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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• 1990
  • 1990-07-03 BR BR909007515A patent/BR9007515A/pt not_active Application Discontinuation
  • 1990-07-03 EP EP90911359A patent/EP0592392A1/de not_active Withdrawn
  • 1990-07-03 AU AU60521/90A patent/AU6052190A/en not_active Abandoned
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  • 1990-07-03 JP JP2510577A patent/JPH05500650A/ja active Pending
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