount in the range from about 0.005 wt % to about 10 wt % based on the weight of the catalyst composition.
5. The process of claim 1, wherein the catalyst also contains a Group 1 alkali metal and/or a Group 2 alkaline earth metal.
6. The process of claim 1, wherein the Group 11 metal is selected from the group consisting of silver, gold, copper, and mixtures thereof.
7. The process of claim 1, wherein the Group 11 metal is present at a molar ratio of Group 11 metal to Group 10 metal of about 0.1 to about 5.
8. The process of claim 1, wherein the effluent also includes cyclopentane and/or cyclopentene and the method further comprises: (c) recovering at least part of the cyclopentane and/or cyclopentene and routing to a product disposition and/or recycling at least part of the cyclopentane and/or cyclopentene to the contacting (a).
9. The process of claim 1, wherein the microporous crystalline metallosilicate has a silica to metal molar ratio in excess of 2.
10. The process of claim 1, wherein the microporous crystalline metallosilicate is selected from the group consisting of 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 material, and mixtures of two or more thereof.
11. The process of claim 1, wherein the microporous crystalline metallosilicate comprises ZSM-5.
12. The process of claim 1, wherein the conditions employed in the contacting (a) comprise a temperature from 400 C. to 700 C. and a partial pressure of acyclic C.sub.5 feedstock from 3 to 100 psia (21 kPa-a to 690 kPa-a) at the reactor inlet.
13. The process of claim 1, wherein the acyclic C.sub.5 feed comprises pentane, pentene, pentadiene, and mixtures thereof.
14. The process of claim 1, wherein the acyclic C.sub.5 feed comprises at least 75% by weight n-pentane.
15. The process of claim 1, wherein the catalyst composition provides a conversion of at least about 70% of the acyclic C.sub.5 feed under conversion conditions including an n-pentane feedstock with equimolar H.sub.2, a temperature in the range of about 550 C. to about 600 C., an n-pentane partial pressure from 3 to 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), and an n-pentane weight hourly space velocity from 5 to 20 hr.sup.1.
16. The process of claim 1, wherein the catalyst composition provides a carbon selectivity to cyclic C.sub.5 compounds of at least about 30% under conversion conditions including an n-pentane feedstock with equimolar H.sub.2, a temperature in the range of about 550 C. to about 600 C., an n-pentane partial pressure from 3 to 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), and an n-pentane weight hourly space velocity from 5 to 20 hr.sup.1.
17. A process for producing cyclic C.sub.5 compounds including cyclopentadiene, the process comprising: (a) contacting a feed containing acyclic C.sub.5 hydrocarbons with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index less than or equal to 12, (ii) platinum or a compound thereof, and (iii) silver or a compound thereof under conditions effective to convert at least part of the acyclic C.sub.5 hydrocarbons in the feed to produce an effluent comprising cyclopentadiene, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU; and (b) recovering cyclopentadiene from the effluent.
18. A process for producing cyclic C.sub.5 compounds including cyclopentadiene, the process comprising: (a) contacting a feed containing acyclic C.sub.5 hydrocarbons with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index less than or equal to 12, (ii) platinum or a compound thereof, and (iii) copper or a compound thereof under conditions effective to convert at least part of the acyclic C.sub.5 hydrocarbons in the feed to produce an effluent comprising cyclopentadiene, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU; and (b) recovering cyclopentadiene from the effluent.
Description
BRIEF DESCRIPTION OF THE FIGURES
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DETAILED DESCRIPTION OF THE EMBODIMENTS
(13) Definitions
(14) For the purpose of this specification and appended claims, the following terms are defined.
(15) The term saturates includes, but is not limited to, alkanes and cycloalkanes.
(16) The term non-saturates includes, but is not limited to, alkenes, dialkenes, alkynes, cyclo-alkenes, and cyclo-dialkenes.
(17) The term cyclics C.sub.5 or cC.sub.5 includes, but is not limited to, cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more thereof. The term cyclic C.sub.5 or cC.sub.5 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.
(18) The term acyclics includes, but is not limited to, linear and branched saturates and non-saturates.
(19) The term aromatic means a planar cyclic hydrocarbyl with conjugated double bonds, such as benzene. As used herein, the term aromatic encompasses compounds containing one or more aromatic rings, including, but not limited to, benzene, toluene, and xylene and polynuclear aromatics (PNAs), which include naphthalene, anthracene, chrysene, and their alkylated versions. The term C.sub.6+ 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.
(20) The term BTX includes, but is not limited to, a mixture of benzene, toluene, and xylene (ortho and/or meta and/or para).
(21) The term coke includes, but is not limited to, a low hydrogen content hydrocarbon that is adsorbed on the catalyst composition.
(22) The term C.sub.n means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
(23) The term C.sub.n+ means hydrocarbon(s) having at least n carbon atom(s) per molecule.
(24) The term C.sub.n means hydrocarbon(s) having no more than n carbon atom(s) per molecule.
(25) The term 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.
(26) The term C.sub.5 feedstock includes a feed stock 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).
(27) All numbers and references to the Periodic Table of Elements are based on the new notation as set out in Chemical and Engineering News, 63(5), 27 (1985), unless otherwise specified.
(28) The term Group 1 alkali metal means an element in Group 1 of the Periodic Table and includes, but is not limited to, Li, Na, K, Rb, Cs, and a mixture of two or more thereof, and excludes hydrogen.
(29) The term 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.
(30) The term oxygen includes O.sub.2, H.sub.2O, CO, and CO.sub.2.
(31) The term Group 10 metal means an element in Group 10 of the Periodic Table and includes Ni, Pd, and Pt.
(32) The term Group 11 metal means an element in Group 11 of the Periodic Table and includes Cu, Ag, and Au.
(33) The term constraint index is defined in U.S. Pat. No. 3,972,832 and U.S. Pat. No. 4,016,218, both of which are incorporated herein by reference.
