CN108349839A - Convert a hydrocarbon to the method and system of cyclopentadiene - Google Patents

Convert a hydrocarbon to the method and system of cyclopentadiene Download PDF

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CN108349839A
CN108349839A CN201680064160.XA CN201680064160A CN108349839A CN 108349839 A CN108349839 A CN 108349839A CN 201680064160 A CN201680064160 A CN 201680064160A CN 108349839 A CN108349839 A CN 108349839A
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reactor
hydrocarbon
effluent
heat transfer
reaction zone
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CN108349839B (en
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L·L·亚奇诺
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • 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
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • 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
    • B01J29/62—Noble metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • 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
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • 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
    • 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 present invention relates to by acyclic C5The method that hydrocarbon is converted into cyclopentadiene, including：In temperature T1It is provided comprising acyclic C at least one adiabatic reaction area5The charging of hydrocarbon, wherein at least one adiabatic reaction area include the first bulk material containing catalyst material；Make the charging and first bulk material at least one adiabatic reaction area contact at reaction conditions with by least part the acyclic C5Hydrocarbon is converted into comprising cyclopentadiene intermediate, unconverted acyclic C5The first effluent of hydrocarbon and optional cyclopentadiene；The first effluent is heated to temperature T2；The first effluent is supplied at least one heat transfer reaction zone；With so that the first effluent and the second bulk material comprising catalyst material is contacted at reaction conditions with by least part cyclopentadiene intermediate and the unconverted acyclic C at least one heat transfer reaction zone5Hydrocarbon is converted into the second effluent comprising cyclopentadiene.

Description

Convert a hydrocarbon to the method and system of cyclopentadiene
Inventor：Larry L.Iaccino
Cross reference to related applications
It is submitted the present invention claims the USSN 62/250,697 submitted on November 4th, 2015 and on 2 2nd, 2016 EP application 16153727.9 priority and right.
Invention field
The present invention relates to can be used for acyclic C5It includes ring-type C that charging, which is converted into,5The reaction of the method for the product of compound Device.
Background of invention
Cyclopentadiene (CPD) and its dimer bicyclopentadiene (DCPD) are ideal raw material, being widely used in In the extensive product of industrial and commercial bank's industry, for example, polymer material, polyester resin, synthetic rubber, solvent, fuel, fuel additive etc..Ring Pentadiene is currently the byproduct of liquid feedstock steam cracking (for example, naphtha and heavier charging).With existing and new Steam cracking device turn to lighter charging, the CPD produced in the case where CPD demands constantly rise is less.Due to supply Limiting caused high cost impact CPD, potential final product uses in the polymer.If can be with unrestricted ratio More CPD are produced, and cost is less than from steam cracking recycling, then can produce the more polymeric articles based on CPD. It is also expected to the other ring-type C of co-production5.Pentamethylene and cyclopentene have very high value as solvent, and cyclopentene can be used as Comonomer produces polymer, it is also possible to make the raw material of other high value chemicals.
It would be advantageous that catalyst system can be used by abundant C5Charging production ring-type C5Compound, including CPD make For primary product, to generate CPD, while lightweight (C is minimized4-) by-product generation.Although lower hydrogen content (such as it is cyclic annular Object, alkene and alkadienes) may be preferably as endothermic heat of reaction reduces and the thermodynamic restriction that converts is improved, but Unsaturation object feeds more expensive than saturate.Because of reactive chemistry and straight chain C5Relative to branched C5Lower value (due to octane number Difference), straight chain C5Skeleton structure is preferable over branched C5Skeleton structure.Plentiful C5Available from Unconventional gas and shale oil, and And due to stringent environmental legislation, reduce the use of automotive fuel.C5Charging is also available from biological raw material.
Various catalytic dehydrogenation technologies are currently used for by C3And C4Alkane production list and alkadienes, but be not cyclic monoolefins or Cyclic diene hydrocarbon.Typical method is using the Pt/Sn being carried on aluminium oxide as active catalyst.Another useful method is adopted With the chromium oxide on aluminium oxide.Referring to B.V.Vora, " Development of Dehydrogenation Catalysts and Processes, " Topics in Catalysis, vol.55, pp.1297-1308,2012；And J.C.Bricker, " Advanced Catalytic Dehydrogenation Technologies for Production of Olefins ", Topics in Catalysis, vol.55, pp.1309-1314,2012.
Yet another common method uses the Pt/Sn being supported on Zn and/or Ca aluminates with dehydrogenation propane.Although these sides Method succeeds on dehydrating alkanes, but they cannot carry out crucial cyclisation for production CPD.Pt-Sn/ aluminium oxide and Pt- Sn/ aluminate catalysts show medium pentane conversion ratio, but these catalyst to cyclic annular C5The selectivity of product and Poor yields.
The Pt catalyst being supported on the aluminium oxide of chlorination be used to low octane rating naphtha reforming be aromatic substances ratio Such as benzene and toluene.Referring to US 3,953,368 (Sinfelt), " Polymetallic Cluster Compositions Useful as Hydrocarbon Conversion Catalysts”.Although these catalyst can effectively make C6With advanced alkane Hydrocarbon dehydrogenation and be cyclized form C6Aromatic ring, but they are for by acyclic C5It is converted into cyclic annular C5It is relatively invalid.These are supported on the oxygen of chlorination Change the cyclic annular C that the Pt catalyst on aluminium shows low yield5And it shows to inactivate in the first two hours time to stream. C6And C7The formation auxiliary of the cyclisation aromatic ring of alkane, but this is not happened at C5In cyclisation.This influence may be partially due to and benzene (cyclic annular C6) and toluene (cyclic annular C7) compare CPD (cyclic annular C57) the hot higher of formation.This is also by being supported on the aluminium oxide of chlorination Pt/Ir and Pt/Sn show.Although these aluminium oxide catalysts carry out C6+The dehydrogenation and cyclisation of substance are to form C6Aromatic ring, But need different catalyst by acyclic C5It is converted into cyclic annular C5。
The method that ZSM-5 catalyst containing Ga be used to produce aromatic substances by light paraffins.Kanazirev's et al. Studies have shown that pentane is easy to pass through Ga2O3/ H-ZSM-5 is converted.Referring to Kanazirev et al., " Conversion of C8Aromatics and n-pentane over Ga2O3/H-ZSM-5mechanically mixed Catalysts,” Catalysis Letters, vol.9, pp.35-42,1991.It does not report and generates ring-type C5, while the virtue of 6wt% or more Race's substance is in 440 DEG C and 1.8hr-1WHSV is generated.Mo/ZSM-5 catalyst also shows that dehydrogenation and/or cyclisation alkane, especially It is methane.Referring to Y.Xu, S.Liu, X.Guo, L.Wang and M.Xie, " Methane activation without using oxidants over Mo/HZSM-5zeolite catalysts,”Catalysis Letters,vol.30,pp.135- 149,1994.It is shown using the high conversion of the pentane of Mo/ZSM-5, there are high yield crackates, but do not produce Raw ring-type C5.This shows that paraffin conversion can be C by the catalyst based on ZSM-56Ring, but not necessarily generate C5Ring.
US 5,254,787 (Dessau) describes the NU-87 catalyst for paraffin dehydrogenation.The catalyst, which is shown, to be made C2-C6+Dehydrogenation is to generate their unsubstituted homologue.C is lucidly given very much in that patent2-5And C6+The difference of alkane It is different：C2-5Dehydrating alkanes generation straight chain or branched monoolefin or alkadienes, and C6+Dehydrating alkanes generate aromatic substances.US5,192, 728 (Dessau) are related to similar chemistry, but use stanniferous crystalline microporous body.It is identical as NU-87 catalyst, C5Dehydrogenation It only shows and generates straight chain or branched monoolefine or alkadienes rather than CPD.
US 5,284,986 (Dessau) describes the dual stage process that pentamethylene and cyclopentene are produced by pentane.It carries out Example in, the first stage be related to by Pt/Sn-ZSM-5 catalyst carry out pentane dehydrogenation and dehydrocyclization be alkane, The mixture of monoolefine and alkadienes and cycloalkane.Then mixture introducing is made of Pd/Sn-ZSM-5 catalyst Second stage reactor, diene, especially CPD, are converted into alkene and saturate there.Cyclopentene schedules to last in the method The product of prestige, and CPD is undesired 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；It is disclosed with US 2,438,404 (Kennedy) and produces CPD by various catalyst by 1,3- pentadienes.Low behaviour Make pressure, the low conversion ratio and low selectivity of often taking turns keeps this method undesirable.In addition, 1,3-pentadiene be not readily to obtain into Material is different from pentane.Referring further to Kennedy et al., " Formation of Cyclopentadiene from 1,3- Pentadiene, " Industrial＆Engineering Chemistry, vol.42, pp.547-552,1950.
Fel ' dblyum etc. are in " Cyclization and dehydrocyclization of C5 hydrocarbons over platinum nanocatalysts and in the presence of hydrogen sulfide,”Doklady Report produces CPD by 1,3-pentadiene, n-pentene and pentane in Chemistry, vol.424, pp.27-30,2009.For 1,3- pentadienes, n-pentene and pentane pass through 2%Pt/SiO at 600 DEG C respectively2Conversion, the yield of CPD is up to 53%, 35% and 21%.Although observing initial generation CPD, violent catalyst in the first few minutes of the reaction is also observed and loses It is living.The experiment carried out on the silica containing Pt shows that pentane passes through Pt-Sn/SiO2Medium conversion ratio, but it is right Cyclic annular C5The selectivity and poor yields of product.Hereinafter, Fel ' dblyum give using H2S is cyclized as 1,3- pentadienes to be promoted Into agent, and in Marcinkowski, " Isomerization and Dehydrogenation of 1,3- Pentadiene, " M.S., University of Central Florida, 1977.Marcinkowski is shown using H2S 700 DEG C of 1,3- pentadienes 80% conversion ratio and 80% the selectivity to CPD.High temperature, limited charging, Yi Jihan The product for needing subsequently to strike off of sulphur it is potentially possible, keep this method undesirable.
L ó pez et al. are in " n-Pentane Hydroisomerization on Pt containing HZSM-5, HBEA And SAPO-11, " Catalysis Letters, vol.122, pp.267-273,2008, pentane is had studied in the packet containing Pt Include the reaction on the zeolite of H-ZSM-5.At moderate temperature (250-400 DEG C), they report height of the pentane on Pt- zeolites Imitate hydroisomerization, but the formation without discussing cyclopentene.Wish to avoid this harmful chemistry, because of branched C5It will not be as straight Chain C5Effectively generate cyclic annular C like that5, as discussed above.
Li et al. people is at " Catalytic dehydroisomerization of n-alkanes to isoalkenes, " Journal of Catalysis, vol.255, pp.134-137,2008, also studied pentane, Al is taken by Fe isomorphisms wherein Dehydrogenation on the zeolite containing Pt in generation.These Pt/ [Fe] ZSM-5 catalyst be for the dehydrogenation and isomerization of pentane it is effective, But under used reaction condition, without ring-type C5It generates, and undesirable skeletal isomerization occurs.
US 5,633,421 discloses dehydrogenation C2-C5Method of the alkane to obtain corresponding alkene.Similarly, 2 US, 982, 798 methods for disclosing the aliphatic hydrocarbon dehydrogenation containing 3-6 carbon atom (including endpoint value).However, 5,633,421 Hes of US US 2,982,798 is without disclosing by acyclic C5Hydrocarbon produces CPD, acyclic C5Hydrocarbon is preferably to feed, because they are abundant With it is cheap.
In addition, design is for the challenge of many of CPD production methods of purpose.For example, C5The reaction that hydrocarbon is converted into CPD is Extremely heat absorption and be easy to carry out in low pressure and high temperature, but pentane and other C5The notable cracking of hydrocarbon can be relatively low Temperature (for example, 450 DEG C -500 DEG C) occurs.Further challenge includes losing catalyst due to the coking during this method to live Property, and further processing is needed to go coke removal from catalyst, and oxygen-containing gas cannot be used directly to be provided to reactor Heat input is without damaging catalyst.
Therefore, there is still a need for it is preferred that commercial rate and under the conditions of by acyclic C5Charging is converted into non aromatic cyclic C5Hydrocarbon, i.e., The method of cyclopentadiene.Furthermore, it is necessary to for the catalysis process of production cyclopentadiene, with high yield from abundant C5Charging production Raw cyclopentadiene, will not excessively generate C4-Pyrolysis product simultaneously has acceptable catalyst ageing properties.In addition, it is necessary to purposeful Ground is by acyclic C5Hydrocarbon produces CPD and copes with the method and system of above-mentioned challenge.
Summary of the invention
The present invention relates in reactor assembly by acyclic C5The method that hydrocarbon is converted into cyclopentadiene, wherein this method include In temperature T1It includes acyclic C to provide at least one5The adiabatic reaction area of the charging of hydrocarbon, wherein at least one adiabatic reaction area packet Containing the first bulk material containing catalyst material；Make the charging and first bulk material at least one adiabatic reaction area Contact at reaction conditions with by least part the acyclic C5Hydrocarbon is converted into comprising cyclopentadiene intermediate, unconverted acyclic C5The first effluent of hydrocarbon and optional cyclopentadiene；The first effluent is heated to temperature T2；The first effluent is supplied to At least one heat transfer reaction zone；With so that the first effluent is being reacted at least one heat transfer reaction zone with the second bulk material Under the conditions of contact with by least part cyclopentadiene intermediate and unconverted acyclic C5Hydrocarbon is converted into comprising cyclopentadiene Second effluent.
Brief description
Fig. 1 is the figure according to the reactor of embodiment of the present invention.
Fig. 2 is the figure according to the reactor with updating device of another embodiment of the present invention.
Fig. 3 is the figure according to the reactor with updating device and regenerating unit of another embodiment of the present invention.
Detailed description of the invention
I. it defines
To facilitate the understanding of the present invention, many terms and phrase is defined below.
As for the disclosure and claim, unless the context clearly determines otherwise, singulative " one ", "one" and "the" includes plural form.
Term "and/or" as used in phrase such as this paper " A and/or B " in mean include " A and B ", " A or B ", " A " and “B”。
As used in this article, term " about " refers to the range of positive and negative 10% value of designated value.For example, phrase is " about 200 " include positive and negative the 10% or 180 to 220 of 200.
Term " saturate " includes, but are not limited to alkane and cycloalkane.
Term " unsaturation object " includes, but are not limited to alkene, alkadienes, alkynes, cycloolefin and cyclodiene.
Term " cyclic annular C5" or " cC5" include, but are not limited to pentamethylene, cyclopentene, cyclopentadiene and they two kinds or More kinds of mixtures.Term " cyclic annular C5" or " cC5" further include any aforementioned substances alkylation homologue, for example, methyl ring Pentane, methyl cyclopentene and methyl cyclopentadiene.For the purposes of the present invention it should be understood that cyclopentadiene is at any time one Under conditions of determining range, including environment temperature and pressure, spontaneous dimerization is condensed by diels-Alder and forms two rings penta 2 Alkene.
Term " acyclic " includes, but are not limited to straight chain and branched saturate and unsaturation object.
Term " aromatics " refers to the flat annular alkyl for having conjugated double bond, such as benzene.As used in this article, term virtue The compound containing one or more aromatic rings is covered in race, includes, but are not limited to benzene, toluene and dimethylbenzene and polynuclear aromatic substance (PNA) comprising naphthalene, anthracene,With their alkylated forms.Term " C6+Aromatic substances " include based on tool there are six or more The compound of the aromatic ring of multiple annular atoms includes, but are not limited to benzene, toluene and dimethylbenzene and polynuclear aromatic substance (PNA), Including naphthalene, anthracene,With their alkylated forms.
Term " BTX " includes, but are not limited to the mixture of benzene, toluene and dimethylbenzene (adjacent and/or and/or to).
Term " coke " includes, but are not limited to be adsorbed onto the low hydrogen content hydrocarbon on carbon monoxide-olefin polymeric.
Term " Cn" refer to the hydrocarbon that each molecule contains n carbon atom, wherein n is positive integer.
Term " Cn+" refer to the hydrocarbon that per molecule has at least n carbon atom.
Term " Cn-" refer to each molecule have no more than n carbon atom hydrocarbon.
Term " hydrocarbon " refers to a kind of compound containing the hydrogen for being keyed to carbon, and covers the hydrocarbon compound of (i) saturation, (ii) not The mixture of substituted hydrocarbon compound and (iii) hydrocarbon compound (saturation and/or unsubstituted), includes with different n values Hydrocarbon compound mixture.
Term " C5Charging " includes the charging containing pentane, such as predominantly pentane and isopentane (also referred to as methyl fourth Alkane), and the charging of pentamethylene and pungent pentane (also referred to as 2,2- dimethylpropanes) on a small quantity.
All numbers and reference about the periodic table of elements are all based on Chemical and Engineering News, 63 (5), 27, (1985), unless otherwise indicated.
Term " the 10th race's metal " refers to the element in the 10th race of the periodic table of elements and includes, but are not limited to Ni, Pd And Pt.
Term " the 11st race's metal " refers to the element in the 11st race of the periodic table of elements and includes, but are not limited to Cu, Ag, Au and the mixture of two or more in them.
Term " the 1st race's alkali metal " refers to the element in the 1st race of the periodic table of elements and includes, but are not limited to Li, Na, K, Rb, Cs and the mixture of two or more in them, and exclude hydrogen.
Term " the 2nd race's alkaline-earth metal " refers to the element in the 2nd race of the periodic table of elements and includes, but are not limited to Be, Mg, Ca, Sr, Ba and the mixture of two or more in them.
As used in this article, term " oxygen-containing " or " oxygenatedchemicals " refer to oxygen and oxygen containing compound, including but not It is limited to, O2, CO2, CO, H2O and oxygen-containing hydrocarbon, such as alcohols, ester, ether etc..
Term " restricted index " is defined in US 3,972,832 and US 4, and 016,218, both it is incorporated by reference this Shen Please.
As used in this article, term " molecular sieve of MCM-22 races " (or " material of MCM-22 races " or " MCM-22 races material Material " or " MCM-22 races zeolite ") include below one or more：
The molecular sieve made of common first degree of crystal structure block structure cell, structure cell have MWW topology frames.(structure cell is The space arrangement of atom, the atom describe crystal structure if being laid in three dimensions.This crystal structure discussion In " Atlas of Zeolite Framework Types ", the 5th edition, 2001, entire contents are included in as reference)；
The molecular sieve made of common second degree of building block is that the 2- dimensions of such MWW topologys frame structure cell are laid with, shape At a unit cell thickness, the single layer of preferably one c- unit cell thickness；
The molecular sieve made of common second degree of building block is the layer of one or more than one unit cell thickness, wherein more By accumulation, filling or the single layer of at least two 1 unit cell thickness is combined to be made in the layer of a unit cell thickness.This second degree The accumulation of building block can be regular fashion, not advise rule mode, random fashion or its any combination thereof；With
The molecular sieve made of any rule of the structure cell with MWW topology frames or random 2- dimensions or 3- dimension combinations
MCM-22 family molecular sieves include d- interplanar distances maximum value in 12.4 ± 0.25,6.9 ± 0.15,3.57 ± 0.07 Hes Those of 3.42 ± 0.07 angstroms of X-ray diffraction pattern molecular sieve.By standard technique using the K- α of copper doublet as entering Radiation and the diffractometer equipped with scintillation counter and correlation computer as collection system are penetrated, acquisition is penetrated for characterizing the X of material Line diffraction data.
As used in this article, term " molecular sieve " and term " microporous crystalline material " or " zeolite " synonymous use.
As used in this article, term " carbon selectivity " refers to each ring-type C in formation5、CPD、C1And C2-4In carbon rub The total mole number of that number divided by the carbon in the pentane of conversion.Phrase is " to cyclic annular C5Carbon selectivity be at least 30% " to refer to, Often 100 moles of carbon is formed in ring-type C in the pentane of conversion5In 30 moles of carbon.
As used in this article, term " conversion ratio " refers in the acyclic C5The carbon mole for being converted into product in charging Number.Phrase " the acyclic C5The conversion ratio for being fed to the product be at least 70% " refer at least 70% mole the nothing Ring C5Charging is converted into product.
As used in this article, term " reactor assembly " refers to a system comprising one or more reactors and For produce cyclopentadiene it is necessary to optional equipment.
As used in this article, term " reactor " refers to any container chemically reacted.Reactor includes independent Reactor and single-reactor device in reaction zone, and in where applicable, across the reaction zone of multiple reactors.It changes Sentence is talked about and is common, and single-reactor can have multiple reaction zones.When specification refers to the first and second reactors, One ordinarily skilled in the art will readily appreciate that such refer to includes two reactors, and with the first and second reactions The single-reactor container in area.Similarly, the first reactor effluent and the first reactor effluent will be understood to comprise point The not effluent of first reaction zone and the second reaction zone from single-reactor.
Reactor/reaction zone can be adiabatic reactor/reaction zone or heat transfer reactor/reaction zone.As used in this article, Term " thermal insulation " refers to, in reaction zone except through flow process fluid outside, there is no heat input to system.For this hair Bright purpose has since the reaction zone for conducting and/or radiating and inevitably lose is also considered as thermal insulation.As herein Middle to use, term " heat transfer " refers to, other than being provided by flow process fluid, heat pass through intentionally device provide it is anti- Answer device/reaction zone.
As used in this article, term " moving bed " reactor refers to such area or container, and wherein solid is (for example, urge Catalyst particles) with the contact of gas flowing make empty tower gas velocity (U) less than the speed needed for solid particle dilute phase pneumatic conveying from And the void fraction of Solid Bed is kept to be less than 95%.In moving-burden bed reactor, solid (for example, catalyst material) can be slowly It is advanced through reactor and can remove and be added reactor head from reactor bottom.Moving-burden bed reactor can be in a variety of flowing moulds It is operated under formula, including sedimentation or moving packed bed pattern (U<Umf), it is bubbled pattern (Umf<U<Umb), slug pattern (Umb<U<Uc), Transformation and turbulent fluidised pattern (Uc<U<Utr) and fast fluidized regime (U>Utr), wherein Umf is minimum fluidization velocity, and Umb is most Small bubbling rate, Uc are the speed of pressure oscillation peak value, and tr is conveying speed.These different fluidized regimes are described in, example Such as, Kunii, D., Levenspiel, O., Chapter 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, by them It is incorporated by reference.
As used in this article, term " sedimentation bed " reactor refers to such area or container, wherein particle and gas stream Contact so that empty tower gas velocity (U) is less than fluidization solid particle (for example, catalyst granules) institute in the reaction zone at least partially Minimum speed (minimum fluidization velocity (the U neededmf)), U<Umf, and/or higher than the minimum fluidization velocity speed operation simultaneously Gas and/or solid performance are maintained at (for example, temperature, gas to minimize gas solids back-mixing by using reactor interval Body or solid composite etc.) gradient along reactor beds axially upwards.The explanation of minimum fluidization velocity is given in, for example, Kunii,D.,Levenspiel,O.,Chapter 3 of Fluidization Engineering,2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, 6 of Chemical Process of S.M., Chapter Equipment,Revised 2ndEdition,Butterworth-Heinemann,Boston,2010.Settling bed reactor can For " cycle sedimentation bed reactor ", this refers to such sedimentation bed, and wherein solid (for example, catalyst material) movement passes through reaction The device and solid (for example, catalyst material) at least partly recycles.For example, solid (for example, catalyst material) can be from anti- It answers device to remove, regenerates, reheat and/or detached from product stream, be then back to reactor.
As used in this article, term " fluid bed " reactor refers to such area or container, and wherein solid is (for example, urge Catalyst particles) with gas flowing contact make empty tower gas velocity (U) be enough fluidization solid particle (that is, be higher than minimum fluidization velocity Umf) and less than the speed needed for solid particle dilute phase pneumatic conveying, to keep the void fraction of Solid Bed to be less than 95%.Such as this Used herein, term " cascade fluid bed " refers to a series of single fluidised bed arrangements, enabling in gas and/or solid Performance (for example, temperature, gas or solid composition, pressure etc.) when solid or gas are left to another from a fluid bed with having There is gradient.The track of minimum fluidization velocity is given in for example, 3 of of Kunii, D., Levenspiel, O., Chapter Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M.,Chapter 6 of Chemical Process Equipment,Revised 2nd Edition,Butterworth- Heinemann,Boston,2010.Fluidized-bed reactor can be mobile fluidized-bed reactor, for example " recirculating fluidized bed reacts Device " refers to such fluid bed, and wherein solid (for example, catalyst material) is mobile passes through reactor and the solid (example Such as, catalyst material) at least partly recycling.For example, solid (for example, catalyst material) can be removed from reactor, regeneration, It reheats and/or is detached from product stream, be then back to reactor.
As used in this article, term " riser " reactor (also referred to as transport reactor) refers to such area or container (for example, vertical type cylinder shape pipe) is used to be delivered up solid only (for example, urging with fast fluidization or pneumatic transfer fluidized regime Catalyst particles).Fast fluidization and pneumatic transport stream pattern feature are that empty tower gas velocity (U) is more than conveying speed (Utr).Quickly Fluidisation and pneumatic transport stream pattern are also described in Kunii, D., Levenspiel, 3 of of O., Chapter Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M.,Chapter 6 of Chemical Process Equipment,Revised 2nd Edition,Butterworth- Heinemann,Boston,2010.Fluidized-bed reactor, such as circulating fluid bed reactor can be used as riser reactor behaviour Make.
As used in this article, term " combustion pipe " reactor refers to stove and is positioned in the radiant section of the stove Parallel reactor pipeline.Pipe reactor contains catalysis material (for example, catalyst granules), and haptoreaction object is to form production Object.
