CA1100468A - Zeolite catalyst and method of manufacture and use thereof - Google Patents
Zeolite catalyst and method of manufacture and use thereofInfo
- Publication number
- CA1100468A CA1100468A CA274,127A CA274127A CA1100468A CA 1100468 A CA1100468 A CA 1100468A CA 274127 A CA274127 A CA 274127A CA 1100468 A CA1100468 A CA 1100468A
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- Canada
- Prior art keywords
- zeolite
- further characterized
- inorganic oxide
- refractory inorganic
- calcined
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- C07C6/123—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 only one hydrocarbon
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method of manufacture providing a catalytic com-posite of improved activity is disclosed. A zeolite of the mordenite crystal structure with a sodium content of less than about 5 wt. % as Na2o is subjected to an aqueous ammoniacal treatment at a pH of at least about 9.5 and cal-cined in intimate admixture with a refractory inorganic oxide to form a catalytic composite therewith. Use of the catalyst for transalkylation of alkylaromatic hydrocarbon is also disclosed.
A method of manufacture providing a catalytic com-posite of improved activity is disclosed. A zeolite of the mordenite crystal structure with a sodium content of less than about 5 wt. % as Na2o is subjected to an aqueous ammoniacal treatment at a pH of at least about 9.5 and cal-cined in intimate admixture with a refractory inorganic oxide to form a catalytic composite therewith. Use of the catalyst for transalkylation of alkylaromatic hydrocarbon is also disclosed.
Description
Crystalline aluminosilicates, or zeolites, of which mordenite is one example, are well known in the art and have found extensive application as hydrocarbon conversion catalysts or as a component thereof. Such mate-rials are of ordered crystalline structure often visualized as a three-dimensional network of fundamental structural units consisting of silicon-centered SiO4 and aluminum-centered A10~ tetrahedra, the tetrahedra being interconnected by a mutual sharing oF apical oxygen atoms and arranged to form cages or cavities in open communication through smaller intracrystalline channels or pore openings whose narrowest cross section has essentially a un1form diameter characteristic of each crystalline aluminosilicate variety.
To effect a chem1cal balance, each A104 tetrahedra has a cation associated therewith -- usually a sodium or other exchangeàble cation. The aforemen-tioned cages or cavities are occupied by water molecules and by the last mentioned cations, both of which exhibit considerable freedom of movement permitting ion-exchange and reversable dehydration.
The crystalline aluminosilicates, or zeolites, employed in the manufacture of the catalytic composite of this invention, are of the mor-denite crystal structure, highly siliceous in nature and generally charac-terized by a siliGa-alumina mole ratio of from about 6 to about 12 as found in nature. The mordenite crystal structure comprises four- and five-membered rings of the SiO~ and A104 tetrahedra so arranged that the crystal lattice comprises pores and channels running parallel along the crystal axis to give a tubular con~iguration. This structure is unique among the crystalline aluminosilicates since the channels or tubes do not intersectS and access to the cages or cavities is in only one direction. For this reason, the mordenite structure is Frequently re-ferred to as two-dimensional. This is in contrast to other well-known crystalline aluminosilicates, for example Faujasite, in which the cavities can be entered from three directions.
Mordenite, clinoptilolite, or mordenite which has been synthesized or acid extracted, caustic extracted, or otherwise treated to increase the silica-alumina mole ratio to about 20:1 or more while maintaining the mordenite crystal structure, may be used in the manufacture of the catalytic composite of this invention.
Crystalline aluminosilicates having a mordenite crystal structure have heretofore been utilized composited with a refractory inorganic oxide, typically alumina, as a hydrocarbon conversion catalyst, and are particularly useful with respect to the transalkylation of alkylaromatic hydrocarbons.
It is an object of this invention to present a new and useful method of manu~acture provlding a catalytic composite of improved activity.
In one of its broad aspects, the present invention embodies a method of manufacture which comprises subjécting a zeolite of the ~ordenite crystal structure and containlng less than about 5 wt. % sodium as Na20, -to an aqueous ammoniacal trea-tment at a pH of at least about 9.5, and cal-cining the thus treated zeolite in intimate admixture with a refractory inorganic oxide to form a catalytic composite therwith.
One of the more specific embodiments relates to a method of manufacture providing a catalytic composite of improved activity which comprises subjecting a zeolite of the mordenite crystal structure contain-ing less than about 5 wt. % sodium as Na20, to an aqueous ammoniacal treat-ment at a pH of From about 10 to about 12, and calcining the thus treated zeolite in intimate admixture with alumina to form a catalytic composite therewith.
A still more specific embodiment is in a method of manufacture which comprises subjecting mordenite, containing less than about 5 wt. %
sodium as Na20, to an aqueous ammoniacal treatment with a pH of from about 10 to about 12 and at a temperature of from about 75 to about 200C. in intimate admixture with alpha-alumina monohydrate, and calcining said zeolite in intimate admixture with said alumina to form a catalytic composite therewith.
Other objects and embodiments of this invention will become apparent in the following detailed specification.
