CA1226269A - Catalytic cracking catalyst and process - Google Patents
Catalytic cracking catalyst and processInfo
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- CA1226269A CA1226269A CA000452087A CA452087A CA1226269A CA 1226269 A CA1226269 A CA 1226269A CA 000452087 A CA000452087 A CA 000452087A CA 452087 A CA452087 A CA 452087A CA 1226269 A CA1226269 A CA 1226269A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
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- Organic Chemistry (AREA)
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- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
CATALYTIC CRACKING CATALYST AND PROCESS
Abstract Catalytic cracking catalysts which contain a basic alkaline earth metal component in amounts greater than 5 percent by weight (expressed as the oxides) are used to crack hydrocarbon feed stocks that contain substantial quantities of metals such as vanadium, nickel, copper and iron.
Abstract Catalytic cracking catalysts which contain a basic alkaline earth metal component in amounts greater than 5 percent by weight (expressed as the oxides) are used to crack hydrocarbon feed stocks that contain substantial quantities of metals such as vanadium, nickel, copper and iron.
Description
~L~26~6~
The present invention relates to catalytic cracking catalysts, and more specifically to cracking catalyst compositions which are particularly effective for the cracking of residual type hydrocarbon feed stocks.
In recent years, the refining industry has been required to process ever increasing quantities of residual type feed stocks. These heavy feed stocks are frequently contaminated with substantial quantities of metals such as vanadium, nickel, iron and copper which adversely affect cracking catalyst used in refinery operations.
Zealot containing cracking catalysts in particular are susceptible to deactivation poisoning by vanadium) and in addition the catalytic selectivity of the catalyst is adversely affected by the presence of iron, copper and nickel.
US. 3,835,031 and US. 4,240,899 describe cracking catalysts which are impregnated with Group IDA metals for the purpose of reducing sulfur oxide emissions during regeneration of the catalyst.
US. 3,409,541 describes catalytic cracking processes wherein deactivation of the catalyst by contaminating metals is decreased by adding to the catalytic inventory a finely divided alkaline earth or I boron type compound which reacts with the metal contaminants to form an inert product that may be removed from the catalytic reaction system.
US. 3,699,037 discloses a catalytic cracking process wherein a finely divided additive such as calcium and magnesium hydroxides, carbonates, oxides, dolomite and/or limestone is added to the catalyst inventory to sorb Six components present in the regenerator flue gas.
US. 4,198,320 describes catalytic cracking
The present invention relates to catalytic cracking catalysts, and more specifically to cracking catalyst compositions which are particularly effective for the cracking of residual type hydrocarbon feed stocks.
In recent years, the refining industry has been required to process ever increasing quantities of residual type feed stocks. These heavy feed stocks are frequently contaminated with substantial quantities of metals such as vanadium, nickel, iron and copper which adversely affect cracking catalyst used in refinery operations.
Zealot containing cracking catalysts in particular are susceptible to deactivation poisoning by vanadium) and in addition the catalytic selectivity of the catalyst is adversely affected by the presence of iron, copper and nickel.
US. 3,835,031 and US. 4,240,899 describe cracking catalysts which are impregnated with Group IDA metals for the purpose of reducing sulfur oxide emissions during regeneration of the catalyst.
US. 3,409,541 describes catalytic cracking processes wherein deactivation of the catalyst by contaminating metals is decreased by adding to the catalytic inventory a finely divided alkaline earth or I boron type compound which reacts with the metal contaminants to form an inert product that may be removed from the catalytic reaction system.
US. 3,699,037 discloses a catalytic cracking process wherein a finely divided additive such as calcium and magnesium hydroxides, carbonates, oxides, dolomite and/or limestone is added to the catalyst inventory to sorb Six components present in the regenerator flue gas.
US. 4,198,320 describes catalytic cracking
-2-~Z~2~9 catalysts which contain colloidal silica and/or alumina additives that are added for the purpose of preventing the deactivation of the catalyst when used to process metals containing feed stocks.
US. 4,222,896 describes a metals tolerant zealot cracking catalyst which contain a magnesia-alumina-aluminum phosphate matrix.
US. 4,283,309 and 4,292,169 describe hydrocarbon conversion catalysts which contain a metals-absorbing matrix that includes a porous inorganic oxide such as alumina, titanic, silica, circonia, magnesia and mixtures thereof.
POT WOW 82/00105 discloses cracking catalysts that are resistant to metals poisoning which comprise two particulate size fractions, and an Six absorbing additive such as aluminum oxide, calcium oxide and/or magnesium oxide.
While the prior art suggests several catalytic systems and compositions which are effective in controlling the adverse poisoning effects of metals contained in residual type feed stocks or limiting Six emissions during regeneration of the catalyst, many of the systems require the use of expensive additives and/or processing systems and are not particularly cost effective when operated on a commercial scale.
It is therefore an object of the present invention to provide improved catalytic cracking catalysts which are capable of cracking hydrocarbon feed stocks that contain substantial quantities of metals and sulfur It is another object to provide fluid cracking catalysts (FCC) which are resistant to metals poisoning and which may be recharged and used in large quantities at reasonable cost.
It is a further object to provide a catalytic Sue cracking process which is capable of handling large quantities of metals, vanadium in particular, without substantial loss of activity or product yield.
These and still further objects of the present invention will become readily apparent to one skilled in the art from the following detailed description and specific examples.
Broadly, my invention contemplates catalytic cracking catalysts which include a basic alkaline earth metal component in amounts ranging from about 5 to 80 weight percent expressed as the oxides, wherein the catalyst is capable of maintaining a high degree of activity when associated with substantial quantities of deactivating metals such as vanadium deposited on the catalyst.
The alkaline earth metal compound used in the practice of the invention is selected from group IDA of the Periodic Table with calcium and magnesium being preferred. In a particularly preferred embodiment of the invention the basic alkaline earth metal component comprises natural or synthetic dolomite which has the general chemical formula Mica (KIWI.
The fluid catalytic cracking catalysts which are combined with the basic alkaline earth metal component, are conventional and well known to those skilled in the art. Typically, the catalysts comprise amorphous manganese oxide gels such as silica-alumina hydrogels, and/or a crystalline zealot dispersed in an inorganic oxide matrix.
Preferred zealots are synthetic faujasite type Y
zealot) and/or shape selective zealots such as ZSM-5. Type Y zealots which are exchanged with hydrogen and/or rare earth metals such as HO and RYE, and those which have been subjected to thermal ~22~2~g treatments such as calcined, rare-earth exchanged Y
(CRY) and/or ZEUS are particularly suited for inclusion in fluid cracking catalyst compositions.
Catalytically active zealot components are typically described in US. patents 3,293,192 and RYE 28,629.
In addition to an active zealot component, the catalysts contain an inorganic oxide matrix. The inorganic oxide matrix is typically a silica-alumina hydrogen, which may be combined with substantial quantities of clay such as kaolin. In addition, it is contemplated in catalyst matrix systems which comprise silica, alumina, silica-alumina sots and gels may be utilized in the practice of the present invention.
