KR20030080224A - Cracking catalyst composition - Google Patents

Abstract

The present invention relates to a cracking catalyst composition comprising a physical mixture of cracking catalyst A 10-90% by weight and cracking catalyst B 90-10% by weight, wherein catalyst A is a zeolite-containing cracking catalyst and catalyst B is the same pore. A catalyst having an average pore volume in the pore diameter range of 20-200 mm 3, higher than catalyst A in the diameter range, and containing no M41S material, the composition may be suitably used for flow catalyst cracking of hydrocarbon feeds having high metal concentrations. It is characterized by being.

Description

Cracking catalyst composition {CRACKING CATALYST COMPOSITION}

The present invention relates to a cracking catalyst composition and its use.

Conventional flow catalyst cracking (FCC) catalysts include zeolite components. One of the problems often faced by the FCC is the poisoning of zeolites by cracking of metals such as nickel and vanadium present in many hydrocarbon feeds needed to crack.

One way to deal with this problem is to protect the zeolite with a metal remover. Broadly, the metal remover contains clays rich in alkaline earth metal compounds such as magnesium, calcium and barium, or rare earth metals. The metal remover may be present in the FCC catalyst particles or in the separation additive particles, ie the physical mixture of the FCC catalyst and the additive particles. The advantage of using a metal remover in the separation additive particles is that the metal removed is further away from the zeolite.

U.S. Pat.No. 5,965,474 includes an additive comprising an M41S material and a conventional faujasite-containing FCC catalyst and a catalyst in which a metal passivating agent selected from a rare earth compound, an alkaline earth metal compound or a combination thereof is added into the pores. A composition is disclosed.

The M41S material has a benzene adsorption capacity of at least about 15 g per 100 g of anhydrous crystals at 50 torr and 25 ° C. and a relative intensity of 100, indicating that after calcination an X-ray diffraction pattern having at least one peak at a position above about 18 kV d-interval -Layered super-sized pore crystalline material as defined in this document as well as in this document. An example of an M41S-material is MCM-41.

The catalyst composition according to this document has several disadvantages.

Firstly, an organic template is required to prepare the M41S material, which is relatively expensive and can only be completely removed by calcination. Removing here excludes regeneration, thus releasing environmentally undesirable emissions.

Secondly, the materials have relatively low thermal stability. For example, Z. Luan et al. (J. Phys. Chem. 99 (1995) pp. 10590-10593) disclose the progressive removal of structural aluminum from the MCM-41 structure above 300 ° C. And, due to the relatively thin outer walls of the materials, their structure readily collapses upon heat treatment (N. Coustel et al., J. Chem. Soc., Chem. Commun., 1994, pp. 967-968). Since FCC processes usually proceed at high temperatures, additives with high thermal stability are preferred. Third, M41S materials have a relatively low high acidity. Because of the relatively low acidity and relatively low thermal stability, M41S materials have much lower cracking activity than conventional FCC catalysts. Therefore, replacing part of the FCC catalyst with the above additives dilutes the catalyst and reduces the cracking activity.

The present invention provides a cracking catalyst composition having good metal removal properties with little or no dilution of the cracking catalyst and having better thermal stability than the M41S material. And, the composition is less expensive than systems based on M41S-materials.

The cracking catalyst composition according to the invention comprises a physical mixture of cracking catalyst A 10-90% by weight and cracking catalyst B 90-10% by weight, said catalyst A being a zeolite-containing cracking catalyst, said catalyst B having the same pore diameter A catalyst having an average pore volume in the pore diameter range of 20-200 mm 3, higher than catalyst A in the range, and containing no M41S material.

As used herein, the term 'cracking catalyst' refers to the microactivity (MAT), ie the conversion rate in the microactivity test using the following general test procedure at the catalyst / feed ratio of 5, after the activity deactivation by steam in the absence of metal, Defined as a conversion rate of at least 32%.

Since catalyst B has significant cracking activity, there is no decrease in cracking activity when using the composition according to the present invention as compared to using a conventional FCC catalyst. Therefore, the activity of the cracking catalyst composition according to the present invention will be in contrast to the activity of conventional FCC catalysts.

In addition, the cracking catalyst composition according to the present invention is thermally stable under FCC treatment conditions.

