JPS61278351A - Cracking catalyst and its use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to catalytic cracking catalysts, particularly catalyst compositions that are particularly effective for cracking residue-type hydrocarbon feedstocks.

Recently, it has become necessary in the oil refining industry to process larger quantities of residual hydrocarbon feedstocks. These heavy feedstocks often contain significant amounts of metals, such as vanadium,
Contaminated with metals such as nickel, iron and copper that have a negative effect on cracking catalysts used in the oil refining process.

Cracking catalysts containing zeolites are particularly susceptible to deactivation (poisoning by vanadine) and the selectivity of the catalyst is adversely affected by the presence of iron, copper and nickel.

U.S. Patent Nos. 3.835.031 and 4.240.
No. 899 describes a cracking catalyst impregnated with a Group IIA metal for the purpose of reducing sulfur oxide emissions during catalyst regeneration.

U.S. Pat. No. 3,409,541 discloses the addition of finely powdered alkaline and boron-type compounds into catalyst production equipment that react with metal contaminants and produce inert products that can be removed from the catalytic reaction system. However, methods for reducing catalyst deactivation by contaminant metals are described.

U.S. Patent No. 3. Ef99,037 discloses that calcium and magnesium hydroxides, carbonates,
Catalytic cranking methods have been described in which finely powdered additives such as oxides, dolomite and/or limestone are added to absorb SOx components present in the regenerator effluent gas.

U.S. Pat. No. 4,198,320 describes a cracking catalyst containing colloidal silica and/or alumina additives added to prevent deactivation of the catalyst when processing metal-containing feedstocks. There is.

U.S. Pat. No. 4,222,898 describes a metal-tolerant zeolite cracking catalyst containing a magnesia-alumina-aluminum phosphate matrix.

U.S. Patent Nos. 4,283,309 and 4,292,
No. 189 describes porous inorganic oxides such as alumina,
Hydrocarbon reforming catalysts have been described that contain matrices that absorb metals including titania, silica, zirconia, magnesia, and mixtures thereof.

U.S. Pat. No. 4,465,779 discloses a cracking catalyst composition comprising a highly active cracking catalyst and, as a separate component, a magnesium compound or a combination of a magnesium compound and a thermally stable compound. things are listed.

U.S. Patent Nos. 4,432,890 and 4.489,
588, consisting of a zeolite and an inverse matrix of amorphous solids containing metal additives, such as magnesium;
Cracking catalyst compositions are described for use in cracking hydrocarbon oil feedstocks containing large amounts of vanadine that can be added to the catalyst during production or use in hydrocarbon reforming.

PCT Wo 82100105 describes a cracking catalyst resistant to poisoning by metals containing two particulate components and an SOW absorption additive such as aluminum oxide, calcium oxide and/or magnesium oxide.

In this way, in the conventional method, the adverse effects of metal poisoning contained in the residue-type feedstock are suppressed, and the SO!
Several catalyst systems and compositions have been suggested that are effective in suppressing the emissions of In this case, it is not cost effective.

It is therefore an object of the present invention to provide an improved cracking catalyst capable of cracking hydrocarbon feedstocks containing high amounts of metal and sulfur. ' Another object of the present invention is to develop a fluidized cracking catalyst (FC) which is resistant to metal poisoning and can be used in large quantities at a reasonable price.
:C).

Yet another object of the present invention is to provide a cracking catalyst that can handle large amounts of metal, particularly vanadine, without substantially reducing activity or product yield.

These and other objects will be readily apparent to those skilled in the art from the detailed description and examples of the invention that follow.

In a broad sense, the present invention is expressed as an oxide of about 5 to 80
The present invention relates to a catalytic cracking catalyst containing a basic alkaline earth metal component in an amount of % by weight and capable of retaining a high degree of activity even when large amounts of deactivating metals, such as vanadine, are deposited on the catalyst.

More specifically, in the present invention, the pore volume is at least 0°lcc/g and the pore diameter is about 200 to 10,000 cc/g.
where Pv is the pore volume in cc/g in the diameter range of about 200 to 10,000 angstroms, and SA is the diameter measured by mercury porosimetry. is the surface area in ra2/g in the range of about 200 to 10,000 angstroms.
A particulate basic alkaline earth metal composition is provided having an internal pore structure characterized by an average pore diameter (APD) greater than about 400 angstroms, determined in the range of 0.00 to 10,000 angstroms. Ru.

The alkaline earth metal compounds used in the present invention are selected from the metals of Group 11A of the Periodic Table, with calcium and magnesium being preferred, and magnesium being most preferred.

