WO2022060353A1 - Catalyseur zéolithique de type mww à haute activité pour l'alkylation d'oléfines légères avec de l'isoparaffine - Google Patents

Catalyseur zéolithique de type mww à haute activité pour l'alkylation d'oléfines légères avec de l'isoparaffine Download PDF

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WO2022060353A1
WO2022060353A1 PCT/US2020/050945 US2020050945W WO2022060353A1 WO 2022060353 A1 WO2022060353 A1 WO 2022060353A1 US 2020050945 W US2020050945 W US 2020050945W WO 2022060353 A1 WO2022060353 A1 WO 2022060353A1
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catalyst
extrudate
zeolite
mcm
emm
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PCT/US2020/050945
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English (en)
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Micaela TABORGA CLAURE
Doron Levin
Ivy D. Johnson
Pavel Kortunov
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Exxonmobil Research And Engineering Company
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Priority to PCT/US2020/050945 priority Critical patent/WO2022060353A1/fr
Publication of WO2022060353A1 publication Critical patent/WO2022060353A1/fr

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    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange

Definitions

  • This application relates to catalyst compositions and methods of preparing catalyst compositions for the alkylation of isoparaffins and, in some applications, the production of high octane alkylates, such as for use as a fuel additive.
  • alkylation of isoparaffins is an important refinery process for the production of high octane alkylate as a blend component for gasoline.
  • Alkylation involves the addition of an alkyl group to an organic molecule.
  • an isoparaffin can be reacted with an olefin to provide an isoparaffin of higher molecular weight.
  • alkylation often involves the reaction of C3-C5 olefins with, for example, isobutane in the presence of an acidic catalyst to form alkylates.
  • Alkylates are valuable blending components for the manufacture of premium gasolines due to their high octane ratings, low sulfur, low olefin, and low aromatic content, and low vapor pressure.
  • liquid acids such as hydrofluoric acid (HF) or sulfuric acid (H2SO4) as catalysts under relatively low temperature conditions.
  • HF hydrofluoric acid
  • H2SO4 sulfuric acid
  • An alternative to liquid acids are solid acids, such as zeolites.
  • zeolites such as zeolites.
  • the MWW framework solid acid catalysts may be used for catalytic alkylation of an olefin with an isoparaffin comprising contacting an olefin feed with an isoparaffincontaining feed under alkylation conversion conditions at a temperature at least equal to the critical temperature of the principal isoparaffin component of the feed.
  • These solid acid catalysts offer enhanced catalyst stability when compared to faujasite-based alkylation catalysts, which can reduce or eliminate the need for frequent catalyst regenerations.
  • embodiments of the present disclosure are directed to catalysts for the alkylation of olefins with isoparaffins include catalysts containing a zeolite having an MWW framework and a collidine uptake of greater than 75 pmol/cm3.
  • embodiments of the present disclosure are directed to catalyst compositions include a zeolite having an MWW framework and a collidine uptake of greater than 75 pmol/cm3, wherein the catalyst composition is prepared by a method including: extruding the catalyst composition to form an extrudate; exchanging the extrudate with an exchange fluid to form an exchanged extrudate; performing a pre-calcination on the exchange extrudate in which the exchanged extrudate is heated at about 350 °C or greater under an inert atmosphere; and calcining the exchanged extrudate at a temperature of about 350 °C or greater under an atmosphere comprising air to form the catalyst composition.
  • embodiments of the present disclosure are directed to catalysts for the alkylation of olefins with isoparaffins, the catalyst including a zeolite having an MWW framework and a 2,2,4-trimethylpentane uptake of greater than 75 pmol/cm3.
  • FIG. 1 is a graphical representation showing isobutane alkylation activity as a function of collidine uptake for a number of catalyst compositions that may incorporate one or more principles of the present disclosure.
  • FIG. 2 is a graphical representation showing isobutane alkylation activity as a function of 2,2,4-trimethylpentane (TMP) uptake for a number of catalyst compositions that may incorporate one or more principles of the present disclosure.
  • TMP 2,2,4-trimethylpentane
  • This application relates to catalysts and catalyst compositions for alkylation of isoparaffins and, in particular, to systems, methods, and apparatuses for alkylation of isoparaffins with olefins to produce high octane alkylates, such as for use as a fuel additive.
  • Cn compound (olefin or paraffin) where n is a positive integer, e.g., 1, 2, 3, 4, 5, etc., means a compound having n number of carbon atom(s) per molecule.
  • Cn+ means a compound having at least n number of carbon atom(s) per molecule.
  • Cn- means a compound having no more than n number of carbon atom(s) per molecule.
  • critical point refers to the liquid-vapor end point of a phase equilibrium curve that designates conditions under which a liquid and vapor may coexist. At temperatures higher than the critical point (a “critical temperature”) a gas cannot be liquefied by pressure alone. At temperatures and pressures higher than the critical point, the material is a supercritical fluid.
  • critical point for isobutane is about 134.6°C and about 3650 kPa
  • critical point for isopentane is about 187.2°C and about 3378 kPa.
  • isobutane is the principal component in a feedstock consisting of 2-butene and isobutane in an isobutane/2 -butene weight ratio of 50/1.
  • the term “heavy olefin,” and grammatical variants thereof, refers to a C8+ hydrocarbon containing at least one carbon-carbon double bond.
  • the term “light olefin,” and grammatical variants thereof, refers to a C2-C7 hydrocarbon containing at least one carbon-carbon double bond.
  • inert gas refers to a gas that does not undergo reaction in the presence of a catalyst, when there is no olefin present.
  • the term “MWW framework type,” and grammatical variants thereof, refers to a type of crystalline microporous material that includes at least two independent sets of 10-membered ring channels and has composite building units of d6r (t-hpr) and mel as defined and discussed in Compendium of Zeolite Framework Types. Building Schemes and Type Characteristics, Henk van Koningsveld (Elsevier, Amsterdam, 2007), incorporated herein by reference in its entirety.