The cracking catalyst composition is 10-90 wt.% Cracking catalyst A and 90-10 wt.% Cracking catalyst B, preferably 30-90 wt.% Cracking catalyst A and 70-10 wt.% Cracking catalyst B, more preferably cracking 50-90 wt.% Catalyst A and 50-10 wt.% Cracking catalyst B, and most preferably 65-80 wt.% Cracking catalyst A and 35-20 wt.% Cracking catalyst B.

Preferably, the average pore volume of catalyst B in the pore diameter range 20-200 mm 3 is 1.5 to 6 times, more preferably 2 to 4 times higher than the pore volume of catalyst A in the pore diameter range.

The pore volume of catalyst B in the pore diameter range is preferably 0.1 to 0.4 ml / g, more preferably 0.1 to 0.2 ml / g.

The pore volume within the indicated pore diameter range is estimated by the cylindrical pore model and measured by the Barrer, Joyner and Halenda (BJH) method using ASAP 2400 from Micromeritics. The sample is pre-treated at 600 ° C. for 1 hour under vacuum.

1 and 2 show the pore size distribution difference between catalyst A and catalyst B, as measured by nitrogen adsorption. In this figure, D denotes the pore diameter and V denotes the volume of nitrogen adsorbed by the catalyst.

Cracking Catalyst A

Cracking catalyst A preferably comprises 10-70 wt.% Zeolite, 0-30 wt.% Alumina, 5-40 wt.% Silica and an equilibrium amount of kaolin. More preferably, catalyst A comprises 20-60 wt.% Zeolite, 0-20 wt.% Alumina, 10-40 wt.% Silica and an equilibrium amount of kaolin. Most preferably, catalyst A comprises 30-50 wt.% Zeolite, 0-20 wt.% Alumina, 10-30 wt.% Silica and an equilibrium amount of kaolin.

Cracking catalyst A may be a conventional FCC catalyst comprising a zeolite and a matrix.

The matrix typically contains silica, alumina, silica-alumina and / or clay. Preferred clay is kaolin.

The zeolite is preferably optionally superstabilized and / or rare earth exchanged faujasite, ie zeolite Y, zeolite USY, zeolite REY or zeolite REUSY.

Catalyst A may further comprise other components commonly used in FCC catalysts.

Catalyst A can be prepared by conventional methods for preparing FCC catalysts comprising the above components.

Cracking Catalyst B

Catalyst B preferably comprises 0-50 wt.% Zeolite, 0-70 wt.% Alumina, 5-40 wt.% Silica, 0-15 wt.% Rare earth metal oxide, and an equilibrium amount of kaolin. More preferably, catalyst B comprises 1-30 wt.% Zeolite, 10-70 wt.% Alumina, 5-35 wt.% Silica, 0-15 wt.% Rare earth metal oxide and an equilibrium amount of kaolin. Even more preferably, catalyst B comprises 5-15 wt.% Zeolite, 15-55 wt.% Alumina, 10-30 wt.% Silica, 1-15 wt.% Rare earth metal oxide and kaolin in equilibrium.

If the catalyst B comprises a molecular sieve, the catalyst B can be zeolitic zeolite Y, zeolite USY, or ZSM zeolite such as ZSM-5, silica aluminum phosphate (SAPO), aluminum phosphate (ALPO) or a combination thereof. have.

Preferably, catalyst B comprises at least one of said zeolites, more preferably a rare earth exchanged zeolite. Even more preferably, catalyst B is an FCC catalyst suitable for the conversion of heavy feeds. The catalyst usually contains more alumina and fewer zeolites than conventional FCC catalysts. Therefore, it is preferable that the catalyst B contains more alumina and less zeolite than the catalyst A.

Catalyst B is preferably impregnated with a rare earth metal compound to produce a rare earth metal oxide (RE ₂ O ₃ ) -containing cracking catalyst B. Suitable rare earth metals are La, Ce, Nd, Pr and mixtures thereof.

Cracking catalyst B may be prepared according to the method disclosed in Brazilian patent application BR 9704925-5A. This document describes a process for preparing FCC catalysts using a pore-forming agent to control the porosity of the catalyst. Preferred pore-forming agents are water-soluble carbohydrates, such as sucrose, maltose, cellobiose, lactose, glucose or fructose, which are easily removed after preparation of the catalyst. Thermogravimetric analysis shows that the pore-former can be almost completely removed since less than 5 wt.% Of the remaining pore-former remains in the catalyst.