Pursuant to the present invention, the zeolite is subjected to an aqueous ammoniacal treatment at a pH of at least about 9.5, and said treatment can be prior to admixture with the refractory inorganic oxide or after admixture therewith, the latter being preFerred. The aqueous ammoniacal treatment can be efferted at a temperature of From about 75 to about 200C.
over a period of from about 1 to about 24 hours. The treatment can be eFfected at subskantially atmospheric pressure in an open vessel at about the reflux temperature of the aqueous ammoniacal solution albeit over a more extended period up to about 24 hours. The treatment is effective 46~
over a substantially shorter period, say from about 1 to about 10 hours at autogenous pressures utilizing a closed vessel. Switable ammoniacal solu-tions include solutions of bases such as ammonium hydroxide, hydroxylamine, hydrazine, tetramethylammonium hydroxide, etc., or strong organic amines like methylamine 9 dimethylamine, ethylamine, diethylamine, propylamine, diisopropylamine, n-butylamine, t-butylamine, diisobutylarnine, n-amylamine, n-hexylamine, ethylene diamine, hexamethylenediamine, benzylamine, aniline, piperazine, piperadine, and the like, the selected base being employed in sufficient concentration to provide a pH of at least about 9.5, and preferably from about 10 to about 12.
The crystalline aluminosilicate, or zeolite, employed herein as a starting material should contain, or should be treated to contain, less than about 5 wt. % sodium as Na20. The sodium can be reduced to an acceptable level by conventional and widely practiced ion-exchange tech-niques. Typically, ammonium cations are exchanged for sodium cations ontreating the zeolite in contact with an aqueous ammonium salt solution, for example an aqueous ammonium chloride solution. The resulting anlmonium-exchanged zeolite is thereafter heat-treated to effect thermal decomposition of the ammonium cations and formation of the hydrogen form of the zeolite.
In any case, the treatment may be e~fected one or more times to reduce the sodium content to less than about 5 wt. % as Na20.
Refractory inorganic oxides for use in accordance with the method of this invention include the naturally occurring as well as the synthetically prepared refractory inorganic oxides. Suitable refractory inorganic oxides are such as alumina, silica, ~irconia, titania, thoria, boria, magnesia, chromia, stannic oxide, and the like, as well as combinations and composites thereof, for example~ alumina~si:lica, alumina-zircon:ia, alumina-tita3lia, etc. Alumina is a preferred refractoxy inorganic oxide for use herein, particularly with respec-t ~o the manufacture of a catalytic composite for use in the trans~
alkylation of alkylaromatic hydroca.rbons. The alumina may be any of the various hydrous aluminum oxides such as alpha-alumina monohydrate of the boehmite structure, alpha~alwnina trihydrate oE the gibbsite structure, ~eta-alumina trihydrate of the bayerite structure, and the like, the first mentioned alpha alumina monohydrate being preferred.
The zeolite may be combined in intimate admixture with the refractory inorganic oxide in any conventional or otherwise convenient manner. For example, the zeolite can he admixed with an alumina precursor subsequently converted to alumina to provide the zeolite in intimate admixture with the aluminaO One preferred alumina precursor for use in this manner is a basic aluminum sul:Eate such as is precipitated from an aqueous solution of aluminum sulfate and ammonium hydroxide at a pH of about 6.
The zeolite may be combined in intimate admixture with refractory inorganic oxi.de in any conventional or otherwise convenient manner to form spheres, pills, pellets, granules, extrudates, or other suitable particle shape. ~ more preferred method comprises commingling ~p _ 5 _ ~ o~
the zeolite wlth a powdered refractory inorganic oxide, adding a binder and/or lubricant to the mixture, and compressing the mixt:ure into pills or pellets of uniform size and shape. Alternatively, and still more preferably, the zeolite is mulled with a powdered form of the refractory inorganic oxide, and with a peptizing agent such as nitric acid, to form an extrudable dough. The dough can be pressured through a die of predetermined size to form extrudate particles utilized as such or rolled into spheres in a spinning drum prior to calcination. In any case, the zeolite can be sub-jected to the aqueous ammoniacal treatment herein contemplated either before bein~ admixed with the refractory inorganic oxide or after being ad~ixed therewith, the latter being preFerred. The zeolite is preferably calcined in intimate admixture with the selected refractory inorganic oxide in a weight ratio of from about 1:3 to about 3:1.
Regardless of whether the zeolite is subjected to the aqueous ammoniacal treatment before or after admixture with refractory inorganic oxide, the treated zeolite is calcined in intimate admixture therewith to form a catalytic composite. Calcination is suitably in an air atmosphere at a temperature of from about 425 to about 750C., preferably at a tem-perature of from about 475 to about 550C.9 over a period of from about 0.5 to about lO hours.
The catalytic composite of this inYention is particularly useful for the transalkylation of alkylaromatic hydrocarbons. Thus, an alkyl-aromatic hydrocarbon having from about 7 to about 15 carbon atoms per molecule is treated at transalkylation conditions including a temperature of from about 200 to about 480 C. and a pressure of from about atmospher~c ' .
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to about 1500 pounds per square inch gauge (psig) in contact with a catalyst comprising essentially the cataly-tic composite of this invention to form products of higher and lower number of carbon atoms than said alkyl-aromatic hydrocarbon. The preferred composition employed as the catalytic composite comprises mordenite in admixture with alumina, said mordenite comprising from about 25 to about 75 wt. % of said composite.
The alkylaromatic hydrocarbon feed stock can be a substantially pure alkylaromatic hydrocarbon of from about 7 to about 15 carbon atoms, a mixture of such alkylaromatic hydrocarbons, or a hydrocarbon fraction rich in said alkylaromatics. Suitable alkylaromatic hydrocarbons include alkylbenzenes and alkylnaphthalenes, preferably with an alkyl group oF
less than about 4 carbon atoms. The catalytic composite is particularly effective in the treatment of the more difficultly transalkylatable toluene to form benzene, xylenes, or other polymethylbenzenes.
