WO2018204036A1 - Procédé de conversion de composés c5 acycliques en composés c5 cycliques et compositions catalytiques formulées utilisées dans celui-ci - Google Patents
Procédé de conversion de composés c5 acycliques en composés c5 cycliques et compositions catalytiques formulées utilisées dans celui-ci Download PDFInfo
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- WO2018204036A1 WO2018204036A1 PCT/US2018/026783 US2018026783W WO2018204036A1 WO 2018204036 A1 WO2018204036 A1 WO 2018204036A1 US 2018026783 W US2018026783 W US 2018026783W WO 2018204036 A1 WO2018204036 A1 WO 2018204036A1
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- Prior art keywords
- zsm
- group
- acyclic
- catalyst
- reactor
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
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- 230000000996 additive effect Effects 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000003498 natural gas condensate Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000009491 slugging Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01J29/40—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
- B01J29/46—Iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Definitions
- This invention relates to a formulated catalyst compositions and their use in a process for the conversion of an acyclic C 5 feedstock to a product comprising cyclic C 5 compounds, such as for example, cyclopentadiene.
- Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are highly desired raw materials used throughout the chemical industry in a wide range of products such as polymeric materials, polyester resins, synthetic rubbers, solvents, fuels, fuel additives, etc.
- cyclopentane and cyclopentene are useful as solvents, and cyclopentene may be used as a monomer to produce polymers and as a starting material for other high value chemicals.
- Cyclopentadiene is currently a minor byproduct of liquid fed steam cracking (for example, naphtha and heavier feed). As existing and new steam cracking facilities shift to lighter feeds, less CPD is produced while demand for CPD is rising. High cost due to supply limitations impacts the potential end product use of CPD in polymers. More CPD-based polymer products and other high value products could be produced, if additional CPD could be produced, at unconstrained rates and preferably at a cost lower than recovery from steam cracking.
- CPD may be produced as the primary product from plentiful Cs feedstock using a catalyst system in a process to produce CPD while minimizing production of light (C 4 ) byproducts.
- C 4 light
- the invention relates to a process for producing cyclic C 5 compounds including cyclopentadiene.
- the process comprises the step of contacting a feedstock with a formulated catalyst composition under acyclic C 5 conversion conditions effective to convert at least part of the acyclic C 5 feedstock to produce an effluent comprising one or more cyclic C5 compounds.
- the acyclic C5 feedstock comprises acyclic C5 hydrocarbons and optionally hydrogen, a light hydrocarbon or a mixture thereof.
- the formulated catalyst composition comprises:
- a microporous crystalline metallosilicate preferably, having a constraint index less than or equal to 12;
- a metal of Group 10 of the Periodic Table or a compound thereof and optionally, a metal selected from the group consisting of rare earth metals, metals of Groups 8, 9, or 11 of the Periodic Table, mixtures or combinations thereof, or a compound thereof;
- the formulated catalyst composition may be made into one or more of an extrudate, a spray dried particle, an oil drop particle, a mulled particle, or a spherical particle.
- the extrudate is a shaped extrudate which may be in cylindrical form or a lobed form.
- the shaped extrudate in lobed form may be a symmetrical lobed form, an asymmetrical lobed form, a symmetrical spiral lobed form or an asymmetrical spiral lobed form.
- the binder comprises one or more of silica, titania, zirconia, metal silicates of Group 1 or Group 13 of the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, surface passivated alumina, and mixtures thereof.
- At least a portion of the formulated catalyst composition may be deposited on a microlith support or a monolith support.
- the microporous crystalline metallosilicate has a framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU.
- the microporous crystalline metallosilicate is a microporous crystalline aluminosilicate.
- the alkali metal is preferably sodium; the alkaline earth metal is preferably magnesium.
- the metal of Group 10 is preferably platinum, and the optional metal is a Group 11 metal, preferably copper or silver.
- the invention relates to a cyclic C 5 composition which comprises one or more of the cyclic C5 compounds which are made by the process of this invention.
- the cyclic C5 composition may be reacted with a substrate comprising a double bond to form a product. Such product may be included in an article.
- FIG. 1 is a graphical representation of a cross-section of a shaped extrudate in cylindrical form.
- FIG. 2A is a graphical representation of a shaped extrudate in symmetrical lobed form.
- FIG. 2B is a graphical representation of a shaped extrudate in symmetrical spiral lobed form.
- FIG. 3A is a graphical representation of a shaped extrudate in asymmetrical lobed form.
- FIG. 3B is a graphical representation of a shaped extrudate in asymmetrical spiral lobed form.
- FIG. 4A shows the total yield to cyclic C5 as a percentage for Example 2.
- FIG. 4B shows the total yield to cyclic C5 as a percentage for Example 3.
- hydrocarbon means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds.
- C n means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
- C5 feedstock includes a feedstock containing n-pentane, such as, for example, a feedstock which is predominately normal pentane and isopentane (also referred to as methylbutane), with smaller fractions of cyclopentane and neopentane (also referred to as 2,2-dimethylpropane).
- n-pentane such as, for example, a feedstock which is predominately normal pentane and isopentane (also referred to as methylbutane), with smaller fractions of cyclopentane and neopentane (also referred to as 2,2-dimethylpropane).
- the term "light hydrocarbon” means light paraffinic and/or olefinic hydrocarbons comprised substantially of hydrogen and carbon only and has one to no more than 4 carbon atoms.
- Periodic Table means the IUPAC Periodic Table of the Elements, dated 01 May 2013, as it appears on the inside cover of The Merck Index, Twelfth Edition, Merck & Co., Inc., 1996.
- spherical particle means a particle that is substantially in the shape of a sphere which is a round solid having a surface in which every point is equidistant from the center of the sphere.
- particles for which distance from surface to surface points differ by +/- 25% will also be considered spherical.
- symmetrical lobed form when referring to a shaped extrudate means an extrudate having the shape substantially as shown in Figure 2A.
- symmetrical spiral lobed form when referring to a shaped extrudate means an extrudate having the shape substantially as shown in Figure 2B.
- asymmetrical lobed form when referring to a shaped extrudate means an extrudate having the shape substantially as shown in Figure 3A, wherein the radius, r 2 is greater than the radius, n.
- asymmetrical spiral lobed form when referring to a shaped extrudate means an extrudate having the shape substantially as shown in Figure 3B.
- washcoat means a catalyst composition which is formulated into a slurry that is deposited on a catalyst support and then dried.
- the term "monolith” when referring to a catalyst support means a monolithic catalyst support which is placed in an orderly pattern in a reactor and which comprises a plurality channels separated by walls that are coated with a catalytic composition.
- microlith when referring to a catalyst support means a catalyst support that is randomly loaded into a reactor and which comprises a one or more channels and/or surfaces that are coated with a catalytic composition.
- saturated or “saturated” includes, but is not limited to, alkanes and cycloalkanes.
- non-saturates includes, but is not limited to, alkenes, dialkenes, alkynes, cyclo-alkenes and cyclo-dialkenes.
