JPH0853678A - Conversion of hydrocarbon feedstock - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for the conversion of a hydrocarbon having an increased elasticity against the depression of conversion incurred at the time of initial contact between a catalyst and a feedstock.

SOLUTION: In a process for the catalytic conversion of a hydrocarbonaceous feedstock which comprises bringing the feedstock into contact with a molecular sieve catalyst of a particulate form at an elevated temperature in a conversion zone, individual particles of the catalyst comprise a core having a shell thereabout and the core comprises an acidic microporous molecular sieve crystal and the shell comprises a substantially non-acidic meso- or macroporous oxide or oxyanion material.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for catalytic conversion of hydrocarbonaceous feedstocks, particularly hydrocarbonaceous feedstocks having enhanced selectivity for the production of hydrocarbons in the gasoline range for the duration of the catalyst life. Fluidized catalytic cracking method, and a catalyst composition that can be used in such a method.

[0002]

Fluid Catalytic Cracking (FCC) for converting hydrocarbonaceous feedstocks with desired grades and boiling ranges into light cracking products which have particular application as motor fuels, diesel fuels, oils and chemical feedstocks. ) Method is well known. In standard FCC processes, the feedstock is contacted with the catalyst at an elevated temperature, which converts the feedstock to the cracked decomposition products that are recovered and some of the product is deposited on the catalyst. To form coke and deactivate the catalyst. The catalyst and product are separated, whereupon the catalyst is passed through a stripping zone where most of the entrained hydrocarbon products are eliminated and recovered, after which the catalyst is removed at the high temperature of residual hydrocarbon deposits and coke. Is sent to a vessel for the regeneration of the catalytic activity by the combustion of the catalyst, after which the regenerated catalyst is recycled to the reaction zone. In recent years it has become common practice to convert high temperature resistant feedstocks in the ever higher boiling range, which conversions require increased tolerances and high tolerance to the deactivation of feedstock contaminants. This was made possible by the development of superior catalysts in the stabilized zeolite class. Such catalysts also require periodic regeneration where the coke formed is burned. Due to the need to operate at specific coke formation levels for heat balance purposes, the yield of certain product cuts, especially gasoline range cuts, tends to decrease with increasing high temperature resistance of the feedstock. Therefore, it is desirable to further increase the selectivity and conversion that can be achieved with these catalysts. Attempts have been made to protect the catalyst from the deactivating effects of carbon-rich hydrocarbonaceous and metallic deposits. Significant improvements have been achieved using a riser reaction zone that allows conversion to occur over a short period of contact between the catalyst and the feedstock, as well as a passivating agent that renders the metal deposits less detrimental to the catalyst. It was These improvements are limited in that deactivation mostly occurs during initial contact of the catalyst with the feedstock, thereby exacerbating the degree of conversion during subsequent stages of the conversion process.

[0003]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a hydrocarbon conversion process having increased resilience to the deterioration in conversion experienced during the initial contact of the catalyst with the feedstock. is there. The present inventors have now found that by inhibiting direct contact between the most high temperature resistant feedstock component and the active catalyst component, such feedstock component is retained in situ on a catalyst that is separate from the active catalyst component. It has been found that a significant increase in conversion to products in the gasoline range can be obtained by forming a form or by a form that can be converted by the active catalyst component without adverse effects, or both.

[0004]

Accordingly, the present invention is directed to catalytic conversion of a hydrocarbonaceous feedstock which comprises contacting the hydrocarbonaceous feedstock with a molecular sieve catalyst in particulate form at an elevated temperature in a conversion zone. In the method, the individual particles of the catalyst consist of a core with a shell around and the core consists of acidic microporous molecular sieve crystals and the shell is substantially non-acidic mesoporous or macroporous. And an oxyanion substance. Preferably, the catalyst shell consists of a substantially non-acidic mesoporous oxide material or oxyanion material.

