Addition of magnetically active moieties for magnetic beneficiation of particulates in fluid bed hydrocarbon processing

Abstract

By continuously or intermittently adding amounts of magnetically active moieties, e.g. iron compounds, over time so that the moiety deposits on a catalyst or sorbent in a fluid catalytic cracker or similar circulating hydrocarbon conversion unit, older catalyst, being more magnetic, can be readily separated from catalyst which has been in the system a shorter time. Separation is readily accomplished by passing the catalyst and/or sorbent through a magnetic field and discarding the more magnetic 50% by wt. or more preferably 20% by wt., while recycling the remainder back to the hydrocarbon conversion unit.

What is claimed is: 
     
       1. A process for processing metal-containing hydrocarbon feedstocks by contacting said feedstock with catalytic and/or non-catalytic particles in a fluid bed hydrocarbon conversion system, said processing comprising: (a) intentionally adding to said conversion system continuously .Iadd.or periodically .Iaddend.a magnetically active moiety so it deposits on the particles over a period of time so that deposition of said moiety on said particles is proportional to the time that said particles have remained in the system;   (b) separating older particles added early to the system from newer particles later added, by magnetic means.   
     
     
       2. A process for processing non-metal-containing hydrocarbon feedstocks by contacting said feedstock with catalytic and/or non-catalytic particles in a fluid bed hydrocarbon conversion system, said process comprising: (a) intentionally adding to said conversion system continuously .Iadd.or periodically .Iaddend.a magnetically active moiety so it deposits on the particles over a period of time so that deposition of said moiety on said particles is proportional to the time that said particles have remained in the system;   (b) separating older particles added early to the system from newer particles later added, by magnetic means.   
     
     
       3. A process as claimed in claim 1, wherein said moiety comprises iron which is added continuously or periodically to the feedstock so as to deposit on the particulate in amounts in the range of about 0.1 to 10 ppm of iron to one part of nickel equivalents. 
     
     
       4. A process as claimed in claim 1, wherein said moiety comprises iron which is added continuously or periodically to the feedstock so as to deposit on the particulate in amounts in the range of about 0.5 to 2 ppm of iron to one part of nickel equivalents. 
     
     
       5. A process as claimed in claim 2, wherein said moiety comprises iron which is added continuously or periodically to the feedstock in amounts of 0.1 ppm to 10 ppm of iron. 
     
     
       6. A process as claimed in claim 3, 4, or 5, wherein said iron moiety is added as an inorganic compound. 
     
     
       7. A process as claimed in claim 3, 4, or 5, wherein said iron moiety is added as an organic compound. 
     
     
       8. A process as claimed in claim 3, 4 or 5, wherein said iron moiety is added as a water soluble compound, which is emulsified in oil and added as an additive. 
     
     
       9. A process as claimed in claim 3, 4, or 5, wherein said iron moiety is added as an oil soluble additive. 
     
     
       10. A process as claimed in claim 3, 4, or 5, wherein said moiety is added in an organic solvent to said feedstock. 
     
     
       11. A process as claimed in claim 1, wherein catalyst particles containing higher amounts of said magnetically .Iadd.active .Iaddend.moiety also contain higher levels of nickel equivalents and are separated by magnetic separation from catalyst particles containing lower amounts of magnetically active ions or elements and also lower nickel equivalents. 
     
     
       12. A process as claimed in claim 1, 3, 4 or 11, wherein the catalyst used to crack said hydrocarbon feedstock has a nickel equivalent, excluding iron, of 500 or greater. 
     
     
       13. A process as claimed in claim 1, 3, 4 or 11, wherein the catalyst used to crack said hydrocarbon feedstock has a nickel equivalent, excluding iron, of 2000 or greater. 
     
     
       14. A process as claimed in claim 1, 2, 3, 4, 11, or 5, wherein the magnetic separation is achieved by means of a high gradient electro magnetic separation device of about 1,000 to 20,000 Gauss field strength. 
     
