EP0858427A1 - Procede destine a synthetiser des materiaux inorganiques poreux - Google Patents

Procede destine a synthetiser des materiaux inorganiques poreux

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Publication number
EP0858427A1
EP0858427A1 EP96938057A EP96938057A EP0858427A1 EP 0858427 A1 EP0858427 A1 EP 0858427A1 EP 96938057 A EP96938057 A EP 96938057A EP 96938057 A EP96938057 A EP 96938057A EP 0858427 A1 EP0858427 A1 EP 0858427A1
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EP
European Patent Office
Prior art keywords
amphipolar
process according
compound
groups
carbon atoms
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.)
Withdrawn
Application number
EP96938057A
Other languages
German (de)
English (en)
Inventor
Francisco René MAS CABRé
Wilhelmus Pannekeet
Robert Smakman
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Akzo Nobel NV
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Akzo Nobel NV
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Filing date
Publication date
Application filed by Akzo Nobel NV filed Critical Akzo Nobel NV
Publication of EP0858427A1 publication Critical patent/EP0858427A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate 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
    • C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound

Definitions

  • the invention pertains to a process for synthesising porous inorganic matenals in the presence of an amphipolar compound
  • Porous inorganic matenals such as porous amorphous aluminas, silicas, silica- aluminas, and crystalline molecular sieves, are applied, int al , in catalysis
  • the catalytic activity and selectivity of porous inorganic matenals, including molecular sieves, is dependent, int.
  • porous inorganic materials notably crystalline molecular sieves, having diffenng pore diameters
  • porous inorganic materials notably crystalline molecular sieves, having diffenng pore diameters
  • large pore molecular sieves which have a pore diameter of the order of 0.7-1.2 nm, the best-known exponent of which is Y zeolite having a pore diameter of 0 8 nm
  • Other "large pore molecular sieves” include X zeolite, ALPO-5, ALPO-8, beta zeolite, MCM-22, MCM-36, and VPI-5
  • This last compound is an aluminium phosphate or a silicoaluminium phosphate with a pore diameter of 1.2 nm
  • the known "large pore molecular sieves” do not always have a sufficiently large pore diameter to admit the desired reactants, e g , large hydrocarbon molecules, yet, on the other, the pore diameter of the MCM-41-type matenals is too large to ensure sufficient catalytic activity
  • molecular sieves having a diameter which lies between the diameters of the known "large pore” zeolites and the MCM-41-type matenals More in particular, there is need for porous inorganic materials, in particular molecular sieves, which have a mode pore diameter of 0.8-2.0 nm.
  • ZSM-5 and beta zeolite are synthesised in the presence of quaternary ammonium ions of the formula R1 R2R3R4N + , wherein R1 , R2, R3, and R4 are alkyl groups having fewer than 6 carbon atoms.
  • the synthesis of ultra-large pore molecular sieves described in WO 91/1 1390 is carried out in the presence of micelle-forming template compounds of the formula R1 R2R3R4CT , wherein Q is a nitrogen atom or phosphorus atom and at least one of R1 , R2, R3, and R4 is an aryl group or alkyl group having 6-36 carbon atoms, and each of the other groups is selected from hydrogen and an alkyl group having 1-5 carbon atoms.
  • the most frequently employed template compound in this publication is a cetyl trimethyl ammonium salt, e.g., a halide or hydroxide.
  • the key aspect of the use of these molecules is that in water above a certain concentration, the critical micelle concentration or CMC, they aggregate to form micelles, and it is these micelles which actually act as templates in the synthesis of the molecular sieves.
  • the pore diameter of the obtained product is dependent on the size of the template employed. Accordingly, by varying the size of the template, it is possible in principle to vary the pore diameter of the obtained product. In actual practice, however, this process is subject to restrictions. For instance, when the object is to obtain products having a pore diameter which lies between the beta zeolite and the MCM-41 pore diameter, two options present themselves.
  • the present invention provides such a process.
  • the process according to the invention is characterised in that a porous inorganic material having an MoPD of 0.8 -2.0 nm, preferably 1.0-2.0 nm, more preferably 1.0- 1.8 nm, is synthesised in the presence of templates containing one or more amphipolar compounds having at least two cationic or anionic head groups and a hydrophobic part
  • at least a portion of the head groups of the amphipolar compound has a cationic nature
  • amphipolar compounds having at least two cationic or anionic head groups and a hydrophobic part opens up a wide range of options
  • an amphipolar compound having at least two cationic or anionic head groups and at least two hydrophobic tail groups With the length of the hydrophobic tail groups remaining the same, these compounds have a lower CMC than the corresponding single amphipolar compounds, which have one head group and one tail group