The transalkylation, or disproportionation, reaction can be effected in contact with the catalytic composite of this invention in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation. A preferred type of operation is of the continuous type. For example, the above described catalyst is disposed in a fixed bed in a reaction zone of a vertical tubular reactor and the alkylaromatic feed stock charged in an upflow or downflow manner, the reaction zone being maintained at a temperature of from about 200~ to about 480~ C., preferably at a temperature of from about 220 to about 460 C. Although pressure doés not appear to be an important variable with respect to the transalkylation reaction of this invention, the pro-cess is generally conducted in the presence of an imposed hydrogen pressure to provide from about 1 to about 10 moles of hydrogen per mole of hydrocarbon.
However, there is no net consumption of hydrogen in the process, and the hydrogen charge is recovered from the reactor effluent and recycled.
The transalkylation reaction can be effected over a wide range of space velocities. In general, the process is conducted at a space velocity of from about 0.2 to about 10. Space velocities herein re-ferred to are liquid hourly space velocities, (L~ISV) i.e., volume of charge per volurne of catalyst per hour. While the catalytic composite prepared by the present method permits unusually high space velocities indicative of high activity, the catalytic composite is particularly note~orthy because of its relatively high stability at a high activity level.
The composite prepared in accordance with the method of this invention may be employed as a component of a catalyst comprising any of the several catalytically active metallic materials in the oxidized or reduced state. Of particular interest are those catalytic composites com-prising one or more metals of Group VIB and VIII including molybdenum, tungsten, chromium, iron, nickel, cobalt, platinum, palladium, ruthenium9 rhodium, osmium and iridium. Thus, the composite of this invention can be utilized advantageously as a catalyst or component thereof to effect a variety of hydrocarbon conversion reactions involving reaction conditions comprising a temperature in the 25-760C. range. The catalysts are particu-larly useful in effecting the hydrocracking of heavy oils, including vacuum residuals, to form petroleum products in the middle distillate range uti-llzing a temperature of from about 260 to about 1560C. and pressures of from about 500 to about 1000 psig. Said~hydrocarbon conversion reactions further include polymerization of olefins, particularly ethylene, propylene~
l-butene, 2-butene, isobutylene and also higher boiling olefins, at .
6~
polymerization reaction conditions. The composite of this invention is also useful as a catalyst or component thereof in effecting the alkylation of isoparaffins with olefins or other alkylating agents including, for example, alkyl halides and -the like; and also the alkylation of isobutane, isopentane, and/or isohexane with ethylene, propylene, l-butene, etc., or mixtures thereof; and also the alkylation of aromatics with olefins or other alkylating agents, particularly the alkylation of benzene, toluene, etc., with propylene, butylene, and higher boiling olefins, including nonenes, decenes, undecenes, etc., the foregoing alkylation reactions being effected at alkylation conditions disclosed in the art. The composite of this invention is further useful in the -isomerization of paraffins, par-ticularly n-butane, n-pentane, n-hexane, n-heptane, n-octane, etc., or mixtures thereof, including isomerization of less highly branched chain saturated hydrocarbons to more hi~hly branched chain saturated hydrocarbons such as the isomerization of 2- or 3-methyl pentane to 2,2- and 2,3-dimethyl-butane, isomerization of naphthenes, for examples the iso~erization of dimethylcyclopentane to methylcyclohexane, isomerization of methylcyclo-pentane to cyclohexane, etc., at isomerization reaction conditions. Other hydrocarbon conversion reactions including the reforming of naphtha to gasoline, dehydroyenation of ethylbenzene to styrene, and hydrogenation of benzene to cyclohexane, are effectively catalyzed utilizing the composite of this lnvention as a catalyst or as a component thereof.
The following examples are presented in illustration of the method of this invention and are not intended as an undue limitation on the gen-erally broad scope of the invention as set out in the appended~claims.
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EXAMPLE I
In this example, a catalytic composite of mordenite and alumina was prepared without the benefit of the a4ueous am~oniacal trea1nnent herein described. Thus, 595 grams of a commercial mordenite (H Zeolon) containing about 0.16 wt. % sodium as Na20 and 16 wt. ~ volatile matter, as evidenced by weight loss on ignition at 900C., was thoroughly dry-mixed with 694 grams of a commercial alpha-alumina monohydrate (Kaiser medium) containing about 28Y3 volatile matter. Approximately 20 milliliters of concentrated nitric acid and 420 milliliters of water was admixed therewith, and the mixture mulled to form an extrudable dough. The resulting dough was ex-truded through a 1/16 inch die and the extrudate segmented and balled in a spinning drum with the formation of 1/16-1/8 inch spheroidal particles.
The spheroiclal product was subsequently calcilled in air at 500C. for 1 hour.
EXAMPLE II
The preparation was repeated in accordance with the method of Example I except that the mordenite was subjected to an aqueous ammoniacal treatment and calcined in intimate admixture with the alumina, the aqueous ammoniacal trPatment in this case being after admixture with the alumina pursuant to one preferred embodiment of this invention. In this instance, the spheroidal product oF Example I was immersed in an aqueous solution of ammonium hydroxide containing 5 wt. % NH3 and having a pH oF about 11.6.
Five volumes of the aqueous ammoniacal solution were employed per volume of spheroidal product treated. The treatment was at atmospheric pressure conditions utilizing a glass flask with an overhead condenser. The treat-ment was effected at reflux temperature -~ about 90C. 9 over a 16 hour period. The thus treated material was subsequently water-washed, dried, and calcined for 1 hour at 500C.