- cyclic C5" or “cC 5” includes, but is not limited to, cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more thereof.
- cyclic C5" or “cC 5” also includes alkylated analogs of any of the foregoing, e.g., methyl cyclopentane, methyl cyclopentene, and methyl cyclopentadiene. It should be recognized for purposes of the invention that cyclopentadiene spontaneously dimerizes over time to form dicyclopentadiene via Diels-Alder condensation over a range of conditions, including ambient temperature and pressure.
- acyclic includes, but is not limited to, linear and branched saturates and non-saturates.
- aromatic means a planar cyclic hydrocarbyl with conjugated double bonds, such as, for example, benzene.
- aromatic encompasses compounds containing one or more aromatic rings, including, but not limited to, benzene, toluene, and xylene, and polynuclear aromatics (PNAs), which include, but are not limited to, naphthalene, anthracene, chrysene, and their alkylated versions.
- C 6+ aromatics includes compounds based upon an aromatic ring having six or more ring atoms, including, but not limited to, benzene, toluene, and xylene and polynuclear aromatics (PNAs) which include, but are not limited to, naphthalene, anthracene, chrysene, and their alkylated versions.
- PNAs polynuclear aromatics
- Group 10 metal means an element in Group 10 of the Periodic Table and includes, but is not limited to, nickel, palladium, platinum, and a mixture of two or more thereof.
- Group 11 metal means an element in Group 11 of the Periodic Table and includes, but is not limited to, copper, silver, gold, and a mixture of two or more thereof.
- Group 1 alkali metal means an element in Group 1 of the Periodic Table and includes, but is not limited to, lithium, sodium, potassium, rubidium, cesium, and a mixture of two or more thereof, and excludes hydrogen.
- Group 2 alkaline earth metal means an element in Group 2 of the Periodic Table and includes, but is not limited to, beryllium, magnesium, calcium, strontium, barium, and a mixture of two or more thereof.
- rare earth metal means an element in the Lanthanide series of the Periodic Table, as well as scandium and yttrium.
- the term rare earth metal includes, but is not limited to, lanthanum, praseodymium, neodymium, cerium, yttrium, and a mixture of two or more thereof.
- MCM-22 family material includes one or more of:
- molecular sieves made from a common first degree crystalline building block unit cell, which unit cell has the MWW framework topology (A unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure. Such crystal structures are discussed in the "Atlas of Zeolite Framework Types,” Fifth edition, 2001, the entire content of which is incorporated as reference.);
- molecular sieves made from a common second degree building block, being a 2- dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
- molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.
- the stacking of such second degree building blocks may be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof;
- the MCM-22 family material includes those molecular sieves having an X-ray diffraction pattern including d-spacing maxima at 12.4+0.25, 6.9+0.15, 3.57+0.07, and 3.42+0.07 Angstrom.
- the X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
- molecular sieve is used synonymously with the term “zeolite” or “microporous crystalline material.”
- the term “selectivity” means the moles of carbon in the respective cyclic C 5 , CPD, Ci, and C2-4 formed divided by total moles of carbon in the pentane converted.
- carbon selectivity to cyclic C5 of at least 30% means that at least 30 moles of carbon in the cyclic C5 is formed per 100 moles of carbon in the pentane converted.
- conversion means the moles of carbon in the acyclic C5 feedstock that is converted to a product.
- conversion of at least 70% of said acyclic C5 feedstock to a product means that at least 70% of the moles of said acyclic C5 feedstock was converted to a product.
- the term “coke” includes, but is not limited to, a low hydrogen content hydrocarbon that is adsorbed on the catalyst composition.
- Alpha Value is used as a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 3,354,078 and in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278, (1966) and Vol. 61, p. 395, (1980), each incorporated herein by reference.
- reactor refers to any vessel(s) in which a chemical reaction occurs. Reactor includes both distinct reactors, as well as reaction zones within a single reactor apparatus and, as applicable, reactions zones across multiple reactors. For example, a single reactor may have multiple reaction zones. Where the description refers to a first and second reactor, the person of ordinary skill in the art will readily recognize such reference includes two reactors, as well as a single reactor vessel having first and second reaction zones. Likewise, a first reactor effluent and a second reactor effluent will be recognized to include the effluent from the first reaction zone and the second reaction zone of a single reactor, respectively.
- adiabatic reactor includes a reactor/reaction zone may be an adiabatic reactor/reaction zone or a diabatic reactor/reaction zone.
- adiabatic refers to a reaction zone for which there is essentially no heat input into the system other than by a flowing process fluid.
- a reaction zone that has unavoidable losses due to conduction and/or radiation may also be considered adiabatic for the purpose of this invention.
- the term “diabatic” refers to a reactor/reaction zone to which heat is supplied by a means in addition to that provided by the flowing process fluid.
- fluidized bed reactor refers to a zone or vessel with contacting of solids (e.g., catalyst particles) and gas flows such that the superficial gas velocity (U) is sufficient to fluidize solid particles (i.e., above the minimum fluidization velocity Umf) and is below the velocity required for dilute-phase pneumatic conveying of solid particles in order to maintain a solids bed with void fraction below 95%.
- a fluidized bed reactor may be a moving fluidized bed reactor, such as a "circulating fluidized bed reactor,” which refers to a fluidized bed with a movement of solids (e.g., catalyst material) through the reactor and at least a partial recirculation of the solids (e.g., catalyst material).
- a fluidized bed reactor includes a reactor with cascaded fluid beds, as defined below.
- cascaded fluid-beds means a series arrangement of individual fluid-beds such that there can be a gradient in gas and/or solid property (such as, temperature, gas, or solid composition, pressure, etc.) as the solid or gas cascades from one fluid-bed to another.
- Locus of minimum fluidization velocity is given in, for example, Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2nd Edition, Butterworth- Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2nd Edition, Butterworth-Heinemann, Boston, 2010.
- the term "moving bed” reactor refers to a zone or vessel with contacting of solids (e.g., catalyst particles) and gas flows such that the superficial gas velocity (U) is below the velocity required for dilute-phase pneumatic conveying of solid particles in order to maintain a solids bed with void fraction below 95%.
- the solids e.g., catalyst material
- the solids may slowly travel through the reactor and may be removed from the bottom of the reactor and added to the top of the reactor.
- a moving bed reactor may operate under several flow regimes, including settling or moving packed-bed regime (U ⁇ Umf), bubbling regime (Umf ⁇ U ⁇ Umb), slugging regime (Umb ⁇ U ⁇ Uc), transition to and turbulent fluidization regime (Uc ⁇ U ⁇ Utr), and fast- fluidization regime (U>Utr), where Umf is minimum fluidizing velocity, Umb is minimum bubbling velocity, Uc is the velocity at which fluctuation in pressure peaks, and tr is transport velocity.
- These different fluidization regimes have been described in, for example, Kunii, D., Levenspiel, O., Chapter 3 of Fluidization Engineering, 2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of Chemical Process Equipment, Revised 2nd Edition, Butterworth-Heinemann, Boston, 2010, which are incorporated by reference.