  • These compounds therefore form micelles at a tail length which is too short for the single amphipolar compounds to form micelles
  • micelles can be obtained which have a smaller cross-section than that of the micelles which can be obtained with single amphipolar compounds
  • products can be obtained which have a diameter between 0 8 and 2 0 nm
  • Suitable micelle-forming amphipolar compounds having at least two cationic head groups and at least two hydrophobic tail groups include the ions of formula (1)
  • Q, Q', and Q" may be the same or different and represent a nitrogen atom or phosphorus atom, n and m each independently have a value of 1-8, y has a value of 0-1000,
  • R1 , R1', and R1" are independently selected from optionally substituted alkyl groups having 3-12 carbon atoms and optionally substituted aryl groups having 4-12 carbon atoms
  • R2, R2 ⁇ R2", R3, R3', and R3" are each independently selected from hydrogen and optionally substituted alkyl groups having 1-6 carbon atoms, with the proviso that each of R1, R , and R1" contains more carbon atoms than each of R2 and R3, R2', and R2" and R3", respectively
  • R4, R4 ⁇ R5, and R5' may be the same or different and are selected from hydrogen and optionally substituted methyl and ethyl.
  • n, m, and/or y has a value higher than 1, the additional groups formed as a result, Q", R4, R5, R4', R5', R1', and R2' need not necessarily have the same value as the other groups thus designated.
  • Q the compound below, wherein n is 2, is also covered by formula (1).
  • Preferred compounds according to formula (1) for use in the process according to the invention are those wherein R4, R4', R5, and R5' all are hydrogen or methyl. Further preference is given to n and m having a value of 2-4. y preferably is 0-10, more preferably 0-4. R1 , R1 ⁇ and R1" preferably have 4-10 carbon atoms, most preferably 6-10. Preferably, all of R1 , R1 ⁇ and R1" are the same. R2, R2', R2", R3, R3', and R3" are preferably all selected independently from methyl, ethyl, and propyl.
  • Examples of suitable micelle-forming amphipolar compounds according to formula (1) are: (2) (CH 3 ) 2 C 6 H 13 N + - CH 2 -CH 2 - + NC 6 H 13 (CH 3 ) 2 (3) (CH 3 ) 2 C 6 H 13 N + - CH 2 -CH 2 -CH 2 - * NC 6 H 13 (CH 3 ) 2
  • ions are neutralised by the presence of an equivalent amount of negative ions, e.g., halogen ions, nitrate ions, sulphate ions, or OH-ions.
  • halogen ions are generally preferred.
  • amphipolar units can also be connected one to the other via the hydrophobic tails.
  • the micelles containing the amphipolar compounds act as templates. In that case it is essential that these micelles are formed under synthesis conditions.
  • templates which contain an amphipolar compound with at least two cationic or anionic head groups and at least two hydrophobic tail groups can, if so desired, contain other components in addition to this amphipolar compound, e.g., other amphipolar compounds.
  • the templates containing one or more amphipolar compounds having at least two cationic or anionic head groups and a hydrophobic part to be used in the process of the present invention may also be made up of polymers which comprise at least two cationic or anionic head groups and a hydrophobic part.
  • the polymer molecules themselves generally function as template, without aggregating to form micelles.
  • Examples of polymers suitable for use as template are poly-4-vinyl pyridinium derivatives such as poly-4-vinyl- 1-methyl pyridinium halogenides, cationic polystyrene derivatives or poly(meth)acrylamide derivatives.
  • the process according to the invention can be employed to synthesise porous inorganic materials essentially made up of oxides of a single atom type, but equally to synthesise porous inorganic materials containing oxides of several types of atoms.
  • the process according to the invention can be used to synthesise porous aluminas or silicas, but equally to synthesise porous metallosilicates, such as aluminosilicates, titanium silicates, zirconium silicates, etc.
  • the present invention has made it possible for the first time to synthesise porous mixed metal oxides with an MoPD of 0.8-2.0 nm.
  • These mixed metal oxides which contain at least 0.2 wt.% of a first oxide and a total of further oxides of at most 99.8 wt.% are also part of the present invention.
  • the novel porous mixed oxide is a porous metallosiiicate. Aluminosilicates are particularly preferred.
  • novel compounds which can be synthesised using the process according to the invention are of the following formula: X a Y b Z c O d N ⁇ Rr wherein
  • X is a trivalent element such as aluminium, iron or gallium
  • Y is a tetravalent element such as silicon or germanium
  • Z is a pentavalent element such as phosphorus
  • O represents an oxygen atom
  • N is a countenon such as sodium
  • R is the amphipolar compound, with a, b, c, d, e, and r standing for the molar fractions of the different components, and the compound as a whole being neutral
  • the process according to the invention is pre-eminently suited to be used for synthesising compounds of the aforesaid formula wherein X is aluminium,
  • Y is silicon, and c has the value 0
