JPH06210178A - Hydrocarbon conversion catalyst - Google Patents

Abstract

PURPOSE: To provide a composition suitable as a catalyst base in hydroprocessing. CONSTITUTION: This composition comprises a crystalline aluminosilicate and a binder, where the aluminosilicate comprises modified Y zeolite having less than 24.37 Å unit cell size, at least 8 wt.% water adsorption capacity of the modified Y zeolite (at 25 deg.C and 0.2 P/P0 value), at least 0.25 ml/g pore volume, and pores having at least 8 nm pore diameter occupy 10-60% of the total pore volume. In the modified Y zeolite, the maximum ratio of the adsorbance in the infra-red frequency region of 3670±10 cm<-1> to that in the infra-red frequency region of 3630±10 cm<-1> is 0.040. Further in this invention, a hydroconversion catalyst and a process based on the catalyst are provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to compositions suitable as catalyst bases in hydrotreating. Furthermore, the present invention also relates to a catalyst composition which can be suitably used for a hydrocarbon conversion method (particularly a hydrothermal cracking method) and a hydrocarbon conversion method using such a catalyst composition.

[0002]

2. Description of the Prior Art Of the many hydroconversion processes known in the art, hydropyrolysis is becoming increasingly important because it provides product flexibility as well as product quality. It is clear that much interest has been focused on the development of hydropyrolysis catalysts, as relatively heavy feedstocks can be subjected to hydropyrolysis.
In the past, catalytic hydropyrolysis was primarily aimed at the production of low boiling point products such as gasoline, whereas hydropyrolysis is now often able to meet the growing demand for high quality middle distillate products. It is an object. Therefore, the objective in current hydropyrolysis is to provide hydropyrolysis catalysts having high selectivity for middle distillates and also high activity and stability.

For this purpose, modern hydrocracking catalysts are
It is generally based on zeolitic materials that are compatible with technologies such as ammonium-ion exchange and various calcinations to improve the performance of hydrothermal cracking catalysts based on zeolitic materials. One type of zeolite that is considered a good starting material for making hydropyrolysis catalysts is U
It is a well-known synthetic zeolite Y as described in S-A-3,130,007. Many modifications have been reported for this material, especially the ultrastable Y-type (US-A-3,
536,605) and superhydrophobic Y type (GB-A-
2,014,970). Generally, these modifications result in a reduction in unit cell size depending on the treatment performed.
EP-B-247679 describes compositions which can be used very attractively as components of hydrocracking catalysts. Surprisingly, we have now found that the use of a composition consisting of a binder and a modified Y zeolite with specific infrared properties gives much more attractive results in terms of gas production and middle distillate yield. It was

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention comprises a crystalline aluminosilicate and a binder wherein the crystalline aluminosilicate has a unit cell size of less than 24.37 Å and a water absorption capacity of at least 8% by weight of the modified Y zeolite (25 ° C.).
And a P / P ₀ value of 0.2) and at least 0.25
modified Y zeolite having a pore volume of ml / g, 10 to 60% of the total pore volume being composed of pores having a diameter of at least 8 nm, said modified Y zeolite being 3
A catalyst for hydrotreating, having an absorbance ratio of up to 0.040 expressed as absorbance in the infrared frequency region of 3670 ± 10 cm ⁻¹ divided by absorbance in the infrared frequency region of 630 ± 10 cm ^−1. It relates to a composition suitable as a base. Preferably the absorbance ratio is 0.03 max, more preferably 0.02 max.
Is. The infrared band is determined by in-situ grid measurements of dry samples at elevated temperature (450 ° C).

Preferably the modified Y zeolite is 24.27.
~ 24.35 Angstroms, more preferably 24.35 Angstroms.
It has unit cell dimensions in the range of 29-24.33 Angstroms. Preferably 10-40% of the total pore volume of the modified Y zeolite is composed of pores having a diameter of at least 8 nm. Preferably, the modified Y zeolite has a water adsorption capacity of 8 to 12% by weight of the modified Y zeolite.
capacity). The pore diameter distribution and water absorption capacity are preferably according to EP-B-247, which is incorporated herein by reference.
It can be determined by the method described in No. 679. Preferably reforming Y zeolites 4-25, more preferably SiO ₂ / Al ₂ O ₃ molar ratio of 8-15.

