WO2021025836A1 - Catalyseurs et alkylation en plusieurs étapes d'isoparaffine - Google Patents

Catalyseurs et alkylation en plusieurs étapes d'isoparaffine Download PDF

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WO2021025836A1
WO2021025836A1 PCT/US2020/042005 US2020042005W WO2021025836A1 WO 2021025836 A1 WO2021025836 A1 WO 2021025836A1 US 2020042005 W US2020042005 W US 2020042005W WO 2021025836 A1 WO2021025836 A1 WO 2021025836A1
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zeolite
reactor
mcm
olefin
catalyst composition
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PCT/US2020/042005
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Doron Levin
Lvy D. JOHNSON
Claure Micaela TABORGA
Matthew S. METTLER
Vinit CHOUDHARY
Kathleen M. Keville
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Exxonmobil Research And Engineering Company
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Publication of WO2021025836A1 publication Critical patent/WO2021025836A1/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
    • 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
    • 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
    • B01J35/617—500-1000 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—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
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • the present disclosure relates to catalysts, processes and apparatuses for alkylation of isoparaffins and, in particular, to catalysts used in alkylation of isoparaffins with olefins to produce high octane rated additive for fuels, such as gasoline.
  • 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.
  • the product is a valuable blending component for gasoline due to its high octane rating, low sulfur, low olefin, and low aromatic content.
  • alkylation often involves the reaction of C2-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.
  • liquid acids such as hydrofluoric acid or sulfuric acid as catalysts.
  • liquid acids provide challenges in disposal of spent acid streams.
  • An alternative to liquid acids are solid acids, such as zeolites.
  • solid acids such as faujasite
  • some solid acids, such as faujasite typically have short catalyst lifetimes which lead to frequent catalyst regeneration and increased costs and may further require the use of precious metals such as platinum and palladium in catalyst regeneration.
  • the production of byproducts, and therefore deactivation of the solid catalysts may be related to reactor temperature, reactor pressure, number of reactor stages, and/or feed isobutane to olefin ratio (i:o ratio), a volume to volume ratio.
  • i:o ratio feed isobutane to olefin ratio
  • Previous approaches in alkylation of paraffins focused on using a single stage reactor where the i:o ratio was set by the composition of the gas entering the single stage reactor. For liquid acids the i:o ratio has typically been 4: 1 to 10: 1, and for solid catalysts the i:o ratio has typically been 40:1 to 50:1, both based solely on the composition of the feedstock entering a single stage reactor.
  • Single stage alkylation reactors may provide lower conversion of isoparaffins and olefins into higher octane rated fuel additives, increased by-product formation, and can be limited in flow rate or i:o ratio, which may, in turn, cause more rapid catalyst deactivation.
  • the present disclosure is related to catalyst compositions including a zeolite having x-ray diffraction pattern peaks at d-spacing, in Angstrom, of: 12.2 ⁇ 0.3, 11.0 ⁇ 0.2, 9.0 ⁇ 0.2, 4.4 ⁇ 0.1, 4.05 ⁇ 0.05, 3.91 ⁇ 0.05, 3.42 ⁇ 0.03, 3.3 ⁇ 0.05.
  • the catalyst composition includes a binder and has a and a BET surface area of from about 400 m 2 /g to about 700 m 2 /g. Additionally, the zeolite may be about 50 wt% or greater of the catalyst composition.
  • the present disclosure also relates to processes for the alkylation of isoparaffins.
  • the alkylation processes may include introducing, in a multistage reactor, an isoparaffin feed, an olefin feed, and a hydrogen feed to a catalyst composition.
  • the present disclosure also relates to methods of making catalyst compositions including introducing a zeolite, and a binder to water to form a first mixture.
  • the zeolite may have x-ray diffraction pattern peaks at d-spacing, in Angstrom, of: 12.2 ⁇ 0.3, 11.0 ⁇ 0.2, 9.0 ⁇ 0.2, 4.4 ⁇ 0.1, 4.05 ⁇ 0.05, 3.91 ⁇ 0.05, 3.42 ⁇ 0.03, 3.3 ⁇ 0.05.
  • the first mixture may be extruded and then dried at a temperature from about 100 °C to about 300 °C to form a dried extrudate.
  • the dried extrudate may be introduced to an exchange fluid to form a second mixture and the second mixture calcined at a temperature of about 350 °C or greater to form the catalyst composition.
  • FIG. 1 A is a depiction of a reactor with one stage configured to receive an olefin feed and an isoparaffin feed.
  • FIG. IB is a depiction of a reactor with two stages configured to receive an olefin feed and an isoparaffin feed, according to an embodiment.
  • FIG. 1C is a depiction of a reactor with four stages configured to receive an olefin feed and an isoparaffin feed, according to an embodiment.
  • FIG. ID is a depiction of a reactor with eight stages configured to receive an olefin feed and an isoparaffin feed, according to an embodiment.
  • FIG. 2 is a plot of 2-butene conversion versus C8 olefin yield for two catalyst compositions, according to an embodiment.
  • FIG. 3 is a plot of 2-butene conversion versus C8 olefin yield for four catalyst compositions, according to an embodiment.
  • a multiple stage reactor may offer improvements over single stage processes including splitting of olefin introduction into various stages which decreases the local concentration of olefin in a catalyst bed, which may provide improved i:o ratios, decreased issues with catalyst deactivation, decreased byproduct formation, and improved conversion of isoparaffins. Improved conversion and decreased catalyst deactivation may result from increased olefin interactions with active catalyst sites resulting from passing over catalyst beds within additional reactor stages.
  • catalysts with higher activity for alkylation rather than olefin oligomerization may lead to lower concentrations of higher olefins, as compared conventional catalysts, and may be formed by increasing the zeolite content of the catalyst and by ion-exchange of zeolites and optional binder(s) before calcination.
  • 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 is 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 134.6 °C and 3650 kPa
  • critical point for isopentane is 187.2 °C and 3378 kPa.
  • a “light olefin” is a C2-C7 hydrocarbon containing at least one carbon-carbon double bond.
  • a “heavy olefin” is a C8+ hydrocarbon containing at least one carbon-carbon double bond.
  • An “inert gas” is a gas that does not undergo reaction in the presence of a catalyst, when there is no olefin present.