  • the term “molecular sieve,” and grammatical variants thereof refers to a substance having pores of molecular dimensions that permit the passage of molecules below a certain size. Examples of molecular sieves include but are not limited to zeolites, silicoaluminophosphate molecular sieves, and the like.
  • crystalline microporous material of the MWW framework type refers to one or more of: (a) 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.
  • molecular sieves made from a second degree building block being a 2-dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, in one or more aspects, 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, where the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of MWW framework topology unit cells, the stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; and
  • accessible volume refers to the unit cell volume remaining after the van der Waals atomic sphere volumes are subtracted.
  • the accessible volume is reported as a percentage of accessible volume out of the total volume.
  • the accessible volume is determined using the water absorption test of ASTM C830.
  • BET surface area refers to the Brunauer-Emmett-Teller method of measuring surface area of a solid via adsorption of gas molecules.
  • the BET surface area is calculated using the ISO 9277 standard.
  • Catalyst compositions disclosed here include zeolite catalysts having physical properties that are suitable for use in alkylation applications, particularly for the alkylation reactions between isoparaffins and olefins.
  • catalyst compositions can be characterized by their alkylation activity, which has been correlated according to the catalyst composition’s ability to uptake a reference molecule, such as collidine or 2,2,4-trimethylpentane (TMP).
  • a reference molecule such as collidine or 2,2,4-trimethylpentane (TMP).
  • One class of catalysts suitable for alkylation applications described herein includes a molecular sieve or zeolite.
  • the molecular sieve may have a Constraint Index of about 5 or less, and may be a crystalline microporous material of the MWW framework type.
  • Crystalline microporous materials of the MWW framework type can include those molecular sieves having an X-ray diffraction pattern comprising 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.
  • Crystalline microporous materials of the MWW framework type include molecular sieves having natural tiling units of t-dac-1, t-euo, t-hpr, t-kah, t-kzd, t-mel, t-mww-1, t-mww-2, and t-srs as defined and discussed in Three-periodic Nets and Tilings: Natural Tilings for Nets, V. A. Blatov, O. Delgado- Friedrichs, M. O'Keeffe and D. M. Proserpio, Acta Crystallogr. A 63, 418-425 (2007), incorporated herein by reference in its entirety.
  • the crystalline microporous material is of the MWW framework type, such as a zeolite.
  • crystalline microporous materials of the MWW framework type include, but are not limited to, MCM-22 (U.S. Patent No. 4,954,325, incorporated herein by reference in its entirety), PSH-3 (U.S. Patent No. 4,439,409, incorporated herein by reference in its entirety), SSZ-25 (U.S. Patent No. 4,826,667, incorporated herein by reference in its entirety), ERB-1 (European Patent No. 0293032), ITQ-1 (U.S. Patent No. 6,077,498, incorporated herein by reference in its entirety), ITQ-2 (International Publication No.
  • MCM-36 U.S. Patent No. 5,250,277, incorporated herein by reference in its entirety
  • MCM-49 U.S. Patent No. 5,236,575, incorporated herein by reference in its entirety
  • MCM-56 U.S. Patent No. 5,362,697, incorporated herein by reference in its entirety
  • UZM-8 U.S. Patent No. 6,756,030, incorporated herein by reference in its entirety
  • UZM-8HS U.S. Patent No. 7,713,513, incorporated herein by reference in its entirety
  • UZM-37 U.S. Patent No. 7,982,084, incorporated herein by reference in its entirety
  • EMM-10 U.S.
  • Patent No. 7,842,277 incorporated herein by reference in its entirety
  • EMM-12 U.S. Patent No. 8,704,025, incorporated herein by reference in its entirety
  • EMM-13 U.S. Patent No. 8,704,023, incorporated herein by reference in its entirety
  • UCB-3 U.S. Patent No. 9,790, 143B2, incorporated herein by reference in its entirety
  • MIT-1 Lio, et. al., Chem Sci. 2015 November 1; 6(11): 6320-6324, incorporated herein by reference in its entirety
  • Catalysts and catalyst compositions disclosed herein can include “self-bound” compositions that contain no, or substantially no, binder or additives.
  • Self-bound catalysts (alternatively referred to as unbound or binder-free catalysts), are catalysts that do not contain a separately added matrix or binder material, are useful and may be produced by the extrusion method described in U.S. Pat. No. 4,582,815, to which reference is made for a description of the method and of the extruded products obtained by its use.
  • the method described herein enables extrudates having high crush strength to be produced on conventional extrusion equipment and accordingly, the method is eminently suitable for producing the high activity self-bound catalysts.
  • catalysts can “consist essentially of’ zeolite, and include no binder or additives and containing only unavoidable levels of impurities or non-active substances.
  • Zeolite catalysts may be contaminated with other crystalline materials in some embodiments, such as ferrierite or quartz. These contaminants may be present in quantities of about 10 wt% or less, such as about 5 wt% or less.
  • the crystalline microporous material of the MWW framework type employed may be an aluminosilicate material having a silica to alumina molar ratio of about 10 or more, such as from about 10 to about 50.
  • Any suitable hydrogenation catalyst may be used as a co-catalyst, including noble metals, such as Pd, Pt, Rh, Ru, Ir, Os, Ag, Au; or non-noble metals, such as Mo, Co, Ni, Fe; and any combination thereof, such as the combination of two noble metals, two non-noble metals, or a combination of noble and non-noble metals.
  • noble metals such as Pd, Pt, Rh, Ru, Ir, Os, Ag, Au
  • non-noble metals such as Mo, Co, Ni, Fe
  • any combination thereof such as the combination of two noble metals, two non-noble metals, or a combination of noble and non-noble metals.
  • the co-catalyst may be supported, suitable support materials may include clay, alumina, silica, titania, zirconia, aluminosilicates, zeolites, carbon, and combination thereof.
  • the silica support can be an amorphous silica support.
  • the support can be a mesoporous crystalline or semi-crystalline support material. Examples of mesoporous silica materials suitable for use as a support can include, but are not limited to, zeolites, such as MCM-41, other M41S structures, SBA-15, and the like, and any combination thereof.
