EP0319538A1 - Modification of zeolites - Google Patents

Modification of zeolites

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Publication number
EP0319538A1
EP0319538A1 EP19870905261 EP87905261A EP0319538A1 EP 0319538 A1 EP0319538 A1 EP 0319538A1 EP 19870905261 EP19870905261 EP 19870905261 EP 87905261 A EP87905261 A EP 87905261A EP 0319538 A1 EP0319538 A1 EP 0319538A1
Authority
EP
European Patent Office
Prior art keywords
zeolite
aluminium
solvent
sicl
compound
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Withdrawn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
EP19870905261
Other languages
German (de)
French (fr)
Inventor
Lovat Victor Charles Imperial College Of Rees
Edward Fook Tin Imperial College Of Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3I Research Exploitation Ltd
Original Assignee
Research Corp Ltd
3I Research Exploitation Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB868620434A external-priority patent/GB8620434D0/en
Priority claimed from GB878709566A external-priority patent/GB8709566D0/en
Application filed by Research Corp Ltd, 3I Research Exploitation Ltd filed Critical Research Corp Ltd
Publication of EP0319538A1 publication Critical patent/EP0319538A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2884—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures the aluminium or the silicon in the network being partly replaced
    • 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
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. 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
    • B01J2229/16—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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite

Definitions

  • This invention relates to a process for the chemical modification of zeolite structures.
  • Zeilites are crystalline hydrated aluminium silicates which have the general chemical formula:
  • M is a cation of valency n and x is greater than or equal to 2.0. Structurally they have a porous framework based on an extended three-dimensional framework of SiO 4 and AlO 4 tetrahedra linked together through common oxygen atoms.
  • the value of x in the above formula for zeolite Y is approximately 5.0 and the resulting framework is not sufficently stable to withstand the high temperatures (800oC) involved in the regenerator unit of cracking plants where coke is burnt off.
  • “coke” is meant the deposits of carbon and low hydrogen content hydrocarbons that build up in petroleum cracking).
  • the SiO 2 /Al 2 O 3 ratio has to be increased.
  • H + ammonium
  • the net result is the production of a partially crystalline material along with some amorphous material and the introduction of some mesopores into the system.
  • the resulting material is an excellent selective catalyst.
  • the other methods which can be used to increase the silicon to aluminium ratio are (a) extraction of aluminium by EDTA (ethylenediaminetetraacetic acid) (b) acid treatment and (c) use of silicon tetrachloride vapour.
  • EP-A-82211 describes the use of an aqueous solution of a fluorosilicate to replace aluminium with silicon in the framework.
  • the use of the SiCl, vapour, as described for example in EP-A-62123 and EP-A-72397, has some useful effects.
  • the vacancies in the framework, produced by the extraction of aluminium are healed by silicon atoms from the tetrachloride, and, the aluminium removed from the framework is converted to its volatile trichloride effecting removal from the system.
  • EP-A-210018 describes another process for the modification of zeolite framework structures which involves treatment of the zeolite with a molten salt medium which contains a reactive component which has a "radius ratio" of less than 0.6, the "radius ratio” being defined as the ratio of the crystal ionic radius of the central atom of the reactive component to that of the the oxygen anion 0 2- .
  • the method is applicable to porous crystalline minerals which have pores large enough to sorb normal hexane.
  • Examples of the components which have the required radius ratio are: the trichlorides of aluminium, boron, iron, phosphorus and gallium, and the tetrachlorides of titanium and tin, the Si 4+ ion being also mentioned.
  • the method may be used to insert aluminium into high silicon zeolite frameworks or otherwise alter the framework without substantial alteration of its structure.
  • An object of the present invention is to provide an improved method for the modification of zeolite framework structures.
  • a method for the modification of the framework structure of a zeolite comprising treating the zeolite with a solution in an organic solvent of a compound of an element capable of structural replacement of aluminium in the framework.