(34) As used herein, the term molecular sieve of the MCM-22 family (or material of the MCM-22 family or MCM-22 family material or MCM-22 family zeolite) 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 as 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; and molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
(35) The MCM-22 family includes those molecular sieves having an X-ray diffraction pattern including d-spacing maxima at 12.40.25, 6.90.15, 3.570.07, and 3.420.07 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.
(36) As used herein, the term molecular sieve is used synonymously with the term microporous crystalline metallosilicate.
(37) As used herein, the term carbon selectivity means the moles of carbon in the respective cyclic C.sub.5, CPD, C.sub.1, and C.sub.2-4 formed divided by total moles of carbon in the pentane converted. The phrase a carbon selectivity to cyclic C.sub.5 of at least 30% means that 30 moles of carbon in the cyclic C.sub.5 is formed per 100 moles of carbon in the pentane converted.
(38) As used herein, the term conversion means the moles of carbon in the acyclic C.sub.5 feedstock that is converted to a product. The phrase a conversion of at least 70% of said acyclic C.sub.5 feedstock to said product means that at least 70% of the moles of said acyclic C.sub.5 feedstock was converted to a product.
(39) As used herein, the term reactor system refers to a system including one or more reactors and all optional equipment used in the production of cyclopentadiene.
(40) As used herein, the term 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. For example, 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.
(41) A reactor/reaction zone may be an adiabatic reactor/reaction zone or adiabatic reactor/reaction zone. As used herein, the term adiabatic refers to a reaction zone for which there is essentially no heat input into the system other than by a flowing process fluid. A reaction zone that has unavoidable losses due to conduction and/or radiation may also be considered adiabatic for the purpose of this invention As used herein, the term diabatic refers to a reactor/reaction zone to which heat is supplied by a means in addition to that provided by the flowing process fluid.
(42) As used herein, 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%. In a moving bed reactor, the solids (e.g., catalyst material) 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<U.sub.mf), bubbling regime (U.sub.mf<U<U.sub.mb), slugging regime (U.sub.mb<U<U.sub.c), transition to and turbulent fluidization regime (U.sub.c<U<U.sub.tr), and fast-fluidization regime (U>U.sub.tr), where Umf is minimum fluidizing velocity, Umb is 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.sup.nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2.sup.nd Edition, Butterworth-Heinemann, Boston, 2010, which are incorporated by reference.
(43) As used herein, 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 (U.sub.mf), U<U.sub.mf, 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. Description of the minimum fluidization velocity is given in, for example, Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2.sup.nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2.sup.nd Edition, Butterworth-Heinemann, Boston, 2010. 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). For example, the solids (e.g., catalyst material) may have been removed from the reactor, regenerated, reheated, and/or separated from the product stream and then returned back to the reactor.
(44) As used herein, 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 U.sub.mf) 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%. As used herein the term 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. Locus of minimum fluidization velocity is given in, for example, Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2.sup.nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2.sup.nd Edition, Butterworth-Heinemann, Boston, 2010. 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). For example, the solids (e.g., catalyst material) may have been removed from the reactor, regenerated, reheated and/or separated from the product stream and then returned back to the reactor.
(45) As used herein 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 (U.sub.tr). Fast fluidization and pneumatic conveying fluidization regimes are also described in Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2.sup.nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2.sup.nd Edition, Butterworth-Heinemann, Boston, 2010. A fluidized bed reactor, such as a circulating fluidized bed reactor, may be operated as a riser reactor.
(46) As used herein, the term fired tubes reactor refers to a furnace and parallel reactor tube(s) positioned within a radiant section of the furnace. The reactor tubes contain a catalytic material (e.g., catalyst particles), which contacts reactant(s) to form a product.
(47) As used herein, the term convectively heated tubes reactor refers to a conversion system comprising parallel reactor tube(s) containing a catalytic material and positioned within an enclosure. While any known reactor tube configuration or enclosure may be used, preferably the conversion system comprises multiple parallel reactor tubes within a convective heat transfer enclosure. Preferably, the reactor tubes are straight rather than having a coiled or curved path through the enclosure (athough coiled or curved tubes may be used). Additionally, the tubes may have a cross section that is circular, elliptical, rectangular, and/or other known shapes. The tubes are preferentially heated with a turbine exhaust stream produced by a turbine burning fuel gas with a compressed gas comprising oxygen. In other aspects, the reactor tubes are heated by convection with hot gas produced by combustion in a furnace, boiler, or excess air burner. However, heating the reactor tubes with turbine exhaust is preferred because of the co-production of shaft power among other advantages.
(48) As used herein, 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 U.sub.mf) and/or the gas is moving in a downward direction so that solid particle fluidization is not possible.
(49) As used herein, the term cyclical refers to a periodic recurring or repeating event that occurs according to a cycle. For example, reactors (e.g., cyclic fixed bed) 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.
(50) As used herein, the term 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.
(51) As used herein, the term 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.
(52) Feedstock
(53) An acyclic C.sub.5 feedstock useful herein is obtainable from crude oil or natural gas condensate, and can include cracked C.sub.5 hydrocarbons (in various degrees of unsaturation: alkenes, dialkenes, alkynes) produced by refining and chemical processes, such as fluid catalytic cracking (FCC), reforming, hydrocracking, hydrotreating, coking, and steam cracking.
(54) In one or more embodiments, the acyclic C.sub.5 feedstock useful in the present process comprises pentane, pentene, pentadiene, and mixtures of two or more thereof. Preferably, in one or more embodiments, the acyclic C.sub.5 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.
(55) The acyclic C.sub.5 feedstock used herein, optionally, does not comprise C.sub.6+ aromatic compounds, such as benzene, toluene, or xylene (ortho, meta or para). In some embodiments, the feedstock comprises less than 5 wt %, preferably less than 1 wt %, preferably less than 0.01 wt %, preferably 0 wt %, C.sub.6+ aromatic compounds.
