US20140221194A1 - Methods for producing zeolite catalysts and methods for producing alkylated aromatic compounds using the zeolite catalysts - Google Patents
Methods for producing zeolite catalysts and methods for producing alkylated aromatic compounds using the zeolite catalysts Download PDFInfo
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- US20140221194A1 US20140221194A1 US14/205,916 US201414205916A US2014221194A1 US 20140221194 A1 US20140221194 A1 US 20140221194A1 US 201414205916 A US201414205916 A US 201414205916A US 2014221194 A1 US2014221194 A1 US 2014221194A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000010457 zeolite Substances 0.000 title claims abstract description 87
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 46
- 150000001491 aromatic compounds Chemical class 0.000 title description 5
- 239000011148 porous material Substances 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 230000002708 enhancing effect Effects 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000007704 transition Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 14
- 238000003801 milling Methods 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 238000009792 diffusion process Methods 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 14
- 238000005804 alkylation reaction Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229920003091 Methocel™ Polymers 0.000 description 5
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- -1 alkylated benzene compound Chemical class 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000019887 Solka-Floc® Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- 230000001965 increasing effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Images
Classifications
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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
-
- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
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- B01J35/40—
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- 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
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
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- 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
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- 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
Definitions
- This invention relates generally to methods for producing catalysts used for the alkylation of aromatic compounds and methods for alkylation of aromatic compounds using such catalysts. More particularly, this invention relates to methods for producing zeolite catalysts having improved catalytic activity in diffusion-resistant applications and methods for producing alkylated aromatic compounds using such zeolite catalysts.
- the alkylation of aromatic hydrocarbons such as benzene with olefins having two, three, or four carbon atoms is a commercially important process.
- the production of ethylbenzene is used to provide a feedstock for styrene production, while the alkylation of benzene with propylene produces isopropylbenzene (cumene). Cumene is an important feedstock to make phenol as well as a good gasoline blending component. Numerous other uses exist for such alkylated aromatic hydrocarbons. In these alkylation processes, new catalysts are continuously needed that have a high overall conversion of the feedstock and have a good selectivity of alkylated benzenes.
- Zeolite catalysts (hereinafter referred to collectively as “zeolites”) have been found to be particularly well-suited for use in the alkylation of aromatic hydrocarbons.
- Zeolites are crystalline aluminosilicate compositions that are microporous and that are formed from corner sharing AlO 2 and SiO 2 tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared, are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al, and structure-directing agents such as alkali metals, alkaline earth metals, amines, and/or organoammonium cations.
- the structure-directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers. Zeolite catalyst compositions also typically include a filler or binder material mixed with the aluminosilicate material, which helps to form the zeolite catalyst into a desired shape. Zeolites are characterized by having pore openings on the external surface of the catalyst, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase, which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure.
- zeolites have been shown to be useful for the alkylation of a variety of aromatic hydrocarbons with a variety of light olefins
- testing has shown that alkylation reactions using zeolite catalysts are highly diffusion limited. The reaction rate is so fast and the diffusion of olefin into and throughout the catalyst to reach all the zeolitic active sites is the rate limiting step. Diffusion within the catalyst depends, in part, on the overall porosity and pore structure of the catalyst and in part on the dispersion of zeolite throughout the matrix. In order to disperse the zeolite throughout the matrix mechanic force through a process such as mulling is applied. However, the compaction invariably reduces the catalyst porosity, increasing the diffusion resistance and thus lowering the catalyst activity.
- a method for producing a zeolite catalyst includes mixing a zeolite material with a filler material comprising transition phase and alpha alumina, a porosity enhancing agent, and water to produce a paste; mulling the paste; extruding the paste to produce a shaped extrudate; and drying and calcining the shaped extrudate to produce a zeolite catalyst, wherein the zeolite catalyst has a total porosity greater than about 0.60 ml/gm and greater than 15% of a total pore volume of pores in the range from about 550 ⁇ to about 31,000 ⁇ .
- a method for producing an alkylated benzene compound includes mixing a zeolite material with a filler material comprising transition phase and alpha alumina, a porosity enhancing agent, and water to produce a paste; mulling the paste; extruding the paste to produce a shaped extrudate; drying and calcining the shaped extrudate to produce a zeolite catalyst, wherein the zeolite catalyst has a total porosity greater than about 0.60 ml/gm and greater than 15% of a total pore volume of pores in the range from about 550 ⁇ to about 31,000 ⁇ ; and contacting a hydrocarbon stream comprising benzene and an olefin in the presence of the zeolite catalyst.