  • the compound according to the formula above is such as it is obtained fresh from the synthesis reaction Generally, this material will be subjected to some treatment, say, an extraction step and/or a calcination step, to remove the amphipolar compound R from the composition
  • the counterion N in this freshly obtained product frequently is sodium, which is there as a result of its presence in the synthesis mixture
  • this sodium will be replaced with other counte ⁇ ons, such as H + , NH 4 + , etc
  • Procedures for removing the amphipolar compound via calcination and countenon exchange processes are well-known to the skilled person and have, for example, been described for MCM-41 , int al , in WO 91/11390
  • a solution of the amphipolar compound is prepared in a solvent
  • the solvent as a rule is water
  • the concentration of the amphipolar compound in the solvent has to be selected such as will give a concentration of the amphipolar compound in the reaction mixture under reaction conditions which is higher than this compound's CMC, so that the reaction mixture will contain micelles
  • the concentration of the amphipolar compound in the reaction medium will be between 1 and 20 wt %, calculated on the water phase
  • the sources of the oxides to be incorporated into the composition have to be added to the solution of the amphipolar compound Should the occasion arise, other components such as an alkali source can be added to the resulting mixture
  • the resulting mixture is subsequently crystallised at a temperature in the range of 0° to 250°C, preferably 10-175°C, more preferably 10-100°C If carried out at a temperature above 100°C, the reaction should be performed under pressure to ensure that it takes place in the liquid phase Carrying out the reaction under autogenous pressure is appropriate
  • the pH of the mixture has a value in the range of 3 to14, preferably 9-14
  • Suitable silica sources include precipitated amo ⁇ hous silica, amorphous silica prepared by flame hydrolysis, water glass, organic silicates, and crystalline inorganic silicates such as zeolites or clays
  • Suitable alumina sources include alumina, aluminium oxyhydroxide, aluminium hydroxide, sodium aluminate, aluminium sulphate, aluminium nitrate, aluminium chlorohydrol, and organic aluminium compounds such as aluminium alkoxides
  • Suitable alkali sources include the oxides or hydroxides of the Group IA and Group IIA elements, or compounds of these elements and silica or alumina, such as water glass or sodium aluminate, or quaternary ammonium bases or guanidine bases Following crystallisation the material is isolated, washed with water, dried, and, optionally, calcined at a temperature in the range of 400° to 750°C in an air and/or nitrogen atmosphere
  • Products prepared by the process according to the invention can be used in a wide range of applications They are especially suitable for use in catalysis, for example, cracking or hydrocracking of hydrocarbon feeds, isome ⁇ sation, alkylation, etc
  • Example 1
  • the SiO 2 :AI 2 O 3 :H 2 O molar ratio in the reaction mixture was 1 : 0.002: 34.20.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature.
  • the specific surface area and the pore size distribution of the specimens were obtained from the nitrogen adsorption isotherm determined at 78 K.
  • the SPESA single point equivalent surface area
  • V a is interpolated from adjacent points in the adsorption isotherm.
  • the pore size distribution was determined according to the method Broekhoff-De Boer (J. Catal. 9, 8-14 (1967)). Because the pore size distribution of these types of products is relatively steep, adjustment of the calculation method was necessary. A matrix was made with 70 steps of 0.05-0.2 nm in the diameter range of 1.25-10 nm and 28 steps of 1-20 nm in the diameter range of 10-200 nm. To determine the values for P/P 0 in accordance with the modified Kelvin equation for the model of cylindrical pores which are open at both sides, such as used in the method Broekhoff-De Boer, the amount of adsorbed liquid nitrogen is inte ⁇ olated from the adso ⁇ tion isotherm. From this data cumulative and differential pore size distributions are calculated.
  • MoPD mode pore diameter
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature. To determine the product's characteristics, a small portion was calcined at 540°C and the nitrogen adsorption curve of the calcined product determined. The data obtained in this manner is listed below.
  • the Alpha value is an approximate indication of the catalytic cracking activity of the product as compared with a standard catalyst. It is based on the relative rate constant (rate of normal hexane conversion per weight of catalyst per unit of time).
  • the standard catalyst is an amorphous silica-alumina cracking catalyst, which is accorded an Alpha value of 1 (rate constant 0.016 sec-1).
  • the Alpha test is described in US 3,354,078, in the Journal of Catalysis. Vol. 4, p. 527 (1965), Journal of Catalysis, Vol. 6, p 278 (1966), and Journal of Catalysis. Vol. 61 , p 395 (1980). The test was carried out at a temperature of 538°C and at a variable flow rate as described in Journal of Catalysis Vol. 61 , p 395 (1980).
  • Product 2A was calcined at 540°C for 1 hour in nitrogen, and subsequently for 6 hours in air.
