EP0000669B1 - Zeolite zsm-11, a method for preparing it, and a process of catalytic conversion using a catalyst comprising it - Google Patents

Zeolite zsm-11, a method for preparing it, and a process of catalytic conversion using a catalyst comprising it Download PDF

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EP0000669B1
EP0000669B1 EP78300219A EP78300219A EP0000669B1 EP 0000669 B1 EP0000669 B1 EP 0000669B1 EP 78300219 A EP78300219 A EP 78300219A EP 78300219 A EP78300219 A EP 78300219A EP 0000669 B1 EP0000669 B1 EP 0000669B1
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zeolite
zsm
alkali metal
mixture
alkylenediamine
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French (fr)
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EP0000669A1 (en
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Louis Dean Rollmann
Ernest William Valyocsik
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Mobil Oil AS
ExxonMobil Oil Corp
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Mobil Oil AS
Mobil Oil Corp
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    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/365—Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate
    • 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
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—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
    • C07C6/123—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/29—MEL, e.g. ZSM-11

Definitions

  • the present invention relates to a new form of ZSM-11 to a process for preparing it and to a method for using it in organic compound conversion reactions.
  • Zeolite ZSM-11 is a relatively new zeolite which when conventionally synthesized frequently has the composition, expressed in terms of mole ratios of oxides in the anhydrous state: wherein M is a mixture of at least one of the quaternary cations of Group VA of the Periodic Table, such as tetrabutylammonium or tetrabutylphosphonium, and alkali metal cations, especially sodium, n is the valence of M and x is from 10 to 150. It has a distinctive X-ray diffraction pattern which establishes its individuality. The original alkali metal cations of ZSM-11 have been exchanged with other cations to form species of the zeolite which have catalytic properties. Zeolite ZSM-11 and its conventional preparation are the subject of U.S. Specification 3,709,979.
  • the known method of synthesising ZSM-11 has been to form a mixture of alumina, silica, alkali metal oxide, water and a quaternary compound of a Group VA element such that the mixture has a composition, in terms of mole ratios of oxides, falling within the following range: wherein M is an alkali metal ion and R' is a quaternary cation of a Group VA element.
  • the reaction mixture is maintained at a temperature of from about 100°C to about 200°C until crystals of ZSM-1 1 are formed.
  • Zeolite ZSM-11 1 is characterised by a crystalline structure whose X-ray diffraction pattern shows the following significant lines:
  • This X-ray diffraction pattern is characteristic of all species of ZSM-1 1. Ion exchanged forms of the zeolite reveal substantially the same pattern possibly with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample and its thermal history.
  • zeolite ZSM-11 possesses, as synthesised, the formula, in terms of mole ratios of oxides: wherein M is an alkali metal ion, R is an alkylenediamine having from 7 to 12 carbon atoms or an organic cation derived therefrom, and x is at least 10, for instance up to 1000, often falling within the range 10 to 150 or 20 to 200.
  • the alkali metal is usually sodium and a preferred alkylene-diamine is a polymethylendiamine of the formula H 2 N ⁇ (CH 2 ) m NH 2 where m is from 7 to 12, preferably from 7 to 10.
  • the zeolite may also exist in the exchanged form, suitable ions replacing those of the as- synthesised form being hydrogen, hydrogen precursors, rare earth, aluminum and/or other metals of groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and/or VIII.
  • the invention also comprehends a method of preparing zeolite ZSM-11 which comprises forming a mixture containing sources of an alkali metal, an oxide or aluminum, an oxide of silicon, water, and an alkylenediamine having from 7 to 12 carbon atoms, the mixture having the composition, in terms of mole ratios of oxides, within the following ranges: wherein R is the alkylenediamine and M is alkali metal ion; and maintaining the mixture at at least 50°C until crystals of the zeolite form.
  • the mixture is maintained between 50 and 250°C, still more preferably between 80 and 200°C for a period of 3 hours to 180, advantageously 30, days.
  • a still further aspect of the invention is the conversion of an organic compound feedstock employing a catalyst comprising zeolite ZSM-11 constituted or synthesised as hereinabove described.