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EXAMPLE III
The preparation of Example I was again repeated except that the mordenite was subjected to an aqueous ammoniacal treatment and calcined in intimate admixture with the a1umina, the aqueous ammoniacal treatment in this case being after admixture with the alumina and at an elevated pres-sure pursuant to one preferred embodiment of this invention. In this instance, the spheroidal product of Example I was sealed in a glass-lined rotating autoclave together with an aqueous ammoniacal solution substan-tially as described in Example II. The aqueous ammoniacal solution was employed in an amount equivalent to 2 volumes per volume oF said spheroidal product. The autoclave was heated to 110C. and the spheroidal product treated at this temperature under autogenous pressure conditions for 2 hours. The thus treated product was recovered, water-washed, dried and calcined at 500C. ~or 1 hour.
The above-described preparations were evaluated with respect to the transalkylation of toluene. In each case, toluene, in admixture with hydrogen to provide a hydrogen/hydrocarbon mole ratio of about 10, was charged downflow through a 50 cubic centimeter bed of approximately 1~8 inch spheroidal catalyst particles ak a liquid hourly space velocity of
To effect a chem1cal balance, each A104 tetrahedra has a cation associated therewith -- usually a sodium or other exchangeàble cation. The aforemen-tioned cages or cavities are occupied by water molecules and by the last mentioned cations, both of which exhibit considerable freedom of movement permitting ion-exchange and reversable dehydration.
The crystalline aluminosilicates, or zeolites, employed in the manufacture of the catalytic composite of this invention, are of the mor-denite crystal structure, highly siliceous in nature and generally charac-terized by a siliGa-alumina mole ratio of from about 6 to about 12 as found in nature. The mordenite crystal structure comprises four- and five-membered rings of the SiO~ and A104 tetrahedra so arranged that the crystal lattice comprises pores and channels running parallel along the crystal axis to give a tubular con~iguration. This structure is unique among the crystalline aluminosilicates since the channels or tubes do not intersectS and access to the cages or cavities is in only one direction. For this reason, the mordenite structure is Frequently re-ferred to as two-dimensional. This is in contrast to other well-known crystalline aluminosilicates, for example Faujasite, in which the cavities can be entered from three directions.
Mordenite, clinoptilolite, or mordenite which has been synthesized or acid extracted, caustic extracted, or otherwise treated to increase the silica-alumina mole ratio to about 20:1 or more while maintaining the mordenite crystal structure, may be used in the manufacture of the catalytic composite of this invention.
Crystalline aluminosilicates having a mordenite crystal structure have heretofore been utilized composited with a refractory inorganic oxide, typically alumina, as a hydrocarbon conversion catalyst, and are particularly useful with respect to the transalkylation of alkylaromatic hydrocarbons.
It is an object of this invention to present a new and useful method of manu~acture provlding a catalytic composite of improved activity.
In one of its broad aspects, the present invention embodies a method of manufacture which comprises subjécting a zeolite of the ~ordenite crystal structure and containlng less than about 5 wt. % sodium as Na20, -to an aqueous ammoniacal trea-tment at a pH of at least about 9.5, and cal-cining the thus treated zeolite in intimate admixture with a refractory inorganic oxide to form a catalytic composite therwith.
One of the more specific embodiments relates to a method of manufacture providing a catalytic composite of improved activity which comprises subjecting a zeolite of the mordenite crystal structure contain-ing less than about 5 wt. % sodium as Na20, to an aqueous ammoniacal treat-ment at a pH of From about 10 to about 12, and calcining the thus treated zeolite in intimate admixture with alumina to form a catalytic composite therewith.
A still more specific embodiment is in a method of manufacture which comprises subjecting mordenite, containing less than about 5 wt. %
sodium as Na20, to an aqueous ammoniacal treatment with a pH of from about 10 to about 12 and at a temperature of from about 75 to about 200C. in intimate admixture with alpha-alumina monohydrate, and calcining said zeolite in intimate admixture with said alumina to form a catalytic composite therewith.
Other objects and embodiments of this invention will become apparent in the following detailed specification.
Pursuant to the present invention, the zeolite is subjected to an aqueous ammoniacal treatment at a pH of at least about 9.5, and said treatment can be prior to admixture with the refractory inorganic oxide or after admixture therewith, the latter being preFerred. The aqueous ammoniacal treatment can be efferted at a temperature of From about 75 to about 200C.
over a period of from about 1 to about 24 hours. The treatment can be eFfected at subskantially atmospheric pressure in an open vessel at about the reflux temperature of the aqueous ammoniacal solution albeit over a more extended period up to about 24 hours. The treatment is effective 46~
over a substantially shorter period, say from about 1 to about 10 hours at autogenous pressures utilizing a closed vessel. Switable ammoniacal solu-tions include solutions of bases such as ammonium hydroxide, hydroxylamine, hydrazine, tetramethylammonium hydroxide, etc., or strong organic amines like methylamine 9 dimethylamine, ethylamine, diethylamine, propylamine, diisopropylamine, n-butylamine, t-butylamine, diisobutylarnine, n-amylamine, n-hexylamine, ethylene diamine, hexamethylenediamine, benzylamine, aniline, piperazine, piperadine, and the like, the selected base being employed in sufficient concentration to provide a pH of at least about 9.5, and preferably from about 10 to about 12.