(56) The acyclic C.sub.5 feedstock used herein, optionally, does not comprise C.sub.4 compounds. In some embodiments, the feedstock comprises less than 5 wt %, preferably less than 1 wt %, preferably less than 0.01 wt %, preferably 0 wt %, C.sub.4 compounds.
(57) The acyclic C.sub.5 feedstock used herein, optionally, does not comprise C.sub.4 compounds and C.sub.6+ aromatic compounds. In some embodiments, the feedstock comprises less than 5 wt %, preferably less than 1 wt %, preferably less than 0.01 wt %, preferably at 0 wt %, of both C.sub.4 and C.sub.6+ aromatic compounds.
(58) Alternately, the C.sub.5 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.
(59) Acyclic C.sub.5 Conversion Process
(60) This invention relates to a process for conversion of an acyclic C.sub.5 feedstock to a product comprising cyclic C.sub.5 compounds. The process comprises the steps of contacting said feedstock and, optionally, hydrogen under acyclic C.sub.5 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.
(61) In one or more embodiments, the product of the process for conversion of an acyclic C.sub.5 feedstock comprises cyclic C.sub.5 compounds. The cyclic C.sub.5 compounds comprise one or more of cyclopentane, cyclopentene, cyclopentadiene, and includes mixtures thereof. In one or more embodiments, the cyclic C.sub.5 compounds comprise at least about 20 wt %, or 30 wt %, or 40 wt %, or 50 wt % cyclopentadiene, or in the range of from about 10 wt % to about 80 wt %, alternately 20 wt % to 70 wt %.
(62) The acyclic C.sub.5 conversion process can be conducted in a wide range of reactor configurations including: convectively heated tubes (as described in U.S. Ser. No. 62/250,674 filed Nov. 4, 2015), fired tubes (as described in U.S. Ser. No. 62/250,693 filed Nov. 4, 2015), a riser reactor (as described in U.S. Ser. No. 62/250,682 filed Nov. 4, 2015), a circulating fluidized bed or a circulating settling bed with counter-current flow (as described in U.S. Ser. No. 62/250,680 filed Nov. 4, 2015), and a cyclic fluidized bed reactor or a cyclic fixed bed reactor (as described in U.S. Ser. No. 62/250,677 filed Nov. 4, 2015). In addition, the C.sub.5 conversion process can be conducted in a single reaction zone or in a plurality of reaction zones, such as an adiabatic reaction zone followed by a diabatic reaction zone (as described in U.S. Ser. No. 62/250,697 filed Nov. 4, 2015).
(63) Typically, the acyclic C.sub.5 hydrocarbon(s) contained in the C.sub.5 feedstock is fed into a first reactor loaded with a catalyst, where the acyclic C.sub.5 hydrocarbons contact the catalyst under conversion conditions, whereupon at least a portion of the acyclic C.sub.5 hydrocarbon(s) molecules are converted into CPD molecules, and a reaction product containing CPD and, optionally, other cyclic hydrocarbons (e.g., C.sub.5 cyclic hydrocarbons such as cyclopentane and cyclopentene) exits the first reactor as a first reactor hydrocarbon effluent. Preferably, a hydrogen co-feedstock comprising hydrogen and, optionally, light hydrocarbons, such as C.sub.1-C.sub.4 hydrocarbons, is also fed into the first reactor (as described in U.S. Ser. No. 62/250,702 filed Nov. 4, 2015). Preferably, at least a portion of the hydrogen co-feedstock is admixed with the C.sub.5 feedstock prior to being fed into the first reactor. The presence of hydrogen in the feed mixture at the inlet location, where the feed first comes into contact with the catalyst, prevents or reduces the formation of coke on the catalyst particles.
(64) In the process described herein, an acyclic C.sub.5 feedstock as described above, optionally together with hydrogen, is contacted with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index of up to 12 (preferably from 1 to 12), (ii) a Group 10 metal or a compound thereof (preferably Pt), and (iii) one or more Group 11 metals (preferably Ag and/or Cu) or a compound thereof under conditions effective to convert at least part of the acyclic C.sub.5 hydrocarbons in the feedstock to produce an effluent comprising one or more cyclic C.sub.5 compounds. The cyclic C.sub.5 compounds may comprise one or more of cyclopentane, cyclopentene, cyclopentadiene, and includes mixtures thereof. In one or more embodiments, the cyclic C.sub.5 compounds in the effluent comprise at least about 20 wt %, or 30 wt %, or 40 wt %, or 50 wt % cyclopentadiene, or in the range of from about 10 wt % to about 80 wt %, alternately 20 wt % to 70 wt %, cyclopentadiene. Cyclopentadiene can then be recovered from the effluent. Other cyclic C.sub.5 compounds, such as cyclopentane and/or cyclopentene, can also be recovered or can be recycled to the conversion process together with some or all of the unreacted acyclic C.sub.5 components.
(65) In one or more embodiments, the acyclic C.sub.5 conversion conditions include at least a temperature, a partial pressure, 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 partial pressure in the range of about 3 to about 100 psia at the reactor inlet (21 kPa-a to 690 kPa-a), or in the range from about 3 to about 50 psia (21 to 345 kPa-a), preferably, in the range from about 3 psia to about 20 psia (21 to 138 kPa-a). The weight hourly space velocity in the range from about 1 to about 50 hr.sup.1, or in the range from about 1 to about 20 hr.sup.1. Such conditions include a molar ratio of the optional hydrogen co-feed to the acyclic C.sub.5 feedstock in the range of about 0 to 3 (e.g., 0.01 to 3.0), or in the range from about 1 to about 2. Such conditions may also include co-feed C.sub.1-C.sub.4 hydrocarbons with the acyclic C.sub.5 feed.