As used in this article, term " Convective Heating pipe " reactor refers to such conversion system, and it includes containing catalysis Material and the parallel reactor pipeline being positioned in shell.Although any of pipe reactor configuration or shell can be used, But it is preferred that the conversion system is included in multiple parallel reactor pipelines in heat convection shell.Preferably, pipe reactor is Straight, rather than with the spiral or bending channel (although spiral or crooked pipeline can also be used) along shell.In addition, pipeline can It is oval with circle, the section of rectangle and/or other known forms.Pipeline preferentially uses turbine combustion fuel gas to utilize Wrap the turbine exhaust gas stream heating that the gas of oxygen containing compression generates.In other aspects, pipe reactor passes through in fuel electricity The convection current of hot gas is generated in pond, stove, boiler or additional air burner by burning to heat.However, useless with turbine It may be preferably as further advantages such as co-production shaft power that gas, which heats the pipe reactor,.
As used in this article, term " fixed bed " or " packed bed " reactor refer to such area or container (for example, vertical Formula or level, cylindrical tube or spherical container), it may include laterally (also referred to as cross flow one), axial flowing and/or radial flow Dynamic gas, wherein solid (for example, catalyst granules) are essentially fixed in reactor, and gas flows so that void tower gas Fast (U) is less than the speed of fluidization solid particle (that is, being less than minimum fluidization velocity Umf) and/or gas move in a downward direction, So that solid particle can not energy fluidizing.
As used in this article, term " periodic " refers to the periodic cycle occurred according to cycle or repeated events. For example, reactor (for example, cyclic annular fixed bed) can be operated periodically with reacting space, to reheat between interval and/or regeneration Every.The duration of intervening step and/or sequence can change over time.
As used in this article, term " fair current " refers to that two kinds of streams (for example, stream (a), stream (b)) are in basic phase Same side flows up.For example, if stream (a) bottom is flow at the top of at least one reaction zone and stream (b) to It is flow to bottom at the top of a few reaction zone, then the flowing of stream (a) will be considered as the fair current of the flowing of stream (b).Anti- Answer scale smaller in area, it is understood that there may be wherein flowing may not be the region of fair current.
As used in this article, term " adverse current " refers to that two kinds of streams (for example, stream (a), stream (b)) are in basic phase To side flow up.For example, if stream (a) bottom is flow at the top of at least one reaction zone and stream (b) to The flows of a reaction zone will be considered as the adverse current of the flowing of stream (b) to top, the then flowing of stream (a) less.Anti- Answer scale smaller in area, it is understood that there may be wherein flowing may not be the region of adverse current.
The range of particle uses the Malvern available from Britain Worcestershire in 1-3500 μm of " average diameter " The Mastersizer of Instruments, Ltd.TM3000 determine.Unless otherwise indicated, granularity is determined with D50.D50 is tired Integrate cloth in 50% particle diameter value.For example, if D50=5.8 μm, 50% particle is equal in the sample Or it is less than 5.8 μm more than 5.8 μm and 50%.(on the contrary, if D90=5.8 μm, 10% particle is more than in the sample 5.8 μm and 90% are less than 5.8 μm of).Range is using micron meter to representative 100 more than the particle of 3.5mm " average diameter " A particulate samples determine.
For the purposes of the present invention, 1psi is equal to 6.895kPa.Specifically, 1psia is equal to 1kPa absolute pressures (kPa-a). Similarly, 1psig is equal to 6.895kPa gauge pressures (kPa-g).
II. acyclic C5Method for transformation
The first aspect of the present invention is by acyclic C5It includes ring-type C that charging, which is converted into,5Compound (for example, cyclopentadiene) The method of product.This approach includes the following steps：Make the charging and optional hydrogen in acyclic C5Under conversion condition a kind of or Multiple catalysts composition, contact is to form the production in the presence of carbon monoxide-olefin polymeric including but not limited to as described herein Object.
In one or more embodiments, acyclic C is converted5The product of the method for charging includes ring-type C5Compound.It is cyclic annular C5Compound includes one or more pentamethylene, cyclopentene, cyclopentadiene, and includes its mixture.In one or more implementations In scheme, cyclic annular C5Compound includes at least about 20wt% or 30wt% or 40wt% or 70wt% cyclopentadiene or range In about 10wt%- about 80wt%, alternatively 20wt%-70wt%.
In one or more embodiments, acyclic C5Conversion condition includes at least temperature, pentane partial pressure and weight space-time Fast (WHSV).Temperature range is in about 400 DEG C-about 700 DEG C or range at about 450 DEG C-about 650 DEG C, it is preferable that range is about 500 DEG C-about 600 DEG C.Pentane partial pressure range is in about 3- about 100psia or range in about 3- about 50psia, it is preferable that range is about 3psia- about 20psia.Weight (hourly) space velocity (WHSV) range is in about 1- about 50hr-1Or range is in about 1- about 20hr-1.Such condition includes Optional hydrogen is co-feeding with acyclic C5The molar ratio range of charging is in about 0-3 or range in about 1- about 2.Such condition can be also Including co-feeding C1-C4Hydrocarbon and acyclic C5Charging.Preferably, co-feeding (as existed) whether includes hydrogen, C1-C4Hydrocarbon or with It is both upper, substantially free of oxygenatedchemicals.It includes to be less than about that substantially free used herein, which refers to co-feeding, above and below this 1.0wt% for example, being below about 0.1wt%, is below about 0.01wt%, is below about 0.001wt% based on the co-feeding weight, Below about 0.0001wt%, it is below about the oxygenatedchemicals of 0.00001wt%.
In one or more embodiments, the present invention relates to the methods for converting pentane to cyclopentadiene, including with Lower step：Make pentane and optional hydrogen (such as presence, typically H2With the ratio presence with pentane 0.01-3.0) and it is a kind of Or multiple catalysts composition, carbon monoxide-olefin polymeric including but not limited to as described herein divide 3- in 400 DEG C -700 DEG C of temperature About 100psia and weight (hourly) space velocity (WHSV) 1- about 50hr-1Contact, to form cyclopentadiene.
In one or more embodiments, the present invention relates in reactor assembly by acyclic C5Hydrocarbon is converted into ring penta 2 The method of alkene, wherein this method include：In temperature T1There is provided at least one adiabatic reaction area includes acyclic C5The charging of hydrocarbon, In at least one adiabatic reaction area include the first bulk material containing catalyst material；Make the charging and the first granular material Material at least one adiabatic reaction area contact at reaction conditions with by least part the acyclic C5Hydrocarbon is converted into comprising ring Pentadiene intermediate, unconverted acyclic C5The first effluent of hydrocarbon and optional cyclopentadiene；Heat the first effluent extremely Temperature T2；The first effluent is supplied at least one heat transfer reaction zone；With make the first effluent with comprising catalyst material Material the second bulk material at least one heat transfer reaction zone contact at reaction conditions with by least partially the ring penta 2 Alkene intermediate and the unconverted acyclic C5Hydrocarbon is converted into the second effluent comprising cyclopentadiene.
A.Charging
In the method, including C5The charging of hydrocarbon, preferably acyclic C5Charging by with the bulk material one comprising catalyst material It rises and is supplied to reaction system.Here useful acyclic C5Charging can be obtained from crude oil or natural-gas condensate, and can Including by refining and chemical method, such as fluid catalytic cracking (FCC), reforming, being hydrocracked, hydrotreating, coking and steaming The cracking C that vapour cracking generates5(various degrees of unsaturation：Alkene, alkadienes, alkynes).
In one or more embodiments, useful acyclic C in method of the invention5It includes pentane to feed, amylene, and penta The mixture of diene and they two or more.Preferably, in one or more embodiments, acyclic C5Charging packet Containing at least about 50wt% or 60wt% or 75wt%. or 90wt% pentanes or range about 50wt%- about 100wt% just Pentane.
Acyclic C5Charging does not include C optionally6Aromatic compounds, such as benzene, preferably C6The presence of aromatic compounds is less than 5wt%, preferably smaller than 1wt% preferably exist and are less than 0.01wt%, preferably 0wt%.
Acyclic C5Charging does not include benzene optionally, toluene or dimethylbenzene (o-, m-, or to), preferably benzene, toluene or diformazan The presence of benzene (o-, m-, or to) compound is less than 5wt%, preferably smaller than 1wt%, preferably exists and is less than 0.01wt%, preferably 0wt%.
Acyclic C5Charging does not include C optionally6+Aromatic compounds, preferably C6+The presence of aromatic compounds is less than 5wt%, excellent Choosing is less than 1wt%, preferably exists and is less than 0.01wt%, preferably 0wt%.
Acyclic C5Charging does not include C optionally6+Compound, preferably C6+The presence of compound is less than 5wt%, preferably smaller than 1wt% preferably exists and is less than 0.01wt%, preferably 0wt%.
Optionally, C5Charging is substantially free of oxygenatedchemicals.Substantially free used herein refers to this up and down for this Charging, for example, being below about 0.1wt%, is below about 0.01wt%, is less than comprising 1.0wt%, the weight based on the charging is less than about About 0.001wt% is below about 0.0001wt%, is below about the oxygenatedchemicals of 0.00001wt%.
Preferably, the C of cyclopentadiene is converted into charging5Hydrocarbon is (for example, acyclic C5Hydrocarbon) amount >=about 5.0wt%, >=about 10.0wt%, >=about 20.0wt%, >=about 30.0wt%, >=about 40.0wt%, >=about 50.0wt%, >=about 60.0wt%, >= About 70.0wt%, >=about 80.0wt% or >=about 90.0wt%.Preferably, at least about 30.0wt% or at least about 60.0wt% The C5Hydrocarbon is (for example, acyclic C5Hydrocarbon) it is converted into cyclopentadiene.The range clearly disclosed includes any of above group for listing value It closes；For example, about 5.0%- about 90.0wt%, about 10.0wt%- about 80.0wt%, about 20.0wt%- about 70.0wt%, about 20.0wt%- about 60.0wt% etc..Preferably, C of about 20.0wt%- about 90.0wt%5Hydrocarbon is (for example, acyclic C5Hydrocarbon) turned Turn to cyclopentadiene, more preferably from about 30.0wt%- about 85.0wt%, more preferably from about 40.0wt%- about 80.0wt%, about 45.0wt%- about 75.0wt%, or about 50.0wt%- about 70.0wt%.
Preferably, including hydrogen and optional light hydrocarbon such as C1-C4The hydrogen of hydrocarbon is co-feeding to be also fed into the first reactor. Preferably, at least part hydrogen is co-feeding with the C5Charging blending, is then fed into the first reactor.At entry position (feed contacted first with catalyst herein), there are hydrogen, prevents or reduces coke on catalyst granules in the incoming mixture Formation.C1-C4Hydrocarbon also can be with C5It is co-feeding.
B. adiabatic reaction area
Charging may be provided at least one temperature T1Adiabatic reaction area, and anti-in at least one adiabatic reaction area It is contacted with the first bulk material containing catalyst material under the conditions of answering with by least part C5Hydrocarbon is (for example, acyclic C5Hydrocarbon) It includes H to be converted into2, cyclopentadiene intermediate, unconverted acyclic C5The first effluent of hydrocarbon and optional cyclopentadiene.At least One adiabatic reaction area can be fixed bed reactors or fluidized-bed reactor.Fixed bed reactors can be vertical fixed-bed or horizontal Fixed bed.Preferably, vertical fixed-bed for axial-flow type is vertical fixed-bed or radial-flow type fixed bed.Preferably, horizontal type fixed bed to be Cross-flow type is horizontal type fixed bed.
Additionally or in the alternative, which may include at least the first adiabatic reaction area, and second is adiabatic anti- Answer area, third adiabatic reaction area, the 4th adiabatic reaction area, pentasyllabic quatrain thermal reaction area, the 6th adiabatic reaction area, four-line poem with seven characters to a line thermal response Area and/or the 8th adiabatic reaction area etc..As understood here, each adiabatic reaction area can be individual reactor or adiabatic reaction Device may include one or more adiabatic reaction areas.Preferably, reactor assembly includes 1-20 adiabatic reaction area, more preferably 1-15 adiabatic reaction area, more preferable 2-10 adiabatic reaction area, more preferable 2-8 adiabatic reaction area.When more than one is adiabatic anti- In the presence of answering area, adiabatic reaction area can be with any suitable deployment arrangements, for example, series connection or parallel.Each adiabatic reaction area can It independently is fixed bed or fluid bed.
Adiabatic reaction area may include at least one internal structure to support first bulk material, be evenly distributed into Material, to collect hydrocarbon products and/or reduce the pressure drop in reaction zone.For example, when adiabatic reaction area be it is vertical fixed-bed when, one or Multiple internal structures, for example, permeable concentric shells, it may include to contain and support bulk material in the reaction zone, and The charging can feed the substantially an open central axis portion of the reaction zone and radially about be flowed in bulk material.In addition or it is standby Selection of land, adiabatic reaction area may include at least one internal structure, preferably a variety of internal structures (for example, 2,3,4,5,6,7,8,9, 10,15,20,30,40,50 kinds etc.).The example of suitable internal structure includes a variety of protection support lattices, compression grid, baffle, canopy, Tower tray, pipe, stick and/or dispensing body.
Charging may be provided to temperature T1Adiabatic reaction area, T1≤ about 700 DEG C ,≤about 675 DEG C ,≤about 650 DEG C ,≤about 625 DEG C ,≤about 600 DEG C ,≤about 575 DEG C ,≤about 550 DEG C ,≤about 525 DEG C ,≤about 500 DEG C ,≤about 475 DEG C ,≤about 450 DEG C, ≤ about 425 DEG C ,≤about 400 DEG C ,≤about 375 DEG C ,≤about 350 DEG C ,≤about 325 DEG C ,≤about 300 DEG C ,≤about 275 DEG C ,≤about 250 DEG C ,≤about 225 DEG C, or≤about 200 DEG C.Preferably, into the charging in adiabatic reaction area (for example, acyclic C5Hydrocarbon) temperature≤about 500 DEG C, more preferably≤about 525 DEG C, more preferably≤about 550 DEG C, more preferably≤about 575 DEG C.The temperature range packet clearly disclosed The combination of any of above value is included, for example, about 200 DEG C-about 700 DEG C, about 250 DEG C-about 600 DEG C, about 350 DEG C-about 650 DEG C, about 375 DEG C-about 500 DEG C etc..Preferably, into the charging in adiabatic reaction area (for example, acyclic C5Hydrocarbon) temperature be about 200 DEG C-about 700 DEG C, more preferably from about 300 DEG C-about 650 DEG C, more preferably from about 400 DEG C-about 600 DEG C, more preferably from about 475 DEG C-about 575 DEG C.In above-mentioned temperature Degree provides the charging (for example, acyclic C5Hydrocarbon) it can advantageously minimize the C5Hydrocarbon is (for example, acyclic C5Hydrocarbon) at them in the catalyst Undesirable cracking before being reacted in the presence of material.
Additionally or in the alternative, before entering adiabatic reaction area, charging can be by one or more heating equipments, for example, packet The heat exchanger in the heating of the convective region of stove is included, above-mentioned temperature is heated to.
At least one adiabatic reaction area is being enough to convert the charging at least partially (for example, acyclic C5Hydrocarbon) it is cyclopentadiene Intermediate and unconverted acyclic C5It is operated under the reaction condition of hydrocarbon and optional cyclopentadiene.As used in this article, " ring penta Diene intermediate " refers to amylene, pentadiene, pentamethylene and cyclopentene.In various aspects, be converted into cyclopentadiene this at least Occur in one adiabatic reaction area.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% acyclic C5Hydrocarbon is converted into cyclopentadiene intermediate.Preferably, charging is (for example, acyclic C5Hydrocarbon) It can be by following range of weight (hourly) space velocity (WHSV) (WHSV, acyclic C5Quality/hour of quality/catalyst of hydrocarbon) it is supplied to adiabatic reaction Area：About 1.0- about 1000.0hr-1.The WHSV can be about 1.0- about 900.0hr-1, about 1.0- about 800.0hr-1, about 1.0- is about 700.0hr-1, about 1.0- about 600.0hr-1, about 1.0- about 500.0hr-1, about 1.0- about 400.0hr-1, about 1.0- about 300.0hr-1, about 1.0- about 200.0hr-1, about 1.0- about 100.0hr-1, about 1.0- about 90.0hr-1, about 1.0- about 80.0hr-1, about 1.0- About 70.0hr-1, about 1.0- about 60.0hr-1, about 1.0- about 50.0hr-1, about 1.0- about 40.0hr-1, about 1.0- about 30.0hr-1, About 1.0- about 20.0hr-1, about 1.0- about 10.0hr-1, about 1.0- about 5.0hr-1, about 2.0- about 1000.0hr-1, about 2.0- is about 900.0hr-1, about 2.0- about 800.0hr-1, about 2.0- about 700.0hr-1, about 2.0- about 600.0hr-1, about 2.0- about 500.0hr-1, about 2.0- about 400.0hr-1, about 2.0- about 300.0hr-1, about 2.0- about 200.0hr-1, about 2.0- about 100.0hr-1, about 2.0- about 90.0hr-1, about 2.0- about 80.0hr-1, about 2.0- about 70.0hr-1, about 2.0- about 60.0hr-1, about 2.0- is about 50.0hr-1, about 2.0- about 40.0hr-1, about 2.0- about 30.0hr-1, about 2.0- about 20.0hr-1, about 2.0- about 10.0hr-1, and About 2.0- about 5.0hr-1.Preferably, WHSV is about 1.0- about 100.0hr-1, more preferably from about 1.0- about 60.0hr-1, more preferably from about 2.0- about 40.0hr-1, more preferably from about 2.0- about 20.0hr-1。
Adiabatic reaction area is left in the first effluent in effluent exit (for example, cyclopentadiene, unconverted acyclic C5 Hydrocarbon) temperature can be≤about 600 DEG C ,≤about 575 DEG C ,≤about 550 DEG C ,≤about 525 DEG C ,≤about 500 DEG C ,≤about 475 DEG C ,≤about 450 DEG C ,≤about 425 DEG C ,≤about 400 DEG C ,≤about 375 DEG C ,≤about 350 DEG C ,≤about 325 DEG C ,≤about 300 DEG C ,≤about 275 DEG C, ≤ about 250 DEG C ,≤about 225 DEG C or≤about 200 DEG C.Preferably, first outflow of the adiabatic reaction area in effluent exit is left Object is (for example, cyclopentadiene, unconverted acyclic C5Hydrocarbon) temperature be≤about 525 DEG C, more preferably≤about 500 DEG C, more preferably≤ About 475 DEG C, more preferably≤about 450 DEG C.The temperature range clearly disclosed includes the combination of any of above value, for example, about 200 DEG C-about 600 DEG C, about 250 DEG C-about 575 DEG C, about 350 DEG C-about 550 DEG C, about 375 DEG C-about 450 DEG C etc..Preferably, thermal insulation is left Reaction zone effluent exit first effluent (for example, cyclopentadiene, unconverted acyclic C5Hydrocarbon) temperature be about 200 DEG C-about 600 DEG C, more preferably from about 250 DEG C-about 575 DEG C, more preferably from about 350 DEG C-about 550 DEG C, more preferably from about 375 DEG C-about 500 DEG C.
Additionally or in the alternative, the reaction condition in adiabatic reaction area may include temperature >=about 300 DEG C, >=about 325 DEG C, >=about 350 DEG C, >=about 375 DEG C, >=about 400 DEG C, >=about 425 DEG C, >=about 450 DEG C, >=about 475 DEG C, >=about 500 DEG C, >=about 525 DEG C, >=about 550 DEG C, >=about 575 DEG C, >=about 600 DEG C, >=about 625 DEG C, >=about 650 DEG C, or >=about 675 DEG C.Additionally or in the alternative, should Temperature can be≤about 300 DEG C ,≤about 325 DEG C ,≤about 350 DEG C ,≤about 375 DEG C ,≤about 400 DEG C ,≤about 425 DEG C ,≤about 450 DEG C ,≤about 475 DEG C ,≤about 500 DEG C ,≤about 525 DEG C ,≤about 550 DEG C ,≤about 575 DEG C ,≤about 600 DEG C ,≤about 625 DEG C ,≤about 650 DEG C ,≤about 675 DEG C, or≤about 700 DEG C.The temperature range clearly disclosed includes the combination of any of above value, for example, about 300 DEG C-about 700 DEG C, about 325 DEG C-about 650 DEG C, and about 450 DEG C-about 600 DEG C etc..Preferably, the temperature can be about 300 DEG C-about 650 DEG C, more preferably from about 325 DEG C-about 600 DEG C, more preferably from about 450 DEG C-about 575 DEG C.
Additionally or in the alternative, the reaction condition in adiabatic reaction area may include pressure≤about 1.0psia ,≤about 2.0psia ,≤ About 3.0psia ,≤about 4.0 ,≤about 5.0psia ,≤about 10.0psia ,≤about 15.0psia ,≤about 20.0psia ,≤about 25.0psia ,≤about 30.0psia ,≤about 35.0psia ,≤about 40.0psia ,≤about 45.0psia ,≤about 50.0psia ,≤ About 55.0psia ,≤about 60.0psia ,≤about 65.0psia ,≤about 70.0psia ,≤about 75.0psia ,≤about 80.0psia, ≤ about 85.0psia ,≤about 90.0psia ,≤about 95.0psia ,≤about 100.0psia ,≤about 125.0psia ,≤about 150.0psia ,≤about 175.0psia, or≤about 200.0psia.Additionally or in the alternative, which can be >=about 1.0psia, >= About 2.0psia, >=about 3.0psia, >=about 4.0psia, >=about 5.0psia, >=about 10.0psia, >=about 15.0psia, >=about 20.0psia, >=about 25.0psia, >=about 30.0psia, >=about 35.0psia, >=about 40.0psia, >=about 45.0psia, >= About 50.0psia, >=about 55.0psia, >=about 60.0psia, >=about 65.0psia, >=about 70.0psia, >=about 75.0psia, >=about 80.0psia, >=about 85.0psia, >=about 90.0psia, >=about 95.0psia, >=about 100.0psia, >=about 125.0psia, >=about 150.0psia, or >=about 175.0psia.The range of the temperature and pressure clearly disclosed and combination are wrapped The combination of any of above value is included, for example, about 1.0psia- about 200.0psia, about 2.0psia- about 175.0psia, about 3.0psia- about 150.0psia etc..Preferably, which can be about 1.0psia- about 200.0psia, more preferably from about 2.0psia- About 175.0psia, the about 100.0psia than such as from about 2.0psia-, more preferably from about 3.0psia- about 150.0psia, than such as from about 3.0psia- about 50.0psia.
Additionally or in the alternative, across the change pressure in adiabatic reaction area, (pressure at feed entrance is subtracted in effluent The pressure in exit) can be >=about 0.5psia, >=about 1.0psia, >=about 2.0psia, >=about 3.0psia, >=about 4.0psia, >=about 5.0psia, >=about 10.0psia, >=about 14.0psia, >=about 15.0, psia, >=about 20.0psia, >=about 24.0psia, >=about 25.0psia, >=about 30.0psia, >=about 35.0psia, >=about 40.0psia, >=about 45.0psia, >= About 50.0psi, >=about 55.0psia, >=about 60.0psia, >=about 65.0psia, >=about 70.0psia, >=about 75.0psia, >= About 80.0psia, >=about 85.0psia, >=about 90.0psia, >=about 95.0psia, >=about 100.0psia, >=about 125.0psia, or >=about 150.0psia.As understood here, " at feed entrance ", " in inlet " " go out in effluent Mouthful place " and it is included in " exporting " entrance and/or exports space of the neutralization generally around them.Additionally or in the alternative, across The change pressure (or pressure drop) (pressure at feed entrance subtracts the pressure in effluent exit) in more adiabatic reaction area can For≤about 2.0psia ,≤about 3.0psia ,≤about 4.0psia ,≤about 5.0psia ,≤about 10.0psia ,≤about 14.0psia, ≤ about 15.0, psia≤about 20.0psia ,≤about 24.0psia ,≤about 25.0psia ,≤about 30.0psia ,≤about 35.0psia ,≤about 40.0psia ,≤about 45.0psia ,≤about 50.0psi ,≤about 55.0psia ,≤about 60.0psia ,≤about 65.0psia ,≤about 70.0psia ,≤about 75.0psia ,≤about 80.0psia ,≤about 85.0psia ,≤about 90.0psia ,≤ About 95.0psia ,≤about 100.0psia ,≤about 125.0psia ,≤about 150.0psia ,≤about 175.0psia, or≤about 200.0psia.The range of the change pressure clearly disclosed includes any of above combination for listing value, for example, about 10psia- is about 70.0psia, about 20.0psia- about 60.0psia, about 30.0psia- about 50.0psia etc..
Additionally or in the alternative, including C1, C2, C3And/or C4The lightweight hydrocarbon flow of hydrocarbon can be conducted to adiabatic reaction area.Lightweight Hydrocarbon flow may include saturation and/or unsubstituted hydrocarbon.Preferably, lightweight hydrocarbon flow is returned from heat transfer reactor effluent stream It receives.
C. the reaction zone to conduct heat
After leaving at least one adiabatic reaction area, first effluent may be provided at least one heat transfer reaction zone and with Including the second bulk material of catalyst material is contacted at reaction conditions at least one heat transfer reaction zone with will at least one Partly the cyclopentadiene intermediate and/or unconverted acyclic C5Hydrocarbon is converted into the second effluent comprising cyclopentadiene.This is extremely Few heat transfer reaction zone can be circulating fluid bed reactor, cycle sedimentation bed reactor, fixed bed reactors, cyclic annular fixed bed Reactor, fluidized-bed reactor, burning pipe reactor (such as it is described in USSN62/250,693, it is submitted on November 4th, 2015, It is incorporated by reference the application) or a Convective Heatings pipe reactor (USSN 62/250,674 is such as described in, in November, 2015 It submits within 4th, is incorporated by reference the application).Fixed bed reactors can be vertical fixed-bed or horizontal type fixed bed.Preferably, It is vertical fixed-bed for axial-flow type is vertical fixed-bed or radial-flow type fixed bed.Preferably, horizontal type fixed bed is the horizontal fixation of cross-flow type Bed.In addition, circulating fluid bed reactor can such as be described in Kunii, D. in bubbling or the operation of turbulent fluidised pattern, Levenspiel,O.,Chapter 3 of Fluidization Engineering,2nd Edition,Butterworth- Heinemann, Boston, 1991 and Walas, 6 of Chemical Process Equipment of S.M., Chapter, Revised 2nd Edition,Butterworth-Heinemann,Boston,2010。
Specifically, which can be burning pipe reactor or Convective Heating pipe reactor.