- the term "fixed bed” or “packed bed” reactor refers to a zone or vessel (such as, vertical or horizontal, cylindrical pipe or a spherical vessel) and may include transverse (also known as cross flow), axial flow, and/or radial flow of the gas, where solids (e.g., catalyst particles) are substantially immobilized within the reactor and gas flows such that the superficial velocity (U) is below the velocity required to fluidize the solid particles (i.e., below the minimum fluidization velocity Umf) and/or the gas is moving in a downward direction so that solid particle fluidization is not possible.
- U superficial velocity
- Umf minimum fluidization velocity
- tubular reactor means a reactor having reactor tubes that are straight rather than having a coiled or curved path through the enclosure (although coiled or curved tubes may be used). Additionally, the tubes may have a cross section that is circular, elliptical, rectangular, and/or other known shapes.
- the tubes are preferentially heated with a turbine exhaust stream produced by a turbine burning fuel gas with a compressed gas comprising oxygen. In other aspects, the reactor tubes are heated by convection with hot gas produced by combustion in a furnace, boiler, or excess air burner. However, heating the reactor tubes with turbine exhaust is preferred because of the co- production of shaft power among other advantages.
- the term "radiantly heated tubular" reactor refers to a furnace and parallel reactor tube(s) positioned within a radiant section of the furnace.
- the reactor tubes contain a catalytic material (e.g., catalyst particles), which contacts reactant(s) to form a product.
- the term "convectively heated tubular" reactor refers to a conversion system comprising parallel reactor tube(s) containing a catalytic material and positioned within an enclosure. While any known reactor tube configuration or enclosure may be used, preferably the conversion system comprises multiple parallel reactor tubes within a convective heat transfer enclosure.
- cyclical refers to a periodic recurring or repeating event that occurs according to a cycle.
- reactors e.g., cyclic fixed bed
- a reaction interval e.g., a reheat interval, and/or a regeneration interval.
- the duration and/or order of the interval steps may change over time.
- compositions, a process, a method of making, or an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition, a process, a method of making, or an element or a group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of said composition, a process, a method of making, or an element or a group of elements, and vice versa.
- One aspect of the invention relates to a process for producing cyclic Cs compounds including cyclopentadiene.
- the process comprises the step of contacting an acyclic Cs feedstock, defined herein, with a formulated catalyst composition, discussed herein, under acyclic Cs conversion conditions effective to convert at least part of the acyclic Cs feedstock to produce an effluent comprising one or more cyclic C 5 compounds.
- the acyclic Cs feedstock comprises acyclic Cs hydrocarbons and optionally hydrogen, a light hydrocarbon or a mixture thereof.
- the acyclic C 5 conversion conditions for the process of this invention include at least a temperature of 450°C to 650°C.
- the molar ratio of the optional hydrogen co-feed to the acyclic C 5 feedstock is in the range of 0.01 to 3.
- the molar ratio of the optional light hydrocarbon co-feed to the acyclic C 5 feedstock is in the range of 0.01 to 5.
- the acyclic C 5 feedstock can have a partial pressure in the range of 3 psia to 100 psia at the reactor inlet (21 to 689 kPa-a).
- the acyclic C 5 feedstock can have a weight hourly space velocity in the range from 1 hr 1 to 50 hr 1 .
- the acyclic C 5 feedstock useful in the invention herein is obtainable from crude oil or natural gas condensate, and can include cracked C 5 (in various degrees of unsaturation: alkenes, dialkenes, alkynes) produced by refining and chemical processes, such as fluid catalytic cracking (FCC), reforming, hydrocracking, hydrotreating, coking, and steam cracking.
- FCC fluid catalytic cracking
- the acyclic Cs feedstock useful in the process of this invention comprises pentane, pentene, pentadiene, and mixtures of two or more thereof.
- the acyclic C 5 feedstock comprises at least 50 wt.%, or 60 wt.%, or 75 wt.%, or 90 wt.% n-pentane, or in the range from 50 wt.% to 100 wt.% n-pentane.
- the acyclic C 5 feedstock optionally, does not comprise C 6 aromatic compounds, such as, benzene, preferably Ce aromatic compounds are present at less than 5 wt.%, preferably less than 1 wt.%, preferably present at less than 0.01 wt.%, preferably at 0 wt.%.
- C 6 aromatic compounds such as, benzene, preferably Ce aromatic compounds are present at less than 5 wt.%, preferably less than 1 wt.%, preferably present at less than 0.01 wt.%, preferably at 0 wt.%.
- the acyclic C 5 feedstock optionally, does not comprise benzene, toluene, or xylene (ortho, meta, or para).
- any benzene, toluene, or xylene (ortho, meta, or para) compounds are present at less than 5 wt.%, preferably less than 1 wt.%, preferably present at less than 0.01 wt.%, preferably at 0 wt.%.
- the acyclic C 5 feedstock optionally, does not comprise C 6+ aromatic compounds, preferably C 6+ aromatic compounds are present at less than 5 wt.%, preferably less than 1 wt.%, preferably present at less than 0.01 wt.%, preferably at 0 wt.%.
- the acyclic Cs feedstock optionally does not comprise C 4- compounds, any C 4 - compounds are present at less than 5 wt.%, preferably less than 1 wt.%, preferably present at less than 0.01 wt.%, preferably at 0 wt.%.
- the formulated catalyst composition comprises a microporous crystalline metallosilicate, preferably, having a constraint index of less than or equal to 12 and a binder, and includes a Group 10 metal of the Periodic Chart or a compound thereof, and, optionally, a metal selected from the rare earth metals and Groups 8, 9, and 11 of the Periodic Chart, mixture or combinations thereof, or a compound thereof, in combination with a Group 1 alkali metal and/or a Group 2 alkaline earth metal or a compound thereof.
- Preferred optional metals are Group 11 metals.
- the Group 11 metal is selected from the group consisting of Cu, Ag, Au, and mixtures of two or more thereof; preferably Cu or Ag.
- a preferred optional Group 9 metal is Rh, which may form an alloy with the Group 10 metal.
- the optional rare earth metal is selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, and mixtures or combinations thereof.
- the alkali metal includes or is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures of two or more thereof.
- the alkaline earth metal is selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, and mixtures of two or more thereof.
- the microporous crystalline metallosilicate has a framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, PER, MRE, MFS, MEL, DDR, EUO, and FAU.
- the microporous crystalline metallosilicate is preferably a microporous crystalline aluminosilicate or zeolite.
- microporous crystalline aluminosilicate is selected from the group consisting of zeolite beta, mordenite, faujasite, Zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, MCM-22 family material, and mixtures of two or more thereof.
- the metallosilicate comprises aluminum and the molar ratio of the alkali metal to aluminum is at least 1. In other embodiments, the molar ratio of the alkaline earth metal to aluminum is at least 1.
- the catalyst composition is made by the method according to the Examples, below.