(66) In one or more embodiments, 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 H is present at a ratio to n-pentane of 0.01 to 3.0) with any one of the catalyst compositions of this invention to form cyclopentadiene at a temperature of 400 C. to 650 C., a partial pressure of 3 to about 100 psia at the reactor inlet (21 kPa-a to 690 kPa-a), and a weight hourly space velocity of 1 to about 50 hr.sup.1.
(67) In the presence of the catalyst, a number of desired and undesirable side reactions may take place. The net effect of the reactions is the production of hydrogen and the increase of total volume (assuming constant total pressure). One particularly desired overall reaction (i.e., intermediate reaction steps are not shown) is:
n-pentane.fwdarw.CPD+3H.sub.2.
(68) Additional overall reactions include, but are not limited to:
n-pentane.fwdarw.1,3-pentadiene+2H.sub.2,
n-pentane.fwdarw.1-pentene+H.sub.2,
n-pentane.fwdarw.2-pentene+H.sub.2,
n-pentane.fwdarw.2-methyl-2-butene+H.sub.2,
n-pentane.fwdarw.cyclopentane+H.sub.2,
cyclopentane.fwdarw.cyclopentene+H.sub.2, or
cyclopentene.fwdarw.CPD+H.sub.2.
(69) Fluids inside the first reactor are essentially in gas phase. At the outlet of the first reactor, a first reactor hydrocarbon effluent, preferably in gas phase, is obtained. The first reactor hydrocarbon effluent may comprise a mixture of the following hydrocarbons, among others: heavy components comprising more than 8 carbon atoms such as multiple-ring aromatics; C.sub.8, C.sub.7, and C.sub.6 hydrocarbons such as one-ring aromatics; CPD (the desired product); unreacted C.sub.5 feedstock material such as n-pentane; C.sub.5 by-products such as pentenes (1-pentene, 2-pentene, e.g.), pentadienes (1,3-pentadiene; 1,4-pentadiene, e.g.), cyclopentane, cyclopentene, 2-methylbutane, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-1,3-butadiene, 2,2-dimethylpropane, and the like; C4 by-products such as butane, 1-butene, 2-butene, 1,3-butadiene, 2-methylpropane; 2-methyl-1-propene, and the like; C.sub.3 by-products such as propane, propene, and the like; and C.sub.2 by-products such as ethane and ethene; methane; and hydrogen.
(70) The first reactor hydrocarbon effluent may comprise CPD at a concentration of C(CPD)1 wt %, based on the total weight of the C.sub.5 hydrocarbons in the first reactor hydrocarbon effluent; and a1C(CPD)1a2, where a1 and a2 can be, independently, 15, 16, 18, 20, 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, 38, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85 as long as a1<a2.
(71) The first reactor hydrocarbon effluent may comprise acyclic diolefins at a total concentration of C(ADO)1 wt %, based on the total weight of the C.sub.5 hydrocarbons in the first reactor hydrocarbon effluent; and b1C(ADO)1b2, where b1 and b2 can be, independently, 20, 18, 16, 15, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, or 0.5, as long as b1<b2. Preferably, 0.5C(ADO)10.
(72) As a result of the use of the catalyst and the choice of reaction conditions in the first reactor, a high CPD to acyclic diolefin molar ratio in the first reactor hydrocarbon effluent can be achieved such that C(CPD)1/C(ADO)11.5, preferably 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, 2.6, 2.8, 3.0, 3.2, 3.4, 3.5, 3.6, 3.8, 4.0, 5.0, 6.0, 8.0, 10, 12, 14, 15, 16, 18, or 20. The high ratio of C(CPD)1/C(ADO)1 significantly reduces CPD loss as a result of Diels-Alder reactions between CPD and acyclic dienes in subsequent processing steps, and therefore, allows the processes of the present invention to achieve high DCPD yield and high DCPD purity for the subsequently produced DCPD fractions.
(73) Desirably, the total absolute pressure and temperature of the first reactor hydrocarbon effluent should be maintained at levels such that the dimerization of CPD to form DCPD is substantially avoided, and the Diels-Alder reactions between CPD and acyclic dienes are substantially inhibited.
(74) Because the overall conversion from acyclic C.sub.5 hydrocarbons to CPD and hydrogen results in substantial volume increase (assuming constant total system pressure), a low partial pressure of CPD and/or a low partial pressure of hydrogen in the reaction mixture favors the conversion of acyclic C.sub.5 hydrocarbons. The total partial pressure of C.sub.5 hydrocarbons and hydrogen in the first reactor effluent at the outlet is desired to be lower than atmospheric pressure. Thus, where insufficient co-feedstock of a C.sub.1-C.sub.4 hydrocarbon or other co-feedstock is introduced into the first reactor, the total overall pressure of the first reactor effluent is desirably sub-atmospheric, in order to achieve a level of satisfactory conversion from acyclic C.sub.5 hydrocarbons to CPD. However, direct separation of a sub-atmospheric stream has the disadvantage of potential oxygen/air ingress into the system, resulting in oxidation of CPD and other hydrocarbons and formation of undesirable species in the system. Thus, it is desirable that the first reactor hydrocarbon effluent is processed to a higher total pressure before separation thereof. Eductor systems, can be used for that purpose (as described in U.S. Ser. No. 62/250,708 filed Nov. 4, 2015).
(75) Catalyst Composition
(76) The catalyst composition employed in the present process comprises a microporous crystalline metallosilicate, typically an aluminosilicate, a Group 10 metal or compound thereof, and a Group 11 metal, or compound thereof. At least part of the Group 11 metal can be part of the framework metal of the metallosilicate.
(77) 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.
(78) Particularly suitable 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. It is recognized that 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 amounts of aluminum.