  • molecular sieve means a substance having pores of molecular dimensions that only 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.
  • framework density is defined as the number of tetrahedrally coordinated atoms (T-atoms) per 1000 A 3 .
  • the framework density is related to the pore volume but might not reflect the size of the pore openings.
  • Framework type and framework density can be determined by x-ray crystallography as described in Van Koningsveld et al. Molecular Sieves Vol. 2 Chapter 1 Zeolite Structure Determination from X-Ray Diffraction. Springer-Verlag (1999).
  • topological density or “TD” is the mean of all ai divided by the dimensionality of the topology (e.g. 3 for zeolites). Therefore, the following equation may be used to determine TD:
  • ai is determined by solving a set of quadratic equations related to the coordination sequence as defined in Grosse-Kunstleve et al. Algebraic Description of Coordination Sequences and Exact Topological Densities for Zeolites, Acta Crystallographica A52, 879 (1996).
  • the TD is the same for all T atoms in a structure. For some frameworks, this calculation can take quite a long time, so an approximation valid to ⁇ 0.001 has been used to calculate the values for each of the Framework Types.
  • ⁇ ai> has been approximated as the mean of ai for the last 100 terms of a CS with 1000 terms (TD1 ()()(): 100). weighted with the multiplicity of the atom position, and divided by three (dimensionality).
  • spherical volume means the diameter of a sphere that may be included within a zeolite crystal. These sphere diameters can be computed geometrically by Delaunay triangulation with the following assumptions: (i) both the framework T- and O-atoms are hard spheres of diameter 2.7 angstrom; (ii) all extra-framework atoms (i.e.
  • diffusion passage means the diameter of a sphere that may diffuse along a zeolite crystal in a single direction. These sphere diameters can be computed geometrically by Delaunay triangulation with the same assumption as in the calculation of spherical volume.
  • accessible volume means 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.
  • 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.
  • a multistage reactor may have one or more interstage spaces between stages.
  • An interstage space may be an open space, a filled space, a separation barrier, a distribution plate or system, or an injection point.
  • Multistage reactors of the present disclosure may be configured to receive an olefin feed at multiple sites or inlets, and the introduction of olefin marks a new reactor stage.
  • the reactor may include multiple catalyst beds located in the same or different housing.
  • a reactor or a stage within a multistage reactor may include a bed of catalyst particles where the particles have insignificant motion in relation to the bed (a fixed bed).
  • injection of the olefin feed can be effected at a single point in the reactor or at multiple points spaced along the reactor.
  • the isoparaffin feed and the olefin feed may be premixed before entering the reactor.
  • a multistage reactor includes a plurality of fixed beds, continuous flow-type reactor stages in either a down flow or up flow mode, where the reactor stages may be arranged in series or parallel.
  • a multistage reactor may include multiple reactor stages in series and/or in parallel.
  • a reactor stage includes a catalyst bed.
  • the reactor stage may have various configurations such as: multiple horizontal beds, multiple parallel packed tubes, multiple beds each in its own reactor shell, or multiple beds within a single reactor shell.
  • a reactor stage includes a fixed bed which provides uniform flow distribution over the entire width and length of the bed to utilize substantially all of the catalyst.
  • a single or multistage reactor can provide heat transfer from reactor stages or catalyst beds in order to provide effective methods for controlling temperature.
  • the efficiency of a single or a multistage reactor containing fixed beds of catalyst may be affected by the pressure drop across a fixed bed.
  • the pressure drop depends on various factors such as the path length, the catalyst particle size, and pore size. A pressure drop that is too large may cause channeling through the catalyst bed, poor efficiency, and increased catalyst deactivation, which increases the frequency of catalyst rejuvenation.
  • the reactor has a cylindrical geometry with axial flows through the catalyst beds.
  • the various designs of the multistage reactor may accommodate control of specific process conditions, e.g. pressure, temperature, LHSV, and OLHSV (olefin liquid hourly space velocity). The combination of LHSV and OLHSV determine catalyst volume and residence time that may provide the desired conversion.
  • Operating pressures may be controlled to reduce or eliminate oligomerization reactions and/or favor alkylation reactions. Additionally, increased reactor pressures may improve conversion rates for the olefin feed and improve selectivity towards the alkylated paraffin over olefin oligomers.
  • Operating pressure may be from about 300 psig to about 1500 psig (about 2068 to 10342 kPag), such as from about 400 psig to about 1200 psig (about 2758 to about 8274 kPag), from about 450 psig to about 1000 psig (about 3102 kPag to 6895 about kPag), from about 550 psig to about 950 psig (about 3792 kPag to about 6550 kPag), from about 650 psig to about 950 psig (about 4481 kPag to about 6550 kPag), from about 750 psig to about 950 psig (about 5171 kPag to about 6550 kPag), or from about 800 psig to about 950 psig (about 5516 to about 6550 kPag).
  • the operating temperature and pressure remain above the critical point for the isoparaffin feed during the reactor run.
  • operating temperatures may be controlled to reduce or eliminate olefin oligomerization reactions and/or favor alkylation of isoparaffins, which may reduce byproduct formation and decrease the frequency of catalyst rejuvenations.
  • Operating temperature may be from about 100 °C or greater, such as about 130 °C or greater, about 140 °C or greater, about 150 °C or greater, or about 160 °C or greater, such as from about 100 °C to about 200 °C, from about 130 °C to about 170 °C, or from about 140 °C to about 160 °C.
  • Operating temperatures may exceed the critical temperature of the isoparaffin feed, or the principal component in the isoparaffin feed.
  • isobutane is the principal component in a feedstock consisting of isobutane and 2-methylbutane in isobutane:2-methylbutane weight ratio of 50:1.
  • the temperature of the multistage reactor or an individual stage within the reactor may affect by-product formation and a temperature higher than 130 °C may decrease heavier olefin concentrations. Furthermore, an increase in temperature may improve conversion of the olefin feed reducing byproduct formation and decreasing the frequency of catalyst rejuvenations. However, for certain olefins, a higher temperature increases olefin isomerization, and olefin isomerization may lead to the formation of alkylation products that are lower in value.
  • a main component of the alkylation product mixture is trimethylpentane which has an octane rating of 100, but if 2-butene is isomerized to 1 -butene the alkylation shifts to higher production of dimethylhexane which has an octane rating of 70, providing less value as a fuel additive. Therefore, temperature may be used to reduce or eliminate heavier olefin concentrations, especially in cases where the olefin is not affected by isomerization, such as propene or isobutene.