  • a silica support may be modified with alumina and the amount of alumina added to modify a silica support may vary.
  • the amount of alumina added to a silica support can be about 0.3 wt% to about 3.0 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 1.8 wt%, about 0.75 wt% to about 1.6 wt%, about 1.0 wt% to about 1.5 wt%, about 1.1 wt% to about 1.5 wt%, or about 1.25 wt% to about 1.5 wt%, encompassing any value and subset therebetween.
  • the amount of alumina added to a silica support can be about 0.3 wt% to about 2.5 wt%, or about 1.0 wt% to about 2.5 wt%, or about 1.1 wt% to about 2.2 wt%, encompassing any value and subset therebetween.
  • the amount of the one metal can be about 0.01 wt% or more based on the total weight of the co-catalyst and support material (if any), for example about 0.05 wt% or more, or about 0.1 wt% or more, or about 0.5 wt% or more, encompassing any value and subset therebetween.
  • the amount of hydrogenation metal can be about 5.0 wt% or less based on the total weight of the co-catalyst and support material (if any), for example about 3.5 wt% or less, about 2.5 wt% or less, about 2.0 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.9 wt% or less, about 0.75 wt% or less, or about 0.6 wt% or less.
  • the amount of hydrogenation metal can be about 0.05 wt% to about 5.0 wt%, or about 0.1 wt% to about 2.5 wt%, or about 0.1 wt% to about 2.0 wt%, or about 0.1 wt% to about 1.5 wt%, or about 0.2 wt% to about 5.0 wt%, or about 0.2 wt% to about 2.5 wt%, or about 0.2 wt% to about 1.5 wt%, or about 0.5 wt% to about 5.0 wt%, or about 0.5 wt% to about 2.5 wt%, or about 0.5 wt% to about 1.5 wt% based on the total weight of the co-catalyst and support material (if any), encompassing any value and subset therebetween.
  • the amount of hydrogenation metal can be about 0.05 wt% to about 5.0 wt%, or about 0.1 wt% to about 2.0 wt%, or about 0.2 wt% to about 1.0 wt% based on the total weight of the co-catalyst and support material (if any), encompassing any value and subset therebetween.
  • the collective amount of hydrogenation metals can be about 0.05 wt% or more based on the total weight of the co-catalyst, such as about 0.1 wt% or more, about 0.2 wt% or more, about 0.3 wt% or more, about 0.4 wt% or more, or about 0.5 wt% or more based on the total weight of the co-catalyst and support material (if any), encompassing any value and subset therebetween.
  • the collective amount of hydrogenation metals can be about 5.0 wt% or less based on the total weight of the co-catalyst and support material (if any), for example about 3.5 wt% or less, about 2.5 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.9 wt% or less, about 0.75 wt% or less, or about 0.6 wt% or less.
  • the combined amount of metal(s) can be about 0.05 wt% to about 5.0 wt%, or about 0.05 wt% to about
  • the amount of metal(s) can be about 0.05 wt% to about 5.0 wt%, or about 0.1 wt% to about 2.5 wt%, or about 0.2 wt% to about 5.0 wt% based on the total weight of the co-catalyst and support material (if any) , encompassing any value and subset therebetween.
  • the ratio of Pt to Pd can be from about 1:3 to about 4: 1, or from about 1:4 to about 3:1, or from about 1:2 to about 4: 1 , or from about 1 :2 to about 3:1, encompassing any value and subset therebetween.
  • the amounts of metal(s) may be measured by methods specified by ASTM for individual metals, including but not limited to, atomic absorption spectroscopy (AAS).
  • the weight ratio of co-catalyst to catalyst may be from about 1:1000 to about 1:1, about 1:500 to about 1:2, about 1:100 to about 1:5, about 1:100 to about 1:10, or about 1:50 to about 1:10, encompassing any value and subset therebetween.
  • the hydrogenation metal may be added directly to the catalyst composition rather than a co-catalyst. Metals may be added to the catalyst composition by any suitable technique known to those skilled in the art, such as impregnation.
  • the amount of the hydrogenation metal can be about 0.01 wt% or more based on the total weight of the catalyst composition and support material (if any), for example about 0.05 wt% or more, or about 0.1 wt% or more, or about 0.5 wt% or more, encompassing any value and subset therebetween.
  • Catalysts and co-catalysts suitable for use in the systems and processes described include an optional binder.
  • Binder materials may include inorganic oxides, such as alumina, silica, titania, zirconia, and mixtures and compounds thereof, may be present in the catalyst in amounts about 60 wt% or less, for example about 50 wt% or less, such as about 40 wt% or less, for example about 30 wt% or less, such as about 20 wt% or less.
  • a non-alumina binder is present, the amount employed may be as little as about 1 wt%, or about 5 wt% or more, for example about 10 wt% or more.
  • a silica binder is employed such as disclosed in U.S. Pat. No. 5,053,374, incorporated herein by reference in its entirety.
  • a zirconia or titania binder is used.
  • a catalyst composition may include zeolite and optional binder.
  • a catalyst composition may include zeolite in about 30 wt% or greater, such as about 40 wt% or greater, about 50 wt% or greater, about 60 wt% or greater, about 70 wt% or greater, about 80 wt% or greater, about 82 wt% or greater, about 84 wt% or greater, about 86 wt% or greater, about 88 wt% or greater, about 90 wt% or greater, about 92 wt% or greater, about 94 wt% or greater, about 95 wt% or greater, about 96 wt% or greater, about 97 wt% or greater, about 98 wt% or greater, about 99 wt% or greater, or about 99.5 wt% or greater, such as from about 40 wt% to about 99.99 wt%, from about 50 wt% to about 99.95 wt%, from about 60 wt% to about
  • Catalyst compositions disclosed herein can be prepared as an extrudate that is conditioned to optimize activity when employed a catalytic reactor.
  • catalyst preparation may the formation of a catalyst extrudate and a conditioning process that includes at least the general steps of cationic exchange, pre-calcination, and calcination.