Other ingredients

In addition to catalysts A and B, it is also noted that the cracking catalyst composition may contain additional components such as additional metal removal additives or additional cracking catalysts. For example, the cracking catalyst composition comprises a zeolite Y-containing catalyst A, a cracking catalyst B, and a catalyst containing a zeolite that improves the octane number, such as ZSM-5.

Fluid Catalytic Cracking

The cracking catalyst composition according to the present invention is particularly useful for FCC units operated by heavy hydrocarbon feeds containing high concentrations of contaminant metals. Examples of such feeds are atmospheric distillation residues (ADR), vacuum residues (VR) with boiling points above 570 ° C., heavy vacuum gas oils (HVGO) and mixtures thereof.

In a fluid catalytic cracking unit, the hydrocarbon feed atomized and vaporized at a temperature of 490 to 560 ° C. is brought into contact with the cracking catalyst composition according to the invention, and the cracked product flowing through the vertical reactor, the reaction zone of the unit in which the cracking reaction takes place. And a suspension of the catalyst composition in the nebulized / vaporized feed. The reaction zone is usually an elongated vertical tube, where the flow is up (increase) or down (decrease). The residence time in the reaction zone of the suspension of the cracked product and the catalyst composition in the atomization / vaporization feed is about 0.3 to 8 seconds.

The catalyst composition is continuously separated from the conversion product, steam immersed and regenerated under oxidation at temperatures above 640 ° C. The regenerated catalyst composition is recycled to the reactor to contact fresh feed of heavy hydrocarbons.

General Test Procedure: Microactivity Test

Microactivity Test (MAT) is a generally suitable method for testing the FCC cracking activity of a catalyst.

In the following examples, the microactivity test was carried out in a confined fluid bed ACE-unit, model R ^+, from Xytel and Kayser Technology. The ACE-unit comprises a pressurized fluidized bed reactor containing a catalyst sample. A known amount of hydrocarbon feed was injected onto the sample. After contacting the catalyst with the feed, the catalyst was regenerated. The reaction temperature used for all tests was 535 ° C., the feed flow rate was 1.2 g / min and the regeneration temperature was 695 ° C.

The test was run using different catalyst / feed ratios. The ratio is obtained by varying the feed injection time from 50 to 150 seconds, with a catalyst / feed ratio of 3 to 10.

Conversion rates considered microactivity (MAT) are defined as the weight percent of feed converted to coke, gas and gasoline. Light cycle oil (LCO) fractions are not considered as products and therefore the conversion is [100- (LCO + residue)].

The feed used was brazilian gas heavy oil with high nitrogen and Conradson carbon content and formed stringent catalytic test conditions. Table 1 shows the characteristics of the feed.

Physical and Chemical Properties of Brazilian Gas Oils Used API 18.6 Density 20/4 ℃ (g / ml) 0.9391 Aniline Point (ppm) 93.2 Total nitrogen (ppm) 3069 Basic nitrogen (ppm) 1001 Ramsbottom Carbon Residue (% w) 0.58 Insoluble matter in n-heptane (% w) <0.1 Sulfur (% w) 0.63 Polyaromatic (% w) 29 Dynamic Viscosity (ASTM D445) (cSt) @ 60 ° 95.95 Initial boiling point, IBP (℃) 325 Final boiling point, FBP (℃) 588 Ni (ppm) <1 V (ppm) <1 Na (ppm) <1

Example 1

This example describes a process for preparing several cracking catalysts.

Catalyst A1 comprised 43 wt.% Of rare earth exchanged Y-zeolites, 5 wt.% Of Al ₂ O ₃ , silica and an equilibrium amount of kaolin.

Catalyst A1 was prepared as follows:

38.0 kg of silica hydrosol (7.5 wt.% Of SiO ₂ ) was prepared by controlled neutralization under acidic pH of sodium silicate solution (29% SiO ₂ , 9% Na ₂ O) using diluted sulfuric acid solution. While stirring the resulting suspension, 4.0 kg of powdered kaolin was added to the freshly prepared hydrosol. Then, 2.4 kg of acidic boehmite suspension was added followed by 16.0 kg of an acidic suspension of rare earth exchanged Y-zeolite. The resulting precursor suspension had a solids content of 20 wt.%.

