Abstract:
An improved &#34;magnetic hook&#34;-promoted catalytic process, catalyst and method of manufacture for heavy hydrocarbon conversion, optionally in the presence of nickel and vanadium on the catalyst and in the feed stock to produce lighter molecular weight fractions, including more gasoline, lower olefins and higher isobutane than normally produced. This process is based on the discovery that two &#34;magnetic hook&#34; elements, namely manganese and chromium, previously employed as magnetic enhancement agents to facilitate removal of old catalyst, or to selectively retain expensive catalysts, can also themselves function as selective cracking catalysts, particularly when operating on feeds containing significant amounts of nickel and vanadium, and especially where economics require operating with high nickel- and vanadium-contaminated and containing catalysts. Under such conditions, these promoted catalysts are more hydrogen and coke selective, have greater activity, and maintain that activity and superior selectivity in the presence of large amounts of contaminant metal, while also making more gasoline at a given conversion.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     Cross references to related application, U.S. patent application Ser. No. 08/326,982, filed Oct. 21, 1994 relates to the general field of the present invention. 
     BACKGROUND OF THE INVENTION 
     I. Field of the Invention 
     This invention relates to the field of adding manganese to hydrocarbon cracking catalysts, generally classified in Class 208, subclass 253 of the U.S. and in International Class C10G-29/D4. 
     II. Description of the Prior Art 
     U.S. Pat. No. 4,412,914 to Hettinger et al. is understood to remove coke deposits on sorbents by decarbonizing and demetalizing with additives including manganese (claim 4, column 26). 
     U.S. Pat. No. 4,414,098 to Zandona et al. uses additives for vanadium management on catalysts (column 15, line 6). 
     U.S. Pat. No. 4,432,890 to Beck et al. mobilizes vanadia by addition of manganese, inter alia, Table A; column 9, line 35-48; column 10, line 40; and column 27, line 3; Table Y; etc. 
     U.S. Pat. No. 4,440,868 to Hettinger et al. refers to selected metal additives in column 11, line 20, but does not apparently expressly mention Mn. 
     U.S. Pat. No. 4,450,241 to Hettinger et al. uses metal additives for endothermic removal of coke deposited on catalytic materials and includes manganese as an example of the additive (column 11, Table C). 
     U.S. Pat. No. 4,469,588 to Hettinger et al. teaches immobilization of vanadia during visbreaking and adds manganese to sorbent materials (column 11, lines 1-13, line 53 and line 65; column 23, line 59 and line 20; claim 1 and claim 17. 
     U.S. Pat. No. 4,485,184 to Hettinger et al. is understood to teach that trapping of metals deposited on catalytic materials concludes manganese as an additive (column 8, line 32; column 10, line 50, Table A; column 11, line 34; column 29, line 55, Table Z; column 31; column 32; claims 5-9. 
     U.S. Pat. No. 4,508,839 to Zandona et al. mentions metal additives including manganese at column 17, line 44 for the conversion of carbo-metallic oils. 
     U.S. Pat. No. 4,513,093 to Beck et al. immobilizes vanadia deposited on sorbent materials by additives, including manganese; column 9, line 35, Table A; column 10, lines 8-9; column 10, line 21. 
     U.S. Pat. No. 4,515,900 to Hettinger et al. is understood to teach that additives, including Mn, are useful in visbreaking of carbo-metallic oils (column 10, line 64 and column 23, line 52, Table E; column 25, line 13, Table 5. 
     U.S. Pat. No. 4,549,958 to Beck et al. teaches immobilization of vanadia on sorbent material during treatment of carbo-metallic oils. Additives include manganese mentioned at column 9, line 37, Table A; column 10, line 10; column 10, line 21; column 21, line 27, Table Y; column 21, line 56, Table Z; claim 37-38. 
     U.S. Pat. No. 4,561,968 to Beck et al. is understood to teach carbo-metallic oil conversion catalyst with zeolite Y-containing catalyst includes immobilization by manganese; column 14, line 43. 
     U.S. Pat. No. 4,612,298 to Hettinger et al. teaches manganese vanadium getter mentioned at column 14, line 31-32. 
     U.S. Pat. No. 4,624,773 to Hettinger et al. is understood to teach large pore catalysts for heavy hydrocarbon conversion and mentions manganese at column 18, line 27. 
     U.S. Pat. No. 4,750,987 to Beck et al. teaches mobilization of vanadia deposited on catalysts with metal additives including manganese; column 9, line 10; column 11, line 6, Table A; column 11, lines 47-49; column 11, lines 67; column 24, lines 14-25; column 28, line 52, Table Y. 
     U.S. Pat. No. 4,877,514 to Hettinger et al. teaches the incorporation of selected metal additives, including manganese, which complex with vanadia to form higher melting mixtures; column 10, lines 43-49; column 14, lines 34-35; column 29, line 37; claims 2, 10 and 13. 
     U.S. Pat. No. 5,106,486 to Hettinger teaches the addition of magnetically active moieties, including manganese, for magnetic beneficiation of particulates in fluid bed hydrocarbon processing; column 4, line 64; claims 1, 2, 11, 32, and 44-48. 
     U.S. Pat. No. 5,198,098 to Hettinger uses magnetic separation of old from new equilibrium particles by means of manganese addition (see claims 1-30). 
     U.S. Pat. No. 5,230,869 to Hettinger et al. is understood to teach the addition of magnetically active moieties for magnetic beneficiation of particulates in fluid bed hydrocarbon processing; column 5, line 4 and claim 1. 
     U.S. Pat. No. 5,364,827 to Hettinger et al. teaches the composition comprising magnetically active moieties for magnetic beneficiation of particulates in fluid bed hydrocarbon processing; column 5, line 4 and claim 5. 
     U.S. Pat. No. 4,836,914 to Inoue et al. mentions magnetic separation of iron content in petroleum mineral oil but is not understood to mention manganese. 
     U.S. Pat. No. 4,956,075 to Angevine et al. adds manganese during the manufacture of large pore crystalline molecular sieve catalysts and particularly uses a manganese ultra stable Y in catalytic cracking of hydrocarbons. 
     U.S. Pat. No. 5,358,630 to Bertus et al. mentions manganese in claims 28 and 40, but not in the specification. The patent relates primarily to methods for &#34;. . . contacting . . . catalyst with a reducing gas under conditions suitable countering effects of contaminating metals thereon and employing at least a portion of said reduced catalysts in cracking said hydrocarbon feed&#34; (column 7, lines 10-12). 
     U.S. Pat. No. 2,575,258 to Corneil et al. mentions manganese as accumulating in the catalysts as a result of erosion of equipment (column 3, line 34). 
     U.S. Pat. No. 3,977,963 to Readal et al. mentions manganese nitrate and manganese benzoate and other manganese compounds, e.g., in the second paragraph under &#34;Descriptions of Preferred Embodiments&#34; and in the Tables under &#34;Detailed Description&#34; and in claim 4. It is directed to the contacting of catalysts with a bismuth or manganese compound to negate the effects of metals poisoning. 
     U.S. Pat. No. 4,036,740 to Readal et al. teaches use of antimony, bismuth, manganese, and their compounds convertible to the oxide form to maintain a volume ratio of carbon dioxide to carbon monoxide in the regeneration zone of a fluid catalytic cracker of at least 2.2. 
     Cimbalo et al., May 15, 1972, teaches the effects of nickel and vanadium on deleterious coke production and deleterious hydrogen production in an FCC unit using zeolite-containing catalyst. 
     SUMMARY OF THE INVENTION 
     I. General Statement of the Invention 
     According to the invention, an improved &#34;magnetic hook&#34;-promoted catalytic process, catalyst and method of manufacture for heavy hydrocarbon conversion, optionally in the presence of nickel and vanadium on the catalyst and in the feedstock to produce lighter molecular weight fractions, including more gasoline and lower olefins and higher isobutane than normally produced has been discovered. This process is based on the discovery that two &#34;magnetic hook&#34; elements, namely manganese and chromium, previously employed as magnetic enhancement agents to facilitate removal of old catalyst, or to selectively retain expensive catalysts, can also themselves function as selective cracking catalysts, particularly when operating on feeds containing significant amounts of nickel and vanadium, and especially where economics require operating with high nickel- and vanadium- contaminated and containing catalysts. Under such conditions, these promoted catalysts are more hydrogen and coke selective, have greater activity, and maintain that activity and superior selectivity in the presence of large amounts of contaminant metal, while also making more gasoline at a given conversion. 
     II. Utility of the Invention 
     Table A summarizes approximate preferred, more preferred, and most preferred levels of the more important parameters of the invention. Briefly stated, the invention comprises, improving gasoline selectivity in a process for the conversion of hydrocarbons containing more than 1 ppm of nickel and more than 1 ppm of vanadium to lower molecular weights comprising gasoline by contacting said hydrocarbons with a circulating zeolite-containing cracking catalyst, which is thereafter regenerated and recycled to contact additional hydrocarbons, the improvement comprising in combination the steps of: a) maintaining a catalyst:oil weight ratio of at least about 2; and b) adding to at least a portion of said cracking catalyst from about 0.1 to 20 wt. % of manganese and/or chromium, in the form of a compound, based on the weight of the catalyst; whereby gasoline selectivity is increased by at least 0.2 wt. % points as compared to said process without said manganese or chromium. More preferably the portion of cracking catalyst to which manganese is added comprises from 5-100 wt. % of the total weight of the circulating catalyst. Still more preferably, the portion contains more than 0.5% by weight of sodium. This process and catalyst is especially effective when used in conjunction with a circulating catalyst containing nickel and vanadium and/or when operating at higher steam and/or temperature severity. 
     The weight of manganese is maintained at about 0.3 or above times the total nickel-plus-vanadium or total metals or total vanadium on the circulating catalyst. The carbon remaining after regeneration is preferably no more than 0.1% of the weight of the carbon deposited on the catalyst during hydrocarbon conversion. Particularly preferred is a process wherein the fresh catalyst is added over time to the circulating catalyst, particularly where the flesh catalyst comprises 0.1-20 wt. % manganese and/or a similar concentration of chromium. The cracking catalyst added continuously can be the same or different from that circulating and can preferably comprise a paraffin-selective cracking catalyst such as Mobil&#39;s ZSM-5. One important advantage of the invention is that the cracking catalyst can be rendered more gasoline selective, coke selective, and hydrogen selective when it contains 0.1-20 wt. % manganese, and is even more selective when contaminated with nickel and vanadium as compared to the selectivity of equivalent catalyst without manganese. The manganese and/or chromium is preferably deposited onto the outer periphery of each microsphere but can be deposited uniformly throughout the microsphere, where the most preferred microspherical catalysts particles are used. Cracking activity can exist in both the zeolite and the matrix. Manganese preferably serves as an oxidation catalyst to accelerate the conversion of carbon to CO and CO 2  and any sulfur in the coke to SO 2 , SO 3  or sulfate and can act as a reductant in the conversion reactor to convert greater than 10% of the retained sulfate in the reactor to SO 2 , sulfur and H 2  S. 
     Cracking catalyst can be prepared by incorporating manganese into a microspherical cracking catalyst by mixing with a solution of a manganese salt with a gelled cracking catalyst and spray drying the gel to form a finished catalyst or a solution of manganese salt can be combined with the normal catalyst preparation procedure and the resulting mixture spray-dried, washed and dried for shipment. Manganese can be added to the microspherical catalyst by impregnating the catalyst with a manganese-containing solution and flash drying. Preferred salts of manganese for catalyst preparation include nitrate, sulfate, chloride, and acetate. The selective cracking catalyst can be prepared by impregnating spray-dried catalyst with MMT (methylcyclopentadienyl manganese tricarbonyl) and drying. The MMT can be dissolved in alcohol or other solvent which can be removed by heating. Alternatively, spray-dried or extruded or other catalyst can be impregnated with a colloidal water suspension of manganese oxide or other insoluble manganese compound and dried. The continuous or periodic addition of a water or organic solution of manganese salts with or without methyl cyclopentadienyl manganese tricarbonyl in a solvent can also be employed with the invention. Manganese compounds, preferably MMT or manganese actuate in mineral spirits or a water solution of a manganese salt, can also be added directly to the catalytic cracker feed and subsequently deposited on the circulating catalyst. 
     The virgin catalysts will preferably possess a magnetic susceptibility of greater than about 1×10 -6  emu/g and this can be promoted to a magnetic hook into the range of about 1-40×10 -6  emu/g or even greater. (Magnetic hooks are discussed in detail in U.S. Pat. Nos. 5,106,486; 5,230,869 and 5,364,827 to Hettinger et al.) The coke produced in the conversion is burned off by contact with oxygen-containing gas in a conventional regenerator and the manganese can serve as an oxidation catalyst in the regenerator to accelerate the conversion of carbon to carbon monoxide and/or carbon dioxide, enhancing the regeneration process. 
     As an additional advantage of the invention, the sulfur in some gasolines can be reduced by 10% or even more as compared to gasoline produced without manganese in the catalyst. 
     A portion of the circulating catalyst can be removed from the process of the invention and treated with nitrogen, steam and greater than 1% oxygen (preferably in the form of air) for 10 minutes to 1 hour or even more at 1200° F., or greater then returned to the process, to effect a partial or complete regeneration of the catalyst. 
     