References herein to microporous, mesoporous and macroporous materials are by specific diameter or range of specific diameters in a given material, as is generally understood in the art. This is done for a porous material as defined below with pore openings as characterized. The limits on the range of pore opening diameters for substances in each class are:
For the present purpose it is most precisely defined by the function to be fulfilled, so that there is some variation depending on the pore geometry and the inorganic oxide material involved. In general, microporous materials have pores with diameters comparable to those of the hydrocarbonaceous constituents to be converted that are substantially non-high temperature resistant, and are therefore selective with respect to the penetration of such constituents into the pores. , Having a pore diameter of less than 1.0 nm, preferably in the range of 0.3 nm to 0.9 nm, and the microporous material is also required for acidolytic activity. The macroporous material may have a diameter at least as large as the diameter of the hydrocarbonaceous component to be converted, suitably larger than 50 nm, preferably 1
It is understood that they have pores with diameters larger than 00 nm and are therefore substantially non-selective for the entry of such components into the pores, and that the macroporous material is also characterized by a substantial lack of acidic sites. It should be. Since there is some variation in pore diameter for a given macroporous material, it is common to define these by the overall (external and internal) surface area, with smaller surface areas averaging the average pores. The diameter is large. Suitably, the macroporous material is 10
m ² / g less than or equal to and preferably most preferably less than 5 m ² / g with a surface area in the range of 0.01~2m ² / g. Materials that fall into the class between micro and macroporosity are known as mesoporous materials, and for this purpose have pores with diameters in the range 1.0 nm to 100 nm, for example in the range of about 1.0 to 50 nm. It is defined that hydrocarbon components can enter in a non-selective manner, and the mesoporous material is also characterized by the substantial absence of acidic sites. As used herein, reference to pores refers to pores in the crystal that are present in the crystal lattice and pores in the particles that are present between discrete molecules in the particles.
With respect to inter-crystal or inter-particle pores present in a melted crystal or particle agglomerate, or between agglomerates present between discrete agglomerates of particles or crystals (may occur during drying of the shell coating) .), Or any other type of pores that may be present in the material itself or that may be present at the time of the shell coating of the catalyst core. A given material is present in different forms and thus in a form exhibiting more than one of the above ranges (e.g. alumina is present in the macroporous alpha form and in the mesoporous gamma form). Or in a single morphology exhibiting more than one of the above ranges (eg, clay has both mesoporous and microporous pores). It will be appreciated that it may alternatively be synthesized.

References herein to the core and shell components of the catalyst are to the zones relatively rich and poor, respectively, of the two catalyst component materials defined above. Preferably, references to core and shell components refer to discrete components consisting of two separate radial bands.
It is to be understood that the core material defined above is substantially free of catalyst shell and vice versa. This makes a fundamental distinction to the present invention, so that in the process of the present invention the feedstock components pass through each zone of the catalyst sequentially, each zone being characterized by a particular conversion method. I understand. More specifically, the outer "shell" zone is the site for the non-acidic pyrolysis of certain feedstock components, and the inner "core" zone is selected to contain the pyrolysis components leaving the shell zone. It is the site for standard acidic cracking conversions of feed ingredients.

The process of the present invention is particularly advantageous in that it achieves increased conversion selectivity of the feedstock to products in the gasoline range and, in addition, has a constant coke yield compared to standard FCC processes. At, resulting in an overall increase in gasoline yield. By the method of the present invention, the high temperature resistant feedstock components are first contacted at elevated temperature with a substantially non-acidic mesoporous or macroporous shell material, which results in their conversion and poor high temperature resistance. Form components, which then pass through the mesopores or macropores to the acidic microporous molecular sieve material of the core and are selectively converted to products, and / or the high temperature resistant feedstock components Deposition in the form of components of increased high temperature resistance level having a high carbon content such that they are resilient to further conversion upon impact on porous or macroporous shell materials, thereby Does not come into contact with acidic microporous molecular sieve material. By selecting a mesoporous or macroporous material that is substantially non-acidic, the initial conversion of the most high temperature tolerant feedstock components is thermally induced, which is believed not to be affected by high carbon content deposits. It depends on the decomposition. Such non-acidic mesoporous or macroporous materials do not compete with acidic microporous molecular sieve cores in the selective conversion of feed ingredients with poor high temperature resistance, and thus by shape selective microporous molecular sieve cores. It is particularly advantageous that there is only a small or substantially negligible competition in the conversion of poorly high temperature resistant feedstock components that may be converted to useful products in a selective manner.