  • Catalyst compositions can be prepared by introducing a zeolite, with or without binders or other additives, and a solvent such as water to form a slurry that is extruded to form an extrudate.
  • a solvent such as water
  • the extrudate is dried before further conditioning.
  • the catalyst extrudate can be treated with an exchange fluid containing a suitable source of cations.
  • exchange fluid may result in the formation of a layered oxide and enhanced interlayer separation.
  • the interlayer separation may be dependent upon the steric volume of the cation introduced.
  • a series of cation exchanges can be carried out. For example, a cation may be exchanged with a cation of greater size, thus increasing the interlayer separation in a step-wise fashion, as compared to cation exchange performed using a cation of smaller size.
  • water may be trapped between the layers of the zeolite.
  • Such exchange fluids contain cations that exchange with cations associated with the zeolite framework, such as sodium cations.
  • the catalyst composition of the present disclosure may be prepared by treating the mixture of zeolite and optional binder with a swelling agent which may cause the zeolite layers to swell or separate and are removable by calcination.
  • Suitable exchange fluids include sources of cations, such as quaternary ammonium cations, such as organoammonium cations, or inorganic ammonium cations, and any combination thereof.
  • Suitable swelling agents may include, but are not limited to, a source of organic cations such as quaternary organoammonium cations or organophosphonium cations, in order to affect an exchange of interspathic cations.
  • Suitable exchange fluids may include, but are not limited to, aqueous or non-aqueous solutions. Additionally, exchange fluids may include ammonium cations. Also, suitable exchange fluids may have a normality of from about 0.1 N to about 5 N, such as from about 0.2 N to about 4 N, from about 0.4 N to about 3 N, or from about 0.5 N to about 2 N, encompassing any value and subset therebetween.
  • Suitable sources of ammonium cations may include, but are not limited to, ammonium nitrate, ammonium hydroxide, ammonium acetate, ammonium chloride, ammonium carbonate, tetramethylammonium nitrate, tetramethylammonium hydroxide, n-octylammonium nitrate, n- octylammonium hydroxide, cetyltrimethylammonium nitrate, cetyltrimethylammonium hydroxide, and any combination thereof.
  • a pH range of about 4 to about 14, such as about 4.5 to about 13.5, encompassing any value and subset therebetween, is typically employed during treatment with the exchange fluid.
  • the catalyst composition is dried prior to the addition of an exchange fluid. Drying the catalyst composition may include thermal treatment at about 300°C or less (below calcination temperatures). Drying may take place at a temperature of from about 100°C to about 300°C, such as from about 105°C to about 250°C, from about 110°C to about 220°C, from about 115°C to about 200°C, or from about 120°C to about 180°C, encompassing any value and subset therebetween.
  • the catalyst composition is not dried prior to the addition of an exchange fluid and is dried and calcined thereafter.
  • the catalyst composition before drying or calcining may have a solids content of about 50 wt% or less, such as about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, or about 25 wt% or less.
  • Conditioning processes disclosed herein can include a pre-calcination step following cation exchange in which the ion-exchanged catalyst composition is heated in an inert (oxygen- free) atmosphere, which may remove organics and directing agents while minimizing oxidation reactions.
  • pre-calcination may remove about 10%-50% of organics, while any remaining organics are later reduced by subsequent processing such as during calcination.
  • pre-calcination is performed under inert gas conditions, such as in the presence of inert gas such as nitrogen or noble gases including argon.
  • Pre-calcination can be performed at temperatures of at about 350 °C or greater, at about 400 °C or greater, or at about 450 °C or greater.
  • pre-calcination can be performed at a temperature in a range of about 350 °C to about 600oC.
  • Pre-calcination may occur in a time frame of from about 1 minute to about 24 hours, such as from about 5 minutes to about 18 hours, from about 10 minutes to about 12 hours, from about 15 minutes to about 6 hours, from about 20 minutes to about 3 hours, from about 25 minutes to about 2 hours, or from about 30 minutes to about 1 hour, encompassing any value and subset therebetween.
  • catalyst compositions disclosed herein can be calcined by heating the catalyst composition in non-inert gases such as oxygen, hydrogen, or air, or in mixtures with inert gases, for example mixtures of air and nitrogen.
  • non-inert gases such as oxygen, hydrogen, or air
  • inert gases for example mixtures of air and nitrogen.
  • the exchange fluid is decomposed or oxidized by the presence of oxygen or air during calcination. While subatmospheric pressure can be employed for the calcination, atmospheric pressure is typical used simply for reasons of convenience.
  • calcination can be performed at a temperature of about 350°C or greater, about 375 °C or greater, about 400°C or greater, about 425 °C or greater, about 450°C or greater, about 475°C or greater, about 500°C or greater, about 525 °C or greater, or about 550°C or greater, such as from about 250°C to about 1000°C, from about 300°C to about 900°C, from about 350°C to about 800°C, from about 400°C to about 700°C, or from about 450°C to about 600°C, encompassing any value and subset therebetween.
  • calcination can be performed at a temperature in a range of about 350°C to about 600oC.
  • Calcination may occur in a time frame of from about 1 minute to about 72 hours, such as from about 5 minutes to about 48 hours, from about 10 minutes to about 36 hours, from about 15 minutes to about 24 hours, from about 20 minutes to about 20 hours, from about 25 minutes to about 18 hours, or from about 30 minutes to about 16 hours, encompassing any value and subset therebetween.
  • the calcined catalyst composition may include layers, which can exhibit high BET surface area (e.g., greater than 400 m2/g), making them highly useful as catalysts or catalytic supports, for hydrocarbon conversion processes, such as alkylation.
  • a calcined catalyst composition of the present disclosure may exhibit a BET surface area of about 400 m2/g or greater, such as about 450 m2/g or greater, about 500 m2/g or greater, about 550 m2/g or greater, or about 600 m2/g or greater, such as from about 400 m2/g to about 2000 m2/g, from about 450 m2/g to about 1500 m2/g, from about 500 m2/g to about 1000 m2/g, from about 550 m2/g to about 900 m2/g, or from about 600 m2/g to about 800 m2/g, encompassing any value and subset therebetween.