- FIG. 1 is a simplified block diagram of a method for producing a zeolite catalyst in accordance with one exemplary embodiment
- FIG. 2 depicts the pore size distribution of exemplary catalysts produced in accordance with the method shown in FIG. 1 ;
- FIG. 3 depicts the percentage of ethylene converted in an alkylation reaction of ethylene and benzene using exemplary catalysts produced in accordance with the method shown in FIG. 1 ;
- FIG. 4 is a simplified block diagram of a method for producing an alkylated benzene compound in accordance with one exemplary embodiment.
- Alkylbenzenes such as ethylbenzene and isopropylbenzene, are produced commercially by the reaction of benzene with ethylene and propylene, respectively.
- the process operates in liquid phase, or at least partially in liquid phase, in order to maintain stable production.
- the reaction of C 2-4 olefins with benzene is relatively fast and operates in a reaction region of a catalyst where the diffusion of olefin into the catalyst is the rate limiting step.
- the rate of the reaction is thereby improved by using a catalyst that allows for a greater diffusion of olefins into the catalyst.
- the diffusion of olefins into the catalyst is improved by providing a catalyst that has high catalyst porosity, desirable pore structures with the zeolite well-dispersed within the catalyst binder matrix.
- method for producing a zeolite catalyst includes optionally milling a stock batch of zeolite to achieve zeolite particles to reduce the aggregate to a specified range of size.
- particle size means the diameter or average dimension of a particle.
- milling proceeds to a particle size distribution such that greater than about 80%, or for example greater than about 90%, of the milled zeolite particles are in the specified range. Milling can be performed using any known method. In one example, dry- or wet-ball milling may be performed in a tumbler apparatus. In another example, wet milling may be performed by running a zeolite slurry through a chamber containing refractory beads agitated using an impeller as exemplified by Eiger bead mill.
- a typical method 100 includes combining or mixing ( 101 ) the zeolite (optionally milled) with a binder (or filler) material and a mulling step ( 102 ), where the zeolite particle is further reduced and dispersed into the binder uniformly.
- the force introduced to break up the zeolite aggregates also reduces the porosity of the catalyst due to the mechanical compaction.
- the reduced porosity adds diffusion resistance, lowering the utilization of the zeolite in the catalyst pellets.
- various organic additives are incorporated with optionally an increased amount of water into the preparation. Such an approach in general helps alleviate the compaction and gives reasonably high porosity, with minimal compaction introduced, but it is not useful in attaining an effective pore structures made up of interconnecting small and large pores.
- a zeolite preparation method 100 that achieves both uniform dispersion of the zeolite throughout the binder matrix and attains effective pore structures desired for delivering olefin throughout the catalyst: Specifically such characteristics are achieved by mulling a mixture of zeolite to reduce and disperse zeolite particles or optionally milled zeolite particle and gamma alumina particle instead of typical binders such as boehmite and pseudo-boehmite alumina, as has been typically performed in the art.
- gamma alumina other transition phase alumina such as chi, kappa, delta, eta, and theta can be used in placement of gamma alumina.
- alpha alumina can be used in placement of gamma alumina as well.
- Gamma and other transition alumina, and alpha alumina powders can be obtained commercially at varying particle size ranges with the particle size of less than 100 microns, more preferably less than 20 microns and most preferably less than 10 microns.
- the amount of alumina may range from about 10 weight % to about 80 weight % on a 100% solids basis, for example from about 20 weight % to about 40 weight %, such as about 30 weight %.
- the amount of zeolite should be an amount that effects sufficient catalytic activity to the ultimately produced catalyst for use in industrial hydrocarbon reactors.
- the amount of zeolite may range from about 20 weight % to about 90 weight % on a 100% solids basis, for example from about 60 weight % to about 80 weight %, such as about 70 weight %.
- the porosity enhancing agent may be incorporated as an organic agent or an inorganic agent.
- the pore enhancing agent is an organic, water-insoluble agent, for example, a powdered cellulose fiber compound sold under the trade name SOLKA-FLOC® by the International Fiber Corporation of North Tonawanda, N.Y., USA.
- Another exemplary pororisty enhancing agent is tylose powder.
- the porosity enhancing agent is an organic, water-soluble agent, for example, a cellulose-derived polymer sold under the trade name Methocel® by the Dow Chemical Company of Midland, Mich., USA.
- the porosity enhancing agent may be provided to the extrudable mixture in an amount from about 2 weight % to about 10 weight % on a 100% solids basis, for example from about 4 weight % to about 8 weight %, such as about 4 or 6 weight %.
- a sufficient amount of water should be added so that the mixture can be extruded into the desired catalyst shape.
- the amount of water may be added so the content of the water ranges from about 30% to about 85% weight of the solids, for example, about 50 weight % to about 70 weight % of the solids.
- This extrudable mixture may be in the form of a dough.