  • the alkylation product mixture contains ⁇ 10 wt%, such as ⁇ 5 wt%, ⁇ 2 wt%, ⁇ 1 wt%, or is substantially free of products of olefin oligomerization.
  • Hydrocarbon flow through a reactor stage containing the catalyst is typically controlled to provide an OLHSV sufficient to convert about 99 percent, or more, by weight of the fresh olefin to alkylation product.
  • OLHSV values are from about 0.01 hr'to about 10 hr 1 , such as about 0.02 hr'to about 1 hr 1 , or such as about 0.03 hr'to about 0.1 hr 1 .
  • the liquid hourly space velocity of the isoparaffin is controlled to meet a target i:o ratio. Because the i:o ratio is vokvol, the isoparaffin liquid hourly space velocity is directly correlated to the OLHSV.
  • FIG. 1A depicts an alkylation reactor 100 A with a single reactor stage 101.
  • Reactor stages(s) may individually or collectively be termed an alkylation zone and include catalyst, such as a solid acid catalyst comprising zeolite of the MWW framework type.
  • the olefin feed is introduced to reactor stage 101 via line 103 and the isoparaffin feed through line 105.
  • An alkylation product mixture exits the reactor through line 107.
  • the i:o ratio is controlled solely by the composition of the olefin feed and the isoparaffin feed entering reactor bed 101
  • FIG. IB depicts a multistage alkylation reactor 100B with two reactor stages: first stage 101a and second stage 101b.
  • the olefin feed is introduced to the reactor beds via lines 103a and 103b and OLHSV values are from about 0.01 hr'to about 10 hr 1 , such as about 0.02 hr'to about 1 hr 1 , or such as about 0.03 hr'to about 0.1 hr 1 .
  • the split introduction of the olefin feed allows a lower concentration (half) of the olefin feed to be introduced locally to each of the first stage 101 A and the second stage 101B.
  • the isoparaffin feed is introduced to alkylation reactor 100B through line 105.
  • Alkylation reactor 100B has an interstage space 109 between first stage 101 A and the second stage 101B to allow for introduction of additional olefin feed through line 103B.
  • lines 103 and 105 have the same composition as in FIG. 1A, then the local i:o ratio is doubled in the configuration of FIG. IB because the olefin feed is divided into two lines 103A and 103B and the olefin introduced via line 103a to first stage 101a can be converted, such as about 90 wt% or greater, about 95 wt% or greater, about 98 wt% or greater, or about 99 wt% or greater is converted in the reaction within first stage 101A, based on the total weight of olefin in the olefin feed introduced via line 103 A.
  • the amount of isoparaffin introduced to interstage 109 and, therefore, introduced to second stage 101B is similar or slightly less than that introduced to first stage 101A.
  • the olefin introduced to interstage 109 (either via line 103B or from the effluent of first stage 101A) and, therefore, introduced to second stage 101b is similar in quantity to that introduced to first stage 101A. Therefore, for example, if an i:o ratio of 100:1 is introduced to first stage 101 A and there is an olefin conversion of 100% then the i:o ratio in second stage 101B would be 99:1, if no additional isoparaffin was added.
  • the selected isoparaffin may be consumed in each stage, such as in amounts of about 10 wt% or less, about 5 wt% or less, about 2 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.1 wt% or less, additional isoparaffin may be added in an interstage space so as to maintain a consistent i : o ratio throughout the multistage reactor.
  • an alkylation product mixture exits the reactor through line 107.
  • FIG. 1C depicts a multistage alkylation reactor lOOC with four reactor stages: first stage 101 A, second stage 101B, third stage 101C, and fourth stage 10 ID.
  • the olefin feed is introduced to the reactor beds via lines 103A, 103B, 103C and 103D and OLHSV values are from about 0.01 hr'to about 10 hr 1 , such as about 0.02 hr Ho about 1 hr 1 , or such as about 0.03 hr Ho about 0.1 hr f
  • the split introduction of the olefin feed allows a lower concentration (one quarter) of the olefin feed to be introduced locally to each of the first stage 101 A, second stage 101B, third stage 101C, and fourth stage 101D.
  • the isoparaffin feed is introduced to alkylation reactor lOOC through line 105.
  • Alkylation reactor lOOC has multiple interstage spaces: first interstage space 109A, second interstage space 109B, and third interstage space 109C between reactor stages 101A, 101B, 101C, and 101D to allow for introduction of additional olefin feed through lines 103B, 103C, and 103D. If lines 103 and 105 have the same composition as in FIG. 1A, then the local i:o ratio is 4 times that found in FIG. 1A, because the olefin feed is divided into four lines 103A, 103B, 103C, and 103D.
  • the i:o ratio in a single stage is only slightly affected by prior stage(s) because the olefin introduced to a prior stage can be largely converted within that stage, but the isoparaffin is introduced at such a ratio that the amount converted may have little effect on the ratio in later stages.
  • the olefin introduced via line 103A to first stage 101A is converted, such as about 90 wt% or greater, about 95 wt% or greater, about 98 wt% or greater, or about 99 wt% or greater is converted in first stage 101 A, based on the total weight of olefin in the olefin feed introduced via line 103 A.
  • first stage 101 A only a small portion of the isoparaffin feed may be converted by the reaction in first stage 101 A, such as about 10 wt% or less of the isoparaffin feed is converted based on the total weight of isoparaffin introduced to first stage 101A, such as about 5 wt% or less, about 2 wt% or less, about lwt% or less, about 0.5 wt% or less, or about 0.1 wt% or less.
  • the amount of isoparaffin introduced to interstage 109A and, therefore, introduced to second stage 101B is similar or slightly less than that introduced to first stage 101A and the olefin introduced to interstage space 109A via line 103B and from the effluent of first stage 101A serves to bring the olefin level back up to a desired i:o ratio. Therefore, for example, if an i:o ratio of 100:1 is introduced to first stage 101A and there is an olefin conversion of 100% then the i:o ratio in second stage 101B would be -99:1, if no additional isoparaffin was added.
