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EP0592392A4 - Low-aluminum boron beta zeolite. - Google Patents

Low-aluminum boron beta zeolite.

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Publication number
EP0592392A4
EP0592392A4 EP19900911359 EP90911359A EP0592392A4 EP 0592392 A4 EP0592392 A4 EP 0592392A4 EP 19900911359 EP19900911359 EP 19900911359 EP 90911359 A EP90911359 A EP 90911359A EP 0592392 A4 EP0592392 A4 EP 0592392A4
Authority
EP
European Patent Office
Prior art keywords
zeolite
accordance
proceεε
oxide
catalyεt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19900911359
Other languages
German (de)
French (fr)
Other versions
EP0592392A1 (en
Inventor
Stacey I Zones
Dennis L Holtermann
Lawrence W Jossens
Donald S Santilli
Andrew Rainis
James N Ziemer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron Research and Technology Co
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Filing date
Publication date
Application filed by Chevron Research and Technology Co filed Critical Chevron Research and Technology Co
Publication of EP0592392A4 publication Critical patent/EP0592392A4/en
Publication of EP0592392A1 publication Critical patent/EP0592392A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • 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
    • 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
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/86—Borosilicates; Aluminoborosilicates

Definitions

  • Natural and synthetic zeolitic crystalline aluminosilicates are useful as catalysts and adsorbents. These aluminosilicate ⁇ have distinct crystal structures which are demonstrated by X-ray diffraction. The crystal structure defines cavities and pores which are characteristic of the different species. The adsorptive and catalytic properties of each crystalline aluminosilicate are determined in part by the dimensions of its pores and cavities. Thus, the utility of a particular zeolite in a particular application depends at least partly on its crystal structure.
  • crystalline aluminosilicate ⁇ are especially useful in such applications as gas drying and separation and hydrocarbon conversion. Although many different crystalline alumino ⁇ ilicates and silicates have been disclosed, there is a continuing need for new zeolites and silicates with desirable properties for ga ⁇ separation and drying, hydrocarbon and chemical conversions, and other applications.
  • Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina.
  • "Nitrogenous zeolites” have been prepared from reaction mixtures containing an organic templating agent, usually a nitrogen-containing organic cation. By varying the synthesis conditions and the composition of the reaction mixture, different zeolites can be formed using the same templating agent.
  • Use of N,N,N-trimethyl cyclopentyl- ammonium iodide in the preparation of Zeolite SSZ-15 molecular sieve is disclosed in U.S. Patent No.
  • Beta zeolite is a known synthetic crystalline aluminosilicate originally described in U.S. Patents Nos. 3,308,069 and Re 28,341 to which reference is made for further details- of this zeolite, its preparation and properties.
  • Synthetic zeoli ic crystalline boro ⁇ ilicates are useful as catalysts.
  • Method ⁇ for preparing high ⁇ ilica content zeolite ⁇ that contain framework boron are known and disclosed In U.S. Patent No. 4,269,813.
  • the amount of boron contained i the zeolite usually may be made to vary by incorporating different amounts of borate ion in the zeolite forming ⁇ olutioa.
  • U.S. Patent No. 4,788,169 describes a method for preparing beta zeolite containing boron.
  • This boron beta zeolite contains 7000 parts per million of aluminum according to the analyses given therein.
  • European Patent Application No. 188,913 claim ⁇ compositions for various intermediate pore boron-containing zeolites with an aluminum content of less than 0.05% by weight.
  • (B)Beta has a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide or mixtures of boron oxide with aluminum, gallium, or iron oxide, greater than about 10:1 and wherein the amount of aluminum is less than 0.10% by weight and having the X-ray diffraction lines of Table 1(a) below.
  • An aluminum-free boron beta zeolite can al ⁇ o be made using the novel method disclosed herein. The amount of aluminum contained in the zeolite depends simply upon the aluminum impurity present in the silica source.
  • This zeolite further has a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (1.0 to 5.0)Q 2 O:(0.1 to 2.0)M 2 O: 2 O 3 :(greater than 10)YO 2 wherein M is an alkali metal cation, W is selected from boron, Y is selected from silicon, germanium and mixtures thereof, and Q is a diquatemary ammonium ion, or mixtures of diquarternary ammonium cation, and tetraethylammonium cation.
  • (B)Beta zeolites preferably have a ⁇ ilicarboria ratio typically in the range of 10:1 to about 100:1.
  • Higher mole ratio ⁇ can be obtained by treating the zeolite with chelating agent ⁇ or acid ⁇ to extract boron from the zeolite lattice.
  • the ⁇ ilicarboria mole ratio can also be increased by using silicon and carbon halides and other similar compounds.
  • the boron in the crystalline network may also be replaced by aluminum, gallium or iron. Procedures for incorporating aluminum are de ⁇ cribed in U.S. Patent No ⁇ . 4,559,315 and 4,550,092 which are hereby incorporated by reference.
  • a method for preparing boron beta zeolite i ⁇ de ⁇ cribed in U.S. Patent No. 4,788,169 A tetraethyl ammonium template i ⁇ used to make this zeolite which contains 7000 part ⁇ per million of aluminum.
  • the method de ⁇ cribed in U.S. Patent No. 4,788,169 cannot be u ⁇ ed to make boron beta zeolite containing less than 1000 part ⁇ per million aluminum.
  • a low-aluminum boron beta zeolite cannot be made by replacing the aluminum with boron in the ⁇ ynthe ⁇ ized boron beta zeolite ⁇ tructure.
  • Successful preparation of the low-aluminum boron beta zeolite requires using a new ⁇ ynthe ⁇ is method described herein.
  • a method for making (B)beta zeolites comprising preparing an aqueous mixture containing sources of a diquatemary ammonium ion, an oxide selected from boron oxide, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof, and having a composition, in term ⁇ of mole ratio ⁇ of oxide ⁇ , falling within the following range ⁇ : Y0 2 / 2 0 3 , 10:1 to 100:1; wherein Y i ⁇ selected from ⁇ ilicon, germanium, and mixture ⁇ thereof, W i ⁇ selected from boron, and Q i ⁇ a diquatemary ammonium ion; maintaining the mixture at a temperature of at lea ⁇ t 100°C until the crystals of said zeolite are formed; and recovering said crystal ⁇ .
  • the pre ⁇ ent invention is based on our finding that low-aluminum boron beta zeolite can be made using a diquatemary ammonium template.
  • the ⁇ tructure of this zeolite is the ⁇ ame a ⁇ the boron beta zeolite ⁇ tructure ⁇ ynthe ⁇ ized u ⁇ ing the tetraethyl ammonium template in U.S. Patent No. 4,788,169.
  • the amount of aluminum incorporated into thi ⁇ ⁇ tructure can be decreased by using a different template than the tetraethyl ammonium template u ⁇ ed in U.S. Patent No. 4,788,169.
  • Typical (B)Beta boro ⁇ ilicate and boroalumino ⁇ ilicate zeolite ⁇ have the X-ray diffraction pattern of Table ⁇ 2 and 4 below.
  • the d- ⁇ pacing ⁇ are ⁇ hown in Table 8 and demonstrate framework sub ⁇ titution.
  • Calcined (B)Beta ha ⁇ a typical pattern a ⁇ ⁇ hown in Table 1(b).
  • the X-ray powder diffraction patterns were determined by standard techniques.
  • the radiation was the K-alpha/doublet of copper and a scintillation counter spectrometer with a strip-chart pen recorder was used.
  • the peak heights I and the positions, as a function of 2 ⁇ where ⁇ is the Bragg angle, were read from the spectrometer chart. From these measured values, the relative intensitie ⁇ , 100I/I , where I i ⁇ the inten ⁇ ity (peak height) of the strongest peak, and d/n, related to interplanar spacings in Angstroms corresponding to the recorded peaks, can be calculated.
  • the X-ray diffraction pattern of Table 1(a) is characteristic of (B)Beta zeolite ⁇ .
  • the zeolite produced by exchanging the metal or other cations present in the zeolite with various other cations yield ⁇ substantially the ⁇ ame diffraction pattern although there can be minor ⁇ hift ⁇ in interplanar ⁇ pacing and minor variation ⁇ in relative inten ⁇ ity.
  • Minor variations in the diffraction pattern can al ⁇ o re ⁇ ult from variation ⁇ in the organic compound used in the preparation and from variations in the silica-to-boria mole ratio from sample to ⁇ ample. Calcination can also cause minor shift ⁇ in the X-ray diffraction pattern. Notwith ⁇ tanding the ⁇ e minor perturbation ⁇ , the basic crystal lattice ⁇ tructure remains unchanged.
  • (B)Beta zeolites can be suitably prepared from an aqueous ⁇ olution containing ⁇ ource ⁇ of an alkali metal borate, a bi ⁇ (l-Azonia, bicyclo[2.2.2] octane- ⁇ , ⁇ alkane diquatemary ammonium ion, and an oxide of ⁇ ilicon or germanium, or mixture of the two.
  • the reaction mixture ⁇ hould have a compo ⁇ ition in terms of mole ratio ⁇ falling within the following range ⁇ : Broad Preferred
  • Y is ⁇ ilicon, germanium or both
  • the organic compound which act ⁇ a ⁇ a ⁇ ource of the quaternary ammonium ion employed can provide hydroxide ion.
  • the quaternary ammonium compound ⁇ are prepared by method ⁇ known in the art, an example of which can be found in U.S. No. 4,508,837.
  • the reaction mixture is prepared using ⁇ tandard zeolitic preparation technique ⁇ .
  • Source ⁇ of boron for the reaction mixture include boro ⁇ ilicate gla ⁇ e ⁇ and most particularly, other reactive borates and borate esters.
  • Typical sources of ⁇ ilicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl ortho ⁇ ilicate ⁇ , and ⁇ ilica hydroxide ⁇ .
  • the reaction mixture i ⁇ maintained at an elevated temperature until the cry ⁇ tal ⁇ of the zeolite are formed.
  • the temperature ⁇ during the hydrothermal crystallization step are typically maintained from about 140°C to about 200°C, preferably from about 150°C to about 170°C and mo ⁇ t preferably from about 135 ⁇ C to about 165 ⁇ C.
  • the cry ⁇ tallization period i ⁇ typically greater than one day and preferably from about three days to about seven days.
  • the hydrothermal cry ⁇ tallization i ⁇ conducted under pre ⁇ sure and usually in an autoclave so that the reaction mixture is subject to autogenou ⁇ pre ⁇ ure.
  • the reaction mixture can be ⁇ tirred during cry ⁇ tallization.
  • the ⁇ olid product is ⁇ eparated from the reaction mixture by standard mechanical separation techniques ⁇ uch a ⁇ filtration.
  • the cry ⁇ tals are water-washed and then dried, e.g., at 90 ⁇ C to 150°C from 8 to 24 hours, to obtain the as ⁇ ynthe ⁇ ized, (B)Beta zeolite cry ⁇ tal ⁇ .
  • the drying ⁇ tep can be performed at atmo ⁇ pheric or ⁇ ubatmo ⁇ pheric pre ⁇ ure ⁇ .
  • the (B)Beta cry ⁇ tal ⁇ can be allowed to nucleate spontaneously from the reaction mixture.
  • the reaction mixture can al ⁇ o be ⁇ eeded with (B)Beta cry ⁇ tal ⁇ both to direct, and accelerate the crystallization, as well as to minimize the formation of unde ⁇ ired alumino ⁇ ilicate contaminant ⁇ .
  • the ⁇ ynthetic (B)Beta zeolite ⁇ can be u ⁇ ed a ⁇ ⁇ ynthesized or can be thermally treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion.
  • the zeolite can be leached with chelating agents, e.g., EDTA or dilute acid solution ⁇ , to increa ⁇ e the ⁇ ilica:boria mole ratio.
  • the zeolite can be u ⁇ ed in intimate combination with hydrogenating components, ⁇ uch a ⁇ tung ⁇ ten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such a ⁇ palladium or platinum, for tlbo ⁇ e application ⁇ in which a hydrogenation-dehydrogenation function i ⁇ de ⁇ ired.
  • Typical replacing cations can include metal cations, e.g., rare earth, Group II and Group VIII metal ⁇ , a ⁇ well a ⁇ their mixture ⁇ .
  • cation ⁇ of metal ⁇ ⁇ uch a ⁇ rare earth Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe, and Co are particularly preferred.
  • the hydrogen, ammonium, and metal component ⁇ can be exchanged into the zeolite.
  • the zeolite can al ⁇ o be impregnated with the metal ⁇ , or, the metal ⁇ can be phy ⁇ ically intimately admixed with the zeolite u ⁇ ing ⁇ tandard method ⁇ known to the art. And, the metal ⁇ can be occluded in the cry ⁇ tal lattice by having the de ⁇ ired metal ⁇ pre ⁇ ent a ⁇ ion ⁇ in the reaction mixture from which the (B)Beta zeolite i ⁇ prepared.
  • Typical ion exchange technique ⁇ involve contacting the ⁇ ynthetic zeolite with a ⁇ olution containing a ⁇ alt of the de ' ⁇ ired replacing cation or cation ⁇ .
  • ⁇ alt ⁇ chlorides and other O 91/00777
  • halides, nitrates, and sulfates are particularly preferred.
  • Representative ion exchange technique ⁇ are di ⁇ clo ⁇ ed in a wide variety of patents including U.S. Nos. 3,140,249; 3,140,251; and 3,140,253.
  • the zeolite is typically washed with water and dried at temperature ⁇ ranging from 650°C to about 315 ⁇ C. After wa ⁇ hing, the zeolite can be calcined in air or inert ga ⁇ at temperature ⁇ ranging from about 200°C to 820°C for period ⁇ of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially u ⁇ eful in hydrocarbon conver ⁇ ion proce ⁇ e ⁇ .
  • the Beta borosilicate and ⁇ ub ⁇ equent metalloboro ⁇ ilicate can he formed into a wide variety of phy ⁇ ical ⁇ hape ⁇ .
  • the zeolite can be in the form of a powder, a granule, or a molded product, ⁇ uch a ⁇ extrudate having particle ⁇ ize ⁇ ufficient to pass through a 2-mesh (Tyler) ⁇ creen and be retained on a 400-me ⁇ h (Tyler) ⁇ creen.
  • the borosilicate can be extruded before drying, or, dried or partially dried and then extruded.
  • the zeolite can be compo ⁇ ited with other materials resi ⁇ tant to the temperature ⁇ and other condition ⁇ employed in organic conver ⁇ ion proce ⁇ es.
  • matrix materials include active and inactive materials ?.nd ⁇ ynthetic or naturally occurring zeolite ⁇ a ⁇ well a ⁇ inorganic material ⁇ ⁇ uch a ⁇ clay ⁇ , ⁇ ilica and metal oxides.
  • the latter may occur naturally or may be in the form of gelatinou ⁇ precipitates, ⁇ ol ⁇ , or gel ⁇ , including mixtures of ⁇ ilica and metal oxide ⁇ .
  • U ⁇ e of an active material in conjunction with the ⁇ ynthetic zeolite, i.e., combined with it, tend ⁇ to improve the conver ⁇ ion and ⁇ electivity of the cataly ⁇ t In certain organic conver ⁇ ion processe ⁇ .