  • the compound is preferably a metal halide of the aluminium- replacing element, examples being: BCl 3 , BBr 3 , SnCl 4 , SnBr 4 , Snl 4 , SiCl 4 , Sil 4 , TiCl 4 , GeCl 4 , GaCl 4 ,
  • organometallic compounds of the selected element may also be suitable, for example, beryllium diphenyl.
  • the zeolite may be, for example, Erionite, Beta, ZSM-5, ZSM-11 (Trade Marks), Mordenite, Chabazite, and Offretite.
  • the selection of the solvent is not critical. Solvents, and solvent mixtures, of small molecular size, such as carbon tetrachloride and ethanol, are suitable but the reaction may be accelerated by the use of a solvent of a molecular size which is too large to enter the channels of the zeolite, one particularly preferred solvent for this purpose being tetraethoxysilane [C 2 H 5 O) 4 Sil.
  • the temperature of the treatment is not of critical importance but would normally be carried out at the reflux temperature of the solvent in order to minimise the treatment time.
  • the method of the invention may include a pretreatment step in which the zeolite is treated with acid to effect a desired degree of dealumination, prior to treatment with the solvent solution compound of the aluminium-replacing element. Since the degree of dealumination with acid is restricted only by the need to maintain the integrity of the zeolitic structure, the use of the acid pretreatment step enables the production of zeolites with very high silicon to aluminium ratios.
  • NaY zeolite was calcined in a muffle furnace at 600oC for a few hours. The zeolite was then cooled to 80-100oC in a desiccator and 25ml of carbon tetrachloride (CCl 4 ) was then added with continuous stirring to form a slurry. various amounts (0.10 to 0.77ml) of silicon tetrachloride (SiCl 4 ) were added to several separate samples of the slurry which were then refluxed at a fixed temperature (58-59°C; 76-77°C) for a period of three hours. The final slurry was then centrifuged to separate the solid and liquid phases.
  • CCl 4 carbon tetrachloride
  • SiCl 4 silicon tetrachloride
  • the calcined zeolite was allowed to cool and treated with sodium chloride solution (1-5M at pH 8-9) repeatedly. The final product was well washed until chloride-free, filtered and dried at 100°C.
  • Example 2 The same procedure as described in Example 1 was used except that 15ml of CCl 4 and 0.3ml SiCl 4 were refluxed with NaY zeolite with different water content at 59°C for 20 minutes. The results are given in Table II below.
  • CCl 4 and 10ml SiCl 4 were refluxed with zeolites with different cationic forms at 58-60oC for one hour.
  • Samples S0.50/57, S1.0/57 and S1.5/57 were mixed with 15ml SiCl 4 and refluxed at 57oC for 30 minutes to produce sample SS0.5/1.5.
  • Example 1 Using the procedure described in Example 1, 15ml of SiCl 4 were refluxed with zeolite produced from Example 1 (Sample Nos. CS0.10/58 + CS0.20/58 + CS0.10/76) at 57°C for 30 minutes. Four cycles were carried out.
  • Table VI reports the results of infra-red characterisation studies and Table VII the results of X-ray diffraction studies, confirming the increase of the Si/Al ratio of the zeolite Y framework.
  • Table VIII below reports the products (in sodium form) resulting from the dealumination of sodium Y zeolites by SiCl 4 in the solvent tetraethoxysilane [( C2 H 5 O) 4 Si] (TES).
  • the methods used were as follows:
  • Table IX reports the product (in sodium form) resulting from the dealumination of sodium Y zeolite by a SiCl 4 /CCl 4 /
  • Table X reports the products (in sodium form) resulting from the dealumination of sodium Y zeolites by SiCl 4 /ethanol solutions.
  • Al/u.c.; ZY[D]) was calcined at 600oC for a few hours and allowed to cool in a desiccator. 20 ml of SiCl 4 were added to the zeolite and stirred for 5 minutes. Five successive portions of CCl 4 of approximately 20ml were added to the zeolite slurry and the CCl 4 was discarded after centrifuging the slurry. 80ml of ethanol were then added and refluxed for one hour. Approximately 50ml of the slurry was withdrawn after 30 minutes and the rest after one hour.