- the source of platinum, a Group 10 metal included and may be selected from the group consisting of platinum nitrate, chloroplatinic acid, platinous chloride, platinum amine compounds, tetraamine platinum hydroxide, and mixtures of two or more thereof.
- the source of copper, a Group 11 metal includes and may be selected from the group consisting of copper nitrate, copper nitrite, copper acetate, copper hydroxide, copper acetylacetonate, copper carbonate, copper lactate, copper sulfate, copper phosphate, copper chloride, and mixtures of two or more thereof.
- the source of silver also a Group 11 metal, includes and may be selected from the group consisting of silver nitrate, silver nitrite, silver acetate, silver hydroxide, silver acetylacetonate, silver carbonate, silver lactate, silver sulfate, silver phosphate, and mixtures of two or more thereof.
- the formulated catalyst composition is typically made into one or more forms.
- the formulated catalyst is extruded to form an extrudate, particularly into a shaped extrudate having a geometric form.
- Such shaped extrudates may be in a cylindrical form or a lobed form.
- the shaped extrudate having a lobed form may be a symmetrical lobed form, an asymmetric lobed form or a spiral lobed form.
- the formulated catalyst composition may be made into a particle, such as, for example, a spray dried particle, an oil drop particle, a mulled particle, or a spherical particle.
- the formulated catalyst composition may be made into a slurry.
- Such slurry materials typically contain the microporous crystalline metallosilicate, such as zeolite, and a filler such as a silicate.
- the binder may be comprised of one or more of silica, titania, zirconia, metal silicates of Group 1 or Group 13 of the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, surface passivated alumina, and mixtures thereof.
- the use of such slurries are well known in the art of catalysts composition used for wash coating and in catalysts used in fluidized bed processes.
- the binder is a microporous crystalline metallosilicate which may be the same as or comprises the same material as the microporous crystalline metallosilicate primary crystal or may be a different microporous crystalline metallosilicate. That is, the metal silicate of Group 11 or Group 13 of the Periodic Table comprises a microporous crystalline metallosilicate; preferred are highly siliceous microporous crystalline metallosilicate, i.e., microporous crystalline metallosilicate with a silica to metal molar ration greater than 500. In such case, this material is made by the method of comprising the step of at least partially hydrothermally converting an amorphous metallosilicate by contacting with a source of hydroxy to form said self -bound microporous crystalline metallosilicate.
- the surface passivated alumina and/or aluminate is produced by treating the alumina with a silica source, a phosphorous source, a boron source, a zinc source, a gallium source, a titanium source, a Group 1 alkali metal or a compound thereof, a Group 2 alkaline earth metal or a compound thereof, and/or a Group 3 rare earth metal or compound thereof (including Yttrium, Lanthanum, Cerium, Praseodymium, and Neodymium); wherein said treating may include thermal or hydrothermal treatment.
- a silica source a phosphorous source, a boron source, a zinc source, a gallium source, a titanium source, a Group 1 alkali metal or a compound thereof, a Group 2 alkaline earth metal or a compound thereof, and/or a Group 3 rare earth metal or compound thereof (including Yttrium, Lanthanum, Cerium, Praseodymium, and Neodymium); where
- the formulated catalyst composition may be made into a slurry.
- the slurry could be made into the form of a washcoat which is applied to a support.
- a washcoat for example, is formed by deagglomerating the sodium form of the zeolite crystals (e.g., Na-ZSM-5), and then the crystals are contacted with sources of the desired Group 10 metal of the Periodic Chart, such as platinum, platinum and silver or platinum and copper, to form a metal-containing Na- ZSM-5.
- the metal containing Na-ZSM-5 may be heat treated.
- the metal containing zeolite could be mixed with a binder, a matrix material.
- the binder could be a mixture of inorganic oxide materials, such as silica, alumina, titania, zirconia and mixtures thereof, to form an aqueous or non-aqueous slurry.
- the slurry could also contain additives such as defoamers and viscosity modifiers to control the slurry properties. Any surface acidity of alumina in the binder could be either minimized or controlled through the addition of alkaline metals, alkaline earth metals or a source of phosphorus to the slurry.
- the slurry may be dried, calcined, and deployed in the process for producing cyclic C 5 compounds herein.
- the slurry could be applied to the support by means such as spraying or dipping to form a coating on the support.
- the coated support could be dried. Additional coatings could be applied to form a desired thickness of catalytic material on the support.
- the final catalytic material receiving the washcoating could be calcined.
- the slurry can be dried (i.e., pan dried) and calcined directly, it is contemplated that the slurry could be used as a washcoat.
- a washcoat the slurry is deposited on a monolith support or a microlith support or formed into a particle via spray drying or via dropping the slurry into an oil bath, prior to being calcined.
- the monolith or microlith support may comprise or include materials such as, for example, silica, ceria, zirconia, titania, silicon carbide, a hydrotalcite material, such as MG30 (Sasol), tungsten carbide, aluminum nitride, alumina, mixed metal oxide ceramic or mixtures of two or more thereof.
- microporous crystalline metallosilicates e.g., zeolite crystals
- a fluidizable particle for example, may be formed by deagglomerating the sodium form zeolite crystals (e.g., Na-ZSM-5), and then the crystals are contacted with sources of the desired Group 10 metal of the Periodic Chart, such as platinum, platinum and silver or platinum and copper, to form a metal-containing Na-ZSM-5.
- the metal-containing Na-ZSM- 5 may be heat treated.
- the metal-containing zeolite could be mixed with a binder, a matrix material.
- the binder could be a mixture of inorganic oxide materials, such as silica, alumina, titania, zirconia and clays such as kaolin and bentonite to form an aqueous slurry.
- the matrix could be peptized. Any surface acidity of alumina in the binder could be either minimized or controlled through the addition of alkaline metals, alkaline earth metals or a source of phosphorus to the spray dry slurry.
- the slurry may be dried, such as by spray drying and then calcined to form a fluid powder of, for example, less than 200 microns in diameter.
- the acidity of the alumina could be controlled by post-treatment with sources of alkaline metals or alkaline earth metals such as by impregnation.
- sources of alkaline metals or alkaline earth metals such as by impregnation.
- Such materials are well known in the art of catalysts for fluidized bed processes such as ZSM-5 containing additive catalysts for the enhanced production of olefins in FCC (e.g., U.S. Patent Nos. 5,456,821 and 5,888,378) and the production of pyridine and alkylpyridines (e.g., U.S. Patent No. 5,994,550).
- the formulated catalyst composition could be calcined, and deployed in the process for producing cyclic C 5 compounds herein.
- Passivation may be accomplished by either treating the formulated catalyst composition with at least one oxide modifier (with or without the addition of a source of phosphorus) and/or by an additional processing step, such as for example, by steaming.
- the formulated catalyst composition which comprises alumina in Example 20, discussed below, may be treated with an oxide modifier or treated with a phosphorus containing compound.