In a particularly preferred embodiment of the invention, the alkaline earth metal component consists of natural or synthetic dolomite of the general formula Mg(CO3)2, MgO or a magnesium-silica gel.

It has a large pore volume with pores larger than about 400 Angstroms at processing temperatures on the order of 1400°F.

In a particularly preferred embodiment, the magnesium oxide-containing component, such as magnesium-silica gel (MgO.SiO2), is prepared in particulate form, where the particles have large pores with diameters greater than about 400 Angstroms. to have a pore volume.

The resulting MgO.Si02 composition may be incorporated into the FCC catalyst particles in an amount of about 2.5-40% by weight, either as an integral component with the FCC catalyst particles or, more preferably, as a separate particulate additive.
Included in the catalyst composition.

Preferred MgO.Si02 gels have an overall MgO weight composition of 30 to 8 oz and a pore volume of diameter greater than about 400 angstroms of at least 0, ic.
e/g, preferably about 0.2 to 1.0 cc/g. MgO・Si02 gel as another granular additive
When added to a CC catalyst, the particle size and density of the additive should be
Preferably, it is similar to the catalyst, ie, the particle size is about 40-80 mm and the average bulk density is 0.5-1.0 g/cc.

A preferred MgO.5i02 gel is prepared by reacting an aqueous solution of sodium silicate with an aqueous solution of magnesium chloride at about 15-50°C to precipitate a gel, which is filtered, slurried in water, and sprayed at about 330-500°C. Once dry, more particulate MgO is added to the MgO*SiO2 gel to bring the final product MgO to 30-80$.

As mentioned above, catalyst compositions containing MgO must have an optimized pore structure as described above in order to be effective in removing vanadine. This is due to the fact that the partial molar volume of magnesium vanadate is larger than that of magnesium oxide. It is believed that the poisoning of cracking catalysts by vanadine is caused by the reaction of V205 with water vapor during the regeneration process, producing the poisoning precursor H3voa [For vapor pressure data, see L.N. Yannopoulos, L. N., Yannopoulos)
Journal of Fist of Physical Chemistry (J,
Phys.

Cbeya, ), Vol. 72, p. 3233 (19138)].

O3voa is isoelectronic to O3poa and is probably a strong acid. Therefore, O3VO4 is SiO2-Al of zeolite
Hydrolysis of the 2O3 network with acid destroys the crystallinity and activity of the zeolite. O3voa reacts with MgO When MgO)2V20s is generated on the surface of the catalyst, the surface of the pores swells due to the large molar volume of (MgO)2V20s. If the pores are too small, they will easily become clogged, which will prevent them from reacting with O3voa.

It has been experimentally determined that the present invention is ineffective unless the average pore diameter is approximately 400 angstroms or more. This effect has been studied in detail for the similar reaction CaO+SO3+CaSO4 [K. Bhatia, S. and Perlmutter, D.
) AIChE Journal Vol. 27, p. 266 and 2
See Vol. 9, p. 79 1° As mentioned above, MgO is a more suitable oxide than other alkalis when used in combination with an FCC catalyst. This is due to the presence of sulfur oxides in the effluent gas in the regenerator, which compete with supra-alkaline sulfates to produce O3voa, as shown by the discussion of the reactions of MgSO4 and CaSO4 with vanadate. This is to do so. All the SOx is SO3, the amount of which is 2000 ppm typical in the regenerator, 20% of the O3VOa, 820% of the typical amount in the regenerator. O7p
Assuming a worst case test with pm and temperature of 970°K (1285°F), the equilibrium constant calculated from the above regenerator conditions (assuming an activity of the condensed phase of 1) is the thermochemical The equilibrium constants for the two reactions can be compared from the analytical data.

2CAS04 (S)+2Ha VOa (g)= (
GaO)2V 20s (S)+2S03 (g)+
3H20 (g) K (9700K) = 472.752M
g504 (S)+2H3VOa (g)= (MgO
)2V 20s (S)+2SO3(g)+3h O
(g) K (970°K) = 8.875X 105[H
3VO4]2 = 2.215 x 10 S In the case of calcium, the equilibrium constant calculated from the regenerator conditions is much larger than the reaction equilibrium constant. Due to Le Chatelier's principle, the reaction with calcium on the left side is more advantageous. The opposite is true for MgO. When calcium is used, Ca5Oa is selectively produced compared to vanadate.

The opposite is true for magnesium.

Fluid catalytic cracking catalysts used in combination with basic alkaline earth metal components are conventional and known to those skilled in the art. Typically, the catalyst is an amorphous inorganic oxide gel, such as a silica-alumina hydrogel, and/or a crystalline zeolite deposited within an inorganic oxide matrix.