  • the calcined product was subjected to an ammonium exchange with a 1 N NH 4 CI solution.
  • the exchanged product was pressed to tablets.
  • the tablets were crushed, and the crushed product was sieved to isolate the fraction with a particle size of 0.4-0.6 mm. These particles were calcined for 6 hours at 550°C.
  • This product had an Alpha value of 2.49, proving enhanced catalytic activity as compared with a standard catalyst.
  • the SiO 2 :AI 2 O 3 :H 2 O molar ratio in the reaction mixture was 1 : 0.002: 34.20.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature. To determine the characteristics of the product, a small portion was calcined at 540°C and the nitrogen adso ⁇ tion curve of the calcined product determined. The process specified above was repeated with a different amount of amphipolar compound. The data obtained in this manner is listed below.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature. The process described above was repeated, except that the quantity of amphipolar compound was varied.
  • the Alpha value for product 4A was determined in the manner described in Example 2. The product was found to have an Alpha value of 2.73.
  • the molar composition of the mixture QUAT:NaOH:AI 2 O 3 :SiO 2 :H 2 O was 0.058:0.230:0.038: 1.00:34.20.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for varying periods at different temperatures, after which the product was filtered off, washed with water, and dried at room temperature.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature. To determine the product's characteristics, a small portion was calcined at 540°C and its nitrogen adsorption curve determined. The data obtained in this manner is listed below.
  • Example 3B A comparison of the properties of the product obtained here with those of the silicate prepared in Example 3B, which was prepared in the same manner with the same weight amount of template, shows that the product obtained here has a lower surface area, a lower pore volume in pores with a diameter below 10 nm, and a lower percentage of pores within PV ⁇ 0.1 MoPD than the product of Example 3B.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature.
  • Example 4B A comparison of the properties of the product obtained here with those of the aluminosilicate prepared in Example 4B, which was prepared in the same manner with the same weight amount of template, shows that the product obtained here has a lower surface area, a lower pore volume in pores with a diameter below 10 nm, and a lower percentage of pores within PV ⁇ 0.1 MoPD.
  • the molar composition of the mixture QUAT:NaOH:AI 2 O 3 :SiO 2 :H 2 O was 0.058:0.230:0.038:1.00:34.20.
  • the mixture was homogenised by stirring for one hour at room temperature. Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature.
  • the molar composition of the NaOH AI 2 O 3 S ⁇ O 2 H 2 0 mixture was 0 230 0 038 1 00 34 20
  • the Alpha value for product 9C was determined in the manner described in Example 2. The product was found to have an Alpha value of 2.11.
  • Example 9C was repeated, except that linear poly-4-vi nyl- 1-methyl pyridinium chloride was used with a molecular weight of 10,000. The results are given below.
  • An aluminosilicate was prepared in the presence of linear poly-4-vinylpyridine, MW 2000.
  • the gel contained 5 0 wt % of poly-4-v ⁇ nylpy ⁇ d ⁇ ne, calculated on the amount of water
  • the mixture was homogenised by stir ⁇ ng for one hour at room temperature Next, the resulting homogeneous mixture was reacted, with stirring, for 24 hours at a temperature of 95°C, after which the product was filtered off, washed with water, and dried at room temperature
  • a compa ⁇ son of this data with the data obtained in Example 9C shows that the product obtained here has a lower surface area and a lower pore volume in pores with a diameter below 10 nm that the product of Example 9C This shows that the use of a template with cationic head groups leads to a better product than the use of a template with neutral head groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un procédé destiné à synthétiser un matériau inorganique poreux possédant un diamètre de pores (MoPD) de l'ordre de 0,8 à 2,0 nm, ce procédé étant caractérisé en ce que l'on effectue la synthèse en présence d'agents structurants contenant un ou plusieurs composés amphipolaires possédant au moins deux groupes de tête cationiques ou anioniques ainsi qu'une partie hydrophobe. De préférence, au moins une portion des groupes de tête du composé amphipolaire possède une nature cationique. Le procédé selon l'invention permet de synthétiser de nouveaux oxydes mixtes poreux, notamment des métallosilicates, et plus particulièrement des aluminosilicates, présentant un diamètre de pores de l'ordre de 0,8 à 2,0 nm. Ces matériaux présentent un intérêt particulier pour la catalyse.
EP96938057A 1995-11-02 1996-10-31 Procede destine a synthetiser des materiaux inorganiques poreux Withdrawn EP0858427A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1001553 1995-11-02
NL1001553A NL1001553C2 (nl) 1995-11-02 1995-11-02 Werkwijze voor de synthese van poreuze keramische materialen.
PCT/EP1996/004781 WO1997016375A1 (fr) 1995-11-02 1996-10-31 Procede destine a synthetiser des materiaux inorganiques poreux