The crystalline aluminosilicate, or zeolite, employed herein as a starting material should contain, or should be treated to contain, less than about 5 wt. % sodium as Na20. The sodium can be reduced to an acceptable level by conventional and widely practiced ion-exchange tech-niques. Typically, ammonium cations are exchanged for sodium cations ontreating the zeolite in contact with an aqueous ammonium salt solution, for example an aqueous ammonium chloride solution. The resulting anlmonium-exchanged zeolite is thereafter heat-treated to effect thermal decomposition of the ammonium cations and formation of the hydrogen form of the zeolite.
In any case, the treatment may be e~fected one or more times to reduce the sodium content to less than about 5 wt. % as Na20.
Refractory inorganic oxides for use in accordance with the method of this invention include the naturally occurring as well as the synthetically prepared refractory inorganic oxides. Suitable refractory inorganic oxides are such as alumina, silica, ~irconia, titania, thoria, boria, magnesia, chromia, stannic oxide, and the like, as well as combinations and composites thereof, for example~ alumina~si:lica, alumina-zircon:ia, alumina-tita3lia, etc. Alumina is a preferred refractoxy inorganic oxide for use herein, particularly with respec-t ~o the manufacture of a catalytic composite for use in the trans~
alkylation of alkylaromatic hydroca.rbons. The alumina may be any of the various hydrous aluminum oxides such as alpha-alumina monohydrate of the boehmite structure, alpha~alwnina trihydrate oE the gibbsite structure, ~eta-alumina trihydrate of the bayerite structure, and the like, the first mentioned alpha alumina monohydrate being preferred.
The zeolite may be combined in intimate admixture with the refractory inorganic oxide in any conventional or otherwise convenient manner. For example, the zeolite can he admixed with an alumina precursor subsequently converted to alumina to provide the zeolite in intimate admixture with the aluminaO One preferred alumina precursor for use in this manner is a basic aluminum sul:Eate such as is precipitated from an aqueous solution of aluminum sulfate and ammonium hydroxide at a pH of about 6.
The zeolite may be combined in intimate admixture with refractory inorganic oxi.de in any conventional or otherwise convenient manner to form spheres, pills, pellets, granules, extrudates, or other suitable particle shape. ~ more preferred method comprises commingling ~p _ 5 _ ~ o~
the zeolite wlth a powdered refractory inorganic oxide, adding a binder and/or lubricant to the mixture, and compressing the mixt:ure into pills or pellets of uniform size and shape. Alternatively, and still more preferably, the zeolite is mulled with a powdered form of the refractory inorganic oxide, and with a peptizing agent such as nitric acid, to form an extrudable dough. The dough can be pressured through a die of predetermined size to form extrudate particles utilized as such or rolled into spheres in a spinning drum prior to calcination. In any case, the zeolite can be sub-jected to the aqueous ammoniacal treatment herein contemplated either before bein~ admixed with the refractory inorganic oxide or after being ad~ixed therewith, the latter being preFerred. The zeolite is preferably calcined in intimate admixture with the selected refractory inorganic oxide in a weight ratio of from about 1:3 to about 3:1.
Regardless of whether the zeolite is subjected to the aqueous ammoniacal treatment before or after admixture with refractory inorganic oxide, the treated zeolite is calcined in intimate admixture therewith to form a catalytic composite. Calcination is suitably in an air atmosphere at a temperature of from about 425 to about 750C., preferably at a tem-perature of from about 475 to about 550C.9 over a period of from about 0.5 to about lO hours.
The catalytic composite of this inYention is particularly useful for the transalkylation of alkylaromatic hydrocarbons. Thus, an alkyl-aromatic hydrocarbon having from about 7 to about 15 carbon atoms per molecule is treated at transalkylation conditions including a temperature of from about 200 to about 480 C. and a pressure of from about atmospher~c ' .
'. ' .
..
.,. ~. .:.,~
to about 1500 pounds per square inch gauge (psig) in contact with a catalyst comprising essentially the cataly-tic composite of this invention to form products of higher and lower number of carbon atoms than said alkyl-aromatic hydrocarbon. The preferred composition employed as the catalytic composite comprises mordenite in admixture with alumina, said mordenite comprising from about 25 to about 75 wt. % of said composite.
The alkylaromatic hydrocarbon feed stock can be a substantially pure alkylaromatic hydrocarbon of from about 7 to about 15 carbon atoms, a mixture of such alkylaromatic hydrocarbons, or a hydrocarbon fraction rich in said alkylaromatics. Suitable alkylaromatic hydrocarbons include alkylbenzenes and alkylnaphthalenes, preferably with an alkyl group oF
less than about 4 carbon atoms. The catalytic composite is particularly effective in the treatment of the more difficultly transalkylatable toluene to form benzene, xylenes, or other polymethylbenzenes.
The transalkylation, or disproportionation, reaction can be effected in contact with the catalytic composite of this invention in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation. A preferred type of operation is of the continuous type. For example, the above described catalyst is disposed in a fixed bed in a reaction zone of a vertical tubular reactor and the alkylaromatic feed stock charged in an upflow or downflow manner, the reaction zone being maintained at a temperature of from about 200~ to about 480~ C., preferably at a temperature of from about 220 to about 460 C. Although pressure doés not appear to be an important variable with respect to the transalkylation reaction of this invention, the pro-cess is generally conducted in the presence of an imposed hydrogen pressure to provide from about 1 to about 10 moles of hydrogen per mole of hydrocarbon.
However, there is no net consumption of hydrogen in the process, and the hydrogen charge is recovered from the reactor effluent and recycled.