  • Inactive material ⁇ can suitably serve as diluents to control the amount of coaver ⁇ ion in a given proce ⁇ ⁇ o that products can be obtained economically without using other means for controlling the rate of reaction.
  • zeolite material ⁇ have been incorporated into naturally occurring clay ⁇ , e.g., bentonite and kaolin.
  • the ⁇ e materials i.e., clay ⁇ , oxide ⁇ , etc., function, in part, a ⁇ binder ⁇ for the cataly ⁇ t. It i ⁇ de ⁇ irable to provide a cataly ⁇ t having good cru ⁇ h ⁇ trength, because in petroleum refining the catalyst i n often ⁇ ubjected to rough handling. Thi ⁇ tend ⁇ to break the cataly ⁇ t down into powders which cause problems in proces ⁇ ing.
  • Naturally occurring clay ⁇ which can be composited with the synthetic zeolites of thi ⁇ invention include the montmorillonite and kaolin families, which families include the sub-bentonite ⁇ and the kaolin ⁇ commonly known as Dixie, McNamee, Georgia, and Florida clay ⁇ or other ⁇ in which the main mineral constituent i ⁇ halloysite, kaolinite, dickite, nacrite, or anauxite.
  • Fibrous clays ⁇ uch a ⁇ sepiolite and attapulgite can al ⁇ o be u ⁇ ed a ⁇ ⁇ upport ⁇ .
  • Such clay ⁇ can be u ⁇ ed in the xa ⁇ tate a ⁇ originally mined or can be initially subjected to calcination, acid treatment or chemical modification.
  • the (B)Beta zeolite ⁇ can be compo ⁇ ited with porou ⁇ matrix material ⁇ and mixture ⁇ of matrix material ⁇ ⁇ uch as ⁇ ilica, alumina, titania, magnesia, ⁇ ilica:alumina, ⁇ ilica- agne ⁇ ia, ⁇ ilica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia a ⁇ well as ternary compositions such as silica-alumina-thoria, ⁇ ilica-alumina-zirconia, ⁇ ilica-alumina-magne ⁇ ia, and silica-magnesia-zirconia.
  • the matrix can be in the form of a cogel.
  • the (B)Beta zeolites can al ⁇ o be compo ⁇ ited with other zeolite ⁇ ⁇ uch a ⁇ ⁇ ynthetic and natural faujasites (e.g., X and Y), erionites, and mordenites. They can al ⁇ o be compo ⁇ ited with purely synthetic zeolites such as those of the ZSM ⁇ erie ⁇ . The combination of zeolite ⁇ can also be compo ⁇ ited in a porous inorganic matrix.
  • Hydrocarbon conver ⁇ ion reaction ⁇ are chemical and catalytic proce ⁇ ses in which carbon-containing compound ⁇ are changed to different carbon-containing compound ⁇ .
  • Example ⁇ of hydrocarbon conver ⁇ ion reaction ⁇ include catalytic cracking, hydrocracking, and olefin and aromatic ⁇ formation reaction ⁇ .
  • the cataly ⁇ ts are useful in other petroleum refining and hydrocarbon conversion reactions such as isomerizing n-paraffin ⁇ and naphthene ⁇ , polymerizing and oligomerizing olefinic or acetylenic compound ⁇ such as isobutylene and butene-1, reforming, alkylating, i ⁇ omerizing polyalkyl ⁇ ub ⁇ tituted aromatic ⁇ (e.g., ortho xylene), and di ⁇ proportionating aromatics (e.g., toluene) to provide mixture ⁇ of benzene, xylene ⁇ , and higher methylbenzenes.
  • isomerizing n-paraffin ⁇ and naphthene ⁇ polymerizing and oligomerizing olefinic or acetylenic compound ⁇ such as isobutylene and butene-1
  • reforming alkylating, i ⁇ omerizing polyalkyl ⁇ ub ⁇ tituted aromatic ⁇ (e.g., ortho
  • the (B)Beta catalyst ⁇ have high ⁇ electivity, and under hydrocarbon conver ⁇ ion condition ⁇ can provide a high percentage of de ⁇ ired product ⁇ relative to total product ⁇ .
  • (B)Beta zeolite ⁇ can be u ⁇ ed in proce ⁇ sing hydrocarbonaceou ⁇ feed ⁇ tock ⁇ .
  • Hydrocarbonaceou ⁇ feed ⁇ tock ⁇ contain carbon compound ⁇ and can be from many different ⁇ ource ⁇ , ⁇ uch a ⁇ virgin petroleum fraction ⁇ , recycle petroleum fraction ⁇ , shale oil, liquefied coal, tar sand oil, and in general, can be any carbon containing fluid ⁇ u ⁇ ceptible to zeolitic catalytic reaction ⁇ .
  • the hydrocarbonaceou ⁇ feed i ⁇ to undergo can contain metal or be free of metals, it can also have high or low nitrogen or ⁇ ulfur impuritie ⁇ . It can be appreciated, however, that in general proce ⁇ ing will be more efficient (and the cataly ⁇ t more active) the lower the metal, nitrogen, and ⁇ ulfur content of the feed ⁇ tock.
  • U ⁇ ing a (B)Beta zeolite cataly ⁇ t which contain ⁇ boron and/or aluminum framework substitution and a hydrogenation promoter, heavy petroleum residual feedstock ⁇ , cyclic stocks, and other hydrocrackate charge stock ⁇ can be hydrocracked at hydrocracking condition ⁇ including a temperature in the range of from 175°C to 485 ⁇ C, molar ratio ⁇ of hydrogen to hydrocarbon charge from 1 to 100, a pre ⁇ ure in the range of from 0.5 to 350 bar, and a liquid hourly ⁇ pace velocity (LHSV) in the range of from 0.1 to 30.
  • hydrocracking condition ⁇ including a temperature in the range of from 175°C to 485 ⁇ C, molar ratio ⁇ of hydrogen to hydrocarbon charge from 1 to 100, a pre ⁇ ure in the range of from 0.5 to 350 bar, and a liquid hourly ⁇ pace velocity (LHSV) in the range of from 0.1 to 30.
  • LHSV liquid hourly ⁇ pace velocity
  • the hydrocracking cataly ⁇ t ⁇ contain an effective amount of at lea ⁇ t one hydrogenation catalyst (component) of the type commonly employed in hydrocracking cataly ⁇ t ⁇ .
  • the hydrogenation component i ⁇ generally selected from the group of hydrogenation cataly ⁇ t ⁇ con ⁇ i ⁇ ting of one or more metal ⁇ of Group VIB and Group VIII, including the ⁇ alt ⁇ , complexe ⁇ , and ⁇ olution ⁇ containing ⁇ uch.
  • the hydrogenation cataly ⁇ t i ⁇ preferably selected from the group of metals, salt ⁇ , and complexe ⁇ thereof of the group con ⁇ i ⁇ ting of at least one of platinum, palladium, rhodium, iridiu , and mixtures thereof or the group con ⁇ isting of at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof.
  • Reference to the catalytically active metal or metals is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, ⁇ ulfide, halide, carboxylate, and the like.
  • the hydrogenation cataly ⁇ t i ⁇ present in an effective amount to provide the hydrogenation function of the hydrocracking catalyst and preferably in the range of from 0.05% to 25% by weight.
  • the catalyst may be employed in conjunction with traditional hydrocracking catalyst ⁇ , e.g., any alumino ⁇ ilicate heretofore employed a ⁇ a component in hydrocracking cataly ⁇ t ⁇ .
  • Repre ⁇ entative of the zeolitic aluminosilicates disclosed heretofore as employable as component part ⁇ of hydrocracking cataly ⁇ t ⁇ are Zeolite Y (including steam ⁇ tabilized, e.g., ultra-stable Y), Zeolite X, Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No.
  • hydrocracking cataly ⁇ t ⁇ are typically employed with an 2 inorganic oxide-matrix component which may be any of the 3 inorganic oxide matrix component ⁇ which have been employed 4 heretofore in the formulation of hydrocracking cataly ⁇ t ⁇ 5 including: amorphou ⁇ catalytic inorganic oxide ⁇ , e.g., 6 catalytically active ⁇ ilica-alumina ⁇ , clay ⁇ , silicas, 7 aluminas, ⁇ ilica-alumina ⁇ , ⁇ ilica-zirconia ⁇ , 8 silica-magne ⁇ ia ⁇ , alumina-borias, alumina-titania ⁇ , and the 9 like and mixture ⁇ thereof.
  • amorphou ⁇ catalytic inorganic oxide ⁇ e.g., 6 catalytically active ⁇ ilica-alumina ⁇ , clay ⁇ , silicas, 7 aluminas, ⁇ ilica-alumina ⁇ , ⁇ ilica-zirconia ⁇ , 8 silica-magne ⁇ ia ⁇ , alumina
  • the traditional hydrocracking 0 cataly ⁇ t component (TC) and (B)Beta may be mixed ⁇ eparately with the matrix component and then mixed or the TC component 2 and (B)Beta may be mixed and then formed with the matrix 3 component.
  • 4 5 (B)Beta can be u ⁇ ed to dewax hydrocarbonaceou ⁇ feed ⁇ by 6 ⁇ electively removing or tran ⁇ forming ⁇ traight chain 7 paraffin ⁇ .
  • the catalytic dewaxing condition ⁇ are dependent 8 i large mea ⁇ ure on the feed u ⁇ ed and upon the de ⁇ ired pour 9 point.
  • the temperature will be between about 0 200°C and about 475 ⁇ C, preferably between about 250 ⁇ C and i about 450 ⁇ C.
  • the pre ⁇ ure i ⁇ typically between about 15 2 p ⁇ ig and about 3000 p ⁇ ig, preferably between about 200 p ⁇ ig 3 and 3000 p ⁇ ig.
  • the LHSV preferably will be from 0.1 to 20, 4 preferably between about 0.2 and about 10. 5 6
  • Hydrogen i ⁇ preferably pre ⁇ ent in the reaction zone during 7 the catalytic dewaxing proce ⁇ .
  • the hydrogen to feed ratio 8 is typically between about 500 and about 30,000 SCF/bbl g ( ⁇ tandard cubic feet per barrel), preferably about 1,000 to 0 about 20,000 SCF/bbl.
  • the (B)Beta hydrodewaxing cataly ⁇ t may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts.
  • the hydrogenation component may be selected from the group of hydrogenation catalyst ⁇ con ⁇ i ⁇ ting of one or more metal ⁇ of Group VIB and Group VIII, including the salts, complexes and ⁇ olution ⁇ containing ⁇ uch metals.
  • the preferred hydrogenation catalyst is at least one of the group of metal ⁇ , salt ⁇ , and complexe ⁇ selected from the group consisting of at least one of platinum, palladium, rhodium, iridium, and mixtures thereof or at least one from the group con ⁇ i ⁇ ting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof.
  • Reference to the catalytically active metal or metals i ⁇ intended to encompass ⁇ uch metal or metal ⁇ in the elemental ⁇ tate or in ⁇ ome form ⁇ uch as an oxide, ⁇ ulfide, halide, carboxylate, and the like.
  • the hydrogenation component i ⁇ pre ⁇ ent in an effective amount to provide an effective hydrodewaxing cataly ⁇ t preferably in the range of from about 0.05 to 5% by weight.
  • (B)Beta can be used to convert straight run naphthas and similar mixture ⁇ to highly aromatic mixture ⁇ .
  • normal and slightly branched chained hydrocarbons preferably having a boiling range above about 40°C and less than about 200°C, can be converted to products having a sub ⁇ tantial aromatic ⁇ content by contacting the hydrocarbon feed with the zeolite at a temperature in the range of from about 400°C to 600°C, preferably 480°C-550 ⁇ C at pre ⁇ ure ⁇ ranging from atmo ⁇ pheric to 10 bar, and LHSV ranging from 0.1 to 15.
  • the hydrogen to hydrocarbon ratio will range between 1 and 10.
  • (B)Beta can be u ⁇ ed in a fixed, fluid or moving bed reformer.
  • the conver ⁇ ion cataly ⁇ t preferably contain a Group VIII metal compound to have ⁇ ufficient activity for commercial u ⁇ e.
  • Group VIII metal compound a ⁇ u ⁇ ed herein i ⁇ meant the metal it ⁇ elf or a compound thereof.
  • the Group VIII noble metal ⁇ and their compound ⁇ , platinum, palladium, and iridium, or combinations thereof can be used.
  • the amount of Group VIII metal pre ⁇ ent in the conver ⁇ ion catalyst should be within the normal range of u ⁇ e in reforming cataly ⁇ t ⁇ , from about 0.05 to 2.0 wt. %, preferably 0.2 to 0.8 wt. %.
  • the performance of the noble metal in (B)Beta may be further enhanced by the pre ⁇ ence of other metals as promotors for aromatization ⁇ electivity.
  • the zeolite/Group VIII metal conversion catalyst can be used without a binder or matrix.
  • the preferred inorganic matrix, where one i ⁇ used, is a silica-ba ⁇ ed binder such a ⁇ Cab-O-Sil or Ludox. Other atrice ⁇ such a ⁇ magne ⁇ ia and titania can be u ⁇ ed.
  • the preferred inorganic matrix i ⁇ nonacidic.
  • the conver ⁇ ion cataly ⁇ t be ⁇ ub ⁇ tantially free of acidity, for example, by poi ⁇ oning the zeolite with a ba ⁇ ic metal, e.g., alkali metal, compound.
  • a ba ⁇ ic metal e.g., alkali metal
  • the ⁇ e high levels of alkali metal, usually sodium or potassium, are unacceptable for mo ⁇ t catalytic application ⁇ becau ⁇ e they greatly deactivate the cataly ⁇ t for crarcking reaction ⁇ .
  • alkali metal i ⁇ removed to low level ⁇ by ion exchange with hydrogen or ammonium ion ⁇ .
  • alkali metal compound a ⁇ u ⁇ ed herein i ⁇ meant elemental or ionic alkali metal ⁇ or their ba ⁇ ic compound ⁇ .
  • unle ⁇ s the zeolite itself is substantially free of acidity, the basic compound i ⁇ required in the pre ⁇ ent proce ⁇ to direct the ⁇ ynthetic reactions to aromatics production.
  • (B)Beta the intrinsic cracking acidity is quite low and neutralization is not usually required.
  • (B)Beta is advantageously u ⁇ ed to catalytically crack hydrocarbon feed ⁇ tock ⁇ in the absence of hydrogen.
  • Preferred conditions involve a fluidized catalytic cracking proce ⁇ which con ⁇ i ⁇ t ⁇ of contacting a hydrocarbon feed ⁇ tock with a cataly ⁇ t in a reaction zone in the ab ⁇ ence of added hydrogen at average cataly ⁇ t temperatures ranging from 800°F to 1500 ⁇ F, separating the cataly ⁇ t from the product effluent, introducing the cataly ⁇ t into a steam-stripping zone, and subsequently into a regeneration zone in the presence of steam and free oxygen containing gas where reaction coke depo ⁇ ited on the cataly ⁇ t i ⁇ burned off at elevated temperature ⁇ ranging from 1000 ⁇ F to 1550 ⁇ F, and then recycling the reactivated cataly ⁇ t to the reaction zone.
