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WO1989003367A1 - Procede de preparation d'une zeolite y modifiee - Google Patents

Procede de preparation d'une zeolite y modifiee Download PDF

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Publication number
WO1989003367A1
WO1989003367A1 PCT/SE1987/000464 SE8700464W WO8903367A1 WO 1989003367 A1 WO1989003367 A1 WO 1989003367A1 SE 8700464 W SE8700464 W SE 8700464W WO 8903367 A1 WO8903367 A1 WO 8903367A1
Authority
WO
WIPO (PCT)
Prior art keywords
ion
exchange
aluminum
calcination
carried out
Prior art date
Application number
PCT/SE1987/000464
Other languages
English (en)
Inventor
Olof Magnus Linsten
Arne Öisten FRESTAD
Original Assignee
Eka Nobel Ab
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
Application filed by Eka Nobel Ab filed Critical Eka Nobel Ab
Priority to PCT/SE1987/000464 priority Critical patent/WO1989003367A1/fr
Priority to EP19870907628 priority patent/EP0339026A1/fr
Publication of WO1989003367A1 publication Critical patent/WO1989003367A1/fr

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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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite

Definitions

  • the present invention relates to a process for preparing a modified zeolite Y having increased sta ⁇ bility and preferably also a small zeolite unit cell size.
  • zeolites, int. al. for catalysts for the processing of petroleum, especially for the production of so-called middistillates
  • an increased stability and, in particular, a small unit cell size or dimension a improve the per- formance of the catalyst (compare for example US-A- 4,419,271).
  • it has been endeavoured in different ways to increase the stability and, in particular, to reduce the unit cell size from the one obtained upon synthesizing (usually a 24.63-24.70 A) to as low a value as possible.
  • GB-A-2,085,861 discloses how zeolite NaY can be modified by a combi ⁇ nation of ammonium and aluminum ion-exchange steps. It appears that this treatment is capable of increasing the catalyst activity and reducing the unit cell size to 24.45-24.52 A. However, it was found that this pro ⁇ duction process gives a low residual ion-exchange degree in respect of the aluminum ions.
  • GB-A-2,014,970 discloses an ultrahydrophobic zeolite
  • EP-B-0,028,938 discloses the use of such a modified zeolite for selective conversion of hydrocarbons boiling above 371°C into midbarrel fuel products having a dis ⁇ tillation range of 149-371°C.
  • GB-A-2,114,594 describes the selective production of hydrocarbon middistillates by using int. al. modified zeolite Y which has been calcined in steam at high temperature and has a unit cell size in the range 24.36-24.58 A, especially below 24.40 A.
  • the present invention is based upon the insight that an increase in stability is obtainable by effecting calcination in steam (water vapour) at 400-900°C after the ion-exchange steps, and that calcination at tem ⁇ peratures lower than 500°C, especially 400-450°C, merely provides a stabilisation, whereas calcination at 500-900°C also provides a further reduction of the unit cell size if, in addition to carrying out the ammonium and aluminum ion-exchange steps, the aluminum ion-exchange step is both preceded by ammonium ion-exchange and calcination steps and succeeded by a calcination step in an atmos ⁇ phere saturated or substantially saturated with water vapour (steam) at 500-900°C.
  • the invention also makes it possible to reduce the unit cell size to values below 24.20 A, which is remarkable.
  • the last calcination can be carried out at a low temperature of 400-500°C, preferably 400-450°C.
  • the calcination period perferably is 0.25-5 hours, the shorter periods being useful for the higher temperatures.
  • a calcination period below 0.25 hours gives an inferior effect, and calcination periods above 5 hours give no notably in ⁇ creased fixation effect.
  • the- last calcination must be carried out at temperatures of at least 500°C, in which case the calcination period may be the same, i.e. 0.25-5 hours.
  • the preferred calcination periods are periods of at least 45 min.
  • the invention is illustrated in the following
  • zeolite NaY was produced in con ⁇ ventional matter from water, alumina, silica and sodium hydroxide.
  • the resulting NaY zeolite had a SiO ⁇ /Al ⁇ O- ⁇ molar ratio of 5.0 corresponding to 13.4% by weight Na_0.