Methods for producing suitable catalyst compositions are described in So 3,974,099, 3,957,689, 4,226,743,
US. 4,222,896 describes a metals tolerant zealot cracking catalyst which contain a magnesia-alumina-aluminum phosphate matrix.
US. 4,283,309 and 4,292,169 describe hydrocarbon conversion catalysts which contain a metals-absorbing matrix that includes a porous inorganic oxide such as alumina, titanic, silica, circonia, magnesia and mixtures thereof.
POT WOW 82/00105 discloses cracking catalysts that are resistant to metals poisoning which comprise two particulate size fractions, and an Six absorbing additive such as aluminum oxide, calcium oxide and/or magnesium oxide.
While the prior art suggests several catalytic systems and compositions which are effective in controlling the adverse poisoning effects of metals contained in residual type feed stocks or limiting Six emissions during regeneration of the catalyst, many of the systems require the use of expensive additives and/or processing systems and are not particularly cost effective when operated on a commercial scale.
It is therefore an object of the present invention to provide improved catalytic cracking catalysts which are capable of cracking hydrocarbon feed stocks that contain substantial quantities of metals and sulfur It is another object to provide fluid cracking catalysts (FCC) which are resistant to metals poisoning and which may be recharged and used in large quantities at reasonable cost.
It is a further object to provide a catalytic Sue cracking process which is capable of handling large quantities of metals, vanadium in particular, without substantial loss of activity or product yield.
These and still further objects of the present invention will become readily apparent to one skilled in the art from the following detailed description and specific examples.
Broadly, my invention contemplates catalytic cracking catalysts which include a basic alkaline earth metal component in amounts ranging from about 5 to 80 weight percent expressed as the oxides, wherein the catalyst is capable of maintaining a high degree of activity when associated with substantial quantities of deactivating metals such as vanadium deposited on the catalyst.
The alkaline earth metal compound used in the practice of the invention is selected from group IDA of the Periodic Table with calcium and magnesium being preferred. In a particularly preferred embodiment of the invention the basic alkaline earth metal component comprises natural or synthetic dolomite which has the general chemical formula Mica (KIWI.
The fluid catalytic cracking catalysts which are combined with the basic alkaline earth metal component, are conventional and well known to those skilled in the art. Typically, the catalysts comprise amorphous manganese oxide gels such as silica-alumina hydrogels, and/or a crystalline zealot dispersed in an inorganic oxide matrix.
Preferred zealots are synthetic faujasite type Y
zealot) and/or shape selective zealots such as ZSM-5. Type Y zealots which are exchanged with hydrogen and/or rare earth metals such as HO and RYE, and those which have been subjected to thermal ~22~2~g treatments such as calcined, rare-earth exchanged Y
(CRY) and/or ZEUS are particularly suited for inclusion in fluid cracking catalyst compositions.
Catalytically active zealot components are typically described in US. patents 3,293,192 and RYE 28,629.
In addition to an active zealot component, the catalysts contain an inorganic oxide matrix. The inorganic oxide matrix is typically a silica-alumina hydrogen, which may be combined with substantial quantities of clay such as kaolin. In addition, it is contemplated in catalyst matrix systems which comprise silica, alumina, silica-alumina sots and gels may be utilized in the practice of the present invention.
Methods for producing suitable catalyst compositions are described in So 3,974,099, 3,957,689, 4,226,743,
3,867l308, and 4,247,420.
The basic alkaline earth metal component may be added to the catalyst composition in the form of a finely divided particulate solid or the component may be added in the form of a soluble salt solution which is subsequently converted to a solid oxide. Magnesium and calcium oxides, hydroxides, carbonates or sulfates are particularly suited forms of the basic alkaline earth metal components which are added to the catalyst either during or after manufacture. In one preferred embodiment, the basic alkaline earth containing component is physically admixed with the particulate catalyst. In another preferred embodiment, the alkaline earth metal component is included in the catalyst composition (matrix) during manufacture. In order to obtain the maximum degree of metals tolerance while avoiding undue deactivation of a zealot component which may be present in the catalyst, the ~L2Z6~6i9 alkaline earth metal component is added to the zealot containing catalyst in a form that does not ion exchange with the zealot component.
In a typical FCC catalyst preparation procedure, a finely divided alkaline earth metal component, such as dolomite, is blended with an aqueous slurry which contains silica-alumina hydrogen, optimally a zealot, and clay to obtain a pump able slurry which is then spray dried to obtain micro spheroidal particles of catalyst having a particle size ranging from about 20 to 100 microns. The spray dried catalyst, which typically contains from about 0 to 35 percent by weight zealot, 25 to 70 percent by weight clay, and 10 to 50 percent by weight matrix binder, such as silica, alumina, silica-alumina hydrogen or sol, and from 5 to 80 percent by weight alkaline earth metal component, is washed and ion exchanged to remove soluble impurities such as sodium and sulfates. After drying to about 10-30 percent total volatile the catalyst is ready to be used in conventional catalytic cracking processes.
Typical FCC processes involve contact of the catalyst with a hydrocarbon feed stock which may contain significant quantities, i.e. from 1 to 200 Pam of vanadium and other metals such as nickel, iron and copper at temperatures on the order of 900 to 1000F to obtain cracked products of lower molecular weight such as gasoline and light cycle oil.
It is found that during the catalytic cracking process, the catalysts contemplated in the present invention can sorb in excess of 0.1 percent and up to 10 percent by weight of metals, particularly vanadium, while maintaining an acceptable level of activity and product selectivity. Typical "conventional" catalysts, which do not contain the alkaline earth metal component 3l2262~9 contemplated herein, lose substantial activity when the metals content (vanadium in particular) exceeds about 0.1 weight percent.
Having described the basic aspects of the present invention, the following examples are given to illustrate the specific embodiments thereof.
Example 1 Catalyst A was prepared by mixing about 10 percent by weight calcined rare earth exchanged type Y zealot (CRY) that has been ammonium sulfate exchanged to contain 0.6 weight percent NATO and 13 weight percent ROY with 10 percent by weight dolomite, and 80 percent by weight kaolin clay. The mixture was combined with small quantities of water and then lo extruded into one-eighth inch diameter extradites. The extradites were oven dried, crushed and sized to obtain a particle size fraction ranging from 60 to 150 mesh tlO0 to 20Q microns). A comparison Catalyst B was prepared using a similar technique, however, the dolomite component was omitted and replaced with clay.
Catalyst B therefore comprised 10 percent by weight RAY
and 90 percent by weight kaolin. A first set of samples of each Catalyst A and B was impregnated with a water solution. A second set of samples of Catalysts and B were impregnated to a level of 0.67 weight percent vanadium, using a solution which contained vandal oxylate dissolved in water. All samples were then pretreated at 900F for 1 hour and then 2 hours at 1400F to burn off residual organic material. The catalyst samples were then subjected to a hydrothermal deactivation treatment which involved contacting the catalyst with 100 percent steam at a pressure of 2 elm at 1350F for 8 hours. The catalysts of this Example I
(as well as the catalysts evaluated in additional Examples) were then tested for catalytic cracking activity using the micro activity test described in ASTM
D-3907. The micro activity (~) of the catalyst samples is expressed in terms of volume percent (vol. I) of feed stock converted. The results are summarized in Table I set forth below.
