EP0939673A1 - Dealuminised nu-86 zeolite and its use in the conversion of hydrocarbons - Google Patents
Dealuminised nu-86 zeolite and its use in the conversion of hydrocarbonsInfo
- Publication number
- EP0939673A1 EP0939673A1 EP97945902A EP97945902A EP0939673A1 EP 0939673 A1 EP0939673 A1 EP 0939673A1 EP 97945902 A EP97945902 A EP 97945902A EP 97945902 A EP97945902 A EP 97945902A EP 0939673 A1 EP0939673 A1 EP 0939673A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zeolite
- catalyst
- acid
- preparation
- group formed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- C01B39/026—After-treatment
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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
- C07C2/02—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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- 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
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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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
- 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
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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
- 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
- the invention relates to a NU-86 zeolite, comprising silicon, and at least one element T chosen from the group formed by aluminum, iron, gallium, and boron, preferably aluminum, characterized in that of the element T has been extracted from the framework and in that it has an overall atomic Si / T greater than approximately 20.
- the extraction of element T from the zeolitic framework (or network) is carried out, by at least a heat treatment, possibly carried out in the presence of water vapor, followed by at least one acid attack, with at least one solution of a mineral or organic acid, or else by a direct acid attack.
- the invention also relates to a catalyst comprising said zeolite at least partially in acid form and the use of said catalyst in the conversion of hydrocarbons, in particular in oligomerization of C2 to C 8 olefins (that is to say comprising of 2 to 8 carbon atoms per molecule).
- the synthesis of the NU-86 zeolite has been described by HERE in patent application EP-A2-463,768.
- the NU-86 zeolite is generally synthesized in the presence of sodium cations and an organic structuring agent which is either octamethonium dibromide or either nonamethonium dibromide.
- composition of the samples of NU-86 zeolites thus prepared have atomic Si / Al ratios between 8.5 and 16 and generally Na / Al ratios greater than 8%.
- the NU-86 zeolite has a three-dimensional microporous system
- this three-dimensional microporous system consists of straight channels whose pore opening is delimited by 1 1 T atoms (T being a tetrahedral atom chosen mainly from the group formed by Si, Al, Ga and Fe), straight channels delimited alternately by openings with 10 and 12 T atoms and sinusoidal channels also delimited alternately by openings with 10 and 12 T atoms.
- pore opening with 10, 1 1 or 12 tetrahedral atoms (T) means pores consisting of 10, 1 1 or 12 sides.
- the determination of the pore diameter present in the NU-86 zeolite led to the following values: 4.8 x 5.8 for the 10-sided pores, 5.7 x 5.7 for the 12-sided pores and 5.5 x 6.2 for pores with 1 1 sides. With such pore diameters, the NU-86 zeolite belongs to the category of zeolites with medium pore diameters.
- the invention relates to the NU-86 zeolite, the T element of which was extracted from the framework by at least one heat treatment, optionally in the presence of water vapor, followed by at least one acid attack by at least one solution of a mineral or organic acid or else by a direct acid attack with at least one solution of a mineral or organic acid, as well as any catalyst comprising said zeolite.
- the invention also relates to the use of such a catalyst in the conversion of hydrocarbons, in particular in the oligomerization of olefins.
- the NU-86 zeolite at least in part, preferably practically totally, in acid form, and comprising an Si / T ratio greater than about 20 leads, when incorporated into a catalyst, to performance catalytic, and in particular to improved activities, stabilities and selectivities in hydrocarbon conversion reactions, compared to the catalysts of the prior art, and in particular compared to the non-dealuminated NU-86 zeolites described in the application for European patent EP-A2-0,463,768, as will be demonstrated below in the examples.
- the invention relates to a NU-86 zeolite, comprising silicon and at least one element T chosen from the group formed by aluminum, iron, gallium, and boron, preferably aluminum, characterized in that the element T has been extracted from the framework and in that it has an overall Si / T atomic ratio greater than approximately 20, more preferably greater than approximately 22, and even more preferably comprised between approximately 22 and approximately 300.
- the invention also relates to a catalyst comprising at least one NU-86 zeolite, from which element T has been extracted from the framework and at least in part, preferably practically totally, in acid form, comprising silicon and at least one element T chosen from the group formed by aluminum, iron, gallium, and boron, preferably aluminum, and at least one matrix (or binder).