  • the (B)Beta can be employed in conjunction with traditional cracking catalysts either as an incorporated con ⁇ tituent component or a ⁇ a separate additive particle.
  • the cataly ⁇ t may be employed in conjunction with traditional cracking cataly ⁇ t ⁇ , compri ⁇ ing any alumino ⁇ ilicate heretofore employed a ⁇ a component in cracking catalysts.
  • Representative of the zeolitic alumino ⁇ ilicate ⁇ di ⁇ clo ⁇ ed heretofore a ⁇ employable a ⁇ component part ⁇ of cracking cataly ⁇ t ⁇ are Zeolite Y (including ⁇ team ⁇ tabilized Y, rare earth Y, chemically modified Y, ultra- ⁇ table Y or 1 combinations thereof).
  • 3 Zeolite ZSM-3 (U.S. Patent No. 3,415,736), fauja ⁇ ite, LZ-10 4 (U.K. Patent 2,014,970, June 9, 1982), ZSM-5-Type Zeolite ⁇ , 5 e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, 6 crystalline ⁇ ilicates such a ⁇ ⁇ ilicalite (U.S. Patent No.
  • zeolite a ⁇ u ⁇ ed herein contemplates not only 3 aluminosilicate ⁇ but ⁇ ubstances in which the aluminum i ⁇ 4 replaced by gallium or boron and ⁇ ub ⁇ tance ⁇ in which ⁇ ilicon 5 i ⁇ replaced by germanium.
  • Other representative acidic 6 aluminosilicates al ⁇ o deemmed employable a ⁇ component part ⁇ 7 are amorphou ⁇ ⁇ ilica-alumina cataly ⁇ t ⁇ , ⁇ ynthetic 8 mica-mont orillonite cataly ⁇ t ⁇ (a ⁇ defined in U.S. Patent g No. 3,252,889), cro ⁇ -linked or pillared clay ⁇ (a ⁇ defined 0 in U.S.
  • Traditional cracking cataly ⁇ t ⁇ containing amount ⁇ of Na 2 0 5 le ⁇ than about one percent by weight are generally 6 preferred.
  • the relative amount ⁇ of the (B)Beta component 7 and traditional cracking component (TC), if any, will depend 8 at lea ⁇ t in part, on the ⁇ elected hydrocarbon feedstock and 9 on the desired product distribution to be obtained 0 therefrom, but in all instance ⁇ , an effective amount of 1 (B)Beta i ⁇ employed.
  • the relative weight ratio of the TC to the (B)Beta i ⁇ generally between about 1:10 and about 500:1, de ⁇ irably between about 4 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and mo ⁇ t preferably i ⁇ between about 1:1 and about 20:1.
  • the cracking catalysts are typically employed with an inorganic oxide matrix component which may be any of the inorganic oxide matrix components which have been employed heretofore in the formulation of FCC catalyst ⁇ including: amorphou ⁇ catalytic inorganic oxide ⁇ , e.g., catalytically active ⁇ ilica-alumina ⁇ , clay ⁇ , ⁇ ynthetic or acid activated clays, silica ⁇ , aluminas, silica-aluminas, silica-zirconia ⁇ , ⁇ ilica-magne ⁇ ia ⁇ , alumina-boria ⁇ , alumina-titania ⁇ , pillared or cross-linked clays, and the like and mixtures thereof.
  • the TC component and (B)Beta may be mixed separately with their respective matrix component and then mixed together or the TC component and (B)Beta may be mixed together and then formed with the matrix component.
  • the mixture of a traditional cracking catalyst and (B)Beta may h e carried out in any manner which result ⁇ in the coincident presence of such in contact with the crude oil feedstock under catalytic cracking conditions.
  • a cataly ⁇ t may be employed containing the traditional cracking catalyst component and (B)Beta in ⁇ ingle cataly ⁇ t particles or (B)Beta with or without a matrix component may be added as a di ⁇ crete component to a traditional cracking catalyst provided its particle has appropriate den ⁇ ity and particle ⁇ ize di ⁇ tribution.
  • (B)Beta can al ⁇ o be u ⁇ ed to oligomerize ⁇ traight and branched chain olefin ⁇ having from about 2-21 and preferably 2-5 carbon atoms.
  • the oligomers which are the products of 1 the proce ⁇ are medium to heavy olefin ⁇ which are u ⁇ eful for 2 both fuels, i.e., gasoline or a gasoline blending stock and 3 chemicals.
  • the oligomerization proce ⁇ s comprise ⁇ contacting the olefin feedstock in the ga ⁇ eou ⁇ ⁇ tate pha ⁇ e with (B)Beta at a 7 temperature of from about 450°F to about 1200°F, a WHSV of 8 from about 0.2 to about 50 and a hydrocarbon partial 9 pre ⁇ ure of from about 0.1 to about 50 atmospheres. 0 1 Also, temperatures below about 450 ⁇ F may be u ⁇ ed to 2 oligomerize the* feedstock, when the feed ⁇ tock i ⁇ in the 3 liquid pha ⁇ e when contacting the zeolite cataly ⁇ t.
  • temperature ⁇ of from about 50 ⁇ F to about 6 450°F, and preferably from 80-400°F may be used and a WHSV 7 of from about 0.05 to 20 and preferably 0.1 to 10.
  • the pres ⁇ ure ⁇ employed must be 9 sufficient to maintain the sy ⁇ tem in the liquid pha ⁇ e.
  • a ⁇ 0 is known in the art, the pre ⁇ ure will be a function of the i number of carbon atoms of the feed olefin and the 2 temperature.
  • Suitable pres ⁇ ure ⁇ include from about 0 p ⁇ ig 3 to about 3000 p ⁇ ig.
  • the zeolite can have the original cations as ⁇ ociated 6 therewith replaced by a wide variety of other cation ⁇ 7 according to technique ⁇ well known in the art.
  • Typical 8 cation ⁇ would include hydrogen, ammonium, and metal cation ⁇ g including mixture ⁇ of the ⁇ ame.
  • metal ⁇ 1 ⁇ uch a ⁇ rare earth metals, manganese, calcium, a ⁇ well a ⁇ 2 metal ⁇ of Group II of the Periodic Table, e.g., zinc, and 3 Group VIII of the Periodic Table, e.g..- nickel.
  • Alpha value ⁇ are defined by a ⁇ tandard te ⁇ t known in the art, e.g., as shown in U.S. Patent No. 3,960,978 which is incorporated totally herein by reference. If required, such zeolites may be obtained by steaming, by use in a conversion proce ⁇ or by any other method which may occur to one ⁇ killed in thi ⁇ art.
  • (B)Beta can be u ⁇ ed to convert light ga ⁇ C 2 -C 8 paraffin ⁇ and/or olefin ⁇ to higher molecular weight hydrocarbon ⁇ including aromatic compounds.
  • Operating temperature ⁇ 100-700 ⁇ C
  • operating pressures of 0-1000 psig and space velocities of 0.5-40 hr ⁇ WHSV can be u ⁇ ed to convert the c 2 ⁇ c 6 P ara ⁇ f in and/or olefins to aromatic compounds.
  • the zeolite will contain a catalyst metal or metal oxide wherein said metal i ⁇ ⁇ elected from the group con ⁇ isting of Group IB, IIB, VIII, and IIIA of the Periodic Table, and mo ⁇ t preferably, gallium or zinc and in the range of from about 0.05-5 wt. %.
  • (B)Beta can be used to condense lower aliphatic alcohols having 1-10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon.
  • the conden ⁇ ation reaction proceed ⁇ at a temperature of about 500-1000°F, a pre ⁇ ure of about 0.5-1000 p ⁇ ig and a ⁇ pace velocity of about 0.5-50 WHSV.
  • the process di ⁇ clo ⁇ ed in U.S. Patent No. 3,984,107 more 1 specifically describes the proces ⁇ condition ⁇ used in this 2 proce ⁇ , which patent i ⁇ incorporated totally herein by 3 reference.
  • the cataly ⁇ t may be in the hydrogen form or may be base 6 exchanged or impregnated to contain amonium or a metal 7 cation complement, preferably in the range of from about 8 0.05-5 wt. %.
  • the metal cation ⁇ that may be pre ⁇ ent include 9 any of the metal ⁇ of the Group ⁇ I-VIII of the Periodic 0 Table. However, in the ca ⁇ e of Group IA metal ⁇ , the cation 1 content ⁇ hould ,in no ca ⁇ e be ⁇ o large a ⁇ to effectively 2 inactivate the cataly ⁇ t. 3 4
  • the cataly ⁇ t can be made highly active and highly ⁇ elective 5 for i ⁇ omerizing, C, to C, hydrocarbon ⁇ .
  • the activity mean ⁇ 6 that the cataly ⁇ t can operate at relatively low temperature ⁇ 7 which thermodynamically favor ⁇ highly branched paraffin ⁇ . 8 Consequently, the cataly ⁇ t can produce a high octane g product.
  • the high ⁇ electivity mean ⁇ that a relatively high 0 liquid yield can be achieved when the cataly ⁇ t i ⁇ run at a i high octane. 2 3
  • the feed is preferably a light straight run 6 fraction, boiling within the range of 30-250 ⁇ F and 7 preferably from 60-200 ⁇ F.
  • the hydrocarbon feed 8 f° r the process compri ⁇ e ⁇ a ⁇ ub ⁇ tantial amount of C 4 to C-, 9 normal and ⁇ lightly branched low octane hydrocarbon ⁇ , more 0 preferably C j - and C g hydrocarbon ⁇ .
  • the pre ⁇ ure in the proce ⁇ i ⁇ preferably between 50-1000 3 p ⁇ ig, more preferably between 100-500 p ⁇ ig.
  • the LHSV i ⁇ preferably between about 1 to about 10 with a value in the range of about 1 to about 4 being more preferred. It is also preferable to carry out the isomerization reaction in the pre ⁇ ence of hydrogen.
  • the temperature i ⁇ preferably between about 200 ⁇ F and about 1000 ⁇ F, more preferably between 400-600 ⁇ F.
  • the initial ⁇ election of the temperature within thi ⁇ broad range i ⁇ made primarily a ⁇ a function of the desired conversion level considering the characteristic ⁇ of the' feed and of the cataly ⁇ t. Thereafter, to provide a relatively constant value for conversion, the temperature may have to be slowly increased during the run to compensate for any deactivation that occurs.
  • a low ⁇ ulfur feed i ⁇ e ⁇ pecially preferred in the pre ⁇ ent proce ⁇ preferably contain ⁇ le ⁇ than 10 ppm, more preferably le ⁇ than 1 ppm, and mo ⁇ t preferably le ⁇ than 0.1 ppm ⁇ ulfur.
  • acceptable levels can be reached by hydrogenating the feed in a pre ⁇ aturation zone with a hydrogenating cataly ⁇ t which i ⁇ re ⁇ i ⁇ tant to sulfur poi ⁇ oning.
  • a platinum on alumina hydrogenating cataly ⁇ t can al ⁇ o work. in which ca ⁇ e, a ⁇ ulfur ⁇ orber is preferably placed downstream of the hydrogenating catalyst, but upstream of the pre ⁇ ent isomerization cataly ⁇ t.
  • Examples of ⁇ ulfur ⁇ orber ⁇ are alkali or alkaline earth metal ⁇ on porou ⁇ refractory inorganic oxide ⁇ , zinc, etc.
  • Hydrode ⁇ ulfurization i ⁇ typically conducted at 315-455 ⁇ C, at 200-2000 p ⁇ ig, and at a LHSV of 1-5.
  • Catalysts and proces ⁇ e ⁇ which are ⁇ uitable for the ⁇ e purpo ⁇ es are known to those skilled in the art.
  • the catalyst can become deactivated by coke.
  • Coke can be removed by contacting the catalyst with an oxygen-containing gas at an elevated temperature.
  • the i ⁇ omerization cataly ⁇ t preferably contain ⁇ a Group VIII metal compound to have ⁇ ufficient activity for commercial u ⁇ e.
  • Group VIII metal compound a ⁇ u ⁇ ed herein i ⁇ meant the metal it ⁇ elf or a compound thereof.
  • the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be usd in conjunction with the noble metal.
  • the most preferred metal i ⁇ the amount of Group VIII metal pre ⁇ ent in the conver ⁇ ion cataly ⁇ t should be within the normal range of use in isomerizing cataly ⁇ t ⁇ , from about 0.05-2.0 wt. %.
  • (B)Beta can be converted to a cataly ⁇ t for u ⁇ e in a proce ⁇ for the alkylation or tran ⁇ alkylation of an aromatic hydrocarbon.
  • the process comprise ⁇ contacting the aromatic hydrocarbon with a C 2 to C 2Q olefin alkylating agent or a polyalkyl aromatic hydrocarbon tran ⁇ alkylating agent, under at lea ⁇ t partial liquid pha ⁇ e condition ⁇ , and in the presence of a catalyst compri ⁇ ing (B)Beta.
  • the (B)Beta zeolite ⁇ hould be predominantly in it ⁇ hydrogen ion form.
  • the zeolite i ⁇ converted to it ⁇ hydrogen form by ammonium exchange followed by calcination.
  • zeolite i ⁇ ⁇ ynthesized with a high enough ratio of organonitrogen cation to sodium ion, calcination alone may be sufficient. It i ⁇ preferred that, after calcination, at lea ⁇ t 80% of the cation ⁇ ite ⁇ are occupied by hydrogen ion ⁇ and/or rare earth ion ⁇ .
  • the pure (B)Beta zeolite may be u ⁇ ed a ⁇ a cataly ⁇ t, but generally, it i ⁇ preferred to mix the zeolite powder with an 3 inorganic oxide binder ⁇ uch a ⁇ alumina, ⁇ ilica, 4 ⁇ ilica/alumina, or naturally occurring clays and form the 5 mixture into tablets or extrudates.
  • the final cataly ⁇ t may 6 contain from 1-99 wt. % (B)Beta zeolite. U ⁇ ually the 7 zeolite content will range form 10-90 wt. %, and more 8 typically from 60-80 wt. %.
  • the preferred inorganic binder g i ⁇ alumina The preferred inorganic binder g i ⁇ alumina.
  • the mixture may be formed into tablet ⁇ or 0 extrudate ⁇ having the de ⁇ ired shape by methods well known in i the art.
  • ⁇ uitable aromatic hydrocarbon feedstocks which 4 may be alkylated or transalkylated by the process of the 5 invention include aromatic compounds ⁇ uch a ⁇ benzene, 6 toluene, and xylene.
  • Mixture ⁇ of aromatic hydrocarbon ⁇ may al ⁇ o be 8 employed.
  • Suitable olefin ⁇ for the alkylation of the aromatic 1 hydrocarbon are tho ⁇ e containing 2-20 carbon atom ⁇ , ⁇ uch a ⁇ 2 ethylene, propylene, butene-1, tran ⁇ butene-2, and 3 ci ⁇ -butene-2, and higher olefins or mixtures thereof.