Combustion pipe reactor may include stove and the parallel reactor pipeline in the radiant section of the stove.Although can It is configured using any of radiation stove pipe reactor, preferably the stove includes multiple parallel reactor pipelines.Suitably The configuration of stove pipe reactor includes being described in US 5,811,065；US 5,243,122；US 4,973,778；US 2012/ 0060824；Those of with US 2012/0197054, these are all incorporated by reference the application.
Pipe reactor any can configure and be located in the stove.The vertical positioning of preferred reactor pipeline, to which charging should The top of pipe reactor enters and product leaves with reactor effluent from the stage of the pipe reactor.Preferably, instead It is straight to answer device pipeline, rather than with the radially spiral of stove or bending channel (although spiral or crooked pipeline can also make With).In addition, pipeline can have circle, oval, the section of rectangle and/or other known forms.Pipe reactor is available to be come from The radiant heat that at least one burner in the radiant section of the stove provides is heated.Any burning known in the art Device type can use, for example, mounted on top surface, the burner of side wall and floor.Preferably, burner can be located in and connect It is close that device entrance is answered to provide higher heat flux and providing lower heat flux close to the outlet of the pipe reactor.If Pipe reactor be it is vertically oriented, then burner preferred orientation close to pipe reactor top entry and with along the pipe The downward burned flame of length.Burner is set to answer device close close to vertical reactor pipeline top positioning and burning downwards Entrance (top) provides higher heat flux, and higher heating is desired there, for example, in order to provide reaction Heat, and sensible heat is needed to heat charging to desired reaction temperature.
Stove can optionally further include one or more shielding devices, position to stop the exit portion from pipe reactor At least part burner flame radiation, it is expected lower heat flux there to avoid higher than desired temperature, for example, Promote the temperature of undesirable coking and/or cracking, the coking and/or cracking are higher than in given catalyst, operating pressure Occur with the temperature of the desired conversion condition temperature range of residence time.If pipe reactor is relative to the combustion burnt downwards Burner it is vertically oriented, then at least one shielding device can be to be positioned as stopping at least one from the pipe reactor bottom part Part Fire Radiation.Preferably, shielding device can be flue gas conduit, and function is the flue gas that pilot burner generates Leave the radiant section of stove.
In addition, pipe reactor includes the bulk material containing catalyst material.The bulk material can be coated in reactor On inner surface of pipeline or can be a part for bulk material fixed bed in pipe reactor.Preferably, pipe reactor includes grain The fixed bed of shape material.The suitable method of the fixed bed of filling and/or reactor design pipeline includes 8,178,075 Hes of US WO 2014/053553, they are included in the application entirely through reference.Pipe reactor may include at least one internal structure, example Such as, concentric shells, to support bulk material and/or reduce the pressure drop in pipe reactor.Additionally or in the alternative, pipe reactor can Internal structure including mixed positioning in pipe reactor is to provide mixing in radial directions.Blend interior structure can be It is located in bed of granular material or in the part for separating two or more bulk material areas of pipe reactor.Additionally or alternatively Ground, pipe reactor may include heat of the promotion from duct wall to carbon monoxide-olefin polymeric on the inside or outside of the pipe reactor The fin of transmission or moulding.Fin or moulding can be provided for positioning close to answering at device entrance higher heat flux and close Lower heat flux at the pipe reactor of outlet.The example of suitable internal structure includes a variety of baffles, canopy, tower tray, pipe, Stick, fin, moulding and/or dispensing body.These internal structures can be coated with catalyst.Suitable internal structure can be metal or pottery Porcelain.Preferred ceramics are with those of high heat conductance, for example, silicon carbide, aluminium nitride, boron carbide and silicon nitride.Preferably, instead Answer device pipeline that there is the pressure drop measured from reactor inlet to reactor outlet during so that charging is contacted with carbon monoxide-olefin polymeric Less than 20psi, more preferably less than 5psi.
Additionally or in the alternative, stove may include radiant section, convection section and flue gas stacked body.The flue gas of heat can lead to It crosses to generate at least one of the radiant section of stove burner and be oriented to air by convection section and leave flue gas and stack Body.Heat from flue gas can heat various streams by the convective transfer from flue gas, for example, charging, Steam updates gas, regeneration gas, vapor fuel preheating and/or burning air preheat, by heat exchanger across convection section or Tube bank.The convection section of stove can contain at least one heat exchanger or tube bank, and flue gas body heat is fed by convection current wherein Material and/or steam.
Additionally or in the alternative, multiple stoves may be present, for example, (each stove may include two or more stoves The radiant section of parallel reactor pipeline containing the bulk material comprising catalyst material).Optionally, may be present and two or more The single convection section and flue gas stacked body that a furnace radiant section is in fluid communication.When there are one or when multiple stoves, reheat Gas or regeneration gas may be provided to the one or more stove, meanwhile, including acyclic C5The charging of hydrocarbon may be provided to not Same one or more stoves.
Convective Heating pipe reactor may include multiple parallel reactor pipelines in convective heat transfer shell.Preferably, instead It is straight to answer device pipeline, rather than with the spiral or bending channel (although spiral or crooked pipeline can also be used) along shell. In addition, pipeline can have circle, oval, the section of rectangle and/or other known forms.Advantageously, pipeline has small cut Face size is to minimize section temperature difference.However, reducing the sectional dimension of pipeline can increase for given throughput rate Number of tubes.Therefore, it is original excellent preferably to consider that minimum section temperature difference and minimum are built into for optimum pipeline size selection Change.Suitable sectional dimension (that is, diameter of cylindrical pipe) can be 1cm-20cm, more preferable 2cm-15cm and most preferably 3cm- 10cm。
In the pipe reactor of Convective Heating, pipe reactor can be by turbine combustion fuel gas and the oxygen containing pressure of packet The turbine exhaust gas stream heating that the gas of contracting generates.In other aspects, pipe reactor can pass through fuel cell, stove, pot The Convective Heating for the hot gas that burning in stove or additional air burner generates.However, heating the reaction with turbine exhaust gas Device pipeline is preferably as the further advantages such as power can be generated jointly.
Wrapping the gas of oxygen containing compression can compress at least one compressor.Preferably, the gas of compression is compression Air.Optionally, the gas of compression may include the air rich in oxygen obtained by being partially separated nitrogen.This field can be used Known any compressor and/or turbine.For the suitable compressor and turbine in method described herein and system Example be described in US 7,536,863, be incorporated by reference the application.Preferably, in addition turbine produces power.Turbine Acc power can be used for operating the gas that compressor carrys out the oxygen containing compression of compressed package.Optionally, generator and/or other may be present Compressor, the power that they can be generated with turbine operate.Generator can also generate electrical power.
Heat can pass through the convection current from turbine exhaust gas stream to the outer surface of the pipe reactor wall.Reactor tube Road any can configure and be located in shell.Preferred reactor pipeline location is useless with the charging and turbine that provide fair current inside the shell Gas.Charging and the turbine exhaust gas stream can be flowed in the same direction to provide high close to the heat flux answered at device entrance In the close heat flux for answering device pipeline exit.It is being desired close to the higher heating of device entrance is answered, for example, for reaction Heat is provided, and heating is fed to the heat of desired reaction temperature.Lower heat is logical close at the pipe reactor exit portion Amount (amount relative to inlet heat flux) is desired, to avoid higher than desired temperature, for example, promoting undesirable coking And/or the temperature of cracking, the coking and/or cracking are higher than in given catalyst, operating pressure and the expectation of residence time Conversion condition temperature range temperature occur.
May be present can make at least one combustion apparatus of other heat input turbine exhaust gas stream.Other Re Ketong Cross the turbine exhaust gas stream that combustion apparatus is supplied to pipe reactor upstream or downstream.Other fuel gas can use turbine Unreacted oxygen burning from turbine exhaust gas stream to the convection current of pipe reactor wall with by before conducting heat in exhaust gas stream Or later, the temperature of the turbine exhaust gas stream is improved.Other heat input can pass through any combustion apparatus known in the art It is provided to turbine exhaust gas stream.The example of suitable combustion apparatus includes duct burner, auxiliary burner, or known use In the miscellaneous equipment of the auxiliary heating of flue gas.
The pipe reactor of Convective Heating contains the bulk material comprising catalyst material.Bulk material can be coated in reaction Device inner surface of pipeline can be a part for the fixed bed of bulk material in pipe reactor.Preferably, pipe reactor includes The fixed bed of bulk material.The suitable method of the fixed bed of filling and/or reactor design pipeline includes US 8, and 178,075, It is all included in by quoting.Pipe reactor may include at least one internal structure, for example, concentric shells, to support granular material Pressure drop in material and/or reduction pipe reactor.Pipe reactor may include internal junction of the mixed positioning in pipe reactor Structure provides mixing in radial directions.Blend interior structure can be to be located in bed of granular material or pipe reactor separates In the part in two or more bulk material areas.Pipe reactor may include the rush on the inside or outside of the pipe reactor The fin transmitted into the heat from duct wall to bulk material or moulding.Fin or moulding can be positioning to provide close to inlet Heat flux is higher than the heat flux close to the pipe reactor exit.The example of suitable internal structure includes a variety of baffles, canopy, Tower tray, pipe, stick, fin, moulding and/or dispensing body.These internal structures can be coated with catalyst.Suitable internal structure can be gold It is belonging to or ceramic.Preferred ceramics are with those of high heat conductance, for example, silicon carbide, aluminium nitride, boron carbide and silicon nitride. Preferably, pipe reactor have during so that charging is contacted with carbon monoxide-olefin polymeric slave reactor inlet to reactor outlet The pressure drop of measurement is less than 20psi, more preferably less than 5psi.
Additionally or in the alternative, heat-transfer arrangement may be present to be transmitted to the heat of additional quantity from turbine exhaust gas by convection current Other streams, for example, updating gas, regeneration gas, charging (before the charging enters pipe reactor), fuel gas, including The gas streams (for example, gas streams of compression) and/or steam of oxygen.Other heat-transfer arrangement, which can be known in the art, appoints What suitable heat-transfer arrangement.Suitable heat-transfer arrangement includes heat exchanger tube.Heat-transfer arrangement can be positioned on the reactor Conduit enclosure to transmit additional heat from turbine exhaust gas before or after heat is transmitted to pipe reactor from turbine exhaust gas.
Additionally or in the alternative, it may be present in convective heat transfer shell that there are two or more parallel reactor pipelines.Example Such as, two or more shells may be present, each shell includes multiple parallel reactor pipelines containing bulk material.Also it may be present Each flow control apparatus of the control turbine exhaust gas to multiple pipe reactors.Suitable flow control apparatus includes control Valve processed, baffle, blinds, damper and/or conduit.Can further include that the turbine exhaust gas is left or around anti-at least partially for transfer It answers device pipeline and turbine exhaust gas is led into other heat recovery equipments or to exhaust gas stacked body.It is such as useless that ancillary equipment also may be present Gas muffler and scraper.
Additionally or in the alternative, which may include that at least first heat transfer reaction zone, the second heat transfer are anti- Area is answered, third heat transfer reaction zone, the 4th heat transfer reaction zone, the 5th heat transfer reaction zone, the 6th heat transfer reaction zone, the 7th, which conducts heat, reacts Area and/or the 8th heat transfer reaction zone etc..As understood here, each reaction zone that conducts heat can be individual reactor or heat transfer reaction Device may include one or more heat transfer reaction zones.Preferably, reactor assembly includes 1-20 heat transfer reaction zone, more preferably 1-15 heat transfer reaction zone, more preferable 1-10 heat transfer reaction zone, more preferable 1-8 heat transfer reaction zone.When there are more than one biographies When thermal reaction area, heat transfer reaction zone can be with any suitable deployment arrangements, for example, series connection or parallel, as above one or more exhausted Thermal reaction area.Each heat transfer reaction zone can be independently circulating fluid bed reactor, cycle sedimentation bed reactor, fixed bed reaction Device, cyclic annular fixed bed reactors, fluidized-bed reactor, burn pipe reactor or Convective Heating pipe reactor.Additionally or in the alternative, Method described herein can further comprise the charging of most of Partial Conversion being moved to the second biography from the first heat transfer reaction zone Thermal reaction area and/or by most of bulk material from this second heat transfer reaction zone be moved to this first heat transfer reaction zone.As herein Middle to use, " major part " refers at least charging of the Partial Conversion of major part and the bulk material, for example, at least about 50.0wt%, at least about 60.0wt%, at least about 70.0wt%, at least about 80.0wt%, at least about 90.0wt%, at least about 95.0wt%, at least about 99.0wt%, and at least about 100.0wt% part.
Heat transfer reaction zone may include at least one internal structure to support first bulk material, be evenly distributed into Material, to collect hydrocarbon products and/or reduce the pressure drop in reaction zone.For example, when the reaction zone that conducts heat is vertical fixed-bed, Yi Zhonghuo A variety of internal structures, for example, permeable concentric shells, it may include in the reaction zone to contain and support bulk material, and should be into Material can feed the substantially an open central axis portion of the reaction zone and radially about be flowed in bulk material.Additionally or alternatively Ground, heat transfer reaction zone may include at least one internal structure, preferably a variety of internal structures (for example, 2,3,4,5,6,7,8,9,10, 15,20,30,40,50 kinds etc.).The example of suitable internal structure includes a variety of protection support lattices, compresses grid, baffle, canopy, tower Disk, pipe, stick and/or dispensing body.
First effluent is (for example, cyclopentadiene intermediate, unconverted acyclic C5Hydrocarbon and optional cyclopentadiene) it can quilt Temperature is provided in T2Heat transfer reaction zone, T2≤ about 700 DEG C ,≤about 675 DEG C ,≤about 650 DEG C ,≤about 625 DEG C ,≤about 600 DEG C ,≤about 575 DEG C ,≤about 550 DEG C ,≤about 525 DEG C ,≤about 500 DEG C ,≤about 475 DEG C ,≤about 450 DEG C ,≤about 425 DEG C ,≤about 400 DEG C ,≤about 375 DEG C ,≤about 350 DEG C ,≤about 325 DEG C ,≤about 300 DEG C ,≤about 275 DEG C ,≤about 250 DEG C ,≤about 225 DEG C or ≤ about 200 DEG C.Preferably, into the first effluent of heat transfer reaction zone (for example, cyclopentadiene intermediate, unconverted acyclic C5Hydrocarbon and optional cyclopentadiene) temperature≤about 575 DEG C, more preferably≤about 550 DEG C, more preferably≤about 525 DEG C, more preferably≤ About 500 DEG C.The temperature range clearly disclosed includes the combination of any of above value, for example, about 200 DEG C-about 700 DEG C, about 250 DEG C-about 600 DEG C, about 350 DEG C-about 650 DEG C, about 375 DEG C-about 500 DEG C etc..Preferably, this into heat transfer reaction zone is first-class Go out the temperature of object (for example, cyclopentadiene intermediate, unconverted acyclic C5Hydrocarbon and optional cyclopentadiene) be about 200 DEG C-about 700 DEG C, more preferably from about 300 DEG C-about 600 DEG C, more preferably from about 400 DEG C-about 550 DEG C, more preferably from about 475 DEG C-about 525 DEG C.Upper It states temperature and provides the first effluent (for example, cyclopentadiene intermediate, unconverted acyclic C5Hydrocarbon and optional cyclopentadiene) C can advantageously be minimized5Hydrocarbon is (for example, acyclic C5Hydrocarbon) they can in the reaction zone that conducts heat in catalyst material in the presence of Undesirable cracking before reaction.
Additionally or in the alternative, before entering and conducting heat reaction zone, see by the first effluent (for example, cyclopentadiene intermediate, Unconverted acyclic C5Hydrocarbon and optional cyclopentadiene) it is heated to by one or more heating equipments (for example, heat exchanger) Temperature is stated, the heating of stove convective region is included in.
At least one heat transfer reaction zone is being enough to convert the first effluent at least partially to the anti-of cyclopentadiene It is operated under the conditions of answering.Preferably, the first effluent can by range in weight (hourly) space velocity (WHSV) below (WHSV, acyclic C5The matter of hydrocarbon Quality/hour of amount/catalyst) it is supplied to heat transfer reaction zone：About 1.0- about 1000.0hr-1.The WHSV can be about 1.0- about 900.0hr-1, about 1.0- about 800.0hr-1, about 1.0- about 700.0hr-1, about 1.0- about 600.0hr-1, about 1.0- about 500.0hr-1, about 1.0- about 400.0hr-1, about 1.0- about 300.0hr-1, about 1.0- about 200.0hr-1, about 1.0- about 100.0hr-1, about 1.0- about 90.0hr-1, about 1.0- about 80.0hr-1, about 1.0- about 70.0hr-1, about 1.0- about 60.0hr-1, about 1.0- is about 50.0hr-1, about 1.0- about 40.0hr-1, about 1.0- about 30.0hr-1, about 1.0- about 20.0hr-1, about 1.0- about 10.0hr-1, about 1.0- about 5.0hr-1, about 2.0- about 1000.0hr-1, about 2.0- about 900.0hr-1, about 2.0- about 800.0hr-1, about 2.0- is about 700.0hr-1, about 2.0- about 600.0hr-1, about 2.0- about 500.0hr-1, about 2.0- about 400.0hr-1, about 2.0- about 300.0hr-1, about 2.0- about 200.0hr-1, about 2.0- about 100.0hr-1, about 2.0- about 90.0hr-1, about 2.0- about 80.0hr-1, about 2.0- About 70.0hr-1, about 2.0- about 60.0hr-1, about 2.0- about 50.0hr-1, about 2.0- about 40.0hr-1, about 2.0- about 30.0hr-1, About 2.0- about 20.0hr-1, about 2.0- about 10.0hr-1, and about 2.0- about 5.0hr-1.Preferably, the WHSV be about 1.0- about 100.0hr-1, more preferably from about 1.0- about 60.0hr-1, more preferably from about 2.0- about 40.0hr-1, more preferably from about 2.0- about 20.0hr-1。
It is further preferred, that substantially isothermal temperature distribution or reversed Temperature Distribution are maintained at least one heat transfer instead Answer area.As used in this article, " the isothermal temperature distribution " of at least one heat transfer reaction zone refers to that at least one heat transfer is anti- The temperature in area is answered to keep virtually constant, for example, in mutually synthermal or within the scope of identical narrow temperature, temperature upper limit and temperature The difference of degree lower limit is no more than about 40 DEG C；More preferably no more than about 20 DEG C.It can be to carry to keep the advantages of substantially isothermal temperature is distributed High product yield, because of acyclic C5Hydrocarbon is to lighter hydrocarbon (C4-) by-product cracking reduce.
As used in this article, " the reversed Temperature Distribution " of at least one heat transfer reaction zone refers to heat transfer reaction zone entrance Temperature of the temperature at place less than heat transfer reaction zone exit." reversed Temperature Distribution " can further include at least one heat transfer reaction zone The temperature of certain interior point is reacted less than the temperature of heat transfer reaction zone inlet as long as the temperature of heat transfer reaction zone inlet is less than heat transfer The temperature in area exit.In other words, when the first effluent is (for example, cyclopentadiene, unconverted acyclic C5Hydrocarbon) to upstream When dynamic, the temperature of at least one heat transfer reaction zone can be from the bottom part of at least one heat transfer reaction zone to top decilitre It is high.On the contrary, the temperature of at least one heat transfer reaction zone can be from the top section of at least one heat transfer reaction zone to bottom Part reduces.Keeping reversed Temperature Distribution that can advantageously minimize at least one heat transfer reaction zone can have in inlet The carbonaceous material for helping the coking of catalyst material is formed.Reversed Temperature Distribution can also carry at least one heat transfer reaction zone For enough reaction time and length in the H for producing enough amounts less than the operation temperature of outlet temperature2, this can be minimized Carbonaceous material is formed at product exit.
Especially, for burning pipe reactor and/or Convective Heating pipe reactor, although in pipe reactor entrance Higher heat flux is provided and in the lower heat flux of pipe reactor near exit or shielding, is stilld provide along pipe reactor The substantially isothermal temperature of central line measurement is distributed.However, preferably optimization pipe reactor designs so that substantial reverse temperature Degree distribution is positively retained in pipe reactor.The advantages of substantially isothermal temperature is distributed is to maximize efficiently using for catalyst With the undesirable C of minimum4-The generation of by-product.
Preferably, isothermal temperature distribution is such distribution, and wherein reactor inlet temperature is in reactor outlet temperature Within plus or minus about 40 DEG C, alternatively within about 20 DEG C, alternatively within about 10 DEG C, alternatively within about 5 DEG C, alternatively, reaction Device inlet temperature is identical as reactor outlet temperature.Alternatively, isothermal temperature distribution is such distribution, wherein reactor inlet temperature Degree is within plus or minus about the 20% of reactor outlet temperature, alternatively within about 10%, alternatively within about 5%, alternatively Ground is within about 1%.
Preferably, isothermal temperature distribution be such distribution, wherein the temperature of the reaction section length in reactor with instead Answer device inlet temperature compared to variation no more than about 40 DEG C, alternatively no more than about 20 DEG C, alternatively no more than about 10 DEG C, alternatively No more than about 5 DEG C.Alternatively, isothermal temperature distribution is such distribution, wherein the temperature of the reaction section length in reactor exists Within plus or minus about the 20% of reactor inlet temperature, alternatively within plus or minus about the 10% of the reactor inlet temperature, alternatively Ground is within about 5%, alternatively within about 1%.
However, to minimize rate of catalyst deactivation, preferably optimizes pipe reactor and design so that substantial reverse temperature Distribution is positively retained in pipe reactor.
For the pipe reactor that burns, Convective Heating pipe reactor and/or cyclic annular fixed bed reactors, " reversed Temperature Distribution " Including such system, wherein temperature changes in the pipe reactor or fixed bed reactors, as long as pipe reactor inlet Or the temperature of cyclic annular fixed bed reactors inlet is less than pipe reactor exit or cyclic annular fixed bed reactors exit Temperature." reversed Temperature Distribution " further contemplates that：Pipe reactor or cyclic annular fixed bed reactors have centerline temperature Ta； Along pipe reactor or cyclic annular fixed bed reactors length, centerline temperature is reduced to temperature Tb；Along pipe reactor Or at the further length of cyclic annular fixed bed reactors, centerline temperature rises to temperature Tc；Finally, in pipe reactor exit Or the centerline temperature in cyclic annular fixed bed reactors exit is reduced to temperature Td；Wherein Tc>Td>Ta>Tb.Enter in pipe reactor The temperature measured at charging contact bulk material first near mouthful can be about 0 DEG C-about 200 DEG C, it is preferable that about 25 DEG C-about 150 DEG C, more preferably from about 50 DEG C-about 100 DEG C, the contact with bulk material is left in effluent less than in pipe reactor near exit Locate the temperature measured.Preferably, the pipe centerline temperature for contacting measured at bulk material first is fed near entrance It can be about 0 DEG C-about 200 DEG C, it is preferable that about 25 DEG C-about 150 DEG C, more preferably from about 50 DEG C-about 100 DEG C, less than in pipe reactor Near exit leaves the pipe centerline temperature measured with the contact position of bulk material in effluent.
Effluent exit leave heat transfer reaction zone second effluent (for example, cyclopentadiene) temperature can be≤ About 600 DEG C ,≤about 575 DEG C ,≤about 550 DEG C ,≤about 525 DEG C ,≤about 500 DEG C ,≤about 475 DEG C ,≤about 450 DEG C ,≤about 425 DEG C ,≤about 400 DEG C ,≤about 375 DEG C ,≤about 350 DEG C ,≤about 325 DEG C ,≤about 300 DEG C ,≤about 275 DEG C ,≤about 250 DEG C ,≤about 225 DEG C or≤about 200 DEG C.Preferably, in the second effluent for leaving heat transfer reaction zone in effluent exit (for example, ring penta Diene) temperature be≤about 550 DEG C, more preferably≤about 575 DEG C, more preferably≤about 600 DEG C.The temperature range packet clearly disclosed The combination of any of above value is included, for example, about 200 DEG C-about 600 DEG C, about 250 DEG C-about 575 DEG C, about 350 DEG C-about 550 DEG C, about 375 DEG C-about 450 DEG C etc..Preferably, effluent exit leave heat transfer reaction zone first effluent (for example, cyclopentadiene, Unconverted acyclic C5Hydrocarbon) temperature be about 200 DEG C-about 600 DEG C, more preferably from about 250 DEG C-about 575 DEG C, more preferably from about 350 DEG C- About 550 DEG C, more preferably from about 375 DEG C-about 450 DEG C.
