EP0000669A1 - Zeolith ZSM-11, Verfahren zu seiner Herstellung und Verfahren zur katalytischen Umwandlung unter Verwendung eines ihn enthaltenden Katalysators - Google Patents
Zeolith ZSM-11, Verfahren zu seiner Herstellung und Verfahren zur katalytischen Umwandlung unter Verwendung eines ihn enthaltenden Katalysators Download PDFInfo
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- EP0000669A1 EP0000669A1 EP78300219A EP78300219A EP0000669A1 EP 0000669 A1 EP0000669 A1 EP 0000669A1 EP 78300219 A EP78300219 A EP 78300219A EP 78300219 A EP78300219 A EP 78300219A EP 0000669 A1 EP0000669 A1 EP 0000669A1
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- zeolite
- zsm
- alkali metal
- alkylenediamine
- mixture
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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
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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
- B01J29/40—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- 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
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- 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
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- 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
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- 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
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- 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 mixturs 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-11 are formed.
- Zeolite ZSM-11 is characterised by a crystalline structure whose X-ray diffraction pattern shows the following significant lines:
- the parenthesis around lines 3.07 and 3.00 indicate that they are separate and distinct lines, but are often superimposed. These values are determined by standard techniques.
- the radiation is the K-alpha doublet of copper, and a Geiger counter spectrometer with a strip chart pen recorder is used.
- the peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, are read from the spectrometer chart. From these, the relative intensities, 100 I/I o , where I is the intensity of the strongest line or peak, and d (obs.), the interplanar spacing in Angstrom units, corresponding to the recorded lines, are calculated.
- This X-ray diffraction pattern is characteristic of all species of ZSM-11. 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:
- the invention also comprehends a method of preparing zeolite ZSM-11 which comprises forming a mixture containing sources of an alkali metal, an oxide of 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 + SiO 2 ), as sodium aluminate (NaOH + A1 2 0 3 ), or the like and to subtract from that sum any moles of acid added. Acid may be added simply as HC1, HN03, H 2 SO 4 , acetic acid, and the like or it may be added as an aluminum sulfate (A1 2 0 3 + HN0 3 ), etc.
- A1 2 0 3 is itself equivalent to 2 moles of acid in this calculation, since A1 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 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 o F to about 600°F and thereafter may be calcined in air-or other inert gas at temperatures ranging from about 500°F to 1500°F for periods of time ranging from 1 to 48 hours 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 ole'fins, 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 zeolites prepared in accordance hereto can be used 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 intimately admixed therewith.
- 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.
- 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 montmorillonite 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 u3ed in the raw state or initially subjected to calcination, acid treatment or chemical modification.
- the ZSM-11 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 and about 14000F, a pressure between about atmospheric and about 200 atmospheres, 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 h r -1 .
- WHSV weight hourly space velocity
- the temperature will be between about 500°F and about 900°F
- the pressure will be from about atmospheric to about 50 atmospheres
- the WHSV will be from about 0.5 hr- 1 to about 50 hr- 1 .
- the temperature will be from about 800°F to about 1200°F
- the pressure will be from about atmospheric to about 10 atmospheres
- 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 to about 1000 o F, a pressure of from about atmospheric to about 60 atmospheres, 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, a pressure of from about 1-60 atmospheres, and a WHS of from about 0.2 hr- 1 to about 100 hr- 1 .
- reaction conditions When said conversion is isomerization of paraffins or olefins, reaction conditions will include a temperature of from about 100-700°F, a pressure of from about 1-60 atmospheres, 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 600-1100 0 F, a pressure of from about 1-50 atmospheres, 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, a pressure of from about 1-50 atmospheres, 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, a pressure of from about 1-50 atmospheres, and a WHSV of from about 0.1 hr- 1 to about 1000 hr- 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, a pressure of from about 1-10 atmospheres, 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, a pressure of from about 10-200 atmospheres, 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% Si0 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 /Al 2 O 3 , H 2 0/Si0 2 , Na/Si02, and R/SiO 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 from 4 to 12, and where each mole of A1 2 0 3 is considered to consume two moles of OH- on conversion to framework A10 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 1600C in a stirred system. From these data one observes that crystallization shifted from other zeolites to ZSM-11 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-/Si0 2 ) diamine so that crystallization was directed to ZSM-5. Similarly, in the interval C 7 -C 12 alkylenediamines, ZSM-11 resulted. Crystallizationswith C 7 -C 10 alkylenediamines were a particularly efficient route to ZSM-11.