  • the ⁇ e olefin ⁇ may be pre ⁇ ent in admixture with the corre ⁇ ponding C 2 to C 2Q paraffin ⁇ , but it i ⁇ preferable to remove any diene ⁇ , acetylene ⁇ , ⁇ ulfur compound ⁇ or nitrogen compound ⁇ which may be pre ⁇ ent in the olefin feed ⁇ tock stream to prevent rapid catalyst deactivation.
  • the tran ⁇ alkylating agent i ⁇ a polyalkyl aromatic hydrocarbon containing two or more alkyl group ⁇ that each may have from two to about four carbon atom ⁇ .
  • ⁇ uitable polyalkyl aromatic hydrocarbon ⁇ include di-, tri-, and tetra-alkyl aromatic hydrocarbons, such a ⁇ diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene) , di-i ⁇ opropylbenzene, di-i ⁇ opropyltoluene, dibutylbenzene, and the like.
  • Preferred polyalkyl aromatic hydrocarbon ⁇ are the dialkyl benzene ⁇ .
  • a particularly preferred polyalkyl aromatic hydrocarbon i ⁇ di-i ⁇ opropylbenzene.
  • Reaction product ⁇ which may be obtained include ethylbenzene from the reaction of benzene with either ethylene or polyethylbenzenes, cumene from the reaction of benzene with propylene or polyi ⁇ opropylbenzene ⁇ , ethyltoluene from the reaction of toluene with ethylene or polyethyltoluene ⁇ , cymene ⁇ from the reaction of toluene with propylene or polyi ⁇ opropyltoluene ⁇ , and ⁇ ecbutylbenzene from the reaction of benzene and n-butene ⁇ or polybutylbenzenes.
  • cumene from the alkylation of benzene with propylene or the transalkylation of benzene with di-i ⁇ opropylbenzene i ⁇ e ⁇ pecially preferred.
  • reaction condition ⁇ are a ⁇ follow ⁇ .
  • the aromatic hydrocarbon feed ⁇ hould be pre ⁇ ent in ⁇ toichiometric exce ⁇ . It i ⁇ preferred that molar ratio of aromatic ⁇ to olefin ⁇ be greater than four-to-one to prevent rapid cataly ⁇ t fouling.
  • the reaction temperature may range from 100-600 ⁇ F, preferably, 250-450°F.
  • the reaction pre ⁇ sure should be sufficient to maintain at lea ⁇ t a partial liquid pha ⁇ e in order to retard cataly ⁇ t fouling. This is typically 50-1000 psig depending on the feedstock and reaction temperature.
  • Contact time may range from 10 ⁇ econd ⁇ to 10 hour ⁇ , but i ⁇ u ⁇ ually from five minute ⁇ to an hour.
  • the WHSV in terms of grams (pound ⁇ ) of aromatic hydrocarbon and olefin per gram (pound) of cataly ⁇ t per hour, i ⁇ generally within the range of about 0.5 to 50.
  • the molar ratio of aromatic hydrocarbon will generally range from about 1:1 to 25:1, and preferably from about 2:1 to 20:1.
  • the reaction temperature may range from about 100-600°F, but it is preferably about 250-450°F.
  • the reaction pre ⁇ ure ⁇ hould be sufficient to maintain at least a partial liquid pha ⁇ e, typically in the range of about 50-1000 p ⁇ ig, preferably 300-600 psig.
  • the WHSV will range from about 0.1-10.
  • the conver ⁇ ion of hydrocarbonaceou ⁇ feed ⁇ can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactor ⁇ depending on the type ⁇ of proce ⁇ s desired.
  • the formulation of the catalyst particles will vary depending on the conversion proces ⁇ and method of operation.
  • reaction ⁇ which can be performed u ⁇ ing the cataly ⁇ t of thi ⁇ invention containing a metal, e.g., platinum, include hydrogenation-dehydrogenation reactions, denitrogenation, and desulfurization reaction ⁇ .
  • Some hydrocarbon conversion ⁇ can be carried out on (B)Beta zeolite ⁇ utilizing the large pore ⁇ hape- ⁇ elective behavior.
  • the ⁇ ub ⁇ tituted (B)Beta zeolite may be u ⁇ ed in preparing cumene or other alkylbenzene ⁇ in proce ⁇ e ⁇ utilizing propylene to alkylate aromatic ⁇ .
  • (B)Beta can be u ⁇ ed in hydrocarbon conver ⁇ ion reaction ⁇ with active or inactive ⁇ upport ⁇ , with organic or inorganic binder ⁇ , and with and without added metal ⁇ .
  • the ⁇ e reaction ⁇ are well known to the art, a ⁇ are the reaction condition ⁇ .
  • (B)Beta can also be used a ⁇ an adsorbent, as a filler in paper, paint, and toothpaste ⁇ , and a ⁇ a water- ⁇ oftening agent in detergent ⁇ .
  • the crystalline salt i ⁇ conveniently converted to the hydroxide form by stirring overnight in water with AGI-X8 hydroxide ion exchange resin to achieve a solution ranging from 0.25-1.5 molar.
  • Example 2 The ⁇ ame experiment i ⁇ ⁇ et up a ⁇ in Example 2 except the diquat in Example 2 i ⁇ replaced by an equivalent amount of TEAOH.
  • the experiment i ⁇ run under analogou ⁇ condition ⁇ although thi ⁇ time the cry ⁇ tallization i ⁇ complete in 6 day ⁇ .
  • Examples 5-10 are given in Table 3, demonstrating the utility of the method of the invention.
  • Example ⁇ 5-7 ⁇ how that (B)Beta can be made at very low Si0 2 /B 2 0, value ⁇ and that higher value ⁇ eventually lead to ⁇ ome ZSM-12 formation a ⁇ well.
  • Example 8 ⁇ how ⁇ that the de ⁇ ired product can be obtained u ⁇ ing Ludox AS-30 a ⁇ ⁇ ilica ⁇ ource. Now the aluminum impurity ha ⁇ ri ⁇ en to 530 ppm.
  • Example ⁇ 9 and 10 ⁇ how that providing the diquat a ⁇ a ⁇ alt to supplement TEAOH can insure formation of pure Boron Beta.
  • Example 9 shows that i ⁇ the ca ⁇ e even without ⁇ eeding.
  • the pre ⁇ ence of the boron in the framework of beta zeolite can be indicated by change ⁇ in d- ⁇ pacing ⁇ .
  • Table 8 compare ⁇ the d- ⁇ pacing ⁇ before and after calcination for ⁇ ome of the ⁇ harper peak ⁇ of the product ⁇ of Example ⁇ 4, 5 and 6.
  • Al ⁇ o ⁇ hown are the value ⁇ for an aluminum beta zeolite prepared by the prior art reference (Re 28,341). It can be ⁇ een that the Boron Beta ⁇ ⁇ how d- ⁇ pacing ⁇ con ⁇ i ⁇ tently ⁇ maller than the aluminum Beta. TABLE 6
  • d/n spacing ⁇ for B-Beta ⁇ are con ⁇ i ⁇ tently le ⁇ than tho ⁇ e for Al-Beta ⁇ .
  • Example 4 wa ⁇ calcined a ⁇ follow ⁇ .
  • the ⁇ ample wa ⁇ heated in a muffle furnace in nitrogen from room temperature up to 540°C at a ⁇ teadily increasing rate over a 7-hour period.
  • the ⁇ ample wa ⁇ maintained at 540°C for four more hour ⁇ and then taken up to 600°C for an additional four hour ⁇ .
  • Nitrogen wa ⁇ pa ⁇ sed over the zeolite at a rate of 20 ⁇ tandard cfm during heating.
  • the calcined product had the X-ray diffraction line ⁇ indicated in Table 9 below.
  • Example 13 Ion exchange of the calcined material from Example 4 wa ⁇ carried out u ⁇ ing NH.N0 3 to convert the zeolite ⁇ from Na form to NH.. Typically the ⁇ ame ma ⁇ of NH.NO, a ⁇ zeolite was slurried into H 2 0 at ratio of 50:1 H-O zeolite. The exchange ⁇ olution wa ⁇ heated at 100 ⁇ C for two hour ⁇ and then filtered. Thi ⁇ proce ⁇ wa ⁇ repeated two time ⁇ . Finally, after the la ⁇ t exchange, the zeolite wa ⁇ wa ⁇ hed ⁇ everal time ⁇ with H 2 0 and dried. Example 13
  • Example 4 0.50 g of the hydrogen form of the zeolite of Example 4 (after treatment according to Example ⁇ 11 and 12 wa ⁇ packed into a 3/8-inch ⁇ tainle ⁇ ⁇ teel tube with alundum on both ⁇ ide ⁇ of the zeolite bed.
  • a Lindburg furnace wa ⁇ u ⁇ ed to heat the reactor tube.
  • Helium was introduced into the reactor tube at 10 cc/minute and atmo ⁇ pheric pre ⁇ ure.
  • the reactor wa ⁇ taken to 250°F for 40 inute ⁇ and then rai ⁇ ed to 800°F.
  • Example 4 The product of Example 4 after treatment as in Example ⁇ 11 and 12 i ⁇ refluxed overnight with Al(N0 3 ) 3 * 9H 2 0 with the latter being the ⁇ ame ma ⁇ a ⁇ the zeolite and u ⁇ ing the ⁇ ame dilution a ⁇ in the ion exchange of Example 12.
  • the product i ⁇ filtered, wa ⁇ hed, and calcined to 540°C.
  • Plea ⁇ e refer to Table 10 and Table 11.
  • Example 20 gave 5% conver ⁇ ion at 800 ⁇ F for C.I. te ⁇ t and CI - 0.30.
  • the boro ⁇ ilicate ver ⁇ ion of (B)Beta wa ⁇ evaluated a ⁇ a reforming cataly ⁇ t.
  • the zeolite powder wa ⁇ impregnated with Pt(NH 3 ) 4 * 2N0 3 to give 0.8 wt. % Pt.
  • the material wa ⁇ calcined up to 550 ⁇ F in air and maintained at thi ⁇ temperature for three hour ⁇ .
  • Table 12 give ⁇ data at 800 and 900°F and 50 and 200 p ⁇ ig, Temperature Pre ⁇ sure(H 2 ) Conversion % Aromatization Selectivi Product Toluene wt. % % Toluene in C ⁇ Aromati c 5 + yield wt. % 5" c ⁇ R0N
  • Example 18 The product of Example 18 now contained a ⁇ econd metal due to cobalt incorporation.
  • the cataly ⁇ t wa ⁇ calcined to 1000°F.
  • a reforming cataly ⁇ t wa ⁇ prepared a ⁇ in Example 23.
  • the cataly ⁇ t wa ⁇ evaluated under the following condition ⁇ :
  • the incorporation of cobalt into the zeolite give ⁇ a more Cr+ selective reforming cataly ⁇ t.
  • the catalyst has good stability at 800°F.
  • the cataly ⁇ t wa ⁇ dried at 600 ⁇ F, cooled in a clo ⁇ ed ⁇ y ⁇ tem, and then vacuum impregnated with an aqueou ⁇ ⁇ olution of Pd(NH 3 ). * 2N0 3 to give 0.5 wt. % loading of palladium.
  • the cataly ⁇ t wa ⁇ then calcined ⁇ lowly, up to 900°F in air and held there for three hour ⁇ .
  • Table 14 gives run conditions and product data for the hydrocracking of hexadecane.
  • the catalyst is quite ⁇ table at the temperature ⁇ given.
  • the data show ⁇ that the catalyst has good isomerization selectivity and that the liquid yield is high compared with the gas make.
  • the hydrogen form of (B)Beta can be used in typical fluidized catalytic cracking (FCC).
  • FCC fluidized catalytic cracking
  • (B)Beta as prepared in Examples 2, 11, 12 and refluxed with Al(N0 3 ) 3 * 9H 2 0 a ⁇ in Example 14, wa ⁇ formulated into a spray dried FCC catalytic octane additive and te ⁇ ted in a fixed fluidized cyclic reactor.
  • the FCC catalytic octane additive contained nominally 25% by weight (B)Beta, 32.5% Kaolin and 42.5% silica/alumina matrix. Fixed fluidized cyclic te ⁇ ting wa ⁇ conducted at 7 cat/oil ratio, with a 1100°F initial cataly ⁇ t temperature.

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Abstract

A crystalline low-aluminum boron beta zeolite is prepared using a diquaternary ion as a template.

Description

LOW-ALUMI UM BORON BETA ZEOLITE
BACKGROUND OF THE INVENTION
Natural and synthetic zeolitic crystalline aluminosilicates are useful as catalysts and adsorbents. These aluminosilicateε have distinct crystal structures which are demonstrated by X-ray diffraction. The crystal structure defines cavities and pores which are characteristic of the different species. The adsorptive and catalytic properties of each crystalline aluminosilicate are determined in part by the dimensions of its pores and cavities. Thus, the utility of a particular zeolite in a particular application depends at least partly on its crystal structure.
Because of their unique molecular sieving characteristics, as well as their catalytic properties, crystalline aluminosilicateε are especially useful in such applications as gas drying and separation and hydrocarbon conversion. Although many different crystalline aluminoεilicates and silicates have been disclosed, there is a continuing need for new zeolites and silicates with desirable properties for gaε separation and drying, hydrocarbon and chemical conversions, and other applications.
Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina. "Nitrogenous zeolites" have been prepared from reaction mixtures containing an organic templating agent, usually a nitrogen-containing organic cation. By varying the synthesis conditions and the composition of the reaction mixture, different zeolites can be formed using the same templating agent. Use of N,N,N-trimethyl cyclopentyl- ammonium iodide in the preparation of Zeolite SSZ-15 molecular sieve is disclosed in U.S. Patent No. 4,610,854; use of 1-azoniaspiro [4.4] nonyl bromide and N,N,N-trimethyl neopentylammoaium iodide in the preparation of a molecular sieve termed "Losod" is disclosed in Helv. Chim. Acta (1974); Vol. 57, p. 1533 (W. Sieber and W. M. Meier); use of quinuclidinium compounds to prepare a zeolite termed "NU-3" is disclosed in European Patent Publication No. 40016; use of l,4-di(l-Azoιιia bicyclo[2.2.2Joctane) lower alkyl compounds in the preparation of Zeolite SSZ-16 molecular sieve is disclosed in U.S. Patent No. 4,508,837; use of N,N,N-trialkyl-I-adamantamine in the preparation of Zeolite SSZ-13 molecular sieve is disclosed in U.S. Patent No. 4,544,538, and for SSZ-24 in U.S. Patent No. 4,665,110.
Beta zeolite is a known synthetic crystalline aluminosilicate originally described in U.S. Patents Nos. 3,308,069 and Re 28,341 to which reference is made for further details- of this zeolite, its preparation and properties.
Synthetic zeoli ic crystalline boroεilicates are useful as catalysts. Methodε for preparing high εilica content zeoliteε that contain framework boron are known and disclosed In U.S. Patent No. 4,269,813. The amount of boron contained i the zeolite usually may be made to vary by incorporating different amounts of borate ion in the zeolite forming εolutioa.