Publications (1)

Publication Number Publication Date
EP0858427A1 true EP0858427A1 (fr) 1998-08-19

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EP96938057A Withdrawn EP0858427A1 (fr) 1995-11-02 1996-10-31 Procede destine a synthetiser des materiaux inorganiques poreux

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Publication number Priority date Publication date Assignee Title
DE19747387A1 (de) * 1997-10-27 1999-04-29 Max Planck Gesellschaft Herstellung poröser und bimodalporöser Silikate und Anorganika durch Templatieren funktioneller Latexteilchen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989001912A1 (fr) * 1987-08-28 1989-03-09 The Dow Chemical Company Compositions de phosphates d'aluminium cristallines
GB8829924D0 (en) * 1988-12-22 1989-02-15 Ici Ltd Zeolites
DK0512026T3 (da) * 1990-01-25 1995-03-20 Mobil Oil Corp Syntetisk porøst krystallinsk materiale, dets fremstilling og anvendelse
GB9013916D0 (en) * 1990-06-22 1990-08-15 Ici Plc Zeolites
US5068096A (en) * 1991-04-08 1991-11-26 Mobil Oil Corporation Synthesis of crystalline silicate MCM-47

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9716375A1 *

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WO1997016375A1 (fr) 1997-05-09
NL1001553C2 (nl) 1997-05-13

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