                       TABLE A______________________________________PROCESS                        More    MostParameter Units    Preferred Preferred                                Preferred______________________________________V in Feed Wt. ppm  1 or more 10 or more                                50 or moreNi in Feed     Wt. ppm  1 or more 10 or more                                50 or moreNi + V on Wt. ppm  above 500 above 1000                                above 5000CatalystV on      Wt. ppm  100-100,000                        above 500                                above 1000CatalystMn on     Wt. %    0.05-20   0.1-15  0.2-10CatalystCatalyst  compos.  Zeo-      USY-    ZSM-5              containing                        containing                                containingCat:Oil ratio     Wt.      2 or more 2.5-12  3-9Mn/Cr on  Wt. %    0.1-20    0.5-15  1-10CatalystMn/Cr              any       impregna-                                --Addition Meth.               tionGasoline  Wt. %    +0.2 or   +0.4 or +1 orSelectivity Δ              more      more    more&#34;Portion&#34; Wt. %    5-100     10-50   15-25with Mn/CrNa in &#34;Portion&#34;     Wt. %    more than more than                                more than              0.5       0.6     0.7Mn:(Ni + V)     Wt. ratio              above 0.3 above 0.5                                above 1on CatalystMn:V on   Wt. ratio              above 0.3 above 0.5                                above 1CatalystCr:(Ni + V)     Wt. ratio              above 0.3 above 0.5                                above 1on CatalystConcarbon in     Wt. %    above 0.1 above 0.3                                1-7feed% of Carbon on     % of     0.5 or less                        0.1 or less                                0.05-0.1Cat. remaining     orig.after regen.Zeolite-in-     Wt. %    1 or more 5 or more                                10 or moreCatalystHydrocarbon     Wt. %    above 2   above 3 above 4Concarb.S in Hydro-     Wt. %    above 0.5 above 1.5                                above 2carbon feedS retention     Wt. %    10 or more                        12 or more                                15 or moreby Mn% Sulfate in     Wt. %    above 10  above 12                                above 15ReactorConvertedCatalyst Form     Form     any       micro-  spray-dried                        spheres micro-                                spheresCat. Mag. 10.sup.-6              above 1   2-40    3-40Suscept.  emu/gCat. Mag. Hook     10.sup.-6              1-50      2-40    3-40Mag. Suscepti-     emu/gbility IncreaseReduction of     %        10 or more                        12 or more                                15 or more50x in Fluegas______________________________________ 
    
     The present invention is useful in the conversion of hydrocarbon feeds, particularly metal-contaminated residual feeds, to lower molecular, weight products, e.g., transportation fuels. As shown below, it offers the substantial advantages of improving catalyst activity, improving gasoline-, coke-, and hydrogen-selectivity and reducing sulfur content of the products, as well as enhancing regeneration of coked catalyst. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a plot of relative activity (by Ashland Oil test, see e.g., U.S. Pat. No. 4,425,259 to Hettinger et al.) versus cat:oil weight ratio for AKC catalyst (the same catalyst except for FIG. 7 used in FIGS. 1-18) with and without manganese. (See Example 1 and Table 1.) 
     FIG. 2 is a plot of wt. % gasoline selectivity versus wt. % conversion in a typical cracking process and compares catalysts with and without manganese. (See Example 3 and Table 3a. ) 
     FIG. 3 is a plot of gasoline yield versus conversion rate constant and compares catalysts with and without manganese. (See Example 3 and Table 3a.) 
     FIG. 4 is a plot of gasoline wt. % selectivity versus conversion comparing catalysts with and without manganese and contaminated with 3000 ppm nickel plus vanadium. (See Example 4 and Table 4.) 
     FIG. 5 is a plot of relative activity versus cat:oil ratio comparing catalysts with and without manganese. (See Example 4 and Table 4.) 
     FIG. 6 is a plot of wt. % gasoline in product versus conversion rate constant for the catalysts with and without manganese showing the improved gasoline percentage with manganese. (See Example 4 and Table 4.) 
     FIG. 7 is a plot of gasoline selectivity versus weight ratio of (X) manganese:vanadium, and (O) manganese:nickel+vanadium. (See Example 8 and Table 8.) 
     FIG. 8 is a plot of relative activity versus cat:oil ratio comparing no manganese with 9200 ppm manganese added by an impregnation technique and with 4000 ppm manganese added by an ion exchange technique. (See Example 10 and Tables 10a, 10b and 10c.) 
     FIG. 9 is a plot of gasoline selectivity versus conversion comparing no manganese versus 9200 ppm impregnated manganese and 4000 ppm ion exchanged manganese. (See Example 10 and Tables 10a, 10b and 10c.) 
     FIG. 10 is a plot of Ashland relative activity versus cat:oil ratio comparing catalysts with and without manganese at different levels of rare earth. (See Example 11 and Table 10.) 
     FIG. 11 is a plot of gasoline selectivity versus gasoline conversion comparing no manganese with impregnated rare earth elements and ion-exchanged manganese, showing manganese, surprisingly, is more effective than rare earths. (See Example 11 and Table 10. ) 
     FIG. 12 is a plot of wt. % isobutane (in mixture with 1-butene/isobutene) versus wt. % conversion for catalysts with no manganese and with 9200 and 4000 ppm manganese. (See Example 12 and Table 10.) 
     FIG. 13 is a plot of the ratio of C 4  saturates to C 4  olefins versus wt. % conversion comparing manganese at levels of 4000 ppm, 9200 ppm of with no manganese and no manganese plus 11,000 ppm rare earth. (See Example 12 and Table 10.) 
     FIG. 14 is a plot of the CO 2  :CO ratio versus percent carbon oxidized off during regeneration (See Example 14) with and without manganese. 
     FIG. 15 is a plot of wt. % gasoline versus wt. % conversion for catalysts with and without manganese and 3200 ppm Ni+V showing improved gasoline yield with manganese. (See Example 15 and Table 12.) 
     FIG. 16 is a plot of hydrogen-make versus conversion showing the improved (reduced) hydrogen make with manganese being deposited as an additive during cracking. (See Example 15 and Table 12.) 
     FIG. 17 is a plot of coke-make versus conversion showing the improved (reduced) coke make with manganese being deposited as an additive during cracking. (See Example 15 and Table 12.) 
     FIG. 18 is a plot of conversion versus cat:oil ratio showing the improved conversion with manganese at cat:oil ratios above about 3. (See Example 15 and Table 12.) 
     FIG. 19 is a plot of relative activity versus manganese content. 
     FIG. 20 is a plot of selectivity versus manganese content. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The following examples are presented to illustrate preferred embodiments of the invention, but the invention is not to be considered as limited by the specific embodiments presented herein. 
     EXAMPLE 1 
     The Invention with Manganese Additive on Cracking Catalyst 
     4.54 grams of manganese II acetate tetrahydrate is dissolved in 100 ml. of boiling distilled water. 100 grams of a commercially available low rare earth-containing (less than 1800 ppm) cracking catalyst is also dispersed in 150 ml. of distilled water. The catalyst slurry and the manganese acetate tetrahydrate solution are mixed rapidly and shaken vigorously for 15 minutes at room temperature. This is repeated four to five times over a 24-hour period, and the slurry then allowed to settle for two hours. Excess liquid is poured off, the settled catalyst slurried once with 100 ml. of distilled water and dewatered through a filter. The filter cake is allowed to air dry and then dried in a microwave oven for four minutes at high intensity setting. The dried sample is calcined at 1200° F. in a ceramic crucible for four hours and allowed to cool in air to room temperature. 
     The finished catalyst is analyzed for manganese content by x-ray fluorescence and found to have 6000 ppm of manganese. 
     Catalyst cracking activity is evaluated by means of a micro-activity test performed by Refining Process Services of Cheswick, Pa. 
     The results obtained for this catalyst are shown in Table 1. 
     
