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WO1995019945A1 - Zeolite and manufacturing process - Google Patents

Zeolite and manufacturing process Download PDF

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Publication number
WO1995019945A1
WO1995019945A1 PCT/EP1995/000236 EP9500236W WO9519945A1 WO 1995019945 A1 WO1995019945 A1 WO 1995019945A1 EP 9500236 W EP9500236 W EP 9500236W WO 9519945 A1 WO9519945 A1 WO 9519945A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
source
catalyst
alkene
product
Prior art date
Application number
PCT/EP1995/000236
Other languages
French (fr)
Inventor
Luc Roger Marc Martens
Johannes Petrus Verduijn
Original Assignee
Exxon Chemical Patents Inc.
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Publication date
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to AU15757/95A priority Critical patent/AU1575795A/en
Publication of WO1995019945A1 publication Critical patent/WO1995019945A1/en

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Classifications

    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • 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
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • This invention relates to a zeolite, to a process for its manufacture, and to its use in the treatment, manufacture or conversion of organic compounds.
  • a preferred process for the manufacture of a preferred, catalyst, ZSM-22 includes the steps of heating a reaction mixture comprising a source of silica (Si0 2 ) , a source of aluminium oxide (AI2O3), a monovalent cation, especially an alkali metal, source, an organic structure directing agent, seeds of preformed ZSM-22, and water, and heating the reaction mixture for a time sufficient to obtain a crystalline product.
  • a reaction mixture comprising a source of silica (Si0 2 ) , a source of aluminium oxide (AI2O3), a monovalent cation, especially an alkali metal, source, an organic structure directing agent, seeds of preformed ZSM-22, and water, and heating the reaction mixture for a time sufficient to obtain a crystalline product.
  • the organic structure directing agent is normally a base or a salt, typically one containing nitrogen, and provides a "template" for zeolite manufacture. Although its use is not essential to all zeolite manufacture, processes employing such a template have many advantages.
  • the organic additive is, however, present in the reaction mixture in excess of the proportion which it represents in the reaction product and, besides being a relatively expensive reactant per se. results in potential contamination of waste water with the concomitant need for expensive removal procedures.
  • the present invention is based on the observation that an acidic form of the zeolite, obtainable by cation exchange of the crystalline product produced as described above, retains high activity if it is calcined at a temperature of at most 500°C.
  • the present invention accordingly provides a process for the manufacture of an acid form of a TON structure zeolite which comprises heating a synthesis mixture comprising water, a source of silica, a source of aluminium or gallium, and, optionally, of iron, boron, zinc, or copper, a source of monovalent inorganic cations, and an organic structure directing agent, the molar ratio of the structure directing agent to aluminium, gallium and, if present, iron, boron, zinc, or copper, measured as oxide, being at most 15:1, advantageously in the range of from 2 to 10:1, and preferably from 2.5 to 7.5:1, for a time sufficient to obtain a crystalline product, carrying out a cation exchange with ammonium ions or protons, and heating the resulting product at a temperature of at most 500°C.
  • seed crystals of the desired zeolite are included in the reaction mixture.
  • the reaction is advantageously carried out -under conditions such that a ZSM-22 zeolite results.
  • the reaction is also advantageously carried out under conditions such that a zeolite having needle-shaped agglomerates results.
  • Application WO 93/16020 describes processes for the manufacture of ZSM-22 zeolites with needle-shaped agglomerates, while Application WO 93/25475 describes preferred processes for making ZSM-22 needle-shaped zeolites.
  • a source of silica is required; this may be, for example, a colloidal silica suspension, e.g. , one sold under the trade name Ludox, or may be a finely divided solid, e.g., one sold under the trade name Aerosil.
  • An appropriate source of aluminium may be an alumina introduced into the synthesis mixture as, e.g., Al 2 ⁇ 3.3H 2 0 previously dissolved in alkali or an aluminium salt, e.g., Al 2 (S0 4 ) 3 .18H 2 0, dissolved in an alkali solution.
  • an aluminium salt e.g., Al 2 (S0 4 ) 3 .18H 2 0, dissolved in an alkali solution.
  • appropriate sources of iron, boron, zinc and copper are available and may be included in addition to aluminium or gallium sources; mixtures of an aluminium source with one or more sources of additional materials may be used.
  • the synthesis mixture contains a source of " ⁇ monovalent cation, for example, an alkali metal, e.g., sodium, potassium or caesium, or a source of ammonium ions.
  • a source of " ⁇ monovalent cation for example, an alkali metal, e.g., sodium, potassium or caesium, or a source of ammonium ions.
  • This may advantageously be provided in the form of a hydroxide, thereby providing an alkaline solution in which the alumina may be introduced.
  • the organic structure directing agent directs the formation of a given molecular sieve by the so-called templating effect.
  • the role of organic molecules in molecular sieve synthesis is well-known and discussed in, for example, e.g. Lok et aJL, Zeolites 1983, Volume 3, pages 282 to 291 and Moretti et aj,, Chim. Ind. (Milan) 67, No. 1 to 2, 21 to 34 (1985).
  • the effect of an organic structure directing agent is that in the produc ⁇ tion of the crystalline framework the organic compound acts as a template around which the crystalline framework grows, or which causes the crystallization to be directed to form a particular crystalline framework.
  • Preferred agents are monoamino- and diamino-alkanes having up to 12 carbon atoms, particularly 4, 6, 8, 10 or 12 carbon atoms, e.g. 1,6-diaminohexane (which is preferred), diethylamine, 1-aminobutane or 2,2 '-diaminodiethylamine; arylamines containing up to 8 carbon atoms, heterocyclic organic compounds, e.g., as N-ethylpyridinium; poly- alkylenepolyamines, e.g. triethylene tetra ine or tetraethylene pentamine, and alkanolamines, e.g. ethanolamine or diethanolamine.