- the overall Si / T atomic ratio of said dealuminated zeolite is greater than approximately 20, preferably greater than approximately 22 and even more preferably between approximately 22 and approximately 300.
- Said catalyst also optionally comprises at least one selected element in the group formed by groups IB and VIII of the periodic table of the elements, preferably chosen from the group formed by Ag, Ni and Pd, Pt, preferably Ni, Pd or Pt.
- the matrix is generally chosen from the elements of the group formed by clays (for example from natural clays such as kaolin or bentonite), magnesia, aluminas, silicas, titanium oxide, boron oxide , zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates and silica-aluminas and carbon, preferably among the elements of the group formed by aluminas and clays.
- clays for example from natural clays such as kaolin or bentonite
- magnesia magnesia
- aluminas silicas
- titanium oxide boron oxide , zirconia
- aluminum phosphates titanium phosphates
- zirconium phosphates zirconium phosphates
- silica-aluminas and carbon preferably among the elements of the group formed by aluminas and clays.
- the NU-86 zeolite from which the element T was extracted from the frame according to the invention has the main lines of its structure as given by European patent application EP-A2-0,463,768, with a line intensity likely to be different from what is indicated in said patent.
- the NU-86 zeolite according to the invention is at least partly, preferably practically totally, in acid form, that is to say in hydrogen form (H + ).
- the Na T atomic ratio is generally less than 0.7% and preferably less than 0.6% and even more preferably less than 0.4%.
- the catalyst according to the invention generally contains from 10 to 99%, and preferably from 20 to 95%, of NU-86 zeolite from which the element T has been extracted from the framework at least partially in acid form.
- the weight content of the said element (s) is generally between 0.01 and 10%, preferably between 0.05 and 7%, and even more preferably between 0.10 and 5%.
- the complement to 100% by weight generally consists of the part of matrix in the catalyst.
- the overall Si / T atomic ratio of the zeolite as well as the chemical composition of the samples are determined by X-ray fluorescence and atomic absorption.
- the total area of the signal is measured for each sample over an angular range (2 ⁇ ) of 6 to 40 °, then, in the same area, the area of the lines in number of pulses for 3-second step recording with 0.02 ° (2 ⁇ ) steps.
- the ratio of these two values, Line area / Total area, is characteristic of the amount of material crystallized in the sample. This ratio or "peak rate" is then compared, for each sample treated, with the peak rate of a standard reference arbitrarily considered to be totally (100%) crystallized.
- the rate of crystallinity is therefore expressed as a percentage compared to a reference, which it is important to choose well, because the relative intensity of the lines varies according to the nature, the proportion and the position of the different atoms in the structural unit, and in particular of the cations and of the structuring.
- the reference chosen is the form calcined in dry air and exchanged 3 times, successively, with a solution of ammonium nitrate of the zeolite NU-86.
- microporous volume from the quantity of nitrogen adsorbed at 77 K for a partial pressure P / Po equal to 0.19, for information only.
- the invention also relates to the preparation of said NU-86 zeolite whose element T is extracted from the framework and from said catalyst.
- the first method known as direct acid attack comprises a first calcination step under dry air flow, at a temperature generally between about 450 and 550 ° C, which aims to remove the organic structuring present in the microporosity zeolite, followed by a step of treatment with an aqueous solution of a mineral acid such as HN03 or HCl or organic such as CH3C02H. This last step can be repeated as many times as necessary in order to obtain the desired level of desalumination. Between these two stages it is possible to carry out one or more ionic exchanges with at least one NH4N03 solution, so as to eliminate at least in part, preferably practically completely, the alkaline cation, in particular sodium. Likewise, at the end of the dealumination treatment by direct acid attack, it is possible to carry out one or more ionic exchanges with at least one NH4NO3 solution, so as to eliminate the residual alkaline cations and in particular sodium.
- the most critical parameters are the temperature of the treatment with the aqueous acid solution, the concentration of the latter, its nature, the ratio between the quantity of acid solution and the mass of zeolite treated, the duration of the treatment and the number of treatments carried out.