  • the combination of isoparaffin and olefin is then introduced to second stage 101B, where the olefin may be converted in second stage 101B, such as about 90 wt% or greater, about 95 wt% or greater, about 98 wt% or greater, or about 99 wt% or greater is converted in second stage 101B, based on the total weight of olefin introduced to interstage space 109A.
  • the isoparaffin feed may be converted by the reaction in second stage 101B, such as about 10 wt% or less of the isoparaffin feed is converted based on the total weight of isoparaffin introduced to interstage space 109A, such as about 5 wt% or less, about 2 wt% or less, about lwt% or less, about 0.5 wt% or less, or about 0.1 wt% or less.
  • additional interstage spaces such as second interstage space 109B, and third interstage space 109C
  • more olefin may be introduced (via lines 103C and 103D) to adjust the i:o ratio as the combined feeds are introduced to additional stages (such as third stage 101C and fourth stage 101D).
  • the selected isoparaffin may be consumed in each stage, such as in amounts of about 10 wt% or less, about 5 wt% or less, about 2 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.1 wt% or less, additional isoparaffin may be added in an interstage space so as to maintain a consistent i:o ratio throughout the multistage reactor.
  • an alkylation product mixture exits the reactor through line 107.
  • FIG. ID depicts a multistage alkylation reactor 100D with eight reactor stages: first stage 101A, second stage 101B, third stage 101C, fourth stage 101D.
  • the olefin feed is introduced to the reactor beds via lines 103 A, 103B, 103C and 103D and OLHSV values are from about 0.01 hr fio about 10 hr 1 , such as about 0.02 hr'to about 1 hr 1 , or such as about 0.03 hr'to about 0.1 hr 1 .
  • the split introduction of the olefin feed allows a lower concentration (one quarter) of the olefin feed to be introduced locally to each of the first stage 101A, second stage 101B, third stage 101C, fourth stage 101D, fifth stage 101E, sixth stage 101F, seventh stage 101G, and eighth stage 101H.
  • the isoparaffin feed is introduced to alkylation reactor 100D through line 105.
  • Alkylation reactor 100D has multiple interstage spaces: first interstage space 109 A, second interstage space 109B, third interstage space 109C, fourth interstage space 109D, fifth interstage space 109E, sixth interstage space 109F, and seventh interstage space 109G between reactor stages 101A, 101B, 101C, 101D, 101E, 101F, 101G, and 101H to allow for introduction of additional olefin feed through lines 103B, 103C, 103D, 103E, 103F, 103G, and 103H. If lines 103 and 105 have the same composition as in FIG. 1A, then the local i:o ratio is 8 times that found in FIG.
  • the olefin introduced via line 103 A to first stage 101 A is converted, such as about 90 wt% or greater, about 95 wt% or greater, about 98 wt% or greater, or about 99 wt% or greater is converted in first stage 101 A, based on the total weight of olefin in the olefin feed introduced via line 103A.
  • first stage 101 A only a small portion of the isoparaffin feed may be converted by the reaction in first stage 101 A, such as about 10 wt% or less of the isoparaffin feed is converted based on the total weight of isoparaffin introduced to first stage 101A, such as about 5 wt% or less, about 2 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.1 wt% or less.
  • the amount of isoparaffin introduced to interstage 109 A and, therefore, introduced to second stage 101B is similar or slightly less than that introduced to first stage 101A and the olefin introduced to interstage space 109A via line 103B and from the effluent of first stage 101 A serves to bring the olefin level back up to a desired i:o ratio. Therefore, for example, if an i:o ratio of 100:1 is introduced to first stage 101 A and there is an olefin conversion of 100% then the i:o ratio in second stage 10 IB would be -99:1, if no additional isoparaffin was added.
  • the combination of isoparaffin and olefin is then introduced to second stage 101B, where the olefin may be converted in second stage 101B, such as about 90 wt% or greater, about 95 wt% or greater, about 98 wt% or greater, or about 99 wt% or greater is converted in second stage 10 IB, based on the total weight of olefin introduced to interstage space 109 A.
  • the isoparaffin feed may be converted by the reaction in second stage 101B, such as about 10 wt% or less of the isoparaffin feed is converted based on the total weight of isoparaffin introduced to interstage space 109 A, such as about 5 wt% or less, about 2 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.1 wt% or less.
  • additional interstage spaces such as second interstage space 109B, and third interstage space 109C
  • more olefin may be introduced (via lines 103C, 103D, 103E, 103F, 103G, and 103H) to adjust the i:o ratio as the combined feeds are introduced to additional stages (such as third stage 101C, fourth interstage space 109D, fifth interstage space 109E, sixth interstage space 109F, and seventh interstage space 109G).
  • the selected isoparaffin may be consumed in each stage, such as in amounts of about 10 wt% or less, about 5 wt% or less, about 2 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.1 wt% or less, additional isoparaffin may be added in an interstage space so as to maintain a consistent i:o ratio throughout the multistage reactor.
  • an alkylation product mixture exits the reactor through line 107.
  • 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 7 carbon atoms.
  • Representative examples of such isoparaffins include 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 2 to 12 carbon atoms.
  • Representative examples of such olefins include 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 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 1.5:1, such as from about 0.1:1 to about 1:1.
  • 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 1.5:1, such as from about 0.1:1 to about 1:1.
  • the concentration of olefin feed can be adjusted by, e.g., staged additions thereof.
  • the ratio of isoparaffin to olefin ratio by volume referred to as the i:o ratio 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, about 120:1 to about 500:1, about 160:1 to about 480:1, about 200:1 to about 450:1, about 220:1 to about 450: 1, about 240: 1 to about 420: 1, or about 240: 1 to about 400: 1.
  • 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 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 low C5- alkane from C6+ alkanes and alkenes produced in the reactor.
  • a higher i:o ratio can provide greater quantities of C5- alkane separated from the alkylation product mixture that can be recycled to the reactor.
  • the isoparaffin feed and/or olefin 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 molecular sieve may be a crystalline microporous material of the MWW framework type.
  • MWW framework type refers to a type of crystalline microporous material that comprises 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 Van Koningsveld, Henk, (Elsevier, Amsterdam, 2007), incorporated by reference.