  • 1,6-diaminohexane which is preferred
  • diethylamine 1-aminobutane or 2,2 '-diaminodiethylamine
  • arylamines containing up to 8 carbon atoms heterocyclic organic compounds,
  • a preferred quantity of template R is a molar ratio of R/Si0 in the synthesis mixture of 0.025 to 0.4.
  • the Si0 2 /Al 2 ⁇ 3 molar ratio in the synthesis mixture is generally not more than 150 and may be as low ' as 40.
  • the Si0 2 /Al 2 ⁇ molar ratio in the synthesis mixture may be from 40 to 120 for the production of needle-shaped agglomerates relatively free from contamination by amorphous or other crystalline structures, and is preferably within the range of from 80 to 100.
  • the Si ⁇ 2 /Al 2 ⁇ 3 molar ratio in the zeolite after crystallization may be up to 30% lower than the molar ration in the synthesis mixture.
  • the Si0 2 /Al 2 0 3 molar ratio in the zeolite is generally not more than 105 and may be as low as 28.
  • the reaction mixture should be rapidly stirred or, advantageously, should contain seeds of preformed ZSM-22. Seeding the reaction mixture compensates for inefficient stirring and may even obviate stirring at all.
  • at least 50 ppm by weight of seeds are used, preferably from 100 to 5000 ppm, more preferably from 500 to 3000 ppm. The smaller the size of crystals, the lower the mass of seeds needed to achieve a desired purity and size of ZSM-22 crystals. The faster the mixture is stirred, similarly, the lower the mass of seeds required.
  • crystallization is effected-»at 120 to 180°C, preferably 150 to 170°C.
  • the crystallization time may be from 10 to 72 hours, typically 15 to 48 hours.
  • the zeolite may be washed with deionized water or with acidified water, and then, optionally after a drying or calcining step, ion exchanged to yield the acidic form.
  • the zeolite is preferably exchanged with ammonium ions (NH 4 + ) and subjected to conditions under which the ammonium ions decompose, with the formation of ammonia and a proton, thus producing the acidic form of the zeolite.
  • the acid form may be obtained by acid exchange with, for example, hydrochloric acid.
  • aluminosilicate crystals that is aluminosilicate crystals having needle morphology with a length to diameter (L/D) ratio of not less than 3
  • the zeolite catalyst so obtained has a greater catalytic activity, at least in alkene oligomerization, giving good conversion with relatively little formation of cracked or saturated products or aromatics, and becomes deactivated in use more slowly, than material that has been calcined at temperatures exceeding 500°C prior to exchange with ammonium ions.
  • the exchange with ammonium ions may be carried out by any suitable method, for example, by treating the crystals with an aqueous solution of ammonium chloride, ammonium nitrate or ammonium hydroxide. Exchange with protons is advantageously carried out by contacting the crystals with a dilute acid solution, e.g., HC1.
  • a dilute acid solution e.g., HC1.
  • the crystals may be calcined at a temperature of from 120° to 500°C, advantageously from 150° to 430°C. Suitable calcination times range from 1 hour to several days, the temperatures in the upper part of the specified temperature range corresponding to the shorter heating times and the temperatures in the lower part of the specified temperature range corresponding to the longer heating times.
  • crystals may be calcined at a temperature of 400°C for from 1 to 20 hours.
  • longer calcination times of at least 2 days and preferably from 3 to 5 days will generally be necessary to achieve adequate voiding of the pores.
  • the calcination conditions should be chosen such that there is still substantial discoloration of the crystals, as compared with the bright white material that is normally obtained after calcination at temperatures exceeding 550°C.
  • the calcination time should be so selected that the crystals have a colour that is distinctly non-white.
  • the crystals may in some cases contain a minor proportion of crystalline material of a second aluminosilicate having a crystal structure that differs from the crystal structure of the aluminosilicate that forms the major proportion of the crystals, the proportion of the second aluminosilicate generally being sufficiently small that the properties of the crystal as a whole, including the external characteristics of the crystal, are determined predominantly by the aluminosilicate that constitutes the major proportion of the crystal.
  • a zeolite catalyst consisting of a major proportion of aluminosilicate material having the crystalline structure of ZSM-22, with co-crystallized aluminosilicate impurities having the crystalline structure of ZSM-5 and crystobalite, may be used.
  • the preferred molar ratios of the different reactants/silicon oxide source in the synthesis mixture in accordance with the present invention are as follows:
  • X + represents an alkali metal or ammonium ion whether free or neutralized.
  • the most preferred X + /Si0 2 ratio is 0.25.
  • the catalyst may be used in the form of powders (including powders consisting wholly or in part of single crystals) .
  • the catalyst may instead be incorporated in shaped agglomerates, for example, tablets, extrudates or spheres, which may be obtained by combining the zeolite with a binder material that is substantially inert under the conditions employed in the oligomerization process.
  • the zeolite catalyst may be present in proportions of' from 1 to 99% by weight, based on the combined weight of the zeolite and binder material.
  • binder material there may be used any suitable material, for example, silica, metal oxides, or clays, such as montmorillonite, bentonite and kaolin clays, the clays optionally being calcined or modified chemically prior to use.
  • suitable matrix materials include silica- alumina, silica-beryllia, silica-magnesia, silica-thoria, silica-titania, silica-alumina-magnesia, silica-alumina- thoria, silica-alumina-zirconia and silica-magnesia- zirconia.
  • the invention is applicable to any TON structure zeolite, for example, ISI-1, Theta-1, Nu-10, KZ-2, and especially ZSM-22.
  • Zeolite catalysts having crystal structures* that are essentially the same as the crystal structures of the above-mentioned zeolite catalysts but differ slightly therefrom in chemical composition may also be used, for example, zeolite catalysts obtained by removal of a number of aluminium ions from, or by steaming of, the above-mentioned zeolite catalysts, or zeolite catalysts obtained by addition of different elements during or after synthesis, for example boron, iron or gallium.