The transalkylation reaction can be effected over a wide range of space velocities. In general, the process is conducted at a space velocity of from about 0.2 to about 10. Space velocities herein re-ferred to are liquid hourly space velocities, (L~ISV) i.e., volume of charge per volurne of catalyst per hour. While the catalytic composite prepared by the present method permits unusually high space velocities indicative of high activity, the catalytic composite is particularly note~orthy because of its relatively high stability at a high activity level.
The composite prepared in accordance with the method of this invention may be employed as a component of a catalyst comprising any of the several catalytically active metallic materials in the oxidized or reduced state. Of particular interest are those catalytic composites com-prising one or more metals of Group VIB and VIII including molybdenum, tungsten, chromium, iron, nickel, cobalt, platinum, palladium, ruthenium9 rhodium, osmium and iridium. Thus, the composite of this invention can be utilized advantageously as a catalyst or component thereof to effect a variety of hydrocarbon conversion reactions involving reaction conditions comprising a temperature in the 25-760C. range. The catalysts are particu-larly useful in effecting the hydrocracking of heavy oils, including vacuum residuals, to form petroleum products in the middle distillate range uti-llzing a temperature of from about 260 to about 1560C. and pressures of from about 500 to about 1000 psig. Said~hydrocarbon conversion reactions further include polymerization of olefins, particularly ethylene, propylene~
l-butene, 2-butene, isobutylene and also higher boiling olefins, at .
6~
polymerization reaction conditions. The composite of this invention is also useful as a catalyst or component thereof in effecting the alkylation of isoparaffins with olefins or other alkylating agents including, for example, alkyl halides and -the like; and also the alkylation of isobutane, isopentane, and/or isohexane with ethylene, propylene, l-butene, etc., or mixtures thereof; and also the alkylation of aromatics with olefins or other alkylating agents, particularly the alkylation of benzene, toluene, etc., with propylene, butylene, and higher boiling olefins, including nonenes, decenes, undecenes, etc., the foregoing alkylation reactions being effected at alkylation conditions disclosed in the art. The composite of this invention is further useful in the -isomerization of paraffins, par-ticularly n-butane, n-pentane, n-hexane, n-heptane, n-octane, etc., or mixtures thereof, including isomerization of less highly branched chain saturated hydrocarbons to more hi~hly branched chain saturated hydrocarbons such as the isomerization of 2- or 3-methyl pentane to 2,2- and 2,3-dimethyl-butane, isomerization of naphthenes, for examples the iso~erization of dimethylcyclopentane to methylcyclohexane, isomerization of methylcyclo-pentane to cyclohexane, etc., at isomerization reaction conditions. Other hydrocarbon conversion reactions including the reforming of naphtha to gasoline, dehydroyenation of ethylbenzene to styrene, and hydrogenation of benzene to cyclohexane, are effectively catalyzed utilizing the composite of this lnvention as a catalyst or as a component thereof.
The following examples are presented in illustration of the method of this invention and are not intended as an undue limitation on the gen-erally broad scope of the invention as set out in the appended~claims.
~9~
: ' .
.
EXAMPLE I
In this example, a catalytic composite of mordenite and alumina was prepared without the benefit of the a4ueous am~oniacal trea1nnent herein described. Thus, 595 grams of a commercial mordenite (H Zeolon) containing about 0.16 wt. % sodium as Na20 and 16 wt. ~ volatile matter, as evidenced by weight loss on ignition at 900C., was thoroughly dry-mixed with 694 grams of a commercial alpha-alumina monohydrate (Kaiser medium) containing about 28Y3 volatile matter. Approximately 20 milliliters of concentrated nitric acid and 420 milliliters of water was admixed therewith, and the mixture mulled to form an extrudable dough. The resulting dough was ex-truded through a 1/16 inch die and the extrudate segmented and balled in a spinning drum with the formation of 1/16-1/8 inch spheroidal particles.
The spheroiclal product was subsequently calcilled in air at 500C. for 1 hour.
EXAMPLE II
The preparation was repeated in accordance with the method of Example I except that the mordenite was subjected to an aqueous ammoniacal treatment and calcined in intimate admixture with the alumina, the aqueous ammoniacal trPatment in this case being after admixture with the alumina pursuant to one preferred embodiment of this invention. In this instance, the spheroidal product oF Example I was immersed in an aqueous solution of ammonium hydroxide containing 5 wt. % NH3 and having a pH oF about 11.6.
Five volumes of the aqueous ammoniacal solution were employed per volume of spheroidal product treated. The treatment was at atmospheric pressure conditions utilizing a glass flask with an overhead condenser. The treat-ment was effected at reflux temperature -~ about 90C. 9 over a 16 hour period. The thus treated material was subsequently water-washed, dried, and calcined for 1 hour at 500C.
. .
* Trademark _ ~ O
.~
,.. ~ . . :
! -.... J
EXAMPLE III
The preparation of Example I was again repeated except that the mordenite was subjected to an aqueous ammoniacal treatment and calcined in intimate admixture with the a1umina, the aqueous ammoniacal treatment in this case being after admixture with the alumina and at an elevated pres-sure pursuant to one preferred embodiment of this invention. In this instance, the spheroidal product of Example I was sealed in a glass-lined rotating autoclave together with an aqueous ammoniacal solution substan-tially as described in Example II. The aqueous ammoniacal solution was employed in an amount equivalent to 2 volumes per volume oF said spheroidal product. The autoclave was heated to 110C. and the spheroidal product treated at this temperature under autogenous pressure conditions for 2 hours. The thus treated product was recovered, water-washed, dried and calcined at 500C. ~or 1 hour.