(79) The microporous crystalline metallosilicates preferably have a constraint index of less than or equal to 12, alternately from 1 to 12, alternately from 2 to 12, alternately from 3 to 12. Aluminosilicates useful herein have a constraint index of less than 12, such as 1 to 12, alternately 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. In a preferred embodiment, the crystalline aluminosilicate has a constraint index of about 3 to about 12 and is ZSM-5.
(80) ZSM-5 is described in U.S. Pat. No. 3,702,886. ZSM-11 is described in U.S. Pat. No. 3,709,979. ZSM-22 is described in U.S. Pat. No. 5,336,478. ZSM-23 is described in U.S. Pat. No. 4,076,842. ZSM-35 is described in U.S. Pat. No. 4,016,245. ZSM-48 is described in U.S. Pat. No. 4,375,573, ZSM-50 is described in U.S. Pat. No. 4,640,829, and ZSM-57 is described in U.S. Pat. No. 4,873,067. ZSM-58 is described in U.S. Pat. No. 4,698,217. Constraint index and a method for its determination are described in U.S. Pat. No. 4,016,218, referenced above. The entire contents of each of the aforementioned patents are incorporated herein by reference.
(81) The MCM-22 family material is selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, and mixtures of two or more thereof. Materials of the MCM-22 family include MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described in EP 0 293 032), ITQ-1 (described in U.S. Pat. No. 6,077,498), and ITQ-2 (described in WO 97/17290), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat. No. 5,362,697), and mixtures of two or more thereof. Related zeolites to be included in the MCM-22 family are UZM-8 (described in U.S. Pat. No. 6,756,030) and UZM-8HS (described in U.S. Pat. No. 7,713,513), both of which are also suitable for use as the molecular sieve of the MCM-22 family.
(82) In one or more embodiments, the microporous crystalline metallosilicate has an Si/M molar ratio (where M is a Group 8, 11, or 13 metal) greater than about 2, or greater than about 25, or greater than about 50, or greater than about 100, or greater than 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 2,000, or from about 50 to 1,200.
(83) In one or more embodiments, the porous crystalline metallosilicate is crystalline aluminosilicate having a SiO.sub.2/Al.sub.2O.sub.3 molar ratio greater than about 3, or greater than about 25, or greater than about 50, or greater than about 100, or greater than about 400, or in the range from about 25 to about 2,000, or from about 50 to about 1,500, or from about 100 to about 1,200, or from about 100 to about 1000, or from about 100 to about 500, or from about 100 to about 400.
(84) In one or more embodiments, the Group 10 metal includes, or is selected from the group consisting of, Ni, Pd, Pt, and mixtures thereof, preferably Pt. The Group 10 metal content of said catalyst composition may be 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 10 metal may be added to the catalyst composition during or after synthesis of the crystalline molecular sieve as any suitable Group 10 metal compound. Thus, for example, where platinum is the, or one of the, Group 10 metals, the platinum may be added as platinum nitrate, chloroplatinic acid, platinous chloride, platinum amine compounds, particularly, tetraamine platinum hydroxide, platinum acetylacetonate, and mixtures of two or more thereof.
(85) In one or more embodiments, the Group 11 metal includes, or is selected from, the group consisting of, silver, gold, copper, and mixtures of two or more thereof, preferably silver. The Group 11 metal content of the catalyst composition is such that the molar ratio of Group 11 metal to Group 10 metal is at least 0.01, based on the molar quantities of each in the catalyst composition. In one or more embodiments, the molar ratio of Group 11 metal to Group 10 metal is in the range from about 0.1 to 10 or from about 0.5 to 5 based on the molar quantities of each in the catalyst composition. The Group 11 metal may be added to the catalyst composition during or after synthesis of the crystalline molecular sieve as any suitable Group 11 metal compound. Thus, for example, where silver is the, or one of the, Group 11 metals, the silver may be added as silver nitrate, silver nitrite, silver acetate, silver hydroxide, silver acetylacetonate, silver carbonate, silver lactate, silver sulfate, silver phosphate, and mixtures of two or more thereof. Where copper is the, or one of the, Group 11 metals, the copper may be added as copper nitrate, copper nitrite, copper acetate, copper hydroxide, copper acetylacetonate, copper carbonate, copper lactate, copper sulfate, copper phosphate, copper chloride, and mixtures of two or more thereof. When Group 10 and/or Group 11 metals are added post synthesis, they may be added by incipient wetness, spray application, solution exchange, chemical vapor disposition, or by other means known in the art.
(86) In one or more embodiments, 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. In one or more embodiments, the Group 11 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.
(87) In one or more embodiments, the catalyst composition has an Alpha Value (as measured prior to the addition of the Group 10 metal) of less than 25, preferably less than 15, alternately of greater than about 1 to less than about 25, preferably 1.1 to less than about 15. Alpha Value is determined as described in U.S. Pat. No. 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).
(88) In additional embodiments of the invention, the catalyst composition may further comprise a Group 1 alkali metal (such as Na and/or K) and/or a Group 2 alkaline earth metal (such as Mg, Ca, and/or Ba).
(89) In additional embodiments of the invention, catalyst composition further comprises a Group 1 alkali metal (Na or K) and/or a Group 2 alkaline earth metal (Mg or Ca) and the molar ratio of Group 1 metal to Al in the molecular sieve is at least 0.1.
(90) In one or more embodiments, the molar ratio of Group 1 metal to framework Al in the molecular sieve is at least about 1, or from at least about 1 up to about 3, preferably at least about 2, more preferably at least about 3.
(91) In one or more embodiments, the molar ratio of Group 2 metal to framework Al in the molecular sieve is at least about 1 (preferably 1 to 3, preferably 1 to 2).