- a sample of zeolite ZSM-11 prepared as in Example 6 is calcined at 1000°F for 2 hours, contacted with ammonium chloride solution to effect ammonium exchange for residual sodium, dried at 200 o F for 4 hours and then calcined at 1000°F for 2 hours.
- the zeolite's catalytic activity is meaured 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 800°F, 200 psig, 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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/820,992 US4108881A (en) | 1977-08-01 | 1977-08-01 | Synthesis of zeolite ZSM-11 |
US820992 | 1977-08-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000669A1 true EP0000669A1 (de) | 1979-02-07 |
EP0000669B1 EP0000669B1 (de) | 1980-09-03 |
Family
ID=25232222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78300219A Expired EP0000669B1 (de) | 1977-08-01 | 1978-08-01 | Zeolith ZSM-11, Verfahren zu seiner Herstellung und Verfahren zur katalytischen Umwandlung unter Verwendung eines ihn enthaltenden Katalysators |
Country Status (9)
Country | Link |
---|---|
US (1) | US4108881A (de) |
EP (1) | EP0000669B1 (de) |
JP (1) | JPS5452699A (de) |
AU (1) | AU515825B2 (de) |
CA (1) | CA1119146A (de) |
DE (1) | DE2860140D1 (de) |
IT (1) | IT1097569B (de) |
NZ (1) | NZ188025A (de) |
ZA (1) | ZA784360B (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0007081A1 (de) * | 1978-07-13 | 1980-01-23 | BASF Aktiengesellschaft | Verfahren zur Herstellung von stickstoffhaltigen kristallinen Metallsilikaten mit Zeolithstruktur, nach dem Verfahren hergestellte Metallsilikate sowie deren Verwendung als Katalysatoren |
EP0014059A1 (de) * | 1979-01-15 | 1980-08-06 | Mobil Oil Corporation | Form von Zeolith ZSM-11, ihre Herstellung und damit durchgeführte katalytische Umwandlung |
EP0042226A1 (de) * | 1980-06-12 | 1981-12-23 | Imperial Chemical Industries Plc | Zeolith EU-1 |
EP0046504A1 (de) * | 1980-08-21 | 1982-03-03 | BASF Aktiengesellschaft | Kristalliner Metallsilikatzeolith ZBM-30 und Verfahren zu seiner Herstellung |
EP0068796A1 (de) * | 1981-06-30 | 1983-01-05 | Amoco Corporation | Verfahren zur Herstellung von AMS-IB kristallinem Borsilikat Molekularsieb |
US4741891A (en) * | 1980-06-12 | 1988-05-03 | Imperial Chemical Industries Plc | Synthesis of zeolite EU-2 |
US4797267A (en) * | 1987-12-23 | 1989-01-10 | Mobil Oil Corporation | Method of producing rod-shaped ZSM-5 zeolite |
WO1996020891A1 (fr) * | 1994-12-30 | 1996-07-11 | China Petro-Chemical Corporation | Zeolite cocristalline zsm-5/zsm-11 contenant des terres rares |
Families Citing this family (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0015132B1 (de) * | 1979-02-21 | 1984-02-22 | Mobil Oil Corporation | Kristalliner Zeolith, dessen Aufbau und Verwendung |
DE2909929A1 (de) * | 1979-03-14 | 1980-09-25 | Basf Ag | Verfahren zur herstellung eines zeolithen vom strukturtyp zsm-5 |
US4229424A (en) * | 1979-04-09 | 1980-10-21 | Mobil Oil Corporation | Crystalline zeolite product constituting ZSM-5/ZSM-11 intermediates |
US4423021A (en) * | 1979-08-08 | 1983-12-27 | Mobil Oil Corporation | Method of preparing silico-crystal ZSM-48 |
US4259306A (en) * | 1979-10-15 | 1981-03-31 | Mobile Oil Corporation | Synthesis of ZSM-39 |
AU535908B2 (en) * | 1979-12-31 | 1984-04-12 | Mobil Oil Corp. | Reforming hydrocarbons |
DE3006471A1 (de) * | 1980-02-21 | 1981-08-27 | Basf Ag, 6700 Ludwigshafen | Kristalline isotaktische zeolithe, verfahren zur herstellung derselben sowie deren verwendung als katalysatoren |
CA1167071A (en) * | 1980-03-15 | 1984-05-08 | William J. Ball | Process for the production of aromatic hydrocarbons |
