CN108349839B - Method and system for converting hydrocarbons to cyclopentadiene - Google Patents

Method and system for converting hydrocarbons to cyclopentadiene Download PDF

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CN108349839B
CN108349839B CN201680064160.XA CN201680064160A CN108349839B CN 108349839 B CN108349839 B CN 108349839B CN 201680064160 A CN201680064160 A CN 201680064160A CN 108349839 B CN108349839 B CN 108349839B
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L·L·亚奇诺
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    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing iron group metals, noble metals or copper
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    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to the preparation of acyclic C5A process for converting hydrocarbons to cyclopentadiene comprising: at a temperature T1Providing at least one adiabatic reaction zone with a catalyst comprising acyclic C5A feed of hydrocarbons, wherein the at least one adiabatic reaction zone comprises a first particulate material comprising a catalyst material; contacting the feed and the first particulate material in the at least one adiabatic reaction zone under reaction conditions to contact at least a portion of the acyclic C5Conversion of hydrocarbons to unconverted acyclic C's containing cyclopentadiene intermediates5A first effluent of hydrocarbons and optionally cyclopentadiene; heating the first effluent to a temperature T2(ii) a Providing the first effluent to the at least one diabatic reaction zone; and contacting the first effluent with a second particulate material comprising a catalyst material in the at least one diabatic reaction zone under reaction conditions to contact at least a portion of the cyclopentadiene intermediates and the unconverted acyclic C5The hydrocarbons are converted to a second effluent comprising cyclopentadiene.

Description

Method and system for converting hydrocarbons to cyclopentadiene
The inventor: larry l.iaccino
Cross Reference to Related Applications
The present invention claims priority and benefit from USSN62/250,697 filed 11/4/2015 and EP application 16153727.9 filed 2/2016.
Technical Field
The invention relates to a process for the preparation of acyclic C5Conversion of feed to contain cyclic C5A reactor for a process for the production of a compound.
Background
Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are highly desirable raw materials and are widely used in a wide variety of products in the chemical industry, such as polymeric materials, polyester resins, synthetic rubbers, solvents, fuels, fuel additives, and the like. Cyclopentadiene is currently a by-product of steam cracking of liquid feeds (e.g., naphtha and heavier feeds). As existing and new steam crackers turn to lighter feeds, less CPD is produced with increasing CPD demand. The high cost due to supply limitations affects the potential end product use of CPD in polymers. If more CPD can be produced in a non-limiting ratio and at a lower cost than that recovered from steam cracking, more CPD-based polymer product can be produced. It is also desirable to co-produce other cyclic C5. Cyclopentane and cyclopentene are of high value as solvents, and cyclopentene can be used as a comonomer to produce polymers and also as a feedstock for other high value chemicals.
It would be advantageous to be able to use a catalyst system consisting of rich C5Feed production of cyclic C5Compounds comprising CPD as a major product to produce CPD while minimizing light weight (C)4-) The production of by-products. While lower hydrogen content (e.g., cyclics, olefins, and diolefins) may be preferred because the reaction endotherm is reduced and the thermodynamic constraints of conversion are improved, non-saturates are more expensive than saturates feeds. Due to the reaction chemistry and the straight chain C5Relative to the branching C5Lower value of (by)In octane number difference), linear C5Skeletal structure preferred to branched C5A framework structure. Rich C5Available from unconventional natural gas and shale oil, and due to strict environmental regulations, reduces motor fuel usage. C5The feed may also be derived from biological feedstocks.
Various catalytic dehydrogenation techniques are currently used to remove hydrogen from C3And C4Alkanes produce mono-and diolefins, but not cyclic mono-or diolefins. Typical processes employ Pt/Sn supported on alumina as the active catalyst. Another useful method employs chromium oxide on alumina. See b.v. vora, "Development of differentiation Catalysis and Processes," Topics in Catalysis, vol.55, pp.1297-1308, 2012; and J.C.Bricker, "Advanced Catalysis reduction Technologies for Production of Olefins", Topics in Catalysis, vol.55, pp.1309-1314, 2012.
Yet another common method employs Pt/Sn supported on Zn and/or Ca aluminates to dehydrogenate propane. Although these processes have been successful in the dehydrogenation of alkanes, they do not allow the cyclization critical for the production of CPD. The Pt-Sn/alumina and Pt-Sn/aluminate catalysts exhibit moderate n-pentane conversion, but the para-cyclic C of these catalysts5The selectivity and yield of the product are poor.
Pt catalyst supported on chlorinated alumina is used to reform low octane naphtha to aromatics such as benzene and toluene. See, U.S. Pat. No. 4,3,953,368 (Sinfelt), "Polymetallic Cluster Compositions Useful as Hydrocarbon Conversion Catalysts". Although these catalysts are effective in promoting C6And dehydrogenation and cyclization of higher alkanes to form C6Aromatic rings, but they will be acyclic C5Conversion to cyclic C5Is less effective. These Pt catalysts supported on chlorided alumina show low yields of cyclic C5And showed deactivation for the first two hours of the stream. C6And C7Formation of the cyclized aromatic ring of the alkane is aided, but this does not occur at C5In the cyclization. This effect may be due in part to the presence of benzene (cyclic C)6) And toluene (Cyclic C)7) Phase contrast CPD (Cyclic C)57) The heat of formation is higher. This is also demonstrated by Pt/Ir and Pt/Sn supported on chlorided alumina. Although these alumina catalysts were subjected to C6+Dehydrogenation and cyclization of substances to form C6Aromatic rings, but requiring different catalysts to be acyclic C5Conversion to cyclic C5。
A Ga-containing ZSM-5 catalyst is used in the process for the production of aromatics from light paraffins. A study by Kanazirev et al showed that n-pentane readily passes through Ga2O3(ii) H-ZSM-5 conversion. See Kanazirev et al, "Conversion of C8Aromatics and n-pentane over Ga2O3[ H-ZSM-5mechanical mixed Catalysts,' Catalysis Letters, vol.9, pp.35-42, 1991 ]. No report of the production of Cyclic C5While 6 wt% or more of aromatic substances are present at 440 ℃ and 1.8hr-1WHSV was produced. The Mo/ZSM-5 catalyst also exhibits dehydrogenated and/or cyclized paraffins, particularly methane. See Y.xu, S.Liu, X.Guo, L.Wang and M.Xie, "Methane activation with out using oxidants over Mo/HZSM-5zeolite catalysts," Catalysis Letters, vol.30, pp.135-149, 1994. The high conversion of n-pentane using Mo/ZSM-5 was demonstrated with high yields of cracked products, but no cyclic C5. This indicates that ZSM-5 based catalysts are capable of converting paraffins to C6Rings, but not necessarily producing C5And (4) a ring.
US5,254,787 (dessuu) describes a NU-87 catalyst for paraffin dehydrogenation. The catalyst exhibits a catalytic activity of2-C6+Dehydrogenated to produce their unsubstituted analogs. In this patent C is given very clearly2-5And C6+Difference in alkane: c2-5Dehydrogenation of alkanes to give linear or branched mono-or diolefins, and C6+Alkane dehydrogenation produces aromatics. US5,192,728 (dessuu) relates to a similar chemistry but employing crystalline microporous materials containing tin. Same as NU-87 catalyst, C5Dehydrogenation is only shown to produce linear or branched mono-or di-olefins instead of CPD.
US5,284,986 (dessuu) describes a two-stage process for the production of cyclopentane and cyclopentene from n-pentane. In the examples carried out, the first stage involves the dehydrogenation and dehydrocyclization of n-pentane over a Pt/Sn-ZSM-5 catalyst to a mixture of paraffins, mono-and diolefins and naphthenes. The mixture is then introduced into a second stage reactor consisting of a Pd/Sn-ZSM-5 catalyst where dienes, particularly CPD, are converted to olefins and saturates. Cyclopentene is the desired product in this process, while CPD is an unwanted by-product.
US 2,438,398; US 2,438,399; US 2,438,400; US 2,438,401; US 2,438,402; US 2,438,403; and US 2,438,404(Kennedy) disclose the production of CPD from 1,3-pentadiene over various catalysts. Low operating pressures, low conversions per pass, and low selectivities make the process undesirable. In addition, 1,3-pentadiene is not a readily available feed, unlike n-pentane. See also, Kennedy et al, "Formation of cyclopendadiene from 1,3-Pentadiene," Industrial & Engineering Chemistry, vol.42, pp.547-552, 1950.
Fel' dblyum et al at "Cyclization and Cyclization of C5The production of CPD from 1,3-pentadiene, n-pentene and n-pentane is reported in carbon over plants and in the presence of hydrogen sulfate, "Doklady Chemistry, vol.424, pp.27-30, 2009. For 1,3-pentadiene, n-pentene and n-pentane, respectively, at 600 deg.C through 2% Pt/SiO2The yield of CPD was as high as 53%, 35% and 21%. Although initial CPD production was observed, severe catalyst deactivation was also observed within the first few minutes of the reaction. Experiments conducted on Pt-containing silica have shown that n-pentane passes through Pt-Sn/SiO2Moderate conversion of, but for cyclic C5The selectivity and yield of the product are poor. Hereinafter, Fel' dblyum gives the use of H2S as a 1,3-Pentadiene cyclization promoter, and is described in Marcinkowski, "isometrization and Dehydrogenation of 1, 3-pentadine," M.S., University of Central Florida, 1977. Marcinkowski shows the use of H280% conversion of S at 700 ℃ of 1,3-pentadiene and 80% selectivity to CPD. The high temperature, limited feed, and potential for sulfur containing products requiring subsequent stripping makes the process undesirable。
L Lo pez et al, in "n-Pentane hydro isometrization on Pt contacting HZSM-5," HBEA and SAPO-11, "Catalysis Letters, vol.122, pp.267-273, 2008, have studied the reaction of n-Pentane on Pt-containing zeolites, including H-ZSM-5. At moderate temperatures (250 ℃ C. and 400 ℃ C.), they reported efficient hydroisomerization of n-pentane over Pt-zeolite, but did not discuss the formation of cyclopentene. It is desirable to avoid this detrimental chemistry because of the branching C5Not like straight chain C5That efficiently produces a cyclic C5As discussed above.
Li et Al in "Catalytic dehydrogenation of n-alkanes to isoalkens," Journal of Catalysis, vol.255, pp.134-137, 2008, also investigated the dehydrogenation of n-pentane over Pt-containing zeolites in which Al is isomorphically substituted by Fe. These Pt/[ Fe ]]ZSM-5 catalyst is effective for the dehydrogenation and isomerization of n-pentane but without the cyclic C under the reaction conditions employed5And undesired skeletal isomerization occurs.
U.S. Pat. No. 5,633,421 discloses dehydrogenation C2-C5Process for the preparation of paraffins to obtain the corresponding olefins. Similarly, US 2,982,798 discloses a process for the dehydrogenation of aliphatic hydrocarbons containing from 3 to 6 carbon atoms, inclusive. However, neither U.S. Pat. No. 5,633,421 nor U.S. Pat. No. 2,982,798 disclose the use of acyclic C5Hydrocarbon production of CPD, acyclic C5Hydrocarbons are desirable feedstocks because they are abundant and inexpensive.
In addition, there are many challenges in designing a targeted CPD production process. E.g. C5The reaction of hydrocarbon conversion to CPD is extremely endothermic and readily proceeds at low pressure and high temperature, but n-pentane and other C' s5Significant cracking of hydrocarbons can occur at relatively low temperatures (e.g., 450 ℃ to 500 ℃). Further challenges include loss of catalyst activity due to coking during the process, and the need for further processing to remove coke from the catalyst, as well as the inability to use oxygen-containing gas to directly provide heat input to the reactor without damaging the catalyst.
Thus, there remains a need for acyclic C that will preferably be used at commercial rates and conditions5Conversion of feedstock to non-aromatic cyclic C5A hydrocarbon, i.e., cyclopentadiene. Furthermore, there is a need for catalytic processes directed to the production of cyclopentadiene in high yield from abundant C5The feed is fed to produce cyclopentadiene without excessive production of C4-Cracking products and having acceptable catalyst aging performance. In addition, it is desirable to purposefully use acyclic C5A method and system for producing CPD from hydrocarbons and addressing the challenges described above.
Summary of The Invention
The invention relates to the use of acyclic C in a reactor system5Process for the conversion of hydrocarbons to cyclopentadiene, wherein the process comprises at a temperature T1Providing at least one polymer containing acyclic C5An adiabatic reaction zone for a feed of hydrocarbons, wherein the at least one adiabatic reaction zone comprises a first particulate material comprising a catalyst material; contacting the feed and the first particulate material in the at least one adiabatic reaction zone under reaction conditions to contact at least a portion of the acyclic C5Conversion of hydrocarbons to unconverted acyclic C's containing cyclopentadiene intermediates5A first effluent of hydrocarbons and optionally cyclopentadiene; heating the first effluent to a temperature T2(ii) a Providing the first effluent to at least one diabatic reaction zone; and contacting the first effluent with a second particulate material in the at least one diabatic reaction zone under reaction conditions to contact at least a portion of the cyclopentadiene intermediates and unconverted acyclic C5The hydrocarbons are converted to a second effluent comprising cyclopentadiene.
Brief Description of Drawings
FIG. 1 is a diagram of a reactor according to an embodiment of the invention.
Fig. 2 is a diagram of a reactor with a rejuvenation apparatus according to another embodiment of the present invention.
FIG. 3 is a diagram of a reactor having a rejuvenation means and a regeneration means according to another embodiment of the invention.
Detailed Description
I. Definition of
To facilitate an understanding of the present invention, a number of terms and phrases are defined below.
As used in the present disclosure and claims, the singular forms "a", "an" and "the" include the plural forms unless the context clearly dictates otherwise.
The term "and/or" as used in phrases such as "a and/or B" herein is meant to include "a and B", "a or B", "a" and "B".
As used herein, the term "about" refers to a range of values that is plus or minus 10% of the specified value. For example, the phrase "about 200" includes plus or minus 10% of 200, or 180 to 220.
The term "saturates" includes, but is not limited to, alkanes and cycloalkanes.
The term "unsaturates" includes, but is not limited to, alkenes, dienes, alkynes, cycloalkenes, and cyclodiolefins.
The term "cyclic C5"or" cC5"includes, but is not limited to, cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more thereof. The term "cyclic C5"or" cC5"also includes alkylated analogs of any of the foregoing, for example, methylcyclopentane, methylcyclopentene, and methylcyclopentadiene. For the purposes of the present invention it is understood that cyclopentadiene spontaneously dimerizes over time under a range of conditions, including ambient temperature and pressure, to form dicyclopentadiene via diels-alder condensation.
The term "acyclic" includes, but is not limited to, straight chain and branched saturates and unsaturates.
The term "aromatic" refers to a planar cyclic hydrocarbon group having 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 Aromatic Substances (PNAs), including naphthalene, anthracene,
Figure BDA0001648294470000061
and their alkylated forms. The term "C6+Aromatic "includes compounds based on aromatic rings having six or more ring atoms, including, but not limited to, benzene, toluene and xylene, and polynuclear aromatics (PN)A) Which include naphthalene, anthracene,
Figure BDA0001648294470000062
and their alkylated forms.
The term "BTX" includes, but is not limited to, mixtures of benzene, toluene, and xylenes (ortho and/or meta and/or para).
The term "coke" includes, but is not limited to, low hydrogen content hydrocarbons that adsorb onto the catalyst composition.
The term "Cn"refers to a hydrocarbon containing n carbon atoms per molecule, where n is a positive integer.
The term "Cn+"refers to a hydrocarbon having at least n carbon atoms per molecule.
The term "Cn-"refers to hydrocarbons having no more than n carbon atoms per molecule.
The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon and encompasses mixtures of (i) saturated hydrocarbon compounds, (ii) unsubstituted hydrocarbon compounds and (iii) hydrocarbon compounds (saturated and/or unsubstituted), including mixtures of hydrocarbon compounds having different values of n.
The term "C5Feed "includes n-pentane containing feeds such as feeds that are primarily n-pentane and isopentane (also known as methylbutane), and minor amounts of cyclopentane and octapentane (also known as 2, 2-dimethylpropane).
All numbers and references relating to the periodic table of elements are based on Chemical and Engineering News, 63(5), 27, (1985) unless otherwise stated.
The term "group 10 metal" refers to an element in group 10 of the periodic table and includes, but is not limited to, Ni, Pd and Pt.
The term "group 11 metal" refers to an element from group 11 of the periodic table and includes, but is not limited to, Cu, Ag, Au and mixtures of two or more thereof.
The term "group 1 alkali metal" refers to an element from group 1 of the periodic table of elements and includes, but is not limited to, Li, Na, K, Rb, Cs and mixtures of two or more thereof, with the exclusion of hydrogen.
The term "group 2 alkaline earth metal" refers to elements in group 2 of the periodic table and includes, but is not limited to, Be, Mg, Ca, Sr, Ba and mixtures of two or more thereof.
As used herein, the term "oxygen-containing" or "oxygenate" refers to oxygen and oxygen-containing compounds, including, but not limited to, O2，CO2，CO，H2O and oxygen-containing hydrocarbons such as alcohols, esters, ethers, and the like.
The term "constraint index" is defined in US 3,972,832 and US 4,016,218, both incorporated by reference into the present application.
As used herein, the term "MCM-22 family molecular sieve" (or "MCM-22 family material" or "MCM-22 family zeolite") includes one or more of the following:
molecular sieves made from common first degree crystal building block unit cells having MWW topological frameworks. (the unit cell is a spatial arrangement of atoms that, if laid down in three-dimensional space, describes a crystal structure. this crystal structure is discussed in the "Atlas of Zeolite Framework Types", fifth edition, 2001, the entire contents of which are incorporated by reference);
molecular sieves made from common second degree building blocks, which are 2-dimensional pavements of such MWW topological framework unit cells, forming a single layer of one unit cell thickness, preferably one c-unit cell thickness;
a molecular sieve made from common second degree building blocks, which are layers of one or more than one unit cell thickness, wherein the layers of more than one unit cell thickness are made by stacking, packing, or combining at least two monolayers of one unit cell thickness. Such stacking of second degree building blocks may be in a regular manner, an irregular manner, a random manner, or any combination thereof; and
molecular sieves made by any regular or random 2-or 3-dimensional combination of unit cells with MWW topological framework
Molecular sieves of the MCM-22 family include those having an X-ray diffraction pattern with d-plane spacing maxima at 12.4 + -0.25, 6.9 + -0.15, 3.57 + -0.07 and 3.42 + -0.07 Angstrom. X-ray diffraction data for characterizing the material were obtained by standard techniques using a double line of K- α of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
As used herein, the term "molecular sieve" is used synonymously with the terms "microporous crystalline material" or "zeolite".
As used herein, the term "carbon selectivity" refers to the individual cyclic C being formed5、CPD、C1And C2-4Divided by the total moles of carbon in the converted pentane. The phrase "para-cyclic C5With a carbon selectivity of at least 30% "is meant that 100 moles of carbon are formed in the cyclic C per mole of pentane converted530 moles of carbon.
As used herein, the term "conversion" refers to the conversion in the acyclic C5Moles of carbon in the feed that is converted to product. The phrase "said acyclic C5A conversion of at least 70% of the product fed to means at least 70% of the moles of said acyclic C5The feed is converted to product.
As used herein, the term "reactor system" refers to a system comprising one or more reactors and all necessary and optional equipment for producing cyclopentadiene.
As used herein, the term "reactor" refers to any vessel in which a chemical reaction occurs. The reactor comprises separate reactors, as well as reaction zones within a single reactor apparatus, and reaction zones that, where applicable, span multiple reactors. In other words and as is common, a single reactor may have multiple reaction zones. When the specification refers to a first and second reactor, those of ordinary skill in the art will readily understand that such reference includes two reactors, as well as a single reactor vessel having a first and second reaction zone. Similarly, the first reactor effluent and the second reactor effluent will be understood to include the effluents from the first reaction zone and the second reaction zone, respectively, of a single reactor.
The reactor/reaction zone may be an adiabatic reactor/reaction zone or a heat transfer reactor/reaction zone. As used herein, the term "adiabatic" means that there is substantially no heat input to the system in the reaction zone other than through the flowing process fluid. For the purposes of the present invention, reaction zones having inevitable losses due to conduction and/or radiation are also considered to be thermally insulating. As used herein, the term "heat transfer" means that heat is intentionally provided through a reactor/reaction zone provided by the apparatus in addition to that provided by the flowing process fluid.
As used herein, the term "moving bed" reactor refers to a zone or vessel in which the contact of the solid (e.g., catalyst particles) and gas flows is such that the superficial gas velocity (U) is lower than the velocity required for dilute phase pneumatic transport of the solid particles to maintain the void fraction of the solid bed below 95%. In a moving bed reactor, solids (e.g., catalyst material) may travel slowly through the reactor and may be removed from the bottom of the reactor and added to the top of the reactor. The moving bed reactor can be operated in a variety of flow modes, including settling or moving packed bed mode (U)<Umf) Bubbling mode (U)mf<U<Umb) Slug mode (U)mb<U<Uc) Transition and turbulent fluidization patterns (U)c<U<Utr) And fast fluidized mode (U)>Utr) Wherein Umf is the minimum fluidization velocity, Umb is the minimum bubbling velocity, Uc is the velocity of the pressure fluctuation peak, and tr is the conveying velocity. These different Fluidization patterns have been described, for example, in Kunii, D., Levenspiel, O., channel 3 of Fluidization Engineering,2nd Edition,Butterworth-Heinemann,Boston,1991 and Walas,S.M.,Chapter 6 of Chemical Process Equipment,Revised 2ndEdition, Butterworth-Heinemann, Boston,2010, which are incorporated by reference.
As used herein, the term "settled bed" reactor refers to a zone or vessel in which particles are contacted with a gas stream such that the air column gas velocity (U) is lower than the minimum velocity required to fluidize solid particles (e.g., catalyst particles) (minimum fluidization velocity (U) in at least a portion of the reaction zonemf))，U<UmfAnd/or operating at a velocity above the minimum fluidization velocity while passingReactor spacing has been used to minimize gas-solid backmixing to maintain a gradient of gas and/or solid properties (e.g., temperature, gas or solid composition, etc.) axially upward along the reactor bed. The specification of the minimum Fluidization velocity is given, for example, by Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston,1991 and Walas, S.M., Chapter 6 of Chemical Process Equipment, reviewed 2ndEdition, Butterworth-Heinemann, Boston, 2010. The settled bed reactor can be a "circulating settled bed reactor," which refers to a settled bed in which solids (e.g., catalyst material) move through the reactor and the solids (e.g., catalyst material) are at least partially recycled. For example, solids (e.g., catalyst material) may be removed from the reactor, regenerated, reheated, and/or separated from the product stream, and then returned to the reactor.
As used herein, the term "fluidized bed" reactor refers to a zone or vessel in which contact of solids (e.g., catalyst particles) with a flow of gas is such that the superficial gas velocity (U) is sufficient to fluidize the solid particles (i.e., above the minimum fluidization velocity U)mf) And lower than the velocity required for dilute phase pneumatic transport of the solid particles, thereby maintaining the void fraction of the solid bed below 95%. As used herein, the term "cascaded fluidized bed" refers to a series arrangement of individual fluidized beds that enables a gradient in gas and/or solid properties (e.g., temperature, gas or solid composition, pressure, etc.) as the solids or gas leave one fluidized bed to another. The trajectory of the minimum Fluidization velocity is given, for example, in Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston,1991 and Walas, S.M., Chapter 6 of Chemical Process Equipment, reviewed 2ndEdition, Butterworth-Heinemann, Boston, 2010. The fluidized bed reactor may be a moving fluidized bed reactor, such as a "circulating fluidized bed reactor," which refers to a fluidized bed in which solids (e.g., catalyst material) move through the reactor and at least a portion of the solids (e.g., catalyst material) are recycled. For example, solids (e.g., catalyst material) may be removed from the reactor and regeneratedReheated and/or separated from the product stream and then returned to the reactor.
As used herein, the term "riser" reactor (also referred to as a transport reactor) refers to a zone or vessel (e.g., a vertical cylindrical tube) for net upward transport of solids (e.g., catalyst particles) in a fast fluidization or pneumatic transport fluidization mode. The fast fluidization and pneumatic transmission fluidization modes are characterized in that the empty tower gas velocity (U) is greater than the conveying velocity (U)tr). Fast Fluidization and pneumatic transport Fluidization patterns are also described in Kunii, D., Levenspiel, O., channel 3 of Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston,1991 and Walas, S.M., Chapter 6 of Chemical Process Equipment, reviewed 2ndEdition, Butterworth-Heinemann, Boston, 2010. A fluidized bed reactor, such as a circulating fluidized bed reactor, may be operated as a riser reactor.
As used herein, the term "combustion conduit" reactor refers to a furnace and parallel reactor conduits positioned within the radiant section of the furnace. The reactor tubes contain catalytic material (e.g., catalyst particles) that contacts the reactants to form products.