  • Crystalline microporous materials of the MWW framework type can include those molecular sieves having an X-ray diffraction pattern comprising d-spacing maxima at 12.2 ⁇ 0.3, 11.0 ⁇ 0.2, 9.0 ⁇ 0.2, 4.4 ⁇ 0.1 4.05 ⁇ 0.05 3.91 ⁇ 0.05, 3.42 ⁇ 0.03, 3.3 ⁇ 0.05; 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 by reference.
  • a crystalline microporous material of the MWW framework type includes zeolites of the MWW framework type.
  • the MWW framework type may further be characterized by a framework density of from about 15 T/1000 A 3 to about 17 T/1000 A 3 , such as about 15.2 T/1000 A 3 to about 16.8 T/1000 A 3 , about 15.5 T/1000 A 3 to about 16.5 T/1000 A 3 , about 15.7 T/1000 A 3 to about 16.1 T/1000 A 3 , or about 15.9 T/1000 A 3 .
  • the MWW framework type may have a topological density of about 0.6 to about 0.9, such as about 0.65 to about 0.85, about 0.7 to about 0.8, about 0.72 to about 0.78, or about 0.74 to about 0.76, such as about 0.75.
  • the MWW framework type may also have a spherical volume with a diameter of about 10.5 A or less, such as about 10.3 A or less, about 10.1 A or less, about 9.9 A or less, or about 9.7 A or less, such as from about 1 A to about 10.5 A, or from about 1 A to about 10.3 A.
  • the MWW framework type may also have a diffusion passage with a diameter of about 5.5 A or less, such as about 5.3 A or less, about 5.1 A or less, about 5 A or less, or about 4.9 A or less, such as from about 1 A to about 5.3 A, or from about 1 A to about 5.1 A.
  • the crystalline microporous material is a zeolite.
  • the term “crystalline microporous material of the MWW framework type” comprises one or more of:
  • 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, incorporated herein by reference);
  • 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 embodiment, 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
  • Examples of crystalline microporous materials of the MWW framework type include MCM-22 (U.S. Patent No. 4,954,325), PSH-3 (U.S. Patent No. 4,439,409), SSZ-25 (U.S. Patent No. 4,826,667), ERB-1 (European Patent No. 0293032), ITQ-1 (U.S. Patent No. 6,077,498), ITQ- 2 (International Publication No. WO97/17290), MCM-36 (U.S. Patent No. 5,250,277), MCM-49 (U.S. Patent No. 5,236,575), MCM-56 (U.S. Patent No. 5,362,697), UZM-8 (U.S. Patent No.
  • the crystalline microporous material of the MWW framework type may be contaminated with other crystalline materials, 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 at about 10 or greater, such as from about 10 to about 50.
  • Catalysts suitable for use in the systems and processes described include a binder.
  • Binder materials including other inorganic oxides than alumina, such as silica, titania, zirconia and mixtures and compounds thereof, may be present in the catalyst in amounts about 90 wt% or less, for example about 80 wt% or less, such as about 70 wt% or less, for example about 60 wt% or less, such as about 50 wt% or less. Where a non-alumina binder is present, the amount employed may be as little as 0.1 wt%, such as about 5 wt% or more, for example about 10 wt% or more.
  • a binder is selected from precipitated silica, colloidal silica, psuedoboehmite alumina, or boehmite type alumina. In at least one embodiment, the binder is psuedoboehmite alumina. In at least one embodiment, a silica binder is employed such as disclosed in U.S. Pat. No. 5,053,374, incorporated by reference. In other embodiments, a zirconia or titania binder is used.
  • the binder may be a crystalline oxide material such as the zeolite- bound-zeolites described in U.S. Pat. Nos. 5,665,325 and 5,993,642, incorporated by reference.
  • the binder material may contain alumina.
  • a catalyst composition may be prepared by introducing a zeolite to an optional binder and water to form a first mixture which is extruded to form an extrudate.
  • the extrudate is dried before addition of an exchange fluid.
  • the mixture after having been introduced to an exchange fluid is calcined.
  • 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 60wt% to about 99
  • a catalyst composition of the present disclosure is prepared by adding an exchange fluid to a mixture of the zeolite and optional binder.
  • 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.
  • Suitable swelling agents may include 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 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.
  • Suitable sources of ammonium cations may include ammonium nitrate, ammonium hydroxide, ammonium acetate, ammonium chloride, ammonium carbonate, tetramethylammonium nitrate, tetramethylammonium hydroxide, n-octylammonium nitrate, n-octylammonium hydroxide, cetyltrimethylammonium nitrate, cetyltrimethylammonium hydroxide, or any combination(s) thereof.
  • a pH range of about 4 to about 14, such as about 4.5 to about 13.5 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.
  • 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.
  • Calcining can be performed by heating the catalyst composition at 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.
  • 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.
  • Calcination may be performed in the presence of inert gas such as nitrogen or argon, or in the presence of non-inert gases such as oxygen, hydrogen, or air, or in mixtures thereof, for example mixtures of air and nitrogen.
  • inert gas such as nitrogen or argon
  • non-inert gases such as oxygen, hydrogen, or air, or in mixtures thereof, 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.
  • exchange fluid may result in the formation of a layered oxide of enhanced interlayer separation, compared to the layered oxide before introduction to the exchange fluid.
  • 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.
  • the calcined catalyst composition may include layers, which can exhibit high BET surface area (e.g. greater than 400 m 2 /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 m 2 /g or greater, such as about 450 m 2 /g or greater, about 500 m 2 /g or greater, about 550 m 2 /g or greater, or about 600 m 2 /g or greater, such as from about 400 m 2 /g to about 2000 m 2 /g, from about 450 m 2 /g to about 1500 m 2 /g, from about 500 m 2 /g to about 1000 m 2 /g, from about 550 m 2 /g to about 900 m 2 /g, or from about 600 m 2 /g to about 800 m 2 /g.
  • 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%.
  • 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.
  • alkylation of isobutane with C3-C5 olefins, such as 2-butene the product may include about 20- 30 wt% of C5-C7 hydrocarbons, 50-75 wt% of octanes and 2.5-20 wt% of C9+ hydrocarbons.
  • the C6 fraction typically includes at least 40 wt%, such as at least 70 wt%, of 2,3-dimethylbutane
  • the C7 fraction typically includes at least 40 wt%, such as at least 80 wt%, of 2,3-dimethylpentane
  • the C8 fraction typically includes at least 50 wt%, such as at least 70 wt%, of 2,3,4-; 2,3,3-; and 2,2,4-trimethylpentane.