In the process of the present invention, the catalyst is suitably contacted with the feed for less than 10 seconds. Suitably, the minimum contact time is 0.1 seconds. Very good results can be obtained using a method in which the feedstock is contacted with the catalyst for 0.2-6 seconds. The method is performed at relatively high temperatures. A preferred temperature range is 450 to 800 ° C, especially 475 to 650 ° C, for example 500 to 550 ° C. The pressure in the method can be varied within wide limits. However, the pressure is preferably such that the feed is substantially in the vapor phase at the temperature during the run or is brought into the vapor phase by contact with the catalyst. The pressure is therefore relatively low, suitably in the range 1-10 bar. Pressures below atmospheric pressure are possible but less preferred. Operating at atmospheric pressure can be economically advantageous. Other gaseous substances such as water vapor and / or nitrogen may be present during the conversion. Weight ratio of catalyst used to feedstock to be converted (catalyst: feedstock ratio, kg / k
g) is in a wide range, for example 150 k per kg of feedstock
It can be changed up to g. Preferably, the catalyst: feedstock weight ratio is from 3 to 100: 1, such as from 5 to 20: 1.

The process according to the invention may suitably be carried out in a moving bed of catalyst. Suitably this is accomplished by passing a fluidizing gas through the catalyst bed. The bed of fluidized catalyst particles that can rise or fall in the flow of the riser or the downcomer is
Suitably it is fluidized to the extent that a dispersed catalyst phase is produced for operation with short contact times. In this respect, in the FCC process the catalyst particles contain only a relatively low content of zeolite component, so that the wear requirements are met. During the process of the present process it is advantageous to regenerate the catalyst after contact with the feed and separation of the products, some coke forming on the catalyst. Regeneration is preferably carried out by subjecting the coke-formed catalyst to a combustion step with an oxidizing gas such as air at elevated temperature.

The choice of mesoporous or macroporous non-acidic oxide or oxyanion material used in the process of the present invention depends to some extent on the feedstock to be converted. For the conversion of high temperature resistant feedstocks, medium or large pores of larger diameter may be required than for conversion of poor high temperature resistant feedstocks. Suitable mesoporous materials are Group 2A, Group 2B, Group 3A, Group 3B, Group 4A of the Periodic Table of the Elements.
Non-acidic oxides or oxyanion compounds of elements selected from the group III, Group 4B and lanthanides, for example clays such as kaolin and metakaolin, alumina, silica, silica-alumina, magnesium aluminate, magnesia, calcia, titania. , Zirconia, yttria, ceria, lantana, tin oxide, aluminum phosphate and mixtures thereof. Examples of suitable substantially non-acidic macroporous materials are alpha-alumina, silica in the form of amorphous silica, silica-alumina in the form of mullite, magnesia-alumina in the form of spinel, Includes magnesia-silica, ceria, yttria, aluminum phosphate and mixtures thereof.

Suitably, the mesoporous or macroporous shell prevents the high temperature resistant feedstock components from entering and exiting the molecular sieve core, but the low temperature resistance feedstock and the components formed in situ. It has a sufficient thickness so as not to interfere with. Suitably, the inflow and outflow of such high temperature resistant feedstock components is determined by a shell or a sufficient radial thickness of the crystals or particles of mesoporous or macroporous material or their agglomerates having sufficient layers in the radial direction. This can be prevented by providing a shell having a thickness to provide a meandering radial groove between adjacent crystals, between particles or between agglomerates. By this means, the probability of the high temperature resistant feedstock component penetrating the shell and impinging on a mesoporous or macroporous wall (where the high temperature resistant feedstock component is pyrolyzed here) is mesoporous. Alternatively, it is higher than the probability of proceeding to the core of the catalyst particles without contacting the macroporous wall. Preferably, the shell comprises a mesoporous or macroporous material of substantially uniform size agglomerates of substantially uniform size particles or crystals, and thus the mesopores or macropores formed therebetween. Is substantially uniform. It should be understood that the cracked catalyst particles are subject to attrition during the circulation process and thus some attrition occurs. Therefore, the thickness of the mesoporous or macroporous shell is adequately retained in the equilibrium catalyst particles which are replaced by fresh catalyst to maintain the overall activity and particle size of the catalyst residue in the FCC unit. The thickness to be applied is selected to be as defined above. This can be determined with respect to the wear resistance of the shell material in a given FCC unit. Preferably, the thickness of the residual mesoporous or macroporous shell in the equilibrium catalyst particles is in the range of 1-20 microns, preferably in the range of 2-10 microns.