As used herein, the term "convection heating tube" reactor refers to a conversion system comprising parallel reactor tubes containing catalytic material and positioned within an outer shell. While any known reactor tube configuration or housing may be used, it is preferred that the conversion system comprise a plurality of parallel reactor tubes within a convective heat exchange housing. Preferably, the reactor tubes are straight, rather than having a spiral or curved path along the shell (although spiral or curved tubes may also be used). Additionally, the conduits may have a cross-section that is circular, elliptical, rectangular, and/or other known shapes. The conduit is preferably heated with a turbine exhaust stream generated by the turbine combustion fuel gas using a compressed gas comprising oxygen. In other aspects, the reactor tubes are heated by convection of hot gases generated by combustion in a fuel cell, furnace, boiler or excess air burner. However, heating the reactor tubes with turbine exhaust gas may be preferred for other advantages such as co-production of shaft power.
As used herein, the term "fixed bed" or "packed bed" reactor refers to a zone or vessel (e.g., vertical or horizontal, cylindrical tube or spherical vessel) that may include transverse (also known as cross-flow), axial flow, and/or radial flow of gas, wherein solids (e.g., catalyst particles) are substantially fixed within the reactor, and the gas flow is such that the superficial gas velocity (U) is lower than the velocity of the fluidized solid particles (i.e., lower than the minimum fluidization velocity U;)mf) And/or the gas is moved in a downward direction so that the solid particles cannot fluidize.
As used herein, the term "periodic" refers to a periodic cycle or repeating event that occurs according to a cycle. For example, a reactor (e.g., a cyclic fixed bed) may be periodically operated to have a reaction interval, a reheating interval, and/or a regeneration interval. The duration and/or order of the interval steps may change over time.
As used herein, the term "co-current" means that the two streams (e.g., stream (a), stream (b)) flow in substantially the same direction. For example, if stream (a) flows from the top to the bottom of at least one reaction zone and stream (b) flows from the top to the bottom of at least one reaction zone, the flow of stream (a) will be considered co-current to the flow of stream (b). On a smaller scale within the reaction zone, there may be regions where the flow may not be co-current.
As used herein, the term "counter-current" means that the two streams (e.g., stream (a), stream (b)) flow in substantially opposite directions. For example, if stream (a) flows from the top to the bottom of at least one reaction zone and stream (b) flows from the bottom to the top of at least one reaction zone, the flow of stream (a) will be considered counter-current to the flow of stream (b). On a smaller scale within the reaction zone, there may be regions where the flow may not be countercurrent.
Particles in the range of 1-3500 μm "mean diameter" Mastersizer available from Malvern Instruments, Ltd. of Worcestershire, UK was usedTM3000 is determined. Unless otherwise stated, the particle size is determined as D50. D50 is the value at 50% of the particle diameter in the cumulative distribution.For example, if D50 ═ 5.8 μm, then 50% of the particles in the sample are equal to or greater than 5.8 μm and 50% are less than 5.8 μm. (conversely, if D90 ═ 5.8 μm, then 10% of the particles in the sample were greater than 5.8 μm and 90% were less than 5.8 μm.). The "average diameter" of the particles in the range of greater than 3.5mm was determined using a micrometer for a representative 100 particle sample.
For the purposes of the present invention, 1psi equals 6.895 kPa. Specifically, 1psia equals 1kPa absolute (kPa-a). Similarly, 1psig equals 6.895kPa gauge (kPa-g).
5Acyclic C conversion process
In a first aspect of the invention, acyclic C5Conversion of feed to contain cyclic C5A product of a compound (e.g., cyclopentadiene). The method comprises the following steps: subjecting the feed and optionally hydrogen to acyclic C5Under conversion conditions in the presence of one or more catalyst compositions, including but not limited to the catalyst compositions described herein, to form the product.
In one or more embodiments, acyclic C is converted5The product of the fed process comprises a cyclic C5A compound is provided. Cyclic C5The compounds include one or more of cyclopentane, cyclopentene, cyclopentadiene, and mixtures thereof. In one or more embodiments, cyclic C5The compound comprises at least about 20 wt%, or 30 wt%, or 40 wt%, or 70 wt% cyclopentadiene, or in the range of about 10 wt% to about 80 wt%, alternatively 20 wt% to 70 wt%.
In one or more embodiments, acyclic C5The conversion conditions include at least temperature, n-pentane partial pressure and Weight Hourly Space Velocity (WHSV). The temperature ranges from about 400 ℃ to about 700 ℃, or ranges from about 450 ℃ to about 650 ℃, preferably ranges from about 500 ℃ to about 600 ℃. The normal pentane partial pressure ranges from about 3 to about 100psia, or ranges from about 3 to about 50psia, and preferably ranges from about 3psia to about 20 psia. The weight hourly space velocity is in the range of from about 1 to about 50hr-1Or in the range of about 1 to about 20hr-1. Such conditions include optional hydrogen co-feed with acyclic C5The molar ratio of the feed is in the range of about 0 to 3, orIn the range of about 1 to about 2. Such conditions may also include co-feeding C1-C4Hydrocarbons with acyclic C5Feeding. Preferably, the co-feed (if present), whether containing hydrogen or not, C1-C4A hydrocarbon, or both, substantially free of oxygenates. As used in this context, "substantially free" means that the co-feed contains less than about 1.0 wt%, based on the weight of the co-feed, of oxygenates, 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%.
In one or more embodiments, the present invention relates to a process for converting n-pentane to cyclopentadiene comprising the steps of: reacting n-pentane and optionally hydrogen (if present, typically H)2Present in a ratio of from 0.01 to 3.0 with n-pentane) with one or more catalyst compositions, including but not limited to the catalyst compositions described herein, at a temperature of from 400 ℃ to 700 ℃, a partial pressure of from 3 to about 100psia, and a weight hourly space velocity of from 1 to about 50hr-1To form cyclopentadiene.
In one or more embodiments, the present invention relates to the introduction of acyclic C into a reactor system5A process for converting hydrocarbons to cyclopentadiene, wherein the process comprises: at a temperature T1Providing at least one adiabatic reaction zone with a catalyst comprising acyclic C5A feed of hydrocarbons, wherein the at least one adiabatic reaction zone comprises a first particulate material comprising a catalyst material; contacting the feed and the first particulate material in the at least one adiabatic reaction zone under reaction conditions to contact at least a portion of the acyclic C5Conversion of hydrocarbons to unconverted acyclic C's containing cyclopentadiene intermediates5A first effluent of hydrocarbons and optionally cyclopentadiene; heating the first effluent to a temperature T2(ii) a Providing the first effluent to at least one diabatic reaction zone; and contacting the first effluent with a second particulate material comprising a catalyst material in the at least one diabatic reaction zone under reaction conditions to contact at least a portion of the cyclopentadiene intermediates and the unconverted acyclic C5The hydrocarbons are converted to a second effluent comprising cyclopentadiene.
A.Feeding of the feedstock
In the method, C is contained5Feed of hydrocarbons, preferably acyclic C5The feed is supplied to the reaction system together with a particulate material comprising a catalyst material. Acyclic C useful herein5The feed can be obtained from crude oil or natural gas condensates and can include cracked C produced by refining and chemical processes such as Fluid Catalytic Cracking (FCC), reforming, hydrocracking, hydrotreating, coking, and steam cracking5(various degrees of unsaturation: olefins, diolefins, alkynes).
In one or more embodiments, acyclic C useful in the methods of the invention5The feed comprises pentane, pentene, pentadiene, and mixtures of two or more thereof. Preferably, in one or more embodiments, acyclic C5The feed comprises at least about 50 wt%, or 60 wt%, or 75 wt%, or 90 wt% n-pentane, or in the range of about 50 wt% to about 100 wt% n-pentane.
Acyclic C5The feed optionally does not contain C6Aromatic compounds, e.g. benzene, preferably C6The aromatic compound is present in an amount of less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, preferably 0 wt%.
Acyclic C5The feed optionally does not contain benzene, toluene, or xylene (ortho, meta, or para), preferably benzene, toluene, or xylene (ortho, meta, or para) compounds are present at less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, preferably 0 wt%.
Acyclic C5The feed optionally does not contain C6+Aromatic compounds, preferably C6+The aromatic compound is present in an amount of less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, preferably 0 wt%.
Acyclic C5The feed optionally does not contain C6+Compounds, preferably C6+The compound is present in an amount of less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 wt%, preferably 0 wt%.
Optionally, C5The feed is substantially free of oxygenates. As used in this context, "substantially free" means that the feed comprises small amountsFrom about 1.0 wt%, based on the weight of the feed, for example, 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 oxygenates.
Preferably, C in the feed is converted to cyclopentadiene5Hydrocarbons (e.g. acyclic C)5Hydrocarbon) greater than or equal to about 5.0 wt.%, greater than or equal to about 10.0 wt.%, greater than or equal to about 20.0 wt.%, greater than or equal to about 30.0 wt.%, greater than or equal to about 40.0 wt.%, greater than or equal to about 50.0 wt.%, greater than or equal to about 60.0 wt.%, greater than or equal to about 70.0 wt.%, greater than or equal to about 80.0 wt.%, or greater than or equal to about 90.0 wt.%. Preferably, at least about 30.0 wt% or at least about 60.0 wt% of the C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) are converted to cyclopentadiene. Ranges expressly disclosed include any combination of the above-listed values; for example, from about 5.0% to about 90.0%, from about 10.0% to about 80.0%, from about 20.0% to about 70.0%, from about 20.0% to about 60.0%, etc. Preferably, about 20.0 wt% to about 90.0 wt% of the C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) are converted to cyclopentadiene, more preferably from about 30.0 wt% to about 85.0 wt%, more preferably from about 40.0 wt% to about 80.0 wt%, from about 45.0 wt% to about 75.0 wt%, or from about 50.0 wt% to about 70.0 wt%.
Preferably, hydrogen and optionally light hydrocarbons such as C1-C4A hydrogen co-feed of hydrocarbons is also fed to the first reactor. Preferably, at least a portion of the hydrogen co-feed is with the C5The feeds were combined and then fed into the first reactor. The presence of hydrogen in the feed mixture at the inlet location where the feed first contacts the catalyst prevents or reduces coke formation on the catalyst particles. C1-C4The hydrocarbon may also be reacted with C5And (4) co-feeding.
B. Adiabatic reaction zone
The feed may be provided to at least one temperature T1And in at least one adiabatic reaction zone with a first particulate material comprising a catalyst material under reaction conditions to contact at least a portion of the C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) to contain H2Cyclopentadiene intermediate, unconverted acyclic C5First effluent of hydrocarbons and optionally cyclopentadiene. The at least one adiabatic reaction zone may be a fixed bed reactor or a fluidized bed reactor. The fixed bed reactor can be a vertical fixed bed or a horizontal fixed bed. Preferably, the vertical fixed bed is an axial flow vertical fixed bed or a radial flow fixed bed. Preferably, the horizontal fixed bed is a cross-flow horizontal fixed bed.
Additionally or alternatively, the at least one adiabatic reaction zone may include at least a first adiabatic reaction zone, a second adiabatic reaction zone, a third adiabatic reaction zone, a fourth adiabatic reaction zone, a fifth adiabatic reaction zone, a sixth adiabatic reaction zone, a seventh adiabatic reaction zone, and/or an eighth adiabatic reaction zone, and the like. As understood herein, each adiabatic reaction zone may be a separate reactor or an adiabatic reactor may contain one or more of the adiabatic reaction zones. Preferably, the reactor system comprises from 1 to 20 adiabatic reaction zones, more preferably from 1 to 15 adiabatic reaction zones, more preferably from 2 to 10 adiabatic reaction zones, more preferably from 2 to 8 adiabatic reaction zones. When more than 1 adiabatic reaction zone is present, the adiabatic reaction zones may be arranged in any suitable configuration, for example, in series or in parallel. Each adiabatic reaction zone may independently be a fixed bed or a fluidized bed.
The adiabatic reaction zone may include at least one internal structure to support the first particulate material to evenly distribute the feed to collect hydrocarbon products and/or reduce pressure drop within the reaction zone. For example, when the adiabatic reaction zone is a vertical fixed bed, one or more internal structures, e.g., a permeable concentric shell, can be included in the reaction zone to contain and support the granular material, and the feed can be fed into the substantially open central axial portion of the reaction zone and flow radially around the granular material. Additionally or alternatively, the adiabatic reaction zone may comprise at least one internal structure, preferably a plurality of internal structures (e.g., 2, 3,4, 5,6, 7, 8, 9, 10, 15, 20, 30, 40, 50, etc.). Examples of suitable internal structures include various support grids, hold-down grids, baffles, sheds, trays, tubes, rods and/or distribution bodies.
The feed may be provided to a temperature T1Adiabatic reaction zone of (2), T1Less than or equal to about 700 deg.C, less than or equal to about 675 deg.C, less than or equal to about 650 deg.C, less than or equal to about 625 deg.C, less than or equal to about 600 deg.C, less than or equal to about 575 deg.C, less than or equal to about 550 deg.C, less than or equal to about 5 deg.C25 ℃, ≦ about 500 ℃, ≦ about 475 ℃, ≦ about 450 ℃, ≦ about 425 ≦ about 400 ℃, ≦ about 375 ℃, ≦ about 350 ℃, ≦ about 325 ≦ about 300 ℃, ≦ about 275 ℃, ≦ about 250 ℃, ≦ about 225 ℃, or ≦ about 200 ℃. Preferably, the feed to the adiabatic reaction zone (e.g., acyclic C)5Hydrocarbons) at a temperature of less than or equal to about 500 deg.C, more preferably less than or equal to about 525 deg.C, more preferably less than or equal to about 550 deg.C, more preferably less than or equal to about 575 deg.C. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., from about 200 ℃ to about 700 ℃, from about 250 ℃ to about 600 ℃, from about 350 ℃ to about 650 ℃, from about 375 ℃ to about 500 ℃, and the like. Preferably, the feed to the adiabatic reaction zone (e.g., acyclic C)5Hydrocarbons) from about 200 ℃ to about 700 ℃, more preferably from about 300 ℃ to about 650 ℃, more preferably from about 400 ℃ to about 600 ℃, more preferably from about 475 ℃ to about 575 ℃. Providing the feed at the above-mentioned temperature (e.g., acyclic C)5Hydrocarbons) can advantageously minimize the C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) are undesirably cracked prior to their reaction in the presence of the catalyst material.
Additionally or alternatively, the feed may be heated to the above-described temperatures by one or more heating devices, for example, a heat exchanger comprising heat in the convection zone of the furnace, prior to entering the adiabatic reaction zone.
At least one adiabatic reaction zone sufficient to convert at least a portion of the feed (e.g., acyclic C)5Hydrocarbons) are cyclopentadiene intermediates and unconverted acyclic C5Hydrocarbon and optionally cyclopentadiene. As used herein, "cyclopentadiene intermediates" refers to pentenes, pentadienes, cyclopentanes, and cyclopentenes. In various aspects, the conversion to cyclopentadiene occurs in the at least one adiabatic reaction zone. Preferably at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 30%, or at least about 40% of the acyclic C5The hydrocarbon is converted to a cyclopentadiene intermediate. Preferably, the feed (e.g., acyclic C)5Hydrocarbons) can be controlled in the following ranges of weight hourly space velocity (WHSV, acyclic C)5Mass of hydrocarbon/mass of catalyst/hour) is fed to the adiabatic reaction zone: about 1.0 to about 1000.0hr-1. The WHSV may be in The range of about 1.0 to about 900.0hr-1About 1.0 to about 800.0hr-1About 1.0 to about 700.0hr-1About 1.0 to about 600.0hr-1About 1.0 to about 500.0hr-1About 1.0 to about 400.0hr-1About 1.0 to about 300.0hr-1About 1.0 to about 200.0hr-1About 1.0 to about 100.0hr-1About 1.0 to about 90.0hr-1About 1.0 to about 80.0hr-1About 1.0 to about 70.0hr-1About 1.0 to about 60.0hr-1About 1.0 to about 50.0hr-1About 1.0 to about 40.0hr-1About 1.0 to about 30.0hr-1About 1.0 to about 20.0hr-1About 1.0 to about 10.0hr-1About 1.0 to about 5.0hr-1About 2.0 to about 1000.0hr-1About 2.0 to about 900.0hr-1About 2.0 to about 800.0hr-1About 2.0 to about 700.0hr-1About 2.0 to about 600.0hr-1About 2.0 to about 500.0hr-1About 2.0 to about 400.0hr-1About 2.0 to about 300.0hr-1About 2.0 to about 200.0hr-1About 2.0 to about 100.0hr-1About 2.0 to about 90.0hr-1About 2.0 to about 80.0hr-1About 2.0 to about 70.0hr-1About 2.0 to about 60.0hr-1About 2.0 to about 50.0hr-1About 2.0 to about 40.0hr-1About 2.0 to about 30.0hr-1About 2.0 to about 20.0hr-1About 2.0 to about 10.0hr-1And about 2.0 to about 5.0hr-1. Preferably, the WHSV is in the range of about 1.0 to about 100.0hr-1More preferably from about 1.0 to about 60.0hr-1More preferably from about 2.0 to about 40.0hr-1More preferably from about 2.0 to about 20.0hr-1。
A first effluent (e.g., cyclopentadiene, unconverted acyclic C) exiting the adiabatic reaction zone at an effluent outlet5Hydrocarbons) may be less than or equal to about 600 deg.C, less than or equal to about 575 deg.C, less than or equal to about 550 deg.C, less than or equal to about 525 deg.C, less than or equal to about 500 deg.C, less than or equal to about 475 deg.C, less than or equal to about 450 deg.C, less than or equal to about 425 deg.C, less than or equal to about 400 deg.C, less than or equal to about 375 deg.C, less than or equal to about 350 deg.C, less than or equal to about 325 deg.C, less than or equal to about 300 deg.C, less than or equal to about 275 deg.. Preferably, the first effluent (e.g., cyclopentadiene, unconverted acyclic C) exiting the adiabatic reaction zone at an effluent outlet5Hydrocarbons) is less than or equal to about 525 deg.C, more preferably less than or equal to about 500 deg.C, more preferably less than or equal to about 475 deg.C, more preferably less than or equal to about 450 deg.C.Specifically disclosed temperature ranges include combinations of any of the above values, e.g., from about 200 ℃ to about 600 ℃, from about 250 ℃ to about 575 ℃, from about 350 ℃ to about 550 ℃, from about 375 ℃ to about 450 ℃, and the like. Preferably, the first effluent (e.g., cyclopentadiene, unconverted acyclic C) exiting the adiabatic reaction zone at an effluent outlet5Hydrocarbons) from about 200 ℃ to about 600 ℃, more preferably from about 250 ℃ to about 575 ℃, more preferably from about 350 ℃ to about 550 ℃, more preferably from about 375 ℃ to about 500 ℃.
Additionally or alternatively, the reaction conditions in the adiabatic reaction zone may include a temperature of greater than or equal to about 300 ℃, < greater than or equal to about 325 ℃, < greater than or equal to about 350 ℃, < greater than or equal to about 375 ℃, < greater than or equal to about 400 ℃, < greater than or equal to about 425 ℃, < greater than or equal to about 450 ℃, < greater than or equal to about 475 ℃, < greater than or equal to about 500 ℃, < greater than or equal to about 525 ℃, < greater than or equal to about 550 ℃, < greater than or equal to about 575 ℃, < greater than or equal to about 600 ℃, <. Additionally or alternatively, the temperature can be less than or equal to about 300 ℃, < less than or equal to about 325 ℃, < less than or equal to about 350 ℃, < less than or equal to about 375 ℃, < less than or equal to about 400 ℃, < less than or equal to about 425 ℃, < less than or equal to about 450 ℃, < less than or equal to about 475 ℃, < less than or equal to about 500 ℃, < less than or equal to about 525 ℃, < less than or equal to about 550 ℃, < less than or equal to about 575 ℃, < less than or equal to about 600 ℃, < less than or equal to about 625. Specifically disclosed temperature ranges include combinations of any of the above values, for example, from about 300 ℃ to about 700 ℃, from about 325 ℃ to about 650 ℃, and from about 450 ℃ to about 600 ℃, and the like. Preferably, the temperature may be from about 300 ℃ to about 650 ℃, more preferably from about 325 ℃ to about 600 ℃, more preferably from about 450 ℃ to about 575 ℃.
Additionally or alternatively, the reaction conditions in the adiabatic reaction zone may include a pressure of less than or equal to about 1.0psia, less than or equal to about 2.0psia, less than or equal to about 3.0psia, less than or equal to about 4.0psia, less than or equal to about 5.0psia, less than or equal to about 10.0psia, less than or equal to about 15.0psia, less than or equal to about 20.0psia, less than or equal to about 25.0psia, less than or equal to about 30.0psia, less than or equal to about 35.0psia, less than or equal to about 40.0psia, less than or equal to about 45.0psia, less than or equal to about 50.0psia, less than or equal to about 55.0psia, less than or equal to about 60.0psia, less than or equal to about 65.0psia, less than or equal to about 70.0psia, less than or equal to about 75.0psia, less than or equal to about 80.0psia, less than or equal to about 85.0psia, less than or equal to about 90.0psia, less than or equal to about 95.0psia, less than or equal to about 100.0psia, less than or equal to about 100. Additionally or alternatively, the pressure may be greater than or equal to about 1.0psia, greater than or equal to about 2.0psia, greater than or equal to about 3.0psia, greater than or equal to about 4.0psia, greater than or equal to about 5.0psia, greater than or equal to about 10.0psia, greater than or equal to about 15.0psia, greater than or equal to about 20.0psia, greater than or equal to about 25.0psia, greater than or equal to about 30.0psia, greater than or equal to about 35.0psia, greater than or equal to about 40.0psia, greater than or equal to about 45.0psia, greater than or equal to about 50.0psia, greater than or equal to about 55.0psia, greater than or equal to about 60.0psia, greater than or equal to about 65.0psia, greater than or equal to about 70.0psia, greater than or equal to about 75.0psia, greater than or equal to about 80.0psia, greater than or equal to about 85.0psia, greater than or equal to about 90.0psia, greater than or equal to about 95.0psia, greater than or equal to about 100.0psia, greater than or. Ranges and combinations of temperatures and pressures specifically disclosed include combinations of any of the above values, for example, from about 1.0psia to about 200.0psia, from about 2.0psia to about 175.0psia, from about 3.0psia to about 150.0psia, and the like. Preferably, the pressure may be from about 1.0psia to about 200.0psia, more preferably from about 2.0psia to about 175.0psia, such as from about 2.0psia to about 100.0psia, more preferably from about 3.0psia to about 150.0psia, such as from about 3.0psia to about 50.0 psia.
Additionally or alternatively, the varying pressure across the adiabatic reaction zone (pressure at the feed inlet minus pressure at the outlet of the effluent) may be greater than or equal to about 0.5psia, greater than or equal to about 1.0psia, greater than or equal to about 2.0psia, greater than or equal to about 3.0psia, greater than or equal to about 4.0psia, greater than or equal to about 5.0psia, greater than or equal to about 10.0psia, greater than or equal to about 14.0psia, greater than or equal to about 15.0, psia, greater than or equal to about 20.0psia, greater than or equal to about 24.0psia, greater than or equal to about 25.0psia, greater than or equal to about 30.0psia, greater than or equal to about 35.0psia, greater than or equal to about 40.0, greater than or equal to about 45.0psia, greater than or equal to about 50.0psia, greater than or equal to about 55.0psia, greater than or equal to about 60.0psia, greater than or equal to about 65.0psia, greater than or equal to about 70.0psia, greater than or equal to about 75.0psia, greater than or equal to about 80.0psia, greater than or equal to about 85.0psia, greater than or equal to about 100.0psia, greater than or equal to about 100. As understood herein, "at the feed inlet," "at the effluent outlet," and "at the outlet" include spaces in and generally around the inlet and/or outlet. Additionally or alternatively, the varying pressure (or pressure drop) across the adiabatic reaction zone (the pressure at the feed inlet minus the pressure at the effluent outlet) may be less than or equal to about 2.0psia, less than or equal to about 3.0psia, less than or equal to about 4.0psia, less than or equal to about 5.0psia, less than or equal to about 10.0psia, less than or equal to about 14.0psia, less than or equal to about 15.0, psia less than or equal to about 20.0psia, less than or equal to about 24.0psia, less than or equal to about 25.0psia, less than or equal to about 30.0psia, less than or equal to about 35.0psia, less than or equal to about 40.0psia, less than or equal to about 45.0psia, less than or equal to about 50.0psi, less than or equal to about 55.0psia, less than or equal to about 60.0psia, less than or equal to about 65.0psia, less than or equal to about 70.0psia, less than or equal to about 75.0psia, less than or equal to about 80.0psia, less than or equal to about 85.0psia, less than or equal to about 90.0psia, less than or equal to about 0psia, less than or equal to about 100psia, less than or equal to about 0. Ranges of varying pressures expressly disclosed include any combination of the above listed values, for example, from about 10psia to about 70.0psia, from about 20.0psia to about 60.0psia, from about 30.0psia to about 50.0psia, and the like.
Additionally or alternatively, comprises C1，C2，C3And/or C4A light hydrocarbon stream of hydrocarbons may be supplied to the adiabatic reaction zone. The light hydrocarbon stream may include saturated and/or unsubstituted hydrocarbons. Preferably, a light hydrocarbon stream is recovered from the heat transfer reactor effluent stream.