  • the product may include about 30-40 wt% of C5 hydrocarbons, 15-25 wt% of C9 hydrocarbons, 25-35 wt% of octanes, and 2.5-10 wt% of C10+ hydrocarbons.
  • 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 at least 3, e.g. at least 4 or 5, or between 3 and 6.
  • the molar ratio of trimethylhexane to dimethylheptane can be at least 1, e.g.
  • 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-C6 isoparaffin to be recycled as part or all of the isoparaffin feed. Furthermore, depending on alkylate demand, part or all of a C9+ fraction can be recovered for use as a distillate blending stock.
  • Isobutane was obtained from a commercial source and used as received.
  • the isobutane purity was 99.6 % with the balance n-butane.
  • Propylene and 2-butene were obtained from a commercial specialty gases source and were used as received.
  • the 2-butene was a mixture of cis-2-butene and trans-2-butene.
  • Catalysts used for isobutane alkylation with light olefins are dried in the reactor under nitrogen flow at 250°C for at least 4 hours prior to use.
  • the catalyst was prepared by combining 65 parts MCM-22 zeolite crystals with 35 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-22 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for 30 minutes. Sufficient water was added to the MCM-22 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/16 inch cylindrical extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121°C) to 325 °F (168°C).
  • the dried extrudate was heated to 1000 °F (538 °C) under flowing nitrogen.
  • the extrudate was 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 was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 421 m 2 /g.
  • MCM-49 zeolite crystals were combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-49 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for 30 minutes. Sufficient water was added to the MCM- 49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was heated to 1000 °F (538 °C) under flowing nitrogen.
  • the extrudate was 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 was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 492 m 2 /g.
  • the dried extrudate was heated to 1000°F (538°C) under flowing nitrogen.
  • the extrudate was 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 dried extrudate was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 487 m 2 /g.
  • MCM-49 zeolite crystals were combined with 80 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-49 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for 30 minutes. Sufficient water was added to the MCM- 49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was heated to 1000°F (538°C) under flowing nitrogen.
  • the extrudate was 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 dried extrudate was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 311 m 2 /g.
  • MCM-49 zeolite crystals were combined with 60 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-49 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for 30 minutes. Sufficient water was added to the MCM- 49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was heated to 1000°F (538°C) under flowing nitrogen.
  • the extrudate was 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 dried extrudate was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 377 m 2 /g.
  • the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate was then 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).
  • BET surface area was measured at 564 m 2 /g.
  • the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C). After drying, the dried extrudate was heated to 1000°F (538°C) under flowing nitrogen. The extrudate was 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 was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 600 m 2 /g.
  • the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C). After drying, the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The dried extrudate was then 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). BET surface area was measured at 469 m 2 /g.
  • the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate was then 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).
  • BET surface area was measured at 514 m 2 /g.
  • the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C). After drying, the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying. The dried extrudate was then 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). BET surface area was measured at 541 m 2 /g.
  • MCM-22 zeolite crystals were combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-22 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for about 30 minutes. Sufficient water was added to the MCM-22 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was heated to 1000 °F (538 °C) under flowing nitrogen.
  • the extrudate was 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 was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 468 m 2 /g.
  • MCM-22 zeolite crystals were combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-22 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for about 30 minutes. Sufficient water was added to the MCM-22 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate was then 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).
  • BET surface area was measured at 482 m 2 /g.
  • MCM-56 zeolite crystals were combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-56 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for about 30 minutes.
  • Sufficient water was added to the MCM-56 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was heated to 1000 °F (538 °C) under flowing nitrogen.
  • the extrudate was 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 was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 491 m 2 /g.
  • MCM-56 zeolite crystals were combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-56 and pseudoboehmite alumina dry powder were placed in a muller or a mixer and mixed for about 30 minutes. Sufficient water was added to the MCM-56 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate was then 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).
  • BET surface area was measured at 480 m 2 /g.
  • MCM-49 zeolite crystals were combined with 20 parts Catapal Cl alumina, on a calcined dry weight basis.
  • the Catapal Cl alumina was obtained from SASOL Chemicals (USA) LLC.
  • the MCM-49 and Catapal Cl alumina dry powder were placed in a muller or a mixer and mixed for about 30 minutes. Sufficient water was added to the MCM-49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was heated to 1000 °F (538 °C) under flowing nitrogen.
  • the extrudate was 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 was then calcined in a nitrogen/air mixture to a temperature of 1000 °F (538 °C). BET surface area was measured at 425 m 2 /g.
  • MCM-49 zeolite crystals were combined with 20 parts Catapal Cl alumina, on a calcined dry weight basis.
  • the Catapal Cl alumina was obtained from SASOL Chemicals (USA) LLC.
  • the MCM-49 and Catapal Cl alumina dry powder were placed in a muller or a mixer and mixed for about 30 minutes. Sufficient water was added to the MCM-49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste was formed into a 1/20 inch quadralobe extrudate using an extruder. After extrusion, the extrudate was dried at a temperature ranging from 250 °F (121 °C) to 325 °F (168 °C).
  • the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate was then 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).
  • BET surface area was measured at 481 m 2 /g.
  • the dried extrudate was ion exchanged with 0.75 N ammonium nitrate solution followed by washing with deionized water and drying.
  • the dried extrudate was then 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).
  • BET surface area was measured at 548 m 2 /g.
  • Example 2 The catalyst of Example 2 was loaded into a pilot plant and operated as a single bed with all feed entering the top of the reactor, as shown in FIG. 1A.
  • the reactor was 60” long and made from 3 ⁇ 4” O.D. Schedule 40 pipe.
  • the reactor was loaded with 50 g of catalyst.
  • the reactor was located in an isothermal sandbath maintained at 302 °F (150 °C). Reactor pressure was 750 psig. Isobutane (99.6% purity) and 2-butene were independently fed to the top of the reactor bed at a relative rate such that the isobutane to 2-butene ratio at the top of the bed was -40:1.
  • the reactor effluent was measured using a FID GC equipped with a 150 m Petrocol column.
  • the 2-butene flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.06 h-1 and subsequently 0.03 h-1.
  • Isobutane flowrates were adjusted as olefin flowrates were adjusted to maintain a constant i:o of -40:1 to the inlet to the catalyst bed.