  • crystals of H-ZSM-22 the lengths of at least 75% of which do not exceed 10 ⁇ m and preferably not larger than 1.0 ⁇ m.
  • the zeolites produced according to the invention are useful in the production and conversion of organic compounds, for example cracking, hydrocracking, dewaxing, isomerization (including e.g., olefin bond isomerization and skeletal isomerization e.g., of butene) , oligomerization, polymerization, alkylation, dealkylation, hydrogenation, dehydrogenation, dehydra ⁇ tion, cyclization and aromatization.
  • the present invention therefore provides a process for the production or conversion of an organic compound comprising the use of a zeolite catalyst prepared in accordance with the invention.
  • the zeolite can also be used (either as initially prepared or in a modified form) in a selective adsorption process e.g. a separation or purification.
  • the zeolites produced according to the invention are, however, especially suitable for use in oligomerizing at least one alkene having from 2 to 12 carbon atoms (hereinafter referred to for simplicity as "C 2 to C 12 alkenes”) .
  • the C to C 12 ⁇ allcene especially C 3 to C ⁇ , more especially propene and/or butene feedstocks may be oligomerized to provide C 5 to C 20 alkenes of initial boiling point 30 to 310°C, preferably 30 to 250°C, in particular the following olefins. Distillation Range, °C
  • the feedstock is contacted with the catalyst at a temperature not exceeding 280°C, preferably a temperature in the range of from 180 to 260°C.
  • the feedstock contains water in a proportion of from 0.05 to 0.25 molar %, based on the hydrocarbon content of the catalyst.
  • the water content may be increased by any suitable means.
  • the feedstock may be passed through a thermostatically controlled water saturator. Since the amount of water required to saturate the alkene feedstock will depend upon the temperature of the feedstock, control of the water content may then be effected by appropriate control of the temperature of the feedstock.
  • the water content of the feedstock is preferably at least 0.06 molar %, based on the hydrocarbon content of the feedstock.
  • the alkene-containing feedstock contains as diluent a hydrocarbon other than a c 2 ⁇ c 12 alkene, for example, a saturated hydrocarbon, that other hydrocarbon is to be included in the hydrocarbon content for the purposes of calculation of the water content.
  • Oxygen-containing compounds may also be present in the feedstock without deleterious effect on the catalyst.
  • a process for oligomerizing C 2 to C 12 alkenes comprising contacting a C 2 to C 12 alkene-containing feedstock with a zeolite produced according to the invention.
  • the zeolite crystals used advantageously have a length to diameter ratio of not less than 3 and a length of not greater than 30 ⁇ m, preferably not greater than 10 ⁇ m and, more especially, not greater than 1 ⁇ m.
  • a C 2 to C 1 alkene-containing feedstock is contacted with a zeolite produced according to the invention.
  • the oligomerization process of the invention has the advantage of being sufficiently versatile to be readily varied to produce oligomers, e.g. , dimers, trimers, tetramers or higher oligomers, as desired, simply by varying reaction conditions. For example, if dimers are required, a lower reaction temperature and/or higher space velocity may be selected. If, in contrast, higher oligomers are required, higher reaction temperatures and/or lower space velocity may be selected.
  • catalyst activity is observed at relatively low temperatures, for example, at temperatures of from 150, typically 180, to 260°C.
  • the proportions of alkanes and aro atics formed are low.
  • the catalyst stability in the process is good in that the catalyst becomes deactivated relatively slowly.
  • the zeolite catalysts used in accordance with the invention are readily regenerable. They are thermally and hydrothermally stable and, for example, can be regenerated by heating in air or oxygen at from 300 to 600°C, preferably from 350 to 500°C, e.g., about 400°C, or in steam at, for example, 500°C.
  • Solution B The ingredients were dissolved in the water in the order shown.
  • Solution B The ingredients were dissolved in the water in the order shown.
  • Solution B and the rinse water were added to Solution A, the rinse water having been used to rinse the vessel which contained solution B.
  • the resulting synthesis mixture had a molar composition of:
  • the synthesis mixture was transferred to a stainless steel autoclave equipped with stirrer operated at 220 rpm and was heated to 165°C over a period of 3 hours, and kept at this temperature for 18.5 hours.
  • the product was filtered and washed with water to pH 9.0 and subsequently dried at 120°C.
  • X-Ray diffraction showed that the product was pure crystalline ZSM-22.
  • the crystals were of needle ⁇ like structure, with a length of about 1 ⁇ m.
  • Solution B The ingredients were added to the water in the order shown.
  • Solution B The ingredients were added to the water in the order shown.
  • the silicate was dissolved in the water, and Solution B added to Solution A.
  • the vessel which had contained Solution B was rinsed with the rinse water and the seed crystals were added to the mixture of Solutions A and B.
  • the resulting synthesis mixture had a molar composition of:
  • the mixture was transferred to an autoclave, heated to 150°C over a period of 3 hours, and maintained at that temperature for 24 hours.
  • the resulting product was filtered, washed with water to pH 9.0, and dried at 120°C.
  • the XRD spectrum showed a ZSM-22 uncontaminated by ZSM-5.
  • Example 2 The mixing procedure of Example 1 was repeated but using different proportions of silica and diaminohexane to yield a synthesis mixture containing:
  • Example 1 The procedure of Example 1 was followed, but Ludox AS40 was used instead of HS40, as a result of which there was no sodium, and the proportions of starting materials were varied to give a synthesis mixture of molar composition:
  • Example 4 The zeolite product of Example 1 was cation exchanged by contacting the product with 0.1N HCl solution for 120 minutes at 80°C. The resulting product was washed, and calcined at 400°C in air for 16 hours.
  • Example 5 The zeolite product of Example 1 was cation exchanged by contacting 12.5 g with 2000 ml of 0 ⁇ 5 N NH 4 C1 solution for 16 hours minutes under reflux. The resulting product was washed, and calcined at 400°C for 16 hours.