                                           TABLE 1__________________________________________________________________________Manganese Addition, Micro-activity Study                                 Base Catalyst                          Base Catalyst                                 plus ManganeseCatalyst Metal                 None   6000 ppm__________________________________________________________________________Steaming Temperature (°F.)                          1425   1425Steaming Time (hours)          24     24Cat:Oil Ratio                  4.60   4.58Reaction Temperature (°F.)                          960    960Reaction Time (seconds)        25     25WHSV                           31.3   31.5Conversion (wt. %)             67.37  74.64Conversion (vol. %)            69.09  76.60Product Yields (wt. %) on Fresh FeedC.sub.2 and lighter            1.41   1.51Hydrogen                       0.11   0.09Methane                        0.45   0.47Ethane                         0.37   0.41Ethylene                       0.48   0.54Carbon                         3.64   3.82Product Yields (wt. %) on Fresh FeedTotal C.sub.3 Hydrocarbon      5.36   4.99Propane                        0.62   0.83Propylene                      4.75   4.16Total C.sub.4 Hydrocarbon      10.54  10.17I-Butane                       3.55   4.48N-Butane                       0.54   0.82Total Butenes                  6.45   4.88Butenes                        3.18   2.05T-Butene-2                     1.86   1.62C-Butene-2                     1.40   1.21C.sub.5 -430° F. Gasoline                          46.42  54.15(Vol. %)                       (56.24)                                 (65.60)430-650° F. LCGO        22.35  18.25650° F. + Decanted Oil  10.28  7.11C.sub.3 + Liquid Recovery      94.95  94.67FCC Gasoline + Alkylate Vol. % 87.4   90.84Isobutane/(C.sub.3 + C.sub.4) Olefin Ratio                          0.32   0.50Coke Selectivity               1.64   1.22Weight Balance                 99.71  98.52Feed Stock                     RPS    RPS ##STR1##                      68.9   72.5 ##STR2##                      81.4   85.6 ##STR3##                      2.06   2.91__________________________________________________________________________ 
    
     It will be noted that in this case both activity, a most important economic property; and gasoline selectivity, an even more important economic property; are higher for the catalyst with manganese. These results clearly show the benefit of manganese as a catalyst promoter. 
     EXAMPLE 2 
     Effect of Manganese at Higher Levels 
     Two additional catalyst preparations, using the same procedure as used for the catalyst in Example #1, are made, but at slightly higher levels of manganese. These two samples are labeled AKC #1 and AKC #2. AKC #1 is shown by x-ray fluorescence to have 9200 ppm of manganese and AKC #2 contained, 15,000 ppm of manganese. 
     AKC #1 and AKC #2 are also submitted for MAT testing, and the results further continued the activity and selectivity results noted in Table 1. See Table 2. 
     
                                           TABLE 2__________________________________________________________________________Manganese Addition                 Base                 CatalystCatalyst Metal        None AKC #1                           AKC #2__________________________________________________________________________Metal Manganese ppm   none 9280 15900Steaming temperature (°F.)                 1425 1425 1425Steaming Time (hours) 24   24   24Feed Stock            RPS  RPS  RPSCat:Oil Ratio         4.6  4.48 4.51Reaction Temperature (°F.)                 960  960  960Reaction Time (seconds)                 25   25   25WHSV                  31.3 32.1 31.9Conversion (wt. %)    67.37                      74.56                           74.21Conversion (vol. %)   69.06                      76.49                           76.15Product Yield, (wt. %) on Fresh FeedC.sub.2 and Lighter   1.41 1.46 1.32Hydrogen              0.11 0.09 0.08Methane               0.45 0.44 0.41Ethane                0.37 0.39 0.36Ethylene              0.48 0.52 0.47Carbon                3.64 4.46 4.73Product Yields (wt. %) on Fresh FeedTotal C.sub.3 Hydrocarbon                 5.36 5.25 4.73Propane               0.62 0.75 0.72Propylene             4.75 4.5  4.01Total C.sub.4 Hydrocarbon                 10.54                      10.79                           9.98I-Butane              3.55 4.46 4.35N-Butane              0.54 0.76 0.75Total Butenes         6.45 5.57 4.88Butenes               3.18 2.41 2.03T-Butene-2            1.86 1.8  1.63C-Butene-2            1.4  1.36 1.22C.sub.5 -430° F. Gasoline                 46.42                      52.60                           53.46(Vol. %)              (56.24)                      (63.72)                           (64.76)430-650° F. LCGO                 22.35                      18.53                           18.72650° F. + Decanted Oil                 10.28                      6.91 7.07C.sub.3 + Liquid Recovery                 94.95                      94.08                           93.95FCC Gasoline + Alkylate Vol. %                 87.4 91.8 89.6Isobutane/(C.sub.3 + C.sub.4) Olefin Ratio                 0.32 0.45 0.49Coke Selectivity      1.64 1.44 1.55Weight Balance        99.7 98.63                           98.13Option                     Normal-                           Normal-                      ized ized ##STR4##             68.9 70.5 72.0 ##STR5##             81.4 83.3 85.0 ##STR6##             2.06 2.93 2.90__________________________________________________________________________ 
    
     As can be seen by this data, manganese again greatly increases activity and selectivity, while making much less coke (on a selectivity basis) and hydrogen. Clearly manganese has a markedly beneficial effect on catalyst performance. 
     EXAMPLE 3 
     Manganese on Higher Levels of Cat:Oil Ratio 
     Referring to Table 3, steamed samples of AKC #1 are MAT evaluated at a series of cat:oil ratios, to better define activity and selectivity. Table 3a shows the results of this study, and Table 3b shows the composition of the gas oil used in these tests. 
     