C. Heat transfer reaction zone
After exiting the at least one adiabatic reaction zone, the first effluent may be provided to the at least one diabatic reaction zone and contacted with a second particulate material comprising a catalyst material in the at least one diabatic reaction zone under reaction conditions to contact at least a portion of the cyclopentadiene intermediates and/or unconverted acyclic C5The hydrocarbons are converted to a second effluent comprising cyclopentadiene. The at least one diabatic reaction zone can be a circulating fluidized bed reactor, a circulating settled bed reactor, a fixed bed reactor, an annular fixed bed reactor, a fluidized bed reactor, a fired tube reactor (as described in USSN62/250,693, filed 11/4/2015, which is incorporated herein by reference) or an a-convection heated tube reactor (as described in USSN62/250,674, filed 11/4/2015, which is incorporated herein by reference). The fixed bed reactor can be a vertical fixed bed or a horizontal fixed bed. Preferably, the vertical fixed bed is an axial flow vertical fixed bed or a radial flow fixed bed. Preferably, the horizontal fixed bed is a cross-flow horizontal fixed bed. In addition, the circulating fluidized bed reactor may be operated in a bubbling or turbulent Fluidization mode, as described in Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston,1991 and Walas, S.M., Chapter 6 of Chemical Process Equipment, reviewed 2nd Edition,Butterworth-Heinemann,Boston,2010。
In particular, the at least one diabatic reaction zone can be a fired tube reactor or a convectively heated tube reactor.
The combustion conduit reactor may include a furnace and parallel reactor conduits located within the radiant section of the furnace. Although any known radiant furnace reactor tube configuration may be used, preferably the furnace comprises a plurality of parallel reactor tubes. Suitable furnace reactor conduit configurations include those described in US5,811,065; US5,243,122; US 4,973,778; US 2012/0060824; and those of US 2012/0197054, all of which are incorporated herein by reference.
The reactor tubes may be positioned in the furnace in any configuration. Preferably the reactor tubes are positioned vertically so that the feed enters the top of the reactor tubes and the product exits the reactor tubes with the reactor effluent. Preferably, the reactor tubes are straight, rather than having a spiral or curved path along the radial furnace (although spiral or curved tubes may also be used). Additionally, the conduits may have a cross-section that is circular, elliptical, rectangular, and/or other known shapes. The reactor tubes may be heated with radiant heat provided from at least one burner located within the radiant section of the furnace. Any burner type known in the art may be used, for example, top, side and floor mounted burners. Preferably, the burner can be positioned to provide a higher heat flux near the reactor tube inlet and a lower heat flux near the reactor tube outlet. If the reactor tube is vertically positioned, the burner is preferably positioned near the top inlet of the reactor tube and has a flame that burns down the length of the tube. Positioning the burner near the top of the vertical reactor tube and burning down provides a higher heat flux near the reactor tube inlet (top) where higher heating is desired, for example, to provide heat of reaction, and sensible heat is required to heat the feed to the desired reaction temperature.
The furnace may optionally further comprise one or more shields positioned to block radiation from at least a portion of the burner flames of the outlet portion of the reactor tubes where a lower heat flux is desired to avoid temperatures above a desired temperature, e.g., a temperature that promotes undesirable coking and/or cracking that occurs at temperatures above a desired conversion condition temperature range at a given catalyst, operating pressure, and residence time. The at least one shield may be positioned to block at least a portion of the flame radiation from the bottom portion of the reactor tube if the reactor tube is positioned vertically relative to the downward firing burner. Preferably, the shield may be a flue gas duct, the function of which is to guide flue gases generated by the burner away from the radiant section of the furnace.
In addition, the reactor conduit contains a particulate material containing a catalyst material. The particulate material may be coated on the inner surface of the reactor tube or may be part of a fixed bed of particulate material within the reactor tube. Preferably, the reactor tubes contain a fixed bed of granular material. Suitable methods of packing and/or designing a fixed bed of reactor tubes include US 8,178,075 and WO 2014/053553, which are incorporated by reference in their entirety. The reactor tubes may include at least one internal structure, e.g., concentric shells, to support the granular material and/or reduce pressure drop within the reactor tubes. Additionally or alternatively, the reactor tube may include internal structures positioned within the reactor tube to provide mixing in a radial direction. The mixing internals may be positioned within the bed of granular material or in portions of the reactor conduit separating two or more zones of granular material. Additionally or alternatively, the reactor tubes may include fins or formations on the inside or outside of the reactor tubes that promote heat transfer from the tube walls to the catalyst composition. The fins or formations may be positioned to provide a higher heat flux near the inlet of the reactor tube and a lower heat flux near the outlet of the reactor tube. Examples of suitable internal structures include various baffles, sheds, trays, tubes, rods, fins, shapes and/or distributors. These internal structures may be coated with a catalyst. Suitable internal structures may be metallic or ceramic. Preferred ceramics are those having high thermal conductivity, for example, silicon carbide, aluminum nitride, boron carbide and silicon nitride. Preferably, the reactor tubes have a pressure drop measured from the reactor inlet to the reactor outlet of less than 20psi, more preferably less than 5psi, during contacting of the feed with the catalyst composition.
Additionally or alternatively, the furnace may include a radiant section, a convection section, and a stack of flue gases. Hot flue gas may be generated by at least one burner in the radiant section of the furnace and directed to the atmosphere through the convection section and out of the stack of flue gas. Heat from the flue gas can be transferred by convection from the flue gas to heat various streams, e.g., feed, steam, regeneration gas, steam fuel preheating and/or combustion air preheating, through heat exchangers or tube bundles spanning the convection section. The convection section of the furnace may contain at least one heat exchanger or tube bundle in which flue gas heat is transferred by convection to the feed and/or steam.
Additionally or alternatively, a plurality of furnaces may be present, for example, two or more furnaces (each furnace may include a radiant section comprising parallel reactor tubes containing a particulate material comprising a catalyst material). Optionally, there may be a single convection section and stack of flue gases in fluid communication with two or more radiant sections of the furnace. When there are one or more furnaces, a reheating gas or a regeneration gas can be supplied to the one or more furnaces while containing acyclic C5The hydrocarbon feed may be provided to a different furnace or furnaces.
A convection heated tube reactor may comprise a plurality of parallel reactor tubes within a convection heat transfer housing. Preferably, the reactor tubes are straight, rather than having a spiral or curved path along the shell (although spiral or curved tubes may also be used). Additionally, the conduits may have a cross-section that is circular, elliptical, rectangular, and/or other known shapes. Advantageously, the conduit has a small cross-sectional dimension to minimize cross-sectional temperature gradients. However, reducing the cross-sectional size of the tubing increases the number of tubing for a given production rate. Therefore, the optimal pipe size selection is preferably optimized in consideration of minimizing the cross-sectional temperature gradient and minimizing the construction cost. Suitable cross-sectional dimensions (i.e. the diameter of the cylindrical pipe) may be from 1cm to 20cm, more preferably from 2cm to 15cm and most preferably from 3cm to 10 cm.
In a convection-heated tube reactor, the reactor tubes may be heated by a turbine exhaust stream produced by a turbine combusting a fuel gas and a compressed gas comprising oxygen. In other aspects, the reactor tubes may be heated by convection of hot gases produced by combustion in a fuel cell, furnace, boiler, or excess air burner. However, heating the reactor tubes with turbine exhaust gas is preferred because of other advantages such as the ability to co-generate power.
The compressed gas comprising oxygen may be compressed in at least one compressor. Preferably, the compressed gas is compressed air. Optionally, the compressed gas may comprise oxygen-enriched air obtained by partial separation of nitrogen. Any compressor and/or turbine known in the art may be used. Examples of suitable compressors and turbines for use in the methods and systems described herein are described in US 7,536,863, which is incorporated herein by reference. Preferably, the turbine additionally produces power. The turbine power may be used to operate the compressor to compress a compressed gas comprising oxygen. Optionally, there may be a generator and/or an additional compressor that may operate with the power generated by the turbine. The generator may also generate electrical power.
Heat may be transferred to the outer surface of the reactor tube wall by convection from the turbine exhaust stream. The reactor tubes may be positioned in the housing in any configuration. Preferably the reactor conduit is positioned within the housing to provide co-current feed and turbine exhaust. The feed and the turbine exhaust stream may flow in the same direction to provide a higher heat flux near the inlet of the reactor tube than near the outlet of the reactor tube. Higher heating near the reactor tube inlet is desirable, for example, to provide heat for the reaction, as well as heat to heat the feed to the desired reaction temperature. A lower heat flux (relative to the amount of heat flux at the inlet) near the exit portion of the reactor tube is desirable to avoid temperatures above that desired, e.g., temperatures that promote undesirable coking and/or cracking that occurs at temperatures above the desired conversion condition temperature range for a given catalyst, operating pressure, and residence time.
There may be at least one combustion device capable of inputting additional heat into the turbine exhaust stream. Additional heat may be provided to the turbine exhaust stream upstream or downstream of the reactor tubes by combustion equipment. Additional fuel gas may be combusted with unreacted oxygen in the turbine exhaust stream to increase the temperature of the turbine exhaust stream before or after heat transfer by convection from the turbine exhaust stream to the reactor tube walls. Additional heat input may be provided to the turbine exhaust stream by any combustion device known in the art. Examples of suitable combustion devices include duct burners, auxiliary burners, or other devices known for auxiliary heating of flue gases.
The convectively heated reactor tubes contain a particulate material comprising a catalyst material. The particulate material may be coated on the inner surface of the reactor tube or may be part of a fixed bed of particulate material within the reactor tube. Preferably, the reactor tubes comprise a fixed bed of granular material. Suitable methods of packing and/or designing a fixed bed of reactor tubes include US 8,178,075, which is incorporated by reference in its entirety. The reactor tubes may include at least one internal structure, e.g., concentric shell, to support the granular material and/or reduce pressure drop within the reactor tubes. The reactor tube may include internal structures positioned within the reactor tube to provide mixing in a radial direction. The mixing internals may be positioned within the bed of granular material or in portions of the reactor conduit separating two or more zones of granular material. The reactor tubes may include fins or formations on the inside or outside of the reactor tubes that facilitate heat transfer from the tube walls to the granular material. The fins or formations may be positioned to provide a higher heat flux near the inlet than near the outlet of the reactor tube. Examples of suitable internal structures include various baffles, sheds, trays, tubes, rods, fins, shapes and/or distributors. These internal structures may be coated with a catalyst. Suitable internal structures may be metallic or ceramic. Preferred ceramics are those having high thermal conductivity, for example, silicon carbide, aluminum nitride, boron carbide and silicon nitride. Preferably, the reactor tubes have a pressure drop measured from the reactor inlet to the reactor outlet of less than 20psi, more preferably less than 5psi, during contacting of the feed with the catalyst composition.
Additionally or alternatively, a heat transfer device may be present to transfer additional amounts of heat by convection from the turbine exhaust to other streams, such as, for example, regeneration gas, feed (before the feed enters the reactor tubes), fuel gas, a gas stream comprising oxygen (e.g., a compressed gas stream), and/or steam. The additional heat transfer device may be any suitable heat transfer device known in the art. Suitable heat transfer devices include heat exchanger tube bundles. A heat transfer device may be positioned at the reactor tube housing such that additional heat is transferred from the turbine exhaust gas before or after heat is transferred from the turbine exhaust gas to the reactor tube.
Additionally or alternatively, there may be two or more parallel reactor tubes within the convective heat transfer housing. For example, there may be two or more housings, each housing containing a plurality of parallel reactor tubes containing granular material. There may also be a flow control device that controls the flow of turbine exhaust gas to each of the plurality of reactor tubes. Suitable flow control devices include control valves, baffles, louvers, dampers, and/or conduits. It may further include diverting at least a portion of the turbine exhaust gas away from or around the reactor conduit and directing the turbine exhaust gas to other heat recovery equipment or to an exhaust stack. Auxiliary equipment such as exhaust gas mufflers and scrapers may also be present.
Additionally or alternatively, the at least one diabatic reaction zone may include at least a first diabatic reaction zone, a second diabatic reaction zone, a third diabatic reaction zone, a fourth diabatic reaction zone, a fifth diabatic reaction zone, a sixth diabatic reaction zone, a seventh diabatic reaction zone, and/or an eighth diabatic reaction zone, and the like. As understood herein, each diabatic reaction zone can be a separate reactor or a diabatic reactor can include one or more of the diabatic reaction zones. Preferably, the reactor system comprises from 1 to 20 diabatic reaction zones, more preferably from 1 to 15 diabatic reaction zones, more preferably from 1 to 10 diabatic reaction zones, more preferably from 1 to 8 diabatic reaction zones. When there are more than 1 heat transfer reaction zone, the heat transfer reaction zones may be arranged in any suitable configuration, for example, in series or in parallel, as above one or more adiabatic reaction zones. Each diabatic reaction zone independently can be a circulating fluidized bed reactor, a circulating settled bed reactor, a fixed bed reactor, an annular fixed bed reactor, a fluidized bed reactor, a fired tube reactor, or a convection-heated tube reactor. Additionally or alternatively, the processes described herein may further comprise moving a majority of the partially converted feed from the first diabatic reaction zone to the second diabatic reaction zone and/or moving a majority of the particulate material from the second diabatic reaction zone to the first diabatic reaction zone. As used herein, "a majority" refers to at least a major portion of the partially converted feed and the particulate material, e.g., at least about 50.0 wt%, at least about 60.0 wt%, at least about 70.0 wt%, at least about 80.0 wt%, at least about 90.0 wt%, at least about 95.0 wt%, at least about 99.0 wt%, and at least about 100.0 wt% of the portion.
The diabatic reaction zone may include at least one internal structure to support the first particulate material to evenly distribute the feed to collect hydrocarbon products and/or reduce pressure drop within the reaction zone. For example, when the diabatic reaction zone is a vertical fixed bed, one or more internal structures, e.g., a permeable concentric shell, can be included in the reaction zone to contain and support the granular material, and the feed can be fed into the substantially open central axial portion of the reaction zone and flow radially around the granular material. Additionally or alternatively, the diabatic reaction zone can 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 various support grids, hold-down grids, baffles, sheds, trays, tubes, rods, and/or distribution bodies.
The first effluent (e.g., cyclopentadiene intermediates, unconverted acyclic C)5Hydrocarbon and optionally cyclopentadiene) can be supplied to a temperature at T2Heat transfer reaction zone of, T2Less than about 700 deg.C, less than about 675 deg.C, less than about 650 deg.C, less than about 625 deg.C, less than about 600 deg.C, less than about 575 deg.C, less than about 550 deg.C, less than about 525 deg.C, less than about 500 deg.C, less than about 475 deg.C, less than about 450 deg.C, less than about 425 deg.C, less than about 400 deg.C, less than about 375 deg.C, less than about 350 deg.C, less than about 325 deg.C, less than about 300 deg.C, less than about 275 deg.C, less than about 250 deg.C, less than about 225 deg.C, or less than about 200 deg.C. Preferably, the first effluent (e.g., cyclopentadiene intermediate) entering the diabatic reaction zoneUnconverted acyclic C5The hydrocarbon and optionally the cyclopentadiene) is less than or equal to about 575 deg.c, more preferably less than or equal to about 550 deg.c, more preferably less than or equal to about 525 deg.c, more preferably less than or equal to about 500 deg.c. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., from about 200 ℃ to about 700 ℃, from about 250 ℃ to about 600 ℃, from about 350 ℃ to about 650 ℃, from about 375 ℃ to about 500 ℃, and the like. Preferably, the temperature of the first effluent entering the diabatic reaction zone (e.g., cyclopentadiene intermediates, unconverted acyclic C's)5The hydrocarbon and optionally cyclopentadiene) is from about 200 ℃ to about 700 ℃, more preferably from about 300 ℃ to about 600 ℃, more preferably from about 400 ℃ to about 550 ℃, more preferably from about 475 ℃ to about 525 ℃. Providing the first effluent (e.g., cyclopentadiene intermediates, unconverted acyclic C) at the above-described temperature5Hydrocarbons and optionally cyclopentadiene) can advantageously minimize C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) before they can react in the presence of the catalyst material in the diabatic reaction zone.
Additionally or alternatively, the first effluent (e.g., cyclopentadiene intermediate, unconverted acyclic C) is passed to a diabatic reaction zone5Hydrocarbons and optionally cyclopentadiene) are heated to the above-described temperatures by one or more heating devices (e.g., heat exchangers), including heating in the convection section of the furnace.
The at least one diabatic reaction zone is operated under reaction conditions sufficient to convert at least a portion of the first effluent to cyclopentadiene. Preferably, the first effluent may be treated at a weight hourly space velocity (WHSV, acyclic C) in the range below5Mass of hydrocarbon/mass of catalyst/hour) is fed to the diabatic reaction zone: about 1.0 to about 1000.0hr-1. The WHSV may be in the range of about 1.0 to about 900.0hr-1About 1.0 to about 800.0hr-1About 1.0 to about 700.0hr-1About 1.0 to about 600.0hr-1About 1.0 to about 500.0hr-1About 1.0 to about 400.0hr-1About 1.0 to about 300.0hr-1About 1.0 to about 200.0hr-1About 1.0 to about 100.0hr-1About 1.0 to about 90.0hr-1About 1.0 to about 80.0hr-1About 1.0 to about 70.0hr-1About 1.0 to about 60.0hr-1About 1.0 to about 50.0hr-1About 1.0 to about 40.0hr-1About 1.0 to about 30.0hr-1About 1.0 to about 20.0hr-1About 1.0 to about 10.0hr-1About 1.0 to about 5.0hr-1About 2.0 to about 1000.0hr-1About 2.0 to about 900.0hr-1About 2.0 to about 800.0hr-1About 2.0 to about 700.0hr-1About 2.0 to about 600.0hr-1About 2.0 to about 500.0hr-1About 2.0 to about 400.0hr-1About 2.0 to about 300.0hr-1About 2.0 to about 200.0hr-1About 2.0 to about 100.0hr-1About 2.0 to about 90.0hr-1About 2.0 to about 80.0hr-1About 2.0 to about 70.0hr-1About 2.0 to about 60.0hr-1About 2.0 to about 50.0hr-1About 2.0 to about 40.0hr-1About 2.0 to about 30.0hr-1About 2.0 to about 20.0hr-1About 2.0 to about 10.0hr-1And about 2.0 to about 5.0hr-1. Preferably, the WHSV is in the range of about 1.0 to about 100.0hr-1More preferably from about 1.0 to about 60.0hr-1More preferably from about 2.0 to about 40.0hr-1More preferably from about 2.0 to about 20.0hr-1。
In addition, it is preferred that a substantially isothermal or reverse temperature profile be maintained in the at least one diabatic reaction zone. As used herein, the "isothermal temperature profile" of the at least one diabatic reaction zone means that the temperature of the at least one diabatic reaction zone remains substantially constant, e.g., the difference between the upper and lower temperature limits does not exceed about 40 ℃ at the same temperature or within the same narrow temperature range; more preferably no more than about 20 deg.c. An advantage of maintaining a substantially isothermal temperature profile may be increased product yield due to acyclic C5Hydrocarbons to lighter hydrocarbons (C)4-) Cracking of the by-products is reduced.
As used herein, the "reverse temperature profile" of the at least one diabatic reaction zone means that the temperature at the inlet of the diabatic reaction zone is lower than the temperature at the outlet of the diabatic reaction zone. "reverse temperature profile" may also include a point within the at least one diabatic reaction zone having a temperature that is lower than the temperature at the inlet of the diabatic reaction zone, so long as the temperature at the inlet of the diabatic reaction zone is lower than the temperature at the outlet of the diabatic reaction zone. In other words, when the first effluent (e.g., cyclopentadiene, Do not)Converted acyclic C5Hydrocarbons), the temperature of the at least one diabatic reaction zone can increase from a bottom portion to a top portion of the at least one diabatic reaction zone. Conversely, the temperature of the at least one diabatic reaction zone can decrease from a top portion to a bottom portion of the at least one diabatic reaction zone. Maintaining a reverse temperature profile in the at least one diabatic reaction zone can advantageously minimize the formation of coked carbonaceous material at the inlet that can contribute to the catalyst material. The reverse temperature profile may also provide sufficient reaction time and length in the at least one diabatic reaction zone to produce a sufficient amount of H at an operating temperature below the exit temperature2This can minimize the formation of carbonaceous material at the product outlet.
In particular, for a fired tube reactor and/or a convectively heated tube reactor, while providing a higher heat flux near the reactor tube inlet and a lower heat flux or shield near the reactor tube outlet, a substantially isothermal temperature profile measured along the centerline of the reactor tube may still be provided. However, it may be preferred to optimize the reactor tube design so that a substantially reversed temperature profile may be maintained in the reactor tube. The advantage of a substantially isothermal temperature profile is to maximize the efficient use of the catalyst and minimize the undesirable C4-The production of by-products.
Preferably, the isothermal temperature profile is a profile wherein the reactor inlet temperature is within plus or minus about 40 ℃, alternatively within about 20 ℃, alternatively within about 10 ℃, alternatively within about 5 ℃ of the reactor outlet temperature, alternatively the reactor inlet temperature is the same as the reactor outlet temperature. Alternatively, an isothermal temperature profile is one in which the reactor inlet temperature is within plus or minus about 20%, alternatively within about 10%, alternatively within about 5%, alternatively within about 1% of the reactor outlet temperature.
Preferably, the isothermal temperature profile is one in which the temperature along the length of the reaction zone within the reactor varies by no more than about 40 ℃, alternatively no more than about 20 ℃, alternatively no more than about 10 ℃, alternatively no more than about 5 ℃ as compared to the reactor inlet temperature. Alternatively, an isothermal temperature profile is a profile in which the temperature along the length of the reaction zone within the reactor is within plus or minus about 20% of the reactor inlet temperature, alternatively within plus or minus about 10%, alternatively within about 5%, alternatively within about 1% of the reactor inlet temperature.
However, to minimize the catalyst deactivation rate, it may be preferable to optimize the reactor tube design so that a substantially reversed temperature profile may be maintained in the reactor tubes.
For a fired-tube reactor, a convectively heated tube reactor and/or an annular fixed-bed reactor, a "reverse temperature profile" includes a system in which the temperature changes in the reactor tube or in the fixed-bed reactor, as long as the temperature at the inlet of the reactor tube or at the inlet of the annular fixed-bed reactor is lower than the temperature at the outlet of the reactor tube or at the outlet of the annular fixed-bed reactor. "reverse temperature profile" further encompasses: the reactor tube or annular fixed bed reactor has a centerline temperature Ta(ii) a At a certain length along the reactor tube or the annular fixed bed reactor, the temperature of the center line is reduced to a temperature Tb(ii) a At a further length along the reactor tube or annular fixed bed reactor, the centerline temperature rises to a temperature Tc(ii) a Finally, the temperature of the central line at the outlet of the reactor tube or at the outlet of the annular fixed-bed reactor is reduced to a temperature Td(ii) a Wherein T isc>Td>Ta>Tb. The temperature measured near the inlet of the reactor tube where the feed first contacts the particulate material may be from about 0 ℃ to about 200 ℃, preferably from about 25 ℃ to about 150 ℃, more preferably from about 50 ℃ to about 100 ℃, lower than the temperature measured near the outlet of the reactor tube where the effluent exits contact with the particulate material. Preferably, the centerline temperature of the conduit, as measured near the conduit inlet where the feed first contacts the particulate material, can be from about 0 ℃ to about 200 ℃, preferably from about 25 ℃ to about 150 ℃, more preferably from about 50 ℃ to about 100 ℃, lower than the centerline temperature of the conduit, as measured near the outlet of the reactor conduit where the effluent exits contact with the particulate material.
The temperature of the second effluent (e.g., cyclopentadiene) exiting the diabatic reaction zone at the effluent outlet can be ≦ about 600 ℃, ≦ about 575 ℃, ≦ about 550 ≦ about 525 ≦ about 500 ℃, ≦ about 475 ℃, ≦ about 450 ≦ about 425 ℃, ≦ about 400 ≦ about 375 ℃, ≦ about 350 ≦ about 325 ℃, ≦ about 300 ≦ about 275 ≦ about 250 ℃, ≦ about 225 ℃ or ≦ about 200 ℃. Preferably, the temperature of the second effluent (e.g., cyclopentadiene) exiting the diabatic reaction zone at the effluent outlet is less than or equal to about 550 deg.C, more preferably less than or equal to about 575 deg.C, more preferably less than or equal to about 600 deg.C. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., from about 200 ℃ to about 600 ℃, from about 250 ℃ to about 575 ℃, from about 350 ℃ to about 550 ℃, from about 375 ℃ to about 450 ℃, and the like. Preferably, the first effluent (e.g., cyclopentadiene, unconverted acyclic C) exiting the diabatic reaction zone at the effluent outlet5Hydrocarbons) from about 200 ℃ to about 600 ℃, more preferably from about 250 ℃ to about 575 ℃, more preferably from about 350 ℃ to about 550 ℃, more preferably from about 375 ℃ to about 450 ℃.