- the second method called thermal treatment (in particular with steam or "steaming") + acid attack comprises, firstly, calcination under dry air flow, at a temperature generally between approximately 450 and 550 ° C, which aims to eliminate the organic structuring agent occluded in the microporosity of the zeolite. Then the solid thus obtained is subjected to one or more ionic exchanges by at least one NH4NO3 solution, so as to eliminate at least in part, preferably practically completely, the alkaline cation, in particular the sodium, present in the cationic position in the zeolite. .
- the zeolite thus obtained is subjected to at least one structural dealumination cycle, comprising at least one heat treatment carried out, optionally and preferably in the presence of water vapor, at a temperature generally between 550 and 900 ° C., and optionally followed by at least one acid attack with an aqueous solution of a mineral or organic acid.
- the calcination conditions in the presence of water vapor temperature, water vapor pressure and duration of the treatment
- the post-calcination acid attack conditions are adapted so as to obtain the desired desalumination level.
- the desalumination cycle of the frame comprising at least one heat treatment step, optionally and preferably carried out in the presence of water vapor, and at least one attack step in an acid medium.
- NU-86 zeolite can be repeated as many times as necessary to obtain the dealuminated NU-86 zeolite having the desired characteristics.
- the heat treatment possibly carried out and preferably in the presence of water vapor, several successive acid attacks, with acid solutions of different concentrations, can be carried out.
- a variant of this second calcination method may consist in carrying out the heat treatment of the NU-86 zeolite containing the organic structuring agent, at a temperature generally between 550 and 850 ° C., optionally and preferably in the presence of water vapor. In this case the stages of calcination of the organic structuring and desalumination of the frame are carried out simultaneously. Then, the zeolite is optionally treated with at least one aqueous solution of a mineral acid (for example HNO3 or HCl) or organic (CH3CO2H for example). Finally, the solid thus obtained can optionally be subjected to at least one ion exchange with at least one NH 4 NO 3 solution, so as to eliminate practically any alkaline cation, in particular sodium, present in the cationic position in the zeolite.
- a mineral acid for example HNO3 or HCl
- CH3CO2H organic
- the preparation of the catalyst can be carried out according to any method known to those skilled in the art. In general, it is obtained by mixing the matrix and the zeolite and then by shaping.
- the possible element of the whole formed by groups IB and VIII of the periodic table of the elements can be introduced either before the shaping, or during the mixing, or else on the zeolite itself before mixing it, or well, preferably after shaping.
- the shaping is generally followed by calcination, generally at a temperature between 250 and 600 ° C.
- the possible element of the set formed by groups IB and VIII of the periodic table of the elements can be introduced after said calcination.
- said element is generally deposited as desired either, preferably, almost completely on the zeolite, or almost completely on the matrix, or partly on the zeolite and partly on the matrix, this choice being made from the manner which is known to the skilled person, by the parameters used during said deposition, such as for example the nature of the precursor chosen to effect said deposition.
- the element of groups IB or VIII preferably chosen from the group formed by Ag, Ni, Pd and Pt, preferably Ni, Pd or Pt, can also optionally be deposited on the zeolite-matrix mixture previously formed by any process known to those skilled in the art. Such a deposition is generally carried out by the technique of dry impregnation, ion exchange (s) or coprecipitation. In the case of ion exchange from precursors based on silver, nickel or platinum, silver salts such as chlorides or nitrates, a tetramine complex of platinum, or nickel such as chlorides, nitrates, acetates or formates.
- This cation exchange technique can also be used to deposit the metal directly on the zeolite powder, before possible mixing with a matrix.
- the possible deposit of element (elements) from groups IB and VIII is generally followed by calcination in air or oxygen, generally between 300 and 600 ° C, preferably between 350 and 550 ° C, and for a period included. between 0.5 and 10 hour (s), preferably between 1 and 4 hour (s).
- the catalyst contains several metals
- these can be introduced either all in the same way or by different techniques, before or after shaping and in any order.
- the technique used is that of ion exchange, several successive exchanges may be necessary to introduce the required quantities of metals.
- one of the preferred methods for preparing the catalyst according to the invention consists in kneading the zeolite in a wet matrix gel (generally obtained by mixing at least one acid and a matrix powder), for example alumina, for a period necessary for obtaining good homogeneity of the paste thus obtained, that is to say for ten minutes, then passing said paste through a die to form extrudates, for example of diameter between 0.4 and 4 mm. Then, after drying for a few minutes at 100 ° C.