  • Example 5 The procedure of Example 5 was repeated but calcination was carried out at 550°C for 16 hours.
  • Comparative Example 3 The procedure of Example 5 was repeated on the product of Comparative Example 1.
  • Example 6 The procedure of Example 5 was followed, using the product of Example 2.
  • Example 4 The product of Example 2 was calcined at 550°C for 16 hours, ion-exchanged with NH 4 C1 as described with reference to Example 5, and again calcined at 550°C for 16 hours.
  • Table 2 below shows the variation in % conversion of propene to oligomer, measured by GC analysis, with catalyst life. In all tables below catalyst life is expressed in terms of total weight of feed processed per unit weight of catalyst.
  • Example 8 The comparison procedure of Example 7 was repeated on the products of Example 6 and of Comparison Example 4, the results being shown in Table 3 below.
  • Example 7 Five samples of the product of Example 3 were exchanged with dilute HC1 and dried at 120°C, the exchange being carried out to result in different residual sodium and potassium levels in the products. The activities of the various products were compared by the procedure of Example 7.
  • Example 9 Two samples of catalyst prepared as in Example 9 were formed into an extrudate with bentonite as Jjinder and calcined, one for 1 hour at 550°C and the other for 10 hours at 400°C, and activity retention compared as in Example 7.

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  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

The reduction in effective catalyst life resulting from higher potassium levels associated with lower template usage when scaling-up zeolite manufacture to commercial levels is overcome by lower temperature calcination of the acid zeolite form.

Description

"Zeolite and Manufacturing; Process"
This invention relates to a zeolite, to a process for its manufacture, and to its use in the treatment, manufacture or conversion of organic compounds.
In our PCT Application WO 93/16020, we describe a process for the oligomerization of C2 to C12 alkenes, in which an alkene-containing feedstock is passed over a zeolite catalyst. Improved alkene conversion and catalyst life are shown to result from the use of hydrated feedstocks.
A preferred process for the manufacture of a preferred, catalyst, ZSM-22, suitable for use in such a process, and having other valuable applications, includes the steps of heating a reaction mixture comprising a source of silica (Si02) , a source of aluminium oxide (AI2O3), a monovalent cation, especially an alkali metal, source, an organic structure directing agent, seeds of preformed ZSM-22, and water, and heating the reaction mixture for a time sufficient to obtain a crystalline product.
More details of this process are given in Application WO 93/25475, the disclosures of that specification and of WO 93/16020 being incorporated by reference herein.
The organic structure directing agent is normally a base or a salt, typically one containing nitrogen, and provides a "template" for zeolite manufacture. Although its use is not essential to all zeolite manufacture, processes employing such a template have many advantages. The organic additive is, however, present in the reaction mixture in excess of the proportion which it represents in the reaction product and, besides being a relatively expensive reactant per se. results in potential contamination of waste water with the concomitant need for expensive removal procedures.
If the proportion of organic additive in the reaction mixture is reduced, however, it is necessary, in order to maintain the balance between cationic and anionic species, to increase the proportion of inorganic cations, normally potassium or, optionally, sodrum, caesium or ammonium, employed. That increase, however, has been found to result in a zeolite of reduced activity, at least in catalysing alkene oligomerization.
The present invention is based on the observation that an acidic form of the zeolite, obtainable by cation exchange of the crystalline product produced as described above, retains high activity if it is calcined at a temperature of at most 500°C.
The present invention accordingly provides a process for the manufacture of an acid form of a TON structure zeolite which comprises heating a synthesis mixture comprising water, a source of silica, a source of aluminium or gallium, and, optionally, of iron, boron, zinc, or copper, a source of monovalent inorganic cations, and an organic structure directing agent, the molar ratio of the structure directing agent to aluminium, gallium and, if present, iron, boron, zinc, or copper, measured as oxide, being at most 15:1, advantageously in the range of from 2 to 10:1, and preferably from 2.5 to 7.5:1, for a time sufficient to obtain a crystalline product, carrying out a cation exchange with ammonium ions or protons, and heating the resulting product at a temperature of at most 500°C.
Advantageously, especially if ZSM-22 is to be produced, seed crystals of the desired zeolite are included in the reaction mixture.
The reaction is advantageously carried out -under conditions such that a ZSM-22 zeolite results. The reaction is also advantageously carried out under conditions such that a zeolite having needle-shaped agglomerates results. The above-mentioned Application WO 93/16020 describes processes for the manufacture of ZSM-22 zeolites with needle-shaped agglomerates, while Application WO 93/25475 describes preferred processes for making ZSM-22 needle-shaped zeolites.
Certain process and material characteristics of the present invention are shared with processes known in the art as commonly practised or as described in the literature.
These may be described briefly, as follows:
A source of silica is required; this may be, for example, a colloidal silica suspension, e.g. , one sold under the trade name Ludox, or may be a finely divided solid, e.g., one sold under the trade name Aerosil.
An appropriate source of aluminium may be an alumina introduced into the synthesis mixture as, e.g., Al2θ3.3H20 previously dissolved in alkali or an aluminium salt, e.g., Al2 (S04) 3.18H20, dissolved in an alkali solution. Similarly, appropriate sources of iron, boron, zinc and copper are available and may be included in addition to aluminium or gallium sources; mixtures of an aluminium source with one or more sources of additional materials may be used.
The synthesis mixture contains a source of "^ monovalent cation, for example, an alkali metal, e.g., sodium, potassium or caesium, or a source of ammonium ions. This may advantageously be provided in the form of a hydroxide, thereby providing an alkaline solution in which the alumina may be introduced.