  • the calcined catalyst composition may further exhibit an accessible volume of about 10% or greater, such as 12% or greater, 15% or greater, or 17% or greater, such as from about 10% to about 40%, from about 12% to about 35%, from about 15% to about 30%, or from about 17% to about 25%, encompassing any value and subset therebetween.
  • Catalyst compositions disclosed herein can be characterized on the ability of the catalyst to uptake collidine. While not limited to any particular theory, the ability of the catalyst composition to uptake collidine has been correlated with the catalyst’s ability to alkylate isobutane as discussed in the examples that follow. Collidine uptake can be measured gravimetrically, using commercially available equipment such as the TA Q5000 TGA micro balance. In order to prepare the sample, the catalyst was dried under inert conditions to remove physisorbed water, such as under nitrogen flow at 200°C for 60 minutes. Samples were then exposed to a flow of collidine in N2 for 60 minutes at a collidine vapor pressure of 3 Torr. After collidine adsorption, the sample was treated in flowing nitrogen for 60 minutes at 200 °C prior to measuring the weight uptake of collidine. The dried catalyst weight and the final weight after exposure and subsequent stripping of collidine were recorded and used to calculate the collidine uptake.
  • catalyst compositions disclosed herein have a collidine uptake of greater than about 75 pmol/cm3, greater than about 80 pmol/cm3, or greater than about 100 pmol/cm3.
  • Catalyst compositions disclosed can also have a collidine uptake in a range between 75 pmol/cm3 and 300 pmol/cm3, 80 and 275 pmol/cm3, or 100 pmol/cm3 and 250 pmol/cm3.
  • Catalyst compositions disclosed herein can be characterized on the ability of the catalyst to uptake 2,2,4-trimethylpentane (TMP). While not limited by any particular theory, the ability of the catalyst composition to uptake 2,2,4-TMP has been correlated with the catalyst’s ability to alkylate isobutane as discussed in the examples that follow. 2,2,4-TMP uptake can be measured gravimetrically, using commercially available equipment such as the TA Q5000 TGA micro balance. In order to prepare the sample, the catalyst was dried under nitrogen at 200°C for 75 minutes, and was then allowed to equilibrate to 150°C for 30 minutes.
  • TMP 2,2,4-trimethylpentane
  • 2,2,4- TMP was sparged for 370 minutes at a vapor pressure of 75 Torr. After sparging, the sample was stripped with nitrogen for 325 minutes prior to measuring the weight uptake of 2,2,4-TMP. The dried catalyst weight and the final weight after sparging and stripping were then used to calculate the 2,2,4-TMP uptake value per catalyst weight. The density of the sample was then used to calculate 2,2,4-TMP uptake per volume of catalyst.
  • catalyst compositions disclosed herein have a 2,2,4-TMP uptake of greater than about 100 pmol/cm3, greater than about 150 pmol/cm3, or greater than about 200 pmol/cm3.
  • Catalyst compositions disclosed can also have a 2,2,4-TMP uptake in a range between 75 and 600 pmol/cm3, between 100 pmol/cm3 and 500 pmol/cm3, or between 150 pmol/cm3 and 400 pmol/cm3.
  • Various aspects of the present disclosure can be conducted in any suitable single or multistage reactor, such as one including fixed-beds, moving beds, swing beds, fluidized beds (including turbulent beds), and/or one or more combinations thereof.
  • a reactor stage begins at the point in which olefin is introduced and ends at either an interstage space or where additional olefin is introduced.
  • the various aspects of the present disclosure conduct alkylation using a solid acid catalyst in a multistage reactor.
  • Catalyst compositions can be utilized for the alkylation of isoparaffins, which can include contacting an isoparaffin feed and an olefin feed with a catalyst for the alkylation reaction, where the catalyst is a zeolite having an MWW framework.
  • Alkylation reactions can be carried out under conditions suitable to enable the alkylation reactions, such as at temperatures ranging from 100°C to 250°C, and at pressures ranging from 500 to 1500 psig.
  • Feedstocks useful in the present alkylation process include at least one isoparaffin feed and at least one olefin feed.
  • the isoparaffin feed used in alkylation processes of the present disclosure may have from about 4 to about 8 carbon atoms (about C4 to about C8), encompassing any value and subset therebetween.
  • Representative examples of such isoparaffins include, but are not limited to, isobutane, isopentane, 3 -methylhexane, 2-methylhexane, 2,3-dimethylbutane, and mixture(s) thereof, typically isobutane.
  • the olefin component of the feedstock may include at least one olefin having from about 2 to about 12 carbon atoms (about C2 to about C12), encompassing any value and subset therebetween.
  • Representative examples of such olefins include, but are not limited to, 2-butene, isobutylene, 1 -butene, propylene, ethylene, pentene, hexene, octene, heptene, or mixture(s) thereof.
  • the olefin component of the feedstock is selected from the group consisting of propylene, butene, pentene, and any combination or mixture(s) thereof.
  • the olefin component of the feedstock may include a mixture of propylene and at least one butene, such as 2-butene, where the weight ratio of propylene to butene is from about 0.01:1 to about 150:1, such as from about 0.1:1 to about 1:1, encompassing any value and subset therebetween.
  • the olefin component of the feedstock may include a mixture of propylene and at least one pentene, where the weight ratio of propylene to pentene is from about 0.01:1 to about 150:1, such as from about 0.1: 1 to about 1:1, encompassing any value and subset therebetween.
  • the concentration of olefin feed can be adjusted by, such as, for example, by staged additions thereof. Using staged additions, isoparaffin/olefin feed concentrations (and therefore the I/O ratio) can be maintained at levels to improve conversion and reduce catalyst deactivation.