TABLE I
Catalyst (Sample No.) V Content, wt.% MA, volt%
A (1) 0 60.1 A (2) 0.67 56.1 (1) 0 70.8 B (2) 0.67 13.2 7~2~ 9 Example 2 A series of catalyst samples was prepared which contained 10 percent by weight calcined rare earth exchanged Y CRY) which contained 3.2 percent NATO
and 14.9 percent ROY, a silica-alumina Vogel which contained 72 percent by weight alumina, and various quantities of clay and dolomite.
The silica-alumina Vogel component was prepared as follows: A sodium silicate solution which contained 4 weight percent sodium silicate having the formula 3.3 Sweeney, a 4 weight percent sodium acuminate solution, and 20 weight percent sulfuric acid solution were mixed together such that the final pi ox the Vogel slurry was 10Ø The flow rates of above solutions were adjusted to give a final product composition of 72% AYE, 28% Sue.
Varying amounts of clay, dolomite, and CRY were then mixed with the Vogel slurry. The slurry was filtered, then reslurried with water to 15% solids content. This slurry was then spray dried to give micro spheroidal catalyst particles of 12 to 100 microns (60 microns average. The catalyst was then washed to remove sodium ions and sulfates, using water, 10 percent ammonium sulfate solution, and then 5 percent ammonium carbonate solution.
The catalyst samples were then impregnated with various quantities of water and vanadium and evaluated using the techniques described in Example 1. The composition of the catalysts and the micro activity test results for catalyst samples having various quantities of vanadium are summarized in Tale II below. In addition, the quantities of hydrogen (Ho) and coke (C) produced during the micro activity test were determined.
I
TABLE II
Catalyst A B C D
Composition, Component, wt.%
Vogel 50 30 30 50 Clay 40 30 20 10 Dolomite 0 10 20 30 Micro activity (vol.%) V content, wt.%
10 I (74 3) (79 9) (70.2) (68.5) % Ho/% C .12/3.2 0.11/3.1 .12/2.8 .12/3.2 0.34 (56.6) (70.4) (66.9) (65.0) % Ho/% C .51/3.2 0.21/2.7 .12/2.9 .13/3.0 0.67 (53.4) (52.2) (70.8) (60.5) % Ho/% C .65/4.1 0.34/3.6 .13/3.1 .13/3.1 1.34 (20.6) (45.2) (69.3) (65.5) % Ho/% C .82/4.8 0.38/3.1 .14/2.7 .11/2.6 ~lL2ZÇ;Z69 The data set forth in Tables I and II clearly indicates that the inclusion of basic alkaline earth component (dolomite results in catalyst compositions which are capable of maintaining a high degree of activity when combined with quantities of vanadium which significantly deactivate conventional catalysts.
Furthermore, it is noted that the inclusion of dolomite does not significantly adversely affect the product distribution, i.e. H2/C production characteristics, lo of the catalysts.
Example 3 A commercial zealot fluid cracking catalyst was physically blended with dolomite powder in the proportions of 90% catalyst with 10% dolomite by weight to obtain Catalyst A. In Catalyst B the dolomite was replaced with inert clay (kaolin). Samples of both Catalysts A and B were impregnated with water/vanadium as in Example l. Each sample was subjected to a hydrothermal deactivation by contacting the catalyst to 100% steam at 2 elms. for 8 hours at 1350F. The samples were then tested for catalytic cracking activity by the micro activity test. The results are summarized in Table III.
1L22~Z~9 TABLE III
Catalyst A
% V (wit %) 0 .67~
MA (vol. I) 75.2% 61.0 Ho (vol. I) .050 .072 Coke (wt. I) 2053 2.20 Catalyst B
% Vote. %1 0 67%
MA (vol. %) 69.2 8.5 Ho (vol. %) .044 .275 Coke (wt. I) 2.45 1.28 Example 3 clearly shows that basic alkaline earth oxides (dolomite) can be physically blended with standard cracking catalyst to obtain catalytic compositions which possess good activity when impregnated with high levels of vanadium.
Example 4 A commercial zealot FCC catalyst was impregnated to 0.34% V by weight. The catalyst was then screened to retain particles having a size greater than 63 microns. Dolomite powder was similarly screened, except the material having a particle size less than 63 microns was retained. The two sized components were then physically blended together in the proportion of 80% catalyst, 20% dolomite and the blended composition was subjected to a hydrothermal steam deactivation treatment as described in Examples 1, 2 and 3, The ISLE
steamed sample was then separated by rescreening through the same screen to separate the FCC catalyst and dolomite components. Table IV shows the TV before and after hydrothermal treatment of the separated components.
TABLE IV
Component V (wt. % before White. % after) r FCC Catalyst 0.34 0.30 Dolomite 0.01 0.49 Example 4 clearly shows that the basic alkaline earth oxide (dolomite) can selectively adsorb vanadium and effectively remove it from the catalyst in a hydrothermal environment such as exists in the regenerator of an FCC process.
The above examples clearly indicate that useful metals tolerance cracking catalysts may be obtained using the teachings of the present invention.
~;~26~;9 SUPPLEMENTARY DISCLOSURE
In accordance with the teachings of the principal disclosure catalytic cracking catalysts which contain a basic alkaline earth metal component in amounts greater than 5 per-cent by weight, expressed as the oxides, are used to crack hydrocarbon feed stocks that contain substantial quantities of metals such as vanadium, nickel, copper and iron.
Broadly, the present invention contemplates catalytic cracking catalysts which include a basic alkaline earth metal component in amounts ranging from about 5 to 80 weight percent expressed as the oxides, wherein the catalyst is capable of maintaining a high degree of activity when associated with substantial quantities of deactivating metals such as vanadium deposited on the catalyst.
Now, and in accordance with the present teachings it has been found that particulate basic alkaline earth metal compost-lions which have an intra-particle pore structure characterized by a pore volume of at least 0.1 cc/g in pores having a diameter of about 200 to 10,000 A, and an average pore diameter (APT) of greater than about 400 A when determined in the pore size range of about 200 to 10,000 A diameter using the relationship:
APT - 4 x 10 x PI
SPA
wherein PI pore volume in cc/g in pores ringing from 200-10,000 A diameter in SPA - surface area in mug in pores ranging from 200-10,000 A diameter, as determined by mercury porosimetry.
The alkaline earth metal compound used in the practice of the invention is selected from group IDA of the periodic Table with calcium and magnesium being Preferred and magnesium the most preferred. In a particularly preferred embodiment of the invention the basic alkaline earth metal component comprises natural or synthetic dolomite which has the general chemical formula Mica (KIWI, Moo, or magnesia-silica gels and a significant pore volume in pores greater than about 400 A at process temperatures of 1400F or so.