Additionally or in the alternative, the reaction condition in heat transfer reaction zone may include temperature >=about 300 DEG C, >=about 325 DEG C, >=about 350 DEG C, >=about 375 DEG C, >=about 400 DEG C, >=about 425 DEG C, >=about 450 DEG C, >=about 475 DEG C, >=about 500 DEG C, >=about 525 DEG C, >=about 550 DEG C, >=about 575 DEG C, >=about 600 DEG C >=about 625 DEG C, >=about 650 DEG C, >=about 675 DEG C, >=about 700 DEG C, >=about 725 DEG C, >=about 750 DEG C, >=about 775 DEG C, >=about 800 DEG C, >=about 825 DEG C, >=about 850 DEG C, >=about 875 DEG C, >=about 900 DEG C, >=about 925 DEG C, >=about 950 DEG C, >=about 975 DEG C, or >=about 1000 DEG C.Additionally or in the alternative, which can be≤about 300 DEG C ,≤about 325 DEG C ,≤about 350 DEG C ,≤about 375 DEG C ,≤about 400 DEG C ,≤about 425 DEG C ,≤about 450 DEG C ,≤about 475 DEG C ,≤about 500 DEG C, ≤ about 525 DEG C ,≤about 550 DEG C ,≤about 575 DEG C ,≤about 600 DEG C ,≤about 625 DEG C ,≤about 650 DEG C ,≤about 675 DEG C ,≤about 700 DEG C ,≤about 725 DEG C ,≤about 750 DEG C ,≤about 775 DEG C ,≤about 800 DEG C ,≤about 825 DEG C ,≤about 850 DEG C ,≤about 875 DEG C ,≤about 900 DEG C ,≤about 925 DEG C ,≤about 950 DEG C ,≤about 975 DEG C, or≤about 1000 DEG C.The temperature range clearly disclosed includes any The combination of above-mentioned value, for example, about 300 DEG C-about 900 DEG C, about 350 DEG C-about 850 DEG C, and about 400 DEG C-about 800 DEG C etc..Preferably, The temperature can be about 300 DEG C-about 900 DEG C, more preferably from about 350 DEG C-about 850 DEG C, more preferably from about 400 DEG C-about 800 DEG C.Optionally, At least one heat transfer reaction zone may include one or more heating equipments to keep temperature therein.Conjunction known in the art The example of suitable heating equipment includes, but are not limited to combustion pipe, and the coil of the heating with high temperature heat transfer fluid, electricity adds Hot device and/or microwave release.As used in this article, " coil " refers to the structure being placed in container, hot with this configuration It transmits fluid and contacts the heat to container contents.Coil can have any suitable cross sectional shape, and can be straight, including U is curved, Including endless tube etc..
Additionally or in the alternative, the reaction condition of reaction zone of conducting heat may include pressure≤about 1.0psia ,≤about 2.0psia ,≤ About 3.0psia ,≤about 4.0 ,≤about 5.0psia ,≤about 10.0psia ,≤about 15.0psia ,≤about 20.0psia ,≤about 25.0psia ,≤about 30.0psia ,≤about 35.0psia ,≤about 40.0psia ,≤about 45.0psia ,≤about 50.0psia ,≤ About 55.0psia ,≤about 60.0psia ,≤about 65.0psia ,≤about 70.0psia ,≤about 75.0psia ,≤about 80.0psia, ≤ about 85.0psia ,≤about 90.0psia ,≤about 95.0psia ,≤about 100.0psia ,≤about 125.0psia ,≤about 150.0psia ,≤about 175.0psia, or≤about 200.0psia.Additionally or in the alternative, which can be >=about 1.0psia, >= About 2.0psia, >=about 3.0psia, >=about 4.0psia, >=about 5.0psia, >=about 10.0psia, >=about 15.0psia, >=about 20.0psia, >=about 25.0psia, >=about 30.0psia, >=about 35.0psia, >=about 40.0psia, >=about 45.0psia, >= About 50.0psia, >=about 55.0psia, >=about 60.0psia, >=about 65.0psia, >=about 70.0psia, >=about 75.0psia, >=about 80.0psia, >=about 85.0psia, >=about 90.0psia, >=about 95.0psia, >=about 100.0psia, >=about 125.0psia, >=about 150.0psia, or >=about 175.0psia.The range of the temperature and pressure clearly disclosed and combination are wrapped The combination of any of above value is included, for example, about 1.0psia- about 200.0psia, about 2.0psia- about 175.0psia, about 3.0psia- about 150.0psia etc..Preferably, which can be about 1.0psia- about 200.0psia, more preferably from about 2.0psia- About 175.0psia, the about 100.0psia than such as from about 2.0psia-, more preferably from about 3.0psia- about 150.0psia, than such as from about 3.0psia- about 50psia.
Additionally or in the alternative, across the change pressure of heat transfer reaction zone, (pressure of first effluent inlet subtracts second The pressure in effluent exit) can be >=about 0.5psia, >=about 1.0psia, >=about 2.0psia, >=about 3.0psia, >=about 4.0psia >=about 5.0psia, >=about 10.0psia, >=about 14.0psia, >=about 15.0, psia, >=about 20.0psia, >=about 24.0psia, >=about 25.0psia, >=about 30.0psia, >=about 35.0psia, >=about 40.0psia, >=about 45.0psia, >= About 50.0psi, >=about 55.0psia, >=about 60.0psia, >=about 65.0psia, >=about 70.0psia, >=about 75.0psia, >= About 80.0psia, >=about 85.0psia, >=about 90.0psia, >=about 95.0psia, >=about 100.0psia, >=about 125.0psia, or >=about 150.0psia.As understood here, " in first effluent entrance " and " being exported in second effluent " It is included in entrance and/or outlet is neutralized essentially around their space.Additionally or in the alternative, across the variation of heat transfer reaction zone Pressure (or pressure drop) (first effluent inlet pressure subtracts second effluent outlet pressure) can be≤about 2.0psia ,≤about 3.0psia ,≤about 4.0psia ,≤about 5.0psia ,≤about 10.0psia ,≤about 14.0psia ,≤about 15.0, psia≤about 20.0psia ,≤about 24.0psia ,≤about 25.0psia ,≤about 30.0psia ,≤about 35.0psia ,≤about 40.0psia ,≤ About 45.0psia ,≤about 50.0psi ,≤about 55.0psia ,≤about 60.0psia ,≤about 65.0psia ,≤about 70.0psia ,≤ About 75.0psia ,≤about 80.0psia ,≤about 85.0psia ,≤about 90.0psia ,≤about 95.0psia ,≤about 100.0psia, ≤ about 125.0psia ,≤about 150.0psia ,≤about 175.0psia, or≤about 200.0psia.The variation pressure clearly disclosed Power range includes any of above combination for listing value, for example, about 10psia- about 70.0psia, about 20.0psia- is about 60.0psia, about 30.0psia- about 50.0psia etc..
Advantageously, when compared with the method that adiabatic reaction area is wherein not present, the heat of at least one heat transfer reaction zone Load can reduce 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% per unit generate cyclopentadiene.As understood here, " thermic load " is Refer to, is transported to charging and effluent (that is, reactants and products) with the Δ H of offer reaction and in heat transfer reaction zone entrance and exit Between the Δ H for experiencing temperature change thermal energy net amount.Preferably, when compared with the method that adiabatic reaction area is wherein not present When, the thermic load area of at least one heat transfer reaction can reduce about 3.0%, about 10.0%, about 15.0%, about 20%, or about The cyclopentadiene that 25.0% per unit generates.Preferably, when compared with the method that adiabatic reaction area is wherein not present, this is at least The thermic load of one heat transfer reaction zone can reduce about 2.0%- about 25.0%, about 4.0%- about 15.0%, or about 6.0%- is about The cyclopentadiene that 10.0% per unit generates.
Additionally or in the alternative, including hydrogen (H2) stream can be conducted to adiabatic reaction area and/or heat transfer reaction zone.It is such Stream may include supplementing hydrogen, be the hydrogen supplied other than any hydrogen that the pervious region of reactor assembly generates.It can be by hydrogen Stream introduces adiabatic reaction area and/or heat transfer reaction zone and generates coke material on bulk material and/or at this to minimize Bulk material is fluidized in adiabatic reaction area and/or the heat transfer reaction zone.Such stream comprising hydrogen can contain light hydrocarbon (example Such as, C1-C4).Preferably, the stream comprising hydrogen is somebody's turn to do substantially free of oxygen, for example, being below about 1.0wt%, is below about 0.1wt%, Below about 0.01wt%, it is below about 0.001wt%, is below about 0.0001wt%, below about 0.00001wt% etc..
Additionally or in the alternative, including C1, C2, C3And/or C4The lightweight hydrocarbon flow of hydrocarbon can be conducted to adiabatic reaction area and/or Conduct heat reaction zone.Lightweight hydrocarbon flow may include saturation and/or unsubstituted C1-C4Hydrocarbon.Such stream may include supplementing lightweight Hydrocarbon is the light hydrocarbon supplied other than any light hydrocarbon that the pervious region of reactor assembly generates.Lightweight hydrocarbon flow can It introduces adiabatic reaction area and/or the reaction zone that conducts heat is to make the gross pressure of second effluent stream have the C less than atmospheric pressure5 The partial pressure and hydrogen partial pressure of the merging of hydrocarbon, while gross pressure being kept to be more than atmospheric pressure.Preferably, lightweight hydrocarbon flow is supplied to adiabatic anti- Area is answered to provide other thermal capacitance and reduce the C in the adiabatic reaction area5Hydrocarbon partial pressure.Additionally or in the alternative, light hydrocarbon material Stream can contain hydrogen.Preferably, lightweight hydrocarbon flow is recycled from heat transfer reactor effluent stream.
D. bulk material
Including catalyst material (for example, carbon monoxide-olefin polymeric) bulk material (for example, the first bulk material, second Shape material) adiabatic reaction area and heat transfer reaction zone are provided to promote the C5Hydrocarbon is (for example, acyclic C5Hydrocarbon) it is converted into cyclopentadiene And/or cyclopentadiene intermediate.On the one hand, which can be in the side with the second bulk material stream in heat transfer reaction zone It is flowed to the direction of adverse current.Additionally or in the alternative, the first effluent can with the second bulk material stream in heat transfer reaction zone It flows in the direction of direction fair current.First bulk material and second bulk material can be same or different.
The carbon monoxide-olefin polymeric that can be used for first and/or second bulk material includes microporous crystalline metal silicate (metallosilicate), such as, crystallize ferrosilicate or it is other containing metal crystalline silicate (such as Wherein metal or metal-containing compound be dispersed in crystalline silicate structure and can be or be not crystalline framework a part that A bit).The microporous crystalline metal silicate framework type that can be herein used as carbon monoxide-olefin polymeric includes, but are not limited to MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU.
Specifically, include those of following framework type for suitable micropore metal silicate here：MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU (such as zeolite beta, modenite, Faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58 With MCM-22 races material), wherein from the race of the 8th, 11 and 13 periodic table of elements one or more metals (preferably Fe, Cu, Ag, It is one or more in Au, B, Al, Ga and/or In) it impregnates and is incorporated into crystalline texture during synthesis or after crystallization.It can recognize Know, metal silicate there can be one or more metals to exist, and such as material is referred to alternatively as ferrosilicate, but it Most probable still contains a small amount of aluminium.
The restricted index that microporous crystalline metal silicate preferably has is the alternatively 1-12 less than 12, alternatively 3-12.It can Have for aluminosilicate here and be less than 12, such as 1-12, alternatively the restricted index of 3-12, and includes, but are not limited to Zeolite beta, modenite, faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM- The mixture of 50, ZSM-57, ZSM-58, MCM-22 race material and they two or more.In preferred embodiment In, the restricted index of crystalline aluminosilicate is about 3- about 12 and is ZSM-5.
ZSM-5 is described in US 3,702,886.ZSM-11 is described in US 3,709,979.ZSM-22 is described in US 5, 336,478.ZSM-23 is described in US 4,076,842.ZSM-35 is described in US 4,016,245.ZSM-48 is described in US 4, 375,573.ZSM-50 is described in US 4,640,829.ZSM-57 is described in US 4,873,067.ZSM-58 is described in US 4, 698,217.Restricted index and and its determine method be described in US 4,016,218.The full content of aforementioned patent all passes through reference It is included in the application.
MCM-22 races material is selected from 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 they two or more The mixture of kind.
The material of MCM-22 races includes MCM-22 (being described in US 4,954,325), PSH-3 (it is described in US 4,439, 409), SSZ-25 (being described in US 4,826,667), ERB-1 (are described in EP 0 293 032), ITQ-1 (it is described in US 6, 077,498) and ITQ-2 (being described in WO 97/17290), MCM-36 (being described in US 5,250,277), MCM-49 (is described in US 5,236,575), the mixture of MCM-56 (being described in US 5,362,697) and they two or more.It is included in this The related zeolite of MCM-22 races is UZM-8 (being described in US 6,756,030) and UZM-8HS (being described in US 7,713,513), this Both it is suitable as the molecular sieve of MCM-22 races.
In one or more embodiments, (wherein M is the 8th, 11 or 13 to the Si/M molar ratios of crystalline metallosilicate Race's metal) be greater than about 3, or greater than about 25, or greater than about 50, or greater than about 100, greater than about 400 or range about 100- about 2,000, or about 100- about 1,500, or about 50- about 2,000, or about 50- about 1,200.
In one or more embodiments, the SiO of crystalline aluminosilicate2/Al2O3Molar 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 range in about 100- about 400, or about 100- about 500, or about 25- about 2,000, or about 50- about 1,500, or about 100- about 1,200, or about 100- about 1,000.
The present invention in another embodiment, microporous crystalline metal silicate (such as aluminosilicate) and the 10th race's metal Or metallic compound and optionally a kind of, two kinds, three or more 1st, 2 or 11 race's metals or metallic compound combination.
In one or more embodiments, the 10th race's metal includes, or is selected from, Ni, Pd and Pt, preferably Pt.It is described to urge 10th race's tenor of agent composition is at least 0.005wt%, the weight based on the carbon monoxide-olefin polymeric.A kind of or more In kind embodiment, the 10th race's content range is in about 0.005wt%- about 10wt%, or about 0.005wt%- about 1.5wt%, base In the weight of the carbon monoxide-olefin polymeric.
In one or more embodiments, the 1st race's alkali metal includes, or is selected from, Li, Na, K, Rb, Cs and they The mixture of two or more, preferably Na.
In one or more embodiments, the 2nd race's alkaline-earth metal be selected from Be, Mg, Ca, Sr, Ba and they two kinds or More kinds of mixtures.
In one or more embodiments, the 1st race's alkali metal exists as oxide and the metal is selected from Li, Na, K, The mixture of Rb, Cs and they two or more.In one or more embodiments, the 2nd race's alkaline-earth metal is as oxygen Compound exists and the metal is selected from Be, magnesium, calcium, the mixture of Sr, Ba and they two or more.One or more In embodiment, the 1st race's alkali metal as oxide exist and the metal be selected from Li, Na, K, Rb, Cs and they two kinds or More kinds of mixtures；With the 2nd race's alkaline-earth metal as oxide exist and the metal be selected from Be, magnesium, calcium, Sr, Ba and they The mixture of two or more.
In one or more embodiments, the 11st race's metal includes, or is selected from, silver, gold, copper, preferably silver or copper.It is described 11st race's tenor of carbon monoxide-olefin polymeric is at least 0.005wt%, the weight based on the carbon monoxide-olefin polymeric.A kind of or In multiple embodiments, the 11st race's content range is in about 0.005wt%- about 10wt%, or about 0.005wt%- about 1.5wt%, Weight based on the carbon monoxide-olefin polymeric.
In one or more embodiments, (the 10th race's metal is being added, preferably before platinum in the α values of carbon monoxide-olefin polymeric Measure) it is less than 25, or it is less than 15, alternatively 1-25, alternatively 1.1-15.α values are such as described in US 3,354,078；The Journal of Catalysis, v.4, p.527 (1965)；V.6, p.278 (1966)；V.61, p.395 (1980) use 538 DEG C of steady temperature and the flow rate of variation measure, and are such as described in detail in Journal of Catalysis, v.61, P.395, in (1980).
In one or more embodiments of aluminosilicate, the molar ratio of the 1st race's alkali metal and Al are 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 aluminosilicate, the molar ratio of the 2nd race's alkali metal and Al are 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 11st race's metal and the 10th race's 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 11st race's alkali Earth metal exists as oxide and the metal is selected from gold, the mixture of silver and copper and they two or more.
In one or more embodiments, in the H containing pentane and equimolar amounts2Charging acyclic C5Conversion condition Under, at about 550 DEG C-about 600 DEG C, pentane is divided in 3-10psia and pentane weight (hourly) space velocity (WHSV) 10-20hr temperature range-1, make The conversion ratio provided with the carbon monoxide-olefin polymeric of the present invention is at least about 70%, or at least about 75%, or at least about 80% or model It is trapped among the acyclic C of about 60%- about 80%5Charging.
In one or more embodiments, in the H containing pentane and equimolar amounts2Charging, temperature range is about 550 DEG C-about 600 DEG C, pentane is divided in 3-10psia and pentane weight (hourly) space velocity (WHSV) 10-20hr-1Acyclic C5Under conversion condition, make With the carbon monoxide-olefin polymeric of any type present invention provide to cyclic annular C5The carbon selectivity of compound is at least about 30%, or extremely Few about 40%, or at least about 50% or range in about 30%- about 80%.
In one or more embodiments, in the H containing pentane and equimolar amounts2Charging, temperature range is about 550 DEG C-about 600 DEG C, pentane is divided in 3-10psia and pentane weight (hourly) space velocity (WHSV) 10-20hr-1Acyclic C5Under conversion condition, make The carbon selectivity to cyclopentadiene provided with the carbon monoxide-olefin polymeric of any type present invention is at least about 30%, or at least about 40%, or at least about 50% or range in about 30%- about 80%.
The present invention carbon monoxide-olefin polymeric can be combined with matrix or adhesive material so that its it is wear-resistant and more tolerant to Its critical conditions exposed when being used in hydrocarbon Transformation Application.The composition of combination can contain the present invention's of 1-99wt% Material, the total weight of matrix (adhesive) and material based on the present invention.The relative scale of microcrystalline materials and matrix can be wide General variation, and crystalline content is about about 90 weight % of 1-, more generally, specifically when compound is with bead, extrudate, ball Agent, the particle that oil droplet is formed, spray drying forms such as particle when preparing, in the range of about 2 weight % to 80 weight % should Composite material.
During using carbon monoxide-olefin polymeric in the method for the invention, coke can be to be deposited on carbon monoxide-olefin polymeric, from And such carbon monoxide-olefin polymeric loses its a part of catalytic activity and becomes to inactivate.Decaying catalyst composition can pass through routine Technology regenerates, and the technology includes High Pressure Hydrogen processing and with the coke on oxygen-containing gas combustion catalyst composition.
In addition suitable carbon monoxide-olefin polymeric includes one or more 6th race's metals on inorganic carrier, the 9th race gold Category or the 10th race's metal, and optional one or more 1st race's alkali metal, the 2nd race's alkaline-earth metal and/or the 11st race's metal.6th Race's metal includes, or is selected from Cr, Mo and W.9th race's metal includes, or is selected from Co, Rh and Ir.10th race's metal includes, or choosing From Ni, Pd and Pt, preferably Pt.Inorganic carrier can be selected from zeolite as described herein, silicoaluminophosphate (that is, SAPO), aluminium phosphoric acid Salt (i.e. ALPO), metalloaluminophosphate (i.e. MeAPO), silica, zirconium oxide, titanium dioxide, aluminium oxide, magnesia, dioxy Change cerium, yttrium oxide, clay, magnesium hydrotalcite, calcium aluminate, zinc aluminate and combination thereof.In MeAPO, metal (Me) may include, But it is not limited to, Co, Fe, Mg, Mn and Zn.In one or more embodiments, the 1st race's alkali metal includes, or is selected from, Li, Na, The mixture of K, Rb, Cs and they two or more, preferably Na.In one or more embodiments, the 2nd race's alkaline earth Metal is selected from Be, Mg, Ca, the mixture of Sr, Ba and they two or more.In one or more embodiments, the 11 race's metals include, or are selected from, silver, gold, copper, preferably silver or copper.
Useful carbon monoxide-olefin polymeric includes crystalline aluminosilicate or ferrosilicate, optionally with it is a kind of, two kinds or more A variety of other metals or metallic compound combination.It preferably combines and includes：
1) crystalline aluminosilicate (such as ZSM-5 or zeolite L) and the 10th race's metal (such as Pt), the 1st race's alkali metal (such as Sodium or potassium) and/or the alkaline-earth metal combination of the 2nd race；
2) crystalline aluminosilicate (such as ZSM-5 or zeolite L) (compares with the 10th race's metal (such as Pt) and the 1st race's alkali metal Such as sodium or potassium) combination；
3) crystalline aluminosilicate (such as ferrosilicate or ZSM-5 of iron processing) and the 10th race's metal (such as Pt) and the 1st Race's alkali metal (such as sodium or potassium) combines；
4) crystalline aluminosilicate (zeolite L) is combined with the 10th race's metal (such as Pt) and the 1st race's alkali metal (such as potassium)；With
5) crystalline aluminosilicate (such as ZSM-5) and the 10th race's metal (such as Pt), the 1st race's alkali metal (such as sodium) and the 11 race's metals (such as silver or copper) combination.
Another useful carbon monoxide-olefin polymeric is the 10th race's metal (ratio being supported on silica (for example, silica) Such as Ni, Pd and Pt, preferably Pt), silica passes through the 1st race's alkali silicate (such as Li, Na, K, Rb and/or Cs silicate) And/or the 2nd race's alkaline-earth-metal silicate (such as Mg, Ca, Sr and/or Ba silicate), preferred potassium silicate, sodium metasilicate, calcium silicates And/or magnesium silicate, preferably potassium silicate and/or sodium metasilicate are modified.10th race's tenor of the carbon monoxide-olefin polymeric is at least 0.005wt%, the weight based on the carbon monoxide-olefin polymeric, it is preferable that range is in about 0.005wt%- about 10wt%, or about 0.005wt%up- about 1.5wt%, the weight based on the carbon monoxide-olefin polymeric.Silica (SiO2) can be to typically serve as urging Any silica of agent carrier, such as with trade name DAVISIL 646 (Sigma Aldrich), Davison 952, DAVISON 948 or Davison 955 (the Davison Chemical Division of W.R.Grace and Company) pins Those of sell.
Additionally or in the alternative, which can be that can carry out acyclic C5It feeds dehydrogenation but can have very little or not have There is the catalyst for the ability being cyclized.Such example of first catalysis material include one or more reduction-states, oxidation state, 6th-the 12 race's metal of race of the state, nitridation state and/or sulphided state of being carbonized；It is supported on heat safe inorganic carrier such as titanium dioxide Silicon, aluminium oxide, titanium oxide, zirconium oxide, cerium oxide, aluminosilicate (amorphous and micropore), other metal silicates be (amorphous With micropore), aluminate (for example, aluminum hydrotalcite)；Perovskite, SAPO, on ALPO and MAPO.Preferably, first catalysis Agent has the tendency of lower promotion acidic site cracking or metallic site cracking to minimize C5-C4-Cracking.
Carbon monoxide-olefin polymeric shape and design are preferably configured to minimize pressure drop during use, improve heat and transmit and most Smallization mass transport phenomenon.Carbon monoxide-olefin polymeric can be formed particle, loaded at random in the reactor or can be reaction The catalyst shape of structuring in device.
Suitable shape of catalyst and design are described in WO 2014/053553, are included in entirely through reference.It urges Agent composition can be the extrudate of a diameter of 2mm-20mm.Optionally, it is one or more that carbon monoxide-olefin polymeric section, which can shape, A blade and/or recessed section.In addition, the blade of carbon monoxide-olefin polymeric and/or recessed section can be spiral.Carbon monoxide-olefin polymeric can For the extrudate of a diameter of 2mm-20mm；And carbon monoxide-olefin polymeric section can shape as one or more blades and/or be recessed Section；And the blade of carbon monoxide-olefin polymeric and/or recessed section can be spiral.Shape may additionally include hole or hole in the shape To increase gap and improve mass transfer.
The catalyst shape example of structuring includes in the thin-walled of reactor and/or the inorganic carrier structure of other formation Catalyst coat.The inorganic carrier structure suitably formed can be metal or ceramic.Preferred ceramics is with high heat conductions Those of property, for example, silicon carbide, aluminium nitride, boron carbide and silicon nitride.The inorganic carrier structure suitably formed can be orderly to tie Structure, such as extruded ceramic material all in one piece and extrusion or roll-in metal monolith.In general, the inorganic carrier structure suitably formed can further include Ceramics or metal foam put forward the structure with 3D printing.Active catalyst coating can pass through washcoated or other ways known It is applied on carrier structure.Preferably, coating layer thickness is less than 1,000 micron；More preferably less than 500 microns；Most preferably 100-300 Micron.
For fixed bed reactors (combustion pipe, convection duct and ring-type), the grain shapes such as blade, recessed, spiral are It is particularly useful, and for fluidized-bed reactor, spherical grain shape is particularly useful.For fixed bed reactors (burning Pipeline, convection duct and ring-type), the grain shapes such as blade, recessed, spiral are particularly useful, and for fluidized-bed reactor, Spherical grain shape is particularly useful.Preferably, fixed bed is used for (for example, cyclic annular fixed bed reactors, combustion pipe reaction Device, Convective Heating pipe reactor etc.) particle be typically a diameter of 2mm-20mm extrudate；And the carbon monoxide-olefin polymeric Section can shape as one or more blades and/or recessed section；And the blade of the carbon monoxide-olefin polymeric and/or recessed section can be Spiral.
About the more information of useful carbon monoxide-olefin polymeric, following application is referred to：
1) 62/250 USSN, on November 4th, 675,2015；
2) 62/250 USSN, on November 4th, 681,2015；
3) 62/250 USSN, on November 4th, 688,2015；
4) 62/250 USSN, on November 4th, 695,2015；With
5) they, are incorporated by reference the application on November 4th, 689,2015 by 62/250 USSN.
Preferably, bulk material includes the platinum on ZSM-5, on the platinum and/or silicate modified silica on zeolite L Platinum.In various aspects, which may include the platinum on ZSM-5, on the platinum and/or silica on zeolite L Platinum and first bulk material may include the 6th race of at least one on inorganic carrier, the 9th race and/or the 10th race's metal.Without airborne Body can be selected from zeolite, SAPO, ALPO, MeAPO, silica, zirconium oxide, titanium oxide, aluminium oxide, magnesia, cerium oxide, oxygen Change yttrium, clay, magnesium hydrotalcite, calcium aluminate, zinc aluminate and combination thereof (physics and/or chemical combination).