Additionally or alternatively, the reaction conditions in the diabatic reaction zone can include a temperature of greater than or equal to about 300 ℃, < greater than or equal to about 325 ℃, < greater than or equal to about 350 ℃, < greater than or equal to about 375 ℃, < greater than or equal to about 400 ℃, < greater than or equal to about 425 ℃, < greater than or equal to about 450 ℃, < greater than or equal to about 475 ℃, < greater than or equal to about 500 ℃, < greater than or equal to about 525 ℃, < greater than or equal to about 550 ℃, < greater than or equal to about 575 ℃, < greater than or equal to about 600 ℃, < greater than or equal to about 625 ℃, < greater than or equal to about 650 ℃, < greater than or equal to about 675 ℃, < about 700 ℃, < greater than or equal to about 725 ℃, < about 750 ≧ about 775 ≧ about 800 ℃, < about 825 ℃, < about 850 ℃. Additionally or alternatively, the temperature can be less than or equal to about 300 ℃, < less than or equal to about 325 ℃, < less than or equal to about 350 ℃, < less than or equal to about 375 ℃, < less than or equal to about 400 ℃, < less than or equal to about 425 ℃, < less than or equal to about 450 ℃, < less than or equal to about 475 ℃, < less than or equal to about 500 ℃, < less than or equal to about 525 ℃, < less than or equal to about 550 ℃, < less than or equal to about 575 ℃, < less than or equal to about 600 ℃, < less than or equal to about 625 ℃, < less than or equal to about 650 ℃, < less than or equal to about 675 ℃, < about 700 ℃, < less than or equal to about 725 ℃, < about 750 ℃, < about 775, < about 800 ℃, < about 825 ℃, < about 850 ℃, < about 875. Specifically disclosed temperature ranges include combinations of any of the above values, for example, from about 300 ℃ to about 900 ℃, from about 350 ℃ to about 850 ℃, and from about 400 ℃ to about 800 ℃, and the like. Preferably, the temperature may be from about 300 ℃ to about 900 ℃, more preferably from about 350 ℃ to about 850 ℃, more preferably from about 400 ℃ to about 800 ℃. Optionally, the at least one diabatic reaction zone may include one or more heating devices to maintain the temperature therein. Examples of suitable heating devices known in the art include, but are not limited to, combustion tubes, heated coils with high temperature heat transfer fluids, electric heaters, and/or microwave launchers. As used herein, "coil" refers to a structure placed within a vessel through which a heat transfer fluid transfers heat to the vessel contents. The coil may have any suitable cross-sectional shape and may be straight, including U-bends, including loops, and the like.
Additionally or alternatively, the reaction conditions in the diabatic reaction zone can include a pressure of less than or equal to about 1.0psia, less than or equal to about 2.0psia, less than or equal to about 3.0psia, less than or equal to about 4.0, less than or equal to about 5.0psia, less than or equal to about 10.0psia, less than or equal to about 15.0psia, less than or equal to about 20.0psia, less than or equal to about 25.0psia, less than or equal to about 30.0psia, less than or equal to about 35.0psia, less than or equal to about 40.0psia, less than or equal to about 45.0psia, less than or equal to about 50.0psia, less than or equal to about 55.0psia, less than or equal to about 60.0psia, less than or equal to about 65.0psia, less than or equal to about 70.0psia, less than or equal to about 75.0psia, less than or equal to about 80.0psia, less than or equal to about 85.0psia, less than or equal to about 90.0psia, less than or equal to about 95.0psia, less than or equal to about 100.0psia, less than or equal to about 100. Additionally or alternatively, the pressure may be greater than or equal to about 1.0psia, greater than or equal to about 2.0psia, greater than or equal to about 3.0psia, greater than or equal to about 4.0psia, greater than or equal to about 5.0psia, greater than or equal to about 10.0psia, greater than or equal to about 15.0psia, greater than or equal to about 20.0psia, greater than or equal to about 25.0psia, greater than or equal to about 30.0psia, greater than or equal to about 35.0psia, greater than or equal to about 40.0psia, greater than or equal to about 45.0psia, greater than or equal to about 50.0psia, greater than or equal to about 55.0psia, greater than or equal to about 60.0psia, greater than or equal to about 65.0psia, greater than or equal to about 70.0psia, greater than or equal to about 75.0psia, greater than or equal to about 80.0psia, greater than or equal to about 85.0psia, greater than or equal to about 90.0psia, greater than or equal to about 95.0psia, greater than or equal to about 100.0psia, greater than or. Ranges and combinations of temperatures and pressures specifically disclosed include combinations of any of the above values, for example, from about 1.0psia to about 200.0psia, from about 2.0psia to about 175.0psia, from about 3.0psia to about 150.0psia, and the like. Preferably, the pressure may be from about 1.0psia to about 200.0psia, more preferably from about 2.0psia to about 175.0psia, such as from about 2.0psia to about 100.0psia, more preferably from about 3.0psia to about 150.0psia, such as from about 3.0psia to about 50 psia.
Additionally or alternatively, the varying pressure across the diabatic reaction zone (pressure at the inlet of the first effluent minus pressure at the outlet of the second effluent) may be greater than or equal to about 0.5psia, greater than or equal to about 1.0psia, greater than or equal to about 2.0psia, greater than or equal to about 3.0psia, greater than or equal to about 4.0psia, greater than or equal to about 5.0psia, greater than or equal to about 10.0psia, greater than or equal to about 14.0psia, greater than or equal to about 15.0, psia, greater than or equal to about 20.0psia, greater than or equal to about 24.0psia, greater than or equal to about 25.0psia, greater than or equal to about 30.0psia, greater than or equal to about 35.0psia, greater than or equal to about 40.0, greater than or equal to about 45.0psia, greater than or equal to about 50.0psi, greater than or equal to about 55.0psia, greater than or equal to about 60.0psia, greater than or equal to about 65.0psia, greater than or equal to about 70.0psia, greater than or equal to about 75.0psia, greater than or equal to about 80.0psia, greater than or equal to about 100.0psia, greater than or equal to about 100psia, greater than or equal to about. As understood herein, "at the first effluent inlet" and "at the second effluent outlet" include spaces in and substantially surrounding the inlet and/or outlet. Additionally or alternatively, the varying pressure (or pressure drop) across the diabatic reaction zone (first effluent inlet pressure minus second effluent outlet pressure) may be less than or equal to about 2.0psia, less than or equal to about 3.0psia, less than or equal to about 4.0psia, less than or equal to about 5.0psia, less than or equal to about 10.0psia, less than or equal to about 14.0psia, less than or equal to about 15.0psia, less than or equal to about 20.0psia, less than or equal to about 24.0psia, less than or equal to about 25.0psia, less than or equal to about 30.0psia, less than or equal to about 35.0psia, less than or equal to about 40.0psia, less than or equal to about 45.0psia, less than or equal to about 50.0psi, less than or equal to about 55.0psia, less than or equal to about 60.0psia, less than or equal to about 65.0psia, less than or equal to about 70.0psia, less than or equal to about 75.0psia, less than or equal to about 80.0psia, less than or equal to about 85.0psia, less than or equal to about 90.0psia, less than or equal to about 0psia, less than or equal to about 100 psia. Specifically disclosed ranges of varying pressures include any combination of the above listed values, for example, from about 10psia to about 70.0psia, from about 20.0psia to about 60.0psia, from about 30.0psia to about 50.0psia, and the like.
Advantageously, the heat load of the at least one diabatic reaction zone can be reduced by about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, about 15.0%, about 20%, or about 25.0% cyclopentadiene produced per unit when compared to a process in which no adiabatic reaction zone is present. As understood herein, "heat duty" refers to the net amount of thermal energy delivered to the feed and effluent (i.e., reactants and products) to provide Δ H for the reaction and Δ H for the change in perceived temperature between the inlet and outlet of the diabatic reaction zone. Preferably, the heat load zone of the at least one heat transfer reaction can be reduced by about 3.0%, about 10.0%, about 15.0%, about 20%, or about 25.0% per unit of cyclopentadiene produced when compared to a process in which no adiabatic reaction zone is present. Preferably, the heat load of the at least one diabatic reaction zone can be reduced by about 2.0% to about 25.0%, about 4.0% to about 15.0%, or about 6.0% to about 10.0% per unit of cyclopentadiene produced when compared to a process in which the adiabatic reaction zone is not present.
Additionally or alternatively, hydrogen (H) is contained2) May be supplied to an adiabatic reaction zone and/or a diabatic reaction zone. Such a stream may include make-up hydrogen, which is hydrogen supplied in addition to any hydrogen produced in a zone prior to the reactor system. The hydrogen stream can be introduced into the adiabatic reaction zone and/or the diabatic reaction zone to minimize the production of coke material on the particulate material and/or to fluidize the particulate material in the adiabatic reaction zone and/or the diabatic reaction zone. Such a hydrogen-containing stream may contain light hydrocarbons (e.g., C)1-C4). Preferably, 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.
Additionally or alternatively, comprises C1，C2，C3And/or C4A light hydrocarbon stream of hydrocarbons may be fed to the adiabatic reaction zone and/or the diabatic reaction zone. The light hydrocarbon stream may include saturated and/or unsubstituted C1-C4A hydrocarbon. Such streams may include make-up light hydrocarbons, which are supplied in addition to any light hydrocarbons produced in a zone prior to the reactor system. The light hydrocarbon stream may be introduced into the adiabatic reaction zone and/or the diabatic reaction zone such that the total pressure of the second effluent stream has a C less than atmospheric pressure5The combined partial pressure of the hydrocarbons and the hydrogen partial pressure while maintaining the total pressure above atmospheric pressure. Preferably, the light hydrocarbon stream is supplied to an adiabatic reaction zone to provide additional heat capacity and to reduce C in the adiabatic reaction zone5The hydrocarbon partial pressure. Additionally or alternatively, the light hydrocarbon stream may containThere is hydrogen. Preferably, a light hydrocarbon stream is recovered from the heat transfer reactor effluent stream.
D. Granular material
Particulate materials (e.g., first particulate material, second particulate material) comprising a catalyst material (e.g., catalyst composition) are provided to the adiabatic reaction zone and the diabatic reaction zone to promote the C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) to cyclopentadiene and/or cyclopentadiene intermediates. In one aspect, the first effluent can flow in a direction counter-current to the direction of the flow of the second particulate material in the diabatic reaction zone. Additionally or alternatively, the first effluent may flow in a direction co-current to the direction of the flow of the second particulate material in the diabatic reaction zone. The first particulate material and the second particulate material may be the same or different.
Catalyst compositions useful for the first and/or second particulate materials include microporous crystalline metallosilicates (metallosilicates), such as crystalline aluminosilicates, crystalline ferrosilicates, or other metal-containing crystalline silicates (such as those in which the metal or metal-containing compound is dispersed in the crystalline silicate structure and may or may not be part of the crystalline framework). Microporous crystalline metallosilicate framework types that may be used herein as catalyst compositions include, but are not limited to, MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU.
In particular, suitable microporous metallosilicates for use herein include those of the following framework types: 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 group materials), wherein one or more metals from the periodic Table of elements from groups 8, 11 and 13 (preferably one or more of Fe, Cu, Ag, Au, B, Al, Ga and/or In) are incorporated into the crystalline structure during synthesis or post-crystallization impregnation. It will be appreciated that the metal silicate may have one or more metals present, and for example the material may be referred to as ferrosilicate, but it most likely still contains a small amount of aluminium.
The microporous crystalline metallosilicate preferably has a constraint index of less than 12, alternatively from 1 to 12, alternatively from 3 to 12. Aluminosilicates useful herein have a constraint index of less than 12, such as 1-12, alternatively 3-12, 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 from about 3 to about 12 and is ZSM-5.
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 US5,336,478. 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 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 indices and methods for their determination are described in US 4,016,218. The foregoing patents are incorporated by reference in their entirety.
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.
The MCM-22 family of materials includes 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 0293032), 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. The relevant zeolites included in this 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 suitable for use as molecular sieves in the MCM-22 family.
In one or more embodiments, the crystalline metallosilicate has a Si/M molar ratio (where M is a group 8, 11, or 13 metal) of greater than about 3, or greater than about 25, or greater than about 50, or greater than about 100, or greater than about 400, or in the range of from about 100 to about 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.
In one or more embodiments, the SiO of the crystalline aluminosilicate2/Al2O3The molar ratio is greater than about 3, or greater than about 25, or greater than about 50, or greater than about 100, or greater than about 400, or in the range of about 100 to about 400, or about 100 to about 500, or about 25 to about 2,000, or about 50 to about 1,500, or about 100 to about 1,200, or about 100 to about 1,000.
In another embodiment of the invention, a 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.
In one or more embodiments, the group 10 metal includes, or is selected from, Ni, Pd and Pt, preferably Pt. The catalyst composition has a group 10 metal content of at least 0.005 wt% based on the weight of the catalyst composition. In one or more embodiments, the group 10 content ranges from about 0.005 wt% to about 10 wt%, or from about 0.005 wt% to about 1.5 wt%, based on the weight of the catalyst composition.
In one or more embodiments, the group 1 alkali metal comprises, or is selected from, Li, Na, K, Rb, Cs, and mixtures of two or more thereof, preferably Na.
In one or more embodiments, the group 2 alkaline earth metal is selected from Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof.
In one or more embodiments, 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. In one or more embodiments, the group 2 alkaline earth metal is present as an oxide and the metal is selected from Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof. In one or more embodiments, 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 a group 2 alkaline earth metal is present as an oxide and the metal is selected from Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof.
In one or more embodiments, the group 11 metal comprises, or is selected from, silver, gold, copper, preferably silver or copper. The catalyst composition has a group 11 metal content of at least 0.005 wt% based on the weight of the catalyst composition. In one or more embodiments, the group 11 content ranges from about 0.005 wt% to about 10 wt%, or from about 0.005 wt% to about 1.5 wt%, based on the weight of the catalyst composition.
In one or more embodiments, the catalyst composition has an alpha value (measured prior to addition of the group 10 metal, preferably platinum) of less than 25, alternatively less than 15, alternatively from 1 to 25, alternatively from 1.1 to 15. Alpha values are 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 and varying flow rate measurement of 538 ℃ as described in detail in Journal of Catalysis, v.61, p.395 (1980).
In one or more embodiments of the aluminosilicate, the group 1 alkali metal to Al molar ratio is at least about 0.5, or at least about 0.5 to about 3, preferably at least about 1, more preferably at least about 2.
In one or more embodiments of the aluminosilicate, the group 2 alkali metal to Al molar ratio is at least about 0.5, or at least about 0.5 to about 3, preferably at least about 1, more preferably at least about 2.
In one or more embodiments, the molar ratio of the group 11 metal to the group 10 metal is at least about 0.1, or at least about 0.1 to about 10, preferably at least about 0.5, more preferably at least about 1. In one or more embodiments, the group 11 alkaline earth metal is present as an oxide and the metal is selected from the group consisting of gold, silver, and copper, and mixtures of two or more thereof.
In one or more embodiments, in the presence of n-pentane and an equimolar amount of H2Of the feed C5Under the conversion conditions, the temperature is in the range of about 550 ℃ to about 600 ℃, the partial pressure of n-pentane is 3-10psia and the weight hourly space velocity of n-pentane is 10-20hr-1The conversion provided using the catalyst composition of the invention is at least about 70%, or at least about 75%, or at least about 80%, orSaid acyclic C ranging from about 60% to about 80%5Feeding.
In one or more embodiments, in the presence of n-pentane and an equimolar amount of H2The temperature range of about 550 ℃ to about 600 ℃, the partial pressure of n-pentane in the range of 3-10psia and the weight hourly space velocity of n-pentane in the range of 10-20hr-1Is acyclic C5Para-cyclic C provided by any one of the catalyst compositions of the present invention under conversion conditions5The carbon selectivity of the compound is at least about 30%, or at least about 40%, or at least about 50%, or in the range of about 30% to about 80%.
In one or more embodiments, in the presence of n-pentane and an equimolar amount of H2The temperature range of about 550 ℃ to about 600 ℃, the partial pressure of n-pentane in the range of 3-10psia and the weight hourly space velocity of n-pentane in the range of 10-20hr-1Is acyclic C5The use of any of the catalyst compositions of the present 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 of from about 30% to about 80%, under conversion conditions.
The catalyst composition of the present invention can be combined with a matrix or binder material to make it resistant to attrition and to the harsh conditions to which it is exposed when used in hydrocarbon conversion applications. The combined composition can contain 1 to 99 wt% of the material of the invention, based on the total weight of the matrix (binder) and the material of the invention. The relative proportions of the microcrystalline material and matrix can vary widely and the crystalline content is from about 1 to about 90 weight percent, more typically, in the range of from about 2 to 80 weight percent of the composite, particularly when the composite is prepared in the form of beads, extrudates, pills, oil droplet-forming particles, spray-dried particles, and the like.
During use of the catalyst composition in the process of the present invention, coke may be deposited on the catalyst composition, such that such catalyst composition loses a portion of its catalytic activity and becomes deactivated. The deactivated catalyst composition can be regenerated by conventional techniques including high pressure hydrogen treatment and combustion of coke on the catalyst composition with an oxygen-containing gas.
Further suitable catalyst compositions comprise one or more group 6 metals, group 9 metals or group 10 metals, and optionally one or more group 1 alkali metals, group 2 alkaline earth metals and/or group 11 metals on an inorganic support. The group 6 metal includes, or is selected from, Cr, Mo and W. The group 9 metal includes, or is selected from, Co, Rh and Ir. The group 10 metal includes, or is selected from, Ni, Pd and Pt, preferably Pt. The inorganic support can be a zeolite selected from the group consisting of zeolites, silicoaluminophosphates (i.e., SAPOs), aluminophosphates (i.e., ALPOs), metalloaluminophosphates (i.e., MeAPO), silicas, zirconias, titanias, aluminas, magnesias, cerias, yttria, clays, magnesium hydrotalcites, calcium aluminates, zinc aluminates, and combinations thereof as described herein. In MeAPO, the metal (Me) may include, but is not limited to, Co, Fe, Mg, Mn, and Zn. In one or more embodiments, the group 1 alkali metal comprises, or is selected from, Li, Na, K, Rb, Cs, and mixtures of two or more thereof, preferably Na. In one or more embodiments, the group 2 alkaline earth metal is selected from Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof. In one or more embodiments, the group 11 metal comprises, or is selected from, silver, gold, copper, preferably silver or copper.
Useful catalyst compositions include crystalline aluminosilicates or ferrosilicates, optionally in combination with one, two or more additional metals or metal compounds. Preferred combinations include:
1) crystalline aluminosilicates (such as ZSM-5 or zeolite L) in combination with group 10 metals (such as Pt), group 1 alkali metals (such as sodium or potassium) and/or group 2 alkaline earth metals;
2) crystalline aluminosilicates (such as ZSM-5 or zeolite L) in combination with a group 10 metal (such as Pt) and a group 1 alkali metal (such as sodium or potassium);
3) crystalline aluminosilicates (such as iron silicate or iron treated ZSM-5) in combination with a group 10 metal (such as Pt) and a group 1 alkali metal (such as sodium or potassium);
4) crystalline aluminosilicates (zeolite L) in combination with group 10 metals (such as Pt) and group 1 alkali metals (such as potassium); and
5) crystalline aluminosilicates such as ZSM-5 are combined with group 10 metals such as Pt, group 1 alkali metals such as sodium and group 11 metals 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., silica) modified by a group 1 alkali metal silicate (such as Li, Na, K, Rb and/or Cs silicate) and/or a group 2 alkaline earth metal silicate (such as Mg, Ca, Sr and/or Ba silicate), preferably potassium silicate, sodium silicate, calcium silicate and/or magnesium silicate, preferably potassium silicate and/or sodium silicate. The group 10 metal content of the catalyst composition is at least 0.005 wt% based on the weight of the catalyst composition, preferably in the range of about 0.005 wt% to about 10 wt%, or about 0.005 wt% up to about 1.5 wt% based on the weight of the catalyst composition. Silicon dioxide (SiO)2) Any silica typically used as a catalyst support may be used, such as those sold under the trade name DAVISIL 646(Sigma Aldrich), Davison 952, Davison 948 or Davison 955 (Davison Chemical Division of w.r.grace and Company).
Additionally or alternatively, the first catalytic material may be capable of undergoing acyclic C5A catalyst that dehydrogenates a feed but may have little or no ability to undergo cyclization. Such examples of the first catalytic material include one or more group 6-group 12 metals in a reduced, oxidized, carbonized, nitrided, and/or sulfided state; inorganic supports supported at high temperature such as silica, alumina, titania, zirconia, ceria, aluminosilicates (amorphous and microporous), other metal silicates (amorphous and microporous), aluminates (e.g., aluminum hydrotalcite); perovskite, SAPO, ALPO and MAPO. Preferably, the first catalyst has a lower propensity to promote acid site cleavage or metal site cleavage to minimize C5-C4-Cracking of (2).
The catalyst composition shape and design is preferably configured to minimize pressure drop during use, improve heat transfer and minimize mass transport phenomena. The catalyst composition may be formed into particles that are randomly loaded in the reactor or may be in the shape of a structured catalyst within the reactor.
Suitable catalyst particle shapes and designs are described in WO 2014/053553, which is incorporated by reference in its entirety. The catalyst composition may be an extrudate having a diameter of from 2mm to 20 mm. Optionally, the catalyst composition cross-section may be shaped as one or more vanes and/or recessed sections. Additionally, the vanes and/or recessed sections of the catalyst composition may be helical. The catalyst composition may be an extrudate having a diameter of from 2mm to 20 mm; and the catalyst composition cross-section may be shaped as one or more vanes and/or recessed sections; and the vanes and/or recessed sections of the catalyst composition may be helical. The shapes may also include holes or pores in the shape to increase voids and improve mass transfer.
Examples of structured catalyst shapes include thin walls of a reactor and/or catalyst coatings on other formed inorganic support structures. Suitable formed inorganic support structures may be metallic or ceramic. Preferred ceramics are those having high thermal conductivity, for example, silicon carbide, aluminum nitride, boron carbide and silicon nitride. Suitable formed inorganic support structures may be ordered structures such as extruded ceramic monoliths and extruded or rolled metal monoliths. Typically, suitable formed inorganic support structures may further include ceramic or metal foam and 3D printed structures. The active catalyst coating may be applied to the support structure by wash coating or other means known in the art. Preferably, the coating thickness is less than 1,000 micrometers; more preferably less than 500 microns; most preferably 100-300 microns.
Particle shapes such as vanes, recesses, spirals, etc., are particularly useful for fixed bed reactors (combustion, convection and annular), while spherical particle shapes are particularly useful for fluidized bed reactors. Particle shapes such as vanes, recesses, spirals, etc., are particularly useful for fixed bed reactors (combustion, convection and annular), while spherical particle shapes are particularly useful for fluidized bed reactors. Preferably, the particles used in a fixed bed (e.g., annular fixed bed reactor, combustion tube reactor, convection tube reactor, etc.) are typically extrudates having a diameter of 2mm to 20 mm; and the catalyst composition cross-section may be shaped as one or more vanes and/or recessed sections; and the vanes and/or recessed sections of the catalyst composition may be helical.
For more information on useful catalyst compositions, see the following applications:
1) USSN62/250,675, 11 months and 4 days 2015;
2) USSN62/250,681, 11 months and 4 days 2015;
3) USSN62/250,688, 11 months and 4 days 2015;
4) USSN62/250,695, 11 months and 4 days 2015; and
5) USSN62/250,689, 11/4/2015, which is incorporated by reference into this application.
Preferably, the particulate material comprises platinum on ZSM-5, platinum on zeolite L and/or platinum on silicate-modified silica. In various aspects, the second particulate material may comprise platinum on ZSM-5, platinum on zeolite L and/or platinum on silica and the first particulate material may comprise at least one group 6, group 9 and/or group 10 metal on an inorganic support. The inorganic support may be selected from zeolites, SAPOs, ALPOs, MeAPO, silica, zirconia, titania, alumina, magnesia, ceria, yttria, clays, magnesium hydrotalcite, calcium aluminate, zinc aluminate, and combinations thereof (physical and/or chemical combinations).
The amount of suitable catalyst material in the particulate material (e.g., first particulate material, second particulate material) can be less than or equal to about 1.0 wt%, less than or equal to about 5.0 wt%, less than or equal to about 10.0 wt%, less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, less than or equal to about 45.0 wt%, less than or equal to about 50.0 wt%, less than or equal to 55.0 wt%, less than or equal to about 60.0 wt%, less than or equal to about 65.0 wt%, less than or equal to about 70.0 wt%, less than or equal to about 75.0 wt%, less than or equal to about 80.0 wt%, less than or equal to about 85.0 wt%, less than or equal to about 90.0 wt%, less than or equal to about 95.0 wt%, less than or equal to about 99.0 wt%, or equal to about 100 wt%. Additionally or alternatively, the particulate material (e.g., the first particulate material, the second particulate material) may comprise the catalyst material in an amount of greater than or equal to about 1.0 wt%, greater than or equal to about 5.0 wt%, greater than or equal to about 10.0 wt%, greater than or equal to about 15.0 wt%, greater than or equal to about 20.0 wt%, greater than or equal to about 25.0 wt%, greater than or equal to about 30.0 wt%, greater than or equal to about 35.0 wt%, greater than or equal to about 40.0 wt%, greater than or equal to about 45.0 wt%, greater than or equal to about 50.0 wt%, greater than or equal to about 55.0 wt%, greater than or equal to about 60.0 wt%, greater than or equal to about 65.0 wt%, greater than or equal to about 70.0 wt%, greater than or equal to about 75.0 wt%, greater than or equal to about 80.0 wt%, greater than or equal to about 85.0 wt%, greater than or equal to about 90.0 wt%, or equal to about 95.0 wt%. Ranges expressly disclosed include any combination of the above-listed values; for example, from about 1.0 wt% to about 100.0 wt%, from about 5.0 wt% to about 100.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 20.0 wt% to about 80.0 wt%, etc. The particulate material (e.g., first particulate material, second particulate material) may comprise the catalyst material in an amount of from about 1.0 wt% to about 100.0 wt%, more preferably from about 5.0 wt% to about 100.0 wt%, more preferably from about 25.0 wt% to about 100.0 wt%, more preferably from about 5.0 wt% to about 90.0 wt%, more preferably from about 10.0 wt% to about 80.0 wt%, more preferably from about 10.0 wt% to about 75.0 wt%, more preferably from about 20.0 wt% to about 70.0 wt%, more preferably from about 25.0 wt% to about 60.0 wt%, more preferably from about 30.0 wt% to about 50.0 wt%.