  • Average 2-butene conversion at 0.06 h-1 was 80.7% and at 0.03 h-1 the average 2-butene conversion was 93.7%.
  • Example 2 The catalyst of Example 2 was loaded into a pilot plant and operated as a 2 reactor bed system, as shown in FIG. IB. Each reactor was 60” long and made from 3 ⁇ 4” O.D. Schedule 40 pipe. Each reactor was loaded with 50 g of catalyst. The reactors were located in an isothermal sandbath maintained at 302 °F (150 °C). Reactor pressure was 750 psig. Isobutane (99.6% purity) was fed to the first reactor bed and the 2-butene flow was split evenly into 2 using Coriolis meters and independently fed to each reactor bed. The relative rates of isobutane and 2-butene were set such that the isobutane to 2-butene ratio at the top of the first reactor bed was -40:1.
  • the reactor effluent exiting Bed 2 was measured using a FID GC equipped with a 150 m Petrocol column.
  • the total 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 Hourly Space Velocity
  • Average 2-butene conversion at 0.06 h-1 was 70.4%.
  • Example 2 The catalyst of Example 2 was loaded into a pilot plant and operated as a 4 reactor bed system, as shown in FIG. 1C. Each reactor was 60” long and made from 3 ⁇ 4” O.D. Schedule 40 pipe. Each reactor was loaded with 50 g of catalyst. The reactors were located in an isothermal sandbath maintained at 302 °F (150 °C). Reactor pressure was 750 psig. Isobutane (99.6% purity) was fed to the first reactor bed and the 2-butene flow was split evenly into 4 using Coriolis meters and independently fed to each reactor bed. The relative rates of isobutane and 2-butene were set such that the isobutane to 2-butene ratio at the top of the first reactor bed was -40: 1.
  • the reactor effluent exiting Bed 4 was measured using a FID GC equipped with a 150 m Petrocol column.
  • the total 2-butene flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.06 h-1 and subsequently 0.03 h-1.
  • Isobutane flowrates were adjusted as olefin flowrates were adjusted to maintain a constant i:o of -40: 1 to the inlet to the catalyst bed.
  • Average 2-butene conversion at 0.06 h-1 was 61.4% and at 0.03 h-1 the average 2- butene conversion was 77.5%.
  • the operation of the 4 bed system resulted in significantly lower olefin conversion.
  • Example 2 The catalyst of Example 2 was loaded into a pilot plant and operated as a 4 reactor bed system, as shown in FIG. 1C. Each reactor was 60” long and made from 3 ⁇ 4” O.D. Schedule 40 pipe. Each reactor was loaded with 150 g of catalyst. The reactors were located in an isothermal sandbath maintained at 302 °F (150 °C). Reactor pressure was 750 psig. Isobutane (99.6% purity) was fed to the first reactor bed and the 2-butene flow was split evenly into 4 using Coriolis meters and independently fed to each reactor bed. The relative rates of isobutane and 2-butene were set such that the isobutane to 2-butene ratio at the top of the first reactor bed was -40: 1.
  • the reactor effluent exiting Bed 4 was measured using a FID GC equipped with a 150 m Petrocol column.
  • the total 2-butene flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.03 h-1.
  • OHSV Olefin Liquid Hourly Space Velocity
  • Average 2-butene conversion at 0.03 h-1 was -82%.
  • the reactor effluent exiting Bed 4 was sent to a distillation column for separation of all C4 and lighter components from the reaction product.
  • the alkylate produced was analyzed via offline GC and shown to have -13.9% C5+ olefins.
  • Example 21 A sample of the 4 stage alkylate produced in Example 21 was hydrogenated using a commercial MaxSatTM hydrogenation catalyst available from ExxonMobil Catalyst & Licensing. Hydrogenation took place in a batch reactor at 200 °C and 800 psig for 8 hours. The hydrogenated alkylate was analyzed by GC and shown to have ⁇ 1% C5+ olefins.
  • Example 3 The catalyst of Example 3 was loaded into a pilot plant and operated as a single bed with all feed entering the top of the reactor, as shown in FIG. 1A.
  • the reactor was 14” long and made from 3/8” O.D. stainless steel tubing.
  • the reactor was loaded with 4 g of catalyst.
  • the reactor was located in an electrically heated furnace and maintained at 302 °F (150 °C).
  • Reactor pressure was 750 psig.
  • a pre-mixed gas blend with isobutane and 2-butene at a 40:1 ratio was fed to the top of the reactor bed.
  • the reactor effluent was measured using a FID GC equipped with a 150 m Petrocol column.
  • the flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.057 h-1. Average 2-butene conversion at 0.057 h-1 was 99.7%
  • OHSV Olefin Liquid Hourly Space Velocity
  • Example 3 The catalyst of Example 3 was loaded into a pilot plant and operated as a single bed with all feed entering the top of the reactor, as shown in FIG. 1A.
  • the reactor was 14” long and made from 3/8” O.D. stainless steel tubing.
  • the reactor was loaded with 4 g of catalyst.
  • the reactor was located in an electrically heated furnace and maintained at 302 °F (150 °C).
  • Reactor pressure was 750 psig.
  • a pre-mixed gas blend with isobutane and 2-butene at a 40:1 ratio was fed to the top of the reactor bed.
  • the reactor effluent was measured using a FID GC equipped with a 150 m Petrocol column.
  • the flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.057 h-1.
  • OHSV Olefin Liquid Hourly Space Velocity
  • alkylate produced in a 4 stage unit in Example 21 was co-fed at a rate of 3.25 cc/hr.
  • Average 2- butene conversion at 0.057 h-1 was 58.1% at 10 days of cofeeding alkylate and continued to drop with time.
  • the presence of -2% C5+ olefins in the feed caused the 2-butene conversion to decrease by -41.6% vs. the base case in Example 23.
  • Example 25 Example 25
  • Example 6 The catalyst of Example 6 was loaded into a pilot plant and operated as a single bed with all feed entering the top of the reactor, as shown in FIG. 1A.
  • the reactor was 14” long and made from 3/8” O.D. stainless steel tubing.
  • the reactor was loaded with 4 g of catalyst.
  • the reactor was located in an electrically heated furnace and maintained at 302 °F (150 °C).