The organic structure directing agent directs the formation of a given molecular sieve by the so-called templating effect. The role of organic molecules in molecular sieve synthesis is well-known and discussed in, for example, e.g. Lok et aJL, Zeolites 1983, Volume 3, pages 282 to 291 and Moretti et aj,, Chim. Ind. (Milan) 67, No. 1 to 2, 21 to 34 (1985). The effect of an organic structure directing agent is that in the produc¬ tion of the crystalline framework the organic compound acts as a template around which the crystalline framework grows, or which causes the crystallization to be directed to form a particular crystalline framework. Preferred agents are monoamino- and diamino-alkanes having up to 12 carbon atoms, particularly 4, 6, 8, 10 or 12 carbon atoms, e.g. 1,6-diaminohexane (which is preferred), diethylamine, 1-aminobutane or 2,2 '-diaminodiethylamine; arylamines containing up to 8 carbon atoms, heterocyclic organic compounds, e.g., as N-ethylpyridinium; poly- alkylenepolyamines, e.g. triethylene tetra ine or tetraethylene pentamine, and alkanolamines, e.g. ethanolamine or diethanolamine.
A preferred quantity of template R, based en the preferred template of 1,6-diaminohexane, is a molar ratio of R/Si0 in the synthesis mixture of 0.025 to 0.4.
The Si02/Al2θ3 molar ratio in the synthesis mixture is generally not more than 150 and may be as low' as 40. The Si02/Al2θ molar ratio in the synthesis mixture may be from 40 to 120 for the production of needle-shaped agglomerates relatively free from contamination by amorphous or other crystalline structures, and is preferably within the range of from 80 to 100. The Siθ2/Al2θ3 molar ratio in the zeolite after crystallization may be up to 30% lower than the molar ration in the synthesis mixture. Thus the Si02/Al203 molar ratio in the zeolite is generally not more than 105 and may be as low as 28.
If ZSM-22 zeolite is being prepared, the reaction mixture should be rapidly stirred or, advantageously, should contain seeds of preformed ZSM-22. Seeding the reaction mixture compensates for inefficient stirring and may even obviate stirring at all. Advantageously at least 50 ppm by weight of seeds, based on the weight of the reaction mixture, are used, preferably from 100 to 5000 ppm, more preferably from 500 to 3000 ppm. The smaller the size of crystals, the lower the mass of seeds needed to achieve a desired purity and size of ZSM-22 crystals. The faster the mixture is stirred, similarly, the lower the mass of seeds required.
Advantageously, crystallization is effected-»at 120 to 180°C, preferably 150 to 170°C. The crystallization time may be from 10 to 72 hours, typically 15 to 48 hours.
After crystallization the zeolite may be washed with deionized water or with acidified water, and then, optionally after a drying or calcining step, ion exchanged to yield the acidic form.
The zeolite is preferably exchanged with ammonium ions (NH4 +) and subjected to conditions under which the ammonium ions decompose, with the formation of ammonia and a proton, thus producing the acidic form of the zeolite. Alternatively the acid form may be obtained by acid exchange with, for example, hydrochloric acid.
Surprisingly, if needle-shaped aluminosilicate crystals (that is aluminosilicate crystals having needle morphology with a length to diameter (L/D) ratio of not less than 3) are exchanged with ammonium ions without first being subjected to the calcination step at a temperature exceeding 500°C customarily employed in the previously known methods, and then heated, or calcined, at a temperature below 500°C, the zeolite catalyst so obtained has a greater catalytic activity, at least in alkene oligomerization, giving good conversion with relatively little formation of cracked or saturated products or aromatics, and becomes deactivated in use more slowly, than material that has been calcined at temperatures exceeding 500°C prior to exchange with ammonium ions.
The exchange with ammonium ions may be carried out by any suitable method, for example, by treating the crystals with an aqueous solution of ammonium chloride, ammonium nitrate or ammonium hydroxide. Exchange with protons is advantageously carried out by contacting the crystals with a dilute acid solution, e.g., HC1.
After exchange with ammonium ions or protons, the crystals may be calcined at a temperature of from 120° to 500°C, advantageously from 150° to 430°C. Suitable calcination times range from 1 hour to several days, the temperatures in the upper part of the specified temperature range corresponding to the shorter heating times and the temperatures in the lower part of the specified temperature range corresponding to the longer heating times.
Thus, for example, crystals may be calcined at a temperature of 400°C for from 1 to 20 hours. At a temperature of 120°C, longer calcination times of at least 2 days and preferably from 3 to 5 days will generally be necessary to achieve adequate voiding of the pores.
The calcination conditions should be chosen such that there is still substantial discoloration of the crystals, as compared with the bright white material that is normally obtained after calcination at temperatures exceeding 550°C. Thus, for a given temperature,-*the calcination time should be so selected that the crystals have a colour that is distinctly non-white.
The crystals may in some cases contain a minor proportion of crystalline material of a second aluminosilicate having a crystal structure that differs from the crystal structure of the aluminosilicate that forms the major proportion of the crystals, the proportion of the second aluminosilicate generally being sufficiently small that the properties of the crystal as a whole, including the external characteristics of the crystal, are determined predominantly by the aluminosilicate that constitutes the major proportion of the crystal. For example, a zeolite catalyst consisting of a major proportion of aluminosilicate material having the crystalline structure of ZSM-22, with co-crystallized aluminosilicate impurities having the crystalline structure of ZSM-5 and crystobalite, may be used. The preferred molar ratios of the different reactants/silicon oxide source in the synthesis mixture in accordance with the present invention are as follows:
Molar Ratio (MR) MR (preferred)
Si02/Al203 40 to 150 80 to 100
H20/Si02 10 to 60 25 to 30
Template/Si0 0.01 to 0.4 0.03 to 0.1 x+/sio2 up to 0.60 0.18 to 0.30
where X+ represents an alkali metal or ammonium ion whether free or neutralized. The most preferred X+/Si02 ratio is 0.25.