- a wet matrix gel generally obtained by mixing at least one acid and a matrix powder
- a matrix powder for example alumina
- the optional element for example nickel
- the optional element can be deposited, for example by ion exchange, said deposit being followed by a final calcination, for example for 2 hours at 400 ° C.
- the shaping of the catalyst according to the invention is generally such that the catalyst is preferably in the form of pellets, aggregates, extrudates or beads, with a view to its use.
- Catalyst preparation is usually completed by calcining, or final calcination, usually at a temperature between 250 C and 600 C, preferably preceded by drying, for example in an oven, at a temperature generally between the temperature ambient and 250 ° C, preferably between 40 and 200 ° C. Said drying step is preferably carried out during the rise in temperature necessary for carrying out said calcination.
- a reduction can take place ex situ or in situ, with respect to the place of use of said catalyst in a given reaction.
- the invention also relates to the use of said catalyst in the conversion of hydrocarbons, in particular in the oligomerization of olefins C2 to C ⁇ .
- the catalyst according to the invention comprising dealuminized NU-86 zeolite makes it possible in particular to obtain:
- the starting olefins for such use can come from any suitable source. They can also be produced by conversion of methanol.
- the charges that can be used are as follows:
- the fresh charge mainly comprises methanol and possibly water (in all proportions water / methanol); it is first sent to a catalytic decomposition zone where it is transformed into water and to light olefins mainly consisting of propene, then, secondly, after separation of the water formed, the light olefins are sent to a zone of oligomerization where they are transformed into a mixture of premium fuel and bases for jet fuel and diesel engine.
- the fresh charge consists only of light C 2 to C Q olefins originating either from a catalytic cracking unit, or from a steam cracking unit, or from a catalytic dehydrogenation unit, or from all other sources of 'supply; this fresh charge is then sent directly to the oligomerization section where it is transformed into a mixture of premium fuel and bases for jet fuel and diesel engine.
- the fresh charge consists of a mixture of the two preceding charges.
- the transformation of methanol into water and into light olefins is generally carried out in the vapor phase in the presence of an acid zeolitic catalyst or an acid molecular sieve operating either in a fixed bed or preferably in a system. fluidized catalytic, at a temperature of about 450 to 650 ° C (preferably between 530 and 590 ° C), under a pressure of 0.01 to 1 MPa (preferably from 0.05 to 0.5 MPa), with a flow rate of liquid charge (space velocity) of approximately 5 to 100 volumes of catalyst per hour.
- oligomerization reaction is carried out in the liquid phase, in the supercritical phase or in the gas phase, in the presence of an acidic zeolitic catalyst according to the invention arranged in the form of a fixed bed, at a temperature of approximately 50 to 400 ° C. (preferably between 150 and 350 ° C), under a pressure of 2 to 10 MPa (preferably between 3 to 7 MPa), with a flow rate of liquid hydrocarbons (space velocity) of approximately 0.3 to 4 volumes per volume of catalyst per hour.
- Example 1 Preparations of the H-NU-86/1 zeolite according to the invention
- the raw material used is a NU-86 zeolite, which has an overall Si / Al atomic ratio equal to 10.2, a sodium content by weight corresponding to an Na / Al atomic ratio (in%) equal to 30.8.
- the NH4-NU-86 zeolite is then subjected to a hydrothermal treatment, in the presence of 100% water vapor at 650 ° C., for 4 hours.
- the zeolite then undergoes an acid attack, using 7N nitric acid, at approximately 100 ° C., for 4 hours, so as to extract the extra-lattice aluminum species formed during the hydrothermal treatment.
- the H-NU-86/1 zeolite in H form has an overall atomic Si / Ai ratio equal to 27.5 and an Na / Ai ratio less than 0.2%. These crystallographic and adsorption characteristics are reported in Table 2, below.
- the H-NU-86/1 zeolite obtained in Example 1 is then formed by extrusion with an alumina gel so as to obtain, after drying and calcination in air dry, the catalyst C1 which contains by weight 70% of zeolite H-NU-86/1 and 30% of alumina.
- the raw material used is the same NU-86 zeolite as that used in Example 1.
- This NU-86 zeolite undergoes, first of all, a so-called dry calcination at 550 ° C. under dry air flow for 10 hours. Then, the solid obtained is subjected to an ion exchange in a solution of NH 4 N ⁇ 3 10 N, at approximately 100 ° C for 4 hours. This operation is repeated three times successively.