The composition according to the invention preferably comprises from 5 to 90% by weight of modified Y zeolite and from 10 to 95% by weight of binder. In a particular embodiment, the composition is composed of a relatively large amount of modified Y zeolite, 50-85% by weight.
Modified Y zeolites of 15% and binders of 15 to 50% by weight are preferred. Suitably the composition according to the invention further comprises an amorphous pyrolytic component. Suitably, this type of composition is 5
Consisting of 0 to 90% by weight of modified Y zeolite and components for amorphous pyrolysis and 10 to 50% by weight of binder, preferably 60 to 85% by weight of modified Y zeolite and amorphous pyrolysis It is composed of components and 15-40% by weight of binder. Suitably, the amount of modified Y zeolite is in the range of 5 to 95%, preferably 10 to 75% of the total amount of modified Y zeolite and components for amorphous pyrolysis. Suitably, amorphous pyrolytic components based on silica can be used. Suitably, silica-alumina is mentioned as a component for amorphous thermal decomposition. In another embodiment, a silica-alumina dispersion in an alumina matrix can be used as the amorphous pyrolysis component. When using amorphous pyrolysis components of this type, the composition according to the invention preferably comprises less than 25% by weight modified Y zeolite, more than 25% by weight binder and at least 30% by weight alumina. It is composed of a silica-alumina dispersion in a matrix.

Preferably the composition comprises at least 30% by weight binder. Preferred are compositions comprising less than 15% by weight modified Y zeolite. Preferably the composition has a binder / modified Y zeolite weight ratio in the range of 2-40. Suitably the composition comprises 40-70% by weight of the dispersion. Suitably the alumina matrix comprises a transitional alumina matrix, preferably a γ-alumina matrix.

The binder present in the composition of the present invention preferably comprises an inorganic oxide or a mixture of inorganic oxides. Both amorphous and crystalline binders can be used. Examples of suitable binders include alumina, magnesia, titania and clay. Minor amounts of other inorganic oxides such as zirconia, titania, magnesia and silica can also be present if desired. Alumina is the preferred binder. Suitably the modified Y zeolite is
SiO ₂ / Al ₂ O ₃ molar ratio of at least increased (predetermined standard, for example, with respect to Na-Y) having a degree of crystallinity retained by. In general, the degree of crystallinity slightly increased with increasing SiO ₂ / Al ₂ O ₃ molar ratio by comparing modified Y zeolites. The present invention further provides, in addition to the above composition, at least one hydrogenation component of a Group VI metal and / or a V group
It relates to a catalyst composition which also comprises at least one hydrogenation component of a Group III metal. Preferably, the catalyst composition according to the invention comprises one or more components of nickel and / or cobalt, one or more components of molybdenum and / or tungsten or one or more components of platinum and / or palladium. And the ingredients of.

The amount of hydrogenation component in the catalyst composition is preferably calculated as metal per 100 parts by weight of total catalyst,
05-10 wt% Group VIII metal component and 2-4
It is in the range of 0 wt% Group VI metal component. The hydrogenation component in the catalyst composition may be an oxidative type or a sulfide type, and particularly a sulfide type. If at least a combination of Group VI metal and Group VIII metal components is present as a (mixed) oxide, it is generally subjected to a sulfidation treatment prior to its proper use in hydropyrolysis. The compositions according to the invention are particularly useful in certain hydroconversion processes, especially hydropyrolysis processes.

The present invention thus provides for the conversion of hydrocarbon oils to low average molecular weight and low average boiling point products by contacting the hydrocarbon oil with the catalyst composition at elevated temperature and pressure in the presence of hydrogen. It also relates to a hydrocarbon oil conversion method consisting of the above. Suitable process conditions for the hydroconversion process are temperatures of 250 to 500 ° C., hydrogen partial pressures of up to 300 bar and 0.1 per hour of catalyst per liter.
It consists of the space-time velocity (kg / l / hr) of the 10 kg feed. A gas / feed ratio of 100-5000 Nl / kg can be suitably used. Preferably, the hydroconversion process has a temperature of 300-450 ° C., a hydrogen partial pressure of 25-200 bar and 0.2-5 k / h of catalyst per liter.
g at space-time velocity of feed. Preferably gas /
Feed ratios used in the range of 250-2000 Nl / kg. Feedstocks that can be suitably processed in the hydroconversion process using the catalysts of the present invention include gas oils, deasphalted oils, coke gas oils and other pyrolysis gas oils, and optionally tar sands, shale oils, residual oils. Includes synthetic crudes derived from upgrading processes or biomass. Combinations of various feedstocks can also be used.