- methods for producing zeolite catalysts in accordance with the present disclosure may include a step of mulling the extrudable mixture.
- Mulling serves to disperse the zeolite particles within the dough mixture, which can increase diffusion within the catalyst.
- mulling can increase the density of the mixture by compacting the mixture, thereby limiting diffusion within the resulting catalyst.
- mulling does not have such typical compaction effect most likely due to the replacement of boehmite alumina with gamma alumina in the catalyst formulation.
- the resulting catalyst showed uniform zeolite dispersion, while attaining an effective pore structure, which is made up of small and large pores. Furthermore, the catalyst showed good physical strength.
- the exemplary method 100 further includes extruding the mixture into a shaped catalyst (step 103 ).
- a shaped catalyst Various shapes are known in the art, for example generally spherical and generally cylindrical. It has been discovered that extruding the catalyst into a multi-lobed shape, for example a tri-lobed shape, increases the surface area of the catalyst for any given diameter, and therefore improves the reactants access to the catalyst active sites, which has been found to be particularly beneficial in diffusion-resistant applications.
- the circumference of an exemplary tri-lobe extruded catalyst shape ranges from about 0.1 inches to about 0.8 inches, for example from about 0.12 inches to about 0.7 inches, such as about 0.15 to about 0.55 inches.
- the diameter of such tri-lobe catalyst will range from about 0.1 inches to about 0.4 inches, for example about 0.120 to about 0.24 inches.
- the ratio of the length of the catalyst to its diameter can range from about 2:1 to about 4:1.
- the ratios of the external surface of the catalyst to its volume are greater than 80 inch ⁇ 1 .
- the extrudate is dried and calcined ( 104 ), and then ammonium exchange to lower sodium contents ( 105 ).
- the extrudate can be dried and calcined in a kiln at a temperature of from about 500° C. to about 700° C. for a time period of from about 20 minutes to about 90 minutes.
- the catalyst is thereafter washed in an aqueous, ammonium-containing bath to remove sodium after the calcination step.
- the ammonium containing bath may include ammonium nitrate or ammonium sulfate at a temperature of from about 30° C. to about 100° C., for example about 60° C.
- the catalyst is washed for a time period of from about 0.5 hours to about 6 hours, for example about 2 hours.
- an exemplary wash solution includes about 1 g of ammonium nitrate and about 5 to 10 grams of water per gram of catalyst.
- Other suitable washing bath compositions will be known to those having ordinary skill in the art.
- Zeolite catalysts prepared in accordance with the foregoing exemplary method have been demonstrated to have a relatively high dispersion of zeolite particles in the catalyst binder matrix, thereby enhancing the amount of zeolite available to the reacting compounds. Furthermore, catalysts prepared in accordance with the foregoing exemplary method have been demonstrated to have a relatively high proportion of large-size pores, thereby improving the intra-particulate diffusion of the reacting compounds within the catalyst. Without being bound by theory, it is postulated that the improved dispersion of zeolite particles is due to the use of a binder material with a different morphology than the zeolite. For example, certain zeolite such as UZM-8 zeolite has a “plate-like” morphology.
- the boehmite may be calcined to form gamma alumina, which has sintered to a large particles with a shape that differs from the plate-like zeolite.
- gamma alumina densification caused by the stacking of plate zeolite and boehmite alumina is minimized.
- the outcome is a porous catalyst with well disperse zeolite and effective pore structure and thus enhanced diffusion properties.
- zeolite catalysts as contemplated herein.
- the examples are provided for illustrative purposes only and are not meant to limit the various embodiments of the methods for producing zeolite catalysts in any way.
- Catalyst Examples 1, 2, and 3 were prepared in accordance with the exemplary method set forth above.
- Catalyst Examples 4 and 5 were prepared using previously known methods as a reference comparison.
- a zeolite stock of UZM-8 material was milled using a single-pass milling procedure to produce a particle distribution having at least 80% of the particles in the range of about 10 microns to about 100 microns.
- the milled zeolite was mixed with an alumina filler material that acted as a binder, at a ratio of about 70:30 zeolite to alumina.
- Examples 1-3 gamma alumina was used, which, as discussed above, results in a greater dispersion of zeolite catalyst due to the difference in shape between the zeolite particles and the gamma alumina particles.
- Examples 4-5 boehmite was used, which, as discussed above, has a plate-like shape similar to milled zeolite. A pore enhancing agent was then added to each mixture.
- Examples 1-3 4% by weight of solids Methocel® was used.
- Example 4 6% by weight solids SOLKA-FLOC® was used.
- Example 5 6% by weight of solids tylose was used.
- FIG. 2 shows the cumulative pore size distribution for catalyst Examples 1-5.