Suitable zeolites are synthetic faujasites (Y-type zeolites) and/or shape-selective zeolites, such as ZSM.
-5. Y-type zeolites ion-exchanged with hydrogels and/or stacked metals, such as HY and REV, and Y-type zeolites ion-exchanged with rare earths and subjected to heat treatment such as force potential.
(GREY) type and/or Z14US type are particularly suitable for inclusion in fluidized cracking catalyst compositions.

Catalytically active zeolite components are typically described in US Pat. No. 3,293,192 and RE28. It is described in ft29.

In addition to the active zeolite component, this catalyst contains an inorganic oxide matrix. The inorganic oxide matrix is typically a silica-alumina hydrogel, which can be combined with a substantial amount of clay, such as kaolin. Catalyst matrix systems consisting of silica, alumina, silica-alumina sols and gels can also be used in the present invention. Methods of making suitable catalyst compositions are described in U.S. Pat. No. 3,974,099;
No. 4,228,743, No. 3,887,3
No. 08: 4.247.420 and U.S. Patent Application No. 361.426, filed March 24, 1982.

The basic alkaline earth metal component can be added to the catalyst composition as finely divided solid particles or in the form of a salt that converts into a substantially solid oxide. Magnesium and calcium oxides, hydroxides, carbonates or sulfates are particularly suitable forms of basic alkaline earth metal components added to the catalyst during or after manufacture. In one preferred embodiment, the ingredients, including the basic alkali class, are physically mixed with the particulate catalyst. In another preferred embodiment, the catalyst composition (
matrix). In order to obtain the highest degree of metal tolerance while avoiding undue deactivation of the zeolite component present in the catalyst, the alkaline earth metal component is added to the zeolite-containing catalyst in a form that does not undergo ion exchange with the zeolite component.

In a typical FCC catalyst manufacturing process, the component is added to the catalyst composition by blending a finely powdered alkaline earth metal component, such as dolomite, with an aqueous slurry containing a silica-alumina gel, optimally a zeolite, and a clay. A pressable slurry is created, which is then formed into microspherical particles with a particle size range of 20-100 IL. The spray-dried catalyst typically contains about 0-35% by weight zeolite, 25-70% by weight clay, and 10-50% by weight matrix, such as silica, alumina, silica-alumina hydrogel or sol, and 5% by weight. It contains ~80% by weight alkaline earth metal components, which are washed and ion-exchanged to remove soluble impurities such as sodium and sulfate.

After drying to about 10-30% volatile components, the catalyst is ready for use in conventional catalytic cracking processes. Typical FCC methods use a significant amount, i.e. 1-2
00 ppm vanadine and other metals such as nickel,
900-1000 @ hydrocarbon feedstock including iron and copper
It consists of contacting with a catalyst at a temperature of around F. to obtain low molecular weight cracking products such as gasoline and gas oil.

During the catalytic cracking step, the catalyst of the present invention is 0.1% by weight.
The alkaline earth metal component of the present invention has been found to absorb up to 10% by weight of metals, especially vanadine, while retaining activity and product selectivity within an acceptable range. Typical "conventional" catalysts do not have a high metal content (
In particular, if the amount (vanadine) exceeds about 0.1%, the activity is substantially lost.

The basic concept of the present invention has been explained above, and the present invention will be explained in more detail with reference to the following examples and accompanying drawings.

Example 1 Y-type zeolite calcined by ion exchange with rare earth elements) (G
REY) was ion-exchanged with ammonium sulfate in advance to form Na2
0 content is 0.6% by weight, Ru2O content is 23% by weight
Catalyst A was prepared by mixing about 10% by weight of this, 10% by weight of dolomite, and 80% by weight of kaolin crystals. This mixture is mixed with a small amount of water and extruded into a diameter 1
/ Make an 8-inch extrudate. The extrudate was oven dried, ground and sized to 60-150 mesh (10
Particles with a particle size range of 0 to 200, ) were obtained. A control catalyst B was made using a similar method but omitting the dolomite component and substituting clay. Therefore, catalyst B is 10
It consists of % by weight REY and 80% by weight kaolin clay. A first sample set consisting of catalysts A and B is impregnated with an aqueous solution. A second sample set consisting of catalysts A and B was prepared using a solution of vanadyl oxalate in water at 0.6
It is impregnated to contain 7% by weight. All samples are then preheated to 800°C for 1 hour and then calcined at 1400"F to remove any remaining organic material. The catalyst samples are then subjected to a hydrothermal deactivation treatment at 2 atmospheres and 800"F at 1350"F. Contact the catalyst with 100 $ of steam for an hour. The dolomite used in this example was heat treated at 1400"F for 2 hours and then had a PV (200-10,000) = 0.385cc/
g, APD (200-10,000) = 1,34
It was 9 angstroms. ASTN 0-3 for the catalyst of this example (and the catalysts used in subsequent examples)
A cracking activity test of the catalyst was conducted using the microactivity test described in 907. The microactivity (MA) of a catalyst sample is expressed in terms of volume percent of the modified feedstock. The results are shown in Table 1 below.