Jo ~22~i2~;~
in a particularly preferred embodiment a magnesium oxide containing component such as a magnesia-silica gel (MgO.SiO2) is prepared in a particulate form wherein the particle has a substantial pore volume in pores having a diameter of greater than about 4009~.
The resulting MgO.SiO2 composition is included in a ~CC catalyst composition either as an integral component of the FCC catalyst particle or more preferably as a separate particulate additive in amounts ranging from about 2.5 to 40 by weight of the composition.
The preferred MgO.SiO2 Mel has the overall weight composition of 30-~0~ Moo, and a pore volume in pores greater than about AYE diameter of at least 0.1 cc/g and preferably from about 0.2 to 1.0 cc/g. Where the MgO.SiO2 gel is added to a FCC catalyst as a separate particulate additive, the particle size and density of the additive is preferably similar to that of the ~CC
catalyst, i.e. particle size range of about 40 to 80 microns and an average bulk density of 0.5 to 1.0 gag A preferred MgO.SiO2 gel is prepared by reacting aqueous sodium silicate and magnesium chloride solutions at a temperature of about 15 to 50C to form a precipitate gel which is recovered by filtration, reslurried in water and spray dried at a temperature of about 330 to 500C. Furthermore, particulate Moo can be added to the MgOoSiO2 gel to give composition of 30-80% Moo to the final product.
As indicated above, the Moo containing catalyst component must have the optimized pore structure described above in order to be effective for vanadium scavenging. This is due to the fact that partial molar volume of magnesium vendetta is greater than magnesium oxide. It is relieved that the vanadium poisoning of cracking catalysts is caused by the poison precursor H3V04 which is formed in the regeneration step from the reaction of VOW and steam (for vapor pressure - I
~2~26~
data sex LEN. Yannopoulos, J. Pays. Chum. 72, 3293 ~1968). Ho VOW is isoelectronic with H3PO4 and is most probably a strong acid. H3VO4 therefore destroys the zealot crystallanity and activity by acid hydrolysis of the Swahili framework of the zealot. As H3VO4 reacts with Moo and forms (MgO)2V2O5 on the surface of pore, the surface of the pore will well due to larger molar volume of (MgO)2V2O5. If the pore is too small, blocking will occur readily and thereby inhibit the further reaction with H3V04. We have experimentally determined that the average pore diameter must be greater than AYE or Jo to be effective. This effect has been extensively studied with similar reaction:
Coo + SO > Casey (see S. K. Bush and D. D. Perlmutter Ache J. 27, 266 and 29, 79).
As indicated above, Moo is the preferred oxide over the other alkaline earths when used in conjunction with FCC catalysts. This is due to the presence of sulfur oxides in the flue gases of the regenerator, which can compete with H3V04 forming alkaline earth Swiss as shown by a consideration of the equilibrium constants for the reactions of McCoy and Casey with vanadic acid. Assuming a worst case test in which all of the Six is assumed to be SO at a typical level of 2000 Pam in the regenerator, 20% HO, 1.07 Pam H3V04 and a temperature of 970K ~1285F) a calculated equilibrium constant assuming unit activity for the condensed phases from the regenerator conditions above can be compared to the equilibrium constant for the two reactions from thermochemical data as follows:
3l2262~9 Casey 2H3V04(91 - (Cove) + 2S03(9) + rug X (970K) - 472.75 McCoy + 2H3V04(g) - (M90)2 2 5 5 2S03(9) 3H20(9) X(970K) 6.675 x lo gala ~~S03] I
thieve ~2.215 x 105 or the case of calcium the calculated equilibrium from regenerator conditions is much greater than the equilibrium constant for the reaction. By the lo Chatlier's principle the reaction will favor the left hand side of reaction with calcium. the opposite is true for the case with Moo. If calcium is used Casey will be preferentially formed over the vendetta, the opposite is true for magnesium.
lo The fluid catalytic cracking catalysts which are combined with the basic alkaline earth metal component, are conventional and well known to those skilled in the art. Typically, the catalysts comprise amorphous inorganic oxide gels such as silica-alumina hydrogels, end/or a crystalline zealot dispersed in an inorganic oxide matrix.
Preferred zealots are synthetic faujasite (type Y
zealot) and/or shape selective zealots such as ZSM-5. Type Y zealots which are exchanged with hydrogen Andre rare earth petals such as HO and RAY, and those which have been subjected to thermal treatments such as calcined, rare-earth exchanged Y
(CRY) Andre Zl4US are particularly suited for inclusion in fluid cracking catalyst compositions.
3L2;~62~;9 Catalytically active zealot components are typically described in US. patents 3,293,192 and RYE 28,629.
In addition to an active zealot component, the catalysts contain an inorganic oxide matrix. The inorganic oxide matrix is typically a silica-alumina Harley, which may be combined with substantial quantities of clay such as kaolin. In addition, it is contemplated in catalyst matrix systems which comprise silica, alumina, ~ilica-alumina owls and gels may be utilized in the practice of the present invention.
Methods for producing suitable catalyst compositions are described in US. 3,974,099, 3,957,689, 4,226,743, 3,B67,30B, 4,247,4~0.
The following additional examples act to further illustrate the present teachings:
Example 5 This example shows the preparation and use of large and small pore Moo based vanadium scavenging additives. A
magnesia-silica gel was prepared by mixing a 3.62% Sue and 10.87% Noah aqueous solution with 13.28% McCoy aqueous soul-lion at equal flow rates through a mix pump to form a MgO.SiO2 gel with composition 60 White Moo 40 wt.% Sue. The temperature of the reaction mixture was 30C for example A to make smaller pore diameters, end 20C for example B for larger pore diameters. The resultant gel in both cases was filtered, reslurried in water to ~10 solids and spray dried at 330C. The spray dried material was washed with 70C HO to remove Nail.
Figure 1 shows the Hug pore size diameter for both preps after calcination for 2 hours at 53BC. Analytical data in Table shows the two Samples have similar properties except that the metals tolerance of an 80~
commercial FCC catalyst (Super D) 20% additive (either A or B) was dramatically improved for example B. This example clearly demonstrates the importance of the -SD lo-~22~2~g larger pyre volume end APT for vanadium scavenging effectiveness, TABLE V
Analytical and Metals Data for Two Moo Additives Theoretical Composition 60% Moo 40~ Sue (AYE) AYE) Run-off Temp. 30C 20C
Moo 64.07 62.58 Sue 38.40 36.41 PI ~20-10,000) cc2/g .06~ .19 APT (20-10l000) A 703 624 Metals impregnation of 80% Super D, 20~ Additive with .67% V. S-13.5 steam.
My (F) .30 .16 C (F) 2.10 1.65 Example 6 . . .
This example again shows the use of high pore volume and low pore volume Moo. Catalyst A is a blend of ~04 Super D, 20~ commercially available high pore volume Moo (from Martin Marietta grade Maxim Catalyst B it a blend of 80~ Super D, 20~ commercially available low pore volume Moo (from Martin Marietta grade Maxim 10). Both catalysts are impregnated by the procedure in Example 1. table VI shows the micro activity results.