- the NU-86 zeolite is then subjected to a treatment with a 0.8N nitric acid solution, at approximately 100 ° C., for 5 hours.
- the zeolite obtained is referenced H-NU-86/2. It is in its H form and has an overall Si / Ai atomic ratio equal to 20.3, and an Na / Al ratio equal to 0.7%. Its crystallographic and adsorption characteristics are reported in Table 3, below. Table 3
- Example 4 The H-NU-86/2 zeolite obtained in Example 4 is then formed by extrusion with an alumina gel so as to obtain, after drying and calcination in dry air, the catalyst C2 which contains by weight 70% H-NU-86/2 zeolite and 30% alumina.
- Example 5 Preparation of the H-NU-86/3 zeolite according to the invention
- the raw material used is the same NU-86 zeolite as that used in Example 1.
- This NU-86 zeolite undergoes, first of all, a so-called dry calcination at 550 ° C. under air and nitrogen flow during 10 hours. Then, the solid obtained is subjected to an ion exchange in a solution of NH4NO3 10N, at approximately 100 ° C. for 4 hours. This operation is repeated three times successively.
- the NU-86 zeolite is then subjected to a treatment with a 2N nitric acid solution, at approximately 100 ° C., for 5 hours.
- the zeolite obtained is referenced H-NU-86/3. It is in its H form and has an overall Si / Ai atomic ratio equal to 26.2, and an Na / Al ratio equal to 0.6%. These crystallographic and adsorption characteristics are reported in Table 4, below.
- the raw material used is the same NU-86 zeolite as that used in Example 1.
- This NU-86 zeolite undergoes, first of all, a so-called dry calcination at 550 ° C. under air and nitrogen flow during 10 hours. Then, the solid obtained is subjected to an ion exchange in a solution of NH4NO3 10N, at approximately 100 ° C. for 4 hours. This operation is repeated three times successively.
- the NU-86 zeolite is then subjected to a treatment with an 8.5N nitric acid solution, at approximately 100 ° C., for 5 hours.
- the zeolite obtained is referenced H-NU-86/4. It is in its H form and has an overall Si / Al atomic ratio equal to 40.3, and an Na / Al ratio equal to 0.15%.
- the H-NU-86/4 zeolite obtained in Example 6 is then formed by extrusion with an alumina gel so as to obtain, after drying and calcination in dry air, the catalyst C3 which contains by weight 70% H-NU-86/4 zeolite and 30% alumina.
- the NU-86 zeolite used in this example is the NH4-NU-86 zeolite prepared in Example 1 of the present invention. However, in the present example the NU-86 zeolite does not undergo dealumination.
- the NH4-NU-86 zeolite obtained in Example 1 is then formed by extrusion with an alumina gel so as to obtain, after drying and calcination in dry air, the catalyst C4 which contains by weight 70% of zeolite H-NU-86 and 30% alumina.
- Example 9 Evaluation of the catalytic cracking properties of methylcyclohexane of catalysts C1, C2, C3, in accordance with the invention, and of catalyst C4 not in accordance with the invention
- the catalytic evaluations are carried out in a fixed bed, at atmospheric pressure.
- the charge used is methylcyclohexane.
- the pph that is to say the spatial velocity of the charge, methylcyclohexane, (expressed in grams of toluene injected per gram of catalyst and per hour) varies so as to obtain a comparable conversion in the 4 tests.
- the reaction temperature is kept constant is equal to 500 ° C.
- Example 10 Evaluation of the catalytic properties in oligomerization of propylene of catalysts C1, C2, C3, in accordance with the invention, and of catalyst C4 not in accordance with the invention
- the catalytic evaluations are carried out in a fixed bed, under 5.5 MPa of nitrogen and at 300 ° C with a VVH of 1 h-1.
- the charge used is a C3 steam cracking cut (5% propane, 95% propylene).
- the reaction temperature being sufficiently high (300 ° C.), the variation of the Si / Al ratio of the active phases NU86 does not influence the activity of the catalysts C1, C2 and C3 in accordance with the invention and C4 not in accordance.