- the microporous crystalline metallosilicate, such as a zeolite, may be contacted with a source of phosphorus prior to contacting with the binder components.
- a source of phosphorus could be contacted with the aqueous slurry, and then the formulated catalyst composition may be heat treated to yield phosphorus oxide.
- the formulated catalyst composition may be treated with an oxide modifier, such as for example, an additional source of silica either as a component in the aqueous slurry or as part of a treatment of the formulated catalyst composition.
- an oxide modifier such as for example, an additional source of silica either as a component in the aqueous slurry or as part of a treatment of the formulated catalyst composition.
- oxide modifier including oxides of phosphorus and silicon, as well as oxides selected from the metals of Group 1 or Group 2 of the Periodic Chart.
- a similar result could potentially be obtained through a catalyst processing step such as steaming the catalyst for a time and at a temperature which modifies the impact of the alumina on the catalytic performance.
- the formulated catalyst composition of this invention is periodically rejuvenated and/or regenerated to remove coke from the composition which has accumulated during use of the composition and optionally oxychlorinated to redisperse metal.
- the process of this invention may be conducted in any suitable reactor.
- the contacting step of the process may be conducted in one of more reactors.
- Suitable reactors for the process include and may be selected from the group consisting of a fluidized bed, a moving bed, a fixed bed or a tubular reactor, radiantly heated tubular reactor, convectively heated tubular reactor, cyclical fixed bed reactor, circulating fluid bed reactor, radiantly heated fluid bed reactor, convectively heated fluid bed reactor, adiabatic reactor and/or electrically heated reactor.
- the process for producing cyclic Cs compounds of this invention comprises one or more cyclic Cs compositions.
- Such composition comprises one or more cyclic Cs compounds.
- These cyclic C 5 compounds include and are selected from the group consisting of cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, pentene, pentadiene, and reaction products of two or more thereof.
- the cyclic C 5 compounds may be reacted with a substrate to form a product.
- the substrate comprise a double bond.
- Such product includes is one or more of a cyclopentadiene, cyclic olefin copolymers, cyclic olefin polymers, polycyclopentene, ethylidene norbornene, EPDM rubber, alcohols, plasticizers, blowing agents, solvents, octane enhancers, gasoline, unsaturated polyester resins, hydrocarbon resin tackifiers, formulated epoxy resins, polydicyclopentadiene, metathesis polymers of norbornene or substituted norbornenes or dicyclopentadiene, tetracyclodocene, or any combination of two or more thereof.
- the Diels Alder reaction derivatives of cyclopentadiene is or comprises norbornene or substituted norbornenes.
- the product may be made into a useful article.
- Such article comprise any of the products made or derived from the process of this invention.
- the article may be one or more of wind turbine blades, composites containing glass or carbon fibers, and formulated adhesives.
- the total BET was measured by nitrogen adsorption/desorption with a Micromeritics Tristar II 3020 instrument after degassing of the calcined zeolite powders for 4 hrs at 350°C. More information regarding the method can be found, for example, in "Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density", S. Lowell et al., Springer, 2004.
- a mixture with ⁇ 22% solids was prepared from 8,800 g of deionized (DI) water, 600 g of 50% NaOH solution, 26g of 43% sodium aluminate solution, 730 g of n-propyl amine 100% solution, 40 g of ZSM-5 seed crystals, and 3,190 g of Ultrasil silica were mixed and then charged into an autoclave after mixing.
- the mixture had the following molar composition:
- the mixture was mixed and reacted at 230°F (110°C) at 350 rpm for 48 hours.
- the resulting reaction slurry was discharged and stored in container.
- the X-ray diffraction (XRD) pattern (not shown) of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
- the scanning electron microscope (SEM) image of the as-synthesized material shows that the material (not shown) was composed of mixture of crystals with size of ⁇ 1 - 2 micron.
- the resulting ZSM-5 crystals had a S1O2/AI2O3 molar ratio of ⁇ 498, Na % of ⁇ 0.37 wt.%, total surface area(SA)/(micropore SA + mesopore SA) of 468/(422 + 45) m 2 /g.
- Example 1 A sample from Example 1 in the sodium form was used to prepare a 65 wt.% ZSM-5 and 35 wt.% silica extrudate. Sixty-five (65) parts by weight of zeolite were mulled with 35 parts by weight of silica. The silica was equally supplied by Ultrasil silica (obtainable from Evonik) and by Ludox HS-40 (obtainable from Sigma-Aldrich). Sufficient water was added to produce a mull mix of ⁇ 63 wt.% solids. The material was extruded into 1/16" (1.59 mm) cylinders. After drying, was calcined for 6 hours in nitrogen at 900°F (483°C).
- Example 1 Another sample from Example 1 was used to prepare a 65 wt.% Na-ZSM-5 and 35 wt.% silica particle with platinum incorporated in the muller.
- 65 parts by weight of zeolite were mulled with sufficient tetraamine platinum hydroxide to result in -0.31 wt.% Pt on the finished catalyst as measured by XRF.
- This platinum source and zeolite were further mulled with 35 parts by weight of silica.
- the silica was equally supplied by Ultrasil silica and by Ludox HS-40. Sufficient water was added to produce a mull mix of 59 wt.% solids. The material was extruded into 1/16" (1.59 mm) cylinders.
- Example 4 On-Oil Testing of Examples 2 and 3
- Example 2 and Example 3 were evaluated for performance.
- the catalyst 0.5 g crushed and sieved to 20 - 40 mesh
- quartz 1.5 g, 60-80 mesh
- the catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse silicon carbide (SiC) particles.
- the reactor was loaded onto the unit and pressure tested to ensure no leaks.
- the catalysts were dried for 1 hour under helium (He) (100 mL/min, 30 psig, 250°C) then reduced for 4 hours under hydrogen (3 ⁇ 4) (200 mL/min, 30 psig, 500°C).
- the catalyst was then tested for performance with feed of n-pentane, 3 ⁇ 4, and balance He, typically at 550°C -600°C, 5.0 psia C5H12, 1.0 molar H 2 :C 5 Hi 2 , 14.7 h 1 WHSV, and 30 psig total.
- Catalyst stability and regenerability was tested post initial tests at 550-600°C by stripping with H2 (200 mL/min, 30 psig, 650°C) for 5 hours then retesting performance at 600°C.
- Example 5 Synthesis of ZSM-5 Crystals containing Silver
- a mixture with ⁇ 22% solids was prepared from 9,400 g of DI water, 535 g of 50% NaOH solution, 768 g of n-propyl amine (n-Pa) 100% solution, 20 g of ZSM-5 seed crystals, 44 g of silver nitrate (> 99%), and 3,360 g of Sipernat-340 silica were mixed in a container and then charged into an autoclave after mixing.
- the mixture had the following molar composition:
- the mixture was mixed and reacted at 230°F (110°C) at 250 rpm for 48 hours.
- the resulting reaction slurry was discharged and stored in a container.
- the XRD pattern (not shown) of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
- the SEM of the as-synthesized material (not shown) exhibited that the material was composed of mixture of crystals with size of 1 - 2 micron.