The precursor suspension is fed to a high-shear atomizer, ie a colloid mill, and then operated at an inlet temperature of 445 ° C. and an outlet temperature of 135 ° C., a flow rate of 4 kg / min and an atomizer rotational force of 13,500 rpm. Spray-dried using a spray-dryer.

6.0 kg of spray-dried product were resuspended in aqueous ammonia and vacuum filtered. The filter cake formed was exchanged with ammonium sulfate and washed with water. Finally, the catalyst was dried in an air-circulating oven at 110 ° C. for 16 hours.

Catalyst A _ref comprised 35 wt.% Rare earth exchanged Y-zeolite, 10 wt.% Al ₂ O ₃ , silica and an equilibrium amount of kaolin. The catalyst was prepared by the same method as Catalyst A1 except for the concentration of zeolite, alumina, silica and kaolin.

Catalyst B1 comprised 5 wt.% Of rare earth exchanged Y-zeolite, 25 wt.% Al ₂ O ₃ , silica and an equilibrium amount of kaolin.

The catalyst was prepared according to the same method as Catalyst A1 using 12.7 kg silica hydrosol (7.5 wt.% SiO ₂ ), 14.0 kg powder kaolin, 32.4 kg acidic boehmite suspension and 2.0 kg rare earth exchanged Y-zeolitic acid suspension. It was. 3.6 kg of sucrose solution was added to the precursor suspension. The spray-dried product showed a slightly darker color than the catalyst A1. This is presumably due to caramelization of sucrose. However, the color of the final catalyst B1 was similar to that of the catalyst A1. Thermogravimetric tests showed that nearly 98% of sucrose was removed during the wash step.

The chemical composition and some physical properties of the catalyst are described in Table 2.

In Table 2, ABD represents Apparent Bulk Density, which is defined as the mass of catalyst per volume unit in the non-compressed bed. ABD is measured after the layer is fixed without compression, and after filling a gauge cylinder of pre-measured volume.

D50 represents the average particle diameter. The diameter of 50% of the catalyst particles is below the above value. D50 was measured by laser light scattering of the catalyst suspension using Malvern 2600.

catalyst A _ref A1 B1 Y-zeolite (%) 35 43 5 Alumina (%) 10 5 25 Silica (%) 20 24 8 Kaolin (%) 35 28 62 ABD (g / ml) 0.80 0.72 0.84 Void volume. H ₂ O (ml / g) 0.27 0.33 0.25 D50 (micron) 78 83 81 BET surface area (㎡ / g) 242 247 156 Micropore Volume (mL / g) 0.082 0.095 0.011 Pore volume 20-200Å (ml / g) 0.058 0.032 0.123 SiO ₂ (%) 62.6 67.9 45.3 Al ₂ O ₃ (%) 33.2 26.7 51.9 Na ₂ O (%) 0.35 0.53 <0.05 RE ₂ O ₃ (%) 2.42 3.31 0.72

Table 2 clearly shows that for the pore volumes of catalysts A1 and A _ref..., The pore volume of catalyst B1 is larger in the pore diameter range 20-200 mm 3. Indeed, the pore volume of catalyst B1 in this range is 3.8 times larger than the pore volume of catalyst A1 in the same range.

The low value for the micropore volume of catalyst B correlates with the low zeolite content, which is the main source of pores with a diameter of 20 mm or less.

Other pore structures of catalysts A1 and B1 are also evident in FIG. 1, which shows the nitrogen adsorption rate versus pore diameter of the two catalysts.

Example 2

This example illustrates the behavior of the cracking catalyst composition in the presence of high vanadium content.

The cracking catalyst composition was prepared from the following cracking catalysts already described in Example 1:

Catalyst A1,

Catalyst B1 and

Catalyst B1 (catalyst B1RE) impregnated with 8 wt.% Rare earth metal.

The cracking catalyst composition according to the present invention was prepared by mixing 75 wt.% Of catalyst A with 25 wt.% Of catalyst B1 or catalyst B1RE.

The cracking catalyst composition was then mixed with FCC-V and provided as a vanadium source. FCC-V is described in B.R.Mitchell in "Industrial and Engineering Chemistry-Product Research and Development", vol. 19, pages 209-213 (1980), a conventional FCC catalyst impregnated with 2 wt.% Of vanadium according to a well known method for impregnating the FCC catalyst.