The mesoporous or macroporous shell may be formed using any suitable binder known in the art, such as silica. By this means, the strength of the catalyst composition against attrition can be increased. Microporous molecular sieve cores may consist of one or more individual crystals, but are typically of convenient size, suitably 1 diameter, for handling in the circulation process.
It consists of clusters of crystals in the form of agglomerates of size in the range 0-100 microns, preferably in the range 40-90 microns, for example in the range 50-60 microns. Such clusters may be formed as known in the art, for example by spray drying in the presence of a suitable binder material such as an organic component, as part of the crystal synthesis.

The acidic molecular sieve to be used in the process of the present invention may suitably be any of the known acidic hydrocarbon conversion catalysts. Preferably, the molecular sieve comprises a shape-selective zeolitic material having a pore size suitable for the selective conversion of the desired feedstock, more preferably in the range 0.3 to 0.9 nm. Examples of suitable zeolites having pore sizes in the range 0.7 to 0.9 nm include faujasite type zeolites such as zeolites Y and X, for example in stabilized form, zeolite beta and zeolite omega. Examples of suitable zeolites having a pore size in the range 0.3 to 0.7 nm are crystalline silica (silicalite), silicoaluminophosphates such as SAPO-4 and SAPO-11, phosphorus such as ALPO-11. Aluminum acid, titanium aluminophosphates and titanium aluminosilicates such as TAPO-11 and TASO-45, boron silicates and ferrierite, erionite, theta and ZSM-5, ZSM-11, ZSM.
-12, ZSM-35, ZSM-23 and ZSM-38
Crystalline (metal) like ZSM type zeolite like
Silicate (where the metal is aluminum, gallium,
It can consist of iron, scandium, rhodium and / or chromium and mixtures thereof. )including. Preferably, the zeolite is in its acidic hydrogen form.

The greatest benefit with respect to enhanced conversion is that the catalyst in the process of the invention is a bulk catalyst co-component.
mponent), but additional benefits may be obtained by using it as an additive catalyst component intended for the selective conversion of the hydrocarbon component produced in situ by the main catalyst component. Should be
It should be understood that. The microporous molecular sieve component of the catalyst of the present invention is suitably supported on a matrix material known for this purpose, which enhances the abrasion resistance of the composition. Suitable matrix materials are selected from clays such as those in the form of kaolin or metakaolin, alumina, silica, silica-alumina, magnesia, titania, zirconia and mixtures thereof. Such matrix material can be included in a mixed phase with the microporous molecular sieve material, thereby forming a supported microporous molecular sieve core. The matrix material is suitably 10:90 to 90: 1 with respect to the microporous material.
It is preferably present in a ratio of 50:50 to 85:15.

Suitable feedstocks to be used in the process of the present invention include any feedstock used in the FCC conversion process, such as long-residue, short-residue, flash-distilled distillate, hydrotreated. And hydrocracked feedstock, gas oil, vacuum gas oil, tar sands, shale oil and coal liquor. Feedstock formulations commonly used in FCC conversion processes include residual fractions derived from crude oils such as heavy residual oils. These fractions contain as a significant component asphaltene, a complex carbonaceous product of the aromatic class that is insoluble in aromatic-free solvents such as paraffinic solvents. The high carbon content of these residue components makes them prone to forming coke precursors during cracking, which adversely affects the cracking of feedstock components that have poor high temperature resistance. Therefore, it is common to treat such feedstocks for asphaltene removal prior to conversion. Deasphalting of oils is carried out by mixing the oil with an aromatic-free paraffinic solvent such as pentane or heptane, from which insoluble asphaltene is precipitated and separated. In a particular advantage of the process of the present invention, a feedstock having a high asphaltene content can be converted directly without any pretreatment to remove the high temperature resistant asphaltene component, so that the asphaltene is as described above. It is pyrolyzed by a porous, high temperature resistant shell material. Special advantages are obtained with the conversion of high temperature resistant feedstocks characterized by a high initial boiling point (e.g. higher than 370 ° C) and a high asphaltene content (e.g. higher than 4% by weight).