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9614187 | 1996-11-19 | ||
FR9614187A FR2755958B1 (en) | 1996-11-19 | 1996-11-19 | DESALUMINATED ZEOLITHE NU-86 AND ITS USE IN HYDROCARBON CONVERSION |
PCT/FR1997/002021 WO1998022213A1 (en) | 1996-11-19 | 1997-11-10 | Dealuminised nu-86 zeolite and its use in the conversion of hydrocarbons |
Publications (1)
Publication Number | Publication Date |
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EP0939673A1 true EP0939673A1 (en) | 1999-09-08 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP97945902A Ceased EP0939673A1 (en) | 1996-11-19 | 1997-11-10 | Dealuminised nu-86 zeolite and its use in the conversion of hydrocarbons |
Country Status (12)
Country | Link |
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US (2) | US6165439A (en) |
EP (1) | EP0939673A1 (en) |
JP (1) | JP4344853B2 (en) |
KR (1) | KR100569655B1 (en) |
CN (1) | CN1110365C (en) |
AU (1) | AU735736B2 (en) |
BR (1) | BR9713100A (en) |
CA (1) | CA2271091A1 (en) |
FR (1) | FR2755958B1 (en) |
NZ (1) | NZ335725A (en) |
RU (1) | RU2184610C2 (en) |
WO (1) | WO1998022213A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017174566A1 (en) | 2016-04-08 | 2017-10-12 | IFP Energies Nouvelles | Use of zeolite nu-86 for naphtha catalytic cracking |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US6123914A (en) * | 1998-12-22 | 2000-09-26 | Exxon Research And Engineering Company | Enhanced boro-aluminosilicate EU-1 (LAW778) |
US7041274B2 (en) * | 1999-10-22 | 2006-05-09 | Intevep, S.A. | Aluminosilicate compositions, preparation and use |
US7011802B2 (en) * | 2000-12-22 | 2006-03-14 | California Institute Of Technology | Synthesis of molecular sieves by hydrothermal treatment with acid |
FR2837199B1 (en) * | 2002-03-15 | 2005-09-16 | Inst Francais Du Petrole | METHOD FOR CONVERTING INTO MULTIPLE STEPS A LOAD COMPRISING FOUR OLEFINS, FIVE ATOMS OF CARBON OR MORE, FOR PRODUCING PROPYLENE |
FR2879620B1 (en) * | 2004-12-21 | 2007-02-23 | Inst Francais Du Petrole | PROCESS FOR THE DIRECT CONVERSION OF A CHARGE COMPRISING FOUR AND / OR FIVE ATOMIC CARBON OLEFINS FOR THE PRODUCTION OF PROPYLENE WITH CO-PRODUCTION OF GASOLINE |
FI120627B (en) * | 2007-08-24 | 2009-12-31 | Neste Oil Oyj | Process for oligomerization of olefins |
KR100996976B1 (en) | 2008-08-27 | 2010-11-29 | 현대엔지니어링 주식회사 | Long-time catalyst for ??? reaction and Preparing method thereof |
FR2984759B1 (en) * | 2011-12-22 | 2013-12-20 | IFP Energies Nouvelles | CATALYST COMPRISING AT LEAST ONE NU-86 ZEOLITE, AT LEAST ONE USY ZEOLITE AND A POROUS MINERAL MATRIX AND METHOD OF HYDROCONVERSION OF HYDROCARBON LOADS USING THE CATALYST |
DK2817262T3 (en) * | 2012-02-21 | 2018-02-12 | Exxonmobil Chemical Patents Inc | MOLECULAR SIGNING MATERIAL, SYNTHESIS AND USE THEREOF |
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US3506400A (en) * | 1966-05-25 | 1970-04-14 | Exxon Research Engineering Co | High silica crystalline zeolites and process for their preparation |
NZ204091A (en) * | 1982-05-18 | 1986-03-14 | Mobil Oil Corp | Manufacture of synthetic crystalling zeolite beta with a low aluminium content |
FR2575741B1 (en) * | 1985-01-09 | 1990-03-16 | Inst Francais Du Petrole | OBTAINING A SILICA-RICH SYNTHETIC OFFERING. APPLICATION TO THE PRODUCTION OF LIGHT OLEFIN-RICH HYDROCARBONS BY PROCESSING METHANOL AND / OR DIMETHYLETHER |