Table 1 A (1) OGo, I A (2) 0.87 56.1B (
1) 0 70.8B(2)
0.87 13.2 Example 2 3.2$c7) Na20 14.9% (7) RE2
03 Y-type zeolite containing ion-exchanged and calcined)
(GREY) A series of catalyst samples were made containing silica-alumina cogels containing 10% by weight, 72% by weight alumina, and varying amounts of clay and dolomite.

The silica-alumina cogel component was prepared as follows. An aqueous sodium silicate solution containing 4% by weight of sodium silicate having the formula 3.38Si02 llNa20, a 4% by weight aqueous solution of sodium aluminate, and a 20% by weight aqueous sulfuric acid solution are mixed together to give a final pH of the co-gel of 10.0. Do it like this. The composition of the final product is 72% Al2O3,
Adjust the flow rate of the above solution.

Varying amounts of clay, dolomite and GREY were mixed with the co-gel slurry. The slurry is filtered and reslurried with water to 15% solids. This slurry was then spray dried to produce microspherical catalyst particles of 12-100 p (-1" average eoJL). The catalyst was then washed using water, a 101 ammonium sulfate solution, and then an ammonium carbonate solution. It removes sodium fist ions and sulfates.

The catalyst samples were then impregnated with various amounts of water and vanadine and evaluated as described in Example 1. This dolomite had the same pore structure characteristics as Example 1. The catalyst composition and microactivity test results for catalysts containing various amounts of vanadine are summarized in Table 2. The amount of hydrogen (H2) and coke produced during the microactivity test was also determined.

The data in Tables 1 and 2 clearly show that the inclusion of a basic alkaline component (dolomite) maintains a high degree of activity even when combined with vanadium in amounts that have a significant deactivation effect on conventional catalysts. This shows that a catalyst composition that can be used can be obtained.

It is further noted that the inclusion of dolomite does not significantly adversely affect the product distribution of the catalyst, ie, H2/C.

Example 3 A commercially available zeolite fluidized cracking catalyst was blended with dolomite powder in a ratio of 90% catalyst to 10% dolomite by weight. In catalyst B, clay (kaolin) was used instead of dolomite. Samples of both catalysts A and B were impregnated with water/vanadine as in Example 1. Dolomite has the same pore structure characteristics as Example 1. The cracking activity of the catalyst was tested by a zero-order microactivity test in which the catalyst was subjected to hydrothermal deactivation by contacting it with 10 oz steam for 8 hours at 1350"F and 2 atmospheres. The results are shown in Table 3.

Table 3 Dislike zv (weight%) 0 0.87HA
(Capacity%) 75.2 B1.7H
2 (volume %) 0.050 0.0?2 cups (weight %) 2.53 2.20 tv (weight %) 0 0.87 HA
(Capacity%) 89.2 8.5H2(
Volume %) 0.044 0.275 One cup (wt %) 2.45 1.28 According to Example 3, it is clear that basic alkaline earth oxide (dolomite) is a standard or ranking catalyst and physical It is shown that it is possible to obtain a catalyst composition with good activity even when impregnated with high concentrations of vanadine.

Example 4 A commercially available FOG zeolite catalyst was impregnated with 0.34 wt% glue. The catalyst was then sieved to retain particles larger than 63p. Dolomite powder was similarly sieved, but
Only powders finer than 63μ were retained. These two sized components are then combined with 802% catalyst and 20% dolomite.
Examples 1 to 3
It was subjected to hydrothermal treatment. Dolomite has the same pore structure characteristics as described in Example 1. The steam treated sample is resieved using the same sieve to separate the FCC catalyst and dolomite. Table 4 shows the V2 of the different components before and after hydrothermal treatment.

Table 4 FCC catalyst 0.34 0.30 Dolomite 0.01 0.413
According to Example 4, a basic alkaline earth oxide (dolomite) selectively absorbs vanadine in an endothermic treatment atmosphere, such as that present in an FCC regenerator, and effectively removes it from the catalyst. is shown.

The Examples clearly demonstrate that useful metal-tolerant cracking catalysts can be obtained using the process of the present invention.