~2~2~g TABLE VI
Catalyst A Catalyst B
PI (20-10,000) m2tg .821 ,065 APED (20-10,000) A 1,266 3,466 Ox VIA 67 67 H2/C .06/2.30 .04/1.73 ,67~ VIA 55 13 H2/C ,08/1.82 .06/.75 101.34% VIA 38 11 I .11/1.51 ,091 :, , .~.
The basic alkaline earth metal component may be added to the catalyst composition in the form of a finely divided particulate solid or the component may be added in the form of a soluble salt solution which is subsequently converted to a solid oxide. Magnesium and calcium oxides, hydroxides, carbonates or sulfates are particularly suited forms of the basic alkaline earth metal components which are added to the catalyst either during or after manufacture. In one preferred embodiment, the basic alkaline earth containing component is physically admixed with the particulate catalyst. In another preferred embodiment, the alkaline earth metal component is included in the catalyst composition (matrix) during manufacture. In order to obtain the maximum degree of metals tolerance while avoiding undue deactivation of a zealot component which may be present in the catalyst, the ~L2Z6~6i9 alkaline earth metal component is added to the zealot containing catalyst in a form that does not ion exchange with the zealot component.
In a typical FCC catalyst preparation procedure, a finely divided alkaline earth metal component, such as dolomite, is blended with an aqueous slurry which contains silica-alumina hydrogen, optimally a zealot, and clay to obtain a pump able slurry which is then spray dried to obtain micro spheroidal particles of catalyst having a particle size ranging from about 20 to 100 microns. The spray dried catalyst, which typically contains from about 0 to 35 percent by weight zealot, 25 to 70 percent by weight clay, and 10 to 50 percent by weight matrix binder, such as silica, alumina, silica-alumina hydrogen or sol, and from 5 to 80 percent by weight alkaline earth metal component, is washed and ion exchanged to remove soluble impurities such as sodium and sulfates. After drying to about 10-30 percent total volatile the catalyst is ready to be used in conventional catalytic cracking processes.
Typical FCC processes involve contact of the catalyst with a hydrocarbon feed stock which may contain significant quantities, i.e. from 1 to 200 Pam of vanadium and other metals such as nickel, iron and copper at temperatures on the order of 900 to 1000F to obtain cracked products of lower molecular weight such as gasoline and light cycle oil.
It is found that during the catalytic cracking process, the catalysts contemplated in the present invention can sorb in excess of 0.1 percent and up to 10 percent by weight of metals, particularly vanadium, while maintaining an acceptable level of activity and product selectivity. Typical "conventional" catalysts, which do not contain the alkaline earth metal component 3l2262~9 contemplated herein, lose substantial activity when the metals content (vanadium in particular) exceeds about 0.1 weight percent.
Having described the basic aspects of the present invention, the following examples are given to illustrate the specific embodiments thereof.
Example 1 Catalyst A was prepared by mixing about 10 percent by weight calcined rare earth exchanged type Y zealot (CRY) that has been ammonium sulfate exchanged to contain 0.6 weight percent NATO and 13 weight percent ROY with 10 percent by weight dolomite, and 80 percent by weight kaolin clay. The mixture was combined with small quantities of water and then lo extruded into one-eighth inch diameter extradites. The extradites were oven dried, crushed and sized to obtain a particle size fraction ranging from 60 to 150 mesh tlO0 to 20Q microns). A comparison Catalyst B was prepared using a similar technique, however, the dolomite component was omitted and replaced with clay.
Catalyst B therefore comprised 10 percent by weight RAY
and 90 percent by weight kaolin. A first set of samples of each Catalyst A and B was impregnated with a water solution. A second set of samples of Catalysts and B were impregnated to a level of 0.67 weight percent vanadium, using a solution which contained vandal oxylate dissolved in water. All samples were then pretreated at 900F for 1 hour and then 2 hours at 1400F to burn off residual organic material. The catalyst samples were then subjected to a hydrothermal deactivation treatment which involved contacting the catalyst with 100 percent steam at a pressure of 2 elm at 1350F for 8 hours. The catalysts of this Example I
(as well as the catalysts evaluated in additional Examples) were then tested for catalytic cracking activity using the micro activity test described in ASTM
D-3907. The micro activity (~) of the catalyst samples is expressed in terms of volume percent (vol. I) of feed stock converted. The results are summarized in Table I set forth below.
TABLE I
Catalyst (Sample No.) V Content, wt.% MA, volt%
A (1) 0 60.1 A (2) 0.67 56.1 (1) 0 70.8 B (2) 0.67 13.2 7~2~ 9 Example 2 A series of catalyst samples was prepared which contained 10 percent by weight calcined rare earth exchanged Y CRY) which contained 3.2 percent NATO
and 14.9 percent ROY, a silica-alumina Vogel which contained 72 percent by weight alumina, and various quantities of clay and dolomite.
The silica-alumina Vogel component was prepared as follows: A sodium silicate solution which contained 4 weight percent sodium silicate having the formula 3.3 Sweeney, a 4 weight percent sodium acuminate solution, and 20 weight percent sulfuric acid solution were mixed together such that the final pi ox the Vogel slurry was 10Ø The flow rates of above solutions were adjusted to give a final product composition of 72% AYE, 28% Sue.
Varying amounts of clay, dolomite, and CRY were then mixed with the Vogel slurry. The slurry was filtered, then reslurried with water to 15% solids content. This slurry was then spray dried to give micro spheroidal catalyst particles of 12 to 100 microns (60 microns average. The catalyst was then washed to remove sodium ions and sulfates, using water, 10 percent ammonium sulfate solution, and then 5 percent ammonium carbonate solution.
The catalyst samples were then impregnated with various quantities of water and vanadium and evaluated using the techniques described in Example 1. The composition of the catalysts and the micro activity test results for catalyst samples having various quantities of vanadium are summarized in Tale II below. In addition, the quantities of hydrogen (Ho) and coke (C) produced during the micro activity test were determined.
I
TABLE II
Catalyst A B C D
Composition, Component, wt.%
Vogel 50 30 30 50 Clay 40 30 20 10 Dolomite 0 10 20 30 Micro activity (vol.%) V content, wt.%
10 I (74 3) (79 9) (70.2) (68.5) % Ho/% C .12/3.2 0.11/3.1 .12/2.8 .12/3.2 0.34 (56.6) (70.4) (66.9) (65.0) % Ho/% C .51/3.2 0.21/2.7 .12/2.9 .13/3.0 0.67 (53.4) (52.2) (70.8) (60.5) % Ho/% C .65/4.1 0.34/3.6 .13/3.1 .13/3.1 1.34 (20.6) (45.2) (69.3) (65.5) % Ho/% C .82/4.8 0.38/3.1 .14/2.7 .11/2.6 ~lL2ZÇ;Z69 The data set forth in Tables I and II clearly indicates that the inclusion of basic alkaline earth component (dolomite results in catalyst compositions which are capable of maintaining a high degree of activity when combined with quantities of vanadium which significantly deactivate conventional catalysts.