DE3661989D1 (en) * | 1985-06-19 | 1989-03-09 | Inst Francais Du Petrole | STABILIZED AND DEALUMINATED ZEOLITE OMEGA |
US5043307A (en) * | 1986-01-03 | 1991-08-27 | Mobil Oil Corp. | Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index |
GB8806675D0 (en) * | 1988-03-21 | 1988-04-20 | Shell Int Research | Process for preparing liquid hydrocarbons |
GB9013916D0 (en) * | 1990-06-22 | 1990-08-15 | Ici Plc | Zeolites |
US5120891A (en) * | 1990-09-26 | 1992-06-09 | Texaco Chemical Company | Process for oligomerizing olefins using a super-dealuminated Y-zeolite |
FR2669618B1 (en) * | 1990-11-26 | 1993-05-07 | Elf Aquitaine | PROCESS FOR DESALUMINATION OF SYNTHETIC BROAD PORE ZEOLITHS, SELECTIVE ORGANOPHILIC CATALYSTS AND ADSORBENTS CONTAINING DESALUMINATED ZEOLITHS OBTAINED ACCORDING TO THE PROCESS AND ESSENTIALLY SILICA BETA ZEOLITH. |
GB9116499D0 (en) * | 1991-07-31 | 1991-09-11 | British Petroleum Co Plc | Treatment method for zeolites |
US5242676A (en) * | 1992-05-11 | 1993-09-07 | Mobil Oil Corp. | Selective surface dealumination of zeolites using dicarboxylic acid |
RU2178451C2 (en) * | 1996-11-27 | 2002-01-20 | Энститю Франсэ Дю Петроль | Method for improving flowability loss temperature for paraffin raw material utilizing zeolite nu-86-based catalyst |
FR2758567B1 (en) * | 1997-01-20 | 1999-02-19 | Inst Francais Du Petrole | PROCESS FOR CRACKING HYDROCARBON CHARGES USING A CATALYST COMPRISING A DEALUMINATED NU-86 ZEOLITE |
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1996
- 1996-11-19 FR FR9614187A patent/FR2755958B1/en not_active Expired - Lifetime
-
1997
- 1997-11-10 EP EP97945902A patent/EP0939673A1/en not_active Ceased
- 1997-11-10 WO PCT/FR1997/002021 patent/WO1998022213A1/en not_active Application Discontinuation
- 1997-11-10 BR BR9713100-8A patent/BR9713100A/en not_active Application Discontinuation
- 1997-11-10 KR KR1019997004379A patent/KR100569655B1/en active IP Right Grant
- 1997-11-10 CN CN97181153A patent/CN1110365C/en not_active Expired - Fee Related
- 1997-11-10 CA CA002271091A patent/CA2271091A1/en not_active Abandoned
- 1997-11-10 JP JP52325698A patent/JP4344853B2/en not_active Expired - Lifetime
- 1997-11-10 AU AU51238/98A patent/AU735736B2/en not_active Ceased
- 1997-11-10 NZ NZ335725A patent/NZ335725A/en not_active IP Right Cessation
- 1997-11-10 RU RU99112951/04A patent/RU2184610C2/en not_active IP Right Cessation
- 1997-11-19 US US08/974,427 patent/US6165439A/en not_active Expired - Lifetime
-
2000
- 2000-11-20 US US09/715,074 patent/US6337428B1/en not_active Expired - Lifetime
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017174566A1 (en) | 2016-04-08 | 2017-10-12 | IFP Energies Nouvelles | Use of zeolite nu-86 for naphtha catalytic cracking |
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NZ335725A (en) | 2001-04-27 |
BR9713100A (en) | 2000-03-28 |
RU2184610C2 (en) | 2002-07-10 |
KR20000053353A (en) | 2000-08-25 |
CA2271091A1 (en) | 1998-05-28 |
KR100569655B1 (en) | 2006-04-11 |
JP2001504079A (en) | 2001-03-27 |
US6165439A (en) | 2000-12-26 |
JP4344853B2 (en) | 2009-10-14 |
AU5123898A (en) | 1998-06-10 |
US6337428B1 (en) | 2002-01-08 |
CN1242718A (en) | 2000-01-26 |
AU735736B2 (en) | 2001-07-12 |
FR2755958B1 (en) | 1999-01-08 |
WO1998022213A1 (en) | 1998-05-28 |
CN1110365C (en) | 2003-06-04 |
FR2755958A1 (en) | 1998-05-22 |
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