                                           TABLE 3a__________________________________________________________________________Effect of Manganese on Cracking Yields MAT Data on AKC #1Steamed Samples Variation Cat:Oil Ratio            Catalyst ID                 AKC        AKC        AKC            AKC #1                 #1 + Mn                       AKC #1                            #1 + Mn                                  AKC #1                                       #1 + Mn__________________________________________________________________________Steaming Temp (°F.)            1400 1400  1400 1400  1400 1400Steaming Time (hours)            5    5     5    5     5    5Cat:Oil Ratio    2.9  3.1   4.0  4.0   4.8  5.1Temperature (°F.)            915  915   915  915   915  915Catalyst Metals Manganese            0    9200  0    9200  0    9200(ppm)Feed Stock       WTGO WTGO  WTGO WTGO  WTGO WTGOWt. % YieldsConversion       64.9 73.2  74.9 78.8  78.4 81.3Hydrogen         0.05 0.05  0.07 0.07  0.08 0.08Methane          0.30 0.34  0.38 0.44  0.45 0.52Ethane/Ethylene  0.58 0.70  0.73 0.90  0.84 1.02Propane          0.58 0.93  0.78 1.30  0.97 1.65Propylene        3.53 3.55  4.43 3.98  4.70 4.08Isobutane        3.63 5.08  4.63 6.06  5.71 6.821-Butene/Isobutene            2.26 1.76  2.48 1.52  1.46 1.58N-Butane         0.59 1.06  0.79 1.37  1.02 1.65Butadiene        0.00 0.00  0.00 0.00  0.00 0.00Cis-2-Butene     0.99 1.02  1.21 0.99  1.23 0.98Trans-2-Butene   1.36 1.36  1.64 1.32  1.67 1.31CO, CO.sub.2, CO.sub.5, H.sub.2 S            0.33 0.35  0.35 0.33  0.32 0.37C.sub.5 - 430° F.            48.42                 53.77 54.28                            56.05 55.90                                       55.96430-630° F.            17.46                 16.39 15.82                            14.27 14.25                                       12.96630° F.   17.63                 10.41 9.28 6.97  7.38 5.82Coke             2.28 3.23  3.15 4.42  4.02 5.30H.sub.2, SCFB    27   29    38   39    46   47H2:Cl Ratio, Mol:Mol            1.25 1.15  1.39 1.21  1.40 1.22Dry Gas          1.25 1.43  1.52 1.74  1.70 1.99Wet Gas          12.94                 14.77 15.96                            16.55 16.75                                       18.07 ##STR7##        74.6 73.5  72.5 71.1  71.3 68.8K = Rate Constant            1.85 2.74  2.98 3.72  3.63 4.35Coke Selectivity % Coke/K            1.23 1.18  1.06 1.19  1.11 1.22H2 Selectivity   0.0270                 0.0183                       0.0235                            0.0188                                  0.0220                                       0.0184AOI Relative Activity            35   100   90   162   118  168__________________________________________________________________________ 
    
     
                       TABLE 3b______________________________________West Texas Gas Oil                          Metals______________________________________Wt. % Sulfur 0.49         API 28.1         Ni &lt; 1 ppmTotal Nitrogen 330 ppm         Ramsbottom Carbon 0.19%                          V &lt; 1 ppmBasic Nitrogen 213 ppm         Na 5 ppm                          Fe 1 pm______________________________________Chemical Composition               Wt. %______________________________________Saturates           67.1Monoromatics        19.5Diaromatics         5.6Greater than Diaromatics               5.6Polars              2.0______________________________________ 
    
     The results show that manganese greatly increases catalyst activity at all cat:oil ratios, namely a 48% increase at a cat:oil ratio of 3.0; a 25% increase at a cat:oil of 4.0; and a 20% increase at cat:oil of 5.0, using the wt. % conversion rate constant, K, for these comparisons. On Ashland&#39;s relative activity basis (see for example U.S. Pat. No. 4,425,259, FIG. 6) it is 186%, 80%, and 42%, respectively. In all cases of cat:oil it is obvious that there is a significant increase in catalyst activity resulting from manganese additive (see FIG. 1). 
     At first glance, it would appear that in this series of tests, manganese is not superior, selectivity wise, to untreated catalyst. However, this is partially due to the considerable differences in conversions at constant cat:oil testing. FIG. 2 is a plot of wt % gasoline selectivity versus wt % conversion. Here it is quite clear that selectivity is also enhanced. For example, at 75 wt % conversion there is clearly an increase of selectivity from 72.4 wt % to 72.9 wt %. For a catalytic cracker operating at 75 wt % conversion and processing 50,000 bbl/day of gas oil, this selectivity difference amounts to an increased yield of gasoline of approximately 250 barrels/day. At $30/bbl this is equivalent to an additional yield of $7500/day or $2.8 mm/year, a very significant amount. FIG. 3 shows a plot of gasoline yield as related to activity as rate constant which is expressed as wt % conversion divided by (100%-wt % conversion). This plot also shows the advantage of manganese promotion. 
     Note that in all cases, even where metal contaminants are absent hydrogen selectivity is enhanced in the presence of manganese and the olefin content of wet gas is lower, the result of the ability of manganese to transfer hydrogen to olefins, an important property in reducing olefin content of gasoline, so important in reformulated gasoline. Note also that isobutane content at constant conversion is up, providing the refiner with greater alkylate capacity, an equally important property in tomorrow&#39;s refinery. 
     EXAMPLE 4 
     Metals on Manganese Promoted Cracking Catalyst 
     Although the results of Examples 1, 2, and 3 conclusively show the benefits of manganese as an additive on catalyst performance, in today&#39;s environment, because of the unavailability of low metals containing crude oil and/or the economic necessity to process a greater portion or all of the reduced crude, a catalyst&#39;s resistance to metals poisoning, and also its ability to deal with crudes of higher sulfur content are also of great concern. In particular, its abilities to deal with vanadium, a well known hydrogen and coke producer, and a notorious destroyer of catalyst activity, and nickel, a hydrogen and coke producer are of special interest. 
     To evaluate the benefit of manganese as a metal resistant additive, an aliquot of catalyst is steamed according to standard conditions as described in Example #3, while a second aliquot is impregnated to 3000 ppm of Nickel+Vanadium (1800 ppm vanadium and 1200 ppm nickel) and then steam deactivated at 1400° F. for 5 hours in 3% air, a condition shown to be quite severe, especially for vanadium poisoned cracking catalyst. Table 4 shows the results of these tests at three different cat:oil ratios, similar to Example #3. 
     
                       TABLE 4______________________________________Effect of Manganese on Cracking Yields MAT Data onAKC #1 3000 ppm Ni + V Samples  Catalyst ID        AKC             AKC         AKC  AKC   #1 +    AKC     #1 +  AKC   #1 +  #1    Mn      #1      Mn    #1    Mn______________________________________Steaming 1400    1400    1400  1400  1400  1400Temp (°F.)Steaming 5       5       5     5     5     5Time (hours)Cat:Oil Ratio    3       3.1     4.0   4.1   4.9   5.0Temperature    915     915     915   915   915   915(°F.)Catalyst Metals    3000    3000    3000  3000  3000  3000Total (1800ppm V, 1200ppm Ni)Manganese    0       9200    0     9200  0     9200ppmWt. % YieldsConversion    65.4    70.4    70.7  77.5  74.5  81.1Hydrogen 0.33    0.38    0.43  0.49  0.51  0.61Methane  0.37    0.41    0.48  0.57  0.59  0.73Ethane/  0.64    0.73    0.74  0.92  0.83  1.08EthylenePropane  0.62    0.99    0.79  1.36  0.93  1.76Propylene    3.41    3.20    3.86  3.62  4.08  3.77Isobutane    3.04    4.25    3.77  5.51  4.33  6.371-Butene/    2.26    1.46    2.42  1.51  2.35  1.45IsobuteneN-Butane 0.56    0.92    0.70  1.27  0.38  1.61Butadiene    0       0       0     0     0     0Cis-2-Butene    0.96    0.81    1.07  0.89  1.12  0.89Trans-2- 1.30    1.08    1.43  1.21  1.50  1.22ButeneCO, CO.sub.2,    0.38    0.35    0.39  0.37  0.47  0.40CO.sub.5, H.sub.2 SC.sub.5 - 430° F.    48.51   51.15   50.27 53.15 51.27 52.30430-630° F.    18.13   17.09   17.27 14.74 15.48 12.52630° F.    16.45   12.54   11.98 7.76  9.97  6.35Coke     3.05    4.62    4.41  6.62  5.74  8.94H.sub.2, SCFB    191     223     253   286   295   358H2:Cl Ratio,    6.93    7.31    7.22  6.78  6.76  6.67Mol:MolDry Gas  1.72    1.88    2.04  2.35  2.40  2.82Wet Gas  12.14   12.71   14.02 15.37 15.14 17.07AOI Rel  38      74      57    141   81    183ActivityK Rate   1.89    2.38    2.41  3.44  2.92  4.29ConstantSelectivity    74.2    72.7    71.1  68.5  68.8  64.5Wt. %Coke Selec-    1.61    1.94    1.82  1.92  1.96  2.08tivity %Coke/KH2 Selectivity    0.17    0.16    0.18  0.14  0.17  0.14______________________________________ 
    
     Here the effect of manganese promotion is even more dramatic. FIG. 4 shows selectivity is affected much less in the presence of large amounts of vanadium and nickel when the catalyst is protected with manganese. 
     For example at 75% conversion FIG. 4 shows that the wt % selectivity of a metal poisoned catalyst drops from 72.4 wt % as shown in Example 3, to 68.0 wt % while the catalyst protected and enhanced by manganese only drops to 70.8 wt %. The gasoline yield difference at constant conversion is 2.8 wt % or 1400 barrels/day or $42,000/day or $15.3 mm/yr increase in income, even without taking into account the much higher catalyst activity, which could reduce fresh catalyst addition rates and reduce overall catalyst costs. 
     Clearly manganese has further enhanced activity and selectivity differences, as the catalyst is subjected to metal poisoning by two severe catalyst poisons, namely nickel and vanadium. This benefit of manganese is also reported here for the first time. 
     As noted, this selectivity advantage for manganese is shown at constant conversion. However, FIG. 5 also shows the very significant activity advantage observed for the manganese promoted metal poisoned catalyst, which is equally striking, and the outstanding increase in gasoline yield shown in FIG. 6. 
     EXAMPLE 5 
     Impregnation of a Highly Active Reduced Crude Conversion (RCC®) Type Catalyst at Varying Levels of Manganese Concentration 
     Table 5a shows the results of manganese on catalyst activity and selectivity as manganese concentrations are increased up to as high as 2% (19,800 ppm) manganese. At constant cat:oil ratio, activity rises some 20-50% and selectivity one-half to twelve and one-half percent as metal increases. (It is well established that selectivity always decreases as conversion increases.) The results clearly show an advantage for manganese as concentrations increase, and while not considered limiting may even indicate an optimum concentration exists. The results also show both the coke and hydrogen factors were significantly improved at all levels of manganese concentrations shown here. Although manganese has been added at levels approaching 2.0% (19,800 ppm), these results confirm that at all levels and up to and including data in Table 5a, that manganese enhances performance, as well as providing protection against contaminating metals. 
     
