AU601803B2 - Dealumination of aluminosilicate zeolites - Google Patents
Dealumination of aluminosilicate zeolites Download PDFInfo
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- AU601803B2 AU601803B2 AU10320/88A AU1032088A AU601803B2 AU 601803 B2 AU601803 B2 AU 601803B2 AU 10320/88 A AU10320/88 A AU 10320/88A AU 1032088 A AU1032088 A AU 1032088A AU 601803 B2 AU601803 B2 AU 601803B2
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- AU
- Australia
- Prior art keywords
- zeolite
- fluoride
- aluminum
- water
- ammonium
- 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.)
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/21—Faujasite, e.g. X, Y, CZS-3, ECR-4, Z-14HS, VHP-R
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
ji
AUSTRALIA
Patents Act 6&i 803 CUMPLEM SPECIFICATICN
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: a S APPLICANT'S REFERENCE: F-4216 Name(s) of Applicant(s): Mobil Oil Corporation Address(es) of Applicant(s): 150 East 42nd Street, New York, New York, UNITED STATES OF AMERICA.
Address for Service is: 4, PHILLIPS 0RPONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: DEALUwIIATICH OF ALUJ1WILICATE ZEOLITES Our Ref 80990 POF Code: 1462/1462 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6003q/1 1 1 DEALUMINATION OF ALUMINOSILICATE ZEOLITES This invention relates to a method of treating an aluminosilicate zeolite to remove tetrahedral aluminum therefrom.
A vast number of naturally-occurring and synthetic aluminosilicate zeolites are known. Among the more commercially important zeolites are zeolite Y S. Patent No. 3,130,007), zeolite beta Patent No. 3,338,069, reissued as RE 28341) and ZSM-5 (U.S.
Patent No. 3,702,886). These zeolites find application in a wide variety of commerical processes, particularly hydrocarbon conversion processes.
The silica-to-alumina ratio of a zeolite is often variable; for example, zeolite Y can be synthesized with a silica-to-alumina ratio ranging from 3 to 6. In some zeolites, for example ZSM-5, the upper limit of silica-to-alumina ratio is virtually unbounded. Thus U.S. Patent No. 3,941,871 discloses a crystalline zeolite essentially free of aluminum and exhibiting an x-ray diffraction pattern characteristic of ZSM-5. Similiarly, U.S. Patent Nos. 4,061,724, 4,073,865 and 4,104,294 describe microporous crystalline silicates or organosilicates in which the aluminum content is at impurity levels.
In addition, it is possible to vary the silica-to-alumina ratio of a naturally-occurring or already-synthesized zeolite by chemical treatment. In particular, in view of the relative instability of aluminum in,the crystal lattice of a zeolite, a number of methods have been proposed for removing framework aluminum from a zeolite.
In U.S. Patent No. 4,503,023 a method is disclosed for S replacing framework aluminum in an aluminosilicate zeolite having a silica-to-alumina ratio of at least 3 with framework silicon by r C contacting the zeolite with an aqueous solution of a fluorosilicate salt having a pH of 3 to 7 and in an amount such as to provide at least 0.075 moles of fluorosilicate salt per 100 grams of the zeolite.
However, although this method has proved effective in raising the silica-to-alumina ratio of zeolites, such as zeolite Y, the treated h *1
LI
I I F-4216 zeolite is found to contain impurities of insoluble metal fluorides, particularly AlF 3 which are not readily removed from the zeolite by simple washing and which can adversely effect the catalytic properties of the zeolite.
However, although this method has proved effective in raising the silica-to-alumina ratio of zeolites, such as zeolite Y, the treated zeolite is found to contain impurities of insoluble metal fluorides, particularly AIF 3 which are not readily removed from the zeolite by simple washing and which can adversely effect the catalytic properties of the zeolite.
In an attempt to overcome this problem, U.S. Patent No.
4,597,956 discloses a method of treating a zeolite which contains insoluble fluoride with an aqueous solution of a soluble aluminum compound, such as aluminum sulfate, nitrate, chloride and acetate such that th3 mole ratio of fluoride anion to aluminum cation is reduced to a value less than 3, preferably 2-2.5.
According to the invention there is provided a method of removing tetrahedral aluminum from an aluminosilicate zeolite 2C containing at least 50 ppm of tetrahedral aluminum, comprising the steps of: contacting the zeolite with an aqueous solution containing a
C
fluorocompound of an element different from aluminum capable of reacting with tetrahedral aluminum in said zeolite to remove said 120c tetrahedral aluminum from the zeolite lattice and produce a tie 0 0 o water-insoluble aluminum fluoride; and contacting the zeolite with an aqueous solution containing a water-soluble fluoride MFn where M has a valence of n and is selected from the group consisting of hydrogen, ammonium and a metal (iAcs verskoA) of Group I or Group II of the Periodic Table kcapable of reacting with said water-insoluble aluminum fluoride to produce a water-soluble species.