Part or all of the feedstock may be used in one or more (hydrogenation) prior to use in the hydroconversion process.
It is desirable to go through the treatment process. Often it is convenient to subject the feedstock to (partial) hydrotreating. The catalyst to be used for this type of hydrotreatment is preferably amorphous hydrogen containing at least one Group VI metal and / or at least one Group VIII metal on an amorphous support. It is a chemical pyrolysis catalyst. In an attractive embodiment of this type of hydrotreatment, two reaction zones arranged in series can be used to transfer the entire effluent from the first reaction zone to the second reaction zone. The first reaction zone is the above first
The second reaction zone comprises a VI
A second zeolite hydropyrolysis catalyst containing at least one metal of Group VIII and / or at least one metal of Group VIII. Preferably, the zeolite catalyst comprises the catalyst composition according to the invention. In this way, a very attractive hydrotreatment of the feedstock is established. The invention therefore also relates to a process for the hydrotreating of hydrocarbon feedstocks, which process comprises the feedstock in the presence of hydrogen on a crystalline support at least one metal of group VI and / or group VIII. Is contacted with the first amorphous hydrogenation pyrolysis catalyst containing at least one metal in the first reaction zone, and at least a part (preferably total eluate) of the eluate from the first reaction zone 2 reaction zones, and in this second reaction zone the eluate from said first reaction zone in the presence of hydrogen at elevated temperature and pressure at least one of the compositions according to the invention and a Group VI metal Contacting with a second zeolite catalyst comprising a composition of one hydrogenation component and / or at least one hydrogenation component of a Group VIII metal.

The first reaction zone may consist of a bed of one or more alumina-containing catalysts, and a second zone
It is clear that the reaction zone contains a bed of one or more zeolite catalysts. Furthermore, it is also clear that the first and second reaction zones can be provided in one or more reactors. Preferably, the reaction zones are arranged in a laminated bed configuration. The hydrotreatment and the process according to the invention can also be carried out in the reactor, preferably in series or in a stacked bed arrangement. The reactor effluent thus obtained may suitably be subjected to a further hydropyrolysis treatment, preferably the treatment according to the invention. Hereinafter, the present invention will be further described with reference to examples.

[0013]

【Example】

(A) Preparation of the catalyst according to the invention Unit cell size of 2.431 nm and SiO ₂ /9.8
Al ₂ O ₃ molar ratio and water absorption capacity of 11.2% by weight (25
C. and P / P ₀ value of 0.2) and 0.42 ml /
g nitrogen pore volume (wherein 30% of the total pore volume is composed of pores having a diameter of at least 8 nm);
Burning loss of weight% and less than 0.01 3670 cm ^-1 /
77.7 g of modified Y zeolite (PQZ) with an infrared absorption ratio of 3630 cm ⁻¹ was mixed with 24 g of hydrated aluminum oxide (Criterion). Then 36.
12 g of NiW solution (Stark: 6 wt% Ni, 2
3 wt% W) and 3.41 g nickel nitrate solution (14
% Ni) and 43.02 g water were added to the powder mixture. After kneading the obtained mixture, it is extruded by a small Bonnot extruder equipped with a die plate.
A 5 mm extrudate was obtained. The extrudate obtained was dried at 120 ° C. for 2 hours and finally calcined at 500 ° C. for 2 hours. The extrudate obtained had a mercury pore volume of 0.61 ml / g. These contained 2.6% by weight nickel and 8.2% by weight tungsten. The finished catalyst contained 80% by weight modified Y zeolite and 20% by weight binder (based on the total amount of zeolite and binder on a dry basis).

(B) Hydropyrolysis Experiment The obtained catalyst was subjected to a hydropyrolysis performance test on a hydrotreated heavy vacuum gas oil having the following properties: C (wt%): 86. 2 H (% by weight): 13.8 d (70/4): 0.826 Viscosity (100 ° C.): 4.87 cS (ASTM-D
-445) Viscosity (60 ° C.): 12.43 cS (ASTM-
D-445) RCT (% by weight): 0.05 (ASTM-D-5
42) I. B. P. (° C.): 205 ° C. 10/20: 332/370 30/40: 392/410 50/60: 428/448 70/80: 467/492 90: 525F. B. P. : 598

First, the catalyst is added to 10% by volume of H ₂ S /
Presulfiding treatment was performed by slowly heating to a temperature of 370 ° C. in H ₂ atmosphere. The catalyst was tested under the following operating conditions at a 1: 1 dilution with 0.2 mm SiC particles: 1.1 kg / l / h WHSV, 1.4.
H ₂ S partial pressure of bar, total pressure of 130 bar, and gas / feed ratio of 1,000 Nl / kg. The experiment was performed by a single pass operation. When performing hydropyrolysis in the kerosene mode of operation, catalytic performance is expressed as 300 ° C. ⁺ 70% by weight conversion of boiling materials in the feed after stabilizing the catalyst. This catalyst per the following results were obtained: required temperature (300 ° C. ⁺ 70% conversion): 328 ℃ 300 ℃ ^- product distribution _{(wt%): C 1 ~C 4:} 6 C 5 ~130 ℃: 43 130 ° C-300 ° C: 51 Chemical hydrogen consumption was 1.2% by weight.