U.S. Patent No. 4,788,169 describes a method for preparing beta zeolite containing boron. This boron beta zeolite contains 7000 parts per million of aluminum according to the analyses given therein. European Patent Application No. 188,913 claimε compositions for various intermediate pore boron-containing zeolites with an aluminum content of less than 0.05% by weight.
SUMMARY OF THE INVENTION
We have prepared a family of crystalline borosilicate molecular sieves with unique properties, referred to herein as "Low-Aluminum Boron Beta Zeolite" or simply "(B)Beta". Thus, according to the present invention, a zeolite composition, (B)Beta, is provided. Also, advantageous uses have been discovered.
(B)Beta has a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide or mixtures of boron oxide with aluminum, gallium, or iron oxide, greater than about 10:1 and wherein the amount of aluminum is less than 0.10% by weight and having the X-ray diffraction lines of Table 1(a) below. An aluminum-free boron beta zeolite can alεo be made using the novel method disclosed herein. The amount of aluminum contained in the zeolite depends simply upon the aluminum impurity present in the silica source.
This zeolite further has a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (1.0 to 5.0)Q2O:(0.1 to 2.0)M2O: 2O3:(greater than 10)YO2 wherein M is an alkali metal cation, W is selected from boron, Y is selected from silicon, germanium and mixtures thereof, and Q is a diquatemary ammonium ion, or mixtures of diquarternary ammonium cation, and tetraethylammonium cation. (B)Beta zeolites preferably have a εilicarboria ratio typically in the range of 10:1 to about 100:1. Higher mole ratioε can be obtained by treating the zeolite with chelating agentε or acidε to extract boron from the zeolite lattice. The εilicarboria mole ratio can also be increased by using silicon and carbon halides and other similar compounds. The boron in the crystalline network may also be replaced by aluminum, gallium or iron. Procedures for incorporating aluminum are deεcribed in U.S. Patent Noε. 4,559,315 and 4,550,092 which are hereby incorporated by reference.
A method for preparing boron beta zeolite iε deεcribed in U.S. Patent No. 4,788,169. A tetraethyl ammonium template iε used to make this zeolite which contains 7000 partε per million of aluminum. The method deεcribed in U.S. Patent No. 4,788,169, however, cannot be uεed to make boron beta zeolite containing less than 1000 partε per million aluminum. Additionally, a low-aluminum boron beta zeolite cannot be made by replacing the aluminum with boron in the εyntheεized boron beta zeolite εtructure. Successful preparation of the low-aluminum boron beta zeolite requires using a new εyntheεis method described herein.
According to one embodiment of the present invention, a method is provided for making (B)beta zeolites, comprising preparing an aqueous mixture containing sources of a diquatemary ammonium ion, an oxide selected from boron oxide, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof, and having a composition, in termε of mole ratioε of oxideε, falling within the following rangeε: Y02/ 203, 10:1 to 100:1; wherein Y iε selected from εilicon, germanium, and mixtureε thereof, W iε selected from boron, and Q iε a diquatemary ammonium ion; maintaining the mixture at a temperature of at leaεt 100°C until the crystals of said zeolite are formed; and recovering said crystalε.
Among other factorε, the preεent invention is based on our finding that low-aluminum boron beta zeolite can be made using a diquatemary ammonium template. The εtructure of this zeolite is the εame aε the boron beta zeolite εtructure εyntheεized uεing the tetraethyl ammonium template in U.S. Patent No. 4,788,169. Surpriεingly, we have found that the amount of aluminum incorporated into thiε εtructure can be decreased by using a different template than the tetraethyl ammonium template uεed in U.S. Patent No. 4,788,169. We have alεo found that thiε zeolite haε unexpectedly outεtanding hydrocarbon converεion properties, particularly including reforming properties with high sulfur tolerance.
DETAILED DESCRIPTION OF THE INVENTION
(B)Beta zeolites, aε synthesized, have a crystalline structure whose X-ray powder diffraction pattern εhowε the following characteriεtic lineε:
2 θ Shape
7.7 Broad 18.40 Very Broad 21.44 22.53 27.50 28.92 Broad 29.90
Typical (B)Beta boroεilicate and boroaluminoεilicate zeoliteε have the X-ray diffraction pattern of Tableε 2 and 4 below. The d-εpacingε are εhown in Table 8 and demonstrate framework subεtitution. Calcined (B)Beta haε a typical pattern aε εhown in Table 1(b).
2 θ Shape
7.7 Broad 13.58 14.87 Broad 18.50 Very Broad 21.83 22.87 Broad 27.38 29.30 Broad 30.08 The X-ray powder diffraction patterns were determined by standard techniques. The radiation was the K-alpha/doublet of copper and a scintillation counter spectrometer with a strip-chart pen recorder was used. The peak heights I and the positions, as a function of 2 θ where θ is the Bragg angle, were read from the spectrometer chart. From these measured values, the relative intensitieε, 100I/I , where I iε the intenεity (peak height) of the strongest peak, and d/n, related to interplanar spacings in Angstroms corresponding to the recorded peaks, can be calculated. The X-ray diffraction pattern of Table 1(a) is characteristic of (B)Beta zeoliteε. The zeolite produced by exchanging the metal or other cations present in the zeolite with various other cations yieldε substantially the εame diffraction pattern although there can be minor εhiftε in interplanar εpacing and minor variationε in relative intenεity. Minor variations in the diffraction pattern can alεo reεult from variationε in the organic compound used in the preparation and from variations in the silica-to-boria mole ratio from sample to εample. Calcination can also cause minor shiftε in the X-ray diffraction pattern. Notwithεtanding theεe minor perturbationε, the basic crystal lattice εtructure remains unchanged.
(B)Beta zeolites can be suitably prepared from an aqueous εolution containing εourceε of an alkali metal borate, a biε(l-Azonia, bicyclo[2.2.2] octane-α, ω alkane diquatemary ammonium ion, and an oxide of εilicon or germanium, or mixture of the two. The reaction mixture εhould have a compoεition in terms of mole ratioε falling within the following rangeε: Broad Preferred
Y02/W203 10-200 30-100 OH/Y02 0.10-1.0 0.25-0.50 Q γo2 0.05-0.50 0.25-0.35 M+/Y02 0.05-0.30 0.05-0.10 H20/Y02 15-300 25-60 Q/Q+M+ 0.30-0.90 0.60-0.80
wherein Q iε a diquatemary ammonium ion, or mixture with tetramethylammonium cation, Y is εilicon, germanium or both, and W iε boron. M iε an alkali metal, preferably εodium. The organic compound which actε aε a εource of the quaternary ammonium ion employed can provide hydroxide ion.
When uεing the quaternary ammonium hydroxide compound aε a template, it haε alεo been found that purer formε of (B)Beta are prepared when there iε an exceεε of compound preεent relative to the amount of alkali metal hydroxide.
The biε(l-Azonla bicyclo[2.2.2]octane) a' ω alkane diquatemary ammonium ion component Q, of the crystallization mixture, iε derived from the quaternary ammonium compound. Preferably, the diquatemary ammonium ion iε derived from a compound of the formula:
21 or 20H
The quaternary ammonium compoundε are prepared by methodε known in the art, an example of which can be found in U.S. No. 4,508,837. The reaction mixture is prepared using εtandard zeolitic preparation techniqueε. Sourceε of boron for the reaction mixture include boroεilicate glaεεeε and most particularly, other reactive borates and borate esters. Typical sources of εilicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl orthoεilicateε, and εilica hydroxideε.
The reaction mixture iε maintained at an elevated temperature until the cryεtalε of the zeolite are formed. The temperatureε during the hydrothermal crystallization step are typically maintained from about 140°C to about 200°C, preferably from about 150°C to about 170°C and moεt preferably from about 135βC to about 165βC. The cryεtallization period iε typically greater than one day and preferably from about three days to about seven days.
The hydrothermal cryεtallization iε conducted under preεsure and usually in an autoclave so that the reaction mixture is subject to autogenouε preεεure. The reaction mixture can be εtirred during cryεtallization.
Once the zeolite cryεtalε have formed, the εolid product is εeparated from the reaction mixture by standard mechanical separation techniques εuch aε filtration. The cryεtals are water-washed and then dried, e.g., at 90βC to 150°C from 8 to 24 hours, to obtain the as εyntheεized, (B)Beta zeolite cryεtalε. The drying εtep can be performed at atmoεpheric or εubatmoεpheric preεεureε.
During the hydrothermal cryεtallization εtep, the (B)Beta cryεtalε can be allowed to nucleate spontaneously from the reaction mixture. The reaction mixture can alεo be εeeded with (B)Beta cryεtalε both to direct, and accelerate the crystallization, as well as to minimize the formation of undeεired aluminoεilicate contaminantε.
The εynthetic (B)Beta zeoliteε can be uεed aε εynthesized or can be thermally treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion. The zeolite can be leached with chelating agents, e.g., EDTA or dilute acid solutionε, to increaεe the εilica:boria mole ratio. The zeolite can be uεed in intimate combination with hydrogenating components, εuch aε tungεten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such aε palladium or platinum, for tlboεe applicationε in which a hydrogenation-dehydrogenation function iε deεired. Typical replacing cations can include metal cations, e.g., rare earth, Group II and Group VIII metalε, aε well aε their mixtureε. Of the replacing metallic cationε, cationε of metalε εuch aε rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe, and Co are particularly preferred.
The hydrogen, ammonium, and metal componentε can be exchanged into the zeolite. The zeolite can alεo be impregnated with the metalε, or, the metalε can be phyεically intimately admixed with the zeolite uεing εtandard methodε known to the art. And, the metalε can be occluded in the cryεtal lattice by having the deεired metalε preεent aε ionε in the reaction mixture from which the (B)Beta zeolite iε prepared.
Typical ion exchange techniqueε involve contacting the εynthetic zeolite with a εolution containing a εalt of the de'εired replacing cation or cationε. Although a wide variety of εaltε can be employed, chlorides and other O 91/00777
halides, nitrates, and sulfates are particularly preferred. Representative ion exchange techniqueε are diεcloεed in a wide variety of patents including U.S. Nos. 3,140,249; 3,140,251; and 3,140,253.
Following contact with the εalt εolution of the deεired replacing cation, the zeolite is typically washed with water and dried at temperatureε ranging from 650°C to about 315βC. After waεhing, the zeolite can be calcined in air or inert gaε at temperatureε ranging from about 200°C to 820°C for periodε of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially uεeful in hydrocarbon converεion proceεεeε.
Regardleεε of the cations present in the εynthesized form of the zeolite, the εpatial arrangement of the atomε which form the baεic crystal lattice of the zeolite remains essentially unchanged. The exchange of cations haε little, if any, effect on the zeolite lattice εtructureε.
The Beta borosilicate and εubεequent metalloboroεilicate can he formed into a wide variety of phyεical εhapeε. Generally εpeaking, the zeolite can be in the form of a powder, a granule, or a molded product, εuch aε extrudate having particle εize εufficient to pass through a 2-mesh (Tyler) εcreen and be retained on a 400-meεh (Tyler) εcreen. In caεeε where the catalyεt iε molded, εuch as by extrusion with an organic binder, the borosilicate can be extruded before drying, or, dried or partially dried and then extruded. The zeolite can be compoεited with other materials resiεtant to the temperatureε and other conditionε employed in organic converεion proceεεes. Such matrix materials include active and inactive materials ?.nd εynthetic or naturally occurring zeoliteε aε well aε inorganic materialε εuch aε clayε, εilica and metal oxides. The latter may occur naturally or may be in the form of gelatinouε precipitates, εolε, or gelε, including mixtures of εilica and metal oxideε. Uεe of an active material in conjunction with the εynthetic zeolite, i.e., combined with it, tendε to improve the converεion and εelectivity of the catalyεt In certain organic converεion processeε. Inactive materialε can suitably serve as diluents to control the amount of coaverεion in a given proceεε εo that products can be obtained economically without using other means for controlling the rate of reaction. Frequently, zeolite materialε have been incorporated into naturally occurring clayε, e.g., bentonite and kaolin. Theεe materials, i.e., clayε, oxideε, etc., function, in part, aε binderε for the catalyεt. It iε deεirable to provide a catalyεt having good cruεh εtrength, because in petroleum refining the catalyst i n often εubjected to rough handling. Thiε tendε to break the catalyεt down into powders which cause problems in procesεing.
Naturally occurring clayε which can be composited with the synthetic zeolites of thiε invention include the montmorillonite and kaolin families, which families include the sub-bentoniteε and the kaolinε commonly known as Dixie, McNamee, Georgia, and Florida clayε or otherε in which the main mineral constituent iε halloysite, kaolinite, dickite, nacrite, or anauxite. Fibrous clays εuch aε sepiolite and attapulgite can alεo be uεed aε εupportε. Such clayε can be uεed in the xa εtate aε originally mined or can be initially subjected to calcination, acid treatment or chemical modification. In addition to the foregoing materialε, the (B)Beta zeoliteε can be compoεited with porouε matrix materialε and mixtureε of matrix materialε εuch as εilica, alumina, titania, magnesia, εilica:alumina, εilica- agneεia, εilica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia aε well as ternary compositions such as silica-alumina-thoria, εilica-alumina-zirconia, εilica-alumina-magneεia, and silica-magnesia-zirconia. The matrix can be in the form of a cogel.
The (B)Beta zeolites can alεo be compoεited with other zeoliteε εuch aε εynthetic and natural faujasites (e.g., X and Y), erionites, and mordenites. They can alεo be compoεited with purely synthetic zeolites such as those of the ZSM εerieε. The combination of zeoliteε can also be compoεited in a porous inorganic matrix.
(B)Beta zeolites are useful in hydrocarbon conversion reactionε. Hydrocarbon converεion reactionε are chemical and catalytic proceεses in which carbon-containing compoundε are changed to different carbon-containing compoundε. Exampleε of hydrocarbon converεion reactionε include catalytic cracking, hydrocracking, and olefin and aromaticε formation reactionε. The catalyεts are useful in other petroleum refining and hydrocarbon conversion reactions such as isomerizing n-paraffinε and naphtheneε, polymerizing and oligomerizing olefinic or acetylenic compoundε such as isobutylene and butene-1, reforming, alkylating, iεomerizing polyalkyl εubεtituted aromaticε (e.g., ortho xylene), and diεproportionating aromatics (e.g., toluene) to provide mixtureε of benzene, xyleneε, and higher methylbenzenes. The (B)Beta catalystε have high εelectivity, and under hydrocarbon converεion conditionε can provide a high percentage of deεired productε relative to total productε. (B)Beta zeoliteε can be uεed in proceεsing hydrocarbonaceouε feedεtockε. Hydrocarbonaceouε feedεtockε contain carbon compoundε and can be from many different εourceε, εuch aε virgin petroleum fractionε, recycle petroleum fractionε, shale oil, liquefied coal, tar sand oil, and in general, can be any carbon containing fluid εuεceptible to zeolitic catalytic reactionε. Depending on the type of proceεεing, the hydrocarbonaceouε feed iε to undergo, the feed can contain metal or be free of metals, it can also have high or low nitrogen or εulfur impuritieε. It can be appreciated, however, that in general proceεεing will be more efficient (and the catalyεt more active) the lower the metal, nitrogen, and εulfur content of the feedεtock.