Example 5 This example demonstrates the preparation and use of a large pore and small pore MgO based additive for vanadine removal, 3.82 K and 10.87%.
Ngo 80 aqueous solution was mixed with 13.28$ HgCl2 aqueous solution by passing it through a mixing pump at the same speed.
MgO・Si with a composition of 5i0240% by weight
A magnesia-silica gel was made by making an O-gel. The temperature of the reaction mixture was 30°C for sample A.
In both cases, the resulting gel was filtered and reslurried with water to a solid content of about 10 ml. 3
Spray dried at 30°C. 70% of the spray-dried material
Mail was removed by washing with water at ℃.

Figure 1 shows the mercury pore diameter of both formulations after 2 hours of stress at 538°C. According to the analytical data in Table 5, the two samples have similar properties. However, an 8 oz commercially available FCC catalyst [Super
r) D] and 20% additive (either Sample A or B) at 2 oz. Sample B shows a dramatically improved metal tolerance. This example clearly shows that large pore volume and APD are important for effectiveness as a vanadine remover.

Table 5 Analysis and metal data of two types of MgO additives Theoretical composition Mg0 60$ 5i024 (1$ Operating temperature ("C) 30 20Mg
0 f14.07 82.5
8Si02 38.40
3B, 41PV (200~io, ooo) cc/g O, 0Ei5
0.1940.67% (7) V, 5-13.
5 (7) Using steam, Super 08oz, Additive 20
The composition was impregnated with metal.

HA 17 41$
M2 (F) 0.30 0.
162 CCF) 2.10
1.85 Example 6 In this example, high pore volume and low pore volume MgO
Demonstrates the usage of Catalyst A is 8oz Super D and 20%
Commercially available high pore volume MgO [Wag-Ch manufactured by Martin and Marietta]
EW30 class]. Catalyst B is a blend of 8 oz Super D and 20% commercially available low pore volume NgO [Wag-Che O grade from Martin Marietta]. Both catalysts were impregnated by the method of Example 1. did. Table 6 shows the results of the microactivity test.

Claims (1)

Claims: 1. (a) a cracking catalyst component; and (b) a basic alkaline earth metal component in an amount of about 5 to 80% by weight, expressed as an oxide, of the alkaline earth metal component; A catalytic cracking catalyst composition characterized in that the pore volume is at least 0.1 cc/g and the average pore diameter is greater than about 400 angstroms for pores having diameters between 200 and 10,000 angstroms. 2.0.1 on the catalyst when used in the catalytic cracking process
A composition according to claim 1 capable of depositing more than % by weight of vanadine. 3. The composition of claim 2 comprising from about 0.1 to about 10% by weight vanadine. 4. The composition of claim 1, wherein the catalyst component comprises synthetic faujasite dispersed in an inorganic oxide matrix. 5. The composition of claim 4, wherein said inorganic oxide matrix comprises silica-alumina gel and clay. 6. The composition according to claim 1, wherein the basic alkaline earth metal compound is selected from the group consisting of calcium and/or magnesium oxides, carbonates, acid salts, and mixtures thereof. 7. The composition according to claim 1, wherein the basic alkaline earth metal component is dolomite. 8. The basic alkaline earth metal component contains MgO from 30 to 8
A composition according to claim 1 comprising 0% by weight of magnesia-silica gel. 9. Claim 1, wherein the basic alkaline earth metal component is dispersed in the matrix as a separate oxide phase.
Compositions as described in Section. 10. The composition of claim 1, wherein the basic alkaline earth metal component is physically mixed as a separate particulate additive. 11. A method for catalytic cracking of a metal-containing hydrocarbon in which the hydrocarbon is brought into contact with a catalyst under catalytic cracking conditions, and a metal that causes deactivation, including vanadine, is deposited on the catalyst, the reaction An improved method for carrying out using the catalyst according to claim 1. 12, consisting of a silica-alumina gel containing MgO in an amount of about 5-80% by weight, the pore volume of which is at least 0.1%.
1 cc/g, and the average pore diameter is 200-10,00
400 in a pore with a diameter of 0 angstroms.
A composition for removing vanadium larger than angstroms. 13. The total pore volume of the composition is 0.2 to 1.0 cc/g
The composition according to claim 12, which is 14. The composition according to claim 12, wherein the composition is formed into particles having a particle size range of 40 to 80μ. 15. The composition of claim 14, wherein the particles have a density of about 0.5 to 1.0 g/cc. 16. The method according to claim 11, wherein the zeolite is a synthetic faujasite. 17. The method according to claim 16, wherein the zeolite is Y-type zeolite which has been ion-exchanged with a rare earth element and calcined.