Comparative example EP-B-247679 known from 24.33
Angstrom unit cell size and 9.85 SiO
₂ / Al ₂ O ₃ molar ratio, water absorption capacity of 11.3% by weight (at P / P ₀ value of 25 ° C. and 0.2), 0.40
Nitrogen pore volume of ml / g (where 18% of the total pore volume consists of pores with a diameter of at least 8 nm) and 1
Burning loss of 4.1% by weight, 0.043 3670 cm
^-1 / the modified Y zeolite having a infrared absorbance ratio of 3630Cm ^-1 and treated with a hydrated aluminum oxide (Criterion Inc.) and a solution of nickel nitrate and ammonium metatungstate, 2.6 wt% of nickel A catalyst was obtained which contained 8% by weight of tungsten. Finished catalyst is 77.5 wt% modified Y zeolite and 22.5 wt%
Binder (based on the total amount of zeolite and binder on a dry basis). This comparative catalyst was subjected to the presulfidation treatment described in the above example and treated with the same feed. After stabilizing the catalyst, the kerosene operating mode (ie 300 ° C in feed ⁺ 70 ° C of boiling material)
The following results were obtained when the hydropyrolysis was carried out (representing the catalytic performance in wt% conversion):

The required temperature (conversion 300 ° C. ⁺ 70% of): 318 ℃ 300 ℃ ^- product distribution _{(wt%): C 1 ~C 4:} 7 C 5 ~130 ℃: 46 130 ℃ ~300 ℃: 47 Chemical hydrogen consumption was 1.2% by weight. As is apparent from the above, the catalyst according to the invention is EP-B-24767.
It is more attractive than the catalysts known from No. 9 in terms of gas production and middle distillate yield.

Claims (17)

[Claims] 1. A unit cell size comprising crystalline aluminosilicate and a binder, wherein the crystalline aluminosilicate has a unit cell size of less than 24.37 Å and a water absorption capacity of at least 8% by weight of the modified Y zeolite (P at 25 ° C. and 0.2. / P
_{(At 0} value) and a pore volume of at least 0.25 ml / g of modified Y zeolite, with a total pore volume of 10
˜60% is composed of pores having a diameter of at least 8 nm and the modified Y zeolite is 3670 divided by the absorbance in the infrared frequency range of 3630 ± 10 cm ^−1.
A composition suitable as catalyst base in hydrotreating, characterized in that it has an absorbance ratio of up to 0.040 expressed as absorbance in the infrared frequency range of ± 10 cm ^-1 . 2. The maximum absorbance ratio is 0.03.
The composition according to. 3. The unit cell size is 24.27 to 24.35.
A composition according to claim 1 or 2 which is in the Angstrom range. 4. The unit cell size is 24.29 to 24.33.
The composition of claim 3 in the Angstrom range. 5. The total pore volume of the modified Y zeolite is 10 to 10.
Composition according to any one of claims 1 to 4, wherein 40% is composed of pores having a diameter of at least 8 nm. 6. The composition according to claim 1, wherein the modified Y zeolite has a water absorption capacity of 8 to 12% by weight of the modified Y zeolite. 7. A SiO ₂ having a modified Y zeolite content of 4 to 25.
/ Al ₂ O ₃ composition according to any one of claims 1-6 having a molar ratio. 8. A modified Y zeolite having a SiO ₂ content of 8 to 15
The composition of claim 8 having a / Al ₂ O ₃ molar ratio. 9. A composition comprising 5 to 90% by weight modified Y zeolite and 10 to 95% by weight binder.
9. The composition according to any one of item 8. 10. The composition according to claim 1, wherein the binder comprises an inorganic oxide or a mixture of inorganic oxides. 11. A binder, a modified Y zeolite as claimed in any one of claims 1 to 10, at least one hydrogenation component of a Group VI metal and / or at least one Group VIII metal. A catalyst composition comprising a seed hydrogenation component. 12. A hydrogenation component comprising one or more components of nickel and / or cobalt and one or more components of molybdenum and / or tungsten or one or more components of platinum and / or palladium. The catalyst composition according to claim 11, which comprises components. 13. The catalyst according to claim 12, wherein the hydrogenation component consists of 0.05 to 10% by weight of nickel and 2 to 40% by weight of tungsten, calculated as metal per 100 parts by weight of the total catalyst. Composition. 14. The catalyst composition according to claim 11, wherein the hydrogenation component is in the sulfide form. 15. The process of converting a hydrocarbon oil to products of low average molecular weight and low average boiling point, wherein the hydrocarbon oil is at elevated temperature and pressure in the presence of hydrogen.
15. A method for converting a hydrocarbon oil, which comprises contacting the catalyst composition according to any one of items 1 to 14. 16. A temperature in the range of 250 to 500 ° C., 30
Hydrogen partial pressure up to 0 bar and space velocity of feed of 0.1 to 10 kg per liter of catalyst per hour.
The method according to 5. 17. A temperature of 300 to 450 ° C., 25 to 20
Hydrogen partial pressure of 0 bar and 0.
17. The method of claim 16 performed at a space velocity of 2-5 kg feed.