The resulting catalyst mixture comprised 56 wt.% Catalyst A1, 19 wt.% Catalyst B1 or B1RE and 25 wt.% FCC-V.

The catalysts were used in two different sieve fractions:> 53 microns (270 mesh) and <43 microns (325 mesh) to separate the catalyst after the test and analyze its vanadium content. A <43 micron fraction of FCC-V and a> 53 micron fraction of the catalysts B1 and B1RE classifications were used. The applied sieve fraction of catalyst A1 varied from experiment to experiment.

The catalyst mixture was deactivated for 5 hours at 788 ° C. using 100% steam to enable vanadium migration. The catalyst mixture was subsequently sieved and the vanadium content of> 53 micron fraction was measured by X-ray fluorescence spectroscopy (XRF).

The vanadium content in> 53 micron fractions of the other cracking catalyst compositions is shown in Table 3.

Experimental Example Catalyst mixture > 53 micron classification V-content (ppm) One A1, <43 microns B1 FCC-V B1 3900 2 A1,> 53 microns B1 FCC-V A1 + B1 2800 3 A1, <43 microns B1RE FCC-V B1RE 8100 4 A1,> 53 microns B1RE FCC-V A1 + B1RE 2600

The results in Table 3 show the high vanadium removal capacity of catalysts B1 and B1RE, with porosities in the pore diameter of 20-200 mm 3 higher than catalyst A1.

The BET surface area and the micropore volume of the cracking catalyst composition before and after Experimental Examples 2 and 4 are the cracking catalyst composition used in Experimental Example 1-4, and the catalyst A _ref undergoes the same deactivation process in the presence of the catalyst FCC-V. Table 4 shows the data of> 53 micron fractions.

Both BET surface area and micropore volume were calculated at adsorption isotherms. To measure the BET surface area, the well-known BET method was used; Harkins and Jura's t-plot method was used at 3.3-5.4 nm to measure micropore volume. For this measurement, Micrometrics ASAP 2400 was used. Samples were pre-treated in vacuum at 600 ° C. for 1 hour.

A _ref A1 + B1 (Experimental Example 2) A1 + B1RE (Experimental Example 4) Before deactivation: BET surface area (㎡ / g) 242 225 217 Micropore Volume (mL / g) 0.082 0.074 0.075 After deactivation: BET surface area (㎡ / g) 73 81 90 Micropore Volume (mL / g) 0.025 0.028 0.033 Residual rate (%) BET surface area 30 36 41 Micropore volume 30 38 44

The data in Table 4 shows the residual ratio of the structural properties of the cracking catalyst composition according to the invention which is good compared to the control catalyst A _ref .

In addition, structure retention is improved by the presence of rare earth in catalyst B.

Example 3

This example illustrates the activity of the cracking catalyst composition according to the invention using a microactivity test. Other catalyst / feed ratios ranging from 3 to 10 were used for this test.

The cracking catalyst composition and control catalyst A _ref of Example 2 were tested after vigorous vapor deactivation in the presence and absence of a vanadium source (catalyst FCC-V). The conditions are mentioned in Example 2. The results are shown in Tables 5A, 5B and 5C. In Table 5A, the conversion rates of the catalyst compositions are compared at the same catalyst / feed ratio. Table 5B compares products formed at the same conversion (iso-conversion) and Table 5C compares conversion and gasoline and residue concentrations at the same coke-forming (iso-coke).

Deactivated without V Deactivated in the presence of V A _ref A1 + B1 A _ref A1 + B1 A1 + B1RE Catalyst / Feed Ratio 7.0 7.0 5.0 5.0 5.0 Conversion (wt.%) 59.7 62.0 40.0 48.9 48.0

Deactivated without V Deactivated in the presence of V A _ref A1 + B1 A _ref A1 + B1 A1 + B1RE Iso-Conversion (wt.%) 60 60 48.0 48.0 48.0 Fuel gas (wt.%) 1.7 2.0 1.9 2.1 2.0 Hydrogen (wt.%) 0.03 0.04 0.27 0.29 0.21 Coke (wt.%) 4.4 4.7 6.0 5.5 5.0 LPG (wt.%) 12.9 13.4 7.6 7.8 8.3 Propylene (wt.%) 3.5 3.3 2.2 2.2 2.3 Gasoline (wt.%) 41.0 40.0 32.5 32.6 32.7 Light circulating oil (wt.%) 14.1 12.6 15.8 16.9 15.9 Residual layer (wt.%) 25.9 27.4 36.2 35.1 36.1 Delta coke (coke / catalyst) 0.60 0.80 0.7 1.2 1.0