The catalyst may be used in the form of powders (including powders consisting wholly or in part of single crystals) . The catalyst may instead be incorporated in shaped agglomerates, for example, tablets, extrudates or spheres, which may be obtained by combining the zeolite with a binder material that is substantially inert under the conditions employed in the oligomerization process. The zeolite catalyst may be present in proportions of' from 1 to 99% by weight, based on the combined weight of the zeolite and binder material. As binder material there may be used any suitable material, for example, silica, metal oxides, or clays, such as montmorillonite, bentonite and kaolin clays, the clays optionally being calcined or modified chemically prior to use. Further examples of suitable matrix materials include silica- alumina, silica-beryllia, silica-magnesia, silica-thoria, silica-titania, silica-alumina-magnesia, silica-alumina- thoria, silica-alumina-zirconia and silica-magnesia- zirconia.
The invention is applicable to any TON structure zeolite, for example, ISI-1, Theta-1, Nu-10, KZ-2, and especially ZSM-22.
Zeolite catalysts having crystal structures* that are essentially the same as the crystal structures of the above-mentioned zeolite catalysts but differ slightly therefrom in chemical composition may also be used, for example, zeolite catalysts obtained by removal of a number of aluminium ions from, or by steaming of, the above-mentioned zeolite catalysts, or zeolite catalysts obtained by addition of different elements during or after synthesis, for example boron, iron or gallium.
Advantageously, there may be used crystals of H-ZSM-22 the lengths of at least 75% of which do not exceed 10 μm and preferably not larger than 1.0 μm.
The zeolites produced according to the invention are useful in the production and conversion of organic compounds, for example cracking, hydrocracking, dewaxing, isomerization (including e.g., olefin bond isomerization and skeletal isomerization e.g., of butene) , oligomerization, polymerization, alkylation, dealkylation, hydrogenation, dehydrogenation, dehydra¬ tion, cyclization and aromatization. The present invention therefore provides a process for the production or conversion of an organic compound comprising the use of a zeolite catalyst prepared in accordance with the invention. The zeolite can also be used (either as initially prepared or in a modified form) in a selective adsorption process e.g. a separation or purification.
The zeolites produced according to the invention are, however, especially suitable for use in oligomerizing at least one alkene having from 2 to 12 carbon atoms (hereinafter referred to for simplicity as "C2 to C12 alkenes") .
More especially, the C to C12~allcene especially C3 to Cς, more especially propene and/or butene feedstocks, may be oligomerized to provide C5 to C20 alkenes of initial boiling point 30 to 310°C, preferably 30 to 250°C, in particular the following olefins. Distillation Range, °C
Products ASTM D1078
Initial Boiling Point Dry Point
Pentenes 30
Hexenes 63
Heptenes 88 97
Octenes 114 126
Nonenes 135 143
Decenes 155 160
Undecenes 167 178
Dodecenes 185 194
Tetramer K 181 200
Tetramer V 186 198
Tetramer D 186 224
Tetramer P 189 225
Trideceneε 204 213
Advantageously, the feedstock is contacted with the catalyst at a temperature not exceeding 280°C, preferably a temperature in the range of from 180 to 260°C.
Advantageously, the feedstock contains water in a proportion of from 0.05 to 0.25 molar %, based on the hydrocarbon content of the catalyst. In the case of an alkene-containing feedstock having an initial water content of less than 0.05 molar %, the water content may be increased by any suitable means. For example, the feedstock may be passed through a thermostatically controlled water saturator. Since the amount of water required to saturate the alkene feedstock will depend upon the temperature of the feedstock, control of the water content may then be effected by appropriate control of the temperature of the feedstock. The water content of the feedstock is preferably at least 0.06 molar %, based on the hydrocarbon content of the feedstock.
If, as may be desired, the alkene-containing feedstock contains as diluent a hydrocarbon other than a c2~c12 alkene, for example, a saturated hydrocarbon, that other hydrocarbon is to be included in the hydrocarbon content for the purposes of calculation of the water content. Oxygen-containing compounds may also be present in the feedstock without deleterious effect on the catalyst.
In a further aspect of the invention there is provided a process for oligomerizing C2 to C12 alkenes comprising contacting a C2 to C12 alkene-containing feedstock with a zeolite produced according to the invention. The zeolite crystals used advantageously have a length to diameter ratio of not less than 3 and a length of not greater than 30 μm, preferably not greater than 10 μm and, more especially, not greater than 1 μm.
In an especially preferred process according to the invention, a C2 to C1 alkene-containing feedstock, more especially a feedstock containing a C3 to C6 alkene, having a water content of from 0.05 to 0.25 molar %, is contacted with a zeolite produced according to the invention.
The oligomerization process of the invention has the advantage of being sufficiently versatile to be readily varied to produce oligomers, e.g. , dimers, trimers, tetramers or higher oligomers, as desired, simply by varying reaction conditions. For example, if dimers are required, a lower reaction temperature and/or higher space velocity may be selected. If, in contrast, higher oligomers are required, higher reaction temperatures and/or lower space velocity may be selected.
Good catalyst activity is observed at relatively low temperatures, for example, at temperatures of from 150, typically 180, to 260°C. The proportions of alkanes and aro atics formed are low. The catalyst stability in the process is good in that the catalyst becomes deactivated relatively slowly.
The zeolite catalysts used in accordance with the invention are readily regenerable. They are thermally and hydrothermally stable and, for example, can be regenerated by heating in air or oxygen at from 300 to 600°C, preferably from 350 to 500°C, e.g., about 400°C, or in steam at, for example, 500°C.
The following Examples illustrate the invention: Preparation of Catalyst Precursor Example 1 Preparation of synthesis mixture: Solution A:
COMPONENT PARTS BY WEIGHT
H20 74.52
Al2(S04)3n H20 (52% A12(S04)3) 3.45
KOH 13.25
1, 6-diaminohexane 5.09
The ingredients were dissolved in the water in the order shown. Solution B:
COMPONENT PARTS BY WEIGHT
H20 74.52
Ludox HS-40 (Silicate) 71.88
Seed Crystals 0.22
Rinse Water 37.26
Solution B and the rinse water were added to Solution A, the rinse water having been used to rinse the vessel which contained solution B. The resulting synthesis mixture had a molar composition of:
8.10 K2O/0.90 Na2O/1.00 Al2O3/90 SiO2/2500 H2O/7.0 Rf K+ 6.0 where R is 1,6-diaminohexane. The Na20 is derived from Ludox HS-40, which contains sodium. The total proportion of K20 content, including free and neutralized base, was 11.10, expressed as K20. The weight of seed crystals, based on the weight of synthesis mixture, was 0.079%.