Uεing a (B)Beta zeolite catalyεt which containε boron and/or aluminum framework substitution and a hydrogenation promoter, heavy petroleum residual feedstockε, cyclic stocks, and other hydrocrackate charge stockε can be hydrocracked at hydrocracking conditionε including a temperature in the range of from 175°C to 485βC, molar ratioε of hydrogen to hydrocarbon charge from 1 to 100, a preεεure in the range of from 0.5 to 350 bar, and a liquid hourly εpace velocity (LHSV) in the range of from 0.1 to 30.
The hydrocracking catalyεtε contain an effective amount of at leaεt one hydrogenation catalyst (component) of the type commonly employed in hydrocracking catalyεtε. The hydrogenation component iε generally selected from the group of hydrogenation catalyεtε conεiεting of one or more metalε of Group VIB and Group VIII, including the εaltε, complexeε, and εolutionε containing εuch. The hydrogenation catalyεt iε preferably selected from the group of metals, saltε, and complexeε thereof of the group conεiεting of at least one of platinum, palladium, rhodium, iridiu , and mixtures thereof or the group conεisting of at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. Reference to the catalytically active metal or metals is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, εulfide, halide, carboxylate, and the like.
The hydrogenation catalyεt iε present in an effective amount to provide the hydrogenation function of the hydrocracking catalyst and preferably in the range of from 0.05% to 25% by weight.
The catalyst may be employed in conjunction with traditional hydrocracking catalystε, e.g., any aluminoεilicate heretofore employed aε a component in hydrocracking catalyεtε. Repreεentative of the zeolitic aluminosilicates disclosed heretofore as employable as component partε of hydrocracking catalyεtε are Zeolite Y (including steam εtabilized, e.g., ultra-stable Y), Zeolite X, Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No. 3,415,736), faujaεite, LZ-10 (U.K. Patent 2,014,970, June 9, 1982), ZSM-5-type zeoliteε, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, cryεtalline εilicateε εuch aε εilicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite, chabazite, FU-1-type zeolite, NU-type zeoliteε, LZ-210-type zeolite, and mixtureε thereof. Traditional hydrocracking catalysts containing amounts of a20 lesε than about one percent by weight are generally preferred. The relative amountε of the (B)Beta component and traditional hydrocracking component, if any, will depend at leaεt in part, on the εelected hydrocarbon feedεtock and on the deεired product diεtribution to be obtained therefrom, but in all inεtanceε an effective amount of (B)Beta is employed. 1 The hydrocracking catalyεtε are typically employed with an 2 inorganic oxide-matrix component which may be any of the 3 inorganic oxide matrix componentε which have been employed 4 heretofore in the formulation of hydrocracking catalyεtε 5 including: amorphouε catalytic inorganic oxideε, e.g., 6 catalytically active εilica-aluminaε, clayε, silicas, 7 aluminas, εilica-aluminaε, εilica-zirconiaε, 8 silica-magneεiaε, alumina-borias, alumina-titaniaε, and the 9 like and mixtureε thereof. The traditional hydrocracking 0 catalyεt component (TC) and (B)Beta may be mixed εeparately with the matrix component and then mixed or the TC component 2 and (B)Beta may be mixed and then formed with the matrix 3 component. 4 5 (B)Beta can be uεed to dewax hydrocarbonaceouε feedε by 6 εelectively removing or tranεforming εtraight chain 7 paraffinε. The catalytic dewaxing conditionε are dependent 8 i large meaεure on the feed uεed and upon the deεired pour 9 point. Generally, the temperature will be between about 0 200°C and about 475βC, preferably between about 250βC and i about 450βC. The preεεure iε typically between about 15 2 pεig and about 3000 pεig, preferably between about 200 pεig 3 and 3000 pεig. The LHSV preferably will be from 0.1 to 20, 4 preferably between about 0.2 and about 10. 5 6 Hydrogen iε preferably preεent in the reaction zone during 7 the catalytic dewaxing proceεε. The hydrogen to feed ratio 8 is typically between about 500 and about 30,000 SCF/bbl g (εtandard cubic feet per barrel), preferably about 1,000 to 0 about 20,000 SCF/bbl. Generally, hydrogen will be εeparated 1 from the product and recycled to the reaction zone. Typical 2 feedεtockε include light gaε-oil, heavy gaε-oilε, and reduced crudeε boiling about 350°F. 4 The (B)Beta hydrodewaxing catalyεt may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts. The hydrogenation component may be selected from the group of hydrogenation catalystε conεiεting of one or more metalε of Group VIB and Group VIII, including the salts, complexes and εolutionε containing εuch metals. The preferred hydrogenation catalyst is at least one of the group of metalε, saltε, and complexeε selected from the group consisting of at least one of platinum, palladium, rhodium, iridium, and mixtures thereof or at least one from the group conεiεting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. Reference to the catalytically active metal or metals iε intended to encompass εuch metal or metalε in the elemental εtate or in εome form εuch as an oxide, εulfide, halide, carboxylate, and the like.
The hydrogenation component iε preεent in an effective amount to provide an effective hydrodewaxing catalyεt preferably in the range of from about 0.05 to 5% by weight.
(B)Beta can be used to convert straight run naphthas and similar mixtureε to highly aromatic mixtureε. Thus, normal and slightly branched chained hydrocarbons, preferably having a boiling range above about 40°C and less than about 200°C, can be converted to products having a subεtantial aromaticε content by contacting the hydrocarbon feed with the zeolite at a temperature in the range of from about 400°C to 600°C, preferably 480°C-550βC at preεεureε ranging from atmoεpheric to 10 bar, and LHSV ranging from 0.1 to 15. The hydrogen to hydrocarbon ratio will range between 1 and 10. (B)Beta can be uεed in a fixed, fluid or moving bed reformer. The converεion catalyεt preferably contain a Group VIII metal compound to have εufficient activity for commercial uεe. By Group VIII metal compound aε uεed herein iε meant the metal itεelf or a compound thereof. The Group VIII noble metalε and their compoundε, platinum, palladium, and iridium, or combinations thereof can be used. The moεt preferred metal iε platinum. The amount of Group VIII metal preεent in the converεion catalyst should be within the normal range of uεe in reforming catalyεtε, from about 0.05 to 2.0 wt. %, preferably 0.2 to 0.8 wt. %. The performance of the noble metal in (B)Beta may be further enhanced by the preεence of other metals as promotors for aromatization εelectivity.
The zeolite/Group VIII metal conversion catalyst can be used without a binder or matrix. The preferred inorganic matrix, where one iε used, is a silica-baεed binder such aε Cab-O-Sil or Ludox. Other atriceε such aε magneεia and titania can be uεed. The preferred inorganic matrix iε nonacidic.
It iε critical ito the εelective production of aromaticε in uεeful quantitieε that the converεion catalyεt be εubεtantially free of acidity, for example, by poiεoning the zeolite with a baεic metal, e.g., alkali metal, compound. The zeolite iε uεually prepared from mixtureε containing alkali metal hydroxides and thuε, have alkali metal contentε of about 1-2 wt. %. Theεe high levels of alkali metal, usually sodium or potassium, are unacceptable for moεt catalytic applicationε becauεe they greatly deactivate the catalyεt for crarcking reactionε. Uεually, the alkali metal iε removed to low levelε by ion exchange with hydrogen or ammonium ionε. By alkali metal compound aε uεed herein iε meant elemental or ionic alkali metalε or their baεic compoundε. Surpriεingly, unleεs the zeolite itself is substantially free of acidity, the basic compound iε required in the preεent proceεε to direct the εynthetic reactions to aromatics production. In the case of (B)Beta the intrinsic cracking acidity is quite low and neutralization is not usually required.
We have also found that (B)Beta is advantageously uεed to catalytically crack hydrocarbon feedεtockε in the absence of hydrogen. Preferred conditions involve a fluidized catalytic cracking proceεε which conεiεtε of contacting a hydrocarbon feedεtock with a catalyεt in a reaction zone in the abεence of added hydrogen at average catalyεt temperatures ranging from 800°F to 1500βF, separating the catalyεt from the product effluent, introducing the catalyεt into a steam-stripping zone, and subsequently into a regeneration zone in the presence of steam and free oxygen containing gas where reaction coke depoεited on the catalyεt iε burned off at elevated temperatureε ranging from 1000βF to 1550βF, and then recycling the reactivated catalyεt to the reaction zone.
For thiε purpoεe, the (B)Beta can be employed in conjunction with traditional cracking catalysts either as an incorporated conεtituent component or aε a separate additive particle.
The catalyεt may be employed in conjunction with traditional cracking catalyεtε, compriεing any aluminoεilicate heretofore employed aε a component in cracking catalysts. Representative of the zeolitic aluminoεilicateε diεcloεed heretofore aε employable aε component partε of cracking catalyεtε are Zeolite Y (including εteam εtabilized Y, rare earth Y, chemically modified Y, ultra-εtable Y or 1 combinations thereof). Zeolite X, Zeolite beta (U.S. Patent 2 No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), 3 Zeolite ZSM-3 (U.S. Patent No. 3,415,736), faujaεite, LZ-10 4 (U.K. Patent 2,014,970, June 9, 1982), ZSM-5-Type Zeoliteε, 5 e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, 6 crystalline εilicates such aε εilicalite (U.S. Patent No. 7 4,061,724), erionite, mordenite, offretite, chabazite, 8 FU-1-type zeolite, NU-type zeolite, LZY-210 type zeolite or 9 other dealuminated zeolite of 24.5A unit cell size or lower, 0 or zeolite grown "in-εitu" in matrix materialε (U.S. Patent 1 Noε. 3,647,718 and 4,493,902), and the mixtureε thereof. 2 The term "zeolite" aε uεed herein contemplates not only 3 aluminosilicateε but εubstances in which the aluminum iε 4 replaced by gallium or boron and εubεtanceε in which εilicon 5 iε replaced by germanium. Other representative acidic 6 aluminosilicates alεo deemmed employable aε component partε 7 are amorphouε εilica-alumina catalyεtε, εynthetic 8 mica-mont orillonite catalyεtε (aε defined in U.S. Patent g No. 3,252,889), croεε-linked or pillared clayε (aε defined 0 in U.S. Patent Noε. 4,176,090; 4,248,739; 4,238,364 and i 4,216,188), and acid activated clayε — bentonite, 2 hectorite, εaponite. 3 4 Traditional cracking catalyεtε containing amountε of Na20 5 leεε than about one percent by weight are generally 6 preferred. The relative amountε of the (B)Beta component 7 and traditional cracking component (TC), if any, will depend 8 at leaεt in part, on the εelected hydrocarbon feedstock and 9 on the desired product distribution to be obtained 0 therefrom, but in all instanceε, an effective amount of 1 (B)Beta iε employed. When a TC component iε employed, the relative weight ratio of the TC to the (B)Beta iε generally between about 1:10 and about 500:1, deεirably between about 4 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and moεt preferably iε between about 1:1 and about 20:1.
The cracking catalysts are typically employed with an inorganic oxide matrix component which may be any of the inorganic oxide matrix components which have been employed heretofore in the formulation of FCC catalystε including: amorphouε catalytic inorganic oxideε, e.g., catalytically active εilica-aluminaε, clayε, εynthetic or acid activated clays, silicaε, aluminas, silica-aluminas, silica-zirconiaε, εilica-magneεiaε, alumina-boriaε, alumina-titaniaε, pillared or cross-linked clays, and the like and mixtures thereof. The TC component and (B)Beta may be mixed separately with their respective matrix component and then mixed together or the TC component and (B)Beta may be mixed together and then formed with the matrix component.
The mixture of a traditional cracking catalyst and (B)Beta may he carried out in any manner which resultε in the coincident presence of such in contact with the crude oil feedstock under catalytic cracking conditions. For example, a catalyεt may be employed containing the traditional cracking catalyst component and (B)Beta in εingle catalyεt particles or (B)Beta with or without a matrix component may be added as a diεcrete component to a traditional cracking catalyst provided its particle has appropriate denεity and particle εize diεtribution.
(B)Beta can alεo be uεed to oligomerize εtraight and branched chain olefinε having from about 2-21 and preferably 2-5 carbon atoms. The oligomers which are the products of 1 the proceεε are medium to heavy olefinε which are uεeful for 2 both fuels, i.e., gasoline or a gasoline blending stock and 3 chemicals. 4 5 The oligomerization proceεs compriseε contacting the olefin feedstock in the gaεeouε εtate phaεe with (B)Beta at a 7 temperature of from about 450°F to about 1200°F, a WHSV of 8 from about 0.2 to about 50 and a hydrocarbon partial 9 preεεure of from about 0.1 to about 50 atmospheres. 0 1 Also, temperatures below about 450βF may be uεed to 2 oligomerize the* feedstock, when the feedεtock iε in the 3 liquid phaεe when contacting the zeolite catalyεt. Thuε, 4 when the olefin feedεtock contactε the zeolite catalyεt in 5 the liquid phaεe, temperatureε of from about 50βF to about 6 450°F, and preferably from 80-400°F may be used and a WHSV 7 of from about 0.05 to 20 and preferably 0.1 to 10. It will 8 be appreciated that the presεureε employed must be 9 sufficient to maintain the syεtem in the liquid phaεe. Aε 0 is known in the art, the preεεure will be a function of the i number of carbon atoms of the feed olefin and the 2 temperature. Suitable presεureε include from about 0 pεig 3 to about 3000 pεig. 4 5 The zeolite can have the original cations asεociated 6 therewith replaced by a wide variety of other cationε 7 according to techniqueε well known in the art. Typical 8 cationε would include hydrogen, ammonium, and metal cationε g including mixtureε of the εame. Of the replacing metallic 0 cations, particular preference is given to cations of metalε 1 εuch aε rare earth metals, manganese, calcium, aε well aε 2 metalε of Group II of the Periodic Table, e.g., zinc, and 3 Group VIII of the Periodic Table, e.g..- nickel. One of the 4 prime requiεiteε iε that the zeolite nave a fairly low aromatization activity, i.e., in which the amount of aromaticε produced iε not more than about 20 wt. %. Thiε iε accompliεhed by uεing a zeolite with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to about 100, aε eaεured by itε ability to crack n-hexane.
Alpha valueε are defined by a εtandard teεt known in the art, e.g., as shown in U.S. Patent No. 3,960,978 which is incorporated totally herein by reference. If required, such zeolites may be obtained by steaming, by use in a conversion proceεε or by any other method which may occur to one εkilled in thiε art.
(B)Beta can be uεed to convert light gaε C2-C8 paraffinε and/or olefinε to higher molecular weight hydrocarbonε including aromatic compounds. Operating temperatureε of 100-700βC, operating pressures of 0-1000 psig and space velocities of 0.5-40 hr~ WHSV can be uεed to convert the c2~c6 Para^fin and/or olefins to aromatic compounds. Preferably, the zeolite will contain a catalyst metal or metal oxide wherein said metal iε εelected from the group conεisting of Group IB, IIB, VIII, and IIIA of the Periodic Table, and moεt preferably, gallium or zinc and in the range of from about 0.05-5 wt. %.