                       TABLE 5a______________________________________MAT Test SummaryMn-Impregnated Samples______________________________________Test No.     D-2836  D-2835  C-5121                              C-5123                                    E-2853Catalyst ID  DZ-40   DZ-40   DZ-40 DZ-40 DZ-40Mn Level (ppm)        Basc    2400    7,700 7,700 19,800Recovery (wt. %)        97.0    97.4    98.0  97.9  97.5Mat Conversion        76.9    82.0    85.5  81.2  81.9(vol. %)Normalized Yields(wt. %)Acid Gas (H.sub.2 S, CO,        0.49    0.51    0.46  0.37  0.47CO.sub.2)Dry Gas      2.26    2.40    2.27  1.78  2.42Hydrogen     0.18    0.15    0.11  0.08  0.17Methane      0.63    0.67    0.65  0.51  0.71Ethane + Ethylene        1.46    1.58    1.51  1.18  1.54Wet Gas      18.23   19.56   18.61 15.09 18.92Propane      2.95    3.19    2.68  2.18  2.86Propylene    3.33    3.58    3.58  2.86  3.56Isobutane    7.08    7.72    7.40  6.09  7.321-Butene +   1.27    1.29    1.21  0.94  1.33IsobutyleneN-Butane     2.05    2.18    2.07  1.72  2.12Cis-2-Butane 0.65    0.68    0.71  0.56  0.74Trans-2-Butene        0.89    0.92    0.95  0.75  0.99Gasoline (C.sub.5 - 430°)        45.46   48.58   52.50 53.44 48.86Cycle Oil (430-630°)        14.02   13.20   12.68 14.60 12.88Slurry (630° F.)        11.89   7.98    6.34  7.81  7.90Coke         7.66    7.78    7.15  6.91  8.54Conversion (wt. %)        74.09   78.82   80.98 77.59 79.21Gasoline Selectivity        61.3    61.6    64.8  68.9  61.7(Wt. %)Activity = K 2.86    3.72    4.26  3.46  3.81H.sub.2 Selectivity        0.063   0.043   0.026 0.023 0.045(% H.sub.2 /K)Coke Selectivity        2.68    2.09    1.68  2.00  2.24(% coke/K)______________________________________ 
    
     Note also that all of the manganese promoted catalysts were much more effective in converting slurry oil to lower molecular weight gasoline and light cycle oil. Table 5b shows that this catalyst contains over 1 wt. % (10,000 ppm) rare earth before promotion with manganese, and yet manganese is able to greatly enhance activity and selectivity over and above a high level of rare earth promotion. 
     
                       TABLE 5b______________________________________Manganese Catalyst Composition______________________________________(Wt. %)Al.sub.2 O.sub.3           33.0SiO.sub.2       51.2TiO.sub.2        1.14Fe.sub.2 O.sub.3            0.50MnO              1.98Rare Earths ppm MetalNeodymium       2800Praseodymium     830Cerium          1400Lanthanum       5900Total           10930______________________________________ 
    
     EXAMPLE 6 
     Impregnation of a Special Paraffin Cracking Catalyst with Manganese at Varying Levels of Manganese from 0.6% to 1.8% 
     In this series of experiments, a specialty catalyst designed to selectivity crack n-paraffins is impregnated with manganese at various concentrations in a manner identical with preparations for regular cracking catalysts (Table 6). This catalyst contained approximately 8.5 wt % ZSM5 in a binder matrix. Naturally, because this catalyst is designed only to crack n-paraffins, or slightly branched paraffins, conversion is not nearly as high, nor is selectivity expected to be competitive with normal cracking catalysts. 
     
                                           TABLE 6__________________________________________________________________________MAT Test SummaryMn-Impregnated SamplesTest No.            E-2824                   B-5095                        C-5120                            B-5096Catalyst II)        ZSM-5                   ZSM-5                        ZSM-5                            ZSM-5__________________________________________________________________________Manganese (ppm)     Base                   6200 13300                            17700Recovery (wt. %)    101.6                   101.3                        101.3                            101.9Normalized Yields (wt. %)Acid Gas (H.sub.2 S, CO, CO.sub.2)               0.06                   0.16 0.22                            0.09Dry Gas             1.10                   2.09 2.03                            2.08Hydrogen            0.02                   0.03 0.03                            0.03Methane             0.10                   0.15 0.14                            0.13Ethane + Ethylene   0.99                   1.90 1.85                            1.92Wet Gas             10.15                   10.99                        10.53                            11.11Propane             0.79                   2.37 2.29                            2.25Propylene           4.53                   3.39 3.30                            3.67Isobutane           0.33                   1.61 1.46                            1.47l-Butene + Isobutylene               2.43                   1.41 1.36                            1.56N-Butane            0.49                   1.16 1.15                            1.10Cis-2-Butane        0.67                   0.45 0.42                            0.45Trans-2-Butene      0.91                   0.60 0.56                            0.61Gasoline (C.sub.5 -430°)               6.24                   10.64                        9.65                            8.99Cycle Oil (430-630°)               8.59                   8.99 8.47                            8.59Slurry (630°+)               73.37                   66.69                        68.51                            68.67Coke                0.48                   0.45 0.59                            0.46Conversion (wt. %)  18.04                   24.32                        23.02                            22.74Coke Selectivity    2.18                   1.41 1.97                            1.59 ##STR8##           34.6                   43.8 41.9                            39.5 ##STR9##           0.22                   0.32 0.30                            0.29__________________________________________________________________________ 
    
     Even here manganese is shown to greatly increase cracking activity 30-50% and also selectivity 14-26%. Note again that coke selectivity is greatly improved. Surprisingly, the yield of isobutane is greatly increased almost five-fold, and both propane and n-butane jumped dramatically, showing the ability of manganese to transfer hydrogen directly to olefins. This ability of manganese to hydrogenate in the short resident time in the reactor, is also an important property in catalytically converting sulfate back to SO 2 , sulfur and H 2  S in the reactor, another important contribution of manganese. The ability of manganese to oxidize CO to CO 2  and SO 2  to SO 3  for retention in the regenerator is of equal importance, lowering sulfur in the product gasoline by 10-20% is also important. 
     EXAMPLE 7 
     RCC® Catalyst Loaded with High Level of Manganese and Metal Contamination 
     This example shows the effect of manganese when deposited in higher concentrations on a highly metal contaminated cracking catalyst from commercial operations on reduced crude (RCC® operation) and then blended in varying amounts of 1 to 99% with the same commercial catalysts. 
     This example shows that impregnation with manganese at very high levels of a residual catalyst containing metal contaminants and then mixing with no-manganese, but metal-contaminated catalyst, results in considerable improvement in performance. (See Table 7.) In this case, a reduced crude catalyst containing a large amount of contaminant metal, 4800 ppm V, 1700 ppm Ni, 8300 ppm Fe and impregnated with 10% manganese is mixed with nine times its weight of the same catalyst, but not containing any manganese, and then subjected to MAT testing. Results of this experiment are shown in Table 7. When this catalyst is blended with one-tenth times its weight of catalyst containing 10% manganese, there is an overall improvement in performance. This can be attributed to the ability of manganese on one catalyst to selectively treat associated no-manganese but metal-loaded catalyst so as to enhance overall performance. In this case a metal contaminated catalyst is loaded with manganese and mixed with non-manganese containing high metal loaded catalyst and then submitted for testing. 
     