  • the ratio of isoparaffin to olefin by volume is about 100/1 or greater, about 120/1 or greater, about 140/1 or greater, about 160/1 or greater, about 180/1 or greater, about 200/1 or greater, about 220/1 or greater, about 240/1 or greater, about 260/1 or greater, about 280/1 or greater, or about 300/1 or greater, such as from about 100/1 to about 500/1, or about 120/1 to about 500/1, or about 160/1 to about 480/1, or about 200/1 to about 450/1, or about 220/1 to about 450/1, or about 240/1 to about 420/1, or about 240/1 to about 400/1, encompassing any value and subset therebetween.
  • the production of olefin oligomers increases with lower I/O ratios.
  • an I/O ratio of about 100/1 or greater may be used.
  • the efficiency of the alkylation process can be reduced at higher I/O ratios, due to a large quantity of isoparaffin present in the alkylation product mixture, which is then separated and recycled to the reactor.
  • the separation and recycling of isoparaffin may occur in a distillation apparatus that allows for distillation of isobutane and lighter alkanes from the nC4 and C5+ alkanes and alkenes produced in the reactor (e.g., a deisobutanizer).
  • a higher I/O ratio can provide greater quantities of isobutane and lighter alkanes separated from the alkylation product mixture that can be recycled to the reactor.
  • a hydrogen feed may be fed to the reactor including hydrogen and, in some instances, inert gases to decrease hydrogen concentration within the feed.
  • concentration of hydrogen in the multistage reactor can be adjusted by, e.g., staged additions thereof.
  • hydrogen/isoparaffin feed concentrations can be maintained at levels sufficient to reduce or eliminate olefin oligomers formed in a stage of the multistage reactor.
  • the molar ratio of hydrogen to isoparaffin is from about 1 : 1000 to about 1:1, about 1:500 to about 1:2, or about 1:100 to about 1:5, encompassing any value and subset therebetween.
  • the isoparaffin feed, the olefin feed, and/or the hydrogen feed may be treated to remove catalyst poisons.
  • catalyst poisons may be removed using guard beds with specific absorbents for reducing the level of S, N, and/or oxygenates to values which do not affect catalyst stability, activity, and selectivity.
  • the product of the alkylation reaction (also referred to as the alkylation product mixture) can include: alkanes resulting from the alkylation of isoparaffin with olefin, unreacted isoparaffin, unreacted olefin, olefin oligomers, other byproducts, including other alkanes and alkenes.
  • the product composition of the isoparaffin-olefin alkylation reaction described is dependent on the reaction conditions and the composition of the olefin feed and isoparaffin feed.
  • the product is a complex mixture of hydrocarbons, since alkylation of the feed isoparaffin by the feed olefin is accompanied by a variety of competing reactions including cracking, olefin oligomerization, and/or further alkylation of the alkylate product by the feed olefin.
  • the product may include about 15-35 wt% of C5-C7 hydrocarbons, 50-85 wt% of C8 hydrocarbons and 1-10 wt% of C9+ hydrocarbons.
  • a process can be selective to desirable high octane components so that, in the case of alkylation of isobutane with C3-C4 olefins, the C6 fraction typically includes at least about 40 wt%, such as at least about 70 wt%, of 2,3-dimethyIbutane, the C7 fraction typically includes at least about 40 wt%, such as at least about 80 wt%, of 2,3-dimethyIpentane and the C8 fraction typically includes at least about 50 wt%, such as at least about 70 wt%, of 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, and 2,2,4- trimethylpentane.
  • the C6 fraction typically includes at least about 40 wt%, such as at least about 70 wt%, of 2,3-dimethyIbutane
  • the C7 fraction typically includes at least about 40 wt%, such as at least about 80 wt%, of
  • the product may include about 20-40 wt% of C5 hydrocarbons, about 15- 35 wt% of C9 hydrocarbons, about 20-35 wt% of C8 hydrocarbons, and about 2-10 wt% of C10+ hydrocarbons.
  • a process can be selective to desirable high octane components so that, in the case of alkylation of isobutane with C5 olefins, the C8 and C9 fractions typically include a higher molar ratio of trimethyl isomers to dimethyl isomers, which is beneficial for increasing octane.
  • the molar ratio of trimethylpentane to dimethylhexane can be about 3 or more, such as about 4 to about 5, or about 3 to about 6.
  • the molar ratio of trimethylhexane to dimethylheptane can be about 1 or more, such as about 1.5 or more, or from about 1 to about 3, encompassing any value and subset therebetween.
  • the product of the isoparaffin-olefin alkylation reaction may be fed to a separation system, such as a distillation train, to recover a C5+ fraction for use as a gasoline octane enhancer. Additionally, the separation system may separate the C4 isoparaffin to be recycled as part or all of the isoparaffin feed (e.g., a deisobutanizer). Furthermore, depending on alkylate demand, part or all of a C9+ fraction can be recovered for use as a distillate blending stock.
  • a separation system such as a distillation train
  • Various portions of the multistage reactors and/or separation systems described herein may be in fluid communication, such as by feed lines, hoses, pipes, troughs, or other conduits, and may be equipped with suitable pumps and valving to facilitate and/or control flow therebetween.
  • a multistage reactor may be in fluid communication with a deisobutanizer, typically in single directional flow.
  • other conduits may be in fluid communication with the multistage reactors and/or separation systems directly or by way of other fluid communication conduits, without departing from the scope of the present disclosure.
  • Embodiments disclosed herein include:
  • Catalyst compositions for alkylation comprise catalysts containing a zeolite having an MWW framework and a collidine uptake of greater than 75 pmol/cm3.
  • Catalyst compositions for alkylation prepared by a method of exchanging, precalcination, and calcination.
  • Catalyst compositions comprise a zeolite having an MWW framework and a collidine uptake of greater than 75 pmol/cm3, wherein the catalyst composition is prepared by a method including: extruding the catalyst composition to form an extrudate; exchanging the extrudate with an exchange fluid to form an exchanged extrudate; performing a pre-calcination on the exchange extrudate in which the exchanged extrudate is heated at about 350 °C or greater under an inert atmosphere; and calcining the exchanged extrudate at a temperature of about 350 °C or greater under an atmosphere comprising air to form the catalyst composition.