- Table 1 Data regarding the total pore volume of each exemplary catalyst, along with the pore volume in the pore size range of about 600 ⁇ to about 31000 ⁇ (large pores), is also provided above in Table 1.
- the catalysts prepared in accordance with the exemplary method exhibit significantly higher porosity in the range from about 600 ⁇ (indicated by first dashed line) to about 31,000 ⁇ (indicated by second dashed line) diameter, and have a greater percentage of total pores in this range.
- the catalysts prepared in accordance with the exemplary method exhibited a total porosity by Hg intrusion of greater than about 0.60 ml/gm and greater than 15% of a total pore volume in the range from about 550 ⁇ to about 31,000 ⁇ .
- the catalysts of Examples 2-5 were then employed in a test-scale reactor for alkylating benzene with ethylene.
- the reaction was run at a temperature of about 215° C. inlet, at a benzene to olefin molar ratio of about 20, and at a pressure of about 550 psig.
- the catalysts prepared in accordance with the exemplary method displayed a higher olefin conversion.
- the results demonstrate the benefit of high total porosity and high proportion of pores in the range from about 600 ⁇ to about 31,000 ⁇ diameter.
- a method 400 for producing alkylated benzene compound using the zeolite catalysts as described above, in accordance with an exemplary embodiment, is described with reference to FIG. 4 .
- the method includes providing a zeolite catalyst (step 401 ).
- the zeolite catalyst can be formed using any of the various embodiments for making zeolite catalysts as described above.
- the zeolite catalyst is formed from a mixture including a zeolite stock material, a gamma alumina filler, a porosity enhancing agent, and water.
- the method further includes contacting a hydrocarbon stream comprising benzene and an olefin in the presence of the zeolite catalyst.
Abstract
A method for producing a zeolite catalyst includes mixing a zeolite material with a filler material comprising transition phase and alpha alumina, a porosity enhancing agent, and water to produce a paste; mulling the paste; extruding the paste to produce a shaped extrudate; and drying and calcining the shaped extrudate to produce a zeolite catalyst, wherein the zeolite catalyst has a total porosity greater than about 0.60 ml/gm and greater than 15% of a total pore volume of pores in the range from about 550 Å to about 31,000 Å.
Description
- This application is a division of prior copending U.S. application Ser. No. 13/450,296 which was filed on Apr. 18, 2012, the contents of which are hereby incorporated by reference in its entirety.
- This invention relates generally to methods for producing catalysts used for the alkylation of aromatic compounds and methods for alkylation of aromatic compounds using such catalysts. More particularly, this invention relates to methods for producing zeolite catalysts having improved catalytic activity in diffusion-resistant applications and methods for producing alkylated aromatic compounds using such zeolite catalysts.
- The alkylation of aromatic hydrocarbons such as benzene with olefins having two, three, or four carbon atoms (hereinafter referred to as “light” olefins), such as ethylene and propylene, is a commercially important process. The production of ethylbenzene is used to provide a feedstock for styrene production, while the alkylation of benzene with propylene produces isopropylbenzene (cumene). Cumene is an important feedstock to make phenol as well as a good gasoline blending component. Numerous other uses exist for such alkylated aromatic hydrocarbons. In these alkylation processes, new catalysts are continuously needed that have a high overall conversion of the feedstock and have a good selectivity of alkylated benzenes.
- Zeolite catalysts (hereinafter referred to collectively as “zeolites”) have been found to be particularly well-suited for use in the alkylation of aromatic hydrocarbons. Zeolites are crystalline aluminosilicate compositions that are microporous and that are formed from corner sharing AlO2 and SiO2 tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared, are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al, and structure-directing agents such as alkali metals, alkaline earth metals, amines, and/or organoammonium cations. The structure-directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers. Zeolite catalyst compositions also typically include a filler or binder material mixed with the aluminosilicate material, which helps to form the zeolite catalyst into a desired shape. Zeolites are characterized by having pore openings on the external surface of the catalyst, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase, which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure.
- While zeolites have been shown to be useful for the alkylation of a variety of aromatic hydrocarbons with a variety of light olefins, testing has shown that alkylation reactions using zeolite catalysts are highly diffusion limited. The reaction rate is so fast and the diffusion of olefin into and throughout the catalyst to reach all the zeolitic active sites is the rate limiting step. Diffusion within the catalyst depends, in part, on the overall porosity and pore structure of the catalyst and in part on the dispersion of zeolite throughout the matrix. In order to disperse the zeolite throughout the matrix mechanic force through a process such as mulling is applied. However, the compaction invariably reduces the catalyst porosity, increasing the diffusion resistance and thus lowering the catalyst activity.