In the above method, where the insoluble fluoride is aluminum fluoride, AlF 3 it is believed that the fluoride MF n reacts with -the aluminum to produce the water-soluble complex fluoraluminate, k~ i F-4216
M
3
AIF
6 Thus, contrary to the teaching of U.S. Patent No.
4,597,956, the treatment method of the invention increases the mole ratio of fluoride anion to aluminum cation to a value above 3 and preferably to 4-6.
In one embodiment of the present invention, the contacting step is effected with an aqueous solution containing said fluorocompound of said element different from aluminum and said water-soluble fluoride MF n whereby steps and are conducted substantially simultaneously.
In an alternative embodiment step is conducted separately from and after step The method of the invention can be used to effect aluminum removal from any aluminosilicate zeolite containing at least 50 ppm of framework Al atoms, although preferred zeolites are zeolite Y and zeolites having a Constraint Index of 1-12 when tested at some temperature in the range of 290-538 0 C (see U.S. Patent No. 4,016,218), particularly zeolite beta and Aluminum removal is effected by treating the zeolite with an aqueous medium containing a fluorocompound of an element different from aluminum. The fluorocompound is chosen so as to be capable of reacting with tetrahedral aluminum in the zeolite, generally by initial hydrolysis to fluoride ions which then extract aluminum from the framework as insoluble AlF 3 and further is chosen so that said t different element is then capable of entering the vacant sites resulting from the aluminum removal. Known suitable fluorocompounds S include ammonium fluorosilicate, (NH 4 2 SiF 6 (to substitute aluminum with silicon), and ammonium fluorotitanate, (NH 4 2 TiF 6 (to substitute aluminum with titanium). Treatment is conveniently effected in known manner and typically at a temperature of 20-1250C for 0.2 to 300 hours or more preferably at a temperature of 50-100 0
C
for 4 to 24 hours. Preferably the treatment soulution contains at least 0.0075 moles of the fluorocompound of the replacement element per hundred grams of the anhydrous zeolite and has a pH less than or equal to 7 or more preferably a pH of 3 to 7. In a particularly it it niri I u-.
F-4216
I
F'
preferred embodiment, zeolite Y having a silica-to-alumina molor ratio not greater than 7 and preferably 3 to 6, is treated as described in U.S. Patent No. 4,503.023 with an aqueous solution of a fluorosilicate, preferably ammonium fluorosilicate, having a pH of to 7 at a temperature of 20 0 C to 95 0 C to produce the zeolite designated in U.S. Patent No. 4,503,023 as LZ-210.
During or after the aluminum removal step, the zeolite is contacted with an aqueous solution of a water-soluble fluoride MF n where M has a valence of n and is selected from the group consisting of hydrogen, ammonium and a metal of Group I or Group II of the Periodic Table capable of reacting in said aqueous solution with insoluble aluminum fluoride generated by the aluminum substitution to produce a water-soluble species. Preferably, the fluoride MF n is ammonium fluoride.
15 Where the MF n treatment is effected simultaneously with the dealumination step, the zeolite is contacted with a single aqueous solution containing said fluorocompound and said fluoride MF preferably such that the solution is 0.001 to 3N is said fluoride.
The presence of the fluoride MF n in the treatment solution is found to inhibit the formation of water-insoluble aluminum fluoride during the aluminum substitution so that simple water washing of the treated zeolite is sufficient to effect substantially complete removal of fluoride impurities in the zeolite. It is also found that the S presence of the fluoride MF n in the fluorocompound treatment solution produces a dealuminized zeolite which is more stable to cracking conditions than a zeolite which has undergone aluminum removal using a treatement solution free of fluoride MF Where the MF treatment is effected after the dealumination step, the zeolite containing insuluble fluoride AlF 3 is treated with an aqueous solution of water-soluble fluoride MF under conditions such that the fluoride MF reacts with the insoluble fluoride to produce a water-soluble species, typically
M
3 A1F 6 without any loss of structural integrity of the zeolite.
Preferably the concentration of the solution is 0.001 to 5N in the 1 r--u-uir i I II -~L~Bn;_~PBIIIP~(* lr-CII~ m~ F-4216 fluoride MFn and the treatment is conducted at 20 to 100C for 0.005 to 20 hours.