  • C Catalyst compositions for alkylation.
  • a catalyst for the alkylation of olefins with isoparaffins the catalyst comprising a zeolite having an MWW framework and a 2,2,4- trimethylpentane uptake of greater than 75 pmol/cm3.
  • Embodiments A-C may have one or more of the following additional elements in any combination:
  • Element 1 wherein the zeolite is one or more selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, EMM-10, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37, SCM-1, SCM-2, and UCB-3.
  • Element 2 wherein the zeolite is one or more selected from the group consisting of MCM-22, MCM-49, MCM-56 and EMM-10 and mixtures thereof.
  • Element 3 wherein the zeolite is EMM- 10.
  • Element 4 wherein the zeolite is about 95 wt% or greater of the total weight of the catalyst.
  • Element 5 wherein the catalyst consists essentially of the zeolite.
  • Element 6 wherein the collidine uptake is between 75 and 300 pmol/cm3.
  • Element 7 wherein the catalyst has a 2,2,4-trimethylpentane uptake of greater than 75 pmol/cm3.
  • Element 8 wherein the catalyst has a 2,2,4-trimethylpentane uptake between 75 pmol/cm3 and 600 pmol/cm3.
  • Element 9 wherein the catalyst has a 2,2,4-trimethylpentane uptake between 100 pmol/cm3 and 500 pmol/cm3.
  • Element 10 wherein the extrudate is dried at a temperature of about 100 °C to about 300 °C prior to exchanging.
  • Element 11 wherein the exchange fluid comprises an ammonium compound.
  • Element 12 wherein the pre-calcination inert atmosphere comprises nitrogen.
  • Element 13 wherein the calcination atmosphere comprises a mixture of air and nitrogen.
  • Element 14 wherein the calcination temperature is in a range of 350 °C to 600oC.
  • Element 15 wherein the zeolite is one or more selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, EMM-10, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37, SCM-1, SCM-2, and UCB-3.
  • Element 16 wherein the zeolite is EMM- 10.
  • Element 17 wherein the zeolite has a 2,2,4-trimethylpentane uptake of between 75 and
  • catalysts and comparative catalyst compositions are prepared and tested.
  • the use of these catalysts for alkylation of isobutane with 2-butene is described in Example 20 and the correlation between catalyst activity and selected catalyst properties are shown in Examples 21 and 22.
  • a comparative catalyst formulation is prepared using 80 parts MCM- 49 zeolite crystals combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-49 and pseudoboehmite alumina dry powder are placed in a muller or a mixer and mixed for about 10 to 30 minutes.
  • Sufficient water is added to the MCM-49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121°C) to 325°F (168°C).
  • the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen.
  • the extrudate is then cooled to ambient temperature, humidified with saturated air or steam and then ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the extrudate is then calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • a comparative catalyst formulation is prepared using 95 parts MCM- 49 zeolite crystals combined with 5 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-49 and pseudoboehmite alumina dry powder are placed in a muller or a mixer and mixed for about 10 to 30 minutes.
  • Sufficient water is added to the MCM-49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121°C) to 325°F (168°C).
  • the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • a comparative catalyst formulation is prepared using 95 parts MCM- 49 zeolite crystals combined with 2.5 parts precipitated silica and 2.5 parts colloidal silica, on a calcined dry weight basis.
  • the MCM-49 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • a comparative catalyst formulation is prepared using 95 parts MCM- 49 zeolite crystals combined with 2.5 parts precipitated silica and 2.5 parts colloidal silica, on a calcined dry weight basis.
  • the MCM-22 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • the extrudate is then calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • Comparative Example 5 [0099]
  • a comparative catalyst formulation is prepared using 95 parts MCM- 22 zeolite crystals combined with 2.5 parts precipitated silica and 2.5 parts colloidal silica, on a calcined dry weight basis.
  • the MCM-22 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • a comparative catalyst formulation is prepared using 95 parts MCM- 22 zeolite crystals combined with 2.5 parts precipitated silica and 2.5 parts colloidal silica, on a calcined dry weight basis.
  • the MCM-22 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121°C) to 325°F (168°C). After drying, the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen. The extrudate is then cooled to ambient temperature, humidified with saturated air or steam and then ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The extrudate is then calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • a zeolite formulation is prepared with a -12% solids mixture containing DI water, 50% NaOH solution, 47% Aluminum sulfate solution, pentamethonium dibromide 50% solution, and Sipernat 340 silica (Evonik Corporation) that was charged to an autoclave.
  • the reaction mixture had the following molar composition shown in Table 1.
  • EMM-10 zeolite crystals prepared in Example 8 are combined with 17.5 parts precipitated silica and 17.5 parts colloidal silica, on a calcined dry weight basis.
  • the EMM- 10 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica, available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • Sufficient water and a 5% NaOH solution (2.5% NaOH by weight) are then added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder.
  • the extrudate After extrusion, the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C). After drying, the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 8 are combined with 10 parts precipitated silica and 10 parts colloidal silica, on a calcined dry weight basis.
  • the EMM- 10 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • Sufficient water and a 5% NaOH solution (2.5% NaOH by weight) are then added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder.
  • the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C). After drying, the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 8 are combined with 10 parts precipitated silica and 10 parts colloidal silica, on a calcined dry weight basis.
  • the EMM- 10 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • Sufficient water and a 5% NaOH solution (2.5% NaOH by weight) are then added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder.
  • the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C). After drying, the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen. The extrudate is then cooled to ambient temperature, humidified with saturated air or steam and then ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The extrudate is then calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM-10 zeolite crystals prepared in Example 7 are combined with 2.5 parts precipitated silica and 2.5 parts colloidal silica, on a calcined dry weight basis.
  • the EMM- 10 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • Sufficient water and a 5% NaOH solution (2.5%NaOH by weight) are then added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder.