Deactivated without V Deactivated in the presence of V A _ref A1 + B1 A _ref A1 + B1 A1 + B1RE Iso-coke (wt.%) 4.5 4.5 5.5 5.5 5.5 Conversion (wt.%) 60.3 59.4 45.8 47.8 50.0 Gasoline (wt.%) 41.0 40.0 31.3 32.5 33.8 Residual layer (wt.%) 25.5 27.9 38.1 35.2 34.5

The results in Table 5 after deactivation in the absence of vanadium source show that there is no significant difference between the activity and selectivity of the cracking catalyst composition and the control catalyst A _ref according to the invention, but the composition according to the invention is slightly more active. Note that

The table also shows that the cracking catalyst composition according to the invention after deactivation in the presence of vanadium exhibits better performance than the control catalyst A _ref , ie high conversion, regardless of selectivity. With the composition comprising the rare earth-containing catalyst B, reduction of coke and hydrogen formation were obtained.

Example 4

In this example, the following catalysts were used:

Catalyst B2 comprises 25 wt.% Silica, 50 wt.% Activated alumina and equilibrium kaolin, with the exception of the absence of zeolite in the catalyst and the amount of silica, alumina and kaolin, using a pre-forming agent, Prepared according to the preparation method for the catalyst B1 (see Example 1).

Catalyst B3 comprises 25 wt.% Silica, 30 wt.% Active alumina and equilibrium kaolin, with the exception of the absence of zeolite and the amount of silica, alumina and kaolin in the catalyst, Prepared according to the preparation method for the catalyst B1 (see Example 1).

Catalyst B4 has the same composition as Catalyst B2 and was prepared without using a pre-forming agent. Thus, the catalyst was prepared according to the preparation method for catalyst A1 (see Example 1), except for the absence of zeolite in the catalyst and the amounts of silica, alumina and kaolin.

Catalyst A2 comprised 50 wt.% Y-zeolite, 25 wt.% Silica and an equilibrium amount of kaolin.

The catalyst FCC is a commercial catalyst comprising 35 wt.% Rare earth-exchanged Y-zeolite, 10 wt.% Alumina, silica and an equilibrium amount of kaolin.

The pore volume in the pore diameter range of 20-200 mm 3 of these catalysts is shown in Table 6.

catalyst Pore volume (ml / g) in the range 20-200 mm 3 B2 0.196 B3 0.179 B4 0.123 FCC 0.061

The cracking catalyst composition according to the present invention comprises a 1: 1 mixture of <43 micron classifier of catalyst A2 and> 53 micron classifier of catalyst B2, B3 or B4 and <53 micron classifier of catalyst FCC and> 53 of catalyst B2 or B4. Prepared from a 2: 1 mixture of micron fractions.

The cracking catalyst composition was deactivated in the presence of vanadium according to Example 2. The V-source was Catalyst FCC-V, a catalyst FCC impregnated with 2% vanadium, using <43 micron classification thereof. After deactivation, the V-content of> 53 micron fractions was measured. Table 7 shows the results of the test.

Experimental Example Catalyst mixture V content (ppm) > 53 microns <43 microns <43 microns > 53 microns One 37.5% B2 37.5% A2 25% FCC-V 5600 2 37.5% B3 37.5% A2 25% FCC-V 4200 3 37.5% B4 37.5% A2 25% FCC-V 3000 4 25% B2 50% FCC 25% FCC-V 6000 5 25% B4 50% FCC 25% FCC-V 4600

Table 7 shows that catalyst B2 has the highest metal removal capacity, followed by catalysts B3 and B4. This shows that the larger the difference between the pore volumes between catalyst A and catalyst B in the pore diameter range of 20-200 mm 3, the more vanadium is removed by catalyst B.

Example 5

The cracking catalyst composition was prepared in a 1: 1 mixture of (a) another sieve fraction of catalyst A2, (b) another sieve fraction of catalyst B2, (c) catalyst A2 and catalyst B2.

After deactivation (see Example 2) in the presence of FCC-V, the V-content of the> 53 micron fraction was measured. The results are shown in Table 8.