- Accordingly, it is desirable to provide methods for producing zeolite catalysts that have better diffusion characteristics and thus improving the utility of zeolite throughout the entire catalyst. The effect of diffusion resistance on active site utilization and thus catalyst activity is especially evident in the aromatic alkylation with olefin including propylene and ethylene. Furthermore, other desirable features and characteristics will become apparent from the subsequent detailed description and the appended claims, taken in conjunction with the accompanying drawings and the foregoing technical field and background.
- Methods for producing zeolite catalysts and methods for producing alkylated aromatic compounds using the zeolite catalysts are disclosed. In an exemplary embodiment, a method for producing a zeolite catalyst includes mixing a zeolite material with a filler material comprising transition phase and alpha alumina, a porosity enhancing agent, and water to produce a paste; mulling the paste; extruding the paste to produce a shaped extrudate; and drying and calcining the shaped extrudate to produce a zeolite catalyst, wherein the zeolite catalyst has a total porosity greater than about 0.60 ml/gm and greater than 15% of a total pore volume of pores in the range from about 550 Å to about 31,000 Å.
- In another exemplary embodiment, a method for producing an alkylated benzene compound includes mixing a zeolite material with a filler material comprising transition phase and alpha alumina, a porosity enhancing agent, and water to produce a paste; mulling the paste; extruding the paste to produce a shaped extrudate; drying and calcining the shaped extrudate to produce a zeolite catalyst, wherein the zeolite catalyst has a total porosity greater than about 0.60 ml/gm and greater than 15% of a total pore volume of pores in the range from about 550 Å to about 31,000 Å; and contacting a hydrocarbon stream comprising benzene and an olefin in the presence of the zeolite catalyst.
- The inventive methods will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and wherein:
-
FIG. 1 is a simplified block diagram of a method for producing a zeolite catalyst in accordance with one exemplary embodiment; -
FIG. 2 depicts the pore size distribution of exemplary catalysts produced in accordance with the method shown inFIG. 1 ; -
FIG. 3 depicts the percentage of ethylene converted in an alkylation reaction of ethylene and benzene using exemplary catalysts produced in accordance with the method shown inFIG. 1 ; and -
FIG. 4 is a simplified block diagram of a method for producing an alkylated benzene compound in accordance with one exemplary embodiment. - The following detailed description is merely exemplary in nature and is not intended to limit the zeolite catalysts, the application and uses of the zeolite catalysts, or the methods of production of the zeolite catalysts described herein. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.
- Alkylbenzenes, such as ethylbenzene and isopropylbenzene, are produced commercially by the reaction of benzene with ethylene and propylene, respectively. The process operates in liquid phase, or at least partially in liquid phase, in order to maintain stable production. The reaction of C2-4 olefins with benzene is relatively fast and operates in a reaction region of a catalyst where the diffusion of olefin into the catalyst is the rate limiting step. The rate of the reaction is thereby improved by using a catalyst that allows for a greater diffusion of olefins into the catalyst. The diffusion of olefins into the catalyst is improved by providing a catalyst that has high catalyst porosity, desirable pore structures with the zeolite well-dispersed within the catalyst binder matrix.
- As such, the various embodiments contemplated herein relate to methods for producing zeolite catalysts with the zeolite component thereof highly dispersed within the catalyst matrix. In a typical extrusion, method for producing a zeolite catalyst includes optionally milling a stock batch of zeolite to achieve zeolite particles to reduce the aggregate to a specified range of size. As used herein, the term “particle size” means the diameter or average dimension of a particle. Preferably, milling proceeds to a particle size distribution such that greater than about 80%, or for example greater than about 90%, of the milled zeolite particles are in the specified range. Milling can be performed using any known method. In one example, dry- or wet-ball milling may be performed in a tumbler apparatus. In another example, wet milling may be performed by running a zeolite slurry through a chamber containing refractory beads agitated using an impeller as exemplified by Eiger bead mill.