- the as-synthesized zeolite crystals had a S1O2/AI2O3 molar ratio of ⁇ 1043, Na of ⁇ 0.22 wt.%, and Ag of -0.95 wt.%.
- a sample of this zeolite crystal in the sodium form was calcined for 6 hours in nitrogen at 900°F (483 °C). After cooling, the sample was re-heated to 900°F (483 °C) in nitrogen and held for three hours. The atmosphere was then gradually changed to 1.1%, 2.1%, 4.2%, and 8.4% oxygen in four stepwise increments. Each step was followed by a thirty minute hold. The temperature was increased to 1000°F (538°C), the oxygen content was increased to 16.8%, and the sample was held at 1000°F (538°C) for 6 hours.
- Example 5 A sample of the zeolite crystals of Example 5 in the sodium form was used to prepare a 65 wt.% zeolite and 35 wt.% silica particle. Sixty-five parts by weight of zeolite were mulled with 35 parts by weight of silica. The silica was equally supplied by Ultrasil silica and by Ludox HS-40. Sufficient water was added to produce a mull mix of -63 wt.% solids. The material was extruded into 1/16" (1.59 mm) cylinders. After drying, was calcined for six hours in nitrogen at 900°F (483°C).
- the sample was re -heated to 900°F (483°C) in nitrogen and held for three hours.
- the atmosphere was then gradually changed to 1.1%, 2.1%, 4.2%, and 8.4% oxygen in four stepwise increments. Each step was followed by a thirty minute hold.
- the temperature was increased to 1000°F (538°C), the oxygen content was increased to 16.8%, and the material was held at 1000°F (538°C) for six hours.
- -0.44 wt.% Pt as measured by XRF was added a portion of the extrudate via incipient wetness impregnation using an aqueous solution of tetraamine platinum hydroxide.
- the catalyst was dried in air at room temperature then at 250°F (121°C), and calcined in air for three hours at 660°F (349°C). The catalyst was then sized to 20/40 mesh for catalytic evaluation.
- Example 6 Another portion of the calcined extrudate of Example 6 was sampled prior to the metal impregnation. - 0.48 wt.% Pt as measured by XRF was added via incipient wetness impregnation using an aqueous solution of tetraamine platinum nitrate. The catalyst was dried in air at room temperature then at 250°F (121 °C), and calcined in air for three hours at 660°F (349°C). The catalyst was then sized to 20/40 mesh for catalytic evaluation.
- Example 8 On-Oil Testing of Examples 5 to 7
- the catalyst sample of Example 5 was evaluated as follows. A sample of 0.2 - 0.8 grams was physically mixed with an appropriate amount of high-purity SiC (40-60 mesh) and loaded into a reactor. The amount of SiC was adjusted so that the overall length of the catalyst bed was 6 in. The catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse SiC particles. The reactor was loaded onto the unit and pressure tested to ensure no leaks. The catalyst samples were dried for 2 hours under helium (He) at 200 mL/min, 60 psia, 250°C, then reduced for 4 hour under 3 ⁇ 4 (200 mL/min, 60 psia, 500°C).
- He helium
- a feed consisting of 7.0 psia n-pentane, 7.0 psia 3 ⁇ 4 and balancing He was introduced to the catalyst bed.
- the total pressure was 60 psia.
- the catalyst was de-edged at 550°C for 8 hours at a WHSV of 3000 (g n-pentane/g Pt h 1 ) and then tested at 575°C for 24 hours at a WHSV of 6000 (g n-pentane/g Pt h 1 )-
- the catalyst was de-edged at 550°C for 8 hours and then tested at 575°C for 24 hours.
- a mixture with ⁇ 22% solids was prepared from 8,800 g of DI water, 600 g of 50% NaOH solution, 26g of 43% sodium aluminate solution, 730 g of n-propyl amine 100% solution, 20 g of ZSM-5 seed crystals, and 3,190 g of Sipernat-340 silica were mixed in a container and then charged into an autoclave after mixing.
- the mixture had the following molar composition:
- the mixture was mixed and reacted at 210°F (99°C) at 350 rpm for 72 hours.
- the resulting reaction slurry was discharged and stored in a container.
- the XRD pattern (not shown) of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
- the SEM (not shown) of the as-synthesized material shows that the material was composed of mixture of crystals with size of 0.5 - 1 micron.
- the as-synthesized crystals had a S1O2/AI2O3 molar ratio of ⁇ 467 and Na of ⁇ 0.25 wt.%.
- a sample of the zeolite of Example 9 in the sodium form was used to prepare a 65 wt.% zeolite and 35 wt.% silica composition. Sixty-five parts by weight of zeolite crystals were mulled with 35 parts by weight of silica. The silica was equally supplied by Ultrasil silica and by Ludox HS-40. Sufficient water was added to produce a mull mix of -64 wt.% solids. The material was extruded into 1/16" (1.59 mm) cylinders. After drying, was calcined for 6 hours in nitrogen at 900°F (483 °C).
- the sample was re-heated to 900°F (483 °C) in nitrogen and held for three hours.
- the atmosphere was then gradually changed to 1.1%, 2.1%, 4.2%, and 8.4% oxygen in four stepwise increments. Each step was followed by a thirty minute hold.
- the temperature was increased to 1000°F, the oxygen content was increased to 16.8%, and the material was held at 1000°F for 6 hours.
- Example 10 A portion of the extrudate of Example 10 was impregnated with a solution containing -7.8 parts Dow 550 Silicone per 100 parts of extrudate in decane. The impregnated sample was dried. It was then calcined by heating in nitrogen at 30 degrees F/minute to 1000°F (538°C) and held at 1000°F (538°C) for one hour. The catalyst was cooled to 950°F (510°C). Air was added to 40 vol% air/60 vol% nitrogen and the temperature was raised to 1000°F (538°C) and held for 6 hours.
- Example 12 On- Oil Testing of Example 11
- Example 11 An extrudate sample (0.2 - 0.8 g) of Example 11 was physically mixed with an appropriate amount of high-purity SiC (40-60 mesh) and loaded into a reactor. The amount of SiC was adjusted so that the overall length of the catalyst bed was 6 in. The catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse SiC particles. The reactor was loaded onto the unit and pressure tested to ensure no leaks. The catalyst was dried for 2 hour under He (200 mL/min, 60 psia, 250°C) then reduced for 4 hour under H 2 (200 mL/min, 60 psia, 500°C).
- a feed consisting of 5.0 psia 1-pentene, 10.0 psia 3 ⁇ 4 and balancing He was introduced to the catalyst bed.
- the total pressure was 60 psia.