  • the method was the same as Method (i) above except that the contact time of the zeolite and SiCl 4 was increased to 15 minutes.
  • SiCl 4 were added to the zeolite and stirred for 5 minutes.
  • ZY[H] sodium Y zeolite
  • the method was the same as Method (vi) except that 1ml of SICl 4 and 14ml of CCl 4 were used in the first refux.
  • the method was the same as Method (vi) except that 10 grams of sodium Y zeolite (ZY[G]), 80ml of SiCl 4 and 100ml of ethanol were used.
  • Table XI reports the products resulting from the dealumination of sodium Y zeolites followed by treatment with various mixtures including SiCl 4 as a component.
  • the dealuminated zeolite is made by treatment of sodium Y zeolite with hydrochloric acid. Dealumination does not occur when the pH of the acid is greater than 2.30, while complete dealumination occurs at pH less than 0.46. It appears that four hydrogen atoms are required to remove one aluminium atom. This acid dealumination results in a structure which is less crystalline than the initial zeolite (due to accumulated defects In the structure ) and is not thermally stable. However, treatment with SiCl 4 -containing mixtures allows insertion of silicon into the zeolite matrix and gives a product of reasonable thermal stability.
  • the treatment with SiCl 4 was by three different methods.

Abstract

Procédé de modification de la structure d'une zéolite, consistant à traiter la zéolite avec une solution dans un solvant organique d'un composé d'un élément pouvant effectuer le remplacement structural de l'aluminium dans la structure, cet élément remplaçant l'aluminium étant sélectionné, par exemple, parmi le bore, l'étain, le silicium, le titane, le germanium, le gallium, le phosphore, le béryllium et le magnésium, de préférence sous la forme d'halogénures ou de composés organométalliques desdits éléments. Des composés représentatifs sont BCl3, BBr3, SnCl4, SnBr4, SnI4, SiCl4, SiI4, TiCl4, GeCl4, GaCl4, PCl5, BeCl2, MgCl2, et le biphénylbéryllium. Dans une forme préférée du procédé, on fait réagir la zéolite avec du tétrachlorure de silicium dans du tétrachlorure de carbone au reflux. Il est toutefois possible de réduire la durée de la réaction par l'utilisation d'un solvant, par exemple du tétraéthoxysilane, possédant une taille moléculaire qui l'empêche de pénétrer dans les canaux de la zéolite.Process for modifying the structure of a zeolite, comprising treating the zeolite with a solution in an organic solvent of a compound of an element capable of effecting the structural replacement of aluminum in the structure, this element replacing the aluminum being selected, for example, from boron, tin, silicon, titanium, germanium, gallium, phosphorus, beryllium and magnesium, preferably in the form of halides or organometallic compounds of said elements. Representative compounds are BCl3, BBr3, SnCl4, SnBr4, SnI4, SiCl4, SiI4, TiCl4, GeCl4, GaCl4, PCl5, BeCl2, MgCl2, and biphenylberyllium. In a preferred form of the process, the zeolite is reacted with silicon tetrachloride in carbon tetrachloride at reflux. It is however possible to reduce the reaction time by the use of a solvent, for example tetraethoxysilane, having a molecular size which prevents it from entering the channels of the zeolite.

Description

Modification of Zeolites
This invention relates to a process for the chemical modification of zeolite structures.
Zeilites are crystalline hydrated aluminium silicates which have the general chemical formula:
M2/nO.Al2O3. x SiO2. y H2O
where M is a cation of valency n and x is greater than or equal to 2.0. Structurally they have a porous framework based on an extended three-dimensional framework of SiO4 and AlO4 tetrahedra linked together through common oxygen atoms.