  • the method of preparation of ZSM-11 according to this invention also provides the benefit of being lower in cost than the conventional since the organic materials used herein are substantially lower in cost than the conventional.
  • the zeolite product therefore, is also of lower cost than conventionally prepared ZSM-11.
  • hydroxide In calculating the mole ratio of hydroxide ions/silica, it is conventional to calculate hydroxide by summing moles of OH-, whether added as NaOH, as quaternary Group VA element hydroxide (in the case of a conventional preparation), as sodium silicate (NaOH+Si0 2 ), as sodium aluminate (NaOH+AI 2 0 3 ), or the like and to subtract from that sum any motes of acid added. Acid may be added simply as HC1, HN0 3 , H 2 SO 4 , acetic acid, and the like or it may be added as an aluminum sulfate (AI 2 O 3 +H 2 SO 4 ).
  • Each mole of AI 2 0 3 is itself equivalent to 2 moles of acid in this calculation, since AI 2 0 3 consumes 2 moles of hydroxide in its conversion to framework aluminate ion.
  • no contribution is assigned to organic bases such as amines in this calculation.
  • Amines present in reaction mixtures having an OH - /SiO 2 ratio of 0.01 are protonated when further acid is added. Until said additional acid exceeds the amine present, the pH remains above 7.
  • the digestion of the gel particles is carried out until crystals form.
  • the solid product is separated from the reaction medium, as by cooling the whole to room temperature, filtering and water washing.
  • the reaction mixture for the synthesis of ZSM-11 can be prepared utilizing materials which can supply the appropriate oxide. Such materials include aluminates, alumina, silicates, silica hydrosol, silica gel, silicic acid and hydroxides. It will be understood that each oxide component utilized in the reaction mixture for preparing ZSM-11 can be supplied by one or more essential reactants and they can be mixed together in any order. For example, any oxide can be supplied by an aqueous solution, sodium hydroxide or by an aqueous solution of a suitable silicate; the alkylenediamine cation can be supplied by a compound of that cation, such as, for example, a salt as well as by the indicated diamine.
  • the reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the ZSM-11 composition will vary with the nature of the reaction mixture employed.
  • the presently prepared ZSM-11 has an extremely low amount of alkali metal, e.g. sodium, ions, as synthesized, and therefore can be utilized as catalytic material for a number of hydrocarbon conversion reactions substantially as synthesized
  • the original cations of the as synthesized ZSM-11 can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations.
  • Preferred replacing cations include metal ions, ammonium ; ions, hydrogen ions and mixtures thereof.
  • Particularly preferred cations are those which render the zeolite catalytically active especially for hydrocarbon conversion.
  • a typical ion exchange technique is to contact the ZSM-11 1 zeolite with a salt of the desired replacing cation or cations.
  • a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates.
  • Representative ion exchange techniques are disclosed in a wide variety of patents including United States Patents 3,140,249; 3,140,251; and 3,140,253.
  • the zeolite is then preferably washed with water and dried at a temperature ranging from 150°F (65°C) to about 600°F (315°C) and thereafter may be calcined in air or other inert gas at temperatures ranging frpm about 500°F (260°C) to 1500°F (815°C) for periods of time ranging from 1 to 48 hrs or more to produce a catalytically-active thermal decomposition product thereof.
  • the hereby prepared zeolite ZSM-11 may be used in a wide variety of organic compound, e.g. hydrocarbon compounds and oxygenates such as methanol, conversion processes.
  • organic compound e.g. hydrocarbon compounds and oxygenates such as methanol
  • conversion processes include, for example, alkylation of aromatics with olefins, aromatization of normally gaseous olefins and paraffins, aromatization of normally liquid low molecular weight paraffins and olefins, isomerization of aromatics, paraffins and olefins, disproportionation of aromatics, transalkylation of aromatics, oligomerization of olefins and cracking and hydrocracking. All of the foregoing catalytic processes are of value since they result in upgrading of the organic charge being processed.
  • Synthetic ZSM-11 1 zeolites prepared in accordance hereto can be ued either in the organic cation or alkali metal form and hydrogen form or another univalent or multivalent cationic form. They can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such components can be exchanged into the composition, impregnated therein or physically imtimately admixed therewith.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium
  • Such components can be impregnated in or on to ZSM-11 such as, for example, by, in the case of platinum, treating the zeolite with a platinum metal-containing ion.
  • suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. Combinations of metals and methods for their introduction can also be used.
  • the aluminosilicate prepared by the instant invention is formed in a wide variety of particle sizes.
  • the particles can be in the form of a powder, a granule, or a molded product, such as extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen.
  • the aluminosilicate can be extruded before drying or dried or partially and then extruded.
  • the ZSM-11 hereby prepared with another material resistant to the temperatures and other conditions employed in organic conversion processes.
  • matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides.
  • Use of a material in conjunction with the ZSM-11 1 i.e. combined therewith, which is active, tends to improve the conversion and/or selectively of the catalyst in certain organic conversion processes.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • zeolite materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin. These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in a petroleum refinery the catalyst is often subjected to rough handling, which tends to break the catalyst down into powder-like materials which cause problems in processing.
  • Naturally occurring clays which can be composited with the hereby synthesized ZSM-11 catalyst include the montmorrillonite and kaolin family, which families include the sub-bentonites, and the kaolins commonly known as Dixie, McNammee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state or initially subjected to calcination, acid treatment or chemical modification.
  • the ZSM-11 1 catalyst hereby synthesized can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica- beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina- zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the matrix can be in the form of a cogel.
  • the relative proportions of finely divided crystalline aluminosilicate ZSM-11 and inorganic oxide gel matrix vary widely with the crystalline aluminosilicate content ranging from about 1 to about 90 percent by weight and more usually in the range of about 2 to about 50 percent by weight of the composite.
  • the organic compound or feedstock containing same may be contacted with a catalyst containing the hereby prepared zeolite ZSM-11, commonly with a silica/alumina mole ratio in the range of from about 20 to about 200, at a temperature between about 100°F (38°C) and about 1400°F (760°C), a pressure between about atmospheric (101 kPa) and about 200 atmospheres (20265 kPa), a hydrogen/organic compound mole ratio of between 0 and about 80, and a weight hourly space velocity (WHSV) of from about 0.1 hr- 1 to about 1000 hr-1.
  • a catalyst containing the hereby prepared zeolite ZSM-11 commonly with a silica/alumina mole ratio in the range of from about 20 to about 200, at a temperature between about 100°F (38°C) and about 1400°F (760°C), a pressure between about atmospheric (101 kPa) and about 200 atmospheres (20265 kPa), a hydrogen/organic compound
  • the temperature will be between about 500° (260°C) and about 900°F (482°C)
  • the pressure will be from about atmospheric (101 kPa) to about 50 atmospheres (5066 kPa) and the WHSV will be from about 0.5 hr-1 to about 50 hr- 1.
  • the temperature will be from about 800°F (427°C) to about 1200°F (649°C)
  • the pressure will be from about atmospheric (101 kPa) to about 10 atmospheres (1013 kPa) and the WHSV will be from about 0.1 hr -1 to about 10 hr -1 .
  • reaction conditions will include a temperature of from about 400°F (204°C) to about 1000°F (538°C), a pressure of from about atmospheric to about 60 atmospheres (6078 kPa), a WHSV of from about 0.5 hr -1 to about 50 hr -1 and an aromatic compound/alkylating agent mole ratio of from about 2 to about 200.
  • reaction conditions When said conversion is isomerization of aromatics such as xylenes, reaction conditions will include a temperature of from about 300-900°F (149-482°C), a pressure of from about 1-60 atmospheres (101-6078 kPa), and a WHSV of from about 0.2 hr -1 to about 100hr -1 .
  • reaction conditions When said conversion is isomerization of paraffins or olefins, reaction conditions will include a temperature of from about 100-700°F (38-371 °C), a pressure of from about 1 ⁇ 60 atmospheres (101 ⁇ 6078 kPa), and a WHSV of from about 0.1 hr -1 to about 2 hr -1 .
  • reaction conditions When said conversion is disproportionation of aromatics, such as toluene.