- the catalyst was de-edged at 550°C for 8 hours at a WHSV of 3000 (g 1-pentene/g Pt h 1 ) and then tested at 575°C for 24 hours at a WHSV of 6000 (g 1-pentene/g Pt h 1 )-
- the zeolite crystals of Example 9 in the sodium form was used to prepare a 65 wt.% zeolite and 35 wt.% silica particle. 65 parts by weight of zeolite were mulled with 35 parts by weight of silica. The silica was equally supplied by Ultrasil silica and by Ludox HS- 40. Sufficient water was added to produce a mull mixture of -62.5 wt.% solids. The mull mixture was extruded into 1/16" (1.59 mm) cylinders extrudates. After drying, the extrudates were heated to 900°F (483 °C) in nitrogen and held for three hours.
- the atmosphere was then gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise increments. Each step was followed by a thirty minute hold.
- the temperature was increased to 1000°F (538°C), the oxygen content was increased to 16.8%, and the material was held at 1000°F (538°C) for 6 hours and cooled.
- a portion of the calcined extrudate was then impregnated sequentially via incipient wetness impregnation.
- the calcined extrudate sample was impregnated with copper (II) nitrate hydrate and dried for 4 hours at 250°F (121°C).
- the calcined extrudate sample was impregnated with tetraamine platinum nitrate and dried.
- the impregnated extrudate was then calcined for three hours in air at 660°F (349°C).
- Sufficient platinum was added to target -0.325 wt.% platinum on the extrudate to form a catalyst and sufficient copper was added to target a - 3 : 1 molar copper: platinum ratio.
- a 20 gram portion of the calcined extrudate was impregnated with copper (II) nitrate hydrate and dried for 4 hours at 250°F (121 °C). It was then impregnated with tetraamine platinum nitrate and dried.
- the impregnated extrudate was dried at 250°F (121°C), and then calcined for three hours in air at 660°F (349°C) to form a catalyst that contained -0.31 wt.% Cu and -0.32 wt.% Pt by XRF.
- Example 15 On- Oil Testing of Examples 13 and 14
- the catalyst samples (0.2 - 0.8 g) of Examples 13 and 14 were physically mixed with an appropriate amount of high-purity SiC (40-60 mesh) and loaded into a reactor. The amount of SiC was adjusted so that the overall length of the catalyst bed was 6 in. The catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse SiC particles. The reactor was loaded onto the unit and pressure tested to ensure no leaks. Each catalyst sample was dried for 2 hour under He (200 mL/min, 60 psia, 250 °C) then reduced for 4 hour under 3 ⁇ 4 (200 mL/min, 60 psia, 500°C).
- the catalyst was de-edged at 550°C for 8 hours at a WHSV of 3000 (g 1-pentene/g Pt h 1 ) and then tested at 575°C for 24 hours at a WHSV of 6000 (g 1-pentene/g Pt h 1 )-
- the zeolite of Example 9 in the sodium form was calcined for 6 hours in nitrogen at 900°F (483°C). After cooling, the sample was re-heated to 900°F (483°C) in nitrogen and held for three hours. The atmosphere was then gradually changed to 1.1%, 2.1%, 4.2%, and 8.4% oxygen in four stepwise increments. Each step was followed by a thirty minute hold. The temperature was increased to 1000°F (538°C), the oxygen content was increased to 16.8%, and the material was held at 1000°F (538°C) for 6 hours. A portion of the sample was impregnated with copper (II) nitrate hydrate and dried for 4 hours at 250°F (121°C).
- the impregnated extrudate was dried at 250°F (121 °C) then calcined for 1 hour in air at 610°F (321 °C).
- the catalyst contained -0.89 wt.% Cu and -0.58 wt.% Pt by XRF.
- Example 14 A portion of the same extruded and calcined extrudate as described in Example 14 was impregnated with copper (II) nitrate hydrate and dried for 4 hours at 250°F (121°C). It was then impregnated with tetraamine platinum nitrate and dried. The impregnated extrudate was dried at 250°F (121°C), then calcined for three hours in air at 660°F (349°C). The catalyst contained -0.62 wt.% Cu and -0.33 wt.% Pt by XRF.
- Example 18 On- Oil Testing of Examples 16 and 17
- the catalyst samples (0.2 - 0.8 g) of Examples 16 and 17 were each physically mixed with an appropriate amount of high-purity SiC (40-60 mesh) and loaded into a reactor. The amount of SiC was adjusted so that the overall length of the catalyst bed was 6 in. The catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse SiC particles. The reactor was loaded onto the unit and pressure tested to ensure no leaks. The catalyst samples were dried for 2 hours under He (200 mL/min, 60 psia, 250°C) then reduced for 4 hour under 3 ⁇ 4 (200 mL/min, 60 psia, 500°C).
- a feed consisting of 5.0 psia 1-pentene, 10.0 psia 3 ⁇ 4 and balancing He was introduced to the catalyst bed.
- the total pressure was 60 psia.
- the catalyst was de-edged at 550°C for 8 hours at a WHSV of 3000 (g 1-pentene/g Pt h 1 ) and then tested at 575°C for 24 hours at a WHSV of 6000 (g 1-pentene/g Pt h 1 )-
- Example 19 Synthesis of ZSM-5 of -450: 1 Si02/A1203 molar ratio and -0.3 micron crystal size.
- a mixture with - 22 wt.% solids was prepared from 8,800 g of DI water, 600 g of 50% NaOH solution, 26g of 43% sodium aluminate solution, 730 g of n-propyl amine 100% solution, 20 g of ZSM-5 (Si/ Ah - 50/1) seed crystals, and 3,190 g of Sipernat-340 silica were mixed in a 5-gal pail container and then charged into a 5-gal autoclave after mixing.
- the mixture had the following molar composition:
- the mixture was mixed and reacted at 210°F (99°C) at 350 rpm for 48 hours.
- the resulting reaction slurry was discharged and stored in a container.
- the XRD pattern (not shown) of the as-synthesized material showed the typical pure phase of ZSM-5 topology.
- the SEMs (not shown) of the as-synthesized material shows that the material was composed of mixture of crystals with uniform crystal size of ⁇ 0.3 micron.
- the as-synthesized Na-ZSM-5 crystals had a S1O2/AI2O3 molar ratio of ⁇ 450 and Na of ⁇ 0.18 wt.%.
- This example describes the preparation of a fluid catalyst slurry suitable for spray drying into fluidizable catalyst particles.
- a portion of the as-synthesized Na-ZSM-5 zeolite crystals of Example 19 was calcined and then impregnated sequentially with both 0.46 wt.% copper via copper nitrate and 0.50 wt.% platinum via tetraamine platinum nitrate.
- the metal- modified zeolite crystals were then calcined at 660°F (349°C) for three hours, and then incorporated into a slurry.
- An aqueous fluid catalyst slurry was prepared by mixing 40 wt.% of this Na-ZSM-5, 30 wt.% of a kaolin clay, and 30 wt.% of a binder composed of 5 parts by weight silica (Ludox LS, obtainable from Sigma-Aldrich) and 1 part by weight formic acid peptized alumina (Condea Pural SBIII, obtainable from Sasol).
- the slurry was dried. After drying, the catalyst sample was calcined in air at 900°F (349°C) for three hours.