In various aspects, the particulate material (e.g., the first particulate material, the second particulate material) can further comprise one or more inert materials. As noted herein, inert materials are understood to include materials that promote negligible amounts (e.g., ≦ about 3%, ≦ about 2%, ≦ about 1%, etc.) of conversion to the feed, intermediate products, or final products under the reaction conditions described herein. The catalyst material and inert material may be combined as part of the same particle and/or may be separate particles. Additionally, the catalyst material and/or inert material may be generally spherical (i.e., < about 20%, < about 30%, < about 40%, < about 50% distortion in diameter), cylindrical, or blade shaped. Additionally, the granular material (e.g., first granular material, second granular material) may be an extrudate, wherein the cross-section may be shaped as one or more vanes and/or recessed segments and the vanes and/or recessed segments may be helical. Preferably, the granular material on the fluidized bed reactor, the circulating fluidized bed reactor and the circulating settled bed reactor is substantially spherical. Additionally, the granular materials (e.g., first granular material, second granular material) may be formed with internal perforations or with other shapes to reduce pressure drop while minimizing inter-granular diffusion limitations.
Suitable amounts of inert material in the particulate material (e.g., first particulate material, second particulate material) may be about 0.0 wt%, > 1.0 wt%, > 5.0 wt%, > 10.0 wt%, > 15.0 wt%, > 20.0 wt%, > 25.0 wt%, > 30.0 wt%, > 35.0 wt%, > 40.0 wt%, > 45.0 wt%, > 50.0 wt%, > 55.0 wt%, > 60.0 wt%, > 65.0 wt%, > 70.0 wt%, > 75.0 wt%, > 80.0 wt%, > 85.0 wt%, > 90.0 wt%, > 95.0 wt%, or 99.0 wt%. Additionally or alternatively, the granular material (e.g., the first granular material, the second granular material) can comprise an amount of inert material of less than or equal to about 1.0 wt%, less than or equal to about 5.0 wt%, less than or equal to about 10.0 wt%, less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, less than or equal to about 45.0 wt%, less than or equal to about 50.0 wt%, less than or equal to about 55.0 wt%, less than or equal to about 60.0 wt%, less than or equal to about 65.0 wt%, less than or equal to about 70.0 wt%, less than or equal to about 75.0 wt%, less than or equal to about 80.0 wt%, less than or equal to about 85.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 0.0 wt% to about 99.0 wt%, from about 0.0 wt% to about 95.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 20.0 wt% to about 80.0 wt%, and the like. Preferably, the particulate material (e.g., the first particulate material, the second particulate material) may comprise the inert material in an amount of from about 0.0 wt% to about 95.0 wt%, more preferably from about 0.0 wt% to about 90.0 wt%, more preferably from about 25.0 wt% to about 90.0 wt%, more preferably from about 30.0 wt% to about 85.0 wt%, more preferably from about 30.0 wt% to about 80.0 wt%.
In various aspects, the catalyst material and/or the inert material (as separate particles or as a combined part of the same particles) may have an average diameter of ≥ 5 μm ≥ 10 μm ≥ 20 μm ≥ 30 μm ≥ 40 μm ≥ 50 μm ≥ 100 μm ≥ 200 μm ≥ 300 μm ≥ 400 μm ≥ 500 μm ≥ 600 μm ≥ 700 μm ≥ 800 μm ≥ 900 μm ≥ 1000 μm ≥ 1100 μm ≥ 1200 μm ≥ 1300 μm ≥ 1400 μm ≥ 1500 μm ≥ 1600 μm ≥ 1700 μm ≥ 2500 μm ≥ 1800 μm ≥ 290μ m ≥ 1200 μm ≥ 1300 μm ≥ 1400 μm ≥ 1500 μm ≥ 2400 μm ≥ 1200 μm, not less than about 3000 μm, not less than about 3100 μm, not less than about 3200 μm, not less than about 3300 μm, not less than about 3400 μm, not less than about 3500 μm, not less than about 3600 μm, not less than about 3700 μm, not less than about 3800 μm, not less than about 3900 μm, not less than about 4000 μm, not less than about 4100 μm, not less than about 4200 μm, not less than about 4300 μm, not less than about 4400 μm, not less than about 5000 μm, not less than about 5500 μm, not less than about 6000 μm, not less than about 6500 μm, not less than about 7500 μm, not less than about 8000 μm, not less than about 8500 μm, not less than about 9000 μm, not less than about 9500 μm, or not less than about 7000 μm, or not less than about 10000 μm. Additionally or alternatively, the catalyst material and/or inert material (as separate particles or as a combined fraction of the same particles) can have an average diameter of less than or equal to about 5 μm, less than or equal to about 10 μm, less than or equal to about 20 μm, less than or equal to about 30 μm, less than or equal to about 40 μm, less than or equal to about 50 μm, less than or equal to about 100 μm, less than or equal to about 200 μm, less than or equal to about 300 μm, less than or equal to about 400 μm, less than or equal to about 500 μm, less than or equal to about 600 μm, less than or equal to about 700 μm, less than or equal to about 800 μm, less than or equal to about 900 μm, less than or equal to about 1000 μm, less than or equal to about 1100 μm, less than or equal to about 1200 μm, less than or equal to about 1300 μm, less than or equal to about 1400 μm, less than or equal to about 1500 μm, less than or equal to about 1700 μm, less than or equal to about 2500 μm, less than or equal to about 800 μm, less than about 900 μm, less than or equal to about 1000 μm, less than or equal to about 800 μm, less than or equal to about 3000 μm, less than or equal to about 3100 μm, less than or equal to about 3200 μm, less than or equal to about 3300 μm, less than or equal to about 3400 μm, less than or equal to about 3500 μm, less than or equal to about 3600 μm, less than or equal to about 3700 μm, less than or equal to about 3800 μm, less than or equal to about 3900 μm, less than or equal to about 4000 μm, less than or equal to about 4100 μm, less than or equal to about 4200 μm, less than or equal to about 4300 μm, less than or equal to about 4400 μm, less than or equal to about 4500 μm, less than or equal to about 5000 μm, less than or equal to about 5500 μm, less than or equal to about 6000 μm, less than or equal to about 6500 μm, less than or equal to about 7500 μm, less than or equal to about 8000 μm, less than or equal to about 8500 μm, less than or equal to about 9000 μm, less. Ranges specifically disclosed include combinations of any of the above listed values, for example, from about 10 μm to about 10000 μm, from about 50 μm to about 10000 μm, from about 100 μm to about 9000 μm, from about 200 μm to about 7500 μm, from about 200 μm to about 5500 μm, from about 100 μm to about 4000 μm, from about 100 μm to about 700 μm, and the like. The catalyst material and/or inert material (either as separate particles or as a combined portion of the same particles) may have an average diameter of from about 25 μm to about 1200 μm, more preferably from about 50 μm to about 1000 μm, more preferably from about 10 μm to about 500 μm, more preferably from about 30 μm to about 400 μm, more preferably from about 40 μm to about 300 μm.
Preferably, in the circulating fluidized bed, the catalyst material and/or inert material (either as separate particles or as an integral part of the same particles) may have an average diameter of from about 100 μm to about 4000 μm, more preferably from about 100 μm to about 700 μm, more preferably from about 100 μm to about 600 μm, more preferably from about 100 μm to about 500 μm. Preferably, in the circulating settled bed, the catalyst material and/or inert material (as separate particles or as a combined fraction of the same particles) may have an average diameter of from about 1000 μm to about 10000 μm, more preferably from about 2000 μm to about 8000 μm, more preferably from about 3000 μm to about 6000 μm, more preferably from about 3500 μm to about 4500 μm.
Preferably, in the fast fluidized bed, the catalyst material and/or inert material (either as separate particles or as an integral part of the same particles) may have an average diameter of from about 100 μm to about 4000 μm, more preferably from about 100 μm to about 700 μm, more preferably from about 100 μm to about 600 μm, more preferably from about 100 μm to about 500 μm. Preferably, in the simulated fluidized bed, the catalyst material and/or inert material (either as separate particles or as a combined portion of the same particles) may have an average diameter of from about 1000 μm to about 10000 μm, more preferably from about 2000 μm to about 8000 μm, more preferably from about 3000 μm to about 6000 μm, more preferably from about 3500 μm to about 4500 μm.
In various aspects, the catalyst material and/or inert material (as separate particles or as a combined part of the same particles) may have an average diameter of greater than or equal to about 0.1mm, greater than or equal to about 0.5mm, greater than or equal to about 1mm, greater than or equal to about 2mm, greater than or equal to about 3mm, greater than or equal to about 4mm, greater than or equal to about 5mm, greater than or equal to about 6mm, greater than or equal to about 7mm, greater than or equal to about 8mm, greater than or equal to about 9mm, greater than or equal to about 10mm, greater than or equal to about 12mm, greater than or equal to about 14mm, greater than or equal to about 16mm, greater than or equal to about 18mm, greater than or equal to about 20mm, greater than or equal to about 22mm, greater than or equal to about 24mm, greater than or equal to about 26mm, greater than or equal to about 28mm, greater than or equal to about 30mm, greater than or equal to about 35mm, greater. Additionally or alternatively, the catalyst material and/or inert material (as separate particles or as a combined fraction of the same particles) can have an average diameter of less than or equal to about 0.1mm, less than or equal to about 0.5mm, less than or equal to about 1mm, less than or equal to about 2mm, less than or equal to about 3mm, less than or equal to about 4mm, less than or equal to about 5mm, less than or equal to about 6mm, less than or equal to about 7mm, less than or equal to about 8mm, less than or equal to about 9mm, less than or equal to about 10mm, less than or equal to about 12mm, less than or equal to about 14mm, less than or equal to about 16mm, less than or equal to about 18mm, less than or equal to about 20mm, less than or equal to about 22mm, less than or equal to about 24mm, less than or equal to about 26mm, about 28mm, less than or equal to about 30mm, less than or equal to about 35mm, less than or. Ranges expressly disclosed include combinations of any of the above-listed values, e.g., from about 0.1mm to about 50mm, from about 1mm to about 35mm, from about 2mm to about 30mm, from about 3mm to about 40mm, and the like. Preferably, the catalyst material and/or inert material (either as separate particles or as a combined portion of the same particles) may have an average diameter of from about 0.5mm to about 30mm, more preferably from about 1mm to about 20mm, more preferably from about 2mm to about 10mm, more preferably from about 3mm to about 8 mm.
Preferably, the second particulate material provides for increasing the sensible heat of the first effluent and/or at least a portion of acyclic C5At least a portion of the heat required for the conversion of the hydrocarbons to the first effluent comprising cyclopentadiene, particularly for the circulating fixed and/or fluidized bed. For example, the second particulate material may provide greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, greater than or equal to about 50%, greater than or equal to about 55%, greater than or equal to about 60%, greater than or equal to about 65%, greater than or equal to about 70%, greater than or equal to about 75%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, greater than or equal to about 95%, or 100% of the desired heat. Ranges expressly disclosed include any combination of the above-listed values; e.g., from about 30% to about 100%, from about 40% to about 95%, from about 50% to about 90%, etc. Preferably, the second particulate material may provide from about 30% to about 100% of said required heat, more preferably from about 50% to about 100% of said required heat, more preferably from about 70% to about 100% of said required heat.
E. Effluent liquid
The effluent (e.g., the first effluent) exiting the adiabatic reaction zone may be comprised of C in the adiabatic reaction zone5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) to produce a plurality of hydrocarbon compositions. The hydrocarbon composition typically has a mixture of hydrocarbon compounds having 1-30 carbon atoms (C)1-C30Hydrocarbon) of 1 to 24 carbon atoms (C)1-C24Hydrocarbon) of 1 to 18 carbon atoms (C)1-C18Hydrocarbon) of 1 to 10 carbon atoms (C)1-C10Hydrocarbon) of 1 to 8 carbon atoms (C)1-C8Hydrocarbons) and 1 to 6 carbon atoms (C)1-C6Hydrocarbons). In particular, the effluent (e.g.,the first effluent) comprises cyclopentadiene intermediates (e.g., pentene, pentadiene, cyclopentane and/or cyclopentene). The cyclopentadiene intermediates can be present in the hydrocarbon portion of the effluent (e.g., the first effluent) in an amount of greater than or equal to about 3.0 wt%, greater than or equal to about 5.0 wt%, greater than or equal to about 10.0 wt%, greater than or equal to about 15.0 wt%, greater than or equal to about 20.0 wt%, greater than or equal to about 25.0 wt%, greater than or equal to about 30.0 wt%, greater than or equal to about 35.0 wt%, or greater than or equal to about 40.0 wt%. Additionally or alternatively, the cyclopentadiene intermediate can be present in the hydrocarbon portion of the effluent (e.g., the first effluent) in an amount of less than or equal to about 5.0 wt%, less than or equal to about 10.0 wt%, less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, or less than or equal to about 45.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 5.0 wt% to about 40.0 wt%, from about 10.0 wt% to about 35.0 wt%, from about 15.0 wt% to about 30.0 wt%, from about 5.0 wt% to about 25.0 wt%, and the like. Optionally, the first effluent may comprise cyclopentadiene.
The effluent (e.g., the second effluent) exiting the diabatic reaction zone can be included in the adiabatic reaction zone and/or the diabatic reaction zone C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) to produce a plurality of hydrocarbon compositions. The hydrocarbon composition typically has a mixture of hydrocarbon compounds having 1-30 carbon atoms (C)1-C30Hydrocarbon) of 1 to 24 carbon atoms (C)1-C24Hydrocarbon) of 1 to 18 carbon atoms (C)1-C18Hydrocarbon) of 1 to 10 carbon atoms (C)1-C10Hydrocarbon) of 1 to 8 carbon atoms (C)1-C8Hydrocarbons) and 1 to 6 carbon atoms (C)1-C6Hydrocarbons). Specifically, the effluent (e.g., the second effluent) comprises cyclopentadiene. The amount of cyclopentadiene that can be present in the hydrocarbon portion of the effluent (e.g., the second effluent) is ≥ 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%, or ≥ about 80.0 wt%. Additionally or alternatively, the cyclopentadiene can be present in the hydrocarbon portion of the effluent (e.g., the second effluent) in an amount of less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%,less than about 35.0 wt%, less than about 40.0 wt%, less than about 45.0 wt%, less than about 50.0 wt%, less than about 55.0 wt%, less than about 60.0 wt%, less than about 65.0 wt%, less than about 70.0 wt%, less than about 75.0 wt%, less than about 80.0 wt%, or less than about 85.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 20.0 wt% to about 85.0 wt%, from about 30.0 wt% to about 75.0 wt%, from about 40.0 wt% to about 85.0 wt%, from about 50.0 wt% to about 85.0 wt%, and the like. Preferably, the cyclopentadiene can be present in the hydrocarbon portion of the second effluent in an amount of from about 10.0 wt% to about 85.0 wt%, more preferably from about 25.0 wt% to about 80.0 wt%, more preferably from about 40.0 wt% to about 75.0 wt%.
In other aspects, the effluent (e.g., the second effluent) can comprise one or more other C's in addition to cyclopentadiene5A hydrocarbon. Other C5Examples of hydrocarbons include, but are not limited to: cyclopentane and cyclopentene. One or more other C's that may be present in the hydrocarbon portion of the effluent (e.g., the second effluent)5The amount of hydrocarbon is greater than or equal to about 10.0 wt%, greater than or equal to about 15.0 wt%, greater than or equal to about 20.0 wt%, greater than or equal to about 25.0 wt%, greater than or equal to about 30.0 wt%, greater than or equal to about 35.0 wt%, greater than or equal to about 40.0 wt%, greater than or equal to about 45.0 wt%, greater than or equal to about 50.0 wt%, greater than or equal to about 55.0 wt%, greater than or equal to about 60.0 wt%, greater than or equal to about 65.0 wt%, or greater than or equal to about 70.0 wt%. Additionally or alternatively, one or more other C's may be present in the hydrocarbon portion of the effluent (e.g., the second effluent)5The amount of hydrocarbon is less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, less than or equal to about 45.0 wt%, less than or equal to about 50.0 wt%, less than or equal to about 55.0 wt%, less than or equal to about 60.0 wt%, less than or equal to about 65.0 wt%, or less than or equal to about 70.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 10.0 wt% to about 70.0 wt%, from about 10.0 wt% to about 55.0 wt%, from about 15.0 wt% to about 60.0 wt%, from about 25.0 wt% to about 65.0 wt%, and the like. Preferably, one or more other C's that may be present in the hydrocarbon portion of the second effluent5The amount of hydrocarbon is from about 30.0 wt% to about 65.0 wt%, more preferably from about 20.0 wt% to about 40.0 wt%, more preferably from about 10.0 wt% to about 25.0 wt%.
In other aspects, the effluent (e.g., first effluent, second effluent) can further comprise one or more aromatics, e.g., having from 6 to 30 carbon atoms, specifically from 6 to 18 carbon atoms. The amount of the one or more aromatic substances that may be present in the hydrocarbon portion of the effluent (e.g., first effluent, second effluent) is about ≧ 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%. Additionally or alternatively, the amount of one or more aromatic substances that can be present in the hydrocarbon portion of the effluent (e.g., first effluent, second effluent) is less than or equal to about 1.0 wt%, less than or equal to about 5.0 wt%, less than or equal to about 10.0 wt%, less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, less than or equal to about 45.0 wt%, less than or equal to about 50.0 wt%, less than or equal to about 55.0 wt%, less than or equal to about 60.0 wt%, or less than or equal to about 65.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 1.0 wt% to about 65.0 wt%, from about 10.0 wt% to about 50.0 wt%, from about 15.0 wt% to about 60.0 wt%, from about 25.0 wt% to about 40.0 wt%, and the like. Preferably, the amount of one or more aromatics that may be present in the hydrocarbon portion of the first effluent is about less than 5 wt%, preferably less than 2 wt%, more preferably less than 1 wt%. Preferably, the one or more aromatics may be present in the hydrocarbon portion of the second effluent in an amount of from about 1.0 wt% to about 15.0 wt%, more preferably from about 1.0 wt% to about 10.0 wt%, more preferably from about 1.0 wt% to about 5.0 wt%. For information on the condition of the effluent, please see the following applications:
1) USSN62/250,678, 11 months and 4 days 2015;
2) USSN62/250,692, 11 months and 4 days 2015;
3) USSN62/250,702, 11 months and 4 days 2015; and
4) USSN62/250,708, 11 months and 4 days 2015; all of which are incorporated herein by reference.
F. Extraction/separation of effluents
In various aspects, the particulate material (e.g., first particulate material, second particulate material) can be entrained in the effluent by a hydrocarbon (e.g., cyclopentadiene and/or cyclopentadiene intermediates) as the effluent (e.g., first effluent, second effluent) travels through and/or exits the adiabatic reaction zone and/or the heat transfer reaction zone. Thus, the process can further include separating the particulate material that can be entrained with the hydrocarbons (e.g., cyclopentadiene and/or cyclopentadiene intermediates) in the effluent (e.g., first effluent, second effluent). Such separation may include removing the particulate material (e.g., first particulate material, second particulate material) from the hydrocarbons (e.g., cyclopentadiene and/or cyclopentadiene intermediates) by any suitable means, such as, but not limited to, cyclones, filters, electrostatic precipitators, heavy liquid contacting and/or other gas solids separation devices, which may be internal and/or external to the at least one reaction zone. The effluent, free of particulate material, may then proceed to a product recovery system. In addition, the removed particulate material may then be fed back into the adiabatic and/or diabatic reaction zone using known methods, e.g., at a substantially top portion of the adiabatic and/or diabatic reaction zone.
In various aspects, hydrocarbons (e.g., cyclopentadiene and/or cyclopentadiene intermediates) can be entrained by the particulate material as the particulate material travels through and/or exits the at least one reaction zone. Hydrocarbons can adsorb onto and/or into the particles, as well as voids between the particles. Thus, the process may further comprise extracting and/or separating hydrocarbons from the particulate material in the effluent. Such extraction and/or separation may include removing hydrocarbons (e.g., cyclopentadiene and/or acyclic C s) from the particulate material by any suitable means5) Such as, but not limited to, a gas such as H2Or methane extraction and/or other gas-solids separation equipment, which may be internal and/or external to the at least one reaction zone. The particulate material having a reduced amount of hydrocarbons may then proceed to a reheating zone, a renewal zone, and/or a regeneration zone, and hydrocarbons extracted from the particulate material may be directed to a product recovery system or to a reactor system.
G. Renewal and reheating
As the reaction occurs in the adiabatic reaction zone and/or the diabatic reaction zone, coke material may form on the particulate material (e.g., first particulate material, second particulate material), particularly on the catalyst material, which may reduce the activity of the catalyst material. Additionally or alternatively, the particulate material (e.g., first particulate material, second particulate material) may be cooled as the reaction proceeds.
i. Update section
In various aspects, the particulate material can travel through and out of a reaction zone (e.g., adiabatic reaction zone, heat transfer reaction zone). The catalyst material exiting a reaction zone (e.g., adiabatic reaction zone, heat transfer reaction zone) is referred to as "spent catalyst material". Such spent catalyst material may certainly be a homogeneous mixture of particles, as the individual particles may have an overall aging profile in the system, the time since the last regeneration and/or the proportion of time in the reaction zone relative to the time in the renewal zone.
Thus, at least a portion of the first particulate material (e.g., spent catalyst material) may be transported from the adiabatic reaction zone to the renewal zone and/or at least a portion of the second particulate material (e.g., spent catalyst material) may be transported from the diabatic reaction zone to the renewal zone. Preferably, in the regeneration zone, spent catalyst material is regenerated (i.e., progressively deposited coke material is removed from spent catalyst material) and only incidental catalyst material heating is performed. Optionally, spent catalyst material may be refreshed and reheated in a refresh zone. Preferably, when the diabatic reaction zone is a fluidized bed reactor, a circulating fluidized bed reactor, or a circulating settled bed reactor, the second particulate material is conveyed to a renewal zone where renewal and reheating can be performed.
The first and/or second particulate materials (e.g., spent catalyst material) may be conveyed to a renewal zone after hydrocarbons have been extracted and/or separated from the first and/or second particulate materials after exiting the adiabatic and/or diabatic reaction zones. The update zone may include one or more heating devices, such as, but not limited to, direct contact, heating coils and/or combustion conduits. Additionally or alternatively, there may be more than 1 update section (e.g., 2 update sections, 3 update sections, 4 update sections, etc.).
In various aspects, in the regeneration zone, the first and/or the second particulate material (e.g., spent catalyst material) may be contacted with a hydrogen stream to remove at least a portion of the progressively deposited coke material on the catalyst material to form a regenerated catalyst material and a volatile hydrocarbon, such as, but not limited to, methane. As used herein, the term "progressively deposited" coke material refers to the amount of coke material deposited on the catalyst material during each pass of the catalyst material through the adiabatic and/or diabatic reaction zones, rather than the cumulative amount of coke material deposited on the catalyst material during multiple passes through the adiabatic and/or diabatic reaction zones. Preferably, the hydrogen stream is substantially free of oxygen, which can destroy and/or reduce the activity of the catalyst material. The renewed catalyst material may then be returned to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone.
The renewal zone (i.e., the temperature to which the particulate material is exposed) may be operated at the following temperatures: greater than or equal to about 400 ℃, greater than or equal to about 450 ℃, greater than or equal to about 500 ℃, greater than or equal to about 550 ℃, greater than or equal to about 600 ℃, greater than or equal to 650 ℃, greater than or equal to about 700 ℃, greater than or equal to 750 ℃, or greater than or equal to about 800 ℃. Additionally or alternatively, the update section may be operated at the following temperatures: less than or equal to about 400 deg.C, less than or equal to about 450 deg.C, less than or equal to about 500 deg.C, less than or equal to about 550 deg.C, less than or equal to about 600 deg.C, less than or equal to 650 deg.C, less than or equal to about 700 deg.C, less than or equal to 750 deg.C, less than or equal to about 800 deg.C, or less than or equal to 850 deg.. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., from about 400 ℃ to about 600 ℃, from about 450 ℃ to about 850 ℃, from about 500 ℃ to about 800 ℃, and the like. Preferably, the update section may be operated at the following temperatures: from about 400 ℃ to about 800 ℃, more preferably from about 600 ℃ to about 750 ℃, more preferably from about 550 ℃ to about 800 ℃, more preferably from about 550 ℃ to about 700 ℃.