  • the zeolite utilised as starting material was then ion-exchanged with a 10% ammonium sulphate solution to 2.8% by weight Na personally0 and then washed with deionised water until the washing water was- sulphate-free.
  • the zeolite was then dried at 100°C to a total solids content of 80-90%, whereupon the dried zeolite was calcined in an atmosphere saturated with steam (water vapour) at 600°C for 2 hours when the unit cell size had decreased to 24.52 A.
  • the next treatment step comprised ion-exchange with ammonium sulphate and washing in the same manner as before to reduce the a ⁇ O content to below 0.25% by weight, whereupon the zeolite thus treated was exposed to ion-exchange with an aluminum sulphate solution (concentration 0.1-8%, typically 5%) until the (NH. ⁇ O content of the zeolite had been reduced from.3.0-4.5 to below 1.5% by weight.
  • the ion-exchange had been performed with an aluminum sulphate solution having a concentration of 8% by weight.
  • the amount of Al in the solution per mole of ion-exchange sites in the zeolite was 8 moles.
  • Table 2 shows a comparison between two zeolites produced in accordance with the invention, one of which had been aluminum ion-exchanged and calcined at 650°C prior to the aluminum ion-exchange (Fig. 6), whereas the starting material for the other zeolite consisted of the conventional zeolite USY produced in conventional manner in accordance with the above and subjected, after the final drying step, to aluminum ion-exchange followed by calcination in an atmosphere saturated with steam and having the temperature 650°C (Fig. 7). It appears from Table 2 that the same results are obtained regardless of whether or not ammonium ion-exchange is carried out between the calcination in a steam atmosphere and the aluminum ion-exchange. TABLE 2
  • Example 1 As starting material, the same zeolite NaY as in Example 1, above, was used, and this starting material was treated in accordance with step (a) by three ion- exchange steps, each lasting 30 min at 60-80°C with an ammonium sulphate solution containing 10% by weight ammonium sulphate. After this ion-exchange the zeolite contained 3.2% by weight Na 2 0. Calcination was then carried out at 650°C for 3 hours to produce a calcined product. The product was then treated exactly in accordance with steps (b) and (c) in Example 1 of GB-A-2,085,861, i.e.
  • step (b) the product was first treated with a 0.05 M aluminum sulphate solution for 45 min at pH 3.3, followed by two ion-exchange treat ⁇ ments with diluted ammonium sulphate solution.
  • the ammonium sulphate solution contained 10% by weight ammonium sulphate and was utilised for each treatment during 30 min at the temperature 60-80°C.
  • the treatment schedule thus corresponds to the schedule according to Fig. 4 in the accompanying drawings.
  • a further batch of the starting material was treated in accordance with step (a), but then' only two ammonium ion-treatments were carried out, each lasting 30 min at 60-80°C with the same diluted ammonium sulphate solution.
  • the resulting reference sample of the product contained 0.42% by weight a 2 0 and had a unit cell size of 24.52 A and a Si0 2 /Al 2 C molar ratio of 5.0.
  • This treatment schedule corresponds essentially to the schedule according to Fig. 3 in the accompanying drawings.
  • Table 4 The properties measured for the different products are indicated in Table 4 which also contains values taken from Example 1 in GB-A-2,085,861.
  • Table 5 indicates the Al 3+ ion-exchange degree after steps (b) and (c).
  • the ion exchange degree has been calculated on the assumption that all available ion-exchange sites have been occupied by ammonium and sodium ions in the reference sample, and that only the aluminum and sodium ions have been affected by the ammonium ion-exchanges under steps
  • Example 1 was repeated, except that the final calcination in steam was carried out at 400-450°C for 45 min in making the product according to the invention, i.e. production was carried out according to the schedule of Fig. 9.
  • the conventional comparison zeolite USY was subjected to the same steam calcination and to one ammonium ion-exchange for 30 min at 60-80°C with an ammonium sulphate solution containing 10% by weight ammonium sulphate. The results are shown in Table 6.
  • ammonium sulphate and aluminum sulphate - have been used in the ion-exchange steps . It will be appreciated by those skilled in the art that other salt forms may also be used, for example chlorides and nitrates .