A large number of natural and synthetic zeilites are known but only a comparative few if these have founf application as catalysts in teh chemical industry. However, the important catalysts faujasite (in the form of the synthetic zeolites X and Y), mordenite and ZSM-5 (Trade Mark) are used in substantial quantity: for example, more than 100,000 tons per year in 1970 were consumed in petroleum cracking. It is synthetic faujasite (as zeolite Y) which is principally used for this purpose. However, as synthesised, the value of x in the above formula for zeolite Y is approximately 5.0 and the resulting framework is not sufficently stable to withstand the high temperatures (800ºC) involved in the regenerator unit of cracking plants where coke is burnt off. (By "coke" is meant the deposits of carbon and low hydrogen content hydrocarbons that build up in petroleum cracking). To improve the thermal stability of the zeolite, the SiO2/Al2O3 ratio has to be increased. Several methods have been proposed but, principally for reasons of cost, the preferred methods are based on the following chemical process:
NaY exchange calcine 500°C H-Y with NH4 under steam that is, the hydrogen (H+) form is made by calcination of the ammonium (NH exchanged form in the presence of steam at high temperatures. This results in some of the aluminium atoms leaving the framework and being deposited in the channel network as extra-framework aluminium. The vacancies are filled by atoms of silicon diffusing from other parts of the crystallites. Obviously the net result is the production of a partially crystalline material along with some amorphous material and the introduction of some mesopores into the system. The resulting material, however, is an excellent selective catalyst.
The other methods which can be used to increase the silicon to aluminium ratio are (a) extraction of aluminium by EDTA (ethylenediaminetetraacetic acid) (b) acid treatment and (c) use of silicon tetrachloride vapour. EP-A-82211 describes the use of an aqueous solution of a fluorosilicate to replace aluminium with silicon in the framework. The use of the SiCl, vapour, as described for example in EP-A-62123 and EP-A-72397, has some useful effects. The vacancies in the framework, produced by the extraction of aluminium, are healed by silicon atoms from the tetrachloride, and, the aluminium removed from the framework is converted to its volatile trichloride effecting removal from the system. However, problems associated with the vapour phase process are (a) the cost of the silicon tetrachloride, (b) the high temperature required, and, (c) the potential danger of collapse of the structure of the framework unless the temperature is strictly controlled. EP-A-210018 describes another process for the modification of zeolite framework structures which involves treatment of the zeolite with a molten salt medium which contains a reactive component which has a "radius ratio" of less than 0.6, the "radius ratio" being defined as the ratio of the crystal ionic radius of the central atom of the reactive component to that of the the oxygen anion 02-. The method is applicable to porous crystalline minerals which have pores large enough to sorb normal hexane. Examples of the components which have the required radius ratio are: the trichlorides of aluminium, boron, iron, phosphorus and gallium, and the tetrachlorides of titanium and tin, the Si4+ ion being also mentioned. The method may be used to insert aluminium into high silicon zeolite frameworks or otherwise alter the framework without substantial alteration of its structure.
An object of the present invention is to provide an improved method for the modification of zeolite framework structures.
According to the present invention there is provided a method for the modification of the framework structure of a zeolite comprising treating the zeolite with a solution in an organic solvent of a compound of an element capable of structural replacement of aluminium in the framework.
The compound is preferably a metal halide of the aluminium- replacing element, examples being: BCl3, BBr3, SnCl4, SnBr4, Snl4, SiCl4, Sil4, TiCl4, GeCl4, GaCl4,
PCle, BeCl2 AlCI3 and MgCl2. However, organometallic compounds of the selected element may also be suitable, for example, beryllium diphenyl.
The zeolite may be, for example, Erionite, Beta, ZSM-5, ZSM-11 (Trade Marks), Mordenite, Chabazite, and Offretite. The selection of the solvent is not critical. Solvents, and solvent mixtures, of small molecular size, such as carbon tetrachloride and ethanol, are suitable but the reaction may be accelerated by the use of a solvent of a molecular size which is too large to enter the channels of the zeolite, one particularly preferred solvent for this purpose being tetraethoxysilane [C2H5O)4Sil.
The temperature of the treatment is not of critical importance but would normally be carried out at the reflux temperature of the solvent in order to minimise the treatment time.
The method of the invention may include a pretreatment step in which the zeolite is treated with acid to effect a desired degree of dealumination, prior to treatment with the solvent solution compound of the aluminium-replacing element. Since the degree of dealumination with acid is restricted only by the need to maintain the integrity of the zeolitic structure, the use of the acid pretreatment step enables the production of zeolites with very high silicon to aluminium ratios.