                       TABLE 7______________________________________Sample ID                 90% RCC catalystNI 1700 ppm               mixed with 10% RCCV 4800 ppm      100% RCC  catalyst containingFe 8300 ppm     Catalyst  90,000 ppm Mn______________________________________Temperature (°F.)           915       915Cat:Oil Ratio   3.0       3.0Manganese       None      8,900 ppmMAT ActivityConversion vol. %           61.1      60.3H.sub.2 wt. %    0.33      0.21Coke wt. %       2.78      2.47Gasoline vol. % 55.97     55.76Gasoline Selectivity (vol. %)           91.5      92.5Coke Factor     1.4       1.2H.sub.2 Factor  11.2      6.9______________________________________ 
    
     Table 7 compares MAT testing on this mixed sample as compared with unblended catalyst from the same sample source. Note that although manganese promoted catalyst is only present in 10% concentration, and has not had an impact on activity, all key economic factors, including gasoline selectivity, and hydrogen and coke factors show improvement, selectivity increasing from 91.5 to 92.5 and hydrogen factor dropping from 11.2 to 6.9 and coke factor dropping from 1.4 to 1.2. At present time it is not clear how this effect is manifested. Nevertheless, the presence of a high manganese loaded equilibrium catalyst serves to convey a benefit to all catalysts present, even when the manganese containing catalyst is present in as low a concentration as 10% and this effect is especially significant in the presence of catalysts containing very large amounts of nickel and vanadium. 
     The process can also be applied to situations where virgin catalyst containing large amounts of manganese as high as to 20 wt. % or more is mixed with equilibrium catalyst from the same operation, containing high levels of vanadium and nickel. 
     EXAMPLE 8 
     Magnetic Separation of RCC® Catalyst Loaded with Manganese and Metal Contamination and Mixed with Similar Catalyst without Manganese 
     This example demonstrates the effect of manganese when deposited in high concentrations on a highly metal contaminated cracking catalyst from commercial operations, and then separated by magnetic separation into varying fractions for recycle or disposal. 
     An RCC® equilibrium catalyst from cracking of reduced crude is impregnated with 8.9% manganese and blended with nine times its weight of an identical untreated catalyst (as in Example 7) and subjected to repeated magnetic separations by means of a rare earth roller, as described in Hettinger patent U.S. Pat. No. 5,198,098, producing seven cuts (see Table 8). 
     The various magnetic cuts from this separation are then submitted for MAT testing, and compared with untreated catalyst as well as the original blend. The equilibrium catalyst described above, before impregnation, contained 1700 ppm nickel, 4800 ppm vanadium, 8300 ppm iron and 0.74 wt % Na 2  O and had a rare earth composition as follows: lanthanum 5700 ppm, cerium 2100 ppm, praseodymium 800 ppm, and neodymium 2800 ppm. 
     Table 8 shows the results of MAT testing and the chemical composition of the various cuts in terms of manganese, nickel, iron and vanadium. The data shows again, as previously shown in Example 7, the overriding beneficial effect of manganese in protecting and enhancing catalyst selectivity at all levels of metal poisoning up to and including 20,700 ppm of nickel plus iron plus vanadium. It shows that as long as the ratio of manganese to total metal, or to nickel-plus-vanadium, or to vanadium stays high, selectivity is enhanced. But as this ratio, especially for nickel plus vanadium, or vanadium alone, begins to drop off, selectivity begins to decline, despite the fact that this catalyst contains a very high metal contaminant level. 
     
                                           TABLE 8__________________________________________________________________________MAT Testing of Magnetic Separated Manganese Containing Catalyst           90% RCC           10% RCC      100% 89,000 ppm                 Blend                      Blend                           Blend                                Blend                                     Blend                                          Blend                                               BlendCatalyst ID      RCC  Mn Blend                 Cut 1                      Cut 2                           Cut 3                                Cut 4                                     Cut 5                                          Cut 6                                               Cut__________________________________________________________________________                                               7Wt. %      100  100   13.0 15.9 15.7 15.1 14.3 7.9  17.8MAT Conv. vol. %      61.1 60.3  51.2 53.0 57.2 53.8 59.6 60.0 65.3Gasoline vol. %      56.0 55.8  49.6 50.6 54.3 49.7 56.3 56.0 58.9Wt. % Coke 2.78 2.47  2.52 2.68 2.57 2.30 2.36 2.61 2.62Wt. % II.sub.2      0.33 0.28  0.26 0.21 0.21 0.21 0.21 0.20 0.21Gasoline Selectivity      91.5 92.5  93.1 92.0 92.9 93.0 92.7 91.7 89.2(vol. %)Nickel ppm 1700 1700  2300 2400 2200 2000 1700 1700 1300Iron ppm   8300 8300  13300                      10200                           9200 8600 7700 7600 6500Vanadium ppm      4800 4800  5100 5200 5300 5200 4900 4800 4200Manganese  0    8900  17900                      14600                           10700                                8800 6300 5100 2000Total Ni + Fe + V      14900           14900 20700                      17800                           16700                                15800                                     14300                                          14100                                               12000 ##STR10## 0    1.37  2.42 1.92 1.42 1.22 0.95 0.78 0.36Total Ni + V      6500 6500  7400 7600 7500 7200 6600 6500 5500 ##STR11## 0    1.85  3.50 2.80 2.01 1.69 1.28 1.06 0.48Sodium (wt. %)      0.56 0.57  0.57 0.57 0.57 0.57 0.57 0.57 0.57__________________________________________________________________________ 
    
     FIG. 7 shows a plot of selectivity versus manganese to metal ratio. Note how rapidly selectivity falls off as the ratio of manganese to vanadium drops to one to one, and is unable to protect catalyst against loss in selectivity. It shows the beneficial effect of very high levels of manganese on catalyst performance. 
     EXAMPLE 9 
     Selectivity Enhancement with a Second &#34;Magnetic Hook&#34; Additive, Chromium 
     Table 9 compares the results of MAT a chromium promoted low rare earth containing cracking catalyst. This catalyst was prepared in a manner similar to manganese promoted catalyst in Example 1 and contained 18,300 ppm of chromium. In this test the chromium promoted catalyst had a vol % selectivity of 82.3% compared to 81.4% for the non-promoted catalyst. It also made slightly less hydrogen. 
     
                       TABLE 9______________________________________&#34;Magnetic Hook&#34; Study            Base Catalyst                        Base CatalystCatalyst Metal   None        Chromium______________________________________Steaming Temperature (°F.)            1425        1425Steaming Time (hours)             24          24Feed Stock       RPS         RPSCat:Oil Ratio     4.60        4.51Reaction Temperature (°F.)             960         960Reaction Time (seconds)             25          25Conversion (wt. %)            67.37       66.26Conversion (vol. %)            69.09       67.87C5 - 430° F. Gasoline            46.42 (56.24)                        46.15 (55.92)430-650° F. LCGO            22.35 (21.95)                        23.18 (22.88)650° F. + Decanted Oil            10.28 (8.96)                        10.56 (9.25)Hydrogen Wt. %    0.11        0.10Wt. % Selectivity            68.9        69.7Vol. % Selectivity            81.4        82.4______________________________________ 
    
     EXAMPLE 10 
     Impregnation Versus Ion Exchange of Manganese in Catalyst Preparation 
     Base catalyst, a low rare earth-containing catalyst of 0.15 wt. % rare earth oxide, is impregnated with manganese as described in Example 2, and compared with an ion exchange manganese-containing catalyst using a solution of 2N, MnSO 4  The final manganese sulfate ion exchanged catalyst contains 4100 ppm of manganese. Samples of base catalyst, along with these two catalysts, are MAT tested at 3, 4 and 5 cat:oil ratios, and the results are shown in Table 10. 
     
                       TABLE 10a______________________________________Effect of Manganese on Cracking YieldsMAT Data on AKC #1        AKC #1   Mn       Mn     ReCatalyst ID  Base     Impreg   Exch   Impreg______________________________________Cat:Oil Ratio        2.9      2.9      3.0    3.0Temperature °F.        915      915      915    915Weight % YieldsAOI Relative Activity        35       100      127    34Conversion   64.9     73.2     75.0   65.4Hydrogen     0.05     0.05     0.06   0.04Methane      0.30     0.34     0.35   0.25Ethane/Ethylene        0.58     0.70     0.80   0.54Propane      0.58     0.93     1.00   0.52Propylene    3.53     3.55     4.05   3.47Isobutane    3.63     5.08     5.00   3.551-Butene/Isobutene        2.26     1.76     1.86   2.30N-Butane     0.59     1.06     0.94   0.55Butadiene    0.00     0.00     0.00   0.00Cis-2-Butene 0.99     1.02     1.02   1.03Trans-2-Butene        1.36     1.36     1.38   1.41CO, CO.sub.2, COS, H.sub.2 S        0.33     0.35     0.29   0.30C.sub.5 -430° F.        48.42    53.77    54.97  49.21430°-630° F.        17.46    16.39    15.85  18.11630° F.        17.63    10.41    9.19   16.45Coke         2.28     3.23     3.24   2.26Wt. % Selectivity        74.6     73.7     73.2   75.2Wt. % isobutane + 1-        5.89     6.84     6.86   5.85butene/isobutene ##STR12##   1.61     2.89     2.69   1.54______________________________________ 
    
     
                       TABLE 10b______________________________________Effect of Manganese on Cracking YieldsMAT Data on AKC #1        AKC #1   Mn       Mn     ReCatalyst ID  Base     Impreg   Exch   Impreg______________________________________Cat:Oil Ratio        4.0      4.0      3.9    4.1Temperature °F.        915      915      915    915Weight % YieldsAOI Relative Activity        90       162      167    59Conversion   74.9     78.8     78.9   71.3Hydrogen     0.07     0.07     0.07   0.05Methane      0.38     0.44     0.46   0.32Ethane/Ethylene        0.73     0.90     0.97   0.67Propane      0.78     1.30     1.36   0.73Propylene    4.43     3.98     4.37   4.05Isobutane    4.63     6.06     6.16   4.711-Butene/Isobutene        2.48     1.52     1.82   2.36N-Butane     0.79     1.37     1.32   0.78Butadiene    0.00     0.00     0.00   0.00Cis-2-Butene 1.21     0.99     1.08   1.15Trans-2-Butene        1.64     1.32     1.47   1.57CO, CO.sub.2, COS, H.sub.2 S        0.35     0.33     0.35   0.36C.sub.5 -430° F.        54.28    56.05    55.35  51.56430°-630° F.        15.82    14.27    13.90  17.08630° F.        9.28     6.97     7.32   11.63Coke         3.15     4.42     4.09   2.98Wt. % Selectivity        72.5     71.1     70.1   72.3Wt. % isobutane + 1-        7.11     7.58     7.98   7.07butene/isobutene ##STR13##   1.87     3.98     3.38   1.99______________________________________ 
    