Additionally or alternatively, the update section may operate at the following pressures: greater than or equal to about 1.0psia, greater than or equal to about 5.0psia, greater than or equal to about 25.0psia, greater than or equal to about 50.0psia, greater than or equal to about 75.0psia, greater than or equal to about 100.0psia, greater than or equal to about 125.0psia, greater than or equal to about 150.0psia, greater than or equal to about 175.0psia, greater than or equal to about 200.0psia, greater than or equal to about 225.0psia, greater than or equal to about 250.0psia, greater than or equal to about 275.0psia, or greater than or equal to about 300.0 psia. Additionally or alternatively, the update section may operate at the following pressures: less than or equal to about 1.0psia, less than or equal to about 5.0psia, less than or equal to about 25.0psia, less than or equal to about 50.0psia, less than or equal to about 75.0psia, less than or equal to about 100.0psia, less than or equal to about 125.0psia, less than or equal to about 150.0psia, less than or equal to about 175.0, psia less than or equal to about 200.0psia, less than or equal to about 225.0psia, less than or equal to about 250.0psia, less than or equal to about 275.0psia, or less than or equal to about 300.0 psia. Specifically disclosed pressure ranges include any combination of the above listed values, for example, from about 1.0psia to about 300.0psia, from about 5.0psia to about 275.0psia, from about 25.0psia to about 250.0psia, and the like. In particular, the update section may operate at the following pressures: from about 1psia to about 300psia, more preferably from about 5psia to about 250psia, and more preferably from about 25psia to about 250 psia.
Preferably, the amount of progressively deposited coke material removed from the catalyst material in the regeneration zone is greater than or equal to about 1.0 wt%, greater than or equal to about 5.0 wt%, greater than or equal to about 10.0 wt%, greater than or equal to about 15.0 wt%, greater than or equal to about 20.0 wt%, greater than or equal to about 25.0 wt%, greater than or equal to about 30.0 wt%, greater than or equal to about 35.0 wt%, greater than or equal to about 40.0 wt%, greater than or equal to about 45.0 wt%, greater than or equal to about 50.0 wt%, greater than or equal to about 55.0 wt%, greater than or equal to about 60.0 wt%, greater than or equal to about 65.0 wt%, greater than or equal to about 70.0 wt%, greater than or equal to about 75.0 wt%, greater than or equal to about 80.0 wt%, greater than or equal to about 85.0 wt%, greater than or equal to about 90.0 wt%, greater than or equal to about 95.0 wt%, or equal to about 100.0 wt%. Preferably, at least about 10 wt%, at least about 20 wt%, at least about 50 wt%, at least about 70 wt%, or at least about 90 wt% of the progressively deposited coke material is removed from the catalyst material. Additionally or alternatively, the progressively deposited coke material is removed from the catalyst material in an amount of less than or equal to about 1.0 wt%, less than or equal to about 5.0 wt%, less than or equal to about 10.0 wt%, less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, less than or equal to about 45.0 wt%, less than or equal to about 50.0 wt%, less than or equal to about 55.0 wt%, less than or equal to about 60.0 wt%, less than or equal to about 65.0 wt%, less than or equal to about 70.0 wt%, less than or equal to about 75.0 wt%, less than or equal to about 80.0 wt%, less than or equal to about 85.0 wt%, less than or equal to about 90.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 1.0 wt% to about 100.0 wt%, from about 5.0 wt% to about 95.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 30.0 wt% to about 90.0 wt%, and the like. Preferably, the progressively deposited coke material is removed from the catalyst material in an amount of from about 1.0 wt% to about 100.0 wt%, more preferably from about 10.0 wt% to about 100.0 wt%, more preferably from about 60.0 wt% to about 100.0 wt%, more preferably from about 90.0 wt% to about 100.0 wt%.
In various aspects, the temperature of the upgraded catalyst material may be greater than or equal to about 400 ℃, > or equal to about 450 ℃, > or equal to about 500 ℃, > or equal to about 550 ℃, > or equal to about 600 ℃, > or equal to 650 ℃, > or equal to about 700 ℃, > or equal to 750 ℃, or greater than or equal to about 800 ℃. Additionally or alternatively, the temperature of the renewed catalyst material may be less than or equal to about 400 deg.C, less than or equal to about 450 deg.C, less than or equal to about 500 deg.C, less than or equal to about 550 deg.C, less than or equal to about 600 deg.C, less than or equal to 650 deg.C, less than or equal to about 700 deg.C, less than or equal to 750 deg.C, less than or equal to about 800 deg.C, or less than or equal to about 850 deg. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., about 400 ℃ to about 800 ℃, about 450 ℃ to about 850 ℃, about 500 ℃ to about 800 ℃, and the like. Preferably, the temperature of the renewed catalyst material may be from about 400 ℃ to about 700 ℃, more preferably from about 500 ℃ to about 750 ℃, more preferably from about 550 ℃ to about 700 ℃.
In one embodiment, the regeneration zone may comprise a plurality of fluid bed tubes disposed within the combustion chamber (or furnace). The combustion chamber may include a radiant section, a shield, and a convection section. May comprise H2CO, light hydrocarbons (C)1-C4) Liquid hydrocarbons (C)5-C25) And/or heavy liquid hydrocarbons (C)25+) And air may be introduced into one or more combustors and ignited. The radiant heat generated in the combustion chamber can then be conducted to the walls of the conduit, thereby providing the heat required to heat the circulating particulate material (e.g., spent catalyst material). The convection section may be used for gas preheating and/or steam production. The combustion chamber may be top or bottom fired. The flue gas may flow in a direction co-current or counter-current to the flow direction of circulation of particulate material (e.g., spent catalyst material) within the plurality of fluid bed conduits. In addition, hydrogen can be used to lift and fluidize the circulation of particulate material (e.g., spent catalyst material) within the plurality of fluid bed conduits. The hydrogen gas may flow in a direction co-current or counter-current to the flow direction of the particulate material (e.g., spent catalyst material).
In another embodiment, the regeneration zone may comprise a plurality of fluid bed tubes disposed within an enclosure in which the tubes may be contacted with hot combustion gases such that the tubes may be heated by convection of hot gases, the hot gases being combustion products from a furnace, gas turbine, or catalytic combustion. The use of convective heating can reduce the membrane temperature to which the particulate material is exposed, thereby reducing the potential for catalyst damage due to excessive heating. The hot combustion gases may flow in a direction co-current or counter-current to the flow direction of the circulation of particulate material (e.g., spent catalyst material) within the plurality of fluid bed tubes. In addition, hydrogen can be used to lift and fluidize the circulation of particulate material (e.g., spent catalyst material) within the plurality of fluid bed conduits. The hydrogen gas may flow in a direction co-current or counter-current to the flow direction of the particulate material (e.g., spent catalyst material).
In another embodiment, the update zone may comprise a fluid bed provided with a plurality of combustion conduits or coils. Each coil or combustion conduit can be individually or co-fired with fuel and air to provide radiant heat that can be transferred through the wall to the fluid bed. Thus, the circulation of particulate material (e.g., spent catalyst material) within the fluid bed may be reheated due to the heat transfer properties of the fluid bed. The circulation of particulate material (e.g., spent catalyst material) within the fluid bed may be in a co-current or counter-current direction to the flow direction of the gas in the combustion conduit. In addition, the flue gas in each combustion conduit can exit the reheat zone and be connected to a common heater directed to the convection chamber, which can be used to heat the feed, preheat (e.g., preheat a hydrogen stream) and produce steam in the reheat zone. The coil may contain hot combustion gases such that the tube is convectively heated by hot gases from the combustion products of the furnace, gas turbine, or catalytic combustion; alternatively, the coil may contain a heat transfer medium (e.g., molten or vaporized metal or salt) that has been heated elsewhere, such as in a furnace.
The modes within the update section may be:
1. a bubbling mode in which the superficial gas velocity is greater than the minimum bubbling velocity, but less than the minimum slug velocity;
2. a slug mode, in which the superficial gas velocity is greater than the minimum slug velocity, but below the transition to turbulent Fluidization velocity for pipe diameters and lengths in slug initiation conditions (e.g., Stewart conditions) (as described in Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2)ndEdition, Butterworth-Heinemann, Boston,1991 and Walas,S.M.,Chapter 6 of Chemical Process Equipment,Revised 2nd Edition,Butterworth-Heinemann,Boston,2010))；
3. Transition to a turbulent fluidization mode, wherein the superficial gas velocity is greater than the transition to turbulent fluidization velocity, but less than the fast fluidization velocity; or
4. Fast fluidization mode, wherein the superficial gas velocity is greater than the fast fluidization velocity.
Preferably, the regeneration zone is operated in mode 1 or 2, which may minimize hydrogen usage in the fluid bed, maximize catalyst material residence time for coke removal and/or improve heat transfer performance.
In another embodiment, in the regeneration zone, the particulate material (e.g., spent catalyst material) may be reheated in direct contact with a hot gas stream that has been heated in another apparatus, such as a furnace, and is effective for coke removal (i.e., H2) Or at least does not result in additional coke deposition (e.g., methane), as opposed to heating within the fluid bed conduits or by combustion conduits or coils.
Additionally or alternatively, the renewed catalyst material may be separated from the hydrogen gas and/or volatile hydrocarbons in one or more separation steps inside or outside the renewal zone by any suitable means, such as, but not limited to, cyclones.
Additionally or alternatively, fresh particulate material may be provided directly to the at least one adiabatic reaction zone, the at least one diabatic reaction zone and/or to the renewal zone prior to entering the at least one adiabatic zone and/or the at least one diabatic reaction zone.
Reheating interval
In various aspects, the particulate material may remain in the reaction zone (e.g., adiabatic reaction zone, diabatic reaction zone) when the particulate material does not travel through the reaction zone. In particular, the second particulate can remain in the diabatic reaction zone (e.g., an annular fixed bed reactor) and the second particulate can be cooled, i.e., reduced in temperature.
Preferably, the first effluent contacts the second granular material in the diabatic reaction zone until the temperature in the diabatic reaction zone is less than or equal to about 300 ℃, ≦ about 325 ℃, ≦ about 350 ℃, ≦ about 375 ℃, ≦ about 400 ℃, ≦ about 425 ≦ about 450 ℃, ≦ about 475 ℃, ≦ about 500 ≦ about 525 ℃, ≦ about 550 ℃, ≦ about 575 ℃, ≦ about 600 ℃, ≦ about 650 ℃ or ≦ about 675 ℃. Ranges expressly disclosed include any combination of the above listed values, e.g., from about 300 ℃ to about 675 ℃, from about 400 ℃ to about 600 ℃, from about 425 ℃ to about 575 ℃, etc. Preferably, the reaction may be carried out until the temperature in the diabatic reaction zone drops to less than about 400 ℃, less than about 450 ℃, less than about 475 ℃, less than about 500 ℃, less than about 550 ℃, less than about 575 ℃, or less than about 600 ℃.
Additionally or alternatively, the duration of time that the first effluent contacts the second granular material in the diabatic reaction zone is no less than about 1 minute, no less than about 2 minutes, no less than about 3 minutes, no less than about 4 minutes, no less than about 5 minutes, no less than about 6 minutes, no less than about 7 minutes, no less than about 8 minutes, no less than about 9 minutes, no less than about 10 minutes, no less than about 15 minutes, no less than about 20 minutes, no less than about 25 minutes, no less than about 30 minutes, no less than about 35 minutes, no less than about 40 minutes, no less than about 45 minutes, no less than about 50 minutes, no less than about 55 minutes, no less than about 60 minutes, no less than about 65 minutes, no less than about 70 minutes, no less than about 75 minutes, no less than about 80 minutes, no less than about 85 minutes, no less than about 90 minutes, no less than about 95 minutes, no less than about 100 minutes, no less than about 110 minutes, or no less than about 120 minutes. Additionally or alternatively, the reaction interval can have a duration of less than or equal to about 1 minute, < about 2 minutes, < about 3 minutes, < about 4 minutes, < about 5 minutes, < about 6 minutes, < about 7 minutes, < about 8 minutes, < about 9 minutes, < about 10 minutes, < about 15 minutes, < about 20 minutes, < about 25 minutes, < about 30 minutes, < about 35 minutes, < about 40 minutes, < about 45 minutes, < about 50 minutes, < about 55 minutes, < about 60 minutes, < about 65 minutes, < about 70 minutes, < about 75 minutes, < about 80 minutes, < about 85 minutes, < about 90 minutes, < about 95 minutes, < about 100 minutes, < about 110 minutes, or < about 120 minutes. Ranges are expressly disclosed, including combinations of any of the above listed values, for example, from about 1 to about 120 minutes, from about 1 to about 90 minutes, from about 4 to about 80 minutes, from about 10 to about 75 minutes, and the like. Preferably, the duration of time that the first effluent contacts the second particulate material in the diabatic reaction zone is from about 1 to about 120 minutes, more preferably from about 1 to about 90 minutes, more preferably from about 1 to about 60 minutes, more preferably from about 1 to about 40 minutes, more preferably from about 1 to about 15 minutes, more preferably from about 1 to about 10 minutes, more preferably from about 2 to about 8 minutes. In particular, the first effluent contacts the second particulate material in the diabatic reaction zone: (i) until the temperature in the diabatic reaction zone drops to less than about 550 ℃ and/or (ii) lasts from about 1 minute to about 90 minutes.
Thus, the process may further include a reheating interval, wherein the first effluent to the at least one diabatic reaction zone (e.g., an annular fixed bed reactor) may be periodically stopped, and a reheating gas may be provided to the at least one diabatic reaction zone to reheat the second particulate material. The reheat gas may contain inerts (e.g., N)2CO, etc.) and/or methane. In various aspects, the reheating gas can comprise an inert and can be supplied to a diabatic reaction zone (e.g., an annular fixed bed reactor) to reheat the second particulate material. After a suitable duration, the reheated gas may exit the diabatic reaction zone via the outlet.
In various aspects, the reheating gas can flow in a direction co-current or counter-current to the flow direction of the first effluent. For example, if the first effluent enters at the top portion of the diabatic reaction zone during the reaction interval, the reheat gas may also enter at the top portion of the diabatic reaction zone during the reheat interval, flowing in a co-current direction with the flow direction of the first effluent. Additionally or alternatively, if the first effluent enters at a top portion of the diabatic reaction zone, during the reheating interval, the reheating gas may enter at a bottom portion of the diabatic reaction zone, flowing in a direction counter-current to the flow direction of the first effluent. Preferably, when the diabatic reaction zone is a fixed circulating bed, the reheated gas flows in a direction counter-current to the direction of flow of the first effluent and/or a reverse temperature profile can be achieved in the diabatic reaction zone.
Preferably, the reheating interval may have a duration of no less than about 1 minute, no less than about 5 minutes, no less than about 10 minutes, no less than about 15 minutes, no less than about 20 minutes, no less than about 25 minutes, no less than about 30 minutes, no less than about 35 minutes, no less than about 40 minutes, no less than about 45 minutes, no less than about 50 minutes, no less than about 55 minutes, no less than about 60 minutes, no less than about 65 minutes, no less than about 70 minutes, no less than about 75 minutes, no less than about 80 minutes, no less than about 85 minutes, no less than about 90 minutes, no less than about 95 minutes, no less than about 100 minutes, no less than about 110 minutes, or no less than about 120 minutes. Additionally or alternatively, the reheating interval can have a duration of less than or equal to about 1 minute, < less than or equal to about 5 minutes, < less than or equal to about 10 minutes, < less than or equal to about 15 minutes, < less than or equal to about 20 minutes, < less than or equal to about 25 minutes, < less than or equal to about 30 minutes, < less than or equal to about 35 minutes, < less than or equal to about 40 minutes, < less than or equal to about 45 minutes, < less than or equal to about 50 minutes, < less than or equal to about 55 minutes, < less than or equal to about 60 minutes, < less than or equal to about 65 minutes, < less than or equal to about 70 minutes, < less than or equal to about 75 minutes, < less than or equal to about 80 minutes, < less than or equal to about 85 minutes, < about 90 minutes, < less than or equal. Ranges expressly disclosed include any combination of the above listed values, for example, from about 1 to about 120 minutes, from about 1 to about 90 minutes, from about 4 to about 80 minutes, from about 10 to about 75 minutes, and the like. Preferably, the reaction interval may have a duration of about 1 to about 120 minutes, more preferably about 1 to about 90 minutes, more preferably about 1 to about 60 minutes, more preferably about 5 to about 40 minutes. Preferably, 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 half the duration of the reaction interval.
Update interval
In addition, coke material may form on the particulate material (e.g., first particulate material, second particulate material), with it being on the catalyst material, which may reduce the activity of the catalyst material. Such catalyst materials having coke formation and/or having a reduced temperature at the end of the reaction interval are referred to as "spent catalyst materials".
Thus, the process may further include a rejuvenation interval in which the feed to the at least one adiabatic reaction zone may be periodically stopped and/or the first effluent to the at least one diabatic reaction zone (e.g., fixed annular bed, fired tubular reactor, convective heating tubular reactor) may be periodically stopped, and a rejuvenation gas may be provided to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone to rejuvenate the particulate material (e.g., first particulate material, second particulate material). The rejuvenating gas can include hydrogen, and the rejuvenating gas can contact the first and/or second particulate materials (e.g., spent catalyst material) to remove at least a portion of the progressively deposited coke material on the catalyst material, thereby forming a rejuvenated catalyst material and a volatile hydrocarbon, such as, but not limited to, methane. Preferably, the hydrogen containing rejuvenating gas is substantially free of oxygen, which can destroy and/or reduce the activity of the catalyst material. After a suitable duration, the rejuvenating gas and optionally volatile hydrocarbons can exit the adiabatic reaction zone and/or the diabatic reaction zone via an outlet.
In particular, the feed to the at least one adiabatic reaction zone may be periodically stopped and/or the first effluent to the at least one diabatic reaction zone may be periodically stopped, and a rejuvenating gas comprising hydrogen may be provided to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone. The rejuvenating gas, which includes hydrogen, can contact the particulate materials (e.g., first particulate material, second particulate material) to remove at least a portion of the progressively deposited coke material on the catalyst material to form a rejuvenated catalyst material and volatile hydrocarbons.
In various aspects, the rejuvenating gas can flow in a direction co-current or counter-current to the direction of flow of the feed and/or the first effluent. For example, if the feed enters at the top portion of the adiabatic reaction zone during a reaction interval, the rejuvenating gas may also enter at the top portion of the adiabatic reaction zone during a rejuvenation interval, flowing in a co-current direction to the flow direction of the feed. Additionally or alternatively, if the feed enters at the top portion of the adiabatic reaction zone, the rejuvenating gas may enter at the bottom portion of the adiabatic reaction zone during the rejuvenation interval, flowing in a direction counter-current to the flow direction of the feed. Preferably, when the diabatic reaction zone is a circulating fixed bed, the rejuvenating gas flows in a direction counter-current to the direction of flow of the first effluent. Preferably, when the diabatic reaction zone is a combustion tube reactor or a convectively heated tube reactor, the rejuvenating gas flows in a co-current direction to the direction of flow of the feed and/or the first effluent. Preferably, this achieves a reverse temperature profile in the diabatic reaction zone.
Preferably, the amount of gradually-deposited coke material removed from the catalyst material during the regeneration interval is greater than or equal to about 1.0 wt%, greater than or equal to about 5.0 wt%, greater than or equal to about 10.0 wt%, greater than or equal to about 15.0 wt%, greater than or equal to about 20.0 wt%, greater than or equal to about 25.0 wt%, greater than or equal to about 30.0 wt%, greater than or equal to about 35.0 wt%, greater than or equal to about 40.0 wt%, greater than or equal to about 45.0 wt%, greater than or equal to about 50.0 wt%, greater than or equal to about 55.0 wt%, greater than or equal to about 60.0 wt%, greater than or equal to about 65.0 wt%, greater than or equal to about 70.0 wt%, greater than or equal to about 75.0 wt%, greater than or equal to about 80.0 wt%, greater than or equal to about 85.0 wt%, greater than or equal to about 90.0 wt%, greater than or equal to about 95.0 wt%, greater than or equal to about 99.0 wt%. Preferably, at least about 10.0 wt% of the progressively 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%. Additionally or alternatively, the progressively deposited coke material is removed from the catalyst material in an amount of less than or equal to about 1.0 wt%, less than or equal to about 5.0 wt%, less than or equal to about 10.0 wt%, less than or equal to about 15.0 wt%, less than or equal to about 20.0 wt%, less than or equal to about 25.0 wt%, less than or equal to about 30.0 wt%, less than or equal to about 35.0 wt%, less than or equal to about 40.0 wt%, less than or equal to about 45.0 wt%, less than or equal to about 50.0 wt%, less than or equal to about 55.0 wt%, less than or equal to about 60.0 wt%, less than or equal to about 65.0 wt%, less than or equal to about 70.0 wt%, less than or equal to about 75.0 wt%, less than or equal to about 80.0 wt%, less than or equal to about 85.0 wt%, less than or equal to about 90.0 wt%, less than or equal to about 95.0 wt%. Ranges expressly disclosed include combinations of any of the above-listed values, for example, from about 1.0 wt% to about 100.0 wt%, from about 5.0 wt% to about 95.0 wt%, from about 10.0 wt% to about 90.0 wt%, from about 30.0 wt% to about 90.0 wt%, and the like. Preferably, the progressively deposited coke material is removed from the catalyst material in an amount of from about 1.0 wt% to about 100.0 wt%, more preferably from about 10.0 wt% to about 100.0 wt%, more preferably from about 90.0 wt% to about 100.0 wt%, more preferably from about 95.0 wt% to about 100.0 wt%.
The refresh interval can have a duration of 90 minutes or less, 60 minutes or less, 30 minutes or less, 10 minutes or less, 5 minutes or less, 1 minute or less, or 10 seconds or less. After the start of the defined transformation process, the renewal can advantageously be carried out for > 10 minutes, for example, > 30 minutes, > 2 hours, > 5 hours, > 24 hours, > 2 days, > 5 days, > 20 days.
Reheating gas can enter the diabatic reaction zone and/or rejuvenating gas can enter the adiabatic reaction zone and/or the diabatic reaction zone at a temperature of greater than or equal to about 400 ℃, < greater than or equal to about 450 ℃, < greater than or equal to about 500 ℃, < greater than or equal to about 550 ℃, < greater than or equal to about 600 ℃, < greater than or equal to 650 ℃, < greater than or equal to about 700 ℃, < greater than or equal to 750 ℃, < greater than or equal to about 800 ℃, < greater than or equal to 850 ℃, or greater than or. Additionally or alternatively, the reheat interval and/or the refresh interval may be operated at the aforementioned temperatures. Preferably, the reheat gas may enter the diabatic reaction zone and/or the rejuvenating gas may enter the adiabatic reaction zone and/or the diabatic reaction zone at a temperature of about 600 deg.C or greater. Additionally or alternatively, the reheat gas may enter the diabatic reaction zone and/or the rejuvenating gas may enter the adiabatic reaction zone and/or the diabatic reaction zone at a temperature of less than or equal to about 400 deg.C, less than or equal to about 450 deg.C, less than or equal to about 500 deg.C, less than or equal to about 550 deg.C, less than or equal to about 600 deg.C, less than or equal to 650 deg.C, less than or equal to about 700 deg.C, less than or equal to 750 deg.C, less than or equal to about 800 deg.C, less than or equal to 850 deg.C. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., about 400 ℃ to about 900 ℃, about 450 ℃ to about 850 ℃, about 500 ℃ to about 800 ℃, and the like. Preferably, the reheat gas may enter the diabatic reaction zone and/or the rejuvenating gas may enter the adiabatic reaction zone and/or the diabatic reaction zone at a temperature of from about 400 ℃ to about 800 ℃, more preferably from about 600 ℃ to about 800 ℃, more preferably from about 625 ℃ to about 700 ℃, more preferably from about 550 ℃ to about 750 ℃.
Additionally or alternatively, pressure reheat gases at greater than or equal to about 1.0psia, greater than or equal to about 5.0psia, greater than or equal to about 25.0psia, greater than or equal to about 50.0psia, greater than or equal to about 75.0psia, greater than or equal to about 100.0psia, greater than or equal to about 125.0psia, greater than or equal to about 150.0psia, greater than or equal to about 175.0, psia, greater than or equal to about 200.0psia, greater than or equal to about 225.0psia, greater than or equal to about 250.0psia, greater than or equal to about 275.0psia, greater than or equal to about 300.0psia, greater than or equal to about 325.0psia, or greater than or equal to about 350.0psia may enter the diabatic reaction zone and/or the renewables may enter the adiabatic reaction zone and/or the diabatic reaction zone. Additionally or alternatively, the reheat interval and/or the refresh interval may be operated at the aforementioned pressures. Preferably, the reheat gas may enter the diabatic reaction zone and/or the regeneration gas may enter the adiabatic reaction zone and/or the diabatic reaction zone at a pressure of greater than or equal to about 100.0 psia. Additionally or alternatively, reheat gases may enter the diabatic reaction zone and/or reheat gases may enter the adiabatic reaction zone and/or the diabatic reaction zone at pressures of less than or equal to about 1.0psia, less than or equal to about 5.0psia, less than or equal to about 25.0psia, less than or equal to about 50.0psia, less than or equal to about 75.0psia, less than or equal to about 100.0psia, less than or equal to about 125.0psia, less than or equal to about 150.0psia, less than or equal to about 175.0psia, less than or equal to about 200.0psia, less than or equal to about 225.0psia, less than or equal to about 250.0psia, less than or equal to about 275.0psia, less than or equal to about 300.0psia, less than or equal to about 325.0 psia. Specifically disclosed pressure ranges include any combination of the above listed values, for example, from about 1.0psia to about 350.0psia, from about 5.0psia to about 275.0psia, from about 25.0psia to about 250.0psia, and the like. In particular, the reheat gas may enter the diabatic reaction zone and/or the rejuvenating gas may enter the adiabatic reaction zone and/or the diabatic reaction zone at a pressure of from about 1psia to about 300psia, more preferably from about 5psia to about 250psia, more preferably from about 25psia to about 250 psia.