As well as increasing the thermal stability of the zeolite increase of the silicon to aluminium ratio improves the Bronsted activity of the OH groups which remain in the dealuminated framework.
The invention will now be described, by way of illustration, in the following Examples.
EXAMPLE 1
About 1 gram of NaY zeolite was calcined in a muffle furnace at 600ºC for a few hours. The zeolite was then cooled to 80-100ºC in a desiccator and 25ml of carbon tetrachloride (CCl4) was then added with continuous stirring to form a slurry. various amounts (0.10 to 0.77ml) of silicon tetrachloride (SiCl4) were added to several separate samples of the slurry which were then refluxed at a fixed temperature (58-59°C; 76-77°C) for a period of three hours. The final slurry was then centrifuged to separate the solid and liquid phases. Three successive portions of CCl4 (approximately 15ml) followed by three successive portions of ethanol (approximately 15ml) were employed during the solid/liquid separation stage. The product was dried on a water bath and treated with sodium chloride solution (1-5M) repeatedly to convert the zeolite to the pure sodium form. The product was then well washed with distilled deionised water (boiled and cooled out of contact with air) until free of chloride, dried at 100ºC and calcined at 600ºC for one hour.
The calcined zeolite was allowed to cool and treated with sodium chloride solution (1-5M at pH 8-9) repeatedly. The final product was well washed until chloride-free, filtered and dried at 100°C.
Analysis of the dealuminated samples was as follows:
(a) Dealuminated samples were calcined at 600ºC to obtain the dry weight and the residues dissolved to determine the aluminium content by EDTA titration.
(b) Sodium was determined by 22Na tracer method.
(c) Silicon was estimated by difference.
(d) Collapse temperature was determined by differential thermal analysis using a Du Pont 990 Thermal Analyser (in nitrogen).
The results are reported in Table I below.
* based on total Al present - 192 Al sites in unit cell (u.c.)
EXAMPLE 2
The same procedure as described in Example 1 was used except that 15ml of CCl4 and 0.3ml SiCl4 were refluxed with NaY zeolite with different water content at 59°C for 20 minutes. The results are given in Table II below.
EXAMPLE 3
Using the procedure described in Example 1 above, 20ml of
CCl4 and 10ml SiCl4 were refluxed with zeolites with different cationic forms at 58-60ºC for one hour.
The results are given in Table III below.
* zeolite Y calcined at 600°C ** 16 Na+ in small cages.
EXAMPLE 4
Using the same procedure as is described in Example 1, 30ml of SiCl4 was refluxed with NaY zeolite at 57º C and samples were withdrawn after 30, 60 and 90 minutes.
The results are reported in Table IV below.
Samples S0.50/57, S1.0/57 and S1.5/57 were mixed with 15ml SiCl4 and refluxed at 57ºC for 30 minutes to produce sample SS0.5/1.5.
EXAMPLE 5
Using the procedure described in Example 1, 15ml of SiCl4 were refluxed with zeolite produced from Example 1 (Sample Nos. CS0.10/58 + CS0.20/58 + CS0.10/76) at 57°C for 30 minutes. Four cycles were carried out.
The results are given in Table V below.
Table VI reports the results of infra-red characterisation studies and Table VII the results of X-ray diffraction studies, confirming the increase of the Si/Al ratio of the zeolite Y framework.
EXAMPLE 6
Table VIII below reports the products (in sodium form) resulting from the dealumination of sodium Y zeolites by SiCl4 in the solvent tetraethoxysilane [(C2H5O)4Si] (TES). The methods used were as follows:
Method A (Sample STES NaY)
About 1 gram of sodium Y zeolite [ZY(H)] was calcined at 600ºC and allowed to cool in a desiccator. 25ml of TES were added to the zeolite followed by 1ml of SiCl4. The mixture was refluxed for one hour.
Method B (Sample STES DY)
The method was as described under Method A above but sodium Y zeolite [ZY(D)] was used.