- With particular attention to
FIG. 1 , atypical method 100 includes combining or mixing (101) the zeolite (optionally milled) with a binder (or filler) material and a mulling step (102), where the zeolite particle is further reduced and dispersed into the binder uniformly. However, the force introduced to break up the zeolite aggregates also reduces the porosity of the catalyst due to the mechanical compaction. The reduced porosity adds diffusion resistance, lowering the utilization of the zeolite in the catalyst pellets. To attain good zeolite dispersion but alleviate the mechanical compaction, various organic additives are incorporated with optionally an increased amount of water into the preparation. Such an approach in general helps alleviate the compaction and gives reasonably high porosity, with minimal compaction introduced, but it is not useful in attaining an effective pore structures made up of interconnecting small and large pores. - It has been unexpectedly discovered, a
zeolite preparation method 100 that achieves both uniform dispersion of the zeolite throughout the binder matrix and attains effective pore structures desired for delivering olefin throughout the catalyst: Specifically such characteristics are achieved by mulling a mixture of zeolite to reduce and disperse zeolite particles or optionally milled zeolite particle and gamma alumina particle instead of typical binders such as boehmite and pseudo-boehmite alumina, as has been typically performed in the art. In addition to gamma alumina other transition phase alumina such as chi, kappa, delta, eta, and theta can be used in placement of gamma alumina. In addition alpha alumina can be used in placement of gamma alumina as well. - Gamma and other transition alumina, and alpha alumina powders can be obtained commercially at varying particle size ranges with the particle size of less than 100 microns, more preferably less than 20 microns and most preferably less than 10 microns. The amount of alumina may range from about 10 weight % to about 80 weight % on a 100% solids basis, for example from about 20 weight % to about 40 weight %, such as about 30 weight %. The amount of zeolite should be an amount that effects sufficient catalytic activity to the ultimately produced catalyst for use in industrial hydrocarbon reactors. For example, the amount of zeolite may range from about 20 weight % to about 90 weight % on a 100% solids basis, for example from about 60 weight % to about 80 weight %, such as about 70 weight %.
- In one embodiment the porosity enhancing agent may be incorporated as an organic agent or an inorganic agent. In an exemplary embodiment, the pore enhancing agent is an organic, water-insoluble agent, for example, a powdered cellulose fiber compound sold under the trade name SOLKA-FLOC® by the International Fiber Corporation of North Tonawanda, N.Y., USA. Another exemplary pororisty enhancing agent is tylose powder. In a further exemplary embodiment, the porosity enhancing agent is an organic, water-soluble agent, for example, a cellulose-derived polymer sold under the trade name Methocel® by the Dow Chemical Company of Midland, Mich., USA. The porosity enhancing agent may be provided to the extrudable mixture in an amount from about 2 weight % to about 10 weight % on a 100% solids basis, for example from about 4 weight % to about 8 weight %, such as about 4 or 6 weight %.
- A sufficient amount of water should be added so that the mixture can be extruded into the desired catalyst shape. For example, the amount of water may be added so the content of the water ranges from about 30% to about 85% weight of the solids, for example, about 50 weight % to about 70 weight % of the solids. This extrudable mixture may be in the form of a dough.
- As previously noted, methods for producing zeolite catalysts in accordance with the present disclosure may include a step of mulling the extrudable mixture. Mulling serves to disperse the zeolite particles within the dough mixture, which can increase diffusion within the catalyst. Typically mulling, however, can increase the density of the mixture by compacting the mixture, thereby limiting diffusion within the resulting catalyst. However, in the presently described exemplary method, mulling does not have such typical compaction effect most likely due to the replacement of boehmite alumina with gamma alumina in the catalyst formulation. As mentioned the resulting catalyst showed uniform zeolite dispersion, while attaining an effective pore structure, which is made up of small and large pores. Furthermore, the catalyst showed good physical strength.
- The
exemplary method 100 further includes extruding the mixture into a shaped catalyst (step 103). Various shapes are known in the art, for example generally spherical and generally cylindrical. It has been discovered that extruding the catalyst into a multi-lobed shape, for example a tri-lobed shape, increases the surface area of the catalyst for any given diameter, and therefore improves the reactants access to the catalyst active sites, which has been found to be particularly beneficial in diffusion-resistant applications. The circumference of an exemplary tri-lobe extruded catalyst shape ranges from about 0.1 inches to about 0.8 inches, for example from about 0.12 inches to about 0.7 inches, such as about 0.15 to about 0.55 inches. The diameter of such tri-lobe catalyst will range from about 0.1 inches to about 0.4 inches, for example about 0.120 to about 0.24 inches. The ratio of the length of the catalyst to its diameter can range from about 2:1 to about 4:1. The ratios of the external surface of the catalyst to its volume are greater than 80 inch−1. - In an embodiment, the extrudate is dried and calcined (104), and then ammonium exchange to lower sodium contents (105). For example, the extrudate can be dried and calcined in a kiln at a temperature of from about 500° C. to about 700° C. for a time period of from about 20 minutes to about 90 minutes. The catalyst is thereafter washed in an aqueous, ammonium-containing bath to remove sodium after the calcination step. For example, the ammonium containing bath may include ammonium nitrate or ammonium sulfate at a temperature of from about 30° C. to about 100° C., for example about 60° C. The catalyst is washed for a time period of from about 0.5 hours to about 6 hours, for example about 2 hours. For an ammonium nitrate solution, an exemplary wash solution includes about 1 g of ammonium nitrate and about 5 to 10 grams of water per gram of catalyst. Other suitable washing bath compositions will be known to those having ordinary skill in the art.
