Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
PROCESS FOR CATALYTIC CRACKING AND EQUILIBRIUM FCC CATALYST
Document Type and Number:
WIPO Patent Application WO/2022/015552
Kind Code:
A1
Abstract:
A process for catalytic cracking of an iron-contaminated fluid catalytic cracking (FCC) feedstock. The process may include combining a FCC catalyst, a slurry containing a magnesium compound, and an iron-contaminated FCC feedstock during a FCC process under fluid catalytic cracking conditions, thereby generating an equilibrium FCC catalyst with reduced iron poisoning. The slurry containing the magnesium compound may not contain a calcium compound.

Inventors:
KUNDU SHANKHAMALA (US)
HU RUIZHONG (US)
CHENG WU-CHENG (US)
ZIEBARTH MICHAEL (US)
Application Number:
PCT/US2021/040746
Publication Date:
January 20, 2022
Filing Date:
July 07, 2021
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
GRACE W R & CO (US)
International Classes:
B01J38/00; C10G11/05; C10G11/18
Domestic Patent References:
WO2005081715A22005-09-09
Foreign References:
US20150096922A12015-04-09
US20040099573A12004-05-27
EP0208868B11990-02-07
US6194337B12001-02-27
US4148714A1979-04-10
US20080210599A12008-09-04
Attorney, Agent or Firm:
LOMPREY, Jeffrey R. (US)
Download PDF:
Claims:
CLAIMS 1. A process for catalytic cracking of an iron-contaminated fluid catalytic cracking (FCC) feedstock, the process comprising: combining a FCC catalyst, a slurry comprising a magnesium compound, and an iron-contaminated FCC feedstock during a FCC process under fluid catalytic cracking conditions, thereby generating an equilibrium FCC catalyst with reduced iron poisoning, wherein the slurry comprising the magnesium compound does not contain a calcium compound. 2. The process of claim 1, wherein combining the FCC catalyst with the slurry comprising the magnesium compound is performed simultaneously with combining with the iron-contaminated FCC feedstock. 3. The process of claim 1, wherein combining the FCC catalyst with the slurry comprising the magnesium compound is performed before or after combining with the iron-contaminated FCC feedstock. 4. The process of claim 1, wherein the slurry comprises particles of the magnesium compound having an average particle size in a range of about 5 nm to about 1 µm. 5. The process of claim 4, wherein the particles of the magnesium compound have the average particle size in the range of about 7 nm to about 300 nm. 6. The process of claim 5, wherein the particles of the magnesium compound have the average particle size in the range of about 15 nm to about 150 nm. 7. The process of claim 1, wherein a concentration of the magnesium compound in the slurry is in a range of about 5 wt% to about 50 wt%, reported as MgO. 8. The process of claim 7, wherein the concentration of the magnesium compound in the slurry is in the range of about 20 wt% to about 40 wt%, reported as MgO. 9. The process of claim 1, wherein a concentration of iron compounds in the iron-contaminated FCC feedstock is in a range of about 0.5 ppm by weight to about 100 ppm by weight, reported as Fe.

10. The process of claim 9, wherein the concentration of the iron compounds in the iron-contaminated FCC feedstock is in the range of about 1 ppm by weight to about 50 ppm by weight, reported as Fe. 11. The process of claim 10, wherein the concentration of the iron compounds in the iron-contaminated FCC feedstock is in the range of about 2 ppm by weight to about 30 ppm by weight, reported as Fe. 12. The process of claim 1, wherein the magnesium compound comprises at least one selected from the group consisting of magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium sulfonate, magnesium acetate, and mixed metal oxides and carbonates of magnesium with aluminum or silicon. 13. The process of claim 1, wherein the slurry comprises water, an organic solvent or a mixture thereof as a liquid phase or dispersant. 14. The process of claim 1, wherein the magnesium compound or a derivative of the magnesium compound is deposited on the equilibrium FCC catalyst after the combining. 15. The process of claim 14, wherein an amount of the magnesium compound or the derivative of the magnesium compound on the equilibrium FCC catalyst is in a range of about 100 ppm to about 30,000 ppm by weight, reported as MgO, of the equilibrium FCC catalyst. 16. The process of claim 15, wherein the amount of the magnesium compound or the derivative of the magnesium compound on the equilibrium FCC catalyst is in the range of about 300 ppm to about 20,000 ppm by weight, reported as MgO, of the equilibrium FCC catalyst. 17. The process of claim 14, wherein an amount of iron compounds on the equilibrium FCC catalyst is in a range of about 500 ppm to 30,000 ppm by weight, reported as Fe, of the equilibrium FCC catalyst. 18. The process of claim 17, wherein the amount of the iron compounds on the equilibrium FCC catalyst is in a range of about 1,000 ppm to about 20,000 ppm by weight, reported as Fe, of the equilibrium FCC catalyst.