  • reaction conditions will include a temperature of from about 600-1 100°F (315-593°C), a pressure of from about 1-50 atmospheres (101 ⁇ 5066 kPa), and a WHSV of from about 0.5 hr -1 to about 20 hr -1 .
  • reaction conditions When said conversion is transalkylation of aromatics, such as benezene, with alkylaromatics, such as trimethylbenzenes, reaction conditions will include a temperature of from about 500-1100°F (260-593°C), a pressure of from about 1-50 atmospheres (101-5066 kPa), and a WHSV of from about 0.5 hr -1 to about 20 hr- 1 .
  • reaction conditions When said conversion is oligomerization of olefins, such as propylene, reaction conditions will include a temperature of from about 500 ⁇ 1100°F (260 ⁇ 593°C), a pressure of from about 1-50 atmospheres (101-5066 kPa), and a WHSV of from about 0.1 hr -1 to about 1000 h -1 .
  • reaction conditions When said conversion is cracking of a gas oil or a residual oil, reaction conditions will include a temperature of from about 600-1400°F (315-760°C), a pressure of from about 1-10 atmospheres (101 ⁇ 1013 kPa), and a WHSV of from about 0.5 hr -1 to about 50 hr -1 .
  • reaction conditions will include a temperature of from about 400-850°F (204-454°C), a pressure of from about 10 ⁇ 200 atmospheres (1013 ⁇ 2065 kPa), a WHSV of from about 0.1 hr -1 to about 10 hr -1 and a H 2 /hydrocarbon mole ratio of from 2 ⁇ 80.
  • Crystallizations were carried out at 160°C in both static and stirred systems and employed Q-brand sodium silicate (27.8% SiO 2 , 8.42% Na 2 0) as a source of silica and Al 2 (SO 4 ) 3 16H 2 0 as a source of alumina.
  • Reaction mixture compositions are described by the mole ratios SiO 2 /AI 2 O 3 , H 2 O/SiO 2 , Na/SiO 2 , and R/Si0 2 , where R is moles of alkylenediamine, in each instance being of the formula H 2 N ⁇ (CH 2 ) m ⁇ NH 2 where m is 4 to 12, and where each mole of AI 2 O 3 is considered to consume two moles of OH- on conversion to framework AIO 2 - .
  • Moles of OH- are defined as moles of OH- added less any moles of mineral acid (H + ) added to the mixture. The pH of all reaction mixtures was above 7.
  • Table II records the results of crystallization experiments conducted at 160°C in a stirred system. From these data one observes that crystallization shifted from other zeolites to ZSM-11 1 as the diamine chain length increased from six carbon atoms to seven carbon atoms. Transition points were reached at C 5 and C 7 . At C 5 alkylenediamine the product ZSM-35 cage appeared unable to accommodate the protonated (note low OH-/SiO 2 ) diamine so that crystallization was directed to ZSM-5. Similarly, in the interval C 7 ⁇ C 12 alkylenediamines, ZSM-11 resulted. Crystallizations with C 7 ⁇ C 10 alkylenediamines were a particularly efficient route to ZSM-11.
  • Examples 1 to 4 and 10 to 15 are comparative Examples.
  • the other Examples produce zeolite in accordance with the formula set forth in claim 1.
  • a sample of zeolite ZSM-11 prepared as in Example 6 is calcined at 1000°F (538°C) for 2 hours, contacted with ammonium chloride solution to effect ammonium exchange for residual sodium, dried at 200°F (93°C) for 4 hours and then calcined at 1000°F (538°C) for 2 hours.
  • the zeolite's catalytic activity is measured by contact with a five-component feedstock comprising equal parts by weight of n-hexane, 3-methylpentane, 2,3-dimethylbutane, benzene and toluene at conditions of 800OF (427°C), 200 psig (1481 kPa), a hydrogen/hydrocarbon mole ratio of 3 and a WHSV of 3 hr- 1 .
  • This test demonstrates simultaneously paraffin cracking, aromatization and aromatics alkylation and interconversion activity of the zeolite.
  • the ratio of rate constants for n-hexane and 3-methylpentane conversion generated by this test is 2.3. Further demonstrated here is that 10% of the cracked paraffin fragments react with available aromatics in the feedstock to produce alkylaromatics with benzene, rather than toluene, being preferentially alkylated.

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EP78300219A 1977-08-01 1978-08-01 Zeolite zsm-11, a method for preparing it, and a process of catalytic conversion using a catalyst comprising it Expired EP0000669B1 (en)

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US05/820,992 US4108881A (en) 1977-08-01 1977-08-01 Synthesis of zeolite ZSM-11
US820992 1977-08-01

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EP0000669B1 true EP0000669B1 (en) 1980-09-03

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US (1) US4108881A (enrdf_load_stackoverflow)
EP (1) EP0000669B1 (enrdf_load_stackoverflow)
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NZ188025A (en) 1980-11-28
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US4108881A (en) 1978-08-22
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