Method C (Samples STES DY 0.5; STES DYl; STES DY2 and STES DY18B)
About 19 grams of sodium If zeolite (ZY[D]) was calcined at 600ºC and allowed to cool in a desiccator. 45 ml of SiCl4 were added to the zeolite with constant stirring for 1-2 minutes follwed by 70ml of TES. The resultant slurry was refluxed for 18 hours. Zeolite slurry samples were withdrawn after 30 minutes, one hour, two hour and 18 hour intervals.
From the results reported in Table VIII below, particularly the results of Method C, it can be seen that dealumination is substantially complete within the first 30 minutes of reaction time. These samples all showed very good crystallinity; as good as the starting sodium Y zeolite.
EXAMPLE 7
Table IX reports the product (in sodium form) resulting from the dealumination of sodium Y zeolite by a SiCl4/CCl4/
C2H5OH solvent mixture.
About one gram of sodium Y zeolite [56A1/u.c., ZY(H)] was calcined at 600ºC for a few hours and allowed to cool in a desiccator. 12.5ml of CCl4 were added to the zeolite followed by 1ml of SiCl4. The mixture was refluxed at 56ºC for 30 minutes when 12.5ml of ethanol were Introduced. Hefluxing at 63ºC was continued for a further 30 minutes.
EXAMPLE 8
Table X below reports the products (in sodium form) resulting from the dealumination of sodium Y zeolites by SiCl4/ethanol solutions.
EXAMPLE 9
Method (i) (Samples SEtDY 0.5 and SEtDY1)
About 5 grams of the sodium form Y zeolite (approximately 56
Al/u.c.; ZY[D]) was calcined at 600ºC for a few hours and allowed to cool in a desiccator. 20 ml of SiCl4 were added to the zeolite and stirred for 5 minutes. Five successive portions of CCl4 of approximately 20ml were added to the zeolite slurry and the CCl4 was discarded after centrifuging the slurry. 80ml of ethanol were then added and refluxed for one hour. Approximately 50ml of the slurry was withdrawn after 30 minutes and the rest after one hour.
Method (ii) (Samples S0.5EtDY0.5 and S0.5EtDY 1)
The method was the same as Method (i) above except that the contact time of the zeolite and SiCl4 was increased to 15 minutes.
Method (iii) (Sample 5S5EtDY)
About 5 grams of sodium Y zeolite (ZY[D]) was calcined at 600°C for a few hours and cooled in a desiccator. 5ml of
SiCl4 were added to the zeolite and stirred for 5 minutes.
50ml of ethanol were then added to the slurry and refluxed for one hour.
Method (iv) (Sample lOSlOEtDY)
The method was the same as Method (iii) above except that
10ml of SiCl4 were used and the SiCl4-zeolite contact time was increased to 10 minutes.
Method (v) (Sample 1CSEt5NaY)
About one gram of sodium Y zeolite (ZY[H] ) was calcined at 600ºC for a few hours and allowed to cool in a desiccator.
About 1ml of SiCl4 was added to the zeolite and stirred for 5 minutes. 25ml of ethanol were then added to the slurry and refluxed for one hour.
Method (vi) (Sample SEtNaY)
About one gram of sodium Y zeolite (ZY[H] ) was calcined at
600ºC for a few hours and allowed to cool in a desiccator. About 15ml of SiCl4 were added to the zeolite and refluxed for 30 minutes. The zeolite slurry was then centrifiged to separate the solid and liquid phases. The zeolite was washed with three successive 10ml portions of CCl4. About 25ml of ethanol were added to the zeolite and refluxed for 15 minutes. Method (vii) (Sample 1SEtNaY)
The method was the same as Method (vi) except that 1ml of SICl4 and 14ml of CCl4 were used in the first refux.
Method (viii) (Sample SEtG)
The method was the same as Method (vi) except that 10 grams of sodium Y zeolite (ZY[G]), 80ml of SiCl4 and 100ml of ethanol were used.