The residual fraction also contains a significant amount of heavy metals,
Thus, the metal will be deposited on the catalyst during the cracking process, thereby degrading the catalyst selectivity for the production of gasoline, leading to the production of unwanted dry gas components. In a further advantage of the process of the invention, some contaminating metals present in the residual fraction are also deposited on macroporous high temperature resistant materials and fixed by coordination with macroporous materials, Will prevent deactivation of the microporous molecular sieve core. Such contaminants include nickel, vanadium, iron and sodium.
In a further aspect of the invention there is provided a catalyst composition in particulate form, wherein the individual particles of catalyst comprise a core with a shell around and the core comprises acidic microporous molecular sieve crystals and There is provided the catalyst composition wherein the shell comprises a substantially non-acidic mesoporous or macroporous oxide material or oxyanion material. The catalyst of the present invention is suitably obtained by a first stage synthesis of an acidic microporous molecular sieve core material, optionally supporting it on a matrix. Second
In the step, a mesoporous or macroporous precursor of the outer shell is introduced around the catalyst core. Preferably, each synthetic step is discontinuous, so that the material obtained from each step is suitably dried before proceeding to the next step.

Preferably, the catalyst core may be prepared by any known means of preparing commercially available FCC catalysts, suitably slurrying the zeolite and matrix precursors separately or together. It is then produced by spray drying or by mixing cooled aqueous solutions of each of the silica salt and the alumina salt and isolating, drying and calcining the resulting solid zeolite-containing catalyst core. The supported zeolite is
It can then be coated with a shell of mesoporous or macroporous material by means known in the art for the deposition of such material, which means affecting the integrity of the microporous molecular sieve core. Should not affect. Suitably, the mesoporous or macroporous shell is the desired mesoporous or macroporous for the particles of the molecular sieve crystals which have been synthesized and once spray dried or complexed in a matrix. By performing a second spray-drying with a solution containing a suitable precursor of the quaternary substance, or by soaking the particles of the molecular sieve crystal complexed with the molecular sieve crystals or matrix material in such a solution and once desired. When the resulting shell thickness has accumulated, the resulting composition is dried, or the particles of the molecular sieve crystals complexed in the molecular sieve crystals or matrix material are substantially inert, mesoporous or macroporous. PH in a solution of high quality oxide or oxyanion precursors (suitable for preferential precipitation of mesoporous or macroporous precursors on the surface of (particles of) molecular sieve crystals. p
It is formed by immersion in H) and conversion to a mesoporous or macroporous material by heat treatment once the desired shell thickness has accumulated. In this way, the shell is formed from particles of crystals or substances having inter-crystal / inter-particle mesopores or macropores.

The catalyst composition thus obtained is then
It can be calcined and subsequently steamed to a desired macroporous morphology suitable for conversion of the amorphous material (if present) in the catalyst shell. Preferably, the catalyst shell is obtained from any of the above techniques from a "sol" containing suitable precursors of mesoporous or macroporous materials. Sols are generally continuous fluids (dispersed fluids) in the art.
It is understood that it consists of substantially regular sized particles dispersed therein. Also preferred is a method using a sol-type solution or a slurry that gives the same homogeneity of particle size and distribution. More preferably, the catalyst shell is under conditions carefully selected for temperature, fluidizing air velocity, sol or slurry concentration and atomization rate, thereby achieving the desired coating and maintaining the integrity of the catalyst particles. Obtained by the spray drying technique described above. In a further aspect of the invention there is provided a hydrocarbonaceous product or fractions thereof as obtained by the process of the invention.

[0019]

The present invention is further illustrated by the following non-limiting examples. Example 1 Preparation of a Catalyst According to the Invention This example shows a commercially available fluid catalytic cracking catalyst consisting of Y-zeolite and matrix material (hereinafter catalyst 1
Say. ) Catalysts 1A to 1J by modification of sample
The production of is described. Catalyst 1 is 0.08 due to nitrogen adsorption
It was determined to have a micropore volume of 1 ml / g. A sample of catalyst 1 was calcined before modification. Example 1A Preparation of Catalyst 1A A sample of Catalyst 1 was placed in a commercial spray coater (STREA-1 from Niro-Aeromatic) and with air having an inlet temperature of 80 ° C. at a blower speed of 4. Fluidized. Silica sol (Nyacol 2040NH4 manufactured by Akzo-Novell) containing 40% by weight of SiO ₂ dry solids in an aqueous solution was supplied to the spray coating apparatus using a liquid discharge pump, and the sol was applied to the fluidizing catalyst 1. Atomizing air having a pressure of 1.0 bar gauge pressure was used for atomizing. After the addition of the sol was completed, fluidization of the catalyst was continued for another 30 minutes (for additional drying). The catalyst was removed and calcined in a well ventilated furnace at 550 ° C. for 2 hours to give product catalyst 1A. The silica sprayed onto the base catalyst 1 has a mass of 14.
8 wt% was determined from the mass difference, which was determined to be 0.068 m determined by nitrogen adsorption on catalyst 1A.
Consistent with the reduction of micropore volume to 1 / g.