The synthesis mixture was transferred to a stainless steel autoclave equipped with stirrer operated at 220 rpm and was heated to 165°C over a period of 3 hours, and kept at this temperature for 18.5 hours.
The product was filtered and washed with water to pH 9.0 and subsequently dried at 120°C.
X-Ray diffraction (XRD) showed that the product was pure crystalline ZSM-22. The crystals were of needle¬ like structure, with a length of about 1 μm.
The potassium and sodium contents of the prβducts prepared as described in Examples 1, 2, and 4 to 6, and in Comparative Examples 1 to 4, are given in Table 1 below. Example 2 Preparation of synthesis mixture: Solution A:
COMPONENT PARTS BY WEIGHT
H20 1000
1, 6-diaminohexane 29.11
KOH (50%) 132.50
Al2(S04)3nH20) 35.02 (52% A12(S04)3)
The ingredients were added to the water in the order shown. Solution B:
COMPONENT PARTS BY WEIGHT
H20 800
Ludox HS-40 (Silicate) 719.64
(Rinse Water) 80.00
(Seed Crystals) 2.80
The silicate was dissolved in the water, and Solution B added to Solution A. The vessel which had contained Solution B was rinsed with the rinse water and the seed crystals were added to the mixture of Solutions A and B.
The resulting synthesis mixture had a molar composition of:
8.10 K2O/0.90 Na20/1.00 Al2O3/90.00 SiO2/2500 H2O/4.0 R/6.0 K+ R being as in Example 1. (Seed proportion: 0.1% by weight.)
The mixture was transferred to an autoclave, heated to 150°C over a period of 3 hours, and maintained at that temperature for 24 hours. The resulting product was filtered, washed with water to pH 9.0, and dried at 120°C. The XRD spectrum showed a ZSM-22 uncontaminated by ZSM-5.
Example 3
The mixing procedure of Example 1 was repeated but using different proportions of silica and diaminohexane to yield a synthesis mixture containing:
8.10 K2O/0.90 Na2O/1.00 Al203/87 SiO2/2500 H2O/3 00 R/6.0 K+- ' R again being as in Example 1. (Seed proportion: 0.1% by weight. )
The heat-up time was 4 hours, and the crystalliza¬ tion time and temperature were 20 hours at 160°C. Filtration and washing were as in Example l; XRD analysis showed a pure ZSM-22 product, with no crystobalite or ZSM-5 contamination. Comparative Example 1 The procedure of Example 1 was followed, but Ludox AS40 was used instead of HS40, as a result of which there was no sodium, and the proportions of starting materials were varied to give a synthesis mixture of molar composition:
8.67 K20/1.00 Al2O3/92.60 Siθ2/3704 H20/27.8 R/K+ 6.0 R again was as in Example 1. (Seed proportion: 0.075% by weight. )
Ion Exchange and Heat Treatment Example 4 The zeolite product of Example 1 was cation exchanged by contacting the product with 0.1N HCl solution for 120 minutes at 80°C. The resulting product was washed, and calcined at 400°C in air for 16 hours.
Example 5 The zeolite product of Example 1 was cation exchanged by contacting 12.5 g with 2000 ml of 0^5 N NH4C1 solution for 16 hours minutes under reflux. The resulting product was washed, and calcined at 400°C for 16 hours.
Comparative Example 2 The procedure of Example 5 was repeated but calcination was carried out at 550°C for 16 hours.
Comparative Example 3 The procedure of Example 5 was repeated on the product of Comparative Example 1. Example 6 The procedure of Example 5 was followed, using the product of Example 2.
Comparative Example 4 The product of Example 2 was calcined at 550°C for 16 hours, ion-exchanged with NH4C1 as described with reference to Example 5, and again calcined at 550°C for 16 hours.
Table 1
Product K (wt %) Na (wt %)
Example 1 0.46 0.013
Example 4 0.24 0.011
Example 5 0.12 0.020
Comparative Example 2 0.16 0.056
Comparative Example 1 0.30 <0.01
Comparative Example 3 0.04 0.0«9
Example 2 0.61 0.036
Example 6 0.23 0.011
Comparative Example 4 0.12 0.006
From the Examples and the results in Table 1, it can be seen that while the as-synthesized product of Comparative Example 1 had a lower potassium content than that of Example 1 this is because the synthesis mixture had a high organic content. Example 7
The catalytic activities of various samples prepared above in olefin oligomerization were evaluated in a fixed bed continuous flow pilot unit using a propene feed diluted with an equal volume of propane, at an hourly space velocity of 2g/g/hr, at a reaction temperature of 205°C, and a pressure of 7 MPa, after catalyst activation at 400°C.
The fall off in activities of the products of Example 5 and Comparative Example 2 with time was compared:
Table 2 below shows the variation in % conversion of propene to oligomer, measured by GC analysis, with catalyst life. In all tables below catalyst life is expressed in terms of total weight of feed processed per unit weight of catalyst.
Table 2
Example 5 Comp. Ex. 2
% conv. % conv.
Catalyst Life, 100 100 92
II II 250 98 26
The greater activity and activity retention of the material calcined at 400°C are apparent. Example 8 The comparison procedure of Example 7 was repeated on the products of Example 6 and of Comparison Example 4, the results being shown in Table 3 below.
Table 3
Example 5 Comp. Ex. 4
% conv. % conv.
Catalyst Life, 50 100 75
II 100 100 36
II It 250 67 16
Again, the extended active life of a catalyst produced according to the invention compared with that produced by a prior art procedure is apparent, despite the lower K and Na values of the prior art material - see Table 1.