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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)
  • Catalysts (AREA)

Abstract

On produit une zéolite Y comprenant des ions d'aluminium obtenus et fixés par échange ionique en soumettant de la zéolite NaY à une série d'étapes de traitement comprenant entre autres un échange ionique d'ammonium et une calcination. Afin d'obtenir et de fixer les ions d'aluminium, on effectue une opération d'échange ionique d'aluminium suivie d'une autre calcination dans une atmosphère de vapeur d'eau saturée ou pratiquement saturée à une température de 400 à 900°C. Si la grandeur des cellules unitaires de la zéolite doit être réduite à 24,15-24,35 Angstroems, en même temps que les ions d'aluminium sont fixés, la dernière étape de calcination mentionnée est effectuée dans une atmosphère de vapeur d'eau saturée ou quasiment saturée à une température de 500 à 900°C.
PCT/SE1987/000464 1987-10-13 1987-10-13 Procede de preparation d'une zeolite y modifiee WO1989003367A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/SE1987/000464 WO1989003367A1 (fr) 1987-10-13 1987-10-13 Procede de preparation d'une zeolite y modifiee
EP19870907628 EP0339026A1 (fr) 1987-10-13 1987-10-13 Procede de preparation d'une zeolite y modifiee

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SE1987/000464 WO1989003367A1 (fr) 1987-10-13 1987-10-13 Procede de preparation d'une zeolite y modifiee

Publications (1)

Publication Number Publication Date
WO1989003367A1 true WO1989003367A1 (fr) 1989-04-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1987/000464 WO1989003367A1 (fr) 1987-10-13 1987-10-13 Procede de preparation d'une zeolite y modifiee

Country Status (2)

Country Link
EP (1) EP0339026A1 (fr)
WO (1) WO1989003367A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030780A (en) * 1990-07-26 1991-07-09 Union Oil Company Of California Aromatic saturation process with a silica-alumina and zeolite catalyst
US5242677A (en) * 1992-06-11 1993-09-07 Pq Corporation Stable zeolite of low unit cell constant and method of making same
CN1036644C (zh) * 1993-11-05 1997-12-10 中国石油化工总公司 一种骨架富硅y分子筛的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6575558B1 (en) 1999-03-26 2003-06-10 Spectra, Inc. Single-pass inkjet printing

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2085861A (en) * 1980-10-28 1982-05-06 Grace W R & Co Thermally-stabilised/aluminium- exchanged type Y zeolite

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2085861A (en) * 1980-10-28 1982-05-06 Grace W R & Co Thermally-stabilised/aluminium- exchanged type Y zeolite

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030780A (en) * 1990-07-26 1991-07-09 Union Oil Company Of California Aromatic saturation process with a silica-alumina and zeolite catalyst
US5242677A (en) * 1992-06-11 1993-09-07 Pq Corporation Stable zeolite of low unit cell constant and method of making same
WO1993025477A1 (fr) * 1992-06-11 1993-12-23 Pq Corporation Zeolite stable a faible constante de cellule elementaire et son procede de preparation
EP0603359B1 (fr) * 1992-06-11 1996-04-24 PQ Corporation Zeolite stable a faible constante de cellule elementaire et son procede de preparation
CN1036644C (zh) * 1993-11-05 1997-12-10 中国石油化工总公司 一种骨架富硅y分子筛的制备方法

Also Published As

Publication number Publication date
EP0339026A1 (fr) 1989-11-02

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