Experimental Example Catalyst mixture V content (ppm0 37.5% 37.5% 25% > 53 microns > 53 microns <43 microns <43 microns One A2 A2 FCC-V 2800 2 B2 B2 FCC-V 4800 3 A2 B2 FCC-V 1100 4 B2 A2 FCC-V 5600

In Experimental Examples 1 and 3, it is evident that the presence of catalyst B2 reduces vanadium contamination in catalyst A2.

The data also shows that the vanadium removal properties of catalyst B are not only a result of their particle size: both> 53 micron and <43 micron classification of catalyst B2 have good metal removal properties.

Example 6

In this experiment, the following catalysts were used:

Catalyst B3 comprised 25 wt.% Silica, 30 wt.% Activated alumina and an equilibrium amount of kaolin. The catalyst is impregnated with lanthanum chloride or RE, which is a mixture of rare earth metal compounds mainly comprising Ce and La, and either 11 wt.% RE ₂ O ₃ (catalyst B3RE) or 11 wt.% La ₂ O ₃ (catalyst B3La). A catalyst with is produced.

Catalyst A3 comprised US wt 45 wt.% Exchanged by RE ₂ O ₃ 3 wt.%, Silica, alumina and equilibrium amount of kaolin.

Catalyst A4 comprised 35 wt.% USY, silica, alumina and equilibrium kaolin exchanged by 12 wt.% RE ₂ O ₃ .

Combinations of catalysts A3 and A4 are common for conventional FCC catalysts.

The cracking catalyst composition was prepared from a 3: 1 mixture of catalyst A3 and catalyst B3RE or B3La.

Example of activity deactivation in the presence of vanadium proceeded as in Example 2. Table 9 discloses the BET surface area of catalyst A4 and cracking catalyst composition after deactivation. Surface area retention after deactivation relative to deactivated surface area is also shown in Table 9.

Catalyst mixture BET surface area (㎡ / g) Residual rate (%) 58.2% A3 16.8% B3RE 25% FCC-V 123 43 58.2% A3 16.8 B3La 25% FCC-V 129 45 75% A4 - 25% FCC-V 102 36

The results show that the surface area residual ratio of the cracking catalyst composition according to the present invention is large compared to cracking catalyst A4.

Example 7

The following catalysts were used in this experimental example:

Catalyst B5 comprised 20 wt.% Boehmite alumina, 5 wt.% Silica and an equilibrium amount of kaolin. The catalyst is optionally impregnated with the rare earth compound to form RE ₂ O ₃ 5 wt.% (Catalyst B5RE).

In contrast to the other catalysts used in the examples herein, where silica is prepared by neutralization of sodium silicate solution, the silica of this catalyst was prepared by ion-exchanging a silica sol using a cation-exchange resin. A process for preparing the ion-exchanged silica sol is disclosed in US Pat. No. 3,649,556. By the ion-exchange method, silica hydrosols having a larger particle size than silica hydrosols obtained by neutralization of sodium silicate are obtained.

Catalyst A3 comprised US wt 45 wt.% Exchanged by RE ₂ O ₃ 3 wt.%, Silica, alumina and equilibrium amount of kaolin.

Cracking catalyst compositions were prepared using the above catalysts deactivated in the presence of vanadium as described in Example 2. Again, another catalyst fraction was used and the V-content of> 53 microns was measured after deactivation.

Catalyst mixture V content (ppm) > 53 microns <43 microns <43 microns > 53 microns 19% A3 56% A3 25% FCC-V 2600 19% B5 56% A3 25% FCC-V 3500 56% A3 19% B5RE 25% FCC-V 2000 19% B5RE 56% A3 25% FCC-V 4000

The results in Table 10 clearly show that rare earths have a positive effect on vanadium removal by catalyst B5.

2 shows the pore size distribution of catalysts B5 and A3 obtained by nitrogen adsorption. It is clear that catalyst B5 has a pore volume in the pore diameter range 20-200 mm 3, which is larger than catalyst A 3. The pore volume of catalyst B5 in the specific pore diameter range was 0.153 ml / g, while the pore volume of A3 in the same range was 0.059 ml / g. Thus, the pore volume of catalyst B5 in the specific pore diameter range was 2.6 times higher than the pore volume of catalyst A3.

Example 8

Microactivity testing was performed according to Example 3 using a cracking catalyst composition (see Example 7) and catalyst A4 (see Example 6) according to the invention comprising a 3: 1 mixture of catalyst A3 and catalyst B5RE.