In various aspects, the reheating and/or rejuvenating catalyst material for the temperature can be greater than or equal to about 400 ℃, > or equal to about 450 ℃, > or equal to about 500 ℃, > or equal to about 550 ℃, > or equal to about 600 ℃, > or equal to 650 ℃, > or equal to about 700 ℃, > or equal to 750 ℃, > or equal to about 800 ℃, > or equal to 850 ℃, or equal to about 900 ℃. Additionally or alternatively, the temperature of the renewed catalyst material may be less than or equal to about 400 deg.C, less than or equal to about 450 deg.C, less than or equal to about 500 deg.C, less than or equal to about 550 deg.C, less than or equal to about 600 deg.C, less than or equal to 650 deg.C, less than or equal to about 700 deg.C, less than or equal to 750 deg.C, less than or equal to about 800 deg.C, less than or equal to 850 deg.C, or less than or. Specifically disclosed temperature ranges include combinations of any of the above values, e.g., about 400 ℃ to about 900 ℃, about 450 ℃ to about 850 ℃, about 500 ℃ to about 800 ℃, and the like. Preferably, the temperature of the renewed catalyst material may be from about 400 ℃ to about 800 ℃, more preferably from about 600 ℃ to about 800 ℃, more preferably from about 550 ℃ to about 750 ℃.
In various aspects, the reheating gas and/or the rejuvenating gas is provided by a suitable device (e.g., a rejuvenating device), such as, but not limited to, a fired heater. For example, in such an apparatus, the reheat gas can be heated to a suitable temperature as described above, and then the reheat gas is provided to the reaction zone. Additionally or alternatively, the reheated gas exiting the diabatic reaction zone may also be returned to the apparatus to be reheated to a suitable temperature as described above and then provided to the diabatic reaction zone. The apparatus may also produce steam and/or heat feed which then enters the adiabatic reaction zone.
Additionally or alternatively, the regenerated catalyst material may be separated from the reheat gases and/or volatile hydrocarbons in one or more separation steps, either inside or outside the regeneration zone, by any suitable means, such as, but not limited to, cyclones. In addition, hydrogen may be used for the separation step.
H. Regeneration
The process may further include a regeneration step to recapture lost catalyst activity due to coke material accumulation and/or metal buildup on the catalyst material during the reaction. Such a regeneration step may be performed when insufficient coke material is removed from the particulate material (e.g., spent catalyst material) in the regeneration zone. Advantageously, the regeneration step operates to remove and add particulate material to at least one reaction zone substantially constant, thereby maintaining continuous operation at high catalyst activity. For example, the catalyst activity may maintain greater than about 10% fresh catalyst activity in the at least one reaction zone, preferably greater than about 30% fresh catalyst activity and most preferably greater than about 60% and less than about 99.9% fresh catalyst activity.
i. Regeneration zone
In various aspects, in the regeneration step, at least a portion of the first particulate material from the at least one adiabatic reaction zone or rejuvenation zone and/or a portion of the second particulate material from the at least one heat transfer reaction or rejuvenation zone can be conveyed to the regeneration zone to produce regenerated catalyst material by methods known in the art. At least a portion of the regenerated catalyst material may be recycled to at least one adiabatic reaction zone, at least one diabatic reaction zone, and/or a rejuvenation zone.
The catalyst material may be continuously withdrawn and returned from the adiabatic reaction zone, the diabatic reaction zone, and/or the rejuvenation zone, or may be periodically withdrawn and returned from the adiabatic reaction zone, the diabatic reaction zone, and/or the rejuvenation zone. For a periodic process, the regeneration time between coke combustion, purging and reduced withdrawal is typically from about 24 hours (about 1 day) to about 240 hours (about 10 days), preferably from about 36 hours (about 1.5 days) to about 120 hours (about 5 days). Alternatively, for the continuous mode, the removal/addition particulate material ratio may be from about 0.0 wt% to about 100 wt% per day of particulate material reserve and preferably from about 0.25 wt% to about 30.0 wt% per day of particulate material reserve, with balanced particulate material addition/removal. Regeneration of the catalyst material may be carried out as a continuous process or may be carried out batchwise, and in both cases, intermediate vessels for reserve accumulation and/or reserve discharge may be required.
The removal and addition of particulate material (e.g., spent catalyst, fresh particulate material, regenerated catalyst material) may be at the same or different locations in the reactor system. Particulate material (e.g., fresh particulate material, regenerated catalyst material) may be added before or after the rejuvenation zone, while removed particulate material (e.g., spent catalyst material) may be added before or after the particulate material (e.g., spent catalyst material) passes through the rejuvenation zone. At least a portion of the regenerated catalyst material may be recycled to the at least one adiabatic reaction zone, the at least one diabatic reaction zone, or the at least one rejuvenation zone. Preferably, regenerated catalyst material and/or fresh particulate material is provided to the regeneration zone to minimize any loss in heat input and to remove any residual species that may be carried over by the regenerated catalyst material from the regeneration zone. Additionally or alternatively, a separator internal or external to the regeneration zone may be used to separate the inert material from the catalyst material, and then regenerated such that only the catalyst material is regenerated. Such separation may be performed using any suitable means based on the size, magnetic, and/or density property differences between the inert material and the regenerated catalyst material.
For the above processes, standpipes having the above-described particle sizes and operating conditions, well known to those skilled in the art, can be used to provide a means for transporting the particulate material between at least one of the reaction zone, the regeneration zone, and/or the regeneration zone. It is known to those skilled in the art that slide valves and lift gases may also be used to help circulate the granular material in the regeneration zone and/or to build up a pressure profile. The lift gas may be the same as the fluidizing gas used in the renewal zone, e.g., may contribute to minimizing hydrogen usage in the reaction system while also reducing the hydrogen stream formed by the coke material.
a. Regeneration interval
In various aspects, a regeneration interval may be performed to obtain a regenerated particulate material (e.g., a first particulate material, a second particulate material) when the particulate material (e.g., the first particulate material, the second particulate material) does not travel through the adiabatic reaction zone and/or the heat transfer reaction zone.
In particular, the feed to the adiabatic reaction zone may be periodically stopped and/or the first effluent to the diabatic reaction zone may be periodically stopped. After stopping the feed and/or the first effluent, a purge of any combustible gas may be performed to below the explosive limit. For example, the feed and/or reactor product (e.g., cyclopentadiene) can be purged below the explosive limit. As used herein, the term "below the explosive limit" means that a sufficient purge of any combustible gas has been conducted so that when the gas flow is changed to the next composition (e.g., regeneration gas), no harmful mixture is formed that could lead to an explosion. For example, if a combustible gas is present in the diabatic reaction zone and it is desired to introduce an oxidant, the system must first be purged with an inert gas to reduce the combustible gas concentration so that the introduction of the oxidant-containing gas does not result in an explosive mixture.
The regeneration gas may then be supplied to the adiabatic reaction zone and/or the diabatic reaction zone, where the particulate materials (e.g., first particulate material, second particulate material) contact the regeneration gas under regeneration conditions to oxidatively remove at least a portion of the coke material deposited cumulatively on the catalyst material to form a regenerated catalyst material. Suitable regeneration gases include, but are not limited to, oxygen and air. The regeneration gas may flow in a direction counter-current or co-current to the flow direction of the feed and/or the first effluent as described above for the reheat gas. The regeneration gas may further comprise an inert material (e.g., N)2). After contacting the regeneration gas in the reaction zone, purging the regeneration gas to below the explosive limit may be performed. Once the purge of regeneration gas is complete, the feed can be provided to the adiabatic reaction zone and/or the second effluent can be provided to the diabatic reaction zone.
Preferably, the regeneration interval may have a duration of greater than or equal to about 0.5 days, greater than or equal to about 1 day, greater than or equal to about 1.5 days, greater than or equal to about 2 days, greater than or equal to about 3 days, greater than or equal to about 4 days, greater than or equal to about 5 days, greater than or equal to about 6 days, greater than or equal to about 7 days, greater than or equal to about 8 days, greater than or equal to about 9 days, greater than or equal to about 10 days, greater than or equal to about 11 days, greater than or equal to about 12 days, greater than or equal to about 13 days, greater than or equal to about 14 days, or greater than or equal to about 15 days. As used herein, the term "day" refers to a period of about 24 hours, while the term "0.5 day" refers to a period of about 12 hours. Additionally or alternatively, the regeneration intervals can have a duration of less than or equal to about 0.5 day, less than or equal to about 1 day, less than or equal to about 1.5 days, less than or equal to about 2 days, less than or equal to about 3 days, less than or equal to about 4 days, less than or equal to about 5 days, less than or equal to about 6 days, less than or equal to about 7 days, less than or equal to about 8 days, less than or equal to about 9 days, less than or equal to about 10 days, less than or equal to about 11 days, less than or equal to about 12 days, less than or equal to about 13 days, less than or equal to about 14 days, or less than or equal to about 15 days. Ranges expressly disclosed include any combination of the above listed values, for example, from about 0.5 to about 15 days, from about 1 to about 12 days, from about 2 to about 11 days, and the like. Preferably, 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.
In various aspects, the regeneration interval can 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, about every 50 days, about every 75 days, about every 100 days, about every 125 days, about every 150 days, about every 170 days, about every 180 days, or about every 200 days. Ranges expressly disclosed include any combination of the above listed values, e.g., from about 1 to about 200 days, from about 1 to about 180 days, from about 2 to about 35 days, etc. Preferably, the regeneration interval may be performed with 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. Preferably, the regeneration interval may be performed with 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.
5III reaction System for converting acyclic C
In another embodiment, methods for converting C to C are provided5Hydrocarbons (e.g. acyclic C)5Hydrocarbon) to cyclopentadiene as shown in fig. 1. Reaction system 1 may comprise a reactor comprising C as described above5Hydrocarbons (e.g. ofAcyclic C5Hydrocarbons) feed stream 2 comprising cyclopentadiene intermediates, unconverted acyclic C5An effluent stream 3 of hydrocarbons and optionally cyclopentadiene; and at least one adiabatic reactor 4 as described above. The at least one adiabatic reactor 4 may include a first particulate material comprising a catalyst material as described above (not shown), a feed inlet (not shown) for providing the feed stream 2 to the reaction system 1, and an effluent outlet (not shown) for removing the first effluent stream 3. A heater 5 (e.g., a heat exchanger) can be present to heat the feed stream 2 to a temperature T1(e.g., about 575 ℃ or higher) which then enters at least one adiabatic reactor 4, as described above. Optionally, H2And/or comprises C1、C2、C3And/or C4A light hydrocarbon stream of hydrocarbons (not shown) may be supplied to the at least one adiabatic reactor 4.
The at least one adiabatic reactor 4 may be a fixed bed reactor (e.g., a horizontal or vertical fixed bed reactor) or a fluidized bed reactor as described above. Preferably, the at least one adiabatic reactor 4 may comprise at least one internal structure (not shown) as described above.
At least one adiabatic reactor 4 may be operated under the reaction conditions as described above to convert at least a portion of the C5Hydrocarbons (e.g. acyclic C)5Hydrocarbons) to cyclopentadiene intermediates. Additionally, the reaction conditions may include a temperature of about 450 ℃ to about 900 ℃ and/or a pressure of about 3psia to about 150 psia. Preferably, at least about 20 wt% of the acyclic C5The hydrocarbon is converted to a cyclopentadiene intermediate.
In addition, the reaction system may further include at least one heat transfer reactor 6 (e.g., a circulating fluidized bed reactor, a circulating settled bed reactor, a fixed bed reactor, an annular fixed bed reactor, a fluidized bed reactor, a fired tube reactor, or a convection-heated tube reactor). Preferably, the at least one heat transfer reactor 6 is a combustion tube reactor comprising a furnace and parallel reactor tubes 7 positioned in the radiant section of the furnace, and may include burners 8 for heating the reactor tubes 7 as described above. At least one heat transfer reactor 6 may comprise a catalyst-containing reactor as described aboveA second particulate material of material (not shown), a feed inlet (not shown) for providing the first effluent stream 3 to the at least one heat transfer reactor 6 and an effluent outlet (not shown) for removing the second effluent stream 9. Further, the at least one heat transfer reactor 6 can be operated at reaction conditions as described above to convert at least a portion of the cyclopentadiene intermediates and/or unconverted acyclic C in the first effluent stream 35The hydrocarbons are converted to a second effluent stream 9 comprising cyclopentadiene. Preferably, the at least one heat transfer reactor 6 has a substantially reverse or isothermal temperature profile as described above. The first effluent stream 3 can be at a temperature T2(e.g., ≦ about 500 ℃) is provided to the at least one heat transfer reactor 6. A heater 10 (e.g., a heat exchanger) can be present to heat the first effluent stream 3, which then enters at least one heat transfer reactor 6. Optionally, the at least one heat transfer reactor 6 may include one or more heating devices (e.g., combustion tubes, heating coils) (not shown) to maintain the temperature therein.
In addition, auxiliary H2(not shown) may be supplied to the at least one adiabatic reactor 4 and/or the at least one heat transfer reactor 6.
Additionally, the reaction system 1 can further comprise at least one cyclone (not shown) for separating the first particulate material and/or the second particulate material, which can be entrained in the hydrocarbons (e.g., cyclopentadiene) in the first effluent stream 3 and/or the second effluent stream 9. Another effluent stream (not shown) substantially free of particulate material may then proceed to a product recovery system.
In another embodiment, the reaction system 1 may further comprise a rejuvenating gas stream 11 for rejuvenating the first granular material, as shown in fig. 2. The rejuvenating gas stream 11 can enter via the feed inlet or via a different inlet (not shown). The regeneration gas stream 11 may comprise hydrogen and optionally an inert (e.g., N)2，CO) is used to remove at least a portion of the progressively deposited coke material on the spent catalyst material to form renewed catalyst material and volatile hydrocarbons. In addition, the renewed catalyst material comprises spent catalyst such as described aboveLess progressive coke material, preferably at least about 10 wt% less progressive coke material than spent catalyst material. After a suitable duration as described above, the rejuvenation gas and optionally the volatile hydrocarbons can leave the at least one adiabatic reactor 4 as a first effluent rejuvenation gas stream (not shown) via an effluent outlet or a different outlet (not shown). The first effluent rejuvenation gas stream may proceed directly to the heat transfer reactor 6 or may first proceed through a heater (not shown). The renewed catalyst material includes less of the staged deposited coke material than the spent catalyst material described above, preferably at least about 10 wt% less of the staged deposited coke material than the spent catalyst material. The rejuvenating gas stream 11 can flow in a direction co-current or counter-current to the flow direction of the feed stream 2.
Additionally or alternatively, the rejuvenation gas stream 11 can enter at least one heat transfer reactor 6 for rejuvenating a second particulate material (not shown). After a suitable duration as described above, the rejuvenation gas and optionally the volatile hydrocarbons can leave the at least one heat transfer reactor 6 as a second effluent rejuvenation gas stream 12 via an effluent outlet or a different outlet (not shown). The renewed catalyst material comprises less of the staged deposited coke material than the spent catalyst material described above, preferably at least about 10 wt% less of the staged deposited coke material than the spent catalyst material. The rejuvenating gas stream 11 can flow in a direction co-current or counter-current to the flow direction of the first effluent stream 3.
Furthermore, the rejuvenation gas stream 11 can be provided by a rejuvenation means 13, as described above, in fluid connection with the at least one adiabatic reactor 4 and/or the at least one heat-transfer reactor 6. A first effluent rejuvenation gas stream (not shown) and a second effluent rejuvenation gas stream 12 can be passed to a compression device 14 and then to a separation unit 15, where a light hydrocarbon-rich gas stream 16 and a light hydrocarbon-lean gas stream 17 can be produced. The light hydrocarbon rich gas stream 16 can be used as fuel. The light hydrocarbon depleted gas stream 17 may be combined with a make-up hydrogen stream 18 and heated in a heater 19 (e.g., a heat exchanger or other heating device) to produce regenerationGas stream 11. The rejuvenation means 13 may comprise one or more heating devices as described above, a rejuvenation inlet for the light hydrocarbon-depleted gas stream 17 and a rejuvenation outlet (not shown) for returning the rejuvenation gas stream 11 to the at least one adiabatic reactor 4 and/or the at least one heat-transfer reactor 6. Separation device 15 may be a membrane system, an adsorption system (e.g., pressure swing, temperature swing), or other known separation device for separating H from light hydrocarbons2The system of (1).
In particular, the upgrader 13 is operated under the above conditions, preferably with the temperature of the upgrader 13 being in the range of about 550 ℃ to about 800 ℃. Additionally, the rejuvenation device 13 can produce a steam stream 20. Furthermore, the rejuvenating means 13 can heat the feed stream 2, and then the feed stream 2 enters the at least one adiabatic reactor 4 (not shown) when the adiabatic reactor is not rejuvenated or regenerated.
In another embodiment, the reaction system 1 may further comprise a regeneration gas stream 21, as shown in fig. 3. The regeneration gas stream 21 may enter the at least one adiabatic reactor 4 and/or the at least one heat transfer reactor 6 (not shown) under regeneration conditions as described above to re-move at least a portion of the coke material deposited on the catalyst material (e.g., spent catalyst material) to form regenerated catalyst material. After a suitable duration as described above, the regeneration gas may leave the at least one heat transfer reactor 6 as a regeneration gas stream 22 for the first cycle and/or the at least one adiabatic reactor 4 as a regeneration gas stream for the second cycle (not shown). The regeneration gas stream of the second cycle may enter the at least one heat transfer reactor 6. The regeneration gas stream 21 may be provided by a regeneration unit 23 as described above in fluid connection with the at least one adiabatic reactor 4 and/or the at least one heat transfer reactor 6.
Additionally or alternatively, the reaction system 1 may further comprise a fresh stream of granular material (not shown) fluidly connected to the at least one reactor 6 (not shown).
Additionally or alternatively, the at least one adiabatic reactor 4 and/or the at least one heat transfer reactor 6 may comprise more than 1 reactor, e.g., 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. Preferably, the reaction system comprises 1 to 20 reactors, more preferably 3 to 15 reactors, more preferably 5 to 10 reactors. Wherein the at least one adiabatic reactor 4 and/or the at least one heat transfer reactor 6 comprises first, second and third reactors, etc., the reactors being operable in parallel and periodically undergoing regeneration and regeneration intervals as needed when granular material needs to be renewed to remove coke material.
Fig. 1,2 and 3 indicate the flow at a specific point in time. It should be appreciated that at other points in time the flow may deviate from that shown in FIGS. 1,2 and 3, as the reactor may be periodically exposed to oil (on-oil) feed conversion, regeneration and/or regeneration cycles.
Further embodiments
The invention further relates to:
embodiment 1. acyclic C in a reactor System5A process for converting hydrocarbons to cyclopentadiene, wherein the process comprises: providing at least one adiabatic reaction zone (e.g., fixed bed, fluidized bed) with a catalyst comprising acyclic C5The hydrocarbon feed being at a temperature T1Wherein the at least one adiabatic reaction zone comprises a first particulate material comprising a catalyst material (e.g., platinum on ZSM-5, platinum on zeolite L, platinum on silicate-modified silica, a group 6, group 9, or group 10 metal on an inorganic support such as zeolite, SAPO, ALPO, MeAPO, silica, zirconia, titania, alumina, magnesia, clay, ceria, zirconia, yttria, magnesium hydrotalcite, calcium aluminate, zinc aluminate, and combinations thereof, and optionally one or more group 1 alkali metals, group 2 alkaline earth metals, and/or group 11 metals) contacting the feed and the first particulate material in the at least one adiabatic reaction zone under reaction conditions to contact at least a portion of the acyclic C5Conversion of hydrocarbons to unconverted acyclic C's containing cyclopentadiene intermediates5A first effluent of hydrocarbons and optionally cyclopentadiene; heating the first effluent to a temperature T2(ii) a Providing the first effluent to at leastA diabatic reaction zone (e.g., a circulating fluidized bed reactor, a circulating settled bed reactor, a fixed bed reactor, an annular fixed bed reactor, a fluidized bed reactor, a fired tube reactor, or a convection-heated tube reactor); contacting the first effluent with a second particulate material comprising a catalyst material (e.g., platinum on ZSM-5, platinum on zeolite L, and/or platinum on silicate-modified silica) in the at least one diabatic reaction zone under reaction conditions to contact the at least a portion of the cyclopentadiene intermediates and/or unconverted acyclic C5Converting the hydrocarbons to a second effluent comprising cyclopentadiene; optionally, will contain C1、C2、C3And/or C4Feeding light hydrocarbons of the hydrocarbons to the at least one adiabatic reaction zone; and optionally adding an auxiliary H2Is fed to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone.
Embodiment 2. the process of embodiment 1, wherein the heat load of the at least one diabatic reaction zone is reduced by at least about 3.0% per unit of cyclopentadiene produced when compared to a process in which the adiabatic reaction zone is not present.
Embodiment 3. the process of embodiment 1 or 2, wherein a reverse temperature profile or isothermal temperature profile is maintained in the at least one diabatic reaction zone.
Embodiment 4. the method of any one of the preceding embodiments, wherein T1And/or T2Less than or equal to about 500 ℃.
Embodiment 5. the process of any of the preceding embodiments, wherein the temperature of the second effluent exiting the at least one diabatic reaction zone is at least about 550 ℃.
Embodiment 6. the process of any of the preceding embodiments, wherein the at least one diabatic reaction zone comprises at least one heating device.
Embodiment 7. the process of any of the preceding embodiments, wherein (i) the reaction conditions in the at least one diabatic reaction zone comprise a temperature of from about 400 ℃ to about 800 ℃ and/or a pressure of from about 3psia to about 150 psia; and/or (ii) the reaction conditions in the at least one adiabatic reaction zone comprise a temperature of from about 450 ℃ to about 900 ℃ and/or a pressure of from about 3psia to about 150 psia.
Embodiment 8. the method of any of the preceding embodiments, wherein at least about 30 wt% of the acyclic C5The hydrocarbon is converted to cyclopentadiene.
Embodiment 9. the process of any of the preceding embodiments, wherein the first effluent flows co-currently or counter-currently to the direction of the flow of the second particulate material in the at least one diabatic reaction zone.
Embodiment 10 the method of any of the preceding embodiments further comprises conveying at least a portion of the first particulate material from the at least one adiabatic reaction zone to an renewal zone and/or conveying at least a portion of the second particulate material from the at least one diabatic reaction zone to the renewal zone.
Embodiment 11 the process of embodiment 10, further comprising contacting the first particulate material and/or the second particulate material with hydrogen to remove at least a portion of the progressively deposited coke material on the catalyst material to form a renewed catalyst material and volatile hydrocarbons; and returning the rejuvenated catalyst material to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone.
Embodiment 12. the process of any of embodiments 10 or 11, wherein the renewal zone is operated at a temperature of about 550 ℃ to about 800 ℃ and/or at least 10 wt% of the progressively deposited coke material is removed from the catalyst material.
Embodiment 13. the process of any of the preceding embodiments further comprises transporting at least a portion of the first particulate material from the at least one adiabatic reaction zone to a regeneration zone and/or transporting at least a portion of the second particulate material from the at least one diabatic reaction zone to the regeneration zone; wherein the first particulate material and/or the second particulate material are contacted with a regeneration gas under regeneration conditions to oxidatively remove at least a portion of the coke material deposited on the catalyst material to form a regenerated catalyst material; and recycling at least a portion of the regenerated catalyst material to the at least one adiabatic reaction zone, the at least one diabatic reaction zone, and/or the rejuvenation zone.
Embodiment 14 the process of any one of embodiments 1,2, 3,4, 5,6, 7, or 8, further comprising periodically stopping the feed to the at least one adiabatic reaction zone and/or the first effluent to the at least one diabatic reaction zone; and providing a rejuvenating gas to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone, optionally wherein the feed and/or the first effluent flow co-currently or counter-currently to the direction of the rejuvenating gas flow.
Embodiment 15 the process of embodiment 14 wherein the rejuvenating gas includes hydrogen and the rejuvenating gas contacts the first particulate material and/or the second particulate material to remove at least a portion of the coke material that has progressively deposited on the catalyst material to form a rejuvenated catalyst material and volatile hydrocarbons.
Embodiment 16 the process of any one of embodiments 1,2, 3,4, 5,6, 7, or 8, further comprising periodically stopping the feed to the at least one adiabatic reaction zone and/or the first effluent to the at least one diabatic reaction zone; providing a refresh gas comprising hydrogen; and contacting the first particulate material and/or the second particulate material with the rejuvenating gas to remove at least a portion of the progressively deposited coke material on the catalyst material to form a rejuvenated catalyst material and volatile hydrocarbons.
Embodiment 17 the method of any one of embodiments 14, 15, or 16, wherein at least about 10.0 wt% of the progressively deposited coke material is removed from the catalyst material.