The invention will now be more particularly described with references to the Examples and the accompanying drawing which is a graph comparing the variation in hexane cracking activity over time for untreated zeolite beta, zeolite beta treated with aqueous ammonium fluorosilicate solution in accordance with Example 1 and (c) zeolite beta treated with aqueous ammcnium silicate/ammonium fluoride solution in accordance with Example 2.
Preferably the concentration of the solution is 0.001 to 5N in the fluoride MFn and the treatment is conducted at 20 to 100 0 C for 0.005 to 20 hours.
The invention will now be more particularly described with references to the Examples and the accompanying drawing, which is a graph comparing the variation in hexane cracking activity over time for untreated zeolite beta, zeolite beta treated with aqueous ammonium fluorosilicate solution in accordance with Example 1 and (c) zeolite beta treated with aqueous ammonium silicate/ammonium fluoride solution in accordance with Example 2.
I
ai- EXAMPLE 1 3.6 g of a silica extrudate of zeolite beta in the hydrogen form with Se silica (65% by wt. zeolite/35% by wt. silica) were ion exchanged with an aqueous solution of 100 ml of IN NH 4 NO3 for 18 hours, whereafter the exchanged catalyst was washed with double-deionized water. The catalyst was then slurried with 45 ml of deionized water and to the slurry were added 35 ml of an aqueous solution containing 0.25 g of ammonium fluorosilicate. The reaction mixture was digested at 80 0 C for 5 hours and the resultant product was washed with double-deionized water, dried at 1300C and designated product A.
The composition and hexane cracking activity at 538 0 C for product A were measured and are listed in Table 1, which also includes corresponding data for the initial catalyst.
U
F-4216 -6- EXAMPLE 2 g of the same zeolite beta extrudate used in Example 1 were exchanged with 200 ml of IN NH 4 NO3 for 24 hours and the exchanged catalyst was washed with double-deionized water. The resultant catalyst was slurried with 90 ml of deionized water and to this slurry were added 5 ml of an aqueous solution containing 0.75 g of ammonium fluorosilicate and 30 ml of 0.2 M ammonium fluoride solution. The product was digested at 80 0 C for 5.75 hours and then washed with double-deionized water, dried at 130 0 C and designated product B. Table 1 also lists the composition and hexane cracking S activity at 538 0 C for product B.
TABLE 1 Starting Example 1 Example 2 Zeolite Product A Product B Composition, wt. Si 2 94.78 96.99 97.1 A 0 2.34 1.1 1.29 S23 F -0.11 0.04 Hexane Cracking Activity at 538 0 C 130 60 From Table 1 it will be seen that the retained fluoride content and the hexane cracking activity of the zeolite treated according to the invention were significantly increased as compared with the zeolite treated with ammonium fluorosilicate alone.
The hexane cracking activities of products A and B and the -cn ccia F-4216 initial catalyst were also measured as a function of time and the results are illustrated graphically in the accompanying drawing. From this drawing it will be seen that product B was more stable than product A in that the hexane cracking activity of product B increased slightly during the 50 minute test, whereas the activity of product A decreased slightly.
EXAMPLE 3 200 g of ammonium zeolite beta were slurried in a solution containing 500 ml double deionized water, 800 ml 0.2M ammonium fluoride, and 1400 ml 0.2M ammonium fluorosilicate. Following ammonium zeolite addition, the slurry was mixed at room temperature for one hour and then digested for 5.5 hrs. at 80 0 C and filtered. The filter cake was thoroughly washed with double deionized warm water 0 C) and dried at 130°C. Table 2 lists the composition, hexane cracking activity and crystallinity for product and starting zeolite.
EXAMPLE 4 217 g of the same zeolite beta as in Example 3 were slurried in a solution containing 500 ml double-deionized water and 820 ml 0.2 ammonium fluoride. The resulting slurry was mixed and heated at 20 80 0 C. 1400 ml of 0.2M ammonium fluorosilicate solution were added to the slurry in 1 ml increments at a rate of 15 ml per min. Following ammonium fluorosilicate addition, the slurry was digested for 2.5 hrs.
at 80 0 C and filtered. The filter cake was thoroughly washed with double deionized warm water (550C) and dried at 130 0 C. Table 2 also lists the composition, hexane cracking activity and crystallinity for the resulting product.