19. The process of claim 17, wherein a weight ratio of the magnesium compound or the derivative of the magnesium compound, as MgO, to the iron compounds, as Fe, on the equilibrium FCC catalyst is greater than about 0.1. 20. The process of claim 19, wherein the weight ratio of the magnesium compound or the derivative of the magnesium compound, as MgO, to the iron compounds, as Fe, on the equilibrium FCC catalyst is greater than about 0.5. 21. The process of claim 19, wherein the equilibrium FCC catalyst has a diffusion coefficient of more than about 5 mm2/min, as measured by an inverse gas chromatography technique. 22. The process of claim 21, wherein the equilibrium FCC catalyst has the diffusion coefficient of at least about 8 mm2/min, as measured by an inverse gas chromatography technique. 23. The process of claim 1, wherein the slurry further comprises antimony or an antimony compound. 24. The process of claim 1, wherein the combining of the FCC catalyst with the slurry and the iron-contaminated FCC feedstock occurs within a FCC unit. 25. An equilibrium FCC catalyst, comprising: an FCC catalyst containing calcium, and having at least one magnesium compound and iron compounds deposited on the FCC catalyst, wherein a weight ratio of the magnesium compound, as MgO, to the iron compounds, as Fe, on the equilibrium FCC catalyst is greater than about 0.1, and a weight ratio of calcium compounds to the magnesium compound on the equilibrium FCC catalyst, reported as CaO/MgO, is less than about 0.25. 26. The equilibrium FCC catalyst of claim 25, wherein the weight ratio of the magnesium compound, as MgO, to the iron compounds, as Fe, on the equilibrium FCC catalyst is greater than about 0.5. 27. The equilibrium FCC catalyst of claim 25, wherein an amount of the magnesium compound is in a range of about 100 ppm to about 30,000 ppm by weight, reported as MgO, of the equilibrium FCC catalyst.

28. The equilibrium FCC catalyst of claim 27, wherein the amount of the magnesium compound is in a range of about 300 ppm to about 20,000 ppm by weight, reported as MgO, of the equilibrium FCC catalyst. 29. The equilibrium FCC catalyst of claim 25, wherein the equilibrium FCC catalyst has magnetic susceptibility in SI units of over 500x10-6. 30. The equilibrium FCC catalyst of claim 29, wherein the equilibrium FCC catalyst has magnetic susceptibility in SI units of over 2000x10-6. 31. The equilibrium FCC catalyst of claim 25, wherein the equilibrium FCC catalyst has a diffusion coefficient greater than or equal to about 5 mm2/min. 32. The equilibrium FCC catalyst of claim 25, wherein the FCC catalyst comprises a faujasite and/or ZSM-5 and/or beta zeolite. 33. The equilibrium FCC catalyst of claim 32, wherein the faujasite zeolite is a Y-type zeolite. 34. The equilibrium FCC catalyst of claim 25, wherein the weight ratio of calcium compounds to the magnesium compound on the FCC catalyst, reported as CaO/MgO, is less than about 0.15. 35. The equilibrium FCC catalyst of claim 32, wherein the equilibrium FCC catalyst comprises the ZSM-5. 36. The equilibrium FCC catalyst of claim 35, wherein the ZSM-5 is present in a level greater than 6 wt%. 37. The equilibrium FCC catalyst of claim 25, wherein a weight ratio of a Ce- containing compound to the magnesium compound, reported as CeO2/MgO, in  the equilibrium FCC catalyst is less than about 0.15. 38. The equilibrium FCC catalyst of claim 37, wherein there is absence of CeO2 crystalline phase detectable by XRD in the equilibrium FCC catalyst.

Description:
  PROCESS FOR CATALYTIC CRACKING AND EQUILIBRIUM FCC  CATALYST   FIELD OF THE INVENTION   [0001] The present invention relates to a process for catalytic cracking, and  more particularly, to a process for catalytic cracking of an iron-contaminated fluid  catalytic cracking (FCC) feedstock and an equilibrium FCC catalyst generated thereof.  BACKGROUND   [0002] The fluid catalytic cracking (FCC) process is a very important refinery  processes. During the FCC process, a catalyst is exposed to different deactivation  mechanisms such as hydrothermal and thermal deactivation and poisoning by feedstock  contaminants such as alkali and alkaline earth metals, nickel, vanadium and iron. Iron  poisoning has gained much attention in recent years as the iron poisoning is observed  more often due to decreasing average feedstock quality over the years. It is known that  Fe brought in by a contaminated FCC feedstock can be deposited on the FCC  catalyst and form a dense layer on an outer surface of the catalyst particles. The  dense layer reduces diffusion of feed molecules going in and cracked molecules  coming out of the catalyst particles, thereby negatively impacting activity and  selectivity of the FCC catalyst. This phenomenon is often referred as iron poisoning  of the FCC catalyst. The iron poisoning of the FCC catalyst can result in operational  issues as well as deterioration of activity and selectivity of the catalyst.   [0003] US Patent No.8372269 discloses a method of metal passivation during  fluid catalytic cracking (FCC). The method includes contacting a metal-containing  hydrocarbon fluid stream in an FCC unit comprising a mixture of a fluid catalytic  cracking catalyst and a particulate metal trap. The particulate metal trap includes a spray  dried mixture of kaolin, magnesium oxide or magnesium hydroxide, and calcium  carbonate.   [0004] US Patent No.6,723,228 discloses an additive used in catalytic cracking  of hydrocarbons, which is in the form of homogeneous liquid and comprises a  composite metal compound. The composite metal compound consists of the oxides, hydroxides, organic acid salts, inorganic acid salts or metal organic complex compounds of at least one of the 1 st group metals and at least one of the 2 nd group metals. The 1 st group metals are selected from the group consisting of the metals of the IIIA, IVA, VA, VIA groups of the Element Period Table. The 2 nd group metals are selected from the group consisting of alkali-earth metals, transition metals, and rare earth metals. The additive can passivate metals and promote the oxidation of CO, and is operated easily with production cost decreased. [0005] US Patent No. 7361264B2 discloses a method of increasing the performance of a fluid catalytic cracking (FCC) catalyst in the presence of at least one metal. The method includes contacting a fluid stream from an FCC unit comprising the fluid catalytic cracking catalyst with a compound comprising magnesium and aluminum, and having an X-ray diffraction pattern displaying at least a reflection at a -theta peak position at about 43 degrees and about 62 degrees, and wherein the  compound has not been derived from a hydrotalcite compound. [0006] International patent publication No. WO 2015/051266 discloses a process for reactivating an iron-contaminated FCC catalyst. The process comprises contacting the iron-contaminated FCC catalyst with an iron transfer agent. The iron transfer agent comprises a magnesia-alumina hydrotalcite material that contains a modifier selected from the group consisting of calcium, manganese, lanthanum, iron, zinc, or phosphate. BRIEF SUMMARY [0007] One example of the present invention is a process for catalytic cracking of an iron-contaminated FCC feedstock. The process may include combining a FCC catalyst, a slurry comprising a magnesium compound, and an iron-contaminated FCC feedstock during a FCC process under fluid catalytic cracking conditions, thereby generating an equilibrium FCC catalyst with reduced iron poisoning. The slurry comprising the magnesium compound may not contain a calcium compound. Unexpectedly, addition of a small amount of the magnesium compound in absence of the calcium compound onto an iron-contaminated FCC catalyst effectively increases diffusivity of hydrocarbons into and out of the FCC catalyst, thereby preserving activity   and selectivity of the FCC catalyst. As a result, the iron poisoning of the FCC catalyst  by the iron-contaminated FCC feedstock is reduced significantly during the FCC  process.   [0008] Another example of the present invention is an equilibrium FCC  catalyst. The equilibrium FCC catalyst may include an FCC catalyst. The FCC catalyst  may contain calcium, and have at least one magnesium compound and iron compounds  deposited on the FCC catalyst. A weight ratio of the magnesium compound, as MgO,  to the iron compounds, as Fe, on the equilibrium FCC catalyst may be greater than  about 0.1. A weight ratio of calcium compounds to the magnesium compound on the  FCC catalyst, reported as CaO/MgO, may be less than about 0.25.   BRIEF DESCRIPTION OF THE DRAWINGS   [0009] The subject matter which is regarded as the disclosure is particularly  pointed out and distinctly claimed in the claims at the conclusion of the specification.  The foregoing and other objects, features, and advantages of the present disclosure are  apparent from the following detailed description taken in conjunction with the  accompanying drawings in which:   [0010] Fig.1 shows electron probe micro-analyzer (EPMA) analysis of  nanoparticles of iron compounds deposited on a FCC catalyst in the related art;   [0011] Fig. 2A shows electron probe micro-analyzer (EPMA) analysis of  nanoparticles of iron compounds deposited on a FCC catalyst according to one  embodiment of the present disclosure; and   [0012] Fig. 2B shows electron probe micro-analyzer (EPMA) analysis of  nanoparticles of a magnesium compound deposited on a FCC catalyst according to one  embodiment of the present disclosure.   DETAILED DESCRIPTION   [0013] The present disclosure will be further described in detail with reference  to the accompanying drawings. When referring to the figures, like structures and  elements shown throughout are indicated with like reference numerals. Obviously, the  described embodiments are only a part of the embodiments of the present disclosure,   not all of the embodiments. All other embodiments obtained by a person of ordinary  skill in the art based on the embodiments of the present disclosure without creative  efforts are within the protection scope of the present disclosure. In the description of  the following embodiments, specific features, structures, materials or characteristics  may be combined in any suitable manner in any one or more embodiments or examples.  [0014] A number modified by “about” herein means that the number can vary  by 10% thereof. A numerical range modified by “about” herein means that the upper  and lower limits of the numerical range can vary by 10% thereof.   [0015] The terminology used in the present disclosure is for the purpose of  describing exemplary examples only and is not intended to limit the present disclosure.  As used in the present disclosure and the appended claims, the singular forms "a,” "an"  and "the" are intended to include the plural forms as well, unless the context clearly  indicates otherwise.   [0016] The following terms, used in the present description and the appended  claims, have the following definition.   [0017] An equilibrium FCC catalyst or “Ecat” is a catalyst in the inventory of  the FCC unit that has been deactivated due to repeated cracking of hydrocarbon  feedstock and regeneration to burn off the coke. A fresh fluid cracking catalyst is a  catalyst as manufactured and sold by catalyst vendors. As the catalyst ages, it undergoes  changes due to attrition, accumulation of feedstock metals and exposure to the severe  hydrothermal environment of the FCC unit. The aged catalyst is characterized by loss  of surface area and acid sites, which result in deterioration of activity and selectivity.  