  • Reactor pressure was 750 psig.
  • a pre-mixed gas blend with isobutane and 2-butene at a 40:1 ratio was fed to the top of the reactor bed.
  • the reactor effluent was measured using a FID GC equipped with a 150 m Petrocol column.
  • the flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.057 h-1.
  • OHSV Olefin Liquid Hourly Space Velocity
  • the hydrogenated alkylate prepared in Example 14 was co-fed at a rate of 3.25 cc/hr.
  • Average 2-butene conversion at 0.057 h-1 was 98.8%%.
  • the presence of -0.15% C5+ olefins in the feed caused the 2-butene conversion to decrease by ⁇ 1% vs. the reference case in Example 23.
  • the substantially smaller decrease in 2-butene conversion when compared to Example 24 shows that the reduction in the amount of heavier olefins entering the bed is effective in minimizing the impact on conversion.
  • Each reactor effluent was measured using a FID GC equipped with a 60 m DB-1 column.
  • the flow to the reactor was set to achieve an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.06 h 1 for samples 26 g and 26 n which were loaded with the highest catalyst weight. Due to the design of the experiment, a variety of 2-butene conversions were obtained due to the different space velocities.
  • OHSV Olefin Liquid Hourly Space Velocity
  • FIG. 2 is a plot of the C8 olefin yield (g C8 olefin / g C5+) as a function of the 2-butene conversion with data from the catalyst of Comparative Example 2 shown as circles 201 and data from the catalyst of Example 6 is shown as stars 203.
  • FIG. 2 demonstrate the advantage of high activity catalysts in 2-butene conversion because catalysts as in Example 6 may provide near complete 2-butene conversion, decreasing the concentration of heavier olefins in any given stage of a multistage reactor and within the product mixture.
  • the catalysts of Comparative Example 2 and Examples 4, 5 and 6 were loaded into parallel microunits as single catalyst beds. Each catalyst was loaded as 6.0 cc of catalyst. The catalysts were diluted with quartz at a level such that the volume of quartz diluent was 0.85 times the catalyst volume. Each catalyst bed was operated as a single reactor with all feed entering the top of the reactor, as shown in Figure 1 (a). The reactors were located in electrically heated furnaces and maintained at 150 °C. Reactor pressure was 700 psig.
  • a pre-mixed gas blend with isobutane and 2-butene at a 40:1 ratio was fed to the top of each reactor bed at an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.06 h-1.
  • OHSV Olefin Liquid Hourly Space Velocity
  • FIG. 3 is a plot of the C8 olefin yield (g C8 olefin / g C5+) as a function of the 2-butene conversion with data from the catalyst of Comparative Example 2 shown as circles 301, data from catalyst of Example 5 is shown as diamonds 303, data from the catalyst of Example 4 is shown as pentagons 305, and the data from the catalyst of Example 6 is shown as stars 307.
  • example 6 shows higher 2-butene conversion rates.
  • the data from this example shows, one can achieve an increase in 2-butene conversion and a decrease in C8 olefin yield by increasing the activity of the catalyst. In this case, activity of the catalyst was increased by increasing the zeolite content of the catalyst from 20 to 95%.
  • Example 7 The catalysts of Example 7, 8, 11 and 12 were loaded into parallel microunits as single catalyst beds. Each catalyst was loaded as 6.0 cc of catalyst. The catalysts were diluted with quartz at a level such that the volume of quartz diluent was 0.85 times the catalyst volume. Each catalyst bed was operated as a single reactor with all feed entering the top of the reactor, as shown in Figure
  • Example 13 The catalysts of Example 13, 14, 15, 16 and 17 were loaded into parallel microunits as single catalyst beds. Each catalyst was loaded as 6.0 cc of catalyst. The catalysts were diluted with quartz at a level such that the volume of quartz diluent was 0.85times the catalyst volume. Each catalyst bed was operated as a single reactor with all feed entering the top of the reactor, as shown in Figure 1 (a). The reactors were located in electrically heated furnaces and maintained at 150 °C. Reactor pressure was 700 psig. A pre-mixed gas blend with isobutane and 2-butene at a 40: 1 ratio was fed to the top of each reactor bed at an Olefin Liquid Hourly Space Velocity (OLHSV) of 0.06 h-1. Each reactor effluent was measured using a FID GC equipped with a 60 m DB-1 column. The
  • catalysts prepared by exchanging the zeolite prior to initial heat treatment leads to higher 2-butene conversion and lower C8 olefin selectivity.
  • the production of undesired heavy olefins in the alkylation reactor leads to a decrease in light olefin conversion lower down in the reactor (or in subsequent stages) as the heavier olefins suppress the activity of the catalyst.
  • a class of active catalysts can be used for light isoparaffin alkylation in a multistage reactor and can be based on the MWW structure, including MCM-22, MCM-49 and MCM-56.
  • High activity may be achieved by maximizing the zeolite content of the catalyst composition while maintaining desired physical properties, which may include the use of a binder.
  • multiple binders are suitable for the preparation of the catalyst composition, including various forms of alumina and silica.
  • catalyst compositions prepared by introducing an exchange fluid to the zeolite and optional binder prior to the initial heat treatment leads to an increase in activity of the catalyst composition.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

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Abstract

La présente invention concerne des compositions de catalyseur comprenant une zéolite ayant des pics de diagramme de diffraction des rayons X à espacement-d, en Angström, de : 12,2 ± 0.3, 11,0 ± 0,2, 9,0 ± 0,2, 4,4 ±0,1, 4,05 ± 0,05, 3,91 ± 0,05, 3,42 ± 0,03, 3,3 ± 0,05. La composition comprend un liant et a une surface BET d'environ 400 m2/g à environ 700 m2/g. La présente invention concerne également des procédés d'alkylation d'isoparaffines comprenant l'introduction, dans un réacteur à plusieurs étages, d'une charge d'isoparaffine, d'une charge d'oléfine et d'une charge d'hydrogène à une composition de catalyseur. La présente invention concerne également des procédés de préparation de compositions de catalyseur comprenant l'introduction d'une zéolite, et un liant à l'eau formant un premier mélange. Le premier mélange peut être extrudé puis séché. L'extrudat séché peut être introduit dans un fluide d'échange puis calciné pour former la composition de catalyseur.
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