Prior to performing the microactivity test, catalyst A4 and the cracking catalyst composition were deactivated by steam in the presence of a vanadium source (FCC-V): see Example 2. To this end, a catalyst mixture or cracking catalyst composition of 25 wt.% Catalyst FCC-V and 75 wt.% Catalyst A4 was prepared.

Tables 11A, 11B and 11C show the results of this test. In Table 11A, the conversion rates of the catalyst compositions are compared at the same catalyst / feed ratio. Table 11B compares products formed at the same conversion (iso-conversion), and Table 11C compares conversion and gasoline and sedimentary concentrations at the same coke-forming (iso-coke).

After deactivation in the presence of V A4 A3 + B5RE A3 + B5 Catalyst / Feed Ratio 5.0 5.0 5.0 Conversion (wt.%) 56.5 64.0 57.7

After deactivation in the presence of V A4 A3 + B5RE A3 + B5 Iso-Conversion (wt.%) 60.0 60.0 60.0 Fuel gas (wt.%) 2.4 2.2 2.4 Hydrogen (wt.%) 0.47 0.31 0.46 Coke (wt.%) 4.6 3.2 4.3 LPG (wt.%) 8.0 8.1 7.4 Propylene (wt.%) 2.4 2.5 2.2 Gasoline (wt.%) 45.0 46.5 46.0 Light circulating oil (wt.%) 18.8 18.8 18.5 Residual layer (wt.%) 21.2 23.2 21.5 Delta coke (coke / catalyst) 0.87 0.71 0.82

After deactivation in the presence of V A4 A3 + B5RE A3 + B5 Iso-coke (wt.%) 4.0 4.0 4.0 Conversion (wt.%) 51.8 66.8 56.6 Gasoline (wt.%) 39.6 49.9 43.8 Residual layer (wt.%) 29.8 17.1 24.8

The results of Tables 11A, 11B and 11C show that the performance of the cracking catalyst composition according to the invention is better than the conventional FCC catalyst (catalyst A4) after deactivation in the presence of vanadium. It has also been shown that better results are obtained with cracking catalyst compositions comprising rare earth metal-containing catalyst B.

Claims (11)

10-90% by weight cracking catalyst A and 90-10% by weight cracking catalyst B, said catalyst A is a zeolite-containing cracking catalyst, said catalyst B being higher than catalyst A in the same pore diameter range, 20 A cracking catalyst composition, characterized in that the catalyst has an average pore volume in the pore diameter range of -200 kPa and does not contain M41S material. The method of claim 1, The cracking catalyst composition, characterized in that the average pore volume of the cracking catalyst B in the pore diameter range of 20-200 mm 3 is 1.5-6 times higher than the average pore volume of the cracking catalyst A in the same pore diameter range. The method according to claim 1 or 2, The cracking catalyst composition, characterized in that the average pore volume of cracking catalyst B in the pore diameter range of 20-200 mm 3 is 0.1-0.4 ml / g. The method according to any one of claims 1 to 3, The cracking catalyst A comprises 10-70 wt.% Zeolite, 0-30 wt.% Alumina, 5-40 wt.% Silica and balance kaolin. The method of claim 4, wherein Wherein said zeolite is selected from zeolite Y, zeolite USY, rare earth metal exchanged zeolite Y, and rare earth metal exchanged zeolite USY. The method according to any one of claims 1 to 5, The cracking catalyst B comprises 0-50 wt.% Zeolite, 0-70 wt.% Alumina, 5-40 wt.% Silica, 0-15 wt.% Rare earth metal oxide and equilibrium amount of kaolin. Cracking Catalyst Composition. The method of claim 6, The cracking catalyst composition B, characterized in that the cracking catalyst comprises 5-15 wt.% Zeolite. The method according to any one of claims 1 to 7, The cracking catalyst B is a cracking catalyst composition, characterized in that it comprises 1-15 wt.% Rare earth metal oxide. Use of a cracking catalyst composition according to any one of claims 1 to 8, characterized in that it is used in a fluid catalytic cracking (FCC) process. Use of the cracking catalyst composition according to any one of claims 1 to 8, characterized in that it is used for flow catalyst cracking of hydrocarbon feeds having a high metal content. The method of claim 10, And said metal is vanadium.