EXAMPLE 10
Table XI below reports the products resulting from the dealumination of sodium Y zeolites followed by treatment with various mixtures including SiCl4 as a component.
The dealuminated zeolite is made by treatment of sodium Y zeolite with hydrochloric acid. Dealumination does not occur when the pH of the acid is greater than 2.30, while complete dealumination occurs at pH less than 0.46. It appears that four hydrogen atoms are required to remove one aluminium atom. This acid dealumination results in a structure which is less crystalline than the initial zeolite (due to accumulated defects In the structure ) and is not thermally stable. However, treatment with SiCl4-containing mixtures allows insertion of silicon into the zeolite matrix and gives a product of reasonable thermal stability.
The treatment with SiCl4 was by three different methods.
Method I - CSH SEBIES
About 0.5 gram of dealuminated Y zeolite (by HCl treatment) in sodium form was dehydrated in an oven at 100ºC for a few hours and then allowed to cool in a desiccator. The zeolite was then mixed with 15ml of CCl4 followed by 0.30ml of SiCl4 and refluxed for 30 minutes.
Method II - HCS SEBIES
The procedure was the same as Method I above except that
10ml of CCl4 and 5ml of SICl4 were used.
Method III - STES SEBIES
About one gram of dealuminated Y zeolite (by HCl treatment) in sodium form (as used in Methods I and II above) was dehydated in an oven at two temperatures (120ºC and 300ºC) for a few hours and then allowed to cool In a desiccator. The zeolite was then mixed with 3ml of SiCl4 with constant stirring for 5 minutes. 20ml of TES was added to the slurry and refluxed for one hour. The highly dealuminated samples (those with fewer than 32 atoms of aluminium per unit cell) had poor crystallinity.

Claims

1. A method for the modification of the framework structure of a zeolite, comprising treating the zeolite with a solution in an organic solvent of a compound of an element capable of structural replacement of aluminium in the framework.
2. A method as claimed in claim 1, in which the aluminium-replacing element is selected from boron, tin, silicon, titanium, germanium, gallium, phosphorus, beryllium aluminium and magnesium.
3. A method as claimed in claim 1 or claim 2, in which the said compound is selected from the halides of the aluminium- replacing element.
4. A method as claimed in claim 3, in which the halide is selected from BCl3 , BBr3 , SnCl4 , SnBr4 , Snl4 ,
SiCl4 , Sil4, TiCl4 , GeCl4 , GaCl4 , PCI5, BeCl2
AlCl3 and MgCl2.
5. A method as claimed in claim 4, in which the halide is silicon tetrachloride.
6. A method as claimed in claim 1 or claim 2, in which the said compound Is an organometallic compound.
7. A method as claimed in claim 6, In which the organometallic compound is beryllium diphenyl.
8. A method as claimed in any preceding claim, in which the organic solvent is carbon tetrachloride or ethanol or a mixture thereof.
9. A method as claimed in any of claims 1 to 7, in which the solvent is an organic liquid having molecules which are too large to enter the channels of the zeolite.
10. A method as claimed in claim 9, in which the solvent is tetraethoxysilane.
11. A method as claimed in any preceding claim, in which the zeolite Is selected from Erionite, Beta, ZSM-5, ZSM-11, Mbrdenite, Chabazite, and Offretite.
12. A method as claimed in any preceding claim, in which the treatment carried out under solvent reflux conditions.
13. A method as claimed in any preceding claim, in which the zeolite is pretreated with acid to remove aluminium therefrom.
14. A method of thermally cracking petrolueum hydrocarbons characterised in that said cracking is conducted in the presence of a modified ziolite, said zeolite being the product of a process as claimed in any ot the preceding claims.
EP19870905261 1986-08-22 1987-08-21 Modification of zeolites Withdrawn EP0319538A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB868620434A GB8620434D0 (en) 1986-08-22 1986-08-22 Zeolites
GB8620434 1986-08-22
GB878709566A GB8709566D0 (en) 1987-04-23 1987-04-23 Zeolites
GB8709566 1987-04-23

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EP0319538A1 true EP0319538A1 (en) 1989-06-14

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