The amount of suitable catalyst material can in the bulk material (for example, the first bulk material, second bulk material) For≤about 1.0wt% ,≤about 5.0wt% ,≤about 10.0wt% ,≤about 15.0wt% ,≤about 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤about 45.0wt% ,≤about 50.0wt% ,≤ 55.0wt% ,≤about 60.0wt% ,≤about 65.0wt% ,≤about 70.0wt% ,≤about 75.0wt% ,≤about 80.0wt% ,≤ About 85.0wt% ,≤about 90.0wt% ,≤about 95.0wt% ,≤about 99.0wt% or about 100.0wt%.Additionally or in the alternative, The amount for the catalyst material that bulk material (for example, the first bulk material, second bulk material) may include is >=about 1.0wt%, >=about 5.0wt%, >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, >=about 40.0wt%, >=about 45.0wt%, >=about 50.0wt%, >=about 55.0wt%, >=about 60.0wt%, >=about 65.0wt%, >=about 70.0wt%, >=about 75.0wt%, >=about 80.0wt%, >=about 85.0wt%, >= About 90.0wt%, or >=about 95.0wt%.The range clearly disclosed includes any of above combination for listing value；For example, about 1.0wt%- about 100.0wt%, about 5.0wt%- about 100.0wt%, about 10.0wt%- about 90.0wt%, about 20.0wt%- is about 80.0wt% etc..The amount for the catalyst material that bulk material (for example, the first bulk material, second bulk material) may include is about 1.0wt%- about 100.0wt%, more preferably from about 5.0wt%- about 100.0wt%, more preferably from about 25.0wt%- about 100.0wt%, More preferably from about 5.0wt%- about 90.0wt%, more preferably from about 10.0wt%- about 80.0wt%, more preferably from about 10.0wt%- is about 75.0wt%, more preferably from about 20.0wt%- about 70.0wt%, more preferably from about 25.0wt%- about 60.0wt%, more preferably from about 30.0wt%- about 50.0wt%.
In various aspects, bulk material (for example, the first bulk material, second bulk material) can further include it is a kind of or A variety of inert materials.It is as noted here, inert material be understood to include under the conditions of reaction described here to charging, in The promotion of mesosome product or final product conversion ratio is the material of negligible quantity (for example,≤about 3% ,≤about 2% ,≤about 1% etc.) Material.Catalyst material and inert material can be combined to the part of identical particle and/or can be separated particle.In addition, catalyst Material and/or inert material can it is substantially spherical (that is,<About 20%,<About 30%,<About 40%,<About 50% diametrically abnormal Become), cylindrical or blade shape.In addition, bulk material (for example, the first bulk material, second bulk material) can be extrudate, It can be spiral that the wherein section, which can shape as one or more blades and/or recessed section and the blade and/or recessed section,.It is preferred that Ground, it is generally spherical in shape that fluidized-bed reactor, circulating fluid bed reactor and cycle, which settle the bulk material on bed reactor,.Separately Outside, bulk material (for example, the first bulk material, second bulk material) can be formed with inner perforated or have other shapes to reduce Pressure drop minimizes an intergranular diffusion limitation simultaneously.
The amount of suitable inert material can be in the bulk material (for example, the first bulk material, second bulk material) About 0.0wt%, >=about 1.0wt%, >=about 5.0wt%, >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, >=about 40.0wt%, >=about 45.0wt%, >=about 50.0wt%, >= About 55.0wt%, >=about 60.0wt%, >=about 65.0wt%, >=about 70.0wt%, >=about 75.0wt%, >=about 80.0wt%, >=about 85.0wt%, >=about 90.0wt%, >=about 95.0wt%, or >=about 99.0wt%.Additionally or in the alternative, bulk material The amount for the inert material that (for example, the first bulk material, second bulk material) may include is≤about 1.0wt% ,≤about 5.0wt% ,≤about 10.0wt% ,≤about 15.0wt% ,≤about 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤about 45.0wt% ,≤about 50.0wt% ,≤about 55.0wt% ,≤about 60.0wt% ,≤ About 65.0wt% ,≤about 70.0wt% ,≤about 75.0wt% ,≤about 80.0wt% ,≤about 85.0wt% ,≤about 90.0wt%, ≤ about 95.0wt%, or≤about 99.0wt%.The range clearly disclosed includes any of above combination for listing value, for example, about 0.0wt%- about 99.0wt%, about 0.0wt%- about 95.0wt%, about 10.0wt%- about 90.0wt%, about 20.0wt%- is about 80.0wt% etc..Preferably, bulk material (for example, the first bulk material, second bulk material) may include the amount of inert material It is about 0.0wt%- about 95.0wt%, more preferably from about 0.0wt%- about 90.0wt%, more preferably from about 25.0wt%- is about 90.0wt%, more preferably from about 30.0wt%- about 85.0wt%, more preferably from about 30.0wt%- about 80.0wt%.
In various aspects, catalyst material and/or inert material are (as separated particle or as the combination of identical particle Part) average diameter that can have is >=about 5 μm, >=about 10 μm, >=about 20 μm, >=about 30 μm, >=about 40 μm, >=about 50 μm, >=about 100 μm, >=about 200 μm, >=about 300 μm, >=about 400 μm, >=about 500 μm, >=about 600 μm, >=about 700 μm, >=about 800 μm, >=about 900 μm, >=about 1000 μm, >=about 1100 μm, >=about 1200 μm, >=about 1300 μm, >=about 1400 μm, >=about 1500 μ M, >=about 1600 μm, >=about 1700 μm, >=about 1800 μm, >=about 1900 μm, >=about 2000 μm, >=about 2100 μm, >=about 2200 μ M, >=about 2300 μm, >=about 2400 μm, >=about 2500 μm, >=about 2600 μm, >=about 2700 μm, >=about 2800 μm, >=about 2900 μ M, >=about 3000 μm, >=about 3100 μm, >=about 3200 μm, >=about 3300 μm, >=about 3400 μm, >=about 3500 μm, >=about 3600 μ M, >=about 3700 μm, >=about 3800 μm, >=about 3900 μm, >=about 4000 μm, >=about 4100 μm, >=about 4200 μm, >=about 4300 μ M, >=about 4400 μm, >=about 4500 μm, >=about 5000 μm, >=about 5500 μm, >=about 6000 μm, >=about 6500 μm, >=about 7000 μ M, >=about 7500 μm, >=about 8000 μm, >=about 8500 μm, >=about 9000 μm, >=about 9500 μm, or >=about 10000 μm.In addition or Alternatively, catalyst material and/or inert material can have (as separated particle or as the built-up section of identical particle) Average diameter be≤about 5 μm ,≤about 10 μm ,≤about 20 μm ,≤about 30 μm ,≤about 40 μm ,≤about 50 μm ,≤about 100 μm ,≤ About 200 μm ,≤about 300 μm ,≤about 400 μm ,≤about 500 μm ,≤about 600 μm ,≤about 700 μm ,≤about 800 μm ,≤about 900 μ M ,≤about 1000 μm ,≤about 1100 μm ,≤about 1200 μm ,≤about 1300 μm ,≤about 1400 μm ,≤about 1500 μm ,≤about 1600 μ M ,≤about 1700 μm ,≤about 1800 μm ,≤about 1900 μm ,≤about 2000 μm ,≤about 2100 μm ,≤about 2200 μm ,≤about 2300 μ M ,≤about 2400 μm ,≤about 2500 μm ,≤about 2600 μm ,≤about 2700 μm ,≤about 2800 μm ,≤about 2900 μm ,≤about 3000 μ M ,≤about 3100 μm ,≤about 3200 μm ,≤about 3300 μm ,≤about 3400 μm ,≤about 3500 μm ,≤about 3600 μm ,≤about 3700 μ M ,≤about 3800 μm ,≤about 3900 μm ,≤about 4000 μm ,≤about 4100 μm ,≤about 4200 μm ,≤about 4300 μm ,≤about 4400 μ M ,≤about 4500 μm ,≤about 5000 μm ,≤about 5500 μm ,≤about 6000 μm ,≤about 6500 μm ,≤about 7000 μm ,≤about 7500 μ M ,≤about 8000 μm ,≤about 8500 μm ,≤about 9000 μm ,≤about 9500 μm, or≤about 10000 μm.The range clearly disclosed Including any of above combination for listing value, for example, about 10 μm-about 10000 μm, about 50 μm-about 10000 μm, about 100 μm-about 9000 μm, about 200 μm-about 7500 μm, about 200 μm-about 5500 μm, about 100 μm-about 4000 μm, about 100 μm-about 700 μm etc.. Catalyst material and/or inert material can have average straight (as separated particle or as the built-up section of identical particle) Diameter is about 25 μm-about 1200 μm, more preferably from about 50 μm-about 1000 μm, more preferably from about 10 μm-about 500 μm, more preferably from about 30 μm- About 400 μm, more preferably from about 40 μm-about 300 μm.
Preferably, in recirculating fluidized bed, catalyst material and/or inert material are (as separated particle or as phase With the built-up section of particle) average diameter that can have is about 100 μm-about 4000 μm, more preferably from about 100 μm-about 700 μm, more Preferably from about 100 μm-about 600 μm, more preferably from about 100 μm-about 500 μm.Preferably, cycle settle bed in, catalyst material and/ Or the average diameter that can have (as separated particle or as the built-up section of identical particle) of inert material be about 1000 μm- About 10000 μm, more preferably from about 2000 μm-about 8000 μm, more preferably from about 3000 μm-about 6000 μm, more preferably from about 3500 μm-about 4500μm。
Preferably, in fast fluidized bed, catalyst material and/or inert material are (as separated particle or as phase With the built-up section of particle) average diameter that can have is about 100 μm-about 4000 μm, more preferably from about 100 μm-about 700 μm, more Preferably from about 100 μm-about 600 μm, more preferably from about 100 μm-about 500 μm.Preferably, in emulating fluid bed, catalyst material and/ Or the average diameter that can have (as separated particle or as the built-up section of identical particle) of inert material be about 1000 μm- About 10000 μm, more preferably from about 2000 μm-about 8000 μm, more preferably from about 3000 μm-about 6000 μm, more preferably from about 3500 μm-about 4500μm。
In various aspects, for fixed-bed operation, catalyst material and/or inert material are (as separated particle or work For the built-up section of identical particle) average diameter that can have is >=about 0.1mm, >=about 0.5mm, >=about 1mm, >=about 2mm, >= About 3mm, >=about 4mm, >=about 5mm, >=about 6mm, >=about 7mm, >=about 8mm, >=about 9mm, >=about 10mm, >=about 12mm, >=about 14mm, >=about 16mm, >=about 18mm, >=about 20mm, >=about 22mm, >=about 24mm, >=about 26mm, >=about 28mm, >=about 30mm, >=about 35mm, >=about 40mm, >=about 45mm, or >=about 50mm.Additionally or in the alternative, catalyst material and/or inert material (are made For separated particle or as the built-up section of identical particle) average diameter that can have is≤about 0.1mm ,≤about 0.5mm ,≤ About 1mm ,≤about 2mm ,≤about 3mm ,≤about 4mm ,≤about 5mm ,≤about 6mm ,≤about 7mm ,≤about 8mm ,≤about 9mm ,≤about 10mm ,≤about 12mm ,≤about 14mm ,≤about 16mm ,≤about 18mm ,≤about 20mm ,≤about 22mm ,≤about 24mm ,≤about 26mm, ≤ about 28mm ,≤about 30mm ,≤about 35mm ,≤about 40mm ,≤about 45mm, or≤about 50mm.The range clearly disclosed includes Any of above combination for listing value, for example, about 0.1mm- about 50mm, about 1mm- about 35mm, about 2mm- about 30mm, about 3mm- is about 40mm etc..Preferably, catalyst material and/or inert material (as separated particle or as the built-up section of identical particle) The average diameter that can have is about 0.5mm- about 30mm, more preferably from about 1mm- about 20mm, more preferably from about 2mm- about 10mm, more preferably About 3mm- about 8mm.
Preferably, which provides the sensible heat for improving the first effluent and/or will at least part Acyclic C5Hydrocarbon is converted into the heat of at least part needed for the first effluent comprising cyclopentadiene, especially for circulating fixed bed And/or for fluid bed.For example, second bulk material can provide >=about 30%, >=about 35%, >=about 40% >=about 45%, >=about 50%, >=about 55%, >=about 60%, >=about 65%, >=about 70%, >=about 75%, >=about 80%, >=about 85%, >=about 90%, the heat of >=about 95% or 100% needs.The range clearly disclosed includes any of above combination for listing value； For example, about 30%- about 100%, about 40%- about 95%, about 50%- about 90% etc..Preferably, which can provide The heat of the needs of about 30%- about 100%, the heat of the needs of more preferably from about 50%- about 100%, more preferably from about 70%- The heat of about 100% needs.
E. effluent
The effluent (for example, first effluent) for leaving adiabatic reaction area may include in the adiabatic reaction area by C5Hydrocarbon (for example, acyclic C5Hydrocarbon) reaction generate a variety of compositions of hydrocarbons.The compositions of hydrocarbons typically mixture with hydrocarbon compound, should Hydrocarbon compound has 1-30 carbon atom (C1-C30Hydrocarbon), 1-24 carbon atom (C1-C24Hydrocarbon), 1-18 carbon atom (C1-C18 Hydrocarbon), 1-10 carbon atom (C1-C10Hydrocarbon), 1-8 carbon atom (C1-C8Hydrocarbon) and 1-6 carbon atom (C1-C6Hydrocarbon).Specifically, Effluent (for example, first effluent) includes cyclopentadiene intermediate (for example, amylene, pentadiene, pentamethylene and/or ring penta Alkene).It is >=about 3.0wt% that cyclopentadiene intermediate, which may be present in the amount in the hydrocarbon part of effluent (for example, first effluent), >=about 5.0wt%, >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, or >=about 40.0wt%.Additionally or in the alternative, cyclopentadiene intermediate may be present in effluent (for example, One effluent) hydrocarbon part in amount be≤about 5.0wt% ,≤about 10.0wt% ,≤about 15.0wt% ,≤about 20.0wt%, ≤ about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt%, or≤about 45.0wt%.Clearly disclose Range include any of above combination for listing value, for example, about 5.0wt%- about 40.0wt%, about 10.0wt%- is about 35.0wt%, about 15.0wt%- about 30.0wt%, about 5.0wt%- about 25.0wt% etc..Optionally, which can wrap Containing cyclopentadiene.
The effluent (for example, second effluent) for leaving heat transfer reaction zone may include in adiabatic reaction area and/or conduct heat anti- Answer C in area5Hydrocarbon is (for example, acyclic C5Hydrocarbon) reaction generate a variety of compositions of hydrocarbons.Compositions of hydrocarbons typically has hydrocarbon compound Mixture, the hydrocarbon compound have 1-30 carbon atom (C1-C30Hydrocarbon), 1-24 carbon atom (C1-C24Hydrocarbon), 1-18 carbon is former Son (C1-C18Hydrocarbon), 1-10 carbon atom (C1-C10Hydrocarbon), 1-8 carbon atom (C1-C8Hydrocarbon) and 1-6 carbon atom (C1-C6Hydrocarbon). Specifically, effluent (for example, second effluent) includes cyclopentadiene.It may be present in effluent (for example, second effluent) Hydrocarbon part in cyclopentadiene amount be >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, >=about 40.0wt%, >=about 45.0wt%, >=about 50.0wt%, >=about 55.0wt%, >=about 60.0wt%, >= About 65.0wt%, >=about 70.0wt%, >=about 75.0wt%, or >=about 80.0wt%.Additionally or in the alternative, it may be present in outflow The amount of cyclopentadiene in the hydrocarbon part of object (for example, second effluent) be≤about 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤about 45.0wt% ,≤about 50.0wt% ,≤about 55.0wt% ,≤ About 60.0wt% ,≤about 65.0wt% ,≤about 70.0wt% ,≤about 75.0wt% ,≤about 80.0wt%, or≤about 85.0wt%.The range clearly disclosed includes any of above combination for listing value, for example, about 20.0wt%- about 85.0wt%, About 30.0wt%- about 75.0wt%, about 40.0wt%- about 85.0wt%, about 50.0wt%- about 85.0wt% etc..Preferably, may be used The amount for the cyclopentadiene being present in the hydrocarbon part of second effluent is about 10.0wt%- about 85.0wt%, more preferably from about 25.0wt%- about 80.0wt%, more preferably from about 40.0wt%- about 75.0wt%.
In other aspects, effluent (for example, second effluent) may include other than cyclopentadiene it is one or more its Its C5Hydrocarbon.Other C5The example of hydrocarbon includes, but are not limited to：Pentamethylene and cyclopentene.Effluent be may be present in (for example, the second outflow Object) hydrocarbon part in one or more other C5The amount of hydrocarbon be >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, >=about 40.0wt%, >=about 45.0wt%, >= About 50.0wt%, >=about 55.0wt%, >=about 60.0wt%, >=about 65.0wt%, or >=about 70.0wt%.Additionally or alternatively Ground may be present in one or more other C in the hydrocarbon part of effluent (for example, second effluent)5The amount of hydrocarbon be≤about 15.0wt% ,≤about 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤ About 45.0wt% ,≤about 50.0wt% ,≤about 55.0wt% ,≤about 60.0wt% ,≤about 65.0wt%, or≤about 70.0wt%.The range clearly disclosed includes any of above combination for listing value, for example, about 10.0wt%- about 70.0wt%, About 10.0wt%- about 55.0wt%, about 15.0wt%- about 60.0wt%, about 25.0wt%- about 65.0wt% etc..Preferably, may be used The one or more other C being present in the hydrocarbon part of second effluent5The amount of hydrocarbon is about 30.0wt%- about 65.0wt%, more Preferably from about 20.0wt%- about 40.0wt%, more preferably from about 10.0wt%- about 25.0wt%.
In other aspects, effluent (for example, first effluent, second effluent) can also include one or more aromatics Matter, for example, having 6-30 carbon atom, specifically 6-18 carbon atom.May be present in effluent (for example, first effluent, Second effluent) hydrocarbon part in the amounts of one or more aromatic substances be about >=about 1.0wt%, >=about 5.0wt%, >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, >= About 40.0wt%, >=about 45.0wt%, >=about 50.0wt%, >=about 55.0wt%, >=about 60.0wt%, or >=about 65.0wt%.Additionally or in the alternative, it may be present in the hydrocarbon part of effluent (for example, first effluent, second effluent) The amount of one or more aromatic substances be≤about 1.0wt% ,≤about 5.0wt% ,≤about 10.0wt% ,≤about 15.0wt% ,≤ About 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤about 45.0wt%, ≤ about 50.0wt% ,≤about 55.0wt% ,≤about 60.0wt%, or≤about 65.0wt%.The range clearly disclosed includes appointing What above-mentioned combination for listing value, for example, about 1.0wt%- about 65.0wt%, about 10.0wt%- about 50.0wt%, about 15.0wt%- about 60.0wt%, about 25.0wt%- about 40.0wt% etc..Preferably, it may be present in the hydrocarbon part of first effluent In one or more aromatic substances amount be approximately less than 5wt%, preferably smaller than 2wt%, more preferably less than 1wt%.Preferably, The amount for the one or more aromatic substances that may be present in the hydrocarbon part of second effluent is about 1.0wt%- about 15.0wt%, more Preferably from about 1.0wt%- about 10.0wt%, more preferably from about 1.0wt%- about 5.0wt%.The information of the case where for effluent, is asked Referring to following application：
1) 62/250 USSN, on November 4th, 678,2015；
2) 62/250 USSN, on November 4th, 692,2015；
3) 62/250 USSN, on November 4th, 702,2015；With
4) 62/250 USSN, on November 4th, 708,2015；They are all incorporated by reference the application.
F. extraction/separation of effluent
In various aspects, bulk material (for example, the first bulk material, second bulk material) can be in effluent (for example, One effluent, second effluent) be advanced through and/or leave adiabatic reaction area and/or heat transfer reaction zone when by hydrocarbon (for example, ring Pentadiene and/or cyclopentadiene intermediate) it is entrained in effluent.Therefore, the method can further comprise that separation can be with hydrocarbon (for example, cyclopentadiene and/or cyclopentadiene intermediate) is entrained in effluent (for example, first effluent, second effluent) Bulk material.It is any suitable that such separation may include passing through from hydrocarbon (for example, cyclopentadiene and/or cyclopentadiene intermediate) Means remove the bulk material (for example, the first bulk material, second bulk material), the means are for example, but be not limited to revolve Wind separator, filter, electrostatic precipitator, heavy liquid make contact and/or other gas-solid separation equipments, can be at least One reaction zone is internally and/or externally.Then product recovery can be advanced to by being free of the effluent of bulk material.In addition, Then the bulk material that removes can be used known method for declining heat and/or heat transfer reaction zone, for example, the thermal insulation and/or The substantially top section of heat transfer reaction zone.
In various aspects, hydrocarbon (for example, cyclopentadiene and/or cyclopentadiene intermediate) can be advanced through in bulk material And/or it is carried secretly by bulk material when leaving at least one reaction zone.Hydrocarbon can be adsorbed onto it is on the particle and/or interior, and Gap between grain.Therefore, the method can further comprise that hydrocarbon is extracted and/or detached from the bulk material in effluent.This The extraction and/or separation of sample may include from bulk material by any suitable means remove hydrocarbon (for example, cyclopentadiene and/or Acyclic C5), the means are for example, but be not limited to gas such as H2Or methane extracts and/or other gas-solid separation equipments, It can at least one reaction zone internally and/or externally.Then, the bulk material of hydrocarbon amount reduction can advance to reheating Area, more new district and/or renewing zone, and the hydrocarbon extracted from bulk material can be guided to product recovery or to reactor system System.
G. it updates and reheats
As reaction is in the adiabatic reaction area and/or the reaction zone that conducts heat, coke material may be formed at bulk material (example Such as, the first bulk material, the second bulk material) on, especially on catalyst material, this may be decreased the work of catalyst material Property.Additionally or in the alternative, bulk material (for example, the first bulk material, second bulk material) can be cooled down with reaction.
I. more new district
In various aspects, bulk material can be advanced through and leave reaction zone (for example, adiabatic reaction area, the reaction of heat transfer Area).The catalyst material for leaving reaction zone (for example, adiabatic reaction area, reaction zone of heat transfer) is referred to as " the catalyst material used up Material ".Such catalyst material used up can must be the homogeneous mixture of particle, because individually particle can have in system In total age distribution, the time and/or time in the reaction region after being regenerated from last time are relative to the time in the more new district Ratio.
Therefore, at least part first bulk material (for example, the catalyst material used up) can be by from adiabatic reaction area It is transported to more new district and/or second bulk material (for example, the catalyst material used up) can be by anti-from heat transfer at least partially Area is answered to be transported to more new district.Preferably, in more new district, the catalyst material used up be updated (that is, from the catalyst used up Material removes the coke material gradually deposited) and only carry out subsidiary catalyst material heating.Optionally, in more new district, The catalyst material used up can be updated and reheating.Preferably, when heat transfer reaction zone be fluidized-bed reactor, it is ciculation fluidized Bed reactor, or cycle sedimentation bed reactor when, which is transported to more new district, can be updated there and It reheats.
First and/or second bulk material can be extracted and/or detached after leaving adiabatic and/or heat transfer reaction zone After hydrocarbon, which is transported to more new district.More new district Ke Bao One or more heating equipments are included, are such as but not limited to, are in direct contact, heating coil and/or combustion pipe.Additionally or alternatively More than one more new district (for example, 2 new districts Ge Geng, 3 new districts Ge Geng, 4 new districts Ge Geng etc.) may be present in ground.
In various aspects, in more new district, this first and/or second bulk material (for example, the catalyst material used up Material) it can be contacted with hydrogen stream to remove the coke material that at least part gradually deposits on the catalyst material to be formed more New catalyst material and volatile hydrocarbon, for example, but being not limited to methane.As used in this article, term " gradually depositing " is burnt Carbon Materials refer to, in each catalyst material by being deposited on the catalyst material during adiabatic and/or heat transfer reaction zone The amount of coke material, rather than multipass it is adiabatic and/or heat transfer reaction zone during be deposited on the catalyst material The cumulant of coke material.Preferably, the work of catalyst material can be destroyed and/or be reduced to hydrogen stream substantially free of oxygen, oxygen Property.Then newer catalyst material may return at least one adiabatic reaction area and/or at least one heat transfer reaction zone.
More new district (that is, temperature that bulk material is exposed to) can be operated in following temperature：>=about 400 DEG C, >=about 450 DEG C, >=about 500 DEG C, >=about 550 DEG C, >=about 600 DEG C, >=650 DEG C, >=about 700 DEG C, >=750 DEG C, or >=about 800 DEG C.In addition or it is standby Selection of land, more new district can be operated in following temperature：≤ about 400 DEG C ,≤about 450 DEG C ,≤about 500 DEG C ,≤about 550 DEG C ,≤about 600 DEG C ,≤650 DEG C ,≤about 700 DEG C ,≤750 DEG C ,≤about 800 DEG C, or≤850 DEG C.The temperature range clearly disclosed includes any The combination of above-mentioned value, for example, about 400 DEG C-about 600 DEG C, about 450 DEG C-about 850 DEG C, about 500 DEG C-about 800 DEG C etc..Preferably, more New district can be operated in following temperature：About 400 DEG C-about 800 DEG C, more preferably from about 600 DEG C-about 750 DEG C, more preferably from about 550 DEG C-about 800 DEG C, more preferably from about 550 DEG C-about 700 DEG C.