Example 1B Preparation of Catalyst 1B The product catalyst 1B was obtained by following the procedure of Example 1A, but varying the amount of silica sol fed to the spray coater.
The silica sprayed on the base catalyst 1 was 22.6% by weight of the mass of the final catalyst 1B, which is also in agreement with the measured reduction in pore volume. Example 1C Preparation of Catalyst 1C The procedure of Example 1A was followed, except that 15.5% by weight of Z
Zirconia sol (Bacote) containing dry solids of rO ₂ was fed to the spray coating equipment to produce product catalyst 1C.
I got The zirconia sprayed onto the base catalyst 1 was 11.3% by weight of the mass of the final catalyst 1C. Example 1D Preparation of Catalyst 1D The procedure of Example 1A was followed, except that 20% by weight CeO 2 was used.
_A cerium acetate sol (Nyacol manufactured by Piku Corporation) containing ₂ dry solids was supplied to a spray coating apparatus to obtain a product catalyst 1D. The ceria sprayed on the base catalyst 1 has a mass of 15.
It was 5% by weight.

Example 1E Preparation of Catalyst 1E The procedure of Example 1A was followed, except that an equimolar ratio of Al: P was used.
A sol-type solution of aluminum phosphate containing 46 g of solids per liter of solution obtained by coprecipitation from the solution of aluminum nitrate and phosphoric acid in Example 1 was supplied to a spray coating apparatus to obtain a product catalyst 1E. The aluminum phosphate sprayed onto the base catalyst 1 was 10% by weight of the mass of the final catalyst 1E. Example 1F Preparation of Catalyst 1F The procedure of Example 1A was followed, except that the magnesium aluminate sol form contained 26 g of solids per liter of solution obtained by coprecipitation from equimolar solutions of magnesium and aluminate. The solution was supplied to a spray coating device to obtain a product catalyst 1F. The magnesium aluminate sprayed on the base catalyst 1 was 8% by weight of the mass of the final catalyst 1F. Example 1G Preparation of Catalyst 1G The procedure of Example 1A was followed, except that 14% by weight of Y ₂ O was used.
Yttriasol containing ₃ dry solids (Peuk
Nyacol manufactured by Corporation was supplied to a spray coating device to obtain a product catalyst 1G. Base catalyst 1
The yttria sprayed on is 12 times the mass of the final catalyst 1G.
% By weight.

Example 1H Preparation of Catalyst 1H The procedure of Example 1A was followed, except that 15% by weight SnO 2 was used.
Stannous acid sol containing ₂ dry solids (Peuk
Nyacol SN-15 made by Corporation
CG) was supplied to the spray coating device to obtain the product catalyst 1H. The tin oxide sprayed onto Base Catalyst 1 was 12% by weight of the final catalyst weight. Example 1I Preparation of catalyst 1I The procedure of Example 1A was followed, except that the molar ratio of A was 3/2.
A mullite sol containing 1 ₂ O ₃ / SiO ₂ (manufactured by Magnesium Electron Chemicals) was supplied to a spray coating apparatus to obtain a product catalyst 1I. The mullite sprayed on base catalyst 1 was 8% by weight of the mass of final catalyst 1I. Example 1J Preparation of Catalyst 1J The procedure of Example 1A was followed, except that a titania "slurry" (Degussa P50) containing 30% by weight solids of TiO _{2 in} water was fed to a spray coater. The physical catalyst 1J was obtained. The titania sprayed on the base catalyst 1 was 10% by weight of the mass of the final catalyst 1J.