(B)Beta can be used to condense lower aliphatic alcohols having 1-10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon. The condenεation reaction proceedε at a temperature of about 500-1000°F, a preεεure of about 0.5-1000 pεig and a εpace velocity of about 0.5-50 WHSV. The process diεcloεed in U.S. Patent No. 3,984,107 more 1 specifically describes the procesε conditionε used in this 2 proceεε, which patent iε incorporated totally herein by 3 reference. 4 5 The catalyεt may be in the hydrogen form or may be base 6 exchanged or impregnated to contain amonium or a metal 7 cation complement, preferably in the range of from about 8 0.05-5 wt. %. "The metal cationε that may be preεent include 9 any of the metalε of the Groupε I-VIII of the Periodic 0 Table. However, in the caεe of Group IA metalε, the cation 1 content εhould ,in no caεe be εo large aε to effectively 2 inactivate the catalyεt. 3 4 The catalyεt can be made highly active and highly εelective 5 for iεomerizing, C, to C, hydrocarbonε. The activity meanε 6 that the catalyεt can operate at relatively low temperatureε 7 which thermodynamically favorε highly branched paraffinε. 8 Consequently, the catalyεt can produce a high octane g product. The high εelectivity meanε that a relatively high 0 liquid yield can be achieved when the catalyεt iε run at a i high octane. 2 3 The preεent proceεε compriεeε contacting the iεomerization 4 catalyεt with a hydrocarbon feed under iεomerization 5 conditionε. The feed is preferably a light straight run 6 fraction, boiling within the range of 30-250βF and 7 preferably from 60-200βF. Preferably, the hydrocarbon feed 8 f°r the process compriεeε a εubεtantial amount of C4 to C-, 9 normal and εlightly branched low octane hydrocarbonε, more 0 preferably Cj- and Cg hydrocarbonε.
The preεεure in the proceεε iε preferably between 50-1000 3 pεig, more preferably between 100-500 pεig. The LHSV iε preferably between about 1 to about 10 with a value in the range of about 1 to about 4 being more preferred. It is also preferable to carry out the isomerization reaction in the preεence of hydrogen. Preferably, hydrogen iε added to give a hydrogen to hydrocarbon ratio (H2/HC) of between 0.5 and 10 H2/HC, more preferably between 1 and 8 H2/HC. The temperature iε preferably between about 200βF and about 1000βF, more preferably between 400-600βF. Aε iε well known to those skilled in the iεomerization art, the initial εelection of the temperature within thiε broad range iε made primarily aε a function of the desired conversion level considering the characteristicε of the' feed and of the catalyεt. Thereafter, to provide a relatively constant value for conversion, the temperature may have to be slowly increased during the run to compensate for any deactivation that occurs.
A low εulfur feed iε eεpecially preferred in the preεent proceεε. The feed preferably containε leεε than 10 ppm, more preferably leεε than 1 ppm, and moεt preferably leεε than 0.1 ppm εulfur. In the caεe of a feed which iε not already low in εulfur, acceptable levels can be reached by hydrogenating the feed in a preεaturation zone with a hydrogenating catalyεt which iε reεiεtant to sulfur poiεoning. An example of a εuitable catalyεt for thiε hydrodeεulfurization proceεε iε an alumina-containing εupport and a minor catalytic proportion of molybdenum oxide, cobalt oxide and/or nickel oxide. A platinum on alumina hydrogenating catalyεt can alεo work. in which caεe, a εulfur εorber is preferably placed downstream of the hydrogenating catalyst, but upstream of the preεent isomerization catalyεt. Examples of εulfur εorberε are alkali or alkaline earth metalε on porouε refractory inorganic oxideε, zinc, etc. Hydrodeεulfurization iε typically conducted at 315-455βC, at 200-2000 pεig, and at a LHSV of 1-5.
It is preferable to limit the nitrogen level and the water content of the feed. Catalysts and procesεeε which are εuitable for theεe purpoεes are known to those skilled in the art.
After a period of operation, the catalyst can become deactivated by coke. Coke can be removed by contacting the catalyst with an oxygen-containing gas at an elevated temperature.
The iεomerization catalyεt preferably containε a Group VIII metal compound to have εufficient activity for commercial uεe. By Group VIII metal compound aε uεed herein iε meant the metal itεelf or a compound thereof. The Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be usd in conjunction with the noble metal. The most preferred metal iε the amount of Group VIII metal preεent in the converεion catalyεt should be within the normal range of use in isomerizing catalyεtε, from about 0.05-2.0 wt. %.
(B)Beta can be converted to a catalyεt for uεe in a proceεε for the alkylation or tranεalkylation of an aromatic hydrocarbon. The process compriseε contacting the aromatic hydrocarbon with a C2 to C2Q olefin alkylating agent or a polyalkyl aromatic hydrocarbon tranεalkylating agent, under at leaεt partial liquid phaεe conditionε, and in the presence of a catalyst compriεing (B)Beta. For high catalytic activity, the (B)Beta zeolite εhould be predominantly in itε hydrogen ion form. Generally, the zeolite iε converted to itε hydrogen form by ammonium exchange followed by calcination. If the zeolite iε εynthesized with a high enough ratio of organonitrogen cation to sodium ion, calcination alone may be sufficient. It iε preferred that, after calcination, at leaεt 80% of the cation εiteε are occupied by hydrogen ionε and/or rare earth ionε.
The pure (B)Beta zeolite may be uεed aε a catalyεt, but generally, it iε preferred to mix the zeolite powder with an 3 inorganic oxide binder εuch aε alumina, εilica, 4 εilica/alumina, or naturally occurring clays and form the 5 mixture into tablets or extrudates. The final catalyεt may 6 contain from 1-99 wt. % (B)Beta zeolite. Uεually the 7 zeolite content will range form 10-90 wt. %, and more 8 typically from 60-80 wt. %. The preferred inorganic binder g iε alumina. The mixture may be formed into tabletε or 0 extrudateε having the deεired shape by methods well known in i the art. 2 3 Examples of εuitable aromatic hydrocarbon feedstocks which 4 may be alkylated or transalkylated by the process of the 5 invention include aromatic compounds εuch aε benzene, 6 toluene, and xylene. The preferred aromatic hydrocarbon iε 7 benzene. Mixtureε of aromatic hydrocarbonε may alεo be 8 employed. 9 0 Suitable olefinε for the alkylation of the aromatic 1 hydrocarbon are thoεe containing 2-20 carbon atomε, εuch aε 2 ethylene, propylene, butene-1, tranεbutene-2, and 3 ciε-butene-2, and higher olefins or mixtures thereof. The 4 preferred olefin iε propylene. Theεe olefinε may be preεent in admixture with the correεponding C2 to C2Q paraffinε, but it iε preferable to remove any dieneε, acetyleneε, εulfur compoundε or nitrogen compoundε which may be preεent in the olefin feedεtock stream to prevent rapid catalyst deactivation.
When tranεalkylation iε deεired, the tranεalkylating agent iε a polyalkyl aromatic hydrocarbon containing two or more alkyl groupε that each may have from two to about four carbon atomε. For example, εuitable polyalkyl aromatic hydrocarbonε include di-, tri-, and tetra-alkyl aromatic hydrocarbons,, such aε diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene) , di-iεopropylbenzene, di-iεopropyltoluene, dibutylbenzene, and the like. Preferred polyalkyl aromatic hydrocarbonε are the dialkyl benzeneε. A particularly preferred polyalkyl aromatic hydrocarbon iε di-iεopropylbenzene.
Reaction productε which may be obtained include ethylbenzene from the reaction of benzene with either ethylene or polyethylbenzenes, cumene from the reaction of benzene with propylene or polyiεopropylbenzeneε, ethyltoluene from the reaction of toluene with ethylene or polyethyltolueneε, cymeneε from the reaction of toluene with propylene or polyiεopropyltolueneε, and εecbutylbenzene from the reaction of benzene and n-buteneε or polybutylbenzenes. The production of cumene from the alkylation of benzene with propylene or the transalkylation of benzene with di-iεopropylbenzene iε eεpecially preferred.
When alkylation iε the proceεε conducted, reaction conditionε are aε followε. The aromatic hydrocarbon feed εhould be preεent in εtoichiometric exceεε. It iε preferred that molar ratio of aromaticε to olefinε be greater than four-to-one to prevent rapid catalyεt fouling. The reaction temperature may range from 100-600βF, preferably, 250-450°F. The reaction preεsure should be sufficient to maintain at leaεt a partial liquid phaεe in order to retard catalyεt fouling. This is typically 50-1000 psig depending on the feedstock and reaction temperature. Contact time may range from 10 εecondε to 10 hourε, but iε uεually from five minuteε to an hour. The WHSV in terms of grams (poundε) of aromatic hydrocarbon and olefin per gram (pound) of catalyεt per hour, iε generally within the range of about 0.5 to 50.
When tranεalkylation is the process conducted, the molar ratio of aromatic hydrocarbon will generally range from about 1:1 to 25:1, and preferably from about 2:1 to 20:1. The reaction temperature may range from about 100-600°F, but it is preferably about 250-450°F. The reaction preεεure εhould be sufficient to maintain at least a partial liquid phaεe, typically in the range of about 50-1000 pεig, preferably 300-600 psig. The WHSV will range from about 0.1-10.
The converεion of hydrocarbonaceouε feedε can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactorε depending on the typeε of proceεs desired. The formulation of the catalyst particles will vary depending on the conversion procesε and method of operation.
Other reactionε which can be performed uεing the catalyεt of thiε invention containing a metal, e.g., platinum, include hydrogenation-dehydrogenation reactions, denitrogenation, and desulfurization reactionε. Some hydrocarbon conversionε can be carried out on (B)Beta zeoliteε utilizing the large pore εhape-εelective behavior. For example, the εubεtituted (B)Beta zeolite may be uεed in preparing cumene or other alkylbenzeneε in proceεεeε utilizing propylene to alkylate aromaticε.
(B)Beta can be uεed in hydrocarbon converεion reactionε with active or inactive εupportε, with organic or inorganic binderε, and with and without added metalε. Theεe reactionε are well known to the art, aε are the reaction conditionε.
(B)Beta can also be used aε an adsorbent, as a filler in paper, paint, and toothpasteε, and aε a water-εoftening agent in detergentε.
The following exampleε illuεtrate the preparation and uεe of (B)Beta.
EXAMPLES
Example 1
Syntheεiε of an Effective Diquatemary Ammonium Compound Boron Beta Cryεtallization
48 gramε of DABCO (1,4 Diazabicyclo [2.2.2] octane) iε εtirred into 800 ml of Ethyl Acetate. 42 gramε of 1,4 Diiodobutane iε added dropwiεe and εlowly while the reaction iε εtirred. Allowing the reaction to run for a few dayε at room temperature produceε a high yield of the precipitated diquate ary compound,
The product iε washed with THF and then ether and then vacuum dried. Melting point ~~ 255βC.
The crystalline salt iε conveniently converted to the hydroxide form by stirring overnight in water with AGI-X8 hydroxide ion exchange resin to achieve a solution ranging from 0.25-1.5 molar.
Example 2
10.85 g of a 0.90M solution of the template from Example 1 is diluted with 3.95 ml H20. 0.23 g of Na2B407"18H20 are disεolved in thiε εolution and then 1.97 g of Caboεil M5 are blended in laεt. The reaction mixture iε heated in a Parr 4745 reactor at 150βC and rotated at 43 rpm on a εpit in a Blue M oven over a 9-day period. The εolid component of the reaction iε filtered, waεhed repeatedly, dried at 115°C and analyzed by X-ray diffraction. The product iε identified aε (B)Beta.
Example 3
The εame experiment iε εet up aε in Example 2 except the diquat in Example 2 iε replaced by an equivalent amount of TEAOH. The experiment iε run under analogouε conditionε although thiε time the cryεtallization iε complete in 6 dayε. The product iε ZSM-5 by XRD. Thiε εhowε that TEAOH doeεn't have enough εelectivity for Beta in the boroεilicate system. TEAOH iε the template uεed in the prior art for εyntheεiε of Beta.
Example 4
202 g of a 0.84M εolution of the template from Example 1 iε mixed with 55 g of H20, and 4.03 g of Na2B.O7"10H2O. 35 g of Caboεil M5 iε blended in laεt and the reaction iε run in a Parr 600-cc εtirred autoclave with liner for 6 dayε at 150°C and εtirred at 50 rpm. The product iε well-cryεtallized Boron Beta. The pattern iε tabulated in Table 2.
TABLE 2
2 θ d n int.
TABLE 2 (Cont. )
Int,
2 2
Examples 5-10 are given in Table 3, demonstrating the utility of the method of the invention. Exampleε 5-7 εhow that (B)Beta can be made at very low Si02/B20, valueε and that higher valueε eventually lead to εome ZSM-12 formation aε well. Example 8 εhowε that the deεired product can be obtained uεing Ludox AS-30 aε εilica εource. Now the aluminum impurity haε riεen to 530 ppm. Exampleε 9 and 10 εhow that providing the diquat aε a εalt to supplement TEAOH can insure formation of pure Boron Beta. Example 9 shows that iε the caεe even without εeeding.
Table 4 εhowε the XRD data for the product of Example 5 and Table 5 iε of Example 6, both in the aε-εyntheεized form.
01
TABLE 3 02
(0.70 m) 06 07
:(a) 5.60 g 08 Yes 25 Beta 09 10
,(a) 5.60 g 11 Yes 75 Beta + ZSM-12 12 13
,(b) 107 g 1.15 g Ludox AS-30 = Yes 30 Beta 14 (0.467 m) 33.3 g 15 16
,(a) 1.6 g 40* X . 3.16 g 9.38 g 0.20 Cabosil No 30 Beta 17 Salt c> 1.75 g 18 19
10(b) 28.5 g(c) 40% = 364 g 616 g 22.6 g Ludox AS-30 = No 30 Beta 20
660 g 21 a 150°C, 11 days, 0 rpm. 22 <b)150°C, 6 days, 50 rpm. 23 'Diquat provided as salt first prepared in Example 1 and not OH exchanged. 24
TABLE 4
2 θ d n int.
TABLE 5
2 θ d/n Int.
B « Broad VB « Very Broad
XRD patternε for the calcined productε of Exampleε 5 and 6 appear in Tableε 6 and 7, reεpectively.
The preεence of the boron in the framework of beta zeolite can be indicated by changeε in d-εpacingε. Table 8 compareε the d-εpacingε before and after calcination for εome of the εharper peakε of the productε of Exampleε 4, 5 and 6. Alεo εhown are the valueε for an aluminum beta zeolite prepared by the prior art reference (Re 28,341). It can be εeen that the Boron Betaε εhow d-εpacingε conεiεtently εmaller than the aluminum Beta. TABLE 6
Int.
Int.
TABLE 7 (Cont. )
Al-B 3.97 3.30 3.03 3.97 3.30 3.03
3.89 3.26 2.97
3.90 3.26 2.98 3.88 3.26 2.97
Note: d/n spacingε for B-Betaε are conεiεtently leεε than thoεe for Al-Betaε.