The above-described preparations were evaluated with respect to the transalkylation of toluene. In each case, toluene, in admixture with hydrogen to provide a hydrogen/hydrocarbon mole ratio of about 10, was charged downflow through a 50 cubic centimeter bed of approximately 1~8 inch spheroidal catalyst particles ak a liquid hourly space velocity of
2.0, and at transall~ylation conditions including a pressure of 500 ps~g.
The temperature of the catalyst bed was adjusted to effect a 40% conversion of a toluene feed stoc~, the temperature in each case being taken as a measure of catalyst activity.
The catalytic composites of Examples I, II and III required tem-peratures of 475, 3~1 and 368C., respectively~ the latter two being prepared according to the method of this invention.
- ~, .. . .
EXAMPLE IV
The preparation of Example I was again repeated except that the mordenite therein described was subjected to an aqueous ammoniacal treat-ment prior to admixture with the alumina, the mordenite being subsequently calcined in intimate admixture with the alumina. In this example, the mordenite was first immersed in the aqueous ammoniacal solution of Example II. Five volumes of solution were employed per volume of mordenite. The aqueous ammoniacal treatment was effected under reflux conditions utilizing a glass flask equipped with an overhead condenser. The treatment was effected over a 16 hour period at substantially atmospheric pressure con-ditions, after which the mordenite was recovered and dried. The mordenite was thereafter thoroughly dry-mixed with the alpha-alumina monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented, and formed into spheres as heretofore described. The spheroidal product was calcined in air for 1 hour at 500C. and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40~
conversion was achieved at 380C.
EXAMPLE V
In this example, the mordenite employed was an ammonium iun-exchanged mordenite as opposed to the aqueous ammoniacal solution-treated mordenite of this invention. Thus, a solution of 260 grams of ammonium nitrate in 2340 cubic centimeters of water was used to a~monium ion-exchange 600 grams of the mordenite. The mordenite was slurried in 600 cc portions of the solu-; tion at about 55C. for about 1/2 hour, the mordenite being recovered by ~:
filtration after each of three such anlmonium ion-exchange treatments. After the final treatment the mordenite was dried at about 950e. The mordenite was thereafter thoroughly dry-mixed with the alpha-alum'lna monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented and ~ormed into spheres as heretofore described. The spheroidal product was calcined in air for 1 hour at 500C., and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40%
conversion was achieved at 463C.
EXAMPLE VI
A substantially pure rnordenite (H Zeolonj, in the form of extrudate particles was calcined in air for 1 hour at 500C. and thereafter eYaluated with respect to the transalkylation of toluene in the described manner. In this instance, a temperature of 508C. was required to achieve a 40% con-version. In a separate experiment, the calcined extrudate was further treated with an aqueous ammoniacal solution substantially in accordance with the method of Example III9 and then further calcined in air at 500C.
for 1 hour. Although the temperature requ;red to effect a 40% conversion of toluene was reduced to 473C., the temperature is substantially higher than that required when the treated mordenite is calcined in intimate admixture with aluminaO
.. :. .
.
* Trademark : .
1~ .~...... . :
The temperature of the catalyst bed was adjusted to effect a 40% conversion of a toluene feed stoc~, the temperature in each case being taken as a measure of catalyst activity.
The catalytic composites of Examples I, II and III required tem-peratures of 475, 3~1 and 368C., respectively~ the latter two being prepared according to the method of this invention.
- ~, .. . .
EXAMPLE IV
The preparation of Example I was again repeated except that the mordenite therein described was subjected to an aqueous ammoniacal treat-ment prior to admixture with the alumina, the mordenite being subsequently calcined in intimate admixture with the alumina. In this example, the mordenite was first immersed in the aqueous ammoniacal solution of Example II. Five volumes of solution were employed per volume of mordenite. The aqueous ammoniacal treatment was effected under reflux conditions utilizing a glass flask equipped with an overhead condenser. The treatment was effected over a 16 hour period at substantially atmospheric pressure con-ditions, after which the mordenite was recovered and dried. The mordenite was thereafter thoroughly dry-mixed with the alpha-alumina monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented, and formed into spheres as heretofore described. The spheroidal product was calcined in air for 1 hour at 500C. and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40~
conversion was achieved at 380C.
EXAMPLE V
In this example, the mordenite employed was an ammonium iun-exchanged mordenite as opposed to the aqueous ammoniacal solution-treated mordenite of this invention. Thus, a solution of 260 grams of ammonium nitrate in 2340 cubic centimeters of water was used to a~monium ion-exchange 600 grams of the mordenite. The mordenite was slurried in 600 cc portions of the solu-; tion at about 55C. for about 1/2 hour, the mordenite being recovered by ~:
filtration after each of three such anlmonium ion-exchange treatments. After the final treatment the mordenite was dried at about 950e. The mordenite was thereafter thoroughly dry-mixed with the alpha-alum'lna monohydrate to provide a 50-50 weight mixture with 20 milliliters of concentrated nitric acid in 420 milliliters of water being subsequently added. After thorough mulling to provide an extrudable dough, the dough was extruded, segmented and ~ormed into spheres as heretofore described. The spheroidal product was calcined in air for 1 hour at 500C., and thereafter evaluated with respect to the transalkylation of toluene in the described manner. A 40%
conversion was achieved at 463C.