Example 2 This example shows the catalytic cracking performance according to the invention in a process using a steam-polluted coated equilibrium catalyst. Catalyst 1B was contacted with steam at 788 ° C. for 5 hours in a fluidized bed to simulate equilibrium catalytic activity, and then in a microactivity test (MAT) apparatus at a temperature of 540 ° C. as shown in Table 1 below. Contacted with the indicated feedstock. The process conditions and product yields are shown in Table 2 below. Example 3 This example shows the catalytic cracking performance according to the invention in a process using a coated equilibrium catalyst contaminated with coke, water vapor and heavy metals. Gas 1750 containing vanadium and nickel in a circulating deactivator (CDU) and steam and catalyst 750 to simulate the activity of an equilibrium catalyst loaded with 7200 mg / kg vanadium and 2400 mg / kg nickel. Contacted at 0 ° C. The deactivated catalyst was treated with MA according to the procedure described in Example 2.
Contacted the feedstock of Example 2 in a T-apparatus. The process conditions and product yields are shown in Table 2 below.

Example 4 (Comparative) Using catalyst 1, the procedure of example 2 was repeated. The process conditions and product yields are shown in Table 2 below. Example 5 (comparative) Using catalyst 1, the procedure of example 3 was repeated. The process conditions and product yields are shown in Table 2 below.

[0025]

Table 1 Table 1 Atmospheric pressure residue of feedstock Specific gravity, API 21.8 Hydrogen,% w 12.3 Sulfur,% w 0.85 Nitrogen,% w 0.2 Vanadium, ppmv 8.60 Nickel, ppmv 4 .10 Conradson carbon,% w 3.66 Kinematic viscosity, at 100 ° C. 16.2 Aromatic carbon,% w 15.5

[0026]

Table 2 Table 2 Example 2 Example 4 Example 3 Example 5 Catalyst 1B Catalyst 1 Catalyst 1A Catalyst 1 ─────────────────────────── ────── T / ° C 540 540 540 540 Catalyst / oil ratio ¹ 3 3 3 3 Yield,% w C _{1 to} C ₄ 18.5 22.0 11.6 10.7 C _{5 to} 221 ° C. 47 9.9 46.6 48.7 42.2 221 to 370 ° C 18.4 17.1 22.7 22.7 370 + ° C 7.6 5.8 8.5 15.3 Coke ¹ 7.6 8.5 8 .5 9.1 ^{1 For a} given catalyst / oil ratio, the degree of conversion and coke yield in the MAT unit is typically higher than in large riser operations.

It is clear from Table 2 that Catalysts 1B and 1A exhibit more attractive product yields and lower coke yields than Comparative Catalyst 1. A comparison of the performance of Examples 2 and 3 reveals an improvement in performance whether or not the catalyst is contaminated with heavy metals.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B01J 29/70 M 35/10 301 Z C10G 11/05 6958-4H 11/18 6958-4H 35 / 095 6958-4H (72) Inventor Carolus Matias Anna Maria Mesters Netherlands 1031 Seem A. Amsteldam, Bathoisuehi 3 (72) Inventor Antonius Franz Isks Heinrich Wierels Netherlands 1031 Seem Amsterdam, Bathouesueich 3 (72) Inventor Gotse Botschhorn The Netherlands 1031 C.M. Amsterdam, Bathouesuech 3

Claims (16)