     
                       TABLE 10c______________________________________Effect of Manganese on Cracking YieldsMAT Data on AKC #1        AKC #1   Mn       Mn     ReCatalyst ID  Base     Impreg   Exch   Impreg______________________________________Cat:Oil Ratio        4.8      5.1      5.2    5.1Temperature °F.        915      915      915    915Weight % YieldsAOI Relative Activity        118      168      146    75Conversion   78.4     81.3     80.4   75.5Hydrogen     0.08     0.08     0.08   0.07Methane      0.45     0.52     0.56   0.40Ethane/Ethylene        0.84     1.02     1.12   0.78Propane      0.97     1.65     1.68   0.91Propylene    4.70     4.08     4.24   4.49Isobutane    5.71     6.82     6.48   5.251-Butene/Isobutene        1.46     1.58     1.45   2.32N-Butane     1.02     1.65     1.53   0.95Butadiene    0.00     0.00     0.00   0.00Cis-2-Butene 1.23     0.98     0.90   1.23Trans-2-Butene        1.67     1.31     1.21   1.63CO, CO.sub.2, COS, H.sub.2 S        0.32     0.37     0.33   0.36C.sub.5 -430° F.        55.90    55.96    55.0   53.22430°-630° F.        14.25    12.86    13.03  15.41630° F.        7.38     5.82     6.53   9.10Coke         4.02     5.30     5.85   3.88Wt. % Selectivity        71.3     68.8     68.4   70.4Wt. % isobutane + 1-        7.17     8.40     7.93   7.57butene/isobutene ##STR14##   3.91     4.32     4.47   2.26______________________________________ 
    
     FIG. 8 is a plot of activity versus cat:oil and shows that the ion exchanged manganese-containing catalyst is as active as the manganese impregnated catalyst, with only 4000 ppm of manganese. Selectivity plotted versus wt. % conversion in FIG. 9 further confirms manganese&#39;s ability to enhance selectivity even when present at a low of 4000 ppm concentration. 
     EXAMPLE 11 
     Comparison of Manganese Versus Rare Earth Ion Exchange AKC #1) 
     The low rare earth containing catalyst (0.15 wt. %) is treated by a similar ion exchange method with a solution of rare earth so as to increase rare earth content in order to compare the effect of manganese ion exchange catalyst compared with that of high rare earth containing catalyst. Rare earths have been used since the early 1960s to enhance cracking catalyst activity. After ion exchange, the rare earth content increases almost ten fold from 0.15 wt. % to 1.11 wt. %, or 1500 ppm to 11,000 ppm. All samples begin with 1500 ppm rare earths (RE). 
     Data shown in Table 10 also contain data from the rare earth promoted catalyst. FIG. 10 also shows the activity of high rare earth promoted catalyst versus the untreated AKC catalyst and the two manganese-containing catalysts. It shows that the rare earths, as compared to manganese, actually lower activity significantly as compared to manganese and the untreated catalyst. Selectivity-wise, the results show that the rare earths are actually detrimental as shown in FIG. 11. These results further demonstrate the unique ability of manganese to enhance both activity and selectivity. 
     EXAMPLE 12 
     Increased Production of Isobutane and Lower Olefins 
     The results of experiments presented in Table 10 also demonstrate that manganese changes the cracking characteristics of these catalysts in a way not previously reported. Previously, the rare earths, as also demonstrated here, were able to transfer hydrogen to olefins and reduce olefin content of the finished product. Unfortunately, as a result, because of the high octane value of olefins, octane numbers drop. It now appears that manganese changes the acidic properties sufficiently so as to increase isomerization before cracking and isobutane production after cracking, while also acting to reduce olefin content. FIG. 12 presents the yield of isobutane versus wt. % conversion and shows manganese significantly changes the yield of isobutane at constant conversion by 10-13% at 75 wt. % conversion. This demonstrates a distinctly different cracking behavior. Plotting the ratio of total C 4  saturates divided by the total C 4  olefins, shown in FIG. 13 further demonstrates manganese&#39;s unique ability to transfer hydrogen to olefins. Note that both low rare earth and high rare earth catalysts do not show this ability to any degree compared to the manganese supported catalysts, thus demonstrating manganese&#39;s high hydrogenation activity. 
     EXAMPLE 13 
     Effect of High Levels of Manganese on Catalyst Performance 
     Three catalysts were impregnated with very high levels of manganese by the following procedure. A finished catalyst containing 16.4 wt. % of manganese is prepared as follows: 36.4 grams of manganese acetate hydrate is dissolved in 26 ml of hot distilled water and heated to boiling for complete solution. This is mixed with 40 grams of DZ-40 dispersed in 50 ml of boiling water. The solution slurry mixture is kept at boiling temperature for two hours after which it is allowed to air dry, and then placed in an oven at 110° C. until drying is complete. This sample is then placed in an Erlenmeyer flask and slowly raised to 1200° F. where it is calcined for four hours. It is then cooled and submitted for MAT testing and chemical analysis. 
     All other samples listed in Table 11 were prepared and treated in the same way. 
     
                                           TABLE 11__________________________________________________________________________High Manganese Catalyst PerformanceMAT Test 915° F. 3.0 Cat:Oil Ratio       Catalyst ID       IC  IA  IB  2C 2A  2B  3C  3A  3B__________________________________________________________________________Catalyst    DZ-40           DZ-40               DZ-40                   RCC                      RCC RCC RPS-F                                  RPS-F                                      RPS-FWt. % Mn    0   10.3               16.4                   0  10.1                          18.9                              0   6.6 17.1ppm Mn      0   103,000               164,000                   0  101,000                          189,000                              0   66,000                                      171,000ppm Fe      4554           4209               4437                   9600                      8970                          7866                              3180                                  2900                                      2760ppm Ni      50  41  38  2072                      1914                          1662                              43  39  32ppm V       58  44  38  4169                      3820                          3348                              116 107 88MAT Vol % Conv       79.8           71.1               62.6                   60.3                      31.5                          25.8                              93.7                                  88.6                                      76.2AOI RA      172 64  24  19.1                      0.7 0.4 830 466 114Corrected and Normalized YieldWt. % C.sub.5 - 430° F.       46.1           48.8               45.2                   46.3                      26.9                          20.7                              42.7                                  51.8                                      51.6Vol C.sub.5 - 430° F.       56.9           59.4               54.9                   56.0                      32.6                          25.2                              53.4                                  63.9                                      62.9Wt. % Coke  7.2 4.59               4.26                   2.78                      3.30                          5.12                              16.31                                  10.83                                      7.15Wt. % conv of 430° F.       77.1           68.4               62.0                   59.9                      35.6                          31.0                              91.0                                  85.4                                      73.7Vol % conv of 430° F.       78.6           70.2               63.5                   61.1                      36.1                          31.3                              92.8                                  87.6                                      75.6Wt. % C5-430° F. select       59.7           71.3               72.9                   77.3                      75.6                          66.9                              46.9                                  60.7                                      70.1Vol % C5-430° F. select       72.4           84.5               86.4                   91.5                      90.4                          80.3                              57.5                                  72.9                                      83.2Wt. % Hydrogen       0.15           0.10               0.08                   0.33                      0.18                          0.13                              0.18                                  0.18                                      0.12__________________________________________________________________________ 
    