I~j
LI
1 i- F-4216 TABLE 2 Wt.% Sio 2 Al 2 0 3 Untreated Zeolite 75.23 3.53 11 Example 3 88.68 1.97 61 Example 4 83.30 2.11 74 F (ppm) t Crystallinity, 100 84 84 Hexane Cracking 793 153 187 Activity EXAMPLE A 10g sample of zeolite Y (Si0 2 /A1 2 0 3 6) in the ammonium form was slurried with 500 ml of 3.4 M ammonium acetate solution 750C. An aqueous solution prepared by dissolving 3.1533g of ammonium hexofluorosilicate in 250 ml of water was added drop-wise to the slurry over a period of 2 h. The mixture was allowed to digest overnight (18 h) at 75 0 C and the resultant product was filtered and washed with 1500 ml of water. The washed material was vacuum dried at room temperature for 1 h and then dried in an oven at 120 0 C for 1 h.
The resultant product was divided into two samples, A and B, each weighing 0.7 g. Sample A was washed with 250 ml of water while sample B was washed with 250 ml of 0.01 M ammonium fluoride solution, the temperature of both wash media being 25 0 C and the contact time being 0.5h. Both washed samples were dried at 120 0 C and analyzed for fluoride content. The water-washed sample A contained 0.60% by weight of fluoride, whereas the ammonium fluoride-washed sample B contained only 0.32% by weight of fluoride.
1
Claims (11)
1. A method of removing tetrahedral aluminum from an aluminosilicate zeolite containing at least 50 ppm of tetrahedral aluminum, comprising the steps of: contacting the zeolite with an aqueous solution containing a fluorocompound of an element different from aluminum capable of reacting with tetrahedral aluminum in said zeolite to remove said tetrahedral aluminum from the zeolite lattice and produce a water-insoluble aluminum fluoride; and contacting the zeolite with an aqueous solution containing a water-soluble fluoride MF where M has a valence of n and is selected from hydrogen, ammonium and a metal of Group I or Group II of the Periodic Table capable of reacting with insoluble aluminum fluuoride to produce a water-soluble species.
2. The method of Claim 1 wherein the zeolite is zeolite Y.
3. The method of Claim 1 wherein the zeolite is zeolite beta.
4. The method of Claim 1 wherein the zeolite is
5. The method of any preceding Claim wherein said 20 fluorocompound is selected from a fluorosilicate and a flurotitanate.
6. The method of any preceding Claim wherein said fluoride MF is ammonium fluoride.
7. The method of any preceding Claim wherein steps and are conducted substantially simultaneously using an aqueous solution containing said fluorocompound and said fluoride MF
8. The method of Claim 6 wherein steps and are conducted at 20-125 0 C for 0.2-300 hours. T ~I~PU~I RII1P LIC I*SU i I~ 19
9. solution 0 001-3N The method of Claim 6 wherein said aqueous containing a water-soluble fluoride MF is in said fluoride MF The method of any one of Claim 1 to 5 wherein step is conducted prior to step
11. The method solution containing a to 5N in said fluoride to 1000 for 0.005 to of Claim 9 wherein water-soluble fluoride MF and step is 20 hours. said aqueous MF 0.001N n conducted at
12. A method substantially as hereinbefore described with reference to any one of the Examples. DATED: 4 July 1990 PHILLIPS ORMONDE FITZPATRICK Attorneys for: MOBIL OIL CORPORATION Qc~dB i-ii a EJD
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US015615 | 1987-02-17 | ||
US07/015,615 US4784684A (en) | 1984-08-08 | 1987-02-17 | Herbicidal pyridinesulfonamides |
Publications (2)
Publication Number | Publication Date |
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AU1032088A AU1032088A (en) | 1988-08-18 |
AU601803B2 true AU601803B2 (en) | 1990-09-20 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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AU10320/88A Ceased AU601803B2 (en) | 1987-02-17 | 1988-01-15 | Dealumination of aluminosilicate zeolites |
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AU (1) | AU601803B2 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0244056A2 (en) * | 1986-03-05 | 1987-11-04 | Mobil Oil Corporation | Dealumination of zeolites |
AU574428B2 (en) * | 1983-08-15 | 1988-07-07 | Mobil Oil Corp. | Zeolite modification with boron trifluoride |
AU579865B2 (en) * | 1984-04-26 | 1988-12-15 | Union Carbide Corporation | Substituted aluminosilicate compositions and process for preparing same |
-
1988
- 1988-01-15 AU AU10320/88A patent/AU601803B2/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU574428B2 (en) * | 1983-08-15 | 1988-07-07 | Mobil Oil Corp. | Zeolite modification with boron trifluoride |
AU579865B2 (en) * | 1984-04-26 | 1988-12-15 | Union Carbide Corporation | Substituted aluminosilicate compositions and process for preparing same |
EP0244056A2 (en) * | 1986-03-05 | 1987-11-04 | Mobil Oil Corporation | Dealumination of zeolites |
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Publication number | Publication date |
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AU1032088A (en) | 1988-08-18 |
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