(92) In one or more embodiments, the use of any one of the catalyst compositions described herein provides a target 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 C.sub.5 feedstock under acyclic C.sub.5 conversion conditions, wherein the target conversion is defined as the conversion that would be obtained for an n-pentane feedstock with equimolar H.sub.2, a temperature in the range of about 550 C. to about 600 C., an n-pentane partial pressure between 3 and 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), such as between 3 and 10 psia (21 kPa-a to 69 kPa-a), and an n-pentane weight hourly space velocity between 5 and 20 hr.sup.1, such as between 10 and 20 hr.sup.1.
(93) In one or more embodiments, the use of any one of the catalyst compositions of this invention provides a carbon selectivity to cyclic C.sub.5 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 50%, under acyclic C.sub.5 conversion conditions including an n-pentane feedstock with equimolar H.sub.2, a temperature in the range of about 550 C. to about 600 C., an n-pentane partial pressure between 3 and 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), such as between 10 psia (21 kPa-a to 69 kPa-a), and an n-pentane weight hourly space velocity between 5 and 20 hr.sup.1, such as between 10 and 20 hr.sup.1.
(94) In one or more embodiments, the use of 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 50%, under acyclic C.sub.5 conversion conditions including an n-pentane feedstock with equimolar H.sub.2, a temperature in the range of about 550 C. to about 600 C., an n-pentane partial pressure between 3 and 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), such as between 3 and 10 psia (21 kPa-a to 69 kPa-a) and an n-pentane weight hourly space velocity between 5 and 20 hr.sup.1, such as between 10 and 20 hr.sup.1.
(95) Useful catalyst compositions comprise a crystalline aluminosilicate, which is optionally combined with one, two, or more additional metals or metal compounds. Preferred combinations include: platinum on MFI silversilicate, platinum on coppersilicate MFI, platinum with silver on ZSM-5, and platinum with copper on ZSM-5.
(96) 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 finely divided crystalline material and inorganic oxide gel matrix 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, in the range of about 2 to about 80 wt % of the composite.
(97) During the use of the catalyst compositions in the processes of this invention, 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.
(98) Catalyst composition shape and design are preferably configured to minimize pressure drop, increase heat transfer, and minimize mass transport phenomena during use. Suitable catalyst shape and design are described in WO 2014/053553, which is incorporated herein by reference. The catalyst composition may, optionally, be an extrudate with a diameter of 2 mm to 20 mm. Optionally, 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. For fixed bed reactors (fired tube, convective tube, and cyclic) lobed, concave, spiral, etc., particle shapes are particularly useful and for fluid bed reactors spherical particle shapes are particularly useful. Preferably, 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.
(99) In various aspects, the catalyst material (and optional matrix material) may have an average diameter of about 5 m to about 50 mm, such as about 25 m to about 3500 m. Preferably, the catalyst material (and optional matrix or binder) may have an average diameter of about 25 m to about 1200 m, more preferably about 50 m to about 1000 m, more preferably about 10 m to about 500 m, more preferably about 30 m to about 400 m, more preferably about 40 m to about 300 m.
(100) Average diameter for particles in the range of 1 to 3500 m is determined using a Mastersizer 3000 available from Malvern Instruments, Ltd., Worcestershire, England. Unless otherwise stated, particle size is determined at D50. D50 is the value of the particle diameter at 50% in the cumulative distribution. For example, if D50=5.8 um, then 50% of the particles in the sample are equal to or larger than 5.8 um and 50% are smaller than 5.8 um. (In contrast, if D90=5.8 um, then 10% of the particles in the sample are larger than 5.8 um and 90% are smaller than 5.8 um.) Average diameter for particles in the range of more than 3.5 mm to 50 mm is determined using a micrometer on a representative sample of 100 particles.
INDUSTRIAL APPLICABILITY
(101) The first hydrocarbon reactor effluent obtained during the acyclic C.sub.5 conversion process containing cyclic, branched, and linear C.sub.5 hydrocarbons and, optionally, containing any combination of hydrogen, C.sub.4 and lighter byproducts, or C.sub.6 and heavier byproducts is a valuable product in and of itself. Preferably, 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.
(102) For example, 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):
(103) ##STR00001##
where R is a heteroatom or substituted heteroatom, substituted or unsubstituted C.sub.1-C.sub.50 hydrocarbyl radical (often a hydrocarbyl radical containing double bonds), an aromatic radical, or any combination thereof. Preferably, 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. In addition to the monoolefin Diels-Alder reaction product depicted in Scheme (I), 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 norbornene, ethylidene norbornene, substituted norbornenes (including oxygen containing norbornenes), norbornadienes, and tetracyclododecene, as illustrated in the following structures:
(104) ##STR00002##
(105) 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.
(106) 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.
(107) Additional components may also be separated from the reactor effluent and used in the formation of high value products. For example, separated cyclopentene is useful for producing polycyclopentene, also known as polypentenamer, as depicted in Scheme (II).
(108) ##STR00003##
(109) Separated cyclopentane is useful as a blowing agent and as a solvent. Linear and branched C.sub.5 products are useful for conversion to higher olefins and alcohols. Cyclic and non cyclic C.sub.5 products, optionally after hydrogenation, are useful as octane enhancers and transportation fuel blend components.
EXAMPLES
(110) The following examples illustrate the present invention. Numerous modifications and variations are possible and it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
(111) Measurement of Total Surface Area by BET
(112) The total BET was measured by nitrogen adsorption/desorption with a Micromeritics Tristar II 3020 instrument after degassing of the calcined zeolite powders for 4 hrs at 350 C. More information regarding the method can be found, for example, in Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density, S. Lowell et al., Springer, 2004.
(113) X-Ray Diffraction Patterns
(114) The X-ray diffraction data (powder XRD or XRD) were collected with a Bruker D4 Endeavor diffraction system with a VNTEC multichannel detector using copper K-alpha radiation. The diffraction data were recorded by scanning mode with 0.018 degrees two-theta, where theta is the Bragg angle, and using an effective counting time of about 30 seconds for each step.