- Zeolite catalysts prepared in accordance with the foregoing exemplary method have been demonstrated to have a relatively high dispersion of zeolite particles in the catalyst binder matrix, thereby enhancing the amount of zeolite available to the reacting compounds. Furthermore, catalysts prepared in accordance with the foregoing exemplary method have been demonstrated to have a relatively high proportion of large-size pores, thereby improving the intra-particulate diffusion of the reacting compounds within the catalyst. Without being bound by theory, it is postulated that the improved dispersion of zeolite particles is due to the use of a binder material with a different morphology than the zeolite. For example, certain zeolite such as UZM-8 zeolite has a “plate-like” morphology. Thus, using a binder that also has a plate-like morphology, such as untreated boehmite, would favor plate “stacking” or densification of the mixture. In contrast, according to the methods presented herein, the boehmite may be calcined to form gamma alumina, which has sintered to a large particles with a shape that differs from the plate-like zeolite. As such, when using gamma alumina, densification caused by the stacking of plate zeolite and boehmite alumina is minimized. The outcome is a porous catalyst with well disperse zeolite and effective pore structure and thus enhanced diffusion properties.
- The following are exemplary embodiments of zeolite catalysts as contemplated herein. The examples are provided for illustrative purposes only and are not meant to limit the various embodiments of the methods for producing zeolite catalysts in any way.
-
-
TABLE 1 Pore Total Volume Pore Pore (600-31000 Å % of Pores in Enhancer/ Density, Volume, diameter), (600-31000 Å Ex # Shape Binder Mulled gm/ml ml/gm ml/gm diameter) 1 Cylinder 4% Yes 0.668 1.024 0.258 25.2 Methocel/ Gamma Alumina 2 Trilobe 4% Yes 0.749 0.899 0.242 26.9 Methocel/ Gamma Alumina 3 Trilobe 4% Yes 0.722 1.191 0.311 26.1 Methocel/ Gamma Alumina 4 Trilobe 6% Solka No 0.754 0.965 0.072 7.5 Floc/ Boehmite 5 Trilobe 6% No 0.757 0.857 0.031 3.6 Tylose/Boehmite - Five exemplary catalysts, Examples 1-5 in Table 1, above, were prepared as follows. Catalyst Examples 1, 2, and 3 were prepared in accordance with the exemplary method set forth above. Catalyst Examples 4 and 5 were prepared using previously known methods as a reference comparison. With regard to each of Examples 1-5, a zeolite stock of UZM-8 material was milled using a single-pass milling procedure to produce a particle distribution having at least 80% of the particles in the range of about 10 microns to about 100 microns. The milled zeolite was mixed with an alumina filler material that acted as a binder, at a ratio of about 70:30 zeolite to alumina. In Examples 1-3, gamma alumina was used, which, as discussed above, results in a greater dispersion of zeolite catalyst due to the difference in shape between the zeolite particles and the gamma alumina particles. In Examples 4-5, boehmite was used, which, as discussed above, has a plate-like shape similar to milled zeolite. A pore enhancing agent was then added to each mixture. In Examples 1-3, 4% by weight of solids Methocel® was used. In example 4, 6% by weight solids SOLKA-FLOC® was used. In Example 5, 6% by weight of solids tylose was used. A sufficient amount of water was added, in an amount of about 65% by weight of the solids to form an extrudable paste or dough. The mixture was mulled in Examples 1-3, but the mixture was not mulled in Examples 4-5. The paste was then extruded through a tri-lobe shaped die in all but Example 1, where a cylinder shape was used. Thereafter, the extruded catalyst was dried, calcined, and washed in aqueous ammonium in accordance with the exemplary method set forth above.
- The catalysts of Examples 1-5 were then analyzed to determine pore size distribution using known mercury penetration techniques.