Additionally or in the alternative, more new district can be operated in following pressures：>=about 1.0psia, >=about 5.0psia, >=about 25.0psia, >=about 50.0psia, >=about 75.0psia, >=about 100.0psia, >=about 125.0psia, >=about 150.0psia, >=about 175.0, psia >=about 200.0psia, >=about 225.0psia, >=about 250.0psia, >=about 275.0psia, or >=about 300.0psia.Additionally or in the alternative, more new district can be operated in following pressures：≤ about 1.0psia ,≤about 5.0psia ,≤about 25.0psia ,≤about 50.0psia ,≤about 75.0psia ,≤about 100.0psia ,≤about 125.0psia ,≤about 150.0psia, ≤ about 175.0, psia≤about 200.0psia ,≤about 225.0psia ,≤about 250.0psia ,≤about 275.0psia, or≤about 300.0psia.The pressure limit clearly disclosed includes any of above combination for listing value, for example, about 1.0psia- is about 300.0psia, about 5.0psia- about 275.0psia, about 25.0psia- about 250.0psia etc..Especially, more new district can with Lower pressure operation：About 1psia- about 300psia, more preferably from about 5psia- about 250psia, more preferably from about 25psia- is about 250psia。
Preferably, in more new district, amount that the coke material that gradually deposits is removed from the catalyst material is >=about 1.0wt%, >=about 5.0wt%, >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >=about 30.0wt%, >=about 35.0wt%, >=about 40.0wt%, >=about 45.0wt%, >=about 50.0wt%, >=about 55.0wt%, >= About 60.0wt%, >=about 65.0wt%, >=about 70.0wt%, >=about 75.0wt%, >=about 80.0wt%, >=about 85.0wt%, >=about 90.0wt%, >=about 95.0wt%, or about 100.0wt%.Preferably, at least about 10wt%, at least about 20wt%, at least About 50wt%, at least about 70wt%, or the coke material gradually deposited of at least about 90wt% are gone from the catalyst material It removes.Additionally or in the alternative, the amount that the coke material gradually deposited is removed from the catalyst material is≤about 1.0wt% ,≤about 5.0wt% ,≤about 10.0wt% ,≤about 15.0wt% ,≤about 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤about 45.0wt% ,≤about 50.0wt% ,≤about 55.0wt% ,≤about 60.0wt% ,≤ About 65.0wt% ,≤about 70.0wt% ,≤about 75.0wt% ,≤about 80.0wt% ,≤about 85.0wt% ,≤about 90.0wt%, ≤ about 95.0wt%, or about 100.0wt%.The range clearly disclosed includes any of above combination for listing value, for example, about 1.0wt%- about 100.0wt%, about 5.0wt%- about 95.0wt%, about 10.0wt%- about 90.0wt%, about 30.0wt%- is about 90.0wt% etc..Preferably, the coke material gradually deposited by the amount removed from the catalyst material be about 1.0wt%- about 100.0wt%, more preferably from about 10.0wt%- about 100.0wt%, more preferably from about 60.0wt%- about 100.0wt%, more preferably from about 90.0wt%- about 100.0wt%.
In various aspects, the temperature of newer catalyst material can be >=about 400 DEG C, >=about 450 DEG C, >=about 500 DEG C, >= About 550 DEG C, >=about 600 DEG C, >=650 DEG C, >=about 700 DEG C, >=750 DEG C, or >=about 800 DEG C.Additionally or in the alternative, newer to urge The temperature of agent material can be≤about 400 DEG C ,≤about 450 DEG C ,≤about 500 DEG C ,≤about 550 DEG C ,≤about 600 DEG C ,≤650 DEG C, ≤ about 700 DEG C ,≤750 DEG C ,≤about 800 DEG C, or≤about 850 DEG C.The temperature range clearly disclosed includes any of above value Combination, for example, about 400 DEG C-about 800 DEG C, about 450 DEG C-about 850 DEG C, about 500 DEG C-about 800 DEG C etc..Preferably, newer catalysis The temperature of agent material can be about 400 DEG C-about 700 DEG C, more preferably from about 500 DEG C-about 750 DEG C, more preferably from about 550 DEG C-about 700 DEG C.
In one embodiment, more new district may include the multiple liquid bed pipelines being placed in combustion chamber (or stove).Combustion It burns room and may include radiant section, shield device and convection section.It may include H2, CO, light hydrocarbon (C1-C4), liquid hydrocarbon (C5-C25) and/or again Matter liquid hydrocarbon (C25+) and the fuel of air can be introduced into one or more burners and igniting.Then, it is generated in the combustion chamber Radiant heat can be transmitted to duct wall, to provide needed for heat cycles bulk material (for example, the catalyst material used up) Heat.Convection section can be used for gas preheating and/or manufacture steam.It combustion chamber can be by top or bottom priming.Flue gas can with The direction of bulk material (for example, the catalyst material used up) recycles in multiple liquid bed pipelines flow direction fair current or adverse current Flowing.In addition, hydrogen can be used for being promoted and fluidize bulk material in multiple liquid bed pipelines (for example, the catalyst material used up Material) cycle.Hydrogen can flow in the direction of flow direction fair current or adverse current with bulk material (for example, the catalyst material used up) It is dynamic.
In another embodiment, more new district may include being placed in multiple liquid bed pipelines in shell, should in the shell Pipeline can be with the contacts combustion gases of heat so that the pipeline can be to come from stove, gas whirlpool by hot gas Convective Heating, hot gas Turbine, or it is catalyzed the combustion product of burning.The film temperature that bulk material is exposed to can be reduced using Convective Heating, to reduce Catalyst breakage caused by due to excessively heating it is potentially possible.Heat burning gases can with it is granular in multiple liquid bed pipelines The flow direction fair current of material (for example, the catalyst material used up) cycle or the direction flowing of adverse current.In addition, hydrogen can be used for Promote and fluidize bulk material (for example, the catalyst material used up) cycle in multiple liquid bed pipelines.Hydrogen can with grain The flow direction fair current of shape material (for example, the catalyst material used up) or the direction flowing of adverse current.
In another embodiment, more new district may include the liquid bed equipped with multiple combustion pipes or coil.Each coil Or combustion pipe available fuel and air are separately or cooperatively lighted a fire to provide the radiant heat that can be passed to liquid bed by wall.Cause This, bulk material (for example, the catalyst material used up) in liquid bed cycle can due to the liquid bed heat transfer performance and It is reheated.In liquid bed bulk material (for example, the catalyst material used up) cycle can in the combustion pipe The flow direction fair current of gas or the direction flowing of adverse current.In addition, the flue gas in each combustion pipe can leave reheating Area is simultaneously connected to the common heater for being oriented to convection cell, can be used for heating charging, and preheating is (for example, preheating hydrogen in reheating area Stream) and manufacture steam.Burning gases of the coil containing heat so that pipeline is come by hot gas Convective Heating, the hot gas From stove, the combustion product of gas turbine, or catalysis burning；Alternatively, coil can contain in other places such as in stove The heat transmission medium (for example, metal or salt of melting or evaporation) heated in son.
Pattern in more new district can be：
1. the pattern of bubbling, wherein empty tower gas velocity are more than minimum bubbling velocity, but less than minimum slug speed；
2. slug pattern, wherein empty tower gas velocity are more than minimum slug speed, but less than the condition of slug starting (for example, Stewart conditions) in pipe diameter and length under be transitioned into turbulent fluidised speed, (be such as described in Kunii, D., Levenspiel,O.,Chapter 3 of Fluidization Engineering,2nd Edition,Butterworth- Heinemann, Boston, 1991 and Walas, 6 of Chemical Process Equipment of S.M., Chapter, Revised 2ndEdition,Butterworth-Heinemann,Boston,2010))；
3. being transitioned into turbulent fluidised pattern, wherein empty tower gas velocity, which is more than, is transitioned into turbulent fluidised speed, but less than quickly stream Change speed；Or
4. fast fluidized regime, wherein empty tower gas velocity are more than fast fluidization speed.
Preferably, more new district 1 or 2 operation in mode, this can minimize the use of the hydrogen in liquid bed, maximize catalyst The material residence time is to carry out coke removal and/or improve heat transfer performance.
In another embodiment, in more new district, bulk material (for example, the catalyst material used up) can be in direct contact Hot gas stream is reheated, and the hot gas stream is in another equipment, for example is heated in stove and can be effectively used for coke Charcoal removes (that is, H2) or it will not at least lead to other coke laydown (for example, methane), this is with liquid bed pipeline interior heating or logical It crosses combustion pipe or coil heats is different.
Additionally or in the alternative, update catalyst material can be inside or outside more new district in one or more separating steps By any suitable means, for example, but being not limited to cyclone separator and being detached with hydrogen and/or volatile hydrocarbon.
Additionally or in the alternative, fresh bulk material can be provided directly at least one adiabatic reaction area, this at least one A heat transfer reaction zone and/or enter at least one adiabatic region and/or the new districts at least one heat transfer reaction zone Qian Zhigaigeng.
Ii. interval is reheated
In various aspects, when bulk material is not advanced through reaction zone (for example, adiabatic reaction area, conduct heat reaction zone), Bulk material can be retained in the reaction zone.Especially, the second granular heat transfer reaction zone that is retained in is (for example, cyclic annular fixed Bed reactor) and this second granular cool down, that is, reduction temperature.
Preferably, the first effluent contacts second bulk material until in the heat transfer reaction zone in the reaction zone that conducts heat In temperature be≤about 300 DEG C ,≤about 325 DEG C ,≤about 350 DEG C ,≤about 375 DEG C ,≤about 400 DEG C ,≤about 425 DEG C ,≤about 450 DEG C ,≤about 475 DEG C ,≤about 500 DEG C ,≤about 525 DEG C ,≤about 550 DEG C ,≤about 575 DEG C ,≤about 600 DEG C ,≤about 650 DEG C or≤ About 675 DEG C.The range clearly disclosed includes any of above combination for listing value, for example, about 300 DEG C-about 675 DEG C, about 400 DEG C-about 600 DEG C, about 425 DEG C-about 575 DEG C etc..Preferably, it can be reacted until the temperature in the heat transfer reaction zone is down to Below about 400 DEG C, it is below about 450 DEG C, is below about 475 DEG C, be below about 500 DEG C, be below about 550 DEG C, is below about 575 DEG C or low In about 600 DEG C.
Additionally or in the alternative, the duration that the first effluent contacts second bulk material in the reaction zone that conducts heat is >=about 1 minute, >=about 2 minutes, >=about 3 minutes, >=about 4 minutes, >=about 5 minutes, >=about 6 minutes, >=about 7 minutes, >=about 8 points Clock, >=about 9 minutes, >=about 10 minutes, >=about 15 minutes, >=about 20 minutes, >=about 25 minutes, >=about 30 minutes, >=about 35 points Clock, >=about 40 minutes, >=about 45 minutes, >=about 50 minutes, >=about 55 minutes, >=about 60 minutes, >=about 65 minutes, >=about 70 points Clock, >=about 75 minutes, >=about 80 minutes, >=about 85 minutes, >=about 90 minutes, >=about 95 minutes, >=about 100 minutes, >=about 110 Minute or >=about 120 minutes.Additionally or in the alternative, the duration that reacting space can have be≤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 Minute ,≤about 15 minutes ,≤about 20 minutes ,≤about 25 minutes ,≤about 30 minutes ,≤about 35 minutes ,≤about 40 minutes ,≤about 45 Minute ,≤about 50 minutes ,≤about 55 minutes ,≤about 60 minutes ,≤about 65 minutes ,≤about 70 minutes ,≤about 75 minutes ,≤about 80 Minute ,≤about 85 minutes ,≤about 90 minutes ,≤about 95 minutes ,≤about 100 minutes ,≤about 110 minutes, or≤about 120 minutes. The range clearly disclosed, including any of above combination for listing value, for example, about 1- about 120 minutes, about 1- about 90 minutes, about 4- about 80 minutes, about 10- about 75 minutes etc..Preferably, the first effluent contacts the second granular material in the reaction zone that conducts heat The duration of material is about 1- about 120 minutes, more preferably from about 1- about 90 minutes, more preferably from about 1- about 60 minutes, more preferably from about 1- About 40 minutes, more preferably from about 1- about 15 minutes, more preferably from about 1- about 10 minutes, more preferably from about 2- about 8 minutes.Especially, it is passing The first effluent contacts second bulk material in thermal reaction area：(i) it is brought down below until in the temperature of the heat transfer reaction zone About 550 DEG C and/or about 1 minute-about 90 minutes (ii) duration.
Therefore, the method can further comprise reheating interval, wherein at least one heat transfer reaction zone (for example, ring Shape fixed bed reactors) first effluent can be stopped periodically, and reheat gas to may be provided to this at least one Reaction zone conduct heat to reheat the second bulk material.Reheating gas may include inert substance (for example, N2, CO etc.) and/or first Alkane.In various aspects, reheats gas and may include inert substance and heat transfer reaction zone can be conducted to (for example, cyclic annular fixed bed is anti- Answer device) to reheat the second bulk material.After the suitable duration, heat transfer reaction can be left via outlet by reheating gas Area.
In various aspects, reheating gas can flow on the direction of flow direction fair current or adverse current with first effluent It is dynamic.For example, if first effluent enters in the top section of heat transfer reaction zone during reacting space, interval is being reheated Between, reheating gas can also enter in the heat transfer reaction zone in top section, in the flow direction with first effluent The side of fair current flows up.Additionally or in the alternative, if the first effluent enters in the top section of heat transfer reaction zone, again During heat-up periods, reheating gas can enter in the bottom part of heat transfer reaction zone, in the flowing with first effluent The side of direction adverse current flows up.Preferably, it when the reaction zone that conducts heat is fixed cycles bed, reheats gas and is flowed out with first The side of the flow direction adverse current of object flows up and/or can realize reversed Temperature Distribution in the heat transfer reaction zone.
Preferably, it is >=about 1 minute to reheat the duration that can have of interval, >=about 5 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.In addition or it is standby Selection of land, it is≤about 1 minute to reheat the duration that can have of interval ,≤about 5 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.The range packet clearly disclosed Any of above combination for listing value is included, for example, about 1- about 120 minutes, about 1- about 90 minutes, about 4- about 80 minutes, about 10- about 75 Minute etc..Preferably, the duration that reacting space can have is about 1- about 120 minutes, and more preferably from about 1- about 90 minutes is more excellent Select about 1- about 60 minutes, more preferably from about 5- about 40 minutes.Preferably, the duration for reheating interval is less than holding for reacting space The continuous time；It is highly preferred that the duration for reheating interval is less than the half of the duration of reacting space.
Iii. update interval
In addition, coke material may be formed on bulk material (for example, the first bulk material, second bulk material), there is it It is on catalyst material, this can reduce the activity of catalyst material.It is such that there is coke shape at the end of reacting space It is referred to as " catalyst material used up " at and/or with the catalyst material of temperature of reduction.
Therefore, the method can further comprise update interval, wherein the charging at least one adiabatic reaction area can quilt Stop periodically and/or at least one heat transfer reaction zone (for example, cyclic annular fixed bed, combustion pipe reactor, Convective Heating pipe Reactor) first effluent can be stopped periodically, and update gas and may be provided at least one adiabatic reaction area And/or at least one heat transfer reaction zone is to update bulk material (for example, the first bulk material, second bulk material).Update Gas may include hydrogen, and the update gas can contact first and/or second bulk material (for example, the catalyst material used up Material) to remove the coke material that at least part gradually deposits on the catalyst material, to form newer catalyst material Material and volatile hydrocarbon, for example, but being not limited to methane.Preferably, including the update gas of hydrogen is substantially free of oxygen, oxygen can destroy And/or reduce the activity of catalyst material.After the suitable duration, updating gas and optional volatile hydrocarbon can be via going out Mouth leaves adiabatic reaction area and/or heat transfer reaction zone.
Especially, it can be stopped periodically to the charging at least one adiabatic reaction area and/or be conducted heat instead at least one It answers the first effluent in area that can be stopped periodically, and includes that may be provided to this at least one adiabatic anti-for the update gas of hydrogen Answer area and/or at least one heat transfer reaction zone.Including the update gas of hydrogen can contact bulk material (for example, the first granular material Material, the second bulk material) to remove the coke material that at least part gradually deposits on the catalyst material to be formed more New catalyst material and volatile hydrocarbon.
In various aspects, update gas can with the charging and/or the first effluent flow direction fair current or adverse current Direction flowing.For example, if top section of the charging in adiabatic reaction area enters during reacting space, it is spaced in update Period, update gas can also enter in the top section in adiabatic reaction area, in the side of the flow direction fair current with the charging To flowing.Additionally or in the alternative, if top section of the charging in adiabatic reaction area enters, between regeneration interval, update Gas can enter in the bottom part in adiabatic reaction area, to be flowed in the direction of the flow direction adverse current with the charging.It is preferred that Ground, when the reaction zone that conducts heat is circulating fixed bed, update gas flows in the direction of the flow direction adverse current with the first effluent It is dynamic.Preferably, when conduct heat pipeline reactor that reaction zone is combustion pipe reactor or Convective Heating when, update gas with this The flowing of the direction of charging and/or the flow direction fair current of the first effluent.Preferably, in the heat transfer reaction zone, this can be realized instead To Temperature Distribution.
Preferably, between regeneration interval, amount that the coke material that gradually deposits is removed from the catalyst material is >= About 1.0wt%, >=about 5.0wt%, >=about 10.0wt%, >=about 15.0wt%, >=about 20.0wt%, >=about 25.0wt%, >= About 30.0wt%, >=about 35.0wt%, >=about 40.0wt%, >=about 45.0wt%, >=about 50.0wt%, >=about 55.0wt%, >=about 60.0wt%, >=about 65.0wt%, >=about 70.0wt%, >=about 75.0wt%, >=about 80.0wt%, >=about 85.0wt%, >=about 90.0wt%, >=about 95.0wt%, >=about 99.0wt%, or about 100.0wt%.Preferably, at least about The coke material gradually deposited of 10.0wt% is removed from the catalyst material, and more preferably at least about 90.0wt% is more excellent Select at least about 95.0wt%, more preferably at least about 99.0wt%.Additionally or in the alternative, the coke material gradually deposited is urged from this Agent material removal amount be≤about 1.0wt% ,≤about 5.0wt% ,≤about 10.0wt% ,≤about 15.0wt% ,≤about 20.0wt% ,≤about 25.0wt% ,≤about 30.0wt% ,≤about 35.0wt% ,≤about 40.0wt% ,≤about 45.0wt% ,≤ About 50.0wt% ,≤about 55.0wt% ,≤about 60.0wt% ,≤about 65.0wt% ,≤about 70.0wt% ,≤about 75.0wt%, ≤ about 80.0wt% ,≤about 85.0wt% ,≤about 90.0wt% ,≤about 95.0wt% ,≤about 99.0wt%, or about 100.0wt%.The range clearly disclosed includes any of above combination for listing value, for example, about 1.0wt%- is about 100.0wt%, about 5.0wt%- about 95.0wt%, about 10.0wt%- about 90.0wt%, about 30.0wt%- about 90.0wt% etc.. Preferably, the coke material gradually deposited is about 1.0wt%- about 100.0wt% by the amount removed from the catalyst material, more excellent About 10.0wt%- about 100.0wt%, more preferably from about 90.0wt%- about 100.0wt% are selected, more preferably from about 95.0wt%- is about 100.0wt%.
The duration that update interval can have is≤90 minutes ,≤60 minutes ,≤30 minutes ,≤10 minutes ,≤5 points Clock ,≤1 minute, or≤10 seconds.After the method for transformation as defined in beginning, update can be advantageously progress >=10 minutes, for example, >= 30 minutes, >=2 hours, >=5 hours, >=24 hours, >=2 days, >=5 days, >=20 days.
At >=about 400 DEG C, >=about 450 DEG C, >=about 500 DEG C, >=about 550 DEG C, >=about 600 DEG C, >=650 DEG C, >=about 700 DEG C, >=750 DEG C, >=about 800 DEG C, >=850 DEG C, or >=about 900 DEG C temperature reheat gas can enter heat transfer reaction zone and/or Adiabatic reaction area and/or heat transfer reaction zone can be entered by updating gas.Additionally or in the alternative, interval and/or update interval are reheated It can be operated under aforementioned temperature.Preferably, heat transfer reaction zone and/or more can be entered by reheating gas in >=about 600 DEG C of temperature New gas can enter adiabatic reaction area and/or heat transfer reaction zone.Additionally or in the alternative, at≤about 400 DEG C ,≤about 450 DEG C ,≤about 500 DEG C ,≤about 550 DEG C ,≤about 600 DEG C ,≤650 DEG C ,≤about 700 DEG C ,≤750 DEG C ,≤about 800 DEG C ,≤850 DEG C, or≤about 900 DEG C of temperature, which reheats gas, can enter adiabatic reaction area and/or heat transfer instead into heat transfer reaction zone and/or update gas Answer area.The temperature range clearly disclosed includes the combination of any of above value, for example, about 400 DEG C-about 900 DEG C, about 450 DEG C-about 850 DEG C, about 500 DEG C-about 800 DEG C etc..Preferably, at about 400 DEG C-about 800 DEG C, more preferably from about 600 DEG C-about 800 DEG C, more preferably About 625 DEG C-about 700 DEG C, more preferably from about 550 DEG C-about 750 DEG C of temperature, which reheats gas, can enter heat transfer reaction zone and/or more New gas can enter adiabatic reaction area and/or heat transfer reaction zone.
Additionally or in the alternative, in >=about 1.0psia, >=about 5.0psia, >=about 25.0psia, >=about 50.0psia, >=about 75.0psia, >=about 100.0psia, >=about 125.0psia, >=about 150.0psia, >=about 175.0, psia, >=about 200.0psia, >=about 225.0psia, >=about 250.0psia, >=about 275.0psia, >=about 300.0psia, >=about 325.0psia, or the pressure reheating gas of >=about 350.0psia can enter heat transfer reaction zone and/or update gas and can enter Adiabatic reaction area and/or heat transfer reaction zone.Additionally or in the alternative, reheating interval and/or update interval can grasp in aforementioned pressure Make.Preferably, reheating gas and can entering heat transfer reaction zone and/or update gas in the pressure of >=about 100.0psia can enter Adiabatic reaction area and/or heat transfer reaction zone.Additionally or in the alternative, in≤about 1.0psia ,≤about 5.0psia ,≤about 25.0psia ,≤about 50.0psia ,≤about 75.0psia ,≤about 100.0psia ,≤about 125.0psia ,≤about 150.0psia, ≤ about 175.0, psia ,≤about 200.0psia ,≤about 225.0psia ,≤about 250.0psia ,≤about 275.0psia ,≤about 300.0psia ,≤about 325.0psia, or≤about 350.0psia pressure, reheat gas can enter heat transfer reaction zone and/or Adiabatic reaction area and/or heat transfer reaction zone can be entered by updating gas.The pressure limit clearly disclosed includes any of above lists The combination of value, for example, about 1.0psia- about 350.0psia, about 5.0psia- about 275.0psia, about 25.0psia- is about 250.0psia waiting.Especially, in about 1psia- about 300psia, more preferably from about 5psia- about 250psia, more preferably from about The pressure of 25psia- about 250psia, which reheats gas, can enter adiabatic reaction area into heat transfer reaction zone and/or update gas And/or heat transfer reaction zone.
In various aspects, the reheating and/or update catalyst material of the temperature can be >=about 400 DEG C, >=about 450 DEG C, >=about 500 DEG C, >=about 550 DEG C, >=about 600 DEG C, >=650 DEG C, >=about 700 DEG C, >=750 DEG C, >=about 800 DEG C, >=850 DEG C, Or >=about 900 DEG C.Additionally or in the alternative, the temperature of newer catalyst material can be≤about 400 DEG C ,≤about 450 DEG C ,≤about 500 DEG C ,≤about 550 DEG C ,≤about 600 DEG C ,≤650 DEG C ,≤about 700 DEG C ,≤750 DEG C ,≤about 800 DEG C ,≤850 DEG C, or≤about 900℃.The temperature range clearly disclosed includes the combination of any of above value, for example, about 400 DEG C-about 900 DEG C, about 450 DEG C- About 850 DEG C, about 500 DEG C-about 800 DEG C etc..Preferably, the temperature of newer catalyst material can be about 400 DEG C-about 800 DEG C, more Preferably from about 600 DEG C-about 800 DEG C, more preferably from about 550 DEG C-about 750 DEG C.
In various aspects, gas and/or update gas are reheated by suitable device (for example, updating device), for example, But it is not limited to, burning heater provides.For example, in the apparatus, suitable temperature as described above can be heated to by reheating gas Degree, then provides the reheating gas to reaction zone.Additionally or in the alternative, the reheating gas for leaving heat transfer reaction zone also may be used The device is returned to be reheated suitable temperature as described above, is provided to heat transfer reaction zone.The device can also be made It makes steam and/or heating charging, the then charging enters adiabatic reaction area.
Additionally or in the alternative, update catalyst material can be inside or outside the new districts one or more separating step Zhong Geng By any suitable means, for example, but being not limited to cyclone separator and being detached with gas and/or volatile hydrocarbon is reheated.In addition, Hydrogen can be used for the separating step.
H. it regenerates
The method can further comprise regeneration step to recapture due to the coke material on catalyst material during reaction Catalyst deactivation caused by material accumulation and/or metal are accumulative.When in this more new district from bulk material (for example, using up Catalyst material) removal coke material deficiency when, such regeneration step can be carried out.Advantageously, regeneration step is run substantially Constant removal and addition bulk material is at least one reaction zone, to the continuous operation being maintained under high catalyst activity. For example, catalyst activity can be kept above about 10% fresh catalyst activity at least one reaction zone, preferably above about 30% fresh catalyst activity and most preferably higher than about 60% and the fresh catalyst activity below about 99.9%.