Comparative Example 1: Synthesis of ZSM-5/0.45 wt % Pt
(115) A synthesis mixture with 20.3% solids was prepared from 10,000 g of deionized (DI) water, 600 g of 50% NaOH solution, 25 g of 45% sodium aluminate solution, 730 g of n-propyl amine 100% solution, 80 g of ZSM-5 seed crystals, and 3,190 g of Ultrasil PM Modified silica (which contains trace amounts of alumina) were mixed in a 5-gal pail container and then charged into a 5-gal autoclave after mixing. The synthesis mixture had the following molar composition:
(116) TABLE-US-00001 SiO.sub.2/Al.sub.2O.sub.3 ~470 H.sub.2O/SiO.sub.2 ~12.1 OH/SiO.sub.2 ~0.16 Na/SiO.sub.2 ~0.16 n-PA/Si ~0.25.
(117) The synthesis mixture was reacted at 230 F. (110 C.) at 250 rpm for 72 hours. The resulting product was filtered and washed with DI water and then dried in the oven at 250 F. (121 C.) overnight. The XRD pattern of the as-synthesized material showed the typical pure phase of ZSM-5 topology (shown in
(118) ZSM-5 having a SiO.sub.2/Al.sub.2O.sub.3 molar ratio of 414 and a sodium content of 0.38 wt % 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 held for 30 minutes. The temperature was increased to 1000 F. (540 C.), the oxygen content was increased to 16.8%, and the material was held at 1000 F. (540 C.) for 6 hours. After cooling, 0.5 wt % Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide. The catalyst composition was dried in air at room temperature for 2 hours, then at 250 F. (121 C.) for 4 hours, and lastly calcined in air at 660 F. (349 C.) for 3 hours. The catalyst composition powder was pressed (15 ton), crushed, and sieved to obtain 20-40 mesh particle size.
Example 2: Synthesis of ZSM-5/0.45 wt % Pt/0.28 wt % Ag
(119) A mixture with about 22% solids was prepared from 8800 g of deionized (DI) water, 600 g of 50% NaOH solution, 26 g of 45% sodium aluminate solution, 730 g of n-propyl amine 100% solution, 40 g of ZSM-5 seed crystals, and 3,190 g of Ultrasil PM Modified silica in a 5-gal pail container and then charged into a 5-gal autoclave after mixing. The mixture had the following molar composition:
(120) TABLE-US-00002 SiO.sub.2/Al.sub.2O.sub.3 ~470 H.sub.2O/SiO.sub.2 ~12.1 OH/SiO.sub.2 ~0.16 Na/SiO.sub.2 ~0.16 n-PA/Si ~0.25.
(121) The mixture was reacted at 230 F. (110 C.) at 250 rpm for 72 hours. The resulting products were filtered and washed with deionized water, then dried overnight at 250 F. (121 C.). The XRD pattern of the as-synthesized material showed the typical pure phase of ZSM-5 topology, see
(122) The resultant 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. (540 C.), the oxygen content was increased to 16.8%, and the material was held at 1000 F. (540 C.) for 6 hours. After cooling, 0.282 wt % Ag was added via incipient wetness impregnation using an aqueous solution of silver nitrate. The sample was dried for four hours at 250 F. (121 C.). Subsequently, 0.45 wt % Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide. The catalyst was dried in air at room temperature then at 250 F. (121 C.), and calcined in air for one hour at 610 F. (321 C.). The catalyst powder was pressed (15 ton), crushed, and sieved to obtain 40-60 mesh particle size.
Example 3: Synthesis of [0.96 wt % Ag]-MFI/0.5 wt % Pt
(123) A mixture with about 22% solids was prepared from 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 PM Modified silica, and 4.4 g of silver nitrate in a 2-liter container and then charged into a 2-liter autoclave after mixing. The mixture had the following molar composition:
(124) TABLE-US-00003 SiO.sub.2/Al.sub.2O.sub.3 >1000 H.sub.2O/SiO.sub.2 ~10.98 OH/SiO.sub.2 ~0.17 Na/SiO.sub.2 ~0.17 n-PA/Si ~0.25.
(125) The mixture was reacted at 230 F. (110 C.) at 250 rpm for 72 hours. The resulting products were filtered and washed with deionized water then dried overnight at 250 F. (121 C.). The XRD pattern of the as-synthesized material showed the typical pure phase of an MFI type microporous crystalline material, see
(126) The resultant 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. (540 C.), the oxygen content was increased to 16.8%, and the material was held at 1000 F. (540 C.) 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 dried in air at room temperature then at 250 F. (121 C.), and calcined in air for three hours at 660 F. (349 C.). The catalyst powder was pressed (15 ton), crushed, and sieved to obtain 40-60 mesh particle size.
Example 4: Catalytic Testing of Comparative Example 1 Material
(127) To test the performance of the Comparative Example 1 material (ZSM-5/0.45% Pt), the catalyst (0.5 g) was physically mixed with quartz (1.5 g, 60-80 mesh) and loaded into a 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 reactor was loaded onto the unit and pressure tested to ensure no leaks. The catalyst was dried for 1 hour under He (100 mL/min, 30 psig, 250 C.) then reduced for 1 hour under H.sub.2 (200 mL/min, 30 psig, 500 C.). The catalyst was then tested for performance with feed of n-pentane, H.sub.2, and balance He, typically at 550-600 C., 5.0 psia (35 kPa-a) C.sub.5H.sub.12, 1.0 molar H.sub.2:C.sub.5H.sub.12, 14.7 h.sup.1 WHSV, and 30 psig (207 kPa) total. Catalyst stability and regenerability were tested post initial tests at 550-600 C. by treatment with H.sub.2 (200 mL/min, 30 psig (207 kPa), 650 C.) for 5 h then re-testing performance at 600 C. Experiments were conducted at high WHSV (15 h.sup.1) to enable observation of catalytic activity and deactivation differences between catalyst candidates. Operation at lower WHSV would be expected to give higher yields of CPD.