During the FCC process, fresh catalyst is added, and aged catalyst is withdrawn, as  needed, to maintain catalytic activity and selectivity as well as to hold proper catalyst  bed levels in the FCC reactor and regenerator vessels. The equilibrium catalyst is a  catalyst in the circulating inventory that reflects a balance between rates of catalyst  deactivation and replacement. Hence, the Ecat includes an age distribution of fresh to  severely deactivated FCC catalyst particles.   [0018] One example of the present invention is a process for catalytic cracking  of an iron-contaminated fluid catalytic cracking (FCC) feedstock. The process may   include combining a FCC catalyst from the circulating inventory of the FCC unit, a  slurry containing a magnesium compound, and an iron-contaminated FCC feedstock  during a FCC process under fluid catalytic cracking conditions, thereby generating an  improved equilibrium FCC catalyst with reduced iron poisoning. The slurry containing  the magnesium compound may not contain a calcium compound.   [0019] The FCC catalyst may be in a form of particles having an average  diameter in a range of about 50 µm to about 110 µm, and contain about 10-60% zeolite  crystals. The zeolite may be the primary catalytic component for selective cracking  reactions. In one embodiment, the zeolite is a synthetic faujasite crystalline material. It  includes material that is manufactured in the sodium form (Standard-Y) by  crystallization of compositions containing silica and alumina, under alkaline  conditions, followed by washing to lower the sodium; and ultrastable Y (“USY”),  produced by increasing the silicon/aluminum atomic ratio of the parent standard-Y  zeolite via a dealumination process. The resulting USY zeolite is much more stable to  the hydrothermal deactivation in commercial FCC units than Standard Y zeolite. The  Standard-Y and USY zeolites can be treated with cations, typically rare earth mixtures,  to remove sodium from the zeolite framework to form REY, CREY and REUSY, which  may increase activity and further stabilize the zeolite to deactivation in the FCC unit.  The zeolite may possess pores in the 7.4-12 Å range. Surface area of the equilibrium  FCC catalyst corresponding to the zeolite, i.e., surface area corresponding to pores in  the range of <20 Å, typically ranges from 20 to 300 m 2 /g, preferably from 40 to 200  m 2 /g, as determined by the t-plot method. The Y zeolites described above can also be  made by crystallization of microspheres comprising calcined kaolin, as described in US  Patent 6656347, US Patent 6942784, and US Patent 5395809.   [0020] In the FCC catalyst, other than the zeolite, the catalyst contains a  matrix. The FCC matrix may include a porous, catalytically active alumina or silica  alumina for improving cracking of the heavier molecules in the feedstock, so-called  bottoms cracking.   [0021] The FCC matrix may also include a specialty alumina for passivating  nickel and traps for passivating vanadium. One example of a nickel-passivating  alumina is an alumina derived from crystalline boehmite, which may be incorporated   in the fresh catalyst at the 3 to 30 wt% range, reported as Al 2 O 3 . One example of a  vanadium trap is a rare earth compound, which may be incorporated in the fresh catalyst  at the range of 1 to 10 wt%, reported as RE 2 O 3 .   [0022] The FCC matrix may further contain clay. While not generally  contributing to the catalytic activity, clay may provide mechanical strength and density  to the overall catalyst particle to enhance its fluidization.   [0023] Finally, the FCC matrix may further contain a binder. This is the glue  that holds the zeolite, active alumina, metals traps, and clay together. The binders may  be typically silica-based, alumina-based, silica-alumina based or clay-based.   [0024] The FCC matrix contributes to pores in the mesopore range (20-500 Å)  as well as macropores (>500 Å). Surface area corresponding to the matrix, i.e., the  surface of pores in the range of from 20 to 10000 Å, of the equilibrium FCC catalyst  typically ranges from 10 to 220 m 2 /g, preferably from 20 to 150 m 2 /g, as determined by  the t-plot method. The final equilibrium FCC catalyst may have a total water pore  volume of 0.2 to 0.6 cm 3 /g.   [0025] The FCC catalyst may comprise physical blends of catalysts and  additives. Additives are used in FCC to perform a certain function, such as changing  the product selectivity to favor propylene or butylene, control the combustion of coke  in the regenerator or assist the refiner in meeting environmental regulations, such as  SOx and NOx emissions or gasoline sulfur specification.   [0026] The additives may include a ZSM-5 based additive; an additive based  on magnesium aluminate spinel, promoted by cerium oxide (CeO 2 ) and vanadium  oxide; and/or platinum- and palladium-based additives.   [0027] The ZSM-5-based additive, such as OlefinsUltra ® from W.R. Grace, is  commonly used to enhance the production of propylene and butylene. The ZSM-5  additive can be blended in the range of 1 to 50 wt% of the total catalyst. The present  invention is particularly beneficial for units desiring high yields of propylene and  butylene.   [0028] The additive based on magnesium aluminate spinel, promoted by cerium  oxide (CeO2) and vanadium oxide, such as Super DESOX ® from W.R. Grace, is  commonly used to control SOx emissions. SOx additives can be blended in the range  of 0.2 to 20 wt% of the total catalyst. Equilibrium catalysts from FCC units that use  high levels of additive to control SOx will have CeO 2 /MgO wt ratio higher than about  0.15 or show presence of crystalline Cerium oxide (CeO2), which is detectable by a x-  ray diffraction technique (XRD).   [0029] The platinum- and palladium-based additives are commonly used to aid  with coke combustion in the regenerator and are typically used in <10 ppm on a Pt or  Pd basis of the total catalyst.   [0030] The magnesium containing slurry may contain particles of the  magnesium compound having an average particle size in a range of about 5 nm to about  1 µm, preferably about 7 nm to about 300 nm, and more preferably about 15 nm to  about 150 nm. A concentration of the magnesium compound in the slurry may be in a  range of about 5 wt% to about 50 wt%, preferably about 20 wt% to about 40 wt%,  reported as MgO. The magnesium compound may include at least one selected from  the group consisting of magnesium oxide, magnesium carbonate, magnesium  hydroxide, magnesium sulfonate, magnesium acetate, and mixed metal oxides and  carbonates of magnesium with aluminum or silicon. The slurry may further contain  water, an organic solvent, or a mixture thereof as a liquid phase or dispersant. The  organic solvent may be a carbon based substance that dissolves or disperses one or more  other substances. For example, the organic solvent may be a hydrocarbon, an  oxygenated hydrocarbon, an alcohol, a surfactant and combinations thereof. In one  embodiment, the slurry further contains antimony or an antimony compound.   [0031] The FCC feedstock may be gas oils, either virgin or cracked. Heavier  feedstocks such as vacuum resid, atmospheric resid and de-asphalted oil can also be  used. While contaminated metals can be present in all the above feedstocks, they are  most prevalent in the heavy streams. The FCC feedstocks are introduced as liquids,  however, they vaporize when they contact hot catalyst flowing from the regenerator,  the FCC cracking reaction then proceeding in the vapor phase. The metals are deposited  initially on the surface of the catalyst, however, over time, some of the metals may   migrate. Because the average age of the catalyst inventory in an FCC unit can be weeks  or months, this means that metals will continue to accumulate on the catalyst the entire  time it circulates in the unit.   [0032] Iron present in the feedstock, when deposited on catalyst, can result in  dehydrogenation reactions, but more importantly, it has been found to obstruct the pores  of the catalyst. When this happens, large molecules cannot diffuse into the pores of the  catalyst, and so cannot be cracked. Iron compounds present in the FCC feedstock are  typically present as porphyrins, naphthenates or inorganic compounds in amounts of 0  to 10000 ppm by weight (mg/kg), as Fe. Different iron-containing compounds may  obstruct the pores to different degrees.   [0033] In one embodiment, a concentration of iron compounds in the iron-  contaminated FCC feedstock may be in a range of about 0.5 ppm by weight to about  100 ppm by weight, preferably about 1 ppm by weight to about 50 ppm by weight, more  preferably about 2 ppm by weight to about 30 ppm by weight, reported as Fe.   [0034] In the case where Fe poisoning negatively affects FCC catalyst through  restriction of hydrocarbon diffusion in and out of the catalyst, a magnesium compound  and a calcium compound may behave differently. It is known that the calcium  compound may enhance the formation of dense iron layer on the outer surface of the  FCC catalyst, thereby resulting in pore blocking (Stud. Surf. Sci. and Catal. (2003) Vol.  149, p. 139). On the contrary, addition of a small amount of a magnesium compound  onto the surface of the iron-contaminated FCC catalyst unexpectedly increases the  diffusivity of hydrocarbons into and out of the FCC catalyst. Without being held to a  particular theory, it is very likely that the small amount of the magnesium  compound on the iron-contaminated FCC catalyst may help to reduce or eliminate  the dense Fe layer formation on the FCC catalyst, and preserve the diffusion of feed  molecules going in and cracked molecules coming out of the FCC catalyst, thereby  preserving activity and selectivity of the FCC catalyst.   [0035] In one embodiment, combining the FCC catalyst with the slurry  containing the magnesium compound is performed simultaneously with combining  with the iron-contaminated FCC feedstock.   [0036] In another embodiment, the slurry containing the magnesium compound  may further include the iron-contaminated FCC feedstock before combining with the  FCC catalyst. In this case, the slurry and the feedstock may be miscible.   [0037] In another embodiment, combining the FCC catalyst with the slurry  containing the magnesium compound is performed before combining with the iron-  contaminated FCC feedstock. For example, first, a slurry containing the magnesium  compound, but not the calcium compound, may be prepared. Then, the FCC catalyst  may be combined with the slurry, followed by combining with the iron-contaminated  FCC feedstock. In this case, the slurry and the feedstock may be miscible or not  miscible.   [0038] In another embodiment, combining the FCC catalyst with the slurry  containing the magnesium compound is performed after combining with the iron-  contaminated FCC feedstock. For example, first, a slurry containing the magnesium  compound, but not the calcium compound, may be prepared. Then, the FCC catalyst  may be combined with the iron-contaminated FCC feedstock, followed by combining  with the slurry. In this case, the slurry and the feedstock may be miscible or not  miscible. The combining of the FCC catalyst with the slurry and the iron-contaminated  FCC feedstock may occur within a FCC unit.   [0039] After the combination of the FCC catalyst, the slurry, and the iron-  contaminated FCC feedstock, the magnesium compound or a derivative of the  magnesium compound may be deposited onto the equilibrium FCC catalyst. During  the FCC process, the magnesium compound may be converted chemically or physically  into the derivative of the magnesium compound, which then remains deposited on the  equilibrium FCC catalyst. The magnesium compound or a derivative of the magnesium  compound may be deposited on or near the outer surface of the equilibrium FCC  catalyst.   [0040] In one embodiment, an amount of the magnesium compound or the  derivative of the magnesium compound on the equilibrium FCC catalyst is in a range  of about 100 ppm to about 30,000 ppm by weight, preferably about 300 ppm to about  20,000 ppm by weight, reported as MgO, of the equilibrium FCC catalyst.   [0041] In one embodiment, an amount of iron compounds on the equilibrium  FCC catalyst is in a range of about 500 ppm to 30,000 ppm by weight, preferably about  1,000 ppm to about 20,000 ppm by weight, reported as Fe, of the equilibrium FCC  catalyst.   [0042] In one embodiment, a weight ratio of the magnesium compound or the  derivative of the magnesium compound, as MgO, to the iron compounds, as Fe, on the  equilibrium FCC catalyst is greater than about 0.1, preferably greater than about 0.5.  [0043] In one embodiment, the equilibrium FCC catalyst has a diffusion  coefficient of more than about 5 mm 2 /min, preferably at least about 8 mm 2 /min, as  measured by an inverse gas chromatography technique.   [0044] An equilibrium FCC catalyst or “Ecat” is a catalyst in the inventory of  the FCC unit that has been deactivated due to repeated cracking of hydrocarbon  feedstock and regeneration to burn off the coke. A fresh fluid cracking catalyst is a  catalyst as manufactured and sold by catalyst vendors. As the catalyst ages, it undergoes  changes due to attrition, accumulation of feedstock metals and exposure to the severe  hydrothermal environment of the FCC unit. The aged catalyst is characterized by loss  of surface area and acid sites, which result in deterioration of activity and selectivity.  During the FCC process, fresh catalyst is added, and aged catalyst is withdrawn, as  needed, to maintain catalytic activity and selectivity as well as to hold proper catalyst  bed levels in the FCC reactor and regenerator vessels. The equilibrium catalyst is a  catalyst in the circulating inventory that reflects a balance between rates of catalyst  deactivation and replacement. Hence, the Ecat includes an age distribution of fresh to  severely deactivated FCC catalyst particles.   [0045] Although the slurry containing the magnesium compound does not  contain a calcium compound such as CaO, there may be a small amount of calcium  compounds as impurity in the FCC feedstock. Calcium may also be an impurity in the  raw materials used to make the fresh catalyst. As a result, a typical equilibrium FCC  catalyst may contain a small amount of calcium compounds.   [0046] Another example of the present invention is an equilibrium FCC  catalyst. The equilibrium FCC catalyst may include an FCC catalyst containing   calcium, and having at least one magnesium compound and iron compounds deposited  on the FCC catalyst. A weight ratio of the magnesium compound, as MgO, to the iron  compounds, as Fe, on the equilibrium FCC catalyst may be in a greater than 0.1. A  weight ratio of calcium compounds to the magnesium compound on the equilibrium  FCC catalyst, reported as CaO/MgO, may be less than about 0.25, preferably less than  about 0.15.   [0047] In one embodiment, the weight ratio of the magnesium compound, as  MgO, to the iron compounds, as Fe, on the equilibrium FCC catalyst is greater than 0.5.  In one embodiment, an amount of the magnesium compound is in a range of about 100  ppm to about 30,000 ppm by weight, preferably about 300 ppm to about 20,000 ppm  by weight, reported as MgO, of the equilibrium FCC catalyst.   [0048] The equilibrium FCC catalyst may have magnetic susceptibility in SI  units of over 500x10 -6 , preferably over 2000x10 -6 .   [0049] In one embodiment, the equilibrium FCC catalyst has a diffusion  coefficient greater than or equal to about 5 mm 2 /min. The FCC catalyst may include a  faujasite and/or ZSM-5 and/or beta zeolite. The faujasite zeolite may be a Y-type  zeolite.   [0050] In one embodiment, the equilibrium FCC catalyst may include a Ce-  containing compound. A weight ratio of the Ce-containing compound to the magnesium  compound, reported as CeO2/MgO, in the equilibrium FCC catalyst may be less than  about 0.15, preferably less than about 0.12. In one embodiment, there is absence of  CeO2 crystalline phase detectable by XRD in the equilibrium FCC catalyst.   [0051] In the description of the specification, references made to the term “one  embodiment,” “some embodiments,” “example,” and “some examples” and the like are  intended to refer that specific features and structures, materials or characteristics  described in connection with the embodiment or example that are included in at least  one embodiment or example of the present disclosure. The schematic expression of the  terms does not necessarily refer to the same embodiment or example. Moreover, the  specific features, structures, materials or characteristics described may be included in  any suitable manner in any one or more embodiments or examples.   [0052] Hereinafter, the present invention will be described in more detail with  reference to Examples. However, the scope of the present invention is not limited to the  following Examples. These examples are intended for illustration purposes only and  are not intended to limit the scope of the present invention.     