Example 11
The product of Example 4 waε calcined aε followε. The εample waε heated in a muffle furnace in nitrogen from room temperature up to 540°C at a εteadily increasing rate over a 7-hour period. The εample waε maintained at 540°C for four more hourε and then taken up to 600°C for an additional four hourε. Nitrogen waε paεsed over the zeolite at a rate of 20 εtandard cfm during heating. The calcined product had the X-ray diffraction lineε indicated in Table 9 below.
TABLE 9
Ion exchange of the calcined material from Example 4 waε carried out uεing NH.N03 to convert the zeoliteε from Na form to NH.. Typically the εame maεε of NH.NO, aε zeolite was slurried into H20 at ratio of 50:1 H-O zeolite. The exchange εolution waε heated at 100βC for two hourε and then filtered. Thiε proceεε waε repeated two timeε. Finally, after the laεt exchange, the zeolite waε waεhed εeveral timeε with H20 and dried. Example 13
Constraint Index Determination
0.50 g of the hydrogen form of the zeolite of Example 4 (after treatment according to Exampleε 11 and 12 waε packed into a 3/8-inch εtainleεε εteel tube with alundum on both εideε of the zeolite bed. A Lindburg furnace waε uεed to heat the reactor tube. Helium was introduced into the reactor tube at 10 cc/minute and atmoεpheric preεεure. The reactor waε taken to 250°F for 40 inuteε and then raiεed to 800°F. Once temperature equilibration waε achieved a 50/50, w/w feed of n-hexane and 3-methylpentane waε introduced into the reactor at a rate of 0.62 cc/hour. Feed delivery waε made via εyringe pump. Direct εampling onto a gaε chromatograph was begun after 10 minutes of feed introduction. Conεtraint Index values were calculated from gas chromatographic data uεing methods known in the art.
Example Conversion No. C.I. at 10 Min. Tem . , cF
13 — 0 800
Example 14
The product of Example 4 after treatment as in Exampleε 11 and 12 iε refluxed overnight with Al(N03)3 *9H20 with the latter being the εame maεε aε the zeolite and uεing the εame dilution aε in the ion exchange of Example 12. The product iε filtered, waεhed, and calcined to 540°C. After pelletizing the zeolite powder and retaining the 20-40 meεh fraction, the catalyεt iε teεted aε in Example 13. Data for the reaction iε given in Table 10 along with a variety of catalyεts made from analogous treatments with other metal saltε.
Exampleε 15-22
Pleaεe refer to Table 10 and Table 11.
TABLE 10
Conεtraint Index Determination For Metal-Treated (B)Beta
Example Metal No. Salt C.I.
13 None — 4 A1(N03)3 1.0 15 Ga(N03)3 0.25 16 Sn(AC)2 0.70 17 MgCL2'6H20 2.0 18 Co(N03)2'6H20 1.0
Table 11 εhowε the data for the treatment of the product of Exampleε 4, 11, 12 with variouε quantitieε of Zn(Ac)2'2H20.
TABLE 11
Example (B)Beta Zn(AC)2'2H20 Wt. % Zn after exch./calc, No.
19 4.5 g 2.20 g 3.12 20 4.5 g 1.10 g 1.95 21 4.5 g 0.55 g 1.38 22 4.5 g 0.25 g 0.76
Example 20 gave 5% converεion at 800βF for C.I. teεt and CI - 0.30.
Example 23
The boroεilicate verεion of (B)Beta waε evaluated aε a reforming catalyεt. The zeolite powder waε impregnated with Pt(NH3)4 *2N03 to give 0.8 wt. % Pt. The material waε calcined up to 550βF in air and maintained at thiε temperature for three hourε. The powder waε pelletized on a Carver preεε at 1000 pεi and broken and meεhed to 24-40.
The catalyεt waε evaluated at 900βF in hydrogen under the following conditionε:
The feed waε an iC-, mixture (Philipε Petroleum Company).
Table 12 giveε data at 800 and 900°F and 50 and 200 pεig, Temperature Preεsure(H2) Conversion % Aromatization Selectivi Product Toluene wt. % % Toluene in Cς Aromati c5+ yield wt. % 5"cβ R0N
a'The Catalyεt iε quite εtable and the valueε are averaged over at leaεt 20 hourε of run time.
Example 24
The product of Example 18 now contained a εecond metal due to cobalt incorporation. The catalyεt waε calcined to 1000°F. Next, a reforming catalyεt waε prepared aε in Example 23. The catalyεt waε evaluated under the following conditionε:
The feed haε an iC, mixture (Philips Petroleum Company). The data for the run iε given in Table 13. After 23 hourε onεtream, the preεεure waε dropped to 100 pεig and thiε data alεo appearε in the table. By compariεon with Example 23, the incorporation of cobalt into the zeolite giveε a more Cr+ selective reforming catalyεt. The catalyst has good stability at 800°F.
A product waε prepared aε in Example 12. Next, the catalyεt waε dried at 600βF, cooled in a cloεed εyεtem, and then vacuum impregnated with an aqueouε εolution of Pd(NH3).*2N03 to give 0.5 wt. % loading of palladium. The catalyεt waε then calcined εlowly, up to 900°F in air and held there for three hourε. Table 14 gives run conditions and product data for the hydrocracking of hexadecane. The catalyst is quite εtable at the temperatureε given.
The data εhowε that the catalyst has good isomerization selectivity and that the liquid yield is high compared with the gas make.
Example 26
The hydrogen form of (B)Beta can be used in typical fluidized catalytic cracking (FCC). (B)Beta, as prepared in Examples 2, 11, 12 and refluxed with Al(N03)3 *9H20 aε in Example 14, waε formulated into a spray dried FCC catalytic octane additive and teεted in a fixed fluidized cyclic reactor. For thiε example, the FCC catalytic octane additive contained nominally 25% by weight (B)Beta, 32.5% Kaolin and 42.5% silica/alumina matrix. Fixed fluidized cyclic teεting waε conducted at 7 cat/oil ratio, with a 1100°F initial catalyεt temperature. A εubεequent gas chromatographic analysis of the liquid product was made to determine calculated octanes. The catalyst inventory during the fixed fluidized cyclic teεting of the (B)Beta FCC catalytic octane additive contained 90% εteamed rare earth FCC catalyst and 10% of calcined (B)Beta FCC catalytic octane additive. Feed properties of the gaε oil uεed during fixed fluidized cyclic teεting are given in Table 15.
TABLE 15 (Cont.)
50% 430°C 70% 499βC 90% 595°C 95% 630°C EP 654°C
Table 16 εhowε calculated reεearch and motor octane numberε from the fixed fluidized cyclic teεtε.
(B)Beta Pluε rence Catalyεt
87.8 76.8
87.5 76.9

Claims

WHAT IS CLAIMED IS:
1. A zeolite having a mole ratio of an oxide εelected from εilicon oxide, germanium oxide, and mixtureε thereof to an oxide εelected from boron oxide, or mixtures of boron oxide with aluminum oxide, gallium oxide or iron oxide, greater than 10:1 and wherein the amount of aluminum iε leεε than 0.10% by weight and having the X-ray diffraction lines of Table 1(b).
2. A zeolite having a compoεition, aε εyntheεized and in the anhydrouε state, in terms of mole ratios of oxides aε followε: (1.0 to 5)Q2O:(0.1 to 2.0)M2O:W2O3:- (greater than 10) Y02 wherein M iε an alkali metal cation, W iε εelected from boron, Y is selected from εilicon, germanium, and mixtureε thereof, Q is a diquatemary ammonium ion and having the X-ray diffraction lines of Table 1(a).
3« A zeolite in accordance with Claim 1 having a mole ratio of an oxide εelected from εilicon oxide to boron oxide greater than 100:1.
4. A zeolite in accordance with Claim 1 wherein a portion of the boroh in said zeolite is replaced by a first row transition metal or a Group IIIA metal.
5. A zeolite in accordance with Claim 4 wherein the replacing metal iε aluminum, gallium, iron, εilicon, zinc and mixtureε thereof.
6. A zeolite prepared by thermally treating the zeolite of Claim 3 at a temperature from about 200°C to 820°C. i 7. A zeolite in accordance with Claim 2 wherein the 2 diquatemary ammonium ion is derived from a compound of 3 the formula: 4
8 9 0 8. A zeolite in accordance with Claim 1 or 2 which has 1 undergone ion exchange with hydrogen, ammonium, rare 2 earth metal. Group IIA metal, or Group VIII metal ions. 3 4 9. A zeolite in accordance with Claim 1 or 2 wherein rare 5 earth metalε. Group IIA metalε, or Group VIII metalε 6 are occluded in the zeolite. 7 8 10. A zeolite compoεition, compriεing the zeolite of Claim 9 1 or 2 and an inorganic matrix. 0 i 11. A method for preparing the zeolite of Claim 1, 2 compriεing: 3 (a) preparing an aqueouε mixture containing εources of 5 a diquatemary ammonium ion, an oxide εelected from boron oxide, and an oxide εelected from 7 εilicon oxide, germanium oxide, and mixtureε 8 thereof; 9 0 (b) maintaining the mixture at a temperature of at leaεt 140°C until the cryεtalε of εaid zeolite 2 fojrm; and 3 4 (c) recovering εaid crystals. 12. A method in accordance with Claim 11 wherein the aqueouε mixture haε a compoεition in termε of mole ratioε of oxideε falling in the rangeε: Y02/W203, greater than 10; Q/Y02, 0.05:1 to 0.50:1; wherein Y iε selected from silicon, germanium, and mixtureε thereof, w i selected from boron, and Q is a bis (1-Azonia bicyclo[2.2.2]octane) α' ω alkane compound.
13. A method in accordance with Claims 11 and 12 wherein the diquatemary ammonium ion is derived from a compound of the formula:
N v_/N-(CH 2«) 21 or 20H
14. A proceεε for converting hydrocarbonε compriεing contacting a hydrocarbonaceouε feed at hydrocarbon converting conditionε with the zeolite of Claim 1 or 2.
15- The proceεs in accordance with Claim 14 which is a hydrocracking procesε compriεing contacting the hydrocarbon feedεtock under hydrocracking conditionε with the zeolite of Claim 1.
16. The process in accordance with Claim 14 which is a catalytic reforming process comprising contacting a hydrocarbonaceous feedεtream under catalytic reforming conditionε with the zeolite of Claim 1.
17. The proceεε in accordance with Claim 14 which iε a proceεε for preparing a product having an increased aromatics content compriεing: (a) contacting a hydrocarbonaceouε feed, which compriεeε normal and slightly branched hydrocarbons having a boiling range above about -40°C and leεε than about 200βC under aromatic ^conversion conditionε with the zeolite of Claim 1, wherein εaid zeolite iε εubεtantially free of acidity; and
(b) recovering an aromatic-containing effluent.
18. The process in accordance with Claim 17 wherein the zeolite contains a Group VIII metal component.
19. The proceεε in accordance with Claim 14 which iε a hydrocracking proceεε compriεing contacting the hydrocarbon feedεtock under hydrocracking conditionε with the zeolite of Claim 1.
20. The proceεε in accordance with Claim 14 which iε a catalytic cracking process compriεing the εtep of contacting the hydrocarbon feedεtock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with a catalyst compriεing the zeolite of Claim 1.
21. A proceεε in accordance with Claim 20 with a catalyεt compoεition compriεing a component which iε the zeolite of Claim 1 and a large pore size crystalline aliminoεilicate cracking component.
22. A proceεε aε defined in Claim 21 wherein the cryεtalline aluminoεilicate cracking component haε a pore εize greater than 8.0 angεtroms. 23. A procesε in accordance with Claim 21 wherein the catalyεt compoεitionε compriεe a phyεical mixture of the two componentε.
24. A proceεε in accordance with Claim 21 wherein one of the componentε iε the zeolite of Claim 1 incorporated in an inorganic oxide εuch aε εilica, alumina, amorphouε silica-alumina, silica-magnesia, silica zirconia, alumina-boria, alumina-titanate, a synthetic clay such aε εynthetic mica-montmorillonite, natural clayε such as kaolin, halloysite, montmorillonite, attapulgite, εepiolite, and εaponite, acid activated clayε, pillared or croεε-linked clayε, and mixtureε thereof.
25. A proceεε in accordance with Claim 21 wherein the two catalyεt componentε are incorporated in an inorganic matrix compriεed of the inorganic oxide of Claim 24.
26. The proceεε in accordance with Claim 14 which iε an iεomerizing proceεε for iεomerizing C. to C-, hydrocarbonε, comprising contacting a catalyεt, compriεing at leaεt one Group VIII metal and the zeolite of Claim 1, with a feed having normal and εlightly branched C4 to C, hydrocarbonε under iεomerization conditionε.
27. A proceεε in accordance with Claim 26 wherein the catalyεt haε been calcined in a εteam/air mixture at an elevated temperature after impregnation of the Group VIII metal.
28. A proceεε in accordance with Claim 26 wherein Group VIII metal iε platinum. 91/00777 PCT/US90/03764
29. The proceεε in accordance with Claim 14 which iε a proceεε fo,r alkylating an aromatic hydrocarbon which compriεeε contacting under alkylating conditionε at leaεt a mole excess of an aromatic hydrocarbon with a C2 to C20 olefin under at leaεt partial liquid phaεe conditionε and in the preεence of a zeolite according to Claim 1.
30. The proceεε in accordance with Claim 29 wherein the aromatic hydrocarbon and olefin are preεent in a molar ratio of about 4:1 to 20:1, reεpectively.
31. The proceεε in accordance with Claim 29 wherein the aromatic hydrocarbon iε a member εelected from the group conεiεting of benzene, toluene and xylene, or mixtureε thereof.
32. The proceεε in accordance with Claim 14 which iε a proceεε for tranεalkylating an aromatic hydrocarbon which compriεeε contacting under tranεalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the preεence of a zeolite according to Claim 1.
33. The proceεε in accordance with Claim 32 wherein εaid aromatic hydrocarbon and εaid polyalkyl aromatic hydrocarbonε are preεent in a molar ratio of about 1:1 to about 25:1, reεpectively.
34. The proceεε in accordance with Claim 32 wherein the aromatic hydrocarbon iε a member εelected from the group conεisting of benzene, toluene and xylene, or mixtures thereof. 35. The proceεε in accordance with Claim 32 wherein the polyalkyl aromatic hydrocarbon is dialkylbenzene.
36. The proceεε in accordance with Claim 14 which iε an oligomerization process comprising contacting an olefin feed under oligomerization conditions with the zeolite of Claim 1.
EP90911359A 1989-07-07 1990-07-03 Low-aluminum boron beta zeolite Withdrawn EP0592392A1 (en)

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JP2004010537A (en) * 2002-06-06 2004-01-15 Mitsubishi Chemicals Corp Template for hydrothermal synthesis, method for producing silicon-containing laminar compound and silicon-containing laminar compound
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MX2018007068A (en) * 2015-12-08 2018-08-01 Basf Se A tin-containing zeolitic material having a bea framework structure.
ES2692818B2 (en) 2017-06-05 2019-11-28 Univ Valencia Politecnica SYNTHESIS OF ZEOLITE BETA IN ITS NANOCRISTALINE FORM, SYNTHESIS PROCEDURE AND ITS USE IN CATALYTIC APPLICATIONS

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