Furthermore, it is noted that the inclusion of dolomite does not significantly adversely affect the product distribution, i.e. H2/C production characteristics, lo of the catalysts.
Example 3 A commercial zealot fluid cracking catalyst was physically blended with dolomite powder in the proportions of 90% catalyst with 10% dolomite by weight to obtain Catalyst A. In Catalyst B the dolomite was replaced with inert clay (kaolin). Samples of both Catalysts A and B were impregnated with water/vanadium as in Example l. Each sample was subjected to a hydrothermal deactivation by contacting the catalyst to 100% steam at 2 elms. for 8 hours at 1350F. The samples were then tested for catalytic cracking activity by the micro activity test. The results are summarized in Table III.
1L22~Z~9 TABLE III
Catalyst A
% V (wit %) 0 .67~
MA (vol. I) 75.2% 61.0 Ho (vol. I) .050 .072 Coke (wt. I) 2053 2.20 Catalyst B
% Vote. %1 0 67%
MA (vol. %) 69.2 8.5 Ho (vol. %) .044 .275 Coke (wt. I) 2.45 1.28 Example 3 clearly shows that basic alkaline earth oxides (dolomite) can be physically blended with standard cracking catalyst to obtain catalytic compositions which possess good activity when impregnated with high levels of vanadium.
Example 4 A commercial zealot FCC catalyst was impregnated to 0.34% V by weight. The catalyst was then screened to retain particles having a size greater than 63 microns. Dolomite powder was similarly screened, except the material having a particle size less than 63 microns was retained. The two sized components were then physically blended together in the proportion of 80% catalyst, 20% dolomite and the blended composition was subjected to a hydrothermal steam deactivation treatment as described in Examples 1, 2 and 3, The ISLE
steamed sample was then separated by rescreening through the same screen to separate the FCC catalyst and dolomite components. Table IV shows the TV before and after hydrothermal treatment of the separated components.
TABLE IV
Component V (wt. % before White. % after) r FCC Catalyst 0.34 0.30 Dolomite 0.01 0.49 Example 4 clearly shows that the basic alkaline earth oxide (dolomite) can selectively adsorb vanadium and effectively remove it from the catalyst in a hydrothermal environment such as exists in the regenerator of an FCC process.
The above examples clearly indicate that useful metals tolerance cracking catalysts may be obtained using the teachings of the present invention.
~;~26~;9 SUPPLEMENTARY DISCLOSURE
In accordance with the teachings of the principal disclosure catalytic cracking catalysts which contain a basic alkaline earth metal component in amounts greater than 5 per-cent by weight, expressed as the oxides, are used to crack hydrocarbon feed stocks that contain substantial quantities of metals such as vanadium, nickel, copper and iron.
Broadly, the present invention contemplates catalytic cracking catalysts which include a basic alkaline earth metal component in amounts ranging from about 5 to 80 weight percent expressed as the oxides, wherein the catalyst is capable of maintaining a high degree of activity when associated with substantial quantities of deactivating metals such as vanadium deposited on the catalyst.
Now, and in accordance with the present teachings it has been found that particulate basic alkaline earth metal compost-lions which have an intra-particle pore structure characterized by a pore volume of at least 0.1 cc/g in pores having a diameter of about 200 to 10,000 A, and an average pore diameter (APT) of greater than about 400 A when determined in the pore size range of about 200 to 10,000 A diameter using the relationship:
APT - 4 x 10 x PI
SPA
wherein PI pore volume in cc/g in pores ringing from 200-10,000 A diameter in SPA - surface area in mug in pores ranging from 200-10,000 A diameter, as determined by mercury porosimetry.
The alkaline earth metal compound used in the practice of the invention is selected from group IDA of the periodic Table with calcium and magnesium being Preferred and magnesium the most preferred. In a particularly preferred embodiment of the invention the basic alkaline earth metal component comprises natural or synthetic dolomite which has the general chemical formula Mica (KIWI, Moo, or magnesia-silica gels and a significant pore volume in pores greater than about 400 A at process temperatures of 1400F or so.
Jo ~22~i2~;~
in a particularly preferred embodiment a magnesium oxide containing component such as a magnesia-silica gel (MgO.SiO2) is prepared in a particulate form wherein the particle has a substantial pore volume in pores having a diameter of greater than about 4009~.
The resulting MgO.SiO2 composition is included in a ~CC catalyst composition either as an integral component of the FCC catalyst particle or more preferably as a separate particulate additive in amounts ranging from about 2.5 to 40 by weight of the composition.
The preferred MgO.SiO2 Mel has the overall weight composition of 30-~0~ Moo, and a pore volume in pores greater than about AYE diameter of at least 0.1 cc/g and preferably from about 0.2 to 1.0 cc/g. Where the MgO.SiO2 gel is added to a FCC catalyst as a separate particulate additive, the particle size and density of the additive is preferably similar to that of the ~CC
catalyst, i.e. particle size range of about 40 to 80 microns and an average bulk density of 0.5 to 1.0 gag A preferred MgO.SiO2 gel is prepared by reacting aqueous sodium silicate and magnesium chloride solutions at a temperature of about 15 to 50C to form a precipitate gel which is recovered by filtration, reslurried in water and spray dried at a temperature of about 330 to 500C. Furthermore, particulate Moo can be added to the MgOoSiO2 gel to give composition of 30-80% Moo to the final product.
As indicated above, the Moo containing catalyst component must have the optimized pore structure described above in order to be effective for vanadium scavenging. This is due to the fact that partial molar volume of magnesium vendetta is greater than magnesium oxide. It is relieved that the vanadium poisoning of cracking catalysts is caused by the poison precursor H3V04 which is formed in the regeneration step from the reaction of VOW and steam (for vapor pressure - I
~2~26~
data sex LEN. Yannopoulos, J. Pays. Chum. 72, 3293 ~1968). Ho VOW is isoelectronic with H3PO4 and is most probably a strong acid. H3VO4 therefore destroys the zealot crystallanity and activity by acid hydrolysis of the Swahili framework of the zealot. As H3VO4 reacts with Moo and forms (MgO)2V2O5 on the surface of pore, the surface of the pore will well due to larger molar volume of (MgO)2V2O5. If the pore is too small, blocking will occur readily and thereby inhibit the further reaction with H3V04. We have experimentally determined that the average pore diameter must be greater than AYE or Jo to be effective. This effect has been extensively studied with similar reaction:
Coo + SO > Casey (see S. K. Bush and D. D. Perlmutter Ache J. 27, 266 and 29, 79).