FIG. 2 shows the cumulative pore size distribution for catalyst Examples 1-5. (Data regarding the total pore volume of each exemplary catalyst, along with the pore volume in the pore size range of about 600 Å to about 31000 Å (large pores), is also provided above in Table 1.) As can be seen, the catalysts prepared in accordance with the exemplary method (Examples 1-3) exhibit significantly higher porosity in the range from about 600 Å (indicated by first dashed line) to about 31,000 Å (indicated by second dashed line) diameter, and have a greater percentage of total pores in this range. In particular, the catalysts prepared in accordance with the exemplary method exhibited a total porosity by Hg intrusion of greater than about 0.60 ml/gm and greater than 15% of a total pore volume in the range from about 550 Å to about 31,000 Å. - The catalysts of Examples 2-5 were then employed in a test-scale reactor for alkylating benzene with ethylene. The reaction was run at a temperature of about 215° C. inlet, at a benzene to olefin molar ratio of about 20, and at a pressure of about 550 psig. As shown in
FIG. 3 , the catalysts prepared in accordance with the exemplary method (Examples 2 and 3 (Example 1 having not been tested)) displayed a higher olefin conversion. The results demonstrate the benefit of high total porosity and high proportion of pores in the range from about 600 Å to about 31,000 Å diameter. - A
method 400 for producing alkylated benzene compound using the zeolite catalysts as described above, in accordance with an exemplary embodiment, is described with reference toFIG. 4 . The method includes providing a zeolite catalyst (step 401). The zeolite catalyst can be formed using any of the various embodiments for making zeolite catalysts as described above. For example, in one embodiment, the zeolite catalyst is formed from a mixture including a zeolite stock material, a gamma alumina filler, a porosity enhancing agent, and water. The method further includes contacting a hydrocarbon stream comprising benzene and an olefin in the presence of the zeolite catalyst. - While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the described embodiment or embodiments. It should be understood that various changes can be made in the processes without departing from the scope defined by the claims, which includes known equivalents and foreseeable equivalents at the time of this disclosure.
Claims (9)
1. A method for producing a zeolite catalyst comprising:
mixing a zeolite material with a filler material comprising transition phase and alpha alumina, a porosity enhancing agent, and water to produce a paste;
mulling the paste;
extruding the paste to produce a shaped extrudate; and
drying and calcining the shaped extrudate to produce a zeolite catalyst, wherein the zeolite catalyst has a total porosity greater than about 0.60 ml/gm and greater than 15% of a total pore volume of pores in the range from about 550 Å to about 31,000 Å.
2. The method of claim 1 , wherein the transition phase alumina is a gamma, chi, kappa, delta, eta, and/or theta alumina.
3. The method of claim 2 , wherein the transition phase alumina is gamma alumina.
4. The method of claim 1 , wherein the transition phase and alpha alumina have a particle size of less than 100 microns, or less than 20 microns, or less than 10 microns.
5. The method of claim 1 further comprising mixing the zeolite, and the transition phase and alpha alumina with a porosity enhancing agent, wherein the porosity enhancing agent comprises an organic, water-soluble porosity enhancing agent, an organic water-insoluble large pore enhancing agent, or a mixture of thereof.
6. The method of claim 1 , wherein extruding the paste to produce a shaped extrudate comprises extruding the paste to form a tri-lobe shaped extrudate having an external surface to volume ratio of greater than 80 inch−1.
7. The method of claim 1 , wherein the mixture comprising the zeolite, transition phase or alpha alumina and porosity enhancing agents is mulled over a period of time from about 10 to about 360 minutes.
8. The method of claim 1 , wherein calcining the shaped extrudate comprises calcining at a temperature from about 500° C. to about 700° C. for a time period from about 20 minutes to about 240 minutes.
9. The method of claim 1 , wherein milling the stock zeolite comprises milling the stock zeolite to produce milled zeolite having an average particle size in the range from about 100 microns to about 10 microns.
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2012
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- 2013-04-08 KR KR1020147017440A patent/KR101728594B1/en active IP Right Grant
- 2013-04-08 BR BR112014016123A patent/BR112014016123A8/en not_active Application Discontinuation
- 2013-04-08 WO PCT/US2013/035556 patent/WO2013158391A1/en active Application Filing
- 2013-04-08 JP JP2014558994A patent/JP2015513459A/en active Pending
- 2013-04-08 SG SG11201402567XA patent/SG11201402567XA/en unknown
- 2013-04-08 MY MYPI2014001530A patent/MY185975A/en unknown
- 2013-04-08 EP EP13778298.3A patent/EP2838655A4/en not_active Withdrawn
- 2013-04-18 TW TW102113837A patent/TWI508778B/en not_active IP Right Cessation
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2014
- 2014-03-12 US US14/205,916 patent/US20140221194A1/en not_active Abandoned
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KR101728594B1 (en) | 2017-04-19 |
CN104245130A (en) | 2014-12-24 |
WO2013158391A1 (en) | 2013-10-24 |
US8759597B2 (en) | 2014-06-24 |
EP2838655A4 (en) | 2015-12-30 |
SG11201402567XA (en) | 2014-06-27 |
JP2015513459A (en) | 2015-05-14 |
US20130281754A1 (en) | 2013-10-24 |
MY185975A (en) | 2021-06-14 |
TW201412398A (en) | 2014-04-01 |
TWI508778B (en) | 2015-11-21 |
BR112014016123A8 (en) | 2017-07-04 |
BR112014016123A2 (en) | 2017-06-13 |
EP2838655A1 (en) | 2015-02-25 |
KR20140102255A (en) | 2014-08-21 |
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