  • the extrudate After extrusion, the extrudate is dried at a temperature ranging from250°F (121°C) to 325°F (168°C). After drying, the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM-10 zeolite crystals prepared in Example 7 are combined with 2.5 parts precipitated silica and 2.5 parts colloidal silica, on a calcined dry weight basis.
  • the EMM- 10 and precipitated silica dry powders are placed in a muller or a mixer and mixed for about 5 to 20 minutes.
  • Colloidal silica available as Ludox HS-40 from W.R. Grace, is then added and mixed for about 5 to 10 minutes.
  • Sufficient water and a 5% NaOH solution (2.5% NaOH by weight) are then added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder.
  • the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C). After drying, the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen. The extrudate is then cooled to ambient temperature, humidified with saturated air or steam and then ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The extrudate is then calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 7, on a calcined dry weight basis were extruded without a binder.
  • the EMM- 10 dry powder are placed in a muller or a mixer and mixed for about 5 to 20 minutes. Sufficient water and a 5% NaOH solution (2.5% NaOH by weight) are then added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121°C) to 325°F (168°C).
  • the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 8 are combined with 35 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the EMM- 10 and pseudoboehmite alumina dry powder are placed in a muller or a mixer and mixed for about 10 to 30 minutes.
  • Sufficient water is added to the EMM- 10 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C).
  • the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 8 are combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the EMM- 10 and pseudoboehmite alumina dry powder are placed in a muller or a mixer and mixed for about 10 to 30 minutes.
  • Sufficient water is added to the EMM- 10 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C).
  • the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 8 are combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the EMM- 10 and pseudoboehmite alumina dry powder are placed in a muller or a mixer and mixed for about
  • extrudable paste 10 to 30 minutes. Sufficient water is added to the EMM-10 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121°C) to 325°F (168°C). After drying, the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen. The extrudate is then cooled to ambient temperature, humidified with saturated air or steam and then ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The extrudate is then calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 7 are combined with 5 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the EMM- 10 and pseudoboehmite alumina dry powder are placed in a muller or a mixer and mixed for about 10 to 30 minutes.
  • Sufficient water is added to the EMM- 10 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121 °C) to 325°F (168°C).
  • the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • EMM- 10 zeolite crystals prepared in Example 8 are combined with 20 parts titania (rutile phase), on a calcined dry weight basis.
  • the EMM-10 and titania dry powder are placed in a muller or a mixer and mixed for about 10 to 30 minutes.
  • the extrudable paste is formed into a 1/20 inch cylindrical extrudate using an extruder. After extrusion, the extrudate is dried at a temperature ranging from 250°F (121°C) to 325°F (168°C). After drying, the dried extrudate is ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The dried extrudate is then is heated to 1000°F (538°C) under flowing nitrogen and finally calcined in a nitrogen/air mixture to a temperature of 1000°F (538°C).
  • Example 1-6, 9-19 The catalysts of Example 1-6, 9-19 were loaded in a fixed bed reactor and operated as a single bed with all feed entering the top of the reactor.
  • the reactor (12.7 mm OD x 10.2mm ID x 640 mm L) was loaded with 6 cc of catalyst premixed with 5 cc of silicon dioxide.
  • Isobutane (97.7%) and 2-butene (2.3%) were fed to the top of the reactor bed at a relative rate such that the isobutane to 2-butene volume ratio at the top of the bed was -40:1.
  • the isobutane alkylation reaction was carried at 150°C and 700 psig.
  • the reactor effluent was measured using a FID GC equipped with a 60 m DB-1 column.
  • the 2-butene flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.06 h-1.
  • OHSV Olefin Liquid
  • First order kinetics are assumed to determine 2-butene and isobutane activity according to the following equations, where LHSV is the liquid hourly space velocity.
  • iC4° activity - ln(l - iC4° conversion)/100)/LHSV
  • 2-butene and isobutane activity of the catalyst of Comparative Example 1 is used to determine relative catalyst activity for the Examples 1-6, 8-18 using the following equations.
  • iC4o Relative Activity (iC4° activity for Catalyst of Example i)/(iC4° activity for Catalyst of Comparative Example 1)
  • TMP Trimethylpentane uptake was measured for a select set of extruded catalysts of Examples 1-19 using a TA Q5000 TGA instrument.
  • the catalyst sample was dried under nitrogen at 200°C for 75 minutes. It was then allowed to equilibrate to 150°C for 30 minutes. After equilibration, 2,2,4-TMP was sparged for 370 minutes at a vapor pressure of 75 Torr. After sparging, the sample was stripped with nitrogen for 325 minutes prior to measuring the weight uptake of 2,2,4-TMP. The dried catalyst weight and the final weight after sparging and stripping were then used to calculate the 2,2,4-TMP uptake value per catalyst weight.
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

Catalyseurs pour l'alkylation d'oléfines avec des isoparaffines comprenant des catalyseurs contenant une zéolite ayant une structure MWW et une absorption de collidine supérieure à 75 μmol/cm3. Les compositions de catalyseur comprennent une zéolite ayant une structure MWW et une absorption de collidine supérieure à 75 μmol/cm3, la composition de catalyseur étant préparée par un procédé comprenant : l'extrusion de la composition de catalyseur pour former un extrudat ; l'échange de l'extrudat avec un fluide d'échange pour former un extrudat échangé ; la réalisation d'une précalcination sur l'extrudat d'échange où l'extrudat échangé est chauffé à environ 350 °C ou plus sous une atmosphère inerte ; et la calcination de l'extrudat échangé à une température d'environ 350 °C ou plus sous une atmosphère comprenant de l'air pour former la composition de catalyseur. L'invention concerne également des catalyseurs pour l'alkylation d'oléfines avec des isoparaffines, le catalyseur comprenant une zéolite ayant une structure MWW et une absorption de 2,2,4-triméthylpentane supérieure à 75 μmol/cm3.
PCT/US2020/050945 2020-09-16 2020-09-16 Catalyseur zéolithique de type mww à haute activité pour l'alkylation d'oléfines légères avec de l'isoparaffine WO2022060353A1 (fr)

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