As indicated above, Moo is the preferred oxide over the other alkaline earths when used in conjunction with FCC catalysts. This is due to the presence of sulfur oxides in the flue gases of the regenerator, which can compete with H3V04 forming alkaline earth Swiss as shown by a consideration of the equilibrium constants for the reactions of McCoy and Casey with vanadic acid. Assuming a worst case test in which all of the Six is assumed to be SO at a typical level of 2000 Pam in the regenerator, 20% HO, 1.07 Pam H3V04 and a temperature of 970K ~1285F) a calculated equilibrium constant assuming unit activity for the condensed phases from the regenerator conditions above can be compared to the equilibrium constant for the two reactions from thermochemical data as follows:
3l2262~9 Casey 2H3V04(91 - (Cove) + 2S03(9) + rug X (970K) - 472.75 McCoy + 2H3V04(g) - (M90)2 2 5 5 2S03(9) 3H20(9) X(970K) 6.675 x lo gala ~~S03] I
thieve ~2.215 x 105 or the case of calcium the calculated equilibrium from regenerator conditions is much greater than the equilibrium constant for the reaction. By the lo Chatlier's principle the reaction will favor the left hand side of reaction with calcium. the opposite is true for the case with Moo. If calcium is used Casey will be preferentially formed over the vendetta, the opposite is true for magnesium.
lo The fluid catalytic cracking catalysts which are combined with the basic alkaline earth metal component, are conventional and well known to those skilled in the art. Typically, the catalysts comprise amorphous inorganic oxide gels such as silica-alumina hydrogels, end/or a crystalline zealot dispersed in an inorganic oxide matrix.
Preferred zealots are synthetic faujasite (type Y
zealot) and/or shape selective zealots such as ZSM-5. Type Y zealots which are exchanged with hydrogen Andre rare earth petals such as HO and RAY, and those which have been subjected to thermal treatments such as calcined, rare-earth exchanged Y
(CRY) Andre Zl4US are particularly suited for inclusion in fluid cracking catalyst compositions.
3L2;~62~;9 Catalytically active zealot components are typically described in US. patents 3,293,192 and RYE 28,629.
In addition to an active zealot component, the catalysts contain an inorganic oxide matrix. The inorganic oxide matrix is typically a silica-alumina Harley, which may be combined with substantial quantities of clay such as kaolin. In addition, it is contemplated in catalyst matrix systems which comprise silica, alumina, ~ilica-alumina owls and gels may be utilized in the practice of the present invention.
Methods for producing suitable catalyst compositions are described in US. 3,974,099, 3,957,689, 4,226,743, 3,B67,30B, 4,247,4~0.
The following additional examples act to further illustrate the present teachings:
Example 5 This example shows the preparation and use of large and small pore Moo based vanadium scavenging additives. A
magnesia-silica gel was prepared by mixing a 3.62% Sue and 10.87% Noah aqueous solution with 13.28% McCoy aqueous soul-lion at equal flow rates through a mix pump to form a MgO.SiO2 gel with composition 60 White Moo 40 wt.% Sue. The temperature of the reaction mixture was 30C for example A to make smaller pore diameters, end 20C for example B for larger pore diameters. The resultant gel in both cases was filtered, reslurried in water to ~10 solids and spray dried at 330C. The spray dried material was washed with 70C HO to remove Nail.
Figure 1 shows the Hug pore size diameter for both preps after calcination for 2 hours at 53BC. Analytical data in Table shows the two Samples have similar properties except that the metals tolerance of an 80~
commercial FCC catalyst (Super D) 20% additive (either A or B) was dramatically improved for example B. This example clearly demonstrates the importance of the -SD lo-~22~2~g larger pyre volume end APT for vanadium scavenging effectiveness, TABLE V
Analytical and Metals Data for Two Moo Additives Theoretical Composition 60% Moo 40~ Sue (AYE) AYE) Run-off Temp. 30C 20C
Moo 64.07 62.58 Sue 38.40 36.41 PI ~20-10,000) cc2/g .06~ .19 APT (20-10l000) A 703 624 Metals impregnation of 80% Super D, 20~ Additive with .67% V. S-13.5 steam.
My (F) .30 .16 C (F) 2.10 1.65 Example 6 . . .
This example again shows the use of high pore volume and low pore volume Moo. Catalyst A is a blend of ~04 Super D, 20~ commercially available high pore volume Moo (from Martin Marietta grade Maxim Catalyst B it a blend of 80~ Super D, 20~ commercially available low pore volume Moo (from Martin Marietta grade Maxim 10). Both catalysts are impregnated by the procedure in Example 1. table VI shows the micro activity results.
~2~2~g TABLE VI
Catalyst A Catalyst B
PI (20-10,000) m2tg .821 ,065 APED (20-10,000) A 1,266 3,466 Ox VIA 67 67 H2/C .06/2.30 .04/1.73 ,67~ VIA 55 13 H2/C ,08/1.82 .06/.75 101.34% VIA 38 11 I .11/1.51 ,091 :, , .~.
Claims (20)
1. A catalytic cracking catalyst composition which comprises:
(a) a cracking catalyst component comprising a synthetic faujasite dispersed in an inorganic oxide matrix, and (b) from about 5 to 80 percent by weight expressed as the oxides of a magnesia-silica gel component.
(a) a cracking catalyst component comprising a synthetic faujasite dispersed in an inorganic oxide matrix, and (b) from about 5 to 80 percent by weight expressed as the oxides of a magnesia-silica gel component.
2. The composition of claim 1 which contains greater than 0.1 percent by weight vanadium deposited thereon during use in a catalytic cracking process.
3. The composition of claim 2 which contains from about 1 to about 10 percent by weight vanadium.
4. The composition of claim 1 wherein said inorganic oxide matrix comprises silica-alumina gel and clay.
5. The composition of claim 1 wherein said magnesia-silica gel is dispersed in said matrix as a separate oxide phase.
6. The composition of claim 1 wherein said magnesia-silica gel is physically mixed as a separate particulate additive.
7. In a method for the catalytic cracking of metals containing hydrocarbons wherein said hydrocarbon is reacted under catalytic cracking conditions with a catalyst, and deactivating metals are deposited on said catalyst, the improvement comprising:
conducting the reaction using the catalyst of claim 1.
conducting the reaction using the catalyst of claim 1.
8. The method of claim 7 wherein said deactivating metal is vanadium in a level range from about 1 to 10 percent by weight.
9. The method of claim 7 wherein the magnesia-silica gel is dispersed within the catalyst as a distinct solid oxide phase.
10. The method of claim 7 wherein the magnesia-silica gel is physically mixed with catalyst powder as a separate particu-late additive.
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
11. The composition of claim 1 wherein said magnesia-silica gel component has a pore volume of at least 0.1 cc/g and an average pore diameter greater than about 400 A° in pores having diameter of 200-10,000 A°.
12. The composition of claim 11 which contains greater than 0.1 percent by weight vanadium deposited on the catalyst during use in a catalytic cracking process.
13. The composition of claim 12 which contains from about 0.1 to about 10 percent by weight vanadium.
14. The composition of claim 11 wherein said magnesia-silica gel is dispersed in said matrix as a separate oxide phase.
15. The composition of claim 11 wherein said magnesia-silica gel is physically mixed as a separate particulate additive.
16. In a method for the catalytic cracking of metals containing hydrocarbons wherein said hydrocarbon is reacted under catalytic cracking conditions with a catalyst, and deactivating metals including vanadium are deposited on said catalyst, the improvement comprising:
conducting the reaction using the catalyst of claim 11.
conducting the reaction using the catalyst of claim 11.