Examples 9 to 13
Five samples of the product of Example 3 were exchanged with dilute HC1 and dried at 120°C, the exchange being carried out to result in different residual sodium and potassium levels in the products. The activities of the various products were compared by the procedure of Example 7.
The results are shown in Table 4, below, the table showing the % conversion of propene after the catalyst life as shown.
Si/Al Activity
K Na Catalyst Life
Example Atomic Ratio wt% wt% 200 400
9 - 31.5 0.16 0.011 100 99.4
10 30 0.21 0.013 99.8 99.0
11 31 0.23 0.015 99.6 97.6
12 29.5 0.31 0.024 99.4 95.6
13 31 0.39 0.024 99.3 96.5
The results show that all samples having been calcined at 400°C, the potassium content has no substantial effect on the catalytic activity.
Example 14
Two samples of catalyst prepared as in Example 9 were formed into an extrudate with bentonite as Jjinder and calcined, one for 1 hour at 550°C and the other for 10 hours at 400°C, and activity retention compared as in Example 7. The activity of that calcined at 550°C fell to 90, measured as % propene converted, after a catalyst life of 200, while at that life the sample calcined at 400°C retained an activity of 96.6%. Because of the potassium level in the bentonite binder no direct comparison of potassium levels in the catalysts was possible. However, in comparison tests employing A1 03 as binder, extruded catalysts calcined at 550°C and having differing potassium levels showed a clear negative correlation between potassium content and activity retention.

Claims

1. A process for the manufacture of an acid form of a TON structure zeolite which comprises heating a synthesis mixture comprising water, a source of silica, a source of aluminium or gallium, and optionally a source of iron, zinc, boron or copper, a source of monovalent inorganic cations, and an organic structure directing agent, the molar ratio of the structure directing agent to aluminium, gallium and, if present, iron, zinc, boron or copper, measured as oxide, being at most 15:1, to obtain a crystalline product, carrying out a cation exchange with ammonium ions or protons, and heating the resulting product at a temperature of at most 500°C.
2. A process as claimed in claim 1, wherein the said molar ratio is within the range of from 2:1 to 10:1.
3. A process as claimed in any one of claim 1 or claim 2, wherein the zeolite produced is H-ZSM-22.
4. A process as claimed in any one of claims 1 to 3, wherein the zeolite is produced in the form of needle- shaped agglomerates.
5. A process as claimed in any one of claims 1 to 4 which is carried out in the presence of seed crystals of the desired zeolite.
6. A process as claimed in any one of claims 1 to 5 wherein crystallization is effected at a temperature within the range of from 120°C to 180°C, preferably from 150°C to 170°C.
7. A process as claimed in any one of claims 1 to
6, wherein the structure directing agent is a mono- or di-aminoalkane.
8. A process as claimed in any one of claims 1 to
7, wherein the cation exchange is carried out on the crystalline product without any intervening calcination.
9. A process as claimed in any one of claims 1 to 8, wherein the cation exchange is carried out with ammonium ions, and wherein the crystalline product is treated with an aqueous solution of an ammonium salt, preferably ammonium chloride, or with an acid, preferably hydrochloric acid.
10. A process as claimed in any one of claims 1 to
9, wherein the monovalent cation is or comprises potassium.
11. A process as claimed in any one of claims 1 to
10, wherein the cation-exchanged and subsequently heated product is mixed with a binder and formed into a shaped structure.
12. A process as claimed in any one of claims 1 to
11, wherein the zeolite crystals produced have a length: diameter ratio of not less than 3:1.
13. A process for the production, selection, purification, or conversion of an organic compound using as catalyst a zeolite prepared by a process as claimed in any one of claims 1 to 12.
14. A process for the oligomerization of at least one alkene having from 2 to 12 carbon atoms which comprises contacting a C2 to C12 alkene-containing feedstock with a zeolite prepared by a process as claimed in any one of claims 1 to 12.
15. The use of a catalyst prepared as defined in any one of claims 1 to 13 in the oligomerization of an alkene.
PCT/EP1995/000236 1994-01-24 1995-01-23 Zeolite and manufacturing process WO1995019945A1 (en)

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WO2011002631A2 (en) 2009-07-03 2011-01-06 Bp Oil International Limited Alkene oligomerization process
WO2011002630A2 (en) 2009-07-03 2011-01-06 Bp Oil International Limited Modified zeolite catalyst
EP2386354A1 (en) 2010-05-14 2011-11-16 Bp Oil International Limited Alkene oligomerization process
WO2014013102A1 (en) 2012-07-19 2014-01-23 Consejo Superior De Investigaciones Científicas (Csic) Method for oligomerising alkenes using the itq-39 zeolite

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EP0345106A1 (en) * 1988-05-19 1989-12-06 Institut Français du Pétrole Zeolites having the structural type of ton, their preparation and their use
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WO1993016020A2 (en) * 1992-01-30 1993-08-19 Exxon Chemical Patents Inc. Alkene oligomerization
WO1993025475A1 (en) * 1992-06-05 1993-12-23 Exxon Chemical Patents Inc. Zsm-22 zeolite

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US4902406A (en) * 1982-04-30 1990-02-20 Mobil Oil Corporation Synthesis of zeolite ZSM-22
EP0345106A1 (en) * 1988-05-19 1989-12-06 Institut Français du Pétrole Zeolites having the structural type of ton, their preparation and their use
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WO2011002631A2 (en) 2009-07-03 2011-01-06 Bp Oil International Limited Alkene oligomerization process
WO2011002630A2 (en) 2009-07-03 2011-01-06 Bp Oil International Limited Modified zeolite catalyst
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WO2014013102A1 (en) 2012-07-19 2014-01-23 Consejo Superior De Investigaciones Científicas (Csic) Method for oligomerising alkenes using the itq-39 zeolite
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