Hydrocracking catalyst for the production of middle distillates

• US 4,738,941 A
• Filed: 04/24/1987
• Issued: 04/19/1988
• Est. Priority Date: 04/26/1984
• Status: Expired due to Term

• Current Assignee: Societe Francaise Des Produits Pour Catalyse Pro-Catalyse Rueil-Malmaison
• Original Assignee: Societe Francaise Des Produits Pour Catalyse Pro-Catalyse
• Inventors: Dufresne, Pierre, Marcilly, Christian
• Primary Examiner(s): DEES, CARL
• Application Number:
  US07/041,946
• Time in Patent Office: 361 Days
• Field of Search: 502/66, 502/74
• US Class Current: 502/66
• CPC Class Codes: B01J 29/106 Y-type faujasite
• CPC Class Codes: C10G 47/16 Crystalline alumino-silicate carriers

Abstract

The invention relates to a new hydrocarbon hydroconversion catalyst, which is a mixture of an amorphous matrix, a zeolite and at least one metal of Group VIII and optionally of Group VI, the zeolite having a SiO₂ /Al₂ O₃ molar ratio of about between 8 and 70, a sodium content of less than 0.15% by weight, a unit mesh parameter a.sub.° of between 24.55 and 24.24×10^-10 m, a sodium ion recovery capacity C_Na, expressed in grams of sodium per 100 grams of modified zeolite, greater than 0.85, a specific surface area greater than 400 m² g^-1, a water vapor adsorption capacity at 25° C. (with a P/Po ratio of 0.10) greater than 6% by weight, a pore distribution between 1 and 20% of the pore volume contained essentially in pores of diameters between 20 and 80×10^-10m, the remaining pore volume being contained essentially in pores of diameters less than 20×10^-10 m, the matrix being characterized by the following textural properties:

S≧100 m².g^-1

Vpt≧0.4 cm³.g^-1

V₇₅ ≧0.25 cm³.g^-1

V₇₅ /Vpt≧0.5.

Claims

1. A catalyst containing by weight

(a) about 15 to 98% of a matrix comprising a γ

, η

, δ

or θ

alumina, a mixture thereof, silica or a silica-alumina, said matrix having the following textural properties;

Vpt ≧

0.5 cm³.g^-1

S ≧

150 m².g^-1

V₇₅ ≧

0.35 cm³.g^-1

V75/^Vpt ≧

0.6

(b) about 1 to 80% of a zeolite having;

an SiO₂ /Al₂ O₃ molar ratio of about between 12 and 40;

a sodium content less than 0.15% by weight determined on the zeolite calcinated at 1100°

C.;

a unit mesh parameter a°

of between 24.38×

10^-10 m and 24.6×

10^-10 m;

a sodium ion recovery capacity C_Na, expressed as grams of sodium per 100 grams of neutralized and calcinated modified zeolite, greater than about 0.85;

a specific surface area greater than about 500 m².g^-1 ;

a water vapor adsorption capacity at 25°

C. (with a P/Po ratio of 0.10) greater than 6% by weight;

a pore distribution between 3 and 15% of the pore volume comprising pores of diameters between 20 and 80×

10^-10 m, the remaining pore volume comprising essentially pores of diameteres less than 20×

10^-10 m;

(c) 0.05 to 10% by weight of nickel or compound of nickel in combination with at least one compound of molybdenum, the total concentration of nickel or nickel compound and of molybdenum compound being between 12 and 30%, the weight ratio (expressed as metal oxides) of nickel/molybdenum being between 0.05 and 8,

said catalyst produced by a process comprising the steps of;

preparing the zeolite from an NaY zeolite generally having an SiO₂ /Al₂ O₃ molar ratio between 4 and 6, a crystalline parameter between 24.60×

10^-10 m to 24.80×

10^-10 m and a surface area of generally between about 750 and 950 m² /g, the preparation of the zeolite consisting essentially of;

reducing the sodium content of the NaY zeolite to a value of less than 3% by weight by at least one exchange with a solution of an ionizable ammonium salt in order to obtain an NH₄ NaY zeolite,

calcinating between about 770° and

780°

C. the NH₄ NaY zeolite in at least one stage (hydrothermal treatment) at a partial water vapor pressure between 0.05 and 10 bars for more than 1 hour, to obtain a stabilized zeolite,

treating the stabilized zeolite in at least one stage with at least one solution of an organic or inorganic acid or acid complexing agent.

2. A catalyst according to claim 1 in which the preparation of the zeolite consists essentially of:

reducing the sodium content of the Y--Na zeolite to a value below about 2.8% by weight by at least one exchange with a solution of an ionizable ammonium salt in order to obtain an NH₄ NaY zeolite,

calcinating the NH₄ NaY zeolite in one stage (hydrothermal treatment) at 770°

-780°

C. under a partial water vapor pressure between about 0.1 and 5 bars for more than one hour to obtain a stabilized zeolite,

treating said stabilized zeolite in at least one stage with a solution of hydrochloric acid or nitric acid of a normality between 0.1 and 11N.

3. A catalyst according to claim 1, produced by a process comprising the steps of:

preparing the zeolite from a Y--Na zeolite generally having an SiO₂ /Al₂ O₃ molar ratio between about 4 and 6, a crystalline parameter between 24.65 and 24.75×

10^-10 m and a specific surface area generally between about 800 and 900 m² /g, and wherein the preparation of the zeolite consists essentially of;

reducing the sodium content of the Y--Na zeolite to a value less than 3% by weight by at least one exchange with a solution of ionizable ammonium salt in order to obtain an NH₄ NaY zeolite,

subjecting the NH₄ NaY zeolite to a first hydrothermal treatment, in at least one stage, at a temperature between 530° and

700°

C, under a partial water vapor pressure of at least 0.026 bar for at least 20 minutes,

reducing the sodium content to a value of less than 1% by weight, by at least one exchange with at least one solution of at least one ionizable ammonium salt, by treatment with at least one solution of at least one organic or inorganic acid, or by simultaneous exchange with at least one solution of at least one ionizable ammonium salt and a treatment with at least one solution of at least one organic or inorganic acid,

subjecting the zeolite thus treated to a second hydrothermal treatment in at least one stage at a temperature about 770°

-780°

C., for more than one hour,

treating the zeolite in at least one stage by at least on solution of organic or inorganic acid, or an acid complexing agent.

4. A catalyst according to claim 2, wherein the normality of the hydrochloric or nitric acid solution is between 0.5 and 3N.

5. A catalyst according to claim 3, wherein the sodium content of the zeolite is reduced to a value of less than 2.8% by weight prior to the first hydrothermal treatment, and is reduced to a value of less than 0.7% by weight subsequent to said treatment.

6. A process according to claim 1, wherein the catalyst is prepared by a process comprising mixing a matrix with a zeolite and introducing in one or several stages, either into the matrix or into the zeolite, or into a mixture thereof, the nickel or nickel compound and the molybdenum compound.