17. A composition for scavenging vanadium which comprises a magnesia-silica gel having the weight composition 30 to 80%
MgO and a pore volume of at least 0.1 cc/g and an average pore diameter greater than about 400 A° diameter in pores ranging from about 200 to 10,000 A° in diameter.
MgO and a pore volume of at least 0.1 cc/g and an average pore diameter greater than about 400 A° diameter in pores ranging from about 200 to 10,000 A° in diameter.
18. The composition of claim 17 wherein said composition has a total pore volume of 0.2 to 1.0 cc/g.
19. The composition of claim 17 wherein the composition is formed into particles having a size range of 40 to 80 microns.
20. The composition of claim 19 wherein the particles have a density of about 0.5 to 1.0 cc/g.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48716583A | 1983-04-21 | 1983-04-21 | |
| US487,165 | 1983-04-21 | ||
| US739,645 | 1985-05-31 | ||
| BR8604971A BR8604971A (en) | 1983-04-21 | 1986-10-10 | COMPOSITION OF CATALYST CRACKING AND CATALYTIC CRACKING PROCESS OF METALS CONTAINING HYDROCARBONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226269A true CA1226269A (en) | 1987-09-01 |
Family
ID=25664142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000452087A Expired CA1226269A (en) | 1983-04-21 | 1984-04-16 | Catalytic cracking catalyst and process |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE899446A (en) |
| BR (1) | BR8604971A (en) |
| CA (1) | CA1226269A (en) |
| DE (1) | DE3414426A1 (en) |
| FR (1) | FR2544736A1 (en) |
| GB (1) | GB2138314B (en) |
| NL (1) | NL8401289A (en) |
| SE (1) | SE8402193L (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0189267A3 (en) * | 1985-01-14 | 1987-06-10 | Engelhard Corporation | Fluidizable composition for catalytic cracking |
| BR8600105A (en) * | 1985-01-14 | 1986-09-23 | Engelhard Corp | CATALYST COMPOSITION AND PROCESS FOR CATALYTIC CRACKING OF PETROLEUM FRACTION FLUID |
| EP0194536B1 (en) * | 1985-03-12 | 1989-08-23 | Akzo N.V. | Barium titanate- containing fluidizable cracking catalyst composition |
| GB8514209D0 (en) * | 1985-06-05 | 1985-07-10 | Unilever Plc | Catalyst additives |
| JPS62152545A (en) * | 1985-12-26 | 1987-07-07 | Jgc Corp | Removal of vanadium adhered to catalyst |
| US5141624A (en) * | 1989-03-30 | 1992-08-25 | Phillips Petroleum Company | Catalytic cracking process |
| US5157006A (en) * | 1991-03-08 | 1992-10-20 | Phillips Petroleum Company | Additive and process for vanadium capture in catalytic cracking |
| US5259949A (en) * | 1991-03-08 | 1993-11-09 | Phillips Petroleum Company | Process for vanadium capture in catalytic cracking utilizing an alcohol-treated strontium hydroxide additive |
| JP3920966B2 (en) * | 1997-06-06 | 2007-05-30 | 東燃ゼネラル石油株式会社 | Additive catalyst for heavy oil cracking |
| JPH11561A (en) | 1997-06-13 | 1999-01-06 | Tonen Corp | Additive catalyst for catalytic cracking of heavy oil |
| US20030050349A1 (en) * | 2001-08-31 | 2003-03-13 | Conoco Inc. | In-situ desulfurization of a feed stream in a catalytic reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL111573C (en) * | 1959-02-24 | |||
| GB884633A (en) * | 1959-04-30 | 1961-12-13 | Nalco Chemical Co | Silica magnesia catalysts and their use in a process for cracking hydrocarbons |
| US3322690A (en) * | 1963-12-10 | 1967-05-30 | Exxon Research Engineering Co | Synthetic crystalline zeolite compositions and preparation thereof |
| GB1112078A (en) * | 1966-05-25 | 1968-05-01 | Grace W R & Co | Silica-alumina-magnesia-magnesium fluoride catalyst for use in cracking hydrocarbons |
| US3507778A (en) * | 1967-09-05 | 1970-04-21 | Exxon Research Engineering Co | Cracking petroleum fractions with a crystalline zeolite catalyst in combination with a phosphate promoted silica-magnesia catalyst |
| US3699037A (en) * | 1970-10-28 | 1972-10-17 | Chevron Res | Catalytic cracking |
| US3835031A (en) * | 1973-05-23 | 1974-09-10 | Standard Oil Co | Catalytic cracking with reduced emission of sulfur oxides |
| SE438449B (en) * | 1980-06-30 | 1985-04-22 | Katalistiks International Bv | CRACKING CATALYST FOR CRACKING THE CALVET IN A FLUIDIZED CATALYST BED WORKING REACTOR |
| EP0074945A1 (en) * | 1981-03-19 | 1983-03-30 | Ashland Oil, Inc. | Immobilization of vanadia deposited on catalytic materials during carbometallic oil conversion |
| MX162472A (en) * | 1981-04-10 | 1991-05-13 | Ashland Oil Inc | CATALYST FOR THE CONVERSION TO LIGHTER PRODUCTS OF HYDROCARBON OIL FOOD |
| GB2116062A (en) * | 1982-03-03 | 1983-09-21 | Gulf Research Development Co | Catalytic cracking composition |
-
1984
- 1984-04-16 CA CA000452087A patent/CA1226269A/en not_active Expired
- 1984-04-16 GB GB08409848A patent/GB2138314B/en not_active Expired
- 1984-04-17 DE DE19843414426 patent/DE3414426A1/en not_active Withdrawn
- 1984-04-17 BE BE0/212785A patent/BE899446A/en not_active IP Right Cessation
- 1984-04-18 SE SE8402193A patent/SE8402193L/en not_active Application Discontinuation
- 1984-04-19 NL NL8401289A patent/NL8401289A/en not_active Application Discontinuation
- 1984-04-20 FR FR8406357A patent/FR2544736A1/en not_active Withdrawn
-
1986
- 1986-10-10 BR BR8604971A patent/BR8604971A/en not_active Application Discontinuation
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| Publication number | Publication date |
|---|---|
| GB2138314B (en) | 1987-07-22 |
| GB8409848D0 (en) | 1984-05-23 |
| DE3414426A1 (en) | 1984-10-25 |
| FR2544736A1 (en) | 1984-10-26 |
| GB2138314A (en) | 1984-10-24 |
| SE8402193D0 (en) | 1984-04-18 |
| BE899446A (en) | 1984-08-16 |
| BR8604971A (en) | 1987-07-14 |
| NL8401289A (en) | 1984-11-16 |
| SE8402193L (en) | 1984-10-22 |
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