EXAMPLE VI
A substantially pure rnordenite (H Zeolonj, in the form of extrudate particles was calcined in air for 1 hour at 500C. and thereafter eYaluated with respect to the transalkylation of toluene in the described manner. In this instance, a temperature of 508C. was required to achieve a 40% con-version. In a separate experiment, the calcined extrudate was further treated with an aqueous ammoniacal solution substantially in accordance with the method of Example III9 and then further calcined in air at 500C.
for 1 hour. Although the temperature requ;red to effect a 40% conversion of toluene was reduced to 473C., the temperature is substantially higher than that required when the treated mordenite is calcined in intimate admixture with aluminaO
.. :. .
.
* Trademark : .
1~ .~...... . :
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of manufacture providing a catalytic composite of improved activity which comprises subjecting a zeolite of the mordenite crystal structure, and containing less than about 5 wt. % sodium as Na20, to an aqueous ammoniacal treatment at a pH of at least about 9.5, and calcining the thus treated zeolite in intimate admixture with a calcined refractory inorganic oxide to form a catalytic composite therewith.
2. The method of claim 1 further characterized in that said zeolite is mordenite.
3. The method of claim 1 further characterized in that said zeolite is clinoptilolite.
4. The method of claim 1 further characterized in that said calcined refractory inorganic oxide is alumina.
5. The method of claim 1 further characterized in that said calcined refractory inorganic oxide is an alpha-alumina monohydrate.
6. The method of claim 1 further characterized in that said zeolite is calcined in intimate admixture with said refractory inorganic oxide in a weight ratio of from about 1-3 to about 3:1.
7. The method of claim 1 further characterized in that said zeolite is calcined in intimate admixture with said refractory inorganic oxide at a temperature of from about 425°
to about 750°C.
to about 750°C.
8. The method of claim 1 further characterized in that said zeolite is calcined in intimate admixture with said refractory inorganic oxide at a temperature of from about 47$°
to about 550°C.
to about 550°C.
9. The method of claim 1 further characterized in that said aqueous ammonia treatment is effected at a pH of from about 10 to about 12.
10. The method of claim 1 further characterized in that said aqueous ammoniacal treatment is effected at a tem-perature of from about 75° to about 200°C.
11. The method of claim 1 further characterized in that said zeolite is subjected to said aqueous ammoniacal treatment in intimate admixture with said refractory inorganic oxide.
12. A catalytic composite whenever prepared by the method of claim 1.
13. In a catalytic process for transalkylating a trans-alkylatable hydrocarbon at conventional reaction conditions, the improvement comprising use of the catalyst of claim 12 as the catalyst of the process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67189576A | 1976-03-29 | 1976-03-29 | |
| US671,895 | 1976-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100468A true CA1100468A (en) | 1981-05-05 |
Family
ID=24696309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA274,127A Expired CA1100468A (en) | 1976-03-29 | 1977-03-16 | Zeolite catalyst and method of manufacture and use thereof |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS52117889A (en) |
| BR (1) | BR7701913A (en) |
| CA (1) | CA1100468A (en) |
| DE (1) | DE2712996C3 (en) |
| ES (1) | ES457247A1 (en) |
| FR (1) | FR2346046A1 (en) |
| GB (1) | GB1573132A (en) |
| IT (1) | IT1075362B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR7807374A (en) * | 1977-11-08 | 1979-07-24 | Standard Oil Co | PROCESS FOR DEPROPORTING A PETROLEUM HYDROCARBON AND CATALYTIC COMPOSITION |
| FR2586674B1 (en) * | 1985-08-28 | 1988-07-15 | Inst Francais Du Petrole | PROCESS FOR DISMUTATION AND TRANSALKYLATION OF AROMATIC HYDROCARBONS IN THE PRESENCE OF A ZEOLITHIC CATALYST |
| GB8911077D0 (en) * | 1989-05-15 | 1989-06-28 | Shell Int Research | Process for isomerising hydrocarbons |
| EP2251082A1 (en) * | 2009-05-14 | 2010-11-17 | BP Chemicals Limited | Carbonylation catalyst and process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644219A (en) * | 1970-02-11 | 1972-02-22 | Universal Oil Prod Co | Preparation of a crystalline aluminosilicate-alumina catalyst composition |
| JPS563148B2 (en) * | 1973-08-13 | 1981-01-23 |
-
1977
- 1977-03-16 CA CA274,127A patent/CA1100468A/en not_active Expired
- 1977-03-23 JP JP3120677A patent/JPS52117889A/en active Granted
- 1977-03-24 DE DE19772712996 patent/DE2712996C3/en not_active Expired
- 1977-03-26 ES ES457247A patent/ES457247A1/en not_active Expired
- 1977-03-28 GB GB1287977A patent/GB1573132A/en not_active Expired
- 1977-03-28 IT IT2175477A patent/IT1075362B/en active
- 1977-03-28 BR BR7701913A patent/BR7701913A/en unknown
- 1977-03-29 FR FR7709340A patent/FR2346046A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2712996B2 (en) | 1978-06-15 |
| GB1573132A (en) | 1980-08-13 |
| FR2346046B1 (en) | 1981-09-04 |
| JPS52117889A (en) | 1977-10-03 |
| IT1075362B (en) | 1985-04-22 |
| DE2712996A1 (en) | 1977-10-06 |
| JPS5731458B2 (en) | 1982-07-05 |
| FR2346046A1 (en) | 1977-10-28 |
| BR7701913A (en) | 1978-08-01 |
| DE2712996C3 (en) | 1979-04-26 |
| ES457247A1 (en) | 1978-02-01 |
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