- Example 21 On- Oil Testing of Example 20
- the catalyst sample of Example 20 was evaluated as follows. A sample of 0.2 - 0.8 grams was physically mixed with an appropriate amount of high-purity SiC (40-60 mesh) and loaded into a reactor. The amount of SiC was adjusted so that the overall length of the catalyst bed was 6 in. The catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse SiC particles. The reactor was loaded onto the unit and pressure tested to ensure no leaks. The catalyst samples were dried for 2 hours under helium (He) (200 niL/min, 60 psia, 250°C) then reduced for 4 hour under H 2 (200 niL/min, 60 psia, 500°C).
- He helium
- a feed consisting of 7.0 psia n-pentane, 7.0 psia H 2 and balancing He was introduced to the catalyst bed.
- the total pressure was 60 psia.
- the catalyst was de-edged at 550°C for 8 hours at a WHSV of 3000 (g n-pentane/g Pt h 1 ) and then tested at 575°C for 24 hours at a WHSV of 6000 (g n-pentane/g Pt h 1 )-
- This example describes the preparation of a wash coat slurry suitable for wash coating onto monoliths, microliths, or other materials.
- Another portion of the as-synthesized Na-ZSM-5 zeolite crystals of Example 19 was calcined and then impregnated sequentially with both 0.46 wt.% copper via copper nitrate and 0.50 wt.% platinum via tetraamine platinum nitrate.
- the metal-modified zeolite crystals were then calcined at 660°F (349°C) for three hours, and then incorporated into a slurry.
- An aqueous fluid slurry was prepared by mixing 60 wt.% of the Na-ZSM-5 of Example 19 and 40 wt.% silica using a mixture of both a colloidal silica (30 wt.%, obtainable from Alfa Aesar) and a fumed silica (10 wt.%, Aerosil 200 obtainable from Evonik Industries). The slurry was dried. After drying, the catalyst sample was calcined in air at 900°F (349°C) for three hours.
- Example 23 On-Oil Testing of Example 22
- the catalyst sample of Example 22 was evaluated as follows. A sample of 0.2 - 0.8 grams was physically mixed with an appropriate amount of high-purity SiC (40-60 mesh) and loaded into a reactor. The amount of SiC was adjusted so that the overall length of the catalyst bed was 6 in. The catalyst bed was held in place with quartz wool and the reactor void space was loaded with coarse SiC particles. The reactor was loaded onto the unit and pressure tested to ensure no leaks. The catalyst samples were dried for 2 hours under helium (He) (200 niL/min, 60 psia, 250°C) then reduced for 4 hour under H 2 (200 niL/min, 60 psia, 500°C).
- He helium
- the catalyst was de-edged at 550°C for 8 hours at a WHSV of 3000 (g n-pentane/g Pt h 1 ) and then tested at 575°C for 24 hours at a WHSV of 6000 (g n-pentane/g Pt h 1 ).
- the cyclopentadiene yield (C%) and selectivity, defined as the cyclo-Cs yield (C%) divided by the sum of Ci - C 4 yields (C%), for this Example 23 over the first 15 hours of testing are 13.0% and 8.9%, respectively.
- a process for producing cyclic C 5 compounds including cyclopentadiene comprising the step of contacting an acyclic C5 feedstock with a formulated catalyst composition under acyclic C5 conversion conditions effective to convert at least part of said acyclic C5 feedstock to produce an effluent comprising one or more cyclic C5 compounds, wherein said acyclic C5 feedstock comprises acyclic C5 hydrocarbons and optionally hydrogen, a light hydrocarbon or a mixture thereof, and said formulated catalyst composition comprises:
- microporous crystalline metallosilicate is a microporous crystalline aluminosilicate.
- microporous crystalline aluminosilicate is selected from the group consisting of zeolite beta, mordenite, faujasite, Zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM- 58, MCM-22 family material, and mixtures of two or more thereof.
- said binder comprises one or more of silica, titania, zirconia, metal silicates of Group 1 or Group 13 of the Periodic Table, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, surface passivated alumina, and mixtures thereof.
- alkali metal is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures of two or more thereof.
- alkaline earth metal is selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, and mixtures of two or more thereof.
- a cyclic C5 composition comprising one or more cyclic C5 compounds made by the process of any one of the preceding numbered embodiments.
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Abstract
L'invention concerne un procédé de conversion d'une charge d'alimentation en C5 acyclique en un produit contenant des composés en C5 cycliques, notamment du cyclopentadiène. L'invention concerne également des compositions catalytiques formulées destinées à être utilisées dans ledit procédé. Le procédé consiste notamment à mettre en contact la charge d'alimentation et, éventuellement, de l'hydrogène dans des conditions de conversion de C5 acyclique en présence d'une composition catalytique pour former ledit produit. La composition catalytique comprend un métallosilicate cristallin microporeux, un métal du groupe 10 ou un composé de celui-ci, un liant, éventuellement, un métal choisi dans le groupe constitué par des métaux de terres rares, des métaux des groupes 8, 9 ou 11, des mélanges ou des combinaisons de ceux-ci, ou un composé de ceux-ci, en combinaison avec un métal alcalin du groupe 1 ou un composé de celui-ci et/ou un métal alcalino-terreux du groupe 2 ou un composé de celui-ci.
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Citations (5)
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US5284986A (en) * | 1988-06-24 | 1994-02-08 | Mobil Oil Corporation | Upgrading of normal pentane to cyclopentene |
US6429339B1 (en) * | 1998-05-28 | 2002-08-06 | Basf Aktiengesellschaft | Method for producing cyclopentanone |
US20090036692A1 (en) * | 2005-06-30 | 2009-02-05 | Asahi Kasei Chemicals Corporation | Process for Production of Substituted Cyclopentanone |
US20130211082A1 (en) * | 2010-07-19 | 2013-08-15 | Onyx Pharmaceuticals, Inc. | Synthesis of Cyclopentaquinazolines |
US20160046553A1 (en) * | 2013-04-05 | 2016-02-18 | Mitsui Chemicals, Inc. | Process for producing cyclohexanone compound |
-
2018
- 2018-05-02 WO PCT/US2018/026783 patent/WO2018204036A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284986A (en) * | 1988-06-24 | 1994-02-08 | Mobil Oil Corporation | Upgrading of normal pentane to cyclopentene |
US6429339B1 (en) * | 1998-05-28 | 2002-08-06 | Basf Aktiengesellschaft | Method for producing cyclopentanone |
US20090036692A1 (en) * | 2005-06-30 | 2009-02-05 | Asahi Kasei Chemicals Corporation | Process for Production of Substituted Cyclopentanone |
US20130211082A1 (en) * | 2010-07-19 | 2013-08-15 | Onyx Pharmaceuticals, Inc. | Synthesis of Cyclopentaquinazolines |
US20160046553A1 (en) * | 2013-04-05 | 2016-02-18 | Mitsui Chemicals, Inc. | Process for producing cyclohexanone compound |
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