US4324940A (en) * | 1980-04-09 | 1982-04-13 | Mobil Oil Corporation | Shape selective acid catalyzed reactions of olefins over crystalline zeolites |
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DE19955557A1 (de) * | 1999-11-18 | 2001-05-23 | Basf Ag | Oxidischer Katalysator mit Zeolithstruktur und Verfahren zu dessen Herstellung |
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CN106673000B (zh) * | 2015-11-09 | 2018-10-23 | 中国石油化工股份有限公司 | 含稀土金属的zsm-11分子筛的合成方法及其合成的分子筛 |
CN106673002B (zh) * | 2015-11-09 | 2018-11-20 | 中国石油化工股份有限公司 | Zsm-11/zsm-5复合分子筛的合成方法及其合成的复合分子筛 |
CN106672999B (zh) * | 2015-11-09 | 2018-10-23 | 中国石油化工股份有限公司 | 含卤素和稀土金属的zsm-11/zsm-5复合分子筛的合成方法及其合成的复合分子筛 |
CN106673001B (zh) * | 2015-11-09 | 2018-11-20 | 中国石油化工股份有限公司 | Zsm-11分子筛的合成方法及其合成的zsm-11分子筛 |
CN106944080B (zh) * | 2016-01-07 | 2018-11-06 | 中国石油化工股份有限公司 | 一种用于乙烷氧化脱氢制乙烯催化剂的制备方法 |
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- 1978-08-01 IT IT26376/78A patent/IT1097569B/it active
- 1978-08-01 NZ NZ188025A patent/NZ188025A/xx unknown
- 1978-08-01 DE DE7878300219T patent/DE2860140D1/de not_active Expired
- 1978-08-01 ZA ZA784360A patent/ZA784360B/xx unknown
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EP0007081A1 (de) * | 1978-07-13 | 1980-01-23 | BASF Aktiengesellschaft | Verfahren zur Herstellung von stickstoffhaltigen kristallinen Metallsilikaten mit Zeolithstruktur, nach dem Verfahren hergestellte Metallsilikate sowie deren Verwendung als Katalysatoren |
EP0014059A1 (de) * | 1979-01-15 | 1980-08-06 | Mobil Oil Corporation | Form von Zeolith ZSM-11, ihre Herstellung und damit durchgeführte katalytische Umwandlung |
US4876412A (en) * | 1980-06-12 | 1989-10-24 | Imperial Chemical Industries Plc | Zeolite EU-2 |
US4537754A (en) * | 1980-06-12 | 1985-08-27 | Imperial Chemical Industries Plc | Zeolite EU-1 and a method of making zeolite EU-1 |
US4741891A (en) * | 1980-06-12 | 1988-05-03 | Imperial Chemical Industries Plc | Synthesis of zeolite EU-2 |
US4836996A (en) * | 1980-06-12 | 1989-06-06 | Imperial Chemical Industries Plc | Method of making zeolite Eu-2 |
EP0042226A1 (de) * | 1980-06-12 | 1981-12-23 | Imperial Chemical Industries Plc | Zeolith EU-1 |
US5098685A (en) * | 1980-06-12 | 1992-03-24 | Imperial Chemical Industries Plc | Zeolite eu-2 |
EP0046504A1 (de) * | 1980-08-21 | 1982-03-03 | BASF Aktiengesellschaft | Kristalliner Metallsilikatzeolith ZBM-30 und Verfahren zu seiner Herstellung |
EP0068796A1 (de) * | 1981-06-30 | 1983-01-05 | Amoco Corporation | Verfahren zur Herstellung von AMS-IB kristallinem Borsilikat Molekularsieb |
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WO1996020891A1 (fr) * | 1994-12-30 | 1996-07-11 | China Petro-Chemical Corporation | Zeolite cocristalline zsm-5/zsm-11 contenant des terres rares |
AU690402B2 (en) * | 1994-12-30 | 1998-04-23 | China Petro-Chemical Corporation | Rare earth-ZSM-5/ZSM-11 cocrystalline zeolite |
CN1041399C (zh) * | 1994-12-30 | 1998-12-30 | 中国石油化工总公司 | 一种含稀土的结晶硅酸铝沸石 |
Also Published As
Publication number | Publication date |
---|---|
JPS6215488B2 (de) | 1987-04-08 |
DE2860140D1 (en) | 1980-12-11 |
JPS5452699A (en) | 1979-04-25 |
US4108881A (en) | 1978-08-22 |
CA1119146A (en) | 1982-03-02 |
IT1097569B (it) | 1985-08-31 |
ZA784360B (en) | 1980-03-26 |
NZ188025A (en) | 1980-11-28 |
EP0000669B1 (de) | 1980-09-03 |
AU3848978A (en) | 1980-02-07 |
AU515825B2 (en) | 1981-04-30 |
IT7826376A0 (it) | 1978-08-01 |
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