I. renewing zone
In various aspects, in regeneration step, at least part from least one adiabatic reaction area or more new district One bulk material and/or it can be transported to regeneration from least one heat transfer reaction or second bulk material of a part in more new district Area by methods known in the art to generate regeneration catalyzing agent material.The regeneration catalyzing agent material can be recycled at least partially To at least one adiabatic reaction area, at least one heat transfer reaction zone and/or more new district.
Catalyst material can continuously be taken out and be returned from adiabatic reaction area, heat transfer reaction zone and/or more new district, or can It is taken out and is returned from adiabatic reaction area, heat transfer reaction zone and/or more new district periodically.For periodic method, typically, The recovery time carried out between coke burning, purging and the taking-up of reduction is about 24 hours (about 1 day)-about 240 hour (about 10 It), preferably from about 36 hours (about 1.5 days)-about 120 hours (about 5 days).Alternatively, for continuous mode, removal/addition is granular Material ratios can be about the daily bulk material deposits of 0.0wt%- about 100wt% and preferably from about 0.25wt%- about 30.0wt% Daily bulk material deposit, wherein there is addition/removal of the bulk material of balance.The regeneration of catalyst material can be used as company Continuous method is carried out or can be conducted batch-wise, and in both cases, it may be desired to the centre for laying in accumulation and/or deposit discharge Container.
The removal and addition of bulk material (for example, the catalyst used up, fresh bulk material, regeneration catalyzing agent material) can The same or different position in reactor assembly.Bulk material (for example, fresh bulk material, regeneration catalyzing agent material) can Be added before or after more new district, and remove bulk material (for example, the catalyst material used up) can bulk material (for example, The catalyst material used up) by being added before or after more new district.At least part regeneration catalyzing agent material can be circulated to At least one adiabatic reaction area, at least one heat transfer reaction zone or at least one more new district.Preferably, regeneration catalyzing Agent material and/or fresh bulk material are provided to more new district can be by again to minimize any loss in heat input and removal Any residual substance that raw catalyst material is carried from renewing zone.Additionally or in the alternative, the internal or external of renewing zone can be used Separator with by inert material from catalyst material detach, then regeneration so that only catalyst material be reproduced.It is such Separation can use any conjunction based on size, magnetism and/or the density performance difference between inert material and regeneration catalyzing agent material Suitable means carry out.
For the above method, the vertical tube well known to those skilled in the art with above-mentioned particle size and operating condition is available In the means for providing the conveying bulk material between at least one reaction zone, more new district and/or renewing zone.Those skilled in the art Known guiding valve and lift gas can also be used for helping recycling bulk material and/or structure pressure distribution in renewing zone.Promote gas Body can be identical as the fluidizing gas for the more new district, such as can be contributed in the reaction system and minimize hydrogen use, simultaneously also Reduce the hydrogen stream that coke material is formed.
A. regeneration intervals
In various aspects, when bulk material (for example, the first bulk material, second bulk material) is not advanced through thermal insulation instead When answering area and/or heat transfer reaction zone, regeneration intervals can be carried out with obtain the regenerated bulk material (for example, the first bulk material, Second bulk material).
Especially, can be stopped periodically to the charging in adiabatic reaction area and/or to heat transfer reaction zone first effluent It can be stopped periodically.After stopping the charging and/or the first effluent, the purging of any fuel gas can be carried out to being less than Explosion limit.For example, charging and/or reactor product (for example, cyclopentadiene) can be by purgings to less than explosion limit.As herein Middle to use, term " being less than explosion limit " refers to the enough purgings carried out to any fuel gas so that works as gas stream It is dynamic when changing into a kind of lower composition (for example, regeneration gas), the harmful mixture that may lead to explode will not be formed.For example, If fuel gas be present in heat transfer reaction zone in and it is expected introduce oxidant, must first use inert gas purge system with Reduce combustable gas concentration so that introduce the gas containing oxidant and not will produce volatile mixture.
Then regeneration gas can be supplied to adiabatic reaction area and/or heat transfer reaction zone, and bulk material is (for example, the there One bulk material, the second bulk material) at regeneration conditions contact regeneration gas to aoxidize remove on catalyst material extremely The coke material of few a part of deposit buildup, to form regeneration catalyzing agent material.Suitable regeneration gas includes, but are not limited to Oxygen and air.Regeneration gas can as it is above-mentioned to reheat gas in the flowing with the charging and/or the first effluent The direction flowing of direction adverse current or fair current.Regeneration gas can further include inert substance (for example, N2).In the reaction region with again After angry body contact, purging regeneration gas can be carried out to less than explosion limit.Once the purging of regeneration gas is completed, then charging can It is provided to adiabatic reaction area and/or then second effluent may be provided to heat transfer reaction zone.
Preferably, the duration that regeneration intervals can have be >=about 0.5 day, >=about 1 day, >=about 1.5 days, >=about 2 days, >=about 3 days, >=about 4 days, >=about 5 days, >=about 6 days, >=about 7 days, >=about 8 days, >=about 9 days, >=about 10 days, >=about 11 days, >= About 12 days, >=about 13 days, >=about 14 days, or >=about 15 days.As used in this article, term " day " refer to about 24 hours when Between, and term " 0.5 day " refers to about 12 hours time.Additionally or in the alternative, the duration that regeneration intervals can have be≤ About 0.5 day ,≤about 1 day ,≤about 1.5 days ,≤about 2 days ,≤about 3 days ,≤about 4 days ,≤about 5 days ,≤about 6 days ,≤about 7 days ,≤ About 8 days ,≤about 9 days ,≤about 10 days ,≤about 11 days ,≤about 12 days ,≤about 13 days ,≤about 14 days, or≤about 15 days.Clearly The range of disclosure includes any of above combination for listing value, for example, about 0.5- about 15 days, about 1- about 12 days, about 2- about 11 days etc.. Preferably, the duration that regeneration intervals can have is about 1- about 15 days, more preferably from about 1- about 10 days, more preferably from about 1.5- about 5 It.
In various aspects, regeneration intervals can be carry out frequency be it is 1 day about every, it is 2 days about every, it is 4 days about every, it is 6 days about every, about It is every 8 days, 10 days about every, it is 12 days about every, it is 14 days about every, it is 16 days about every, it is 18 days about every, it is 20 days about every, it is 22 days about every, about every 24 It, it is 26 days about every, it is 28 days about every, it is 30 days about every, it is 35 days about every, it is 40 days about every, it is 45 days about every, it is 50 days about every, it is 75 days about every, about It is every 100 days, 125 days about every, it is 150 days about every, it is 170 days about every, 180 days about every or 200 days about every.The range clearly disclosed Including any of above combination for listing value, for example, about 1- about 200 days, about 1- about 180 days, about 2- about 35 days etc..Preferably, then It is every 1-50 days that raw interval, which can be the frequency carried out, more preferably per 10-45 days, more preferably per 20-40 days, more preferably per 30-35 It.Preferably, it is 1-50 days that regeneration intervals, which can be the frequency carried out, more preferable 10-45 days, more preferable 20-40 days, more preferably 30-35 days.
III. acyclic C is converted5Reaction system
In another embodiment, it provides for by C5Hydrocarbon is (for example, acyclic C5Hydrocarbon) it is converted into the reaction system of cyclopentadiene System 1, as shown in fig. 1.Reaction system 1 may include including C as described above5Hydrocarbon is (for example, acyclic C5Hydrocarbon) feed steam 2, packet Intermediate containing cyclopentadiene, unconverted acyclic C5The effluent stream 3 of hydrocarbon and optional cyclopentadiene；With it is at least one as above The adiabatic reactor 4.At least one adiabatic reactor 4 may include the institute as above of the first bulk material containing catalyst material (not shown) is stated, for providing the feed steam 2 to the feed entrance (not shown) of reaction system 1 and for removing the first outflow The effluent of material stream 3 exports (not shown).Heater 5 (such as heat exchanger) may be present to heat the feed steam 2 to temperature T1(for example, about 575 DEG C or higher), as described above, then it enters at least one adiabatic reactor 4.Optionally, H2And/or packet Containing C1、C2、C3And/or C4The lightweight hydrocarbon flow (not shown) of hydrocarbon can be conducted at least one adiabatic reactor 4.
At least one adiabatic reactor 4 can be fixed bed reactors as described above (for example, horizontal or vertical fixed-bed anti- Answer device) or fluidized-bed reactor.Preferably, which may include at least one as described above internal Structure (not shown).
At least one adiabatic reactor 4 can be operated under reaction condition as described above with by least part the C5Hydrocarbon (for example, acyclic C5Hydrocarbon) it is converted into cyclopentadiene intermediate.In addition, the reaction condition may include about 450 DEG C-about 900 DEG C of temperature The pressure of degree and/or about 3psia- about 150psia.Preferably, acyclic C of at least about 20wt%5Hydrocarbon is converted into ring penta 2 Alkene intermediate.
In addition, reaction system can further comprise at least one heat transfer reactor 6 (for example, circulating fluid bed reactor, is followed Ring settles bed reactor, fixed bed reactors, cyclic annular fixed bed reactors, fluidized-bed reactor, burn pipe reactor or convection current Heat pipe reactor).Preferably, which is combustion pipe reactor, it includes stove and is located in The parallel reactor pipeline 7 of the radiant section of the stove, it may include the burner 8 for heating the pipe reactor 7 as described above. At least one heat transfer reactor 6 may include the second bulk material (not shown) for including catalyst material as described above, be used for First effluent stream 3 is provided to the feed entrance (not shown) of at least one heat transfer reactor 6 and for removing second Go out the effluent outlet (not shown) of material stream 9.In addition, at least one heat transfer reactor 6 can be in reaction item as described above It is operated with by the cyclopentadiene intermediate of at least part in the first effluent stream 3 and/or unconverted nothing under part Ring C5Hydrocarbon is converted into the second effluent stream 9 comprising cyclopentadiene.Preferably, which has Substantial reverse as described above or isothermal temperature distribution.First effluent stream 3 can be in temperature T2(for example,≤about 500 DEG C) It is provided at least one heat transfer reactor 6.Heater 10 (for example, heat exchanger) may be present to heat the first effluent material 3 are flowed, then it enters at least one heat transfer reactor 6.Optionally, which may include one or more A heating equipment (for example, combustion pipe, heating coil) (not shown) is to keep temperature therein.
In addition, auxiliary H2(not shown) can be conducted at least one adiabatic reactor 4 and/or at least one heat transfer is anti- Answer device 6.
In addition, reaction system 1 can further comprise at least one cyclone separator (not shown) for detaching this first Shape material and/or this is second granular, they can be entrained in the hydrocarbon in first effluent stream 3 and/or second effluent stream 9 In (for example, cyclopentadiene).Then, another effluent stream (not shown) substantially free of bulk material may continue to product Recovery system.
In another embodiment, reaction system 1 can further comprise that update gas streams 11 are granular for updating first Material, as shown in Figure 2.Updating gas streams 11 can enter via feed entrance or via different entrance (not shown).More New gas streams 11 may include hydrogen and optional inert substance (for example, N2,CO it) is used to remove on the catalyst material used up extremely The coke material that a few part gradually deposits is to form newer catalyst material and volatile hydrocarbon.In addition, newer catalysis Agent material includes the coke material gradually deposited more less than the catalyst material used up as described above, is preferably urged than what is used up Agent material lacks the coke material of at least about 10wt% gradually deposited.After the suitable duration as described above, gas is updated Body and optional volatile hydrocarbon can be exported via effluent or different outlet (not shown) updates gas as first effluent Stream (not shown) leaves at least one adiabatic reactor 4.First effluent update gas streams can directly proceed to conduct heat Reactor 6 can be advanced through heater (not shown) first.Newer catalyst material includes than using up as described above The less coke material gradually deposited of catalyst material, the preferably few at least about 10wt% of the catalyst material than using up are gradually The coke material of deposition.Update gas streams 11 can be flowed up in the side of flow direction fair current or adverse current with feed steam 2.
Additionally or in the alternative, it is granular for updating second can to enter at least one heat transfer reactor 6 for update gas streams 11 Material (not shown).After the suitable duration as described above, updates gas and optional volatile hydrocarbon can be via effluent Outlet or different outlet (not shown) leave at least one heat transfer reactor as second effluent update gas streams 12 6.Newer catalyst material includes the coke material that gradually deposits fewer than the catalyst material used up as described above, preferably The coke material of the few at least about 10wt% of catalyst material than using up gradually deposited.Updating gas streams 11 can be with first The flow direction fair current of effluent stream 3 or the side of adverse current flow up.
In addition, update gas streams 11 can by as described above at least one adiabatic reactor 4 and/or this at least The updating device 13 that one heat transfer reactor 6 fluidly connects provides.First effluent updates gas streams (not shown) and second Effluent update gas streams 12 can be sent to compression device 14, be then sent to separator 15, can be generated there rich in light The gas streams 16 of matter hydrocarbon and the gas streams 17 of depleted light hydrocarbon.Gas streams 16 rich in light hydrocarbon can be used as fuel.It is poor Gas streams 17 containing light hydrocarbon can merge with supplement hydrogen stream 18 and in heater 19 (for example, heat exchanger or other heating are set It is standby) in be heated to production update gas streams 11.Updating device 13 may include one or more heating equipments as described above, The update entrance of gas streams 17 for depleted light hydrocarbon and will update gas streams 11 return at least one adiabatic reaction The update of device 4 and/or at least one heat transfer reactor 6 exports (not shown).Separator 15 can be film system, absorption system (for example, transformation, alternating temperature) or other known for detaching H from light hydrocarbon2System.
Especially, updating device 13 operates under these conditions, and the temperature of preferably updating device 13 is about 550 DEG C-about 800 ℃.In addition, updating device 13 can produce vapor stream 20.In addition, updating device 13 can heat feed steam 2, then charging is expected Stream 2 is entering 4 (not shown) of at least one adiabatic reactor when adiabatic reactor is not updated or regenerates.
In another embodiment, reaction system 1 can further comprise regeneration gas stream 21, as shown in Figure 3.Regeneration Gas streams 21 can enter at least one adiabatic reactor 4 under regeneration condition as described above and/or at least one heat transfer is anti- 6 (not shown) of device is answered, to move coke material that at least part is deposited on the catalyst material again (for example, using up Catalyst material), to form regeneration catalyzing agent material.After the suitable duration as described above, regeneration gas can be from At least one heat transfer reactor 6 is opened as the regeneration gas stream 22 of first circulation and/or leaves at least one thermal insulation instead Answer regeneration gas stream (not shown) of the device 4 as second circulation.The regeneration gas stream of second circulation can enter this at least one A heat transfer reactor 6.Regeneration gas stream 21 can by as described above at least one adiabatic reactor 4 and/or this extremely The regenerating unit 23 that few heat transfer reactor 6 fluidly connects provides.
Additionally or in the alternative, reaction system 1 can further comprise fluidly connecting with 6 (not shown) of at least one reactor Fresh bulk material stream (not shown).
Additionally or in the alternative, at least one adiabatic reactor 4 and/or at least one heat transfer reactor 6 may include more In 1 reactor, for example, at least first reactor, second reactor, third reactor, the 4th reactor, the 5th reactor, 6th reactor, the 7th reactor, the 8th reactor etc..Preferably, reaction system includes 1-20 reactor, more preferable 3-15 A reactor, more preferable 5-10 reactor.Wherein at least one adiabatic reactor 4 and/or at least one heat transfer reaction Device 6 includes first, second, and third reactor etc., reactor can be operated in parallel and as needed bulk material need update with It is updated periodically and regeneration intervals when removing coke material.
Fig. 1,2 and 3 indicate the flowing in particular point in time.It should be appreciated that point flowing may at other times Situation shown in slip chart 1,2 and 3 because reactor may periodically be exposed to oily (on-oil) charging conversion, update and/or Regeneration cycle.
IV. further embodiment
The invention further relates to：
Embodiment 1. is in reactor assembly by acyclic C5The method that hydrocarbon is converted into cyclopentadiene, wherein this method packet It includes：There is provided at least one adiabatic reaction area (for example, fixed bed, fluid bed) includes acyclic C5The charging of hydrocarbon is in temperature T1, wherein At least one adiabatic reaction area includes the first bulk material containing catalyst material (for example, the platinum on ZSM-5, on zeolite L Platinum, the platinum on silicate modified silica, the 6th race, the 9th race or the 10th race's metal on inorganic carrier are described inorganic Carrier such as zeolite, SAPO, ALPO, MeAPO, silica, zirconium oxide, titanium oxide, aluminium oxide, magnesia, clay, oxidation Cerium, zirconium oxide, yttrium oxide, magnesium hydrotalcite, calcium aluminate, zinc aluminate and combination thereof, and optional one or more 1st races Alkali metal, the 2nd race's alkaline-earth metal and/or the 11st race's metal), make the charging and first bulk material at least one thermal insulation Reaction zone contact at reaction conditions with by least part the acyclic C5Hydrocarbon is converted into comprising cyclopentadiene intermediate, unconverted Acyclic C5The first effluent of hydrocarbon and optional cyclopentadiene；The first effluent is heated to temperature T2；By the first effluent Be supplied at least one heat transfer reaction zone (for example, circulating fluid bed reactor, cycle sedimentation bed reactor, fixed bed reactors, Cyclic annular fixed bed reactors, fluidized-bed reactor, burn pipe reactor or Convective Heating pipe reactor)；Make the first effluent With include catalyst material (for example, the platinum on ZSM-5, the platinum on zeolite L and/or the platinum on silicate modified silica) The second bulk material contacted at reaction conditions at least one heat transfer reaction zone with by least part ring penta 2 Alkene intermediate and/or unconverted acyclic C5Hydrocarbon is converted into the second effluent comprising cyclopentadiene；Optionally, it will include C1、 C2、C3And/or C4The light hydrocarbon feed of hydrocarbon is at least one adiabatic reaction area；H will optionally be assisted2It feeds to this at least One adiabatic reaction area and/or at least one heat transfer reaction zone.
The method of 2. embodiment 1 of embodiment, wherein when compared with the method that wherein the adiabatic reaction area is not present The thermic load of at least one heat transfer reaction zone reduces the cyclopentadiene of at least about 3.0% per unit generation.
The method of 3. embodiment 1 or 2 of embodiment, wherein keeping reversed temperature at least one heat transfer reaction zone Distribution or isothermal temperature distribution.
The method of any one of 4. foregoing embodiments of embodiment, wherein T1And/or T2Less than or equal to about 500 DEG C.
The method of any one of 5. foregoing embodiments of embodiment, wherein leave at least one heat transfer reaction zone this The temperature of two effluents is at least about 550 DEG C.
The method of any one of 6. foregoing embodiments of embodiment, wherein at least one heat transfer reaction zone include at least one A heating equipment.
The method of any one of 7. foregoing embodiments of embodiment, wherein (i) at least one heat transfer reaction zone Reaction condition includes about 400 DEG C-about 800 DEG C of temperature and/or the pressure of about 3psia- about 150psia；And/or (ii) this extremely Reaction condition in a few adiabatic reaction area includes about 450 DEG C-about 900 DEG C of temperature and/or about 3psia- about 150psia Pressure.
The method of any one of 8. foregoing embodiments of embodiment, the acyclic C of wherein at least about 30wt%5Hydrocarbon is converted For cyclopentadiene.
The method of any one of 9. foregoing embodiments of embodiment, the wherein first effluent are at least one heat transfer The fair current in the direction of the second bulk material stream or counter-current flow in reaction zone.
The method of any one of 10. foregoing embodiments of embodiment further comprises at least part first granular material Material from least one adiabatic reaction area be transported to more new district and/or by least part second bulk material from this at least one A heat transfer reaction zone is transported to the more new district.
The method of 11. embodiment 10 of embodiment further comprises making first bulk material and/or this is second granular Material is contacted with hydrogen to remove the coke material that at least part gradually deposits on the catalyst material, newer to be formed Catalyst material and volatile hydrocarbon；With by newer catalyst material be back at least one adiabatic reaction area and/or this extremely Few heat transfer reaction zone.
The method of any one of 12. embodiment 10 or 11 of embodiment, wherein the more new district is at about 550 DEG C-about 800 DEG C Temperature operation and/or at least 10wt% the coke material gradually deposited by from the catalyst material remove.
The method of any one of 13. foregoing embodiments of embodiment further comprises, by least part, this is first granular Material from least one adiabatic reaction area be delivered to renewing zone and/or by least part second bulk material from this at least One heat transfer reaction zone is delivered to the renewing zone；Wherein first bulk material and/or second bulk material and regeneration gas It contacts to aoxidize to remove at regeneration conditions and is deposited on the coke material on the catalyst material at least partially to be formed Regeneration catalyzing agent material；With by least part the regenerated catalyst material circulation at least one adiabatic reaction area, this is extremely A few heat transfer reaction zone and/or the more new district.
The method of any one of 14. embodiment 1,2,3,4,5,6,7 or 8 of embodiment, further comprises stopping periodically Only arrive the charging at least one adiabatic reaction area and/or the first effluent at least one heat transfer reaction zone；With for this At least one adiabatic reaction area and/or at least one heat transfer reaction zone provide update gas, optionally, wherein the charging and/ The first effluent with update gas stream direction fair current or upstream flow.
The method of 15. embodiment 14 of embodiment, wherein the update gas include hydrogen and the update gas contact this One bulk material and/or second bulk material are to remove the coke material that at least part gradually deposits on the catalyst material Material is to form newer catalyst material and volatile hydrocarbon.
The method of any one of 16. embodiment 1,2,3,4,5,6,7 or 8 of embodiment, further comprises stopping periodically Only arrive the charging at least one adiabatic reaction area and/or the first effluent at least one heat transfer reaction zone；It provides more New gas includes hydrogen；With so that first bulk material and/or second bulk material is contacted with the update gas to remove at least The coke material that a part gradually deposits on the catalyst material is to form newer catalyst material and volatile hydrocarbon.
The method of any one of 17. embodiment 14,15 or 16 of embodiment, wherein at least about 10.0wt%'s should be by The coke material for walking deposition is removed from the catalyst material.
The method of any one of 18. embodiment 14,15,16 or 17 of embodiment, further comprises stopping arriving periodically The charging at least one adiabatic reaction area and/or to this it is at least one heat transfer reaction zone first effluent；Supply regeneration gas Body is at least one adiabatic reaction area and/or at least one heat transfer reaction zone；With make first bulk material and/or should Second bulk material contacts to aoxidize to remove with the regeneration gas at regeneration conditions is deposited on the catalyst at least partially Coke material on material is to form regeneration catalyzing agent material, and optionally the wherein regeneration gas was with 1 day about every-about 180 days Interval contact first bulk material and/or second bulk material.
The method of any one of 19. foregoing embodiments of embodiment, wherein first bulk material and the second granular material Material is same or different.
The method of any one of 20. foregoing embodiments of embodiment, wherein first bulk material further include inertia Material and/or second bulk material further include inert material.
The invention further relates to embodiment 21-26：
Embodiment 21. is in reactor assembly by acyclic C5The method that hydrocarbon is converted into cyclopentadiene, wherein this method packet It includes：
In temperature T1There is provided at least one adiabatic reaction area includes acyclic C5The charging of hydrocarbon, wherein at least one thermal insulation Reaction zone includes the first bulk material containing catalyst material；
The charging and first bulk material is set to be contacted at reaction conditions near at least one adiabatic reaction area The a few part acyclic C5Hydrocarbon is converted into comprising cyclopentadiene intermediate, unconverted acyclic C5Hydrocarbon and optional cyclopentadiene First effluent；
The first effluent is heated to temperature T2；
The first effluent is supplied at least one heat transfer reaction zone；With
Make the first effluent and the second bulk material at least one heat transfer reaction zone contact at reaction conditions with By at least part cyclopentadiene intermediate and the unconverted acyclic C5Hydrocarbon is converted into the second outflow comprising cyclopentadiene Object；
The method of 22. embodiment 21 of embodiment, wherein first bulk material further include inert material and/or Second bulk material further includes inert material.
The method of 23. embodiment 21 of embodiment, the wherein catalyst material include the platinum on ZSM-5, on zeolite L Platinum on platinum and/or silica.
The method of 24. embodiment 21 of embodiment, wherein first bulk material and second bulk material are different 's.
The method of 25. embodiment 24 of embodiment, wherein second bulk material include the platinum on ZSM-5, on zeolite L Platinum and/or platinum on silicate modified silica and first bulk material include on inorganic carrier at least one the 6 races, the 9th race or the 10th race's metal, and optional one or more 1st race's alkali metal, the 2nd race's alkaline-earth metal and/or the 11st Race's metal；With
The method of 26. embodiment 25 of embodiment, the wherein inorganic carrier be selected from zeolite, SAPO, ALPO, MeAPO, two Silica, zirconium oxide, titanium oxide, aluminium oxide, magnesia, clay, cerium oxide, yttrium oxide, zirconium oxide, magnesium hydrotalcite, calcium, aluminic acid Salt, zinc aluminate and combination thereof.
Commercial Application
Acyclic C5What is obtained during method for transformation contains cyclic annular, branched and straight chain C5Hydrocarbon and optionally hydrogeneous, C4With lightweight by-product Object or C6With any combination of first hydrocarbon reactor effluent of heavy byproduct, have in itself valuable product and Itself it is exactly valuable product.Preferably, CPD and/or DCPD can be to be detached from reactor effluent to obtain purification Product stream can be used for producing a variety of high-value products.