EXAMPLES   Characterization Methods   [0053] Average particle size of FCC catalyst is measured according to ASTM  D4464, Standard Test Method for Particle Size Distribution of Catalytic Materials by  Laser Light Scattering. Particle size of MgO nanoparticles is determined by Dynamic  Light Scattering, as described in ASTM E2490, Standard Guide for Measurement of  Particle Size Distribution of Nanomaterials in Suspension by Photon Correlation  Spectroscopy (PCS). Chemical composition or elemental analysis is performed by an  inductively coupled plasma (ICP) technique. Surface Area is determined according to  ASTM D3663-03(2015), Standard Test Method for Surface Area of Catalysts and  Catalyst Carriers. Zeolite surface area and matrix surface area are determined according  to ASTM D4365-19, Standard Test Method for Determining Micropore Volume and  Zeolite Area of a Catalyst. Unit Cell Size is determined according to ASTM D3942-  03(2013), the standard Test Method for Determination of the Unit Cell Dimension of a  Faujasite-Type Zeolite. Cracking reaction was carried out in an Advanced Cracking  Evaluations (ACE TM ) fixed fluid bed reactor at 1004 ^F, using a resid feedstock with a  30 second feed injection time. Catalyst dosage was varied to obtain a range of  conversion at catalyst to oil ratios of 4.5, 6 and 8. Elemental mapping was conducted  on a JEOL JXA-8230 Electron Probe Microanalyzer, equipped with both an Energy  Dispersive Spectrometer (EDS) and a Wavelength Dispersive Spectrometer (WDS).  For imaging and mapping particle cross section, particles were placed in an epoxy, and  the resin was cured overnight at room temperature. The sample stub was then cut with  a diamond blade, and polished to a smooth surface.   [0054] The determination of Grace Effective Diffusion Coefficient (GeDC) is  based on the principle of inverse gas chromatography and is carried out on an Agilent   HP 7890 GC, configured by PAC Analytical Controls. For each test, a quartz glass  column of 12 cm length and 2 mm ID is packed with 100 mg of catalyst. The probe  molecule, 1,2,4-Trimethylcyclohexane is prepared as a 5 wt% solution in carbon  disulfide. Nitrogen is used as carrier gas. For each sample, the GC runs were conducted  at seven carrier flow settings, between 70 to 99 mL/min. At each carrier flow rate, a  methane pulse is used for dead time determination. The chromatograms are analyzed  by the van Deemter Equation to determine the GeDC, as described in the US Patent  Application No.2017/0267934 A1.   [0055] The magnetic susceptibility of the samples was measured with a  Bartington MS3 meter in combination with the MS2B sensor operated in a HF/LF  mode. A minimum of 17 g of the sample was filled into a 20 mL HDPE vial. Before  each measurement, a blank was measured for 5 s before the sample was placed in the  meter and measured for 10 s. All results are reported in SI units.   Comparative Examples 1 & 2   [0056] An equilibrium FCC catalyst (Ecat), as Comparative Example 1, is taken  from a commercial FCC unit with a Grace effective diffusion coefficient (GeDC) of 13  mm 2 /min. The equilibrium FCC catalyst was deactivated in a fluidized-bed laboratory  reactor using the Cyclic Propylene Steam (CPS) deactivation protocol for 40 hours, 60  cycles at 1350 ºF to obtain a deactivated equilibrium FCC catalyst, as Comparative  Example 2. The CPS deactivation procedure has been described in Wallenstein et. al.,  Appl. Catal. A., Vol. 204, 89-106 (2000). GeDC of the deactivated equilibrium FCC  catalyst decreased to 7 mm 2 /min, as shown in Table 1.   Comparative Example 3   [0057] An aliquot of the equilibrium FCC catalyst as Comparative Example 1  was spray coated with 7000 ppmw of Fe using nanoparticles of the iron compounds,  Iron(III) oxyhydroxide, suspended in an aqueous solution, followed by the same CPS  deactivation in Comparative Example 2 to obtain a deactivated equilibrium FCC  catalyst coated with only iron compounds, as Comparative Example 3. The procedure  for spray coating has been described in Wallenstein et. al., Appl. Catal. A., Vol. 462-  463, 91-99 (2013). The electron probe micro-analyzer (EPMA) analysis shows that   nanoparticles of the iron compounds are deposited mainly on an outer surface of  equilibrium FCC catalyst particles and formed a thin shell surrounding the equilibrium  FCC catalyst particles, as shown in Fig. 1. GeDC of the resulted deactivated  equilibrium FCC catalyst coated with only iron compounds decreased to 3 mm 2 /min,  as shown in Table 1. The magnetic susceptibility of the resulted deactivated equilibrium  FCC catalyst coated with only iron compounds increased with the addition of iron  compounds by more than an order of magnitude, as shown in Table 1. Both the decrease  in GeDC and the increase in magnetic susceptibility are consistent with observations in  commercial FCC units experiencing Fe poisoning.     Example 1   [0058] Another aliquot of the equilibrium FCC catalyst as Comparative  Example 1 was spray coated with 7000 ppmw of Fe using nanoparticles of the iron  compounds, Iron(III) oxyhydroxide, suspended in an aqueous solution, and 17000  ppmw of MgO using nanoparticles of MgO/Mg(OH) 2 suspended in an aqueous  solution, followed by the same CPS deactivation as Comparative Example 2 to obtain  a deactivated equilibrium FCC catalyst coated with iron compounds and a magnesium  compound, as Example 1. GeDC of the resulted deactivated equilibrium FCC catalyst  coated with iron compounds and the magnesium compound only decreased to 10  mm 2 /min, as shown in Table 1. EPMA analysis shows that nanoparticles of iron  compounds and MgO/Mg(OH) 2 are mainly deposited on the outer surface of the  equilibrium FCC catalyst particles and formed a thin shell surrounding the equilibrium  FCC catalyst particles, as shown in Figs.2A and 2B respectively.   [0059] Table 1. Comparison of properties of equilibrium FCC catalysts:

    [0060] As shown in Table I, the analysis results show that for the Ecat with  added Fe as in Comparative Example 3, GeDC decreased much more than those without  added Fe as in Comparative Example 2. In contrast, for the Ecat with added Fe and  added Mg as in Example 1, GeDC decreased much less than that with added Fe alone  as in Comparative Example 3 and that without any treatment as in Comparative  Example 2. These results demonstrate that addition of a small amount of a magnesium  compound such as MgO to the external surface of the equilibrium FCC catalyst helps  to alleviate the negative impact of added Fe on the diffusivity of hydrocarbons in and  out of the catalyst, thereby significantly reducing the iron poisoning of the catalyst.  [0061] The three deactivated Ecat samples, Comparative Examples 2 & 3 and  Example 1, were tested by ACE using a feedstock with properties shown in Table 2.  [0062] Table 2. Properties of FCC feedstock

    [0063] Table 3. ACE yields at 80 wt% conversion     [0064] The results are listed in Table 3. Compared to the deactivated Ecat  (Comparative Example 2) at constant conversion of 80 wt%, the deactivated Ecat with  added Fe only (Comparative Example 3) has lower activity, as evidenced by the higher  catalyst to oil ratio required to achieve equal conversion, higher coke and higher  bottoms yields. The Fe only catalyst (Comparative Example 3) also has higher  tendency toward saturating olefins, as evidence by the higher hydrogen transfer index  (defined as the ratio of isobutane/isobutene), lower C4 olefins, lower gasoline olefins  and lower octane. The activity and selectivity differences observed in the ACE testing  are consistent with activity and selectivity differences commonly observed in  commercial FCC units where catalyst inventory is poisoned by Fe.   [0065] In contrast, compared to the deactivated Ecat with added Fe only  (Comparative Example 3), the deactivated Ecat with added Fe and Mg (Example 1) has  unexpectedly higher activity, as evidenced by the lower catalyst to oil ratio required to  achieve equal conversion, lower coke and lower bottoms yields. The catalyst with  added Fe and Mg (Example 1) has lower hydrogen transfer index and higher C4 olefins,  higher gasoline olefins and higher octane. These results demonstrate that the Fe  poisoning effect have been unexpectedly reduced or eliminated by the addition of MgO.  Comparative Examples 4-6   [0066] The following Examples and Comparative Examples demonstrate the  superiority of MgO over CaO in reducing the loss of diffusivity due to Fe poisoning.  An aliquot of the same Ecat from Comparative Example 1 was spray coated with  nanoparticles of iron compounds, Iron(III) oxyhydroxide,, (Comparative Example 4).  New aliquots of the same Ecat from Comparative Example 1 were spray coated with  nanoparticles of iron compounds, Iron(III) oxyhydroxide, followed by two levels  (11400 and 20200 ppmw as CaO, as Comparative Examples 5 & 6 respectively) of  CaO, using a calcium nitrate solution. The metal-impregnated samples were  deactivated in a fluidized bed reactor using CPS deactivation protocol, as described in  Comparative Example 2.   Examples 2 & 3   [0067] New aliquots of the same Ecat from Comparative Example 1 were  spray coated with nanoparticles of iron compounds, Iron(III) oxyhydroxide, followed  by two levels (7300 and 16200 ppmw as MgO, as Examples 2 & 3 respectively) of the  MgO/Mg(OH) 2 suspension described in Example 1, and the metals-impregnated  samples were deactivated in a fluidized bed reactor using CPS deactivation protocol,  as described in Comparative Example 2.   [0068] GeDC, magnetic susceptibility and chemical analysis of the 6 CPS  deactivated Ecat samples are listed in Table 4. The results show that the magnetic  susceptibility increases for all samples with added Fe. The GeDC decreases for the  sample with only added Fe, as in Comparative Example 4. With addition of Fe and  MgO in Examples 2 and 3, the GeDC is about the same as the deactivated Ecat without  added Fe and much higher than the sample with added Fe only. For comparison, the  GeDC values of samples spray coated with Fe and CaO were about the same as that of  the Fe only sample. The results again demonstrate that addition of MgO to the external  surface of the FCC catalyst helps to alleviate the negative impact of added Fe in limiting  diffusion of hydrocarbons in and out of the catalyst. However, the addition of a calcium  compound provides no benefit to improving the diffusivity of Fe-poisoned catalyst.  [0069] The descriptions of the various embodiments of the present invention  have been presented for purposes of illustration, but are not intended to be exhaustive  or limited to the embodiments disclosed. Many modifications and variations will be  apparent to those of ordinary skill in the art without departing from the scope and spirit  of the described embodiments. The terminology used herein was chosen to best explain  the principles of the embodiments, the practical application or technical improvement  over technologies found in the marketplace, or to enable others of ordinary skill in the  art to understand the embodiments disclosed herein.     m, followed by CPS   Comp. Exam. 5  Comp. Exam. 6  Ecat   Deactivated Ecat   Deactivated Ecat  g #2  with Fe & Ca #1  with Fe & Ca #2      60.2  55.9  20200  11400  11500  11200  400  400  0.32  0.30  1.99  1.96  619  586  1609  1451  3260  3050  2  2  4 291  3522  0.04  0.04  47.07  28.43