Embodiment 18 the process of any one of embodiments 14, 15, 16 or 17, further comprising periodically stopping the feed to the at least one adiabatic reaction zone and/or the first effluent to the at least one diabatic reaction zone; supplying a regeneration gas to the at least one adiabatic reaction zone and/or to the at least one diabatic reaction zone; and contacting the first particulate material and/or the second particulate material with the regeneration gas under regeneration conditions to oxidatively remove at least a portion of the coke material deposited on the catalyst material to form a regenerated catalyst material, optionally wherein the regeneration gas contacts the first particulate material and/or the second particulate material at intervals of from about every 1 day to about 180 days.
Embodiment 19. the method of any of the preceding embodiments, wherein the first particulate material and the second particulate material are the same or different.
Embodiment 20 the method of any one of the preceding embodiments, wherein the first particulate material further comprises an inert material and/or the second particulate material further comprises an inert material.
The invention further relates to embodiments 21 to 26:
embodiment 21. acyclic C in a reactor System5A process for converting hydrocarbons to cyclopentadiene, wherein the process comprises:
at a temperature T1Providing at least one adiabatic reaction zone with a catalyst comprising acyclic C5A feed of hydrocarbons, wherein the at least one adiabatic reaction zone comprises a first particulate material comprising a catalyst material;
contacting the feed and the first particulate material in the at least one adiabatic reaction zone under reaction conditions to contact at least a portion of the acyclic C5Conversion of hydrocarbons to unconverted acyclic C's containing cyclopentadiene intermediates5A first effluent of hydrocarbons and optionally cyclopentadiene;
heating the first effluent to a temperature T2；
Providing the first effluent to at least one diabatic reaction zone; and
contacting the first effluent with a second particulate material in the at least one diabatic reaction zone under reaction conditions to contact at least a portion of the cyclopentadiene intermediate and the unconverted acyclic C5Converting the hydrocarbons to a second effluent comprising cyclopentadiene;
embodiment 22 the method of embodiment 21, wherein the first particulate material further comprises an inert material and/or the second particulate material further comprises an inert material.
Embodiment 23 the process of embodiment 21 wherein the catalyst material comprises platinum on ZSM-5, platinum on zeolite L and/or platinum on silica.
Embodiment 24 the method of embodiment 21, wherein the first particulate material and the second particulate material are different.
Embodiment 25 the process of embodiment 24, wherein the second particulate material comprises platinum on ZSM-5, platinum on zeolite L and/or platinum on silicate-modified silica and the first particulate material comprises at least one group 6, group 9 or group 10 metal, and optionally one or more group 1 alkali metals, group 2 alkaline earth metals and/or group 11 metals on an inorganic support; and
embodiment 26 the process of embodiment 25, wherein the inorganic support is selected from the group consisting of zeolites, SAPOs, ALPOs, meapos, silicas, zirconias, titanias, aluminas, magnesias, clays, ceria, yttria, zirconia, magnesium hydrotalcites, calcium, aluminates, zinc aluminates, and combinations thereof.
Industrial applications
Acyclic C5Containing cyclic, branched and linear C obtained during the conversion process5Hydrocarbon and optionally containing hydrogen, C4And light by-products or C6And heavy by-products, which are valuable products in and of themselves. Preferably, CPD and/or DCPD can be separated from the reactor effluent to obtain a purified product stream, which can be used to produce a variety of high value products.
For example, a purified product stream containing 50 wt% or more, or preferably 60 wt% or more DCPD can be used to produce hydrocarbon resins, unsubstituted polyester resins, and epoxy materials. The purified product stream containing 80 wt% or more, or preferably 90 wt% or more CPD can be used to produce diels-alder reaction products formed according to reaction scheme (I) below:
scheme I
Figure BDA0001648294470000691
Wherein R is a heteroatom or substituted heteroatom, substituted or unsubstituted C1-C50A hydrocarbyl group (often a double bond-containing hydrocarbyl group), an aromatic group, or any combination thereof. Preferably, substitutedThe radical or group contains one or more elements of groups 13 to 17, preferably groups 15 or 16, more preferably nitrogen, oxygen, or sulfur. In addition to the diels-alder reaction products of mono-olefins depicted in scheme (I), the purified product stream containing 80 wt% or more, or preferably 90 wt% or more CPD can be used to form diels-alder reaction products of CPD with one or more of: another CPD molecule, a conjugated diene, acetylene, propadiene, a disubstituted olefin, a trisubstituted olefin, a cyclic olefin and substituted versions of the foregoing. Preferred diels-alder reaction products include norbornene, ethylidene norbornene, substituted norbornenes (including oxygenated norbornenes), norbornadiene, and tetracyclododecenes as shown in the following structures:
Figure BDA0001648294470000701
the foregoing diels-alder reaction products are useful for producing copolymers of polymers and cyclic olefin co-olefins such as ethylene. The resulting cyclic olefin copolymers and cyclic olefin polymer products are useful in a variety of applications, such as packaging films.
The purified product stream containing 99 wt% or more DCPD can be used to produce CPD polymers using, for example, a Ring Opening Metathesis Polymerization (ROMP) catalyst. The DCPD polymer products are useful for forming articles, particularly molded parts, such as wind turbine blades and automotive parts.
Additional components may also be separated from the reactor effluent and used to form high value products. For example, the isolated cyclopentene can be used to produce a polycyclopentene, also known as a polypentene rubber, as depicted in scheme (II).
Scheme II
Figure BDA0001648294470000702
The isolated cyclopentane can be used as blowing agent as well as solvent. Straight and branched C5The product is useful for conversion to higher olefins and alcohols.Cyclic and acyclic C5The product, optionally after hydrogenation, can be used as an octane enhancer and a transportation fuel blending component.
Examples
The following examples illustrate the invention. Many modifications and variations are possible, and it is understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. Room temperature was 23 ℃ unless otherwise stated.
EXAMPLE 1 ZSM-5 catalyst composition Synthesis
From 10,000g Deionized (DI) water, 600g of 50% NaOH solution, 25g of 45% sodium aluminate solution, 730g of n-propylamine 100% solution, 80g of ZSM-5 seed crystals and 3,190g of Ultrasil PMTMThe synthesis mixture prepared from the modified silica having about 20.3% solids was mixed in a 5 gallon container and then added to a 5 gallon autoclave after mixing. The synthesis mixture had the following molar composition:
Figure BDA0001648294470000711
the synthesis mixture was mixed and reacted at 230 ℃ F. (110 ℃) for 72 hours at 250 rpm. The resulting product was filtered and washed with deionized water, then dried in an oven at about 250 ° F (121 ℃) overnight. The XRD pattern of the as-synthesized material (not shown) shows a pure phase of typical ZSM-5 topology and the material consists of a mixture of large crystals about 2 microns in size. A portion of the as-synthesized crystals were converted (for characterization) to the hydrogen form by ion exchange three times with ammonium nitrate solution at room temperature, then dried at 250 ° F (121 ℃) and calcined at 1000 ° F (540 ℃) for 6 hours. SiO of ZSM-5 crystal obtained2/Al2O3The molar ratio was about 414 and the total Surface Area (SA)/(microporous SA + hollow SA) was 490(440+51) m2A hexane absorption of 117mg/g and an alpha value of 31. The second part of the material was used as-synthesized for Pt impregnation.
Mixing SiO2/Al2O3ZSM-5 with a molar ratio of 414 and a sodium content of 0.38 wt.% in nitrogenCalcination was carried out at 900 ℃ F. (482 ℃) for 6 hours. After cooling, the sample was reheated to 900 ° F (482 ℃) in nitrogen and held for 3 hours. The atmosphere was then gradually changed to 1.1, 2.1, 4.2 and 8.4% oxygen in four steps. Each step was held for 30 minutes. The temperature was increased to 1000 ° F (540 ℃), the oxygen content was increased to 16.8%, and the material was held at 1000 ° F (540 ℃) 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 dried at 250 ° F (121 ℃) for 4 hours, and finally calcined in air at 660 ° F (349 ℃) for 3 hours. The catalyst composition powder was pressed (15 tons), crushed and sieved to obtain a particle size of 20-40 mesh.
Example 2 evaluation of catalyst composition Properties
The catalyst composition of example 1 (0.5g) was physically mixed with quartz (1.5g, 60-80 mesh) and charged to a reactor. The catalyst composition was dried under He (100mL/min, 30psig (207kPa), 250 ℃) for 1 hour, then under H2(200mL/min, 30psig (207kPa), 500 ℃) for 1 hour. Then using n-pentane and H2And balance He, typically at 550-5H121.0 mol of H2：C5H12，14.7h-1The catalyst composition was tested at WHSV and 30psig (207kPa) total. Passing through H at 550-600 DEG C2After 5 hours of initial testing of the treatment (200mL/min, 30psig (207kPa), 650 ℃), the catalyst compositions were tested for stability and regeneration performance, and then re-tested for performance at 600 ℃.
Cyclopentadiene and three equivalents of hydrogen are produced by dehydrogenation and cyclization of n-pentane (equation 1). This is accomplished by flowing n-pentane over the solid Pt-containing catalyst composition at an elevated temperature. The performance of ZSM-5 (414: 1)/0.5% Pt of example 1 is based on n-pentane conversion, cyclic C5Production (cC)5) Cleavage yield and stability. These results are summarized in table 2A, table 2B, fig. 3A and fig. 3B.
Figure BDA0001648294470000721
TABLE 2A
Figure BDA0001648294470000722
TABLE 2B
Figure BDA0001648294470000723
Tables 2A and 2B show the values at 5.0psia (35kPa-a) C5H12,1: 1 mol of H2：C514.7WHSV, n-pentane conversion at various temperatures for a total of 45psia (310kPa-a) of 0.5g ZSM-5 (414: 1)/0.5 wt% Pt catalyst composition, and cyclic C5、CPD、C1And C2-4Selectivity and yield of cleavage product (average of 8 hours at each temperature). In Table 2A, the selectivities and yields are for the cyclic C formed respectively5，CPD，C1And C2-4The hydrocarbons are expressed in mole percent; i.e. molar selectivity for the cyclic C formed separately5，CPD，C1And C2-4Divided by the total moles of pentane converted. In Table 2B, the selectivities and yields are for the cyclic C formed separately5，CPD，C1And C2-4The hydrocarbons are expressed as a percentage of carbon; i.e. carbon selectively in the respectively formed cyclic C5，CPD，C1And C2-4Divided by the total moles of carbon in the converted pentane.
As can be seen, tables 2A and 2B show greater than 80% pentane conversion at high WHSV, and 40% para-cyclic C at 595 ℃5Selectivity of the substance. While not a specific end product, cyclopentane and cyclopentene can be recycled to produce CPD. At each temperature and at 650 ℃ in H2Activity was maintained for 8 hours after 5 hours of treatment.
Example 3 reactor Performance modeling
The above data sets and similar experimental data were used to guide the construction of models at Invensys Systems Inc. PRO/II 9.1.4 (for examples 3A-3H) and Invensys Systems Inc. PRO/II 9.3.4 (for examples 3I-3N) to evaluate performance at various commercially relevant operating conditions and different reactor configurations. Depending on the particular situation of modeling, variations in results may occur, but the model still shows the relative benefits of the present invention. Many modifications and variations are possible, and it is understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. .
2Example 3A-8psia Outlet, H Co-feed, Combustion tube reactor
As a comparative example, an 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion pipeline reactor was fed with a 0.5: 1.0 molar ratio of hydrogen: n-pentane simulation; sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.609 lb-mole of n-pentane, 0.8045 lb-mole of hydrogen and a flare reactor heat load of 0.1775MM BTU were required.
Example 3B-8psia Outlet, Combustion tube reactor
As a comparative example, an 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a pressure of 0.0: 1.0 molar ratio of hydrogen: simulating the feeding of n-pentane; sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.5638 lb-mole of n-pentane, 0.0 lb-mole of H were required2And the combustion tube reactor thermal load was 0.1741MM BTU. Although this is an even more attractive CPD yield and reduced heat load than example phase 3A, the catalyst used to convert n-pentane to CPD is free of H2With co-feeds, coke will rapidly coke.
2 4Example 3C-8psia Outlet, H Co-feed, CH Co-feed, Combustion tube reactor
As a comparative example, an 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a pressure of 0.5: 1.0: 3.8854 molar ratio of hydrogen: n-pentane: CH (CH)4Simulation of the feed of (a); sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.2412 lb-mole of n-pentane, 0.6207 lb-mole of hydrogen and the flare reactor thermal load of 0.1647MM BTU were required. This is an even more attractive CPD yield and reduced heat load compared to examples 3A and 3B.
2 4Example 3D-8psia Outlet, H Co-feed, CH Co-feed, adiabatic Pre-reactor, Combustion tube delayed reaction Reactor
As an illustration of the invention, a 500 ℃ inlet, 72.0psia outlet, adiabatic reactor, then 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a 0.5: 1.0: 3.8854 molar ratio of H2: n-pentane: CH (CH)4Simulating the feeding of (1); sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.2412 lb-mole of n-pentane, 0.6207 lb-mole of H, was required2And the combustion tube reactor thermal load was 0.1542MM BTU. Although this is the same yield as CPD as example 3C, the heat load is reduced compared to examples 3A, 3B and 3C; the heat load was reduced by 6.4% compared to 3C.
2Example 3E-16psia Outlet, H Co-feed, Combustion tube reactor
Comparative examples similar to 3A were simulated at superatmospheric pressure. 16psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor at 0.5: 1.0 molar ratio of H2: simulating the feeding of n-pentane; sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 2.846 lb-mole of n-pentane, 1.423 lb-mole of H were required2And the combustion tube reactor thermal load was 0.2358MM BTU.This has eliminated O2Potential problems with entry, but increased feed rates and heat loads were required compared to the above examples.
2 4Example 3F-16psia Outlet, H Co-feed, CH Co-feed, Combustion tube reactor
To study the performance of example 3E, 16psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a pressure of 0.5: 1.0: 3.8854 molar ratio of H2: n-pentane: CH (CH)4Simulating the feeding of (1); sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD, 1.609 lb-mole of n-pentane in the flare reactor effluent, 0.8045 lb-mole of H was required2And a burner tube heat load of 0.1903MM BTU. Although this is an even more attractive CPD yield than example 3E and the heat load is reduced compared to example 3E, there is still potential for improvement by application of the present invention.
2 4Example 3G-8psia Outlet, H Co-feed, CH Co-feed, adiabatic Pre-reactor, Combustion tube delayed reaction Reactor
As an illustration of the invention, a 500 ℃ inlet, 72.0psia outlet, adiabatic reactor, then 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a 0.5: 1.0: 3.8854 molar ratio of H2: n-pentane: CH (CH)4Simulating the feeding of (1); sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.609 lb-mole of n-pentane, 0.8045 lb-mole of H, was required2And the combustion tube reactor thermal load was 0.1767MM BTU. Although this is the same CPD yield as example 3F, the heat load is reduced by 7.5% compared to 3F.
4Example 3H-8psia Outlet, CH Co-feed, adiabatic Pre-reactor, Combustion tube delayed reactor
As an illustration of the invention, 500 ℃ inlet, 72.0psia outlet, adiabatic reactionReactor, then 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor at 0.0: 1.0: 3.8854 molar ratio of H2: n-pentane: CH (CH)4Simulating the feeding of (1); sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.517 lb-mole of n-pentane, 0.0 lb-mole of H were required2And the combustion tube reactor thermal load was 0.1652MM BTU. Use of the invention allows for reduction or elimination of H2Co-feeding, since the adiabatic reactor will produce H before the process stream enters the heat transfer reactor2This is more prone to coking. The CPD yield is thus improved compared to example 3F (i.e., less n-pentane is required to produce the same amount of CPD) and the heat load is reduced by 13.2% compared to 3F.
2Example 3I-8psia Outlet, H Co-feed, Combustion tube reactor
As a comparative example, an 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a pressure of 1.0: 1.0 molar ratio of hydrogen: simulating the feeding of n-pentane; sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.647 lb-mole of n-pentane, 1.647 lb-mole of hydrogen and the flare reactor heat load of 0.1802MM BTU were required.
2Example 3J-8psia Outlet, H Co-feed, adiabatic Pre-reactor, Combustion tube delayed reactor
As an illustration of the invention, a 500 ℃ inlet, a 13psia outlet, an adiabatic reactor, then an 8psia outlet, a 500 ℃ inlet, a 575 ℃ outlet, a combustion tube reactor was operated at a pressure of 1.0: 1.0 molar ratio of H2: the feed of n-pentane simulates and provides sufficient residence time for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.647 lb-mole of n-pentane and 1.647 lb-mole of H were required2And a combustion tube reactor heat load of 0.1688MM BTU. With this the CPD yield was the same as in example 3I, butThe heat load is reduced by 6.3%.
2Example 3K-8psia Outlet, H Co-feed, adiabatic Pre-reactor, Combustion tube delayed reactor
As a further demonstration of the invention, 575 ℃ inlet, 13psia outlet, adiabatic reactor, then 8psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a pressure of 1.0: 1.0 molar ratio of H2: the feed of n-pentane simulates and provides sufficient residence time for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.647 lb-mole of n-pentane and 1.647 lb-mole of H were required2And the combustion tube reactor thermal load was 0.1589MM BTU. Although this was the same CPD yield as example 3I, the heat duty was reduced by 11.8%, and such reduction in heat duty was higher than that achieved in example 3J due to the higher inlet temperature of the adiabatic pre-reactor.
2 4Example 3L-16psia Outlet, H Co-feed, CH Co-feed, Combustion tube reactor
As a comparative example, a 16psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion pipeline reactor was operated at a pressure of 1.0: 1.0: 4.35 molar ratio of hydrogen: n-pentane: feed simulation of methane; sufficient residence time is provided for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.647 lb-mole of n-pentane, 1.647 lb-mole of hydrogen and the flare reactor heat load of 0.1951MM BTU were required.
2 4Example 3M-16psia Outlet, H Co-feed, CH Co-feed, adiabatic Pre-reactor, Combustion tube delayed reaction Reactor
As an illustration of the invention, a 500 ℃ inlet, a 21psia outlet, an adiabatic reactor, then a 16psia outlet, a 500 ℃ inlet, a 575 ℃ outlet, a combustion tube reactor was operated at a pressure of 1.0: 1.0: 4.35 molar ratio of H2: n-pentane: feed simulation of methane and provision of CPD concentrationSufficient residence time to reach its thermodynamic concentration at reactor exit conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.647 lb-mole of n-pentane and 1.647 lb-mole of H were required2And the combustion tube reactor thermal load was 0.1735MM BTU. Although this was the same CPD yield as example 3L, the heat load was reduced by 11.1%.
2 4Example 3N-16psia Outlet, H Co-feed, CH Co-feed, adiabatic Pre-reactor, Combustion tube delayed reaction Reactor
As an illustration of the invention, 575 ℃ inlet, 21psia outlet, adiabatic reactor then 16psia outlet, 500 ℃ inlet, 575 ℃ outlet, combustion tube reactor was operated at a pressure of 1.0: 1.0: 4.35 molar ratio of H2: n-pentane: the feed of methane was simulated and provided sufficient residence time for the CPD concentration to reach its thermodynamic concentration at reactor outlet conditions. To produce 1 lb-mole of CPD in the flare reactor effluent, 1.647 lb-mole of n-pentane and 1.647 lb-mole of H were required2And the combustion tube reactor thermal load was 0.1735MM BTU. While this was the same CPD yield as example 3L, the heat duty was reduced by 20.6%, and such heat duty reduction was higher than that achieved in example 3M due to the higher inlet temperature of the adiabatic pre-reactor.
These examples demonstrate that given the feed composition and heat transfer reactor operating conditions and the use of the present invention (i.e., the addition of an adiabatic reactor upstream of the heat transfer reactor), the CDP yield is improved (i.e., less n-pentane is required to produce the same amount of CPD) and the heat load is reduced.
All documents described herein are incorporated by reference, including any priority documents and/or test procedures, as long as they are not inconsistent herewith. It will be apparent from the foregoing general description and this detailed description that, 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. Similarly, the term "comprising" is considered synonymous with the term "including". Similarly, whenever a composition, element or group of elements is preceded by the transitional phrase "comprising," it is to be understood that we also contemplate that the same composition or group of elements has the transitional phrase "consisting essentially of," "consisting of," "selected from" or "being" before the composition, element or group of elements, and vice versa.

Claims (25)

1. Acyclic C in a reactor system5A process for converting hydrocarbons to cyclopentadiene, wherein the process comprises:
at a temperature T1Providing at least one adiabatic reaction zone with a catalyst comprising acyclic C5A feed of hydrocarbons, wherein the at least one adiabatic reaction zone comprises a first particulate material comprising a catalyst material;
contacting the feed and the first particulate material in the at least one adiabatic reaction zone under reaction conditions to contact at least a portion of the acyclic C5Conversion of hydrocarbons to unconverted acyclic C's containing cyclopentadiene intermediates5A first effluent of hydrocarbons and optionally cyclopentadiene;
heating the first effluent to a temperature T2；
Providing the first effluent to at least one diabatic reaction zone; and
contacting the first effluent with a second particulate material in the at least one diabatic reaction zone under reaction conditions to contact at least a portion of the cyclopentadiene intermediate and the unconverted acyclic C5The hydrocarbons are converted to a second effluent comprising cyclopentadiene.
2. The process of claim 1, wherein the heat load of the at least one diabatic reaction zone is reduced by at least 3.0% per unit of cyclopentadiene produced when compared to a process in which the adiabatic reaction zone is not present.
3. The process of claim 1, wherein a reverse temperature profile or an isothermal temperature profile is maintained in the at least one diabatic reaction zone, wherein a reverse temperature profile means that the temperature at the inlet of the diabatic reaction zone is lower than the temperature at the outlet of the diabatic reaction zone and an isothermal temperature profile means that the temperature of the at least one diabatic reaction zone is maintained substantially constant.
4. The process of claim 1, wherein the at least one adiabatic reaction zone is a fixed bed reactor or a fluidized bed reactor.
5. The method of claim 1, wherein T1And/or T2Less than or equal to 500 ℃.
6. The process of claim 1, wherein the temperature of the second effluent exiting the at least one diabatic reaction zone is at least 550 ℃.
7. The method of claim 1, further comprising including C1，C2，C3And/or C4A light hydrocarbon co-feed of hydrocarbons is supplied to the at least one adiabatic reaction zone.
8. The method of claim 1, further comprising reacting H2Is fed to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone.
9. The process of claim 1, wherein the at least one diabatic reaction zone comprises at least one heating device.
10. The process of claim 1, wherein the reaction conditions in the at least one diabatic reaction zone comprise a temperature of from 400 ℃ to 800 ℃ and a pressure of from 3psia to 150 psia.
11. The process of claim 1, wherein the reaction conditions in the at least one adiabatic reaction zone comprise a temperature of from 450 ℃ to 900 ℃ and a pressure of from 3psia to 150 psia.
12. The process of claim 1, wherein at least 30 wt% of the acyclic C5The hydrocarbon is convertedAnd converted into cyclopentadiene.
13. The process of claim 1, wherein the at least one diabatic reaction zone is a circulating settled bed reactor, a fixed bed reactor, a fluidized bed reactor, a fired tube reactor, or a convectively heated tube reactor.
14. The method of claim 13, wherein the fluidized bed reactor is a circulating fluidized bed reactor; and/or the fixed bed reactor is a cyclic fixed bed reactor.
15. The process of claim 13, wherein the second particulate material is a catalyst composition comprising platinum on ZSM-5, platinum and/or platinum on zeolite L, and wherein the catalyst composition is formed into a structured catalyst shape on silicate-modified silica.
16. The process of claim 13 or 15, wherein the at least one diabatic reaction zone comprises a reactor comprising parallel reactor tubes, and wherein the reactor tubes have a pressure drop of less than 20psi measured from reactor inlet to reactor outlet during contacting the first effluent and second particulate material.
17. The process of claim 1, wherein the first effluent flows co-currently or counter-currently to the direction of the flow of the second particulate material in the at least one diabatic reaction zone.
18. The process of claim 1, further comprising periodically stopping the feed to the at least one adiabatic reaction zone and/or the first effluent to the at least one diabatic reaction zone; and providing a rejuvenating gas to the at least one adiabatic reaction zone and/or the at least one diabatic reaction zone.
19. The process of claim 18, wherein the feed and/or the first effluent flow co-currently or counter-currently to the direction of the flow of the rejuvenating gas.
20. The method of claim 18 or 19, wherein the rejuvenating gas includes hydrogen and the rejuvenating gas is contacted with the first particulate material and/or the second particulate material to remove at least a portion of the progressively deposited coke material on the catalyst material, thereby forming a rejuvenated catalyst material and volatile hydrocarbons.
21. The method of claim 20, wherein at least 10.0 wt% of the progressively deposited coke material is removed from the catalyst material.
22. The process of claim 1, further comprising periodically stopping the feed to the at least one adiabatic reaction zone and/or the first effluent to the at least one diabatic reaction zone; supplying a regeneration gas to the at least one adiabatic reaction zone and/or to the at least one diabatic reaction zone; and contacting the first particulate material and/or the second particulate material with the regeneration gas under regeneration conditions to oxidatively remove at least a portion of the coke material deposited on the catalyst material to form a regenerated catalyst material.
23. The method of claim 22, wherein the regeneration gas is contacted with the first particulate material and/or the second particulate material at intervals of from 1 day to 180 days.
24. The method of claim 1, wherein the first particulate material and the second particulate material are the same.
25. The method of claim 1, wherein the first particulate material and the second particulate material are different.
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