For example, containing 50wt% or more, or the product stream of preferably 60wt% or more purifications of DCPD can be used for producing Hydrocarbon resin, unsubstituted polyester resin and epoxy material.Containing 80wt% or more, or preferably 90wt% or more CPD purification Product stream can be used for producing the Diels-Alder reaction product that is formed according to following reaction scheme (I)：
Scheme I
Wherein R is hetero atom or substituted hetero atom, substituted or unsubstituted C1-C50Alkyl is (often double bond containing Alkyl), aromatic group or any combination thereof.Preferably, substituted base or group contain one or more 13-17 races, excellent Select the element of the 15th or 16 races, more preferable nitrogen, oxygen or sulphur.In addition to the monoolefine diels-Alder for being drawn on scheme (I) is anti- Answer product, containing 80wt% or more, or preferably 90wt% or more purifications of CPD product stream can be used in being formed CPD with One or more Diels-Alder reaction products in below：Another CPD molecules, conjugated diene, acetylene, allene, two The substituted form of substituted alkene, trisubstituted alkene, cycloolefin and aforementioned substances.Preferred Diels-Alder reaction Product includes norbornene, vinylidene base norbornene, substituted norbornene (including oxygen-containing norbornene), norbornadiene And tetracyclododecen, as shown in the following structure：
Aforementioned Diels-Alder reaction product can be used for producing polymer and cyclic olefin copolyalkenamer such as ethylene Copolymer.Gained cyclic olefin copolymer and cyclic olefin polymer product can be used for a variety of applications, such as packaging film.
The product stream of the purification of the DCPD containing 99wt% or more may be used in such as ring-opening metathesis polymerization (ROMP) and urge Agent produces CPD polymer.DCPD polymer products can be used to form product, specifically moulding part, such as wind turbine Machine blade and automobile component.
Also other component can be detached from reactor effluent and uses it for forming high-value product.For example, separation Cyclopentene can be used for producing polycyclic amylene, also referred to as cauprene, as drawn in scheme (II).
Scheme II
The pentamethylene of separation can be used as foaming agent and be used as solvent.Straight chain and branched C5Product can be used for being converted to higher Grade alkene and alcohols.Cyclic annular and non-annularity C5Product optionally after hydrogenation can be used as octane enhancer and transport fuel is blended Component.
Embodiment
Following example illustrate the present invention.Many remodeling and variation are feasible, and are appreciated that, in appended power Profit require in the range of, the present invention can in a manner of specifically describing herein other than in the way of put into practice.Room temperature is 23 DEG C, unless otherwise Explanation.
Embodiment 1-ZSM-5 carbon monoxide-olefin polymerics synthesize
By 10,000g deionizations (DI) water, 600g 50%NaOH solution, 45% sodium aluminate solutions of 25g, 730g n-propylamines 100% solution, 80gZSM-5 crystal seeds and 3,190g Ultrasil PMTMPrepared by modified silica has about 20.3% The synthetic mixture of solid mixes in 5 gallons of containers, and 5 gallons of autoclaves are then added upon mixing.Synthetic mixture has Mole composition below：
Synthetic mixture is mixed and is reacted 72 hours in 250rpm at 230 °F (110 DEG C).Products therefrom is filtered and is used in combination Deionized water is washed, and is then dried overnight in an oven at about 250 °F (121 DEG C).The XRD diagram case of the material of original sample after synthesis (not shown) shows that the pure phase of typical ZSM-5 topologys and the material are made of the mixture of the big crystal of about 2 microns of size. By a part synthesize after original sample crystal by room temperature with ammonium nitrate solution three times ion exchange come convert (for characterizing) at Then hydrogen form is calcined 6 hours in 250 °F of (121 DEG C) dryings and at 1000 °F (540 DEG C).The SiO of gained ZSM-5 crystal2/ Al2O3Molar ratio is about 414, and total surface area (SA)/(the hollow SA of micropore SA+) is 490 (440+51) m2/ g, hexane absorption value are 117mg/g and α values are 31.The material of second part is impregnated with being used for Pt after synthesizing as former state.
By SiO2/Al2O3The ZSM-5 that molar ratio is 414 and sodium content is 0.38wt% is in nitrogen at 900 °F (482 DEG C) Calcining 6 hours.After cooling, sample is heated to 900 °F (482 DEG C) in nitrogen and is kept for 3 hours.Then by atmosphere point four Step is altered in steps as 1.1,2.1,4.2 and 8.4% oxygen.Each step is kept for 30 minutes.Temperature is improved to 1000 °F (540 DEG C), oxygen content is improved to 16.8%, and retain the material in 1000 °F (540 DEG C) 6 hours.After cooling, via start impregnation 0.5wt%Pt is added using the aqueous solution of tetramine platinic hydroxide.By carbon monoxide-olefin polymeric in air in drying at room temperature 2 hours, Then it in 250 °F of (121 DEG C) dryings 4 hours, is finally calcined 3 hours at 660 °F (349 DEG C) in air.By catalyst combination Object powder squeezes (15 tons), crushes and be sieved to obtain the particle size of 20-40 mesh.
Embodiment 2- carbon monoxide-olefin polymeric performance evaluations
By the carbon monoxide-olefin polymeric (0.5g) of embodiment 1 and quartzy (1.5g, 60-80 mesh) physical mixed and it is packed into reaction Device.Carbon monoxide-olefin polymeric is 1 hour dry at He (100mL/min, 30psig (207kPa), 250 DEG C), then in H2 It is restored 1 hour under (200mL/min, 30psig (207kPa), 500 DEG C).Then pentane, H are used2With the charging of surplus He, allusion quotation Type at 550-600 DEG C, 5.0psia (35kPa-a) C5H12, 1.0 moles of H2：C5H12, 14.7h-1WHSV and total 30psig (207kPa) tests carbon monoxide-olefin polymeric.At 550-600 DEG C by with H2Processing (200mL/min, 30psig (207kPa), 650 DEG C) after 5 hours initial testings, carbon monoxide-olefin polymeric stability and regenerability are tested, then in 600 DEG C of re-test performances.
The hydrogen of cyclopentadiene and three equivalents generates (equation 1) by pentane dehydrogenation and cyclisation.This is by making pentane exist Raised temperature flows through solid-state carbon monoxide-olefin polymeric containing Pt to complete.The ZSM-5 (414 of embodiment 1：1) performance of/0.5%Pt Based on pentane conversion ratio, ring-type C5Produce (cC5), cracking yield and stability evaluates.These results are summarized in table 2A, table 2B, Fig. 3 A and Fig. 3 B.
Table 2A
Table 2B
Table 2A and table 2B is shown in 5.0psia (35kPa-a) C5H12, 1：1 mole of H2：C5, 14.7WHSV, total 0.5g ZSM-5 (414 under conditions of 45psia (310kPa-a)：1)/0.5wt%Pt carbon monoxide-olefin polymerics are at various temperatures Pentane conversion ratio, and ring-type C5、CPD、C1And C2-4(8 at each temperature are small for the selectivity and yield of pyrolysis product When average value).In table 2A, selectivity and yield are to the cyclic annular C that is respectively formed5, CPD, C1And C2-4Hydrocarbon is with molar percentage Expression；That is, molar selectivity is the cyclic annular C being respectively formed5, CPD, C1And C2-4Molal quantity divided by the pentane of conversion always rub You.In table 2B, selectivity and yield are the cyclic annular C being respectively formed5, CPD, C1And C2-4Hydrocarbon is with carbon percentage expression；That is, carbon selects Selecting property is in the cyclic annular C being respectively formed5, CPD, C1And C2-4In carbon molal quantity divided by the carbon in the pentane of conversion total moles Number.
As it can be seen, table 2A and 2B are shown in the conversion of pentane rate more than 80% under high WHSV, and at 595 DEG C 40% couple of ring-type C5The selectivity of substance.Although not being specific final product, pentamethylene and cyclopentene can be recycled with life Produce CPD.Each temperature and at 650 DEG C in H2Activity maintains 8 hours after processing 5 hours.
Embodiment 3- reactor performances model
Data above group and similar experimental data are for guiding in Invensys Systems Inc.PRO/II 9.1.4 (being used for embodiment 3A-3H) and Invensys Systems Inc.PRO/II 9.3.4 (being used for embodiment 3I-3N) structure model To estimate the performance in various business relevant operating condition and different reactor configurations.Depending on the concrete condition of modeling, The variation of result can occur, but model still shows the relative merit of the present invention.Many remodeling and variation are feasible, and energy Understand, within the scope of the appended claims, the present invention can in a manner of specifically describing herein other than in the way of put into practice..
The outlets embodiment 3A-8psia, H2It is co-feeding, combustion pipe reactor
As comparative example, the outlets 8psia, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor is to feed 0.5：1.0 The hydrogen of molar ratio：Pentane is simulated；It is dynamic to reach its heat in reactor outlet condition that enough residence times are provided for CPD concentration State concentration.For the 1lb- moles of CPD of generation in combustion pipe reactor effluent, 1.609lb- moles of pentane is needed, 0.8045lb- moles of hydrogen and burning pipe reactor thermic load 0.1775MM BTU.
The outlets embodiment 3B-8psia, combustion pipe reactor
As comparative example, the outlets 8psia, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor is with 0.0：1.0 mole The hydrogen of ratio：The charging of pentane is simulated；Enough residence times are provided to reach its heat in reactor outlet condition for CPD concentration Dynamic concentration.For the 1lb- moles of CPD of generation in combustion pipe reactor effluent, 1.5638lb- moles of pentane is needed, 0.0lb- moles of H2With burning pipe reactor thermic load 0.1741MM BTU.Although even more having suction than this with embodiment phase 3A The CPD yields and thermic load of gravitation are reduced, for pentane to be converted to the catalyst of CPD in no H2Co-feeding situation It is lower by rapid coke.
The outlets embodiment 3C-8psia, H2It is co-feeding, CH4It is co-feeding, combustion pipe reactor
As comparative example, the outlets 8psia, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor is with 0.5：1.0： 3.8854 the hydrogen of molar ratio：Pentane：CH4Charging simulation；Enough residence times are provided in reactor for CPD concentration Exit condition reaches its hot dynamic concentration.In order to generate 1lb- moles of CPD in combustion pipe reactor effluent, need 1.2412lb- moles of pentane, 0.6207lb- moles of hydrogen and burning pipe reactor thermic load 0.1647MM BTU.With embodiment 3A compares this even the CPD yields of more attractive and thermic load reduction with 3B.
The outlets embodiment 3D-8psia, H2It is co-feeding, CH4Co-feeding, adiabatic lead reactor, combustion pipe delay are anti- Answer device
As the displaying of the present invention, 500 DEG C of entrances, 72.0psia is exported, adiabatic reactor, and then 8psia is exported, and 500 DEG C entrance, 575 DEG C of outlets, combustion pipe reactor is with 0.5：1.0：3.8854 the H of molar ratio2：Pentane：CH4Charging mould It is quasi-；Enough residence times are provided to reach its hot dynamic concentration in reactor outlet condition for CPD concentration.In order in combustion tube 1lb- moles of CPD is generated in road reactor effluent, needs 1.2412lb- moles of pentane, 0.6207lb- moles of H2And burning Pipe reactor thermic load 0.1542MM BTU.Although this is yield identical as CPD's with embodiment 3C, with embodiment 3A, 3B and 3C is reduced compared to thermic load；Thermic load relatively reduces 6.4% with 3C.
The outlets embodiment 3E-16psia, H2It is co-feeding, combustion pipe reactor
It is simulated with superatmospheric pressure similar to the comparative example of 3A.16psia is exported, 500 DEG C of entrances, 575 DEG C of outlets, burning Pipeline reactor is with 0.5：1.0 the H of molar ratio2：The charging of pentane is simulated；For CPD concentration provide enough residence times with Reach its hot dynamic concentration in reactor outlet condition.In order to generate 1lb- moles of CPD in combustion pipe reactor effluent, Need 2.846lb- moles of pentane, 1.423lb- moles of H2With burning pipe reactor thermic load 0.2358MM BTU.This has disappeared In addition to O2The potential problems of entrance, but the inlet amount and thermic load that need improve compared with above example.
The outlets embodiment 3F-16psia, H2It is co-feeding, CH4It is co-feeding, combustion pipe reactor
In order to study the performance of embodiment 3E, the outlets 16psia, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor With 0.5：1.0：3.8854 the H of molar ratio2：Pentane：CH4Charging simulation；For CPD concentration provide enough residence times with Reach its hot dynamic concentration in reactor outlet condition.In order to generate 1lb- moles of CPD in combustion pipe reactor effluent, 1.609lb- moles of pentane needs 0.8045lb- moles of H2With burning pipe reactor thermic load 0.1903MM BTU.Although this It is even more attractive CPD yields than embodiment 3E, and thermic load is reduced compared with embodiment 3E, by applying this hair Bright, there are still improved potentiality.
The outlets embodiment 3G-8psia, H2It is co-feeding, CH4Co-feeding, adiabatic lead reactor, combustion pipe delay are anti- Answer device
As the displaying of the present invention, 500 DEG C of entrances, 72.0psia is exported, adiabatic reactor, and then 8psia is exported, and 500 DEG C entrance, 575 DEG C of outlets, combustion pipe reactor is with 0.5：1.0：3.8854 the H of molar ratio2：Pentane：CH4Charging mould It is quasi-；Enough residence times are provided to reach its hot dynamic concentration in reactor outlet condition for CPD concentration.In order in combustion tube 1lb- moles of CPD is generated in road reactor effluent, needs 1.609lb- moles of pentane, 0.8045lb- moles of H2And burning Pipe reactor thermic load 0.1767MM BTU.Although this is CPD yields identical with embodiment 3F, thermic load reduces compared with 3F 7.5%.
The outlets embodiment 3H-8psia, CH4Co-feeding, adiabatic lead reactor, combustion pipe deferred reaction device
As the displaying of the present invention, 500 DEG C of entrances, 72.0psia is exported, adiabatic reactor, and then 8psia is exported, and 500 DEG C entrance, 575 DEG C of outlets, combustion pipe reactor is with 0.0：1.0：3.8854 the H of molar ratio2：Pentane：CH4Charging mould It is quasi-；Enough residence times are provided to reach its hot dynamic concentration in reactor outlet condition for CPD concentration.In order in combustion tube 1lb- moles of CPD is generated in road reactor effluent, needs 1.517lb- moles of pentane, 0.0lb- moles of H2It is anti-with combustion tube Answer device thermic load 0.1652MM BTU.Allow to reduce or eliminate H using the present invention2It is co-feeding, because adiabatic reactor will be in work Skill stream generates H before entering heat transfer reactor2, this is easier to coking.Therefore CPD yields are improved compared with embodiment 3F (that is, it needs to less pentane to produce the CPD of identical amount) and thermic load reduce 13.2% compared with 3F.
The outlets embodiment 3I-8psia, H2It is co-feeding, combustion pipe reactor
As comparative example, the outlets 8psia, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor is with 1.0：1.0 mole The hydrogen of ratio：The charging of pentane is simulated；Enough residence times are provided to reach its heat in reactor outlet condition for CPD concentration Dynamic concentration.For the 1lb- moles of CPD of generation in combustion pipe reactor effluent, 1.647lb- moles of pentane is needed, 1.647lb- moles of hydrogen and burning pipe reactor thermic load 0.1802MM BTU.
The outlets embodiment 3J-8psia, H2Co-feeding, adiabatic lead reactor, combustion pipe deferred reaction device
As the displaying of the present invention, 500 DEG C of entrances, 13psia is exported, adiabatic reactor, and then 8psia is exported, 500 DEG C Entrance, 575 DEG C of outlets, combustion pipe reactor is with 1.0：The H of 1.0 molar ratios2：The charging of pentane is simulated, and dense for CPD Degree provides enough residence times to reach its hot dynamic concentration in reactor outlet condition.In order in combustion pipe reactor stream Go out 1lb- moles of CPD of generation in object, needs 1.647lb- moles of pentane, 1.647lb- moles of H2It is negative with burning pipe reactor heat Lotus 0.1688MM BTU.As this and embodiment 3I are identical CPD yields, but thermic load reduces 6.3%.
The outlets embodiment 3K-8psia, H2Co-feeding, adiabatic lead reactor, combustion pipe deferred reaction device
As the further displaying to the present invention, 575 DEG C of entrances, 13psia is exported, adiabatic reactor, and then 8psia goes out Mouthful, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor is with 1.0：The H of 1.0 molar ratios2：The charging of pentane is simulated, and Enough residence times are provided to reach its hot dynamic concentration in reactor outlet condition for CPD concentration.In order in combustion pipe 1lb- moles of CPD is generated in reactor effluent, needs 1.647lb- moles of pentane, 1.647lb- moles of H2It is anti-with combustion tube Answer device thermic load 0.1589MM BTU.Although this is CPD yields identical with embodiment 3I, thermic load reduces 11.8%, And the reduction of such thermic load is higher than realizing in embodiment 3J, this is because adiabatic lead reactor is higher Inlet temperature.
The outlets embodiment 3L-16psia, H2It is co-feeding, CH4It is co-feeding, combustion pipe reactor
As comparative example, the outlets 16psia, 500 DEG C of entrances, 575 DEG C of outlets, combustion pipe reactor is with 1.0：1.0： The hydrogen of 4.35 molar ratios：Pentane：The charging of methane is simulated；Enough residence times are provided to go out in reactor for CPD concentration Pig's tongue part reaches its hot dynamic concentration.In order to generate 1lb- moles of CPD in combustion pipe reactor effluent, need 1.647lb- moles of pentane, 1.647lb- moles of hydrogen and burning pipe reactor thermic load 0.1951MM BTU.
The outlets embodiment 3M-16psia, H2It is co-feeding, CH4Co-feeding, adiabatic lead reactor, combustion pipe delay are anti- Answer device
As the displaying of the present invention, 500 DEG C of entrances, 21psia is exported, adiabatic reactor, and then 16psia is exported, 500 DEG C Entrance, 575 DEG C of outlets, combustion pipe reactor is with 1.0：1.0：The H of 4.35 molar ratios2：Pentane：The charging of methane is simulated, And enough residence times are provided to reach its hot dynamic concentration in reactor outlet condition for CPD concentration.In order to burn 1lb- moles of CPD is generated in pipeline reactor effluent, needs 1.647lb- moles of pentane, 1.647lb- moles of H2And burning Pipe reactor thermic load 0.1735MM BTU.Although this is CPD yields identical with embodiment 3L, thermic load reduces 11.1%.
The outlets embodiment 3N-16psia, H2It is co-feeding, CH4Co-feeding, adiabatic lead reactor, combustion pipe delay are anti- Answer device
As the displaying of the present invention, 575 DEG C of entrances, the outlets 21psia, then 16psia is exported adiabatic reactor, 500 DEG C Entrance, 575 DEG C of outlets, combustion pipe reactor is with 1.0：1.0：The H of 4.35 molar ratios2：Pentane：The charging of methane is simulated, And enough residence times are provided to reach its hot dynamic concentration in reactor outlet condition for CPD concentration.In order to burn 1lb- moles of CPD is generated in pipeline reactor effluent, needs 1.647lb- moles of pentane, 1.647lb- moles of H2And burning Pipe reactor thermic load 0.1735MM BTU.Although this is CPD yields identical with embodiment 3L, thermic load reduces 20.6%, and such thermic load is reduced higher than realizing in embodiment 3M, this is because adiabatic lead reactor Higher inlet temperature.
These embodiments (are added to given feed composition and heat transfer reactor operating condition and and conduct heat using the present invention The adiabatic reactor of reactor upstream) it is shown, the yield of CDP, which is improved, (needs less pentane to prepare The CPD of identical amount) and thermic load reduction.
All Files as described herein are incorporated by reference, including any priority document and/or test program, only Want them not inconsistent with this paper., it is apparent that although from foregoing general description and the specific embodiment The form of the present invention is illustrate and described, but various repair can be carried out without departing from the spirit and scope of the present invention Change.Therefore, this is not meant to therefore the present invention is restricted.Similarly, term "comprising" is considered as same with term " comprising " Justice.Similarly, when adding transition phrase "comprising" before composition, element or one group of element, it should be appreciated that we also examine Having considered identical composition or element group has a transition phrase " substantially by ... form ", " consist of ", " being selected from " or " for " is before the composition, element or one group of element, and vice versa.

Claims (27)

1. by acyclic C in reactor assembly5The method that hydrocarbon is converted into cyclopentadiene, wherein this method include：
In temperature T1There is provided at least one adiabatic reaction area includes acyclic C5The charging of hydrocarbon, wherein at least one adiabatic reaction Area includes the first bulk material containing catalyst material；
The charging and first bulk material is set to be contacted at reaction conditions with will at least one at least one adiabatic reaction area The partly acyclic C5Hydrocarbon is converted into comprising cyclopentadiene intermediate, unconverted acyclic C5The first of hydrocarbon and optional cyclopentadiene Effluent；
The first effluent is heated to temperature T2；
The first effluent is supplied at least one heat transfer reaction zone；With
The first effluent is set to be contacted at reaction conditions near at least one heat transfer reaction zone with the second bulk material Few part cyclopentadiene intermediate and the unconverted acyclic C5Hydrocarbon is converted into the second effluent comprising cyclopentadiene.
2. method described in claim 1, wherein when compared with the method that wherein the adiabatic reaction area is not present, this at least one The cyclopentadiene that the thermic load per unit of a heat transfer reaction zone generates reduces at least 3.0%.
3. method as claimed in claim 1 or 2, wherein reversed Temperature Distribution or isothermal temperature distribution are maintained at least one biography In thermal reaction area.
4. claim 1-3 any one of them methods, wherein at least one adiabatic reaction area are fixed bed reactors or stream Fluidized bed reactor.
5. claim 1-4 any one of them methods, wherein T1And/or T2Less than or equal to about 500 DEG C.
6. claim 1-5 any one of them methods, wherein leaving the second effluent of at least one heat transfer reaction zone Temperature be at least about 550 DEG C.
7. claim 1-6 any one of them methods, further comprise including C1, the light hydrocarbon of C2, C3 and/or C4 hydrocarbon are total Charging feeds at least one adiabatic reaction area.
8. claim 1-7 any one of them methods, further comprise H2Feed at least one adiabatic reaction area and/or At least one heat transfer reaction zone.
It is set 9. claim 1-8 any one of them methods, wherein at least one heat transfer reaction zone include at least one heating It is standby.
10. claim 1-9 any one of them methods, wherein the reaction condition at least one heat transfer reaction zone includes The pressure of about 400 DEG C-about 800 DEG C of temperature and about 3psia- about 150psia.
11. claim 1-10 any one of them methods, wherein the reaction condition packet at least one adiabatic reaction area Include the pressure of about 450 DEG C-about 900 DEG C of temperature and about 3psia- about 150psia.
12. claim 1-11 any one of them methods, the acyclic C of wherein at least about 30wt%5Hydrocarbon is converted into ring penta 2 Alkene.
13. claim 1-12 any one of them methods, wherein at least one heat transfer reaction zone are reacted for recirculating fluidized bed Device, cycle sedimentation bed reactor, fixed bed reactors, cyclic annular fixed bed reactors, fluidized-bed reactor, burn pipe reactor or Convective Heating pipe reactor.
14. the method described in claim 13, wherein second bulk material are to include the platinum on ZSM-5, the platinum on zeolite L And/or the carbon monoxide-olefin polymeric of platinum, and wherein the carbon monoxide-olefin polymeric is formed on silicate modified silica The catalyst shape of structuring.
15. the method described in claim 13 or 14, wherein the reaction zone that at least conducts heat includes parallel reactor pipeline Reactor, and wherein the pipe reactor has during making the first effluent and the second bulk material contacts from reactor The pressure drop less than 20psi that entrance is measured to reactor outlet.
16. claim 1-15 any one of them methods, the wherein first effluent at least one heat transfer reaction zone In the second bulk material stream direction fair current or upstream flow.
17. claim 1-12 any one of them methods further comprise stopping periodically at least one adiabatic reaction The charging in area and/or to this it is at least one heat transfer reaction zone first effluent；With at least one adiabatic reaction area and/or At least one heat transfer reaction zone provides update gas.
18. the method described in claim 17, the wherein charging and/or the first effluent are with suitable with the direction of update gas stream Stream upstream flows.
19. the method described in claim 17 or 18, wherein the update gas include hydrogen and make the update gas contact this first Bulk material and/or second bulk material are to remove the coke material that at least part gradually deposits on the catalyst material Material, to form newer catalyst material and volatile hydrocarbon.
20. claim 17-19 any one of them methods, the coke material gradually deposited of wherein at least about 10.0wt% It is removed from the catalyst material.
21. claim 1-12 any one of them methods further comprise stopping periodically at least one adiabatic reaction The charging in area and/or to this it is at least one heat transfer reaction zone first effluent；Regeneration gas is supplied at least one thermal insulation Reaction zone and/or at least one heat transfer reaction zone；With make first bulk material and/or second bulk material with this again Angry body contact at regeneration conditions to aoxidize remove at least part be deposited on coke material on the catalyst material from And form regeneration catalyzing agent material.
22. the method described in claim 21, wherein make the regeneration gas with 1 day about every-about 180 days intervals contact this first Bulk material and/or second bulk material.
23. claim 1-22 any one of them methods, wherein first bulk material and second bulk material are identical 's.
24. claim 1-22 any one of them methods, wherein first bulk material and second bulk material are different 's.
25. product derives from the product of the method production of any one of claim 1-24.
26. the product described in claim 25, the wherein product derive from material, which derives from the product and double bond containing substrate Diels-Alder reaction.
27. the product described in claim 25, the wherein product product therein are selected from cyclopentadiene, bicyclopentadiene, ring Amylene, pentamethylene, amylene, pentadiene, norbornene, tetracyclododecane, substituted norbornene, the Di Er of cyclopentadiene This-Alder reaction derivative, cyclic olefine copolymer, cyclic olefin polymer, polycyclic amylene, unsubstituted polyester resin, hydrocarbon tree Fat tackifier, the epoxy resin of preparation, poly- bicyclopentadiene, norbornene or substituted norbornene or bicyclopentadiene are appointed The metathesis polymer of what combination thereof, wind turbine blade, the composite material containing glass or carbon fiber, the bonding of preparation Agent, vinylidene base norbornene, EPDM rubber, alcohols, plasticizer, foaming agent, solvent, octane enhancer, gasoline and they Mixture.
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