(128) The results of the catalytic testing are summarized in Table 1 and show that at 595 C. the catalyst produced greater than 80% conversion of pentane, with 50% selectivity to cyclic C.sub.5 species and 39% selectivity to CPD. Yield to cracking products is between 13 and 17 C %.
(129) TABLE-US-00004 TABLE 1 Conver- Temper- sion ature (%) Selectivity (C %) Yield (C %) ( C.) C.sub.5H.sub.12 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5 CPD C.sub.1 C.sub.2-4 545 71 40 24 2.8 15 28 17 2.0 11 570 80 45 32 3.1 16 36 26 2.5 13 595 84 50 39 3.3 16 42 33 2.8 14 595, 76 48 38 4.1 17 37 29 3.1 13 Post H.sub.2
Example 5: Catalytic Testing of Example 2 Material
(130) The catalytic testing described in Example 4 was repeated with the Example 2 material (ZSM-5/0.45 wt % Pt/0.28 wt % Ag) and the results are summarized in Table 2 and
(131) TABLE-US-00005 TABLE 2 Temperature Conversion (%) Selctivity (C %) Yield (C %) ( C.) C.sub.5H.sub.12 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5:C.sub.1-4 550 66 41 25 0.8 6.8 27 16 0.6 4.5 5.3 575 79 48 34 1.5 11 38 27 1.2 8.7 3.8 600 84 51 42 1.8 12 43 35 1.5 10 3.7 600, Post H.sub.2 71 56 46 1.3 7.0 40 33 0.9 4.9 6.8
Example 6: Catalytic Testing of Example 3 Material
(132) The catalytic testing described in Example 4 was repeated with the Example 3 material ([0.96 wt % Ag]-MFI/0.5 wt % Pt) and the results are summarized in Table 3 and
(133) TABLE-US-00006 TABLE 3 Temperature Conversion (%) Selectivity (C %) Yield (C %) ( C.) C.sub.5H.sub.12 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5:C.sub.1-4 550 63 44 22 0.9 7.9 28 14 0.6 5.0 5.0 575 75 49 30 1.4 11 37 23 1.1 8.0 4.1 600 82 52 38 1.8 12 43 31 1.5 10 3.7 600, Post H.sub.2 77 52 39 2.7 13 41 30 2.1 10 3.3
Example 7: Long Term Stability Testing of Example 3 Material
(134) The long term stability of the Example 3 material ([0.96% Ag]-MFI/0.5% Pt) was tested at 600 C. over 100 hours with in-situ H.sub.2 treatment and on-oil periods switching every hour. 0.5 gm of the catalyst of Example 3 was tested at 5.0 psia (35 kPa-a) C.sub.5H.sub.12, 1:1 molar H.sub.2:C.sub.5, 14.7 WHSV, and 45 psia total (310 kPa-a) during on-oil period; 200 cm.sup.3 min.sup.1 H.sub.2 at 600 C. and 45 psia total (310 kPa-a) (no balance) during H.sub.2 treatment cycle.
Example 8: Synthesis of ZSM-5/0.43 wt % Pt/0.16 wt % Cu
(135) The synthesis of Example 2 was repeated except the silver impregnation was replaced by adding 0.16 wt % Cu via incipient wetness impregnation using an aqueous solution of copper (II) nitrate hydrate. The sample was dried for four hours at 250 F. (121 C.). Subsequently, 0.43 wt % Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide. The catalyst was dried in air at room temperature then at 250 F. (121 C.), and calcined in air for one hour at 610 F. (321 C.).
Example 9: Synthesis of [0.74 wt % Cu]-MFI/0.5 wt % Pt
(136) A mixture with 22% solids was prepared from 940 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 PM Modified silica, and 8.8 g of copper nitrate hydrate were mixed in a 2-liter container and then charged into a 2-liter autoclave after mixing. The mixture had the following molar composition:
(137) TABLE-US-00007 SiO.sub.2/Al.sub.2O.sub.3 >1000 H.sub.2O/SiO.sub.2 ~10.98 OH/SiO.sub.2 ~0.17 Na/SiO.sub.2 ~0.17 n-PA/Si ~0.25.
(138) The mixture was reacted at 230 F. (110 C.) at 250 rpm for 72 hours. The resulting products were filtered & washed with DI water and then dried in the oven at 250 F. (121 C.) overnight. The XRD pattern of the as-synthesized material showed the typical pure phase of an MFI type microporous crystalline material, see
(139) 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. (540 C.) for 6 hours. Subsequently, 0.51 wt % Pt was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide. The catalyst was dried in air at room temperature then at 250 F. (121 C.), and calcined in air for three hours at 660 F. (349 C.).
Example 10: Catalytic Testing of Example 9 Material
(140) The catalytic testing described in Example 4 was repeated with the Example 9 material ([0.74 wt % Cu]-MFI/0.5 wt % Pt) and the results are summarized in Table 4 and
(141) TABLE-US-00008 TABLE 4 Temperature Conversion (%) Selectivity (C %) Yield (C %) ( C.) C.sub.5H.sub.12 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5 CPD C.sub.1 C.sub.2-4 cC.sub.5:C.sub.1-4 550 58 32 19 0.4 4.0 18 11 0.2 2.4 7.2 575 69 40 28 0.5 4.9 27 19 0.3 3.4 7.3 600 79 48 38 0.6 6.5 38 30 0.5 5.1 6.8 600, Post H.sub.2 62 51 41 0.5 4.3 32 26 0.3 2.7 10.5
(142) All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term comprising is considered synonymous with the term including. Likewise whenever a composition, an element or a group of elements is preceded with the 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.