[Claims] 1. A method of catalytic conversion of a hydrocarbonaceous feedstock comprising contacting a hydrocarbonaceous feedstock with a particulate form of a molecular sieve catalyst at an elevated temperature in a conversion zone, wherein individual particles of the catalyst are rotated. A core with a shell, and the core consisting of acidic microporous molecular sieve crystals and the shell consisting of a substantially non-acidic mesoporous or macroporous oxide material or oxyanion material The above method characterized by the above. 2. A process which is carried out in a moving bed of catalyst, wherein the catalyst is kept in the feed for less than 10 seconds and suitably longer than 0.1 seconds, preferably 0.2-6 seconds, 150 kg per kg of feed. Up to a catalyst, preferably in a weight ratio of 5 to 100: 1, eg 7 to 20: 1, at relatively high temperatures, preferably 450 to 800 ° C., more preferably 475 to 650 ° C., eg at temperatures in the range 500 to 550 ° C. And suitably 1
The method of claim 1, wherein the contacting is at a pressure in the range of 10 bar. 3. Feedstocks are long, short, flash distillates, hydrotreated and hydrocracked feedstocks, gas oils, vacuum gas oils, tar sands, shale. More preferably includes a residual fraction selected from oils and coal liquors and preferably derived from crude oils such as heavy residual oils and more preferably has a high initial boiling point, eg above 370 ° C. and a high asphaltene content eg 4% by weight. The method of claim 1 or 2 having a higher asphaltene content. 4. The catalyst core comprises a microporous material having a pore diameter less than 1.0 nm, preferably in the range 0.3 nm to 0.9 nm, and the shell 1.0 nm to 10 nm.
4. The method according to any one of claims 1 to 3, consisting of a mesoporous material having a pore diameter of 0 nm, for example about 2.0 to 50 nm, or a macroporous material having a pore diameter of greater than 50 nm. 5. The process according to claim 1, wherein the core and shell components of the catalyst are present as discrete components consisting of two separate radial zones. 6. The substantially non-acidic mesoporous material is a group 2A, 2B, 3A, 3B, or 4 of the periodic table of elements.
Non-acidic oxides or oxyanion compounds of elements selected from Group A, Group 4B and Lanthanide groups, such as clays such as kaolin and metakaolin, alumina, silica, silica-alumina, magnesium aluminate, magnesia, calcia, titania. , Zirconia, yttria, ceria, lantana, tin oxide, aluminum phosphate and mixtures thereof, or a substantially non-acidic macroporous material is in the form of an alpha-alumina, silica such as amorphous silica. Any of claims 1 to 5, selected from the group consisting of silica, alumina, for example in the form of mullite, magnesia-alumina, for example in the form of spinel, magnesia-silica, ceria, yttria, aluminum phosphate and mixtures thereof. Method of paragraph 1. 7. The mesoporous or macroporous shell remaining in the equilibrium catalyst particles has a thickness in the range of 1 to 20 microns, preferably in the range of 2 to 10 microns. Method of terms. 8. The method of claim 1, wherein the shell comprises a mesoporous or macroporous material of a substantially uniform size agglomerate of substantially uniform size particles or crystals. Method of paragraph 1. 9. A catalyst shell is obtained on a preformed core by spray drying, soaking, impregnating or precipitating a sol containing suitable precursors of medium or macroporous material, preferably by spray drying. 9. The method according to any one of claims 1-8. 10. The catalyst shell comprises a substantially non-acidic mesoporous oxide material or oxyanion material.
10. The method according to any one of 9 to 9. 11. A shape-selective zeolitic material, the molecular sieve of which has a pore size in the range of 0.3 to 0.9 nm, eg a faujasite type zeolite such as zeolites Y and X, eg in stabilized form, Including zeolite beta and zeolite omega, those having a pore size in the range of 0.7 to 0.9 nm or crystalline silica (silicalite), silicoaluminophosphates such as SAPO-4 and SAPO-11, ALPO-11 Aluminum phosphates such as TAPO-11 and TASO-45
Titanium aluminophosphates and titanium aluminosilicates, boron silicates and ferrierite, erionite, theta and ZSM-5, ZSM-11, Z
SM-12, ZSM-35, ZSM-23 and ZSM-
0, including crystalline (metal) silicates, such as ZSM type zeolites such as 38, where the metal may consist of aluminum, gallium, iron, scandium, rhodium and / or chromium and mixtures thereof. .3 ~
11. The method of any one of claims 1-10, which comprises having a pore size in the range of 0.7 nm. 12. The method of claim 11, wherein the zeolite is substantially in its acidic hydrogen form. 13. The method according to claim 1, wherein the catalyst is used as a main catalyst component and / or as an additive catalyst component intended for the selective conversion of hydrocarbon components produced in situ by the main catalyst component. The method according to any one of the items. 14. The method according to claim 1, which is a fluid catalytic cracking method.
13. The method according to any one of 13. 15. A catalyst composition comprising a core of acidic microporous molecular sieve crystals having a shell of a substantially non-acidic mesoporous or macroporous oxide material or oxyanion material around. 16. A hydrocarbonaceous product or fractions thereof when obtained by the process of the invention.