     These three catalysts are: 1) a virgin Davison catalyst DZ-40, developed jointly by Ashland Petroleum Company and Davison, division of W. R. Grace &amp; Co., for resid cracking, and covered by U.S. Pat. Nos. 4,440,868; 4,480,047; 4,508,839; 4,588,702; and 4,612,298 and described in a publication &#34;Development of a Reduced Crude Cracking Catalyst&#34; by W. P. Hettinger, Jr.; Catalytic; Chapter 19, pages 308-340; In Fluid Cracking ACS Symposium Series 375; M. Occelli, Editor 1988; 2) a second catalyst is an equilibrium catalyst taken from the regenerator of the original residual cat cracker, the extensively patented RCC® unit invented by Ashland Petroleum Company and first placed in operation in Catlettsburg, Ky., in 1983. This is labeled RCC® equilibrium catalyst; 3) the third catalyst is a resid type virgin catalyst obtained from Refining Process Services and labeled RPS-F. 
     Table 11 presents the results of tests on these three catalysts when containing intermediate and very high levels (164,000-189,000 ppm) (16.4-18.9 wt. %) of manganese. It will be noted that although such high levels of manganese began to reduce activity, production of gasoline is actually greater in many cases, again confirming that even at very high levels of manganese, (16.4-18.9 wt. %) some significant activity is still maintained, and more importantly, selectivity is generally enhanced. 
     For example, for DZ-40 at 10.3 wt. % manganese, the yield of gasoline is 59.4 vol. %; a very high liquid recovery, and much greater than the 56.9 vol. % gasoline when manganese is absent. Volume % selectivity for 16.4 wt. % Mn is 86.4, a very high value compared with 72.4 vol. % for untreated catalyst. 
     Volume % selectivity is exceptionally high for RCC® catalyst containing manganese. Even though conversion fell off with high levels of metal present in this catalyst, selectivity (vol. %) remained at one of the highest levels, 90.4 vol. %, demonstrating that even at contaminating levels as high as 6200 ppm of Ni+V and 9600 ppm for iron, manganese still has a unique impact on gasoline selectivity while limiting the behavior of nickel and vanadium. 
     Finally, in the third series, manganese has a very positive impact on gasoline, amounting to 62.9 vol. % gasoline when the catalyst contained 17.1 wt. % of manganese, and 63.9 vol. % yield at 6.6 wt. % of manganese. 
     This confirms that catalyst containing manganese at levels as high as 18.9 wt. % can maintain a superior selectivity for making gasoline with metals on catalyst as high as 2072 ppm of Ni, 4169 ppm of vanadium, 9600 ppm of iron, and 5500 ppm (0.55 wt. %) of sodium. 
     EXAMPLE 14 
     Carbon and Carbon Monoxide Oxidation Promotor 
     In carrying out regeneration of spent catalysts from catalytic cracking, the ability of a catalyst to enhance the burning rate of coke to carbon monoxide and convert to carbon dioxide is a key property. In particular, the ability to quickly convert CO to CO 2  and rapidly establish equilibrium between, oxygen, carbon monoxide and carbon dioxide is desirable. An even more critical characteristic of an oxidation catalyst is how quickly it can establish this equilibrium so that heat balance and temperature control are easily maintained. Great fluctuations in burning rate which can occur in pockets of the regenerator can cause very large temperature rises. FIG. 14 shows that manganese incorporated cracking catalyst, in addition to its other unique properties, is a superior oxidative catalyst. 
     Samples of the commercial catalyst AKC #1 with and without 9200 ppm of manganese are steamed for 5 hours at 788° C. with 100% steam. 
     For carbon oxidation testing, the steamed catalysts with and without manganese are further impregnated with about 0.30 wt. % Ni, using nickel octoate. The impregnated samples are then coked at 500° C. using isobutylene to 2.5-3.5 wt. % carbon. Carbon burning rate is then determined by passing air over the catalyst samples at 718° C. with a flow of 0.25 SCF/hr/g of catalyst. 
     FIG. 14 shows that burning of carbon to high ratios of CO 2  over CO occurs very quickly over the manganese containing catalyst, rising to a ratio of CO 2  :CO of 2.0 after 10% has been burned, and remains at 2:1 after 50% has been removed. This relative burning rate of up to 3:1 or greater compared with non-manganese containing catalyst confirms the efficiency of manganese promoted catalysts as also superior oxidation catalysts. 
     EXAMPLE 15 
     Superior Manganese Supported Cracking Catalyst Prepared by On-Stream Deposition and in the Presence of Nickel and Vanadium 
     A catalyst containing 1100 ppm nickel and 2100 ppm vanadium is prepared by spiking an RCC LCO with nickel octoate and vanadyl naphthanate and depositing the metals over 10 cycles of cracking and regeneration in a fixed-fluidized bed. This catalyst, however, is a moderate rare earth containing catalyst, 1.23 wt. %, and has been steam treated in a fixed-fluidized bed prior to impregnation with metals. A second sample is prepared by depositing manganese octoate dispersed in RCC® light cycle oil along with nickel octoate and vanadyl naphthahate on a second aliquot of the steam treated catalyst. As with the base, no-manganese sample, the metals are cracked onto the catalyst over 10 reaction/regeneration cycles in a fixed-fluidized bed. Total manganese deposited on the catalyst is 2000 ppm. The two catalysts (with and without manganese) are then submitted to MAT testing at 2.5, 3 and 4 cat:oil ratio (see Table 12). 
     
                                           TABLE 12__________________________________________________________________________MAT Test Summary      No Manganese                  With 2000 ppm Manganese__________________________________________________________________________MAT Test No.      B-6025          B-6026              B-2858                  C-5176                      B-4049                          B-6060                              B-6070Cat:Oil Ratio      2.5 3.0 4.1 2.6 2.9 3.0 3.9Conversion (wt. %)      67.8          71.2              74.2                  66.1                      70.8                          71.1                              75.5Yields (wt. %)Dry Gas    1.87          2.34              2.21                  1.49                      1.82                          1.98                              2.32Hydrogen SCFB      339 432 414 257 368 356 414Hydrogen   0.58          0.74              0.71                  0.44                      0.63                          0.61                              0.71Methane    0.43          0.56              0.54                  0.33                      0.40                          0.45                              0.55Ethane + Ethylene      0.86          1.04              0.96                  0.72                      0.79                          0.92                              1.06Wet Gas    12.06          13.70              13.97                  11.33                      12.30                          12.18                              14.23Propane    0.80          0.99              1.23                  0.81                      0.81                          0.97                              1.29Propylene  3.16          3.63              3.36                  2.95                      3.25                          3.17                              3.46Isobutane  3.71          4.36              4.81                  3.64                      3.79                          3.92                              4.921-Butene + Isobutylene      1.68          1.76              1.49                  1.46                      1.64                          1.47                              1.47N-Butane   0.72          0.87              1.10                  0.68                      0.76                          0.78                              1.08Butadiene  0.00          0.00              0.00                  0.00                      0.00                          0.00                              0.00Cis-2-Butane      0.85          0.89              0.85                  0.76                      0.88                          0.79                              0.85Trans-2-Butene      1.14          1.20              1.13                  1.03                      1.17                          1.08                              1.16Gasoline (wt. %)      48.89          48.72              50.00                  48.27                      51.45                          51.00                              51.35Cycle Oil (wt. %)      18.96          16.65              16.46                  19.26                      17.91                          17.79                              15.65Slurry (wt. %)      13.19          12.17              9.34                  14.66                      11.34                          11.06                              8.85Coke (wt. %)      4.83          6.23              7.94                  4.62                      5.02                          5.78                              7.49Selectivity (wt. %)      72  68  67  73  73  72  68__________________________________________________________________________ 
    
     FIG. 15 shows the yield of gasoline as a function of wt. % conversion. At 72 wt. % conversion, for example, there is 2 wt. % increase in gasoline. As pointed out in earlier examples, such an increase has a very major impact on income. In addition to this appreciable selectivity enhancement, FIG. 16 shows the reduction in hydrogen production amounting to an 8-17% reduction over a conversion of 68-74 wt. %. Coke reduction also is significant, amounting to 14% at 73 wt. % conversion. 
     This example clearly demonstrates that as little as 2000 ppm of manganese offsets the effect of nickel and vanadium in terms of gasoline yield, coke and hydrogen. (See FIGS. 15-17) It also demonstrates that a manganese-promoted catalyst can be realized by deposition on a circulating catalyst to reach a concentration appropriate for feedstocks with varying metal levels. 
     EXAMPLE 16 
     Magnetic Hook Properties of These Selective Cracking Catalysts 
     All of the catalysts used in preceding examples, possess among other attributes, highly magnetic properties. While it is only possible to speculate at this time, it may be that the unusual properties of &#34;magnetic hook&#34; promoted catalysts can be attributed to the unimpaired electrons associated with &#34;magnetic hook&#34; elements. It seems quite likely that they may provide an environment which changes in a very subtle, but beneficially significant way, the nature of the cracking mechanism. 
     Table 13 shows the magnetic properties of catalysts cited in previous examples. It is apparent that all &#34;magnetic hook&#34; promoted catalysts, showing the unusual selectivity properties of the invention have a magnetic susceptibility value greater than 1.0×10 -6  emu/g, or in the case of metal contaminated catalysts, an increase in magnetic susceptibility greater than 1.0×10 -6  emu/g, when incorporated as a &#34;magnetic hook&#34; promoter. 
     
                       TABLE 13______________________________________CatalystAll virgin catalysts after calcination               Magnetic Susceptibilityat 1200° F. for 4 hours               Xg × 10.sup.-6 emu/g______________________________________Example 1No &#34;Magnetic Hook&#34;  0.60Magnetic Hook Catalyst               2.67Example 2AKC No. 1           3.00AKC No. 2           4.21Example 5No Magnetic Hook    0.60Low Magnetic Hook   1.16Intermediate Magnetic Hook               4.23High Magnetic Hook  4.97Example 6No Magnetic Hook    0.82Low Magnetic Hook   2.46Intermediate Magnetic Hook               4.07High Magnetic Hook  4.55Example 7No Magnetic Hook    35.6Plus Magnetic Hook  45.7Increase with Magnetic Hook               10.1Example 918,200 ppm chromium 1.63Example 13Catalyst A no Magnetic Hook               0.49103,000 ppm Magnetic Hook               19.5               Δ Increase 19.0 emu/gm164,000 ppm Magnetic Hook               33.00               Δ Increase 32.5 emu/gmCatalyst B no Magnetic Hook               36.3101,000 ppm Magnetic Hook               53.8               Δ Increase 17.5 emu/gm189,000 ppm Magnetic Hook               56.5               Δ Increase 20.2 emu/gmCatalyst C no Magnetic Hook               0.3966,000 ppm Magnetic Hook               17.7               Δ Increase 17.3 emu/gm171,000 ppm Magnetic Hook               24.62               Δ Increase 24.2 emu/gm______________________________________ 
    
     FIG. 19 shows the steam stability enhancement of activity of various manganese contents. 
     FIG. 20 shows the effect of manganese content on selectivity, weight percent selectivity versus various manganese contents. 
     Modifications 
     Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variation on these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein. 
     Reference to documents made in the specification is intended to result in such patents or literature being expressly incorporated herein by reference.