     
       15. A process as claimed in claim 1, 2, 3, 4, 11, or 5, wherein the magnetic separation is achieved by means comprising a rare earth-containing magnetic roller. 
     
     
       16. A process as claimed in claim 1, 2, 3, 4, 11, or 5, wherein the magnetic separation is achieved by means comprising a ferrite roller magnetic separator. 
     
     
       17. A process as claimed in claim 14, wherein the magnetic separation is by means comprising a superconducting high gradient electro magnetic separator (SCHGMS) wherein the SCHGMS operates in the range of about 10,000 to 50,000 Gauss magnetic field strength. 
     
     
       18. A process as claimed in claim 17, wherein the SCHGMS operates in the range of about 10,000 to 30,000 Gauss field strength. 
     
     
       19. A process as claimed in claim 1, 2, 3, 4, 11, or 5, wherein the feedstock has a Conradson Carbon number greater than 1. 
     
     
       20. A process as claimed in claim 1, 2, 3, 4, 11, or 5, wherein the feedstock has an API gravity between 10 and 30. 
     
     
       21. A process as claimed in claim 1, 2, 3, 4, 11, or 5, wherein the process is carried out in a reduced crude conversion unit. 
     
     
       22. A process claimed in claim 1, 2, 3, 4, 11, or 5, wherein the process is carried out in a fluid catalytic cracker. 
     
     
       23. A process claimed in claim 1, 2, 4 or 11, wherein the particles have a nickel equivalent, excluding iron, of 1000 ppm or greater. 
     
     
       24. A process claimed in claim 3, 4, 11, or 5, wherein said moiety comprises iron as ferrous or ferric sulfate. 
     
     
       25. A process as claimed in claim 1, 2, 3, 4 or 11, wherein said moiety comprises iron as a water soluble salt. 
     
     
       26. A process as claimed in claim 1, 2, 3, 4 or 11, wherein said moiety comprises iron as an oil soluble compound. 
     
     
       27. A process as claimed in claim 1, 2, 3, 4 or 11, wherein said moiety comprises iron which is added as an organic compound. 
     
     
       28. A process as claimed in claim 1, 2, 3, 4 or 11, wherein said moiety comprises iron which is added as an emulsion. 
     
     
       29. A process as claimed in claim 1, 2, 3, 4 or 11, wherein said moiety comprises an iron compound .[.which is added continuously.].. 
     
     
       30. A process as claimed in claim 1, 2, 3, 4 or 11, wherein said moiety comprises an iron compound which is added cylically or periodically. 
     
     
       31. A process as claimed in claim 1, 3, 4 or 11, wherein said magnetically active moiety, does not substantially reduce catalyst selectivity or activity, and is added at a rate commensurate with metal contamination in the feedstock. 
     
     
       32. A process as claimed in claim 1, 3, 4 or 11, wherein said magnetically active moiety does not substantially reduce catalyst selectivity or activity and is added to the catalyst or particulate at a rate commensurate with metal contamination in the feedstock. 
     
     
       33. A process claimed in claim 1, 3, 4 or 11, wherein said moiety comprises iron and said iron is added to the feedstock or to the catalyst or particulate at a rate 0.5 to 2 times the vanadium concentration in the feedstock whereby there is formed an iron vanadate. 
     
     
       34. A process according to claim 1, 2, 3, 4, 11, or 5, wherein the magnetic separation occurs at a catalyst temperature in the range of from about -100° F. to 300° F. 
     
     
       35. A process as claimed in claim 1, 2, 3 or 4, whereby iron is added .[.continuously.]. to the catalyst by spraying an iron-containing solution directly onto the circulating catalyst. 
     
     
       36. In a process for processing hydrocarbon fractions by catalytic cracking with a mixture of a first catalyst having an iron content and a second catalyst, the improvement comprising impregnating the second catalyst with iron equal to two or more times the iron content of said first catalyst so as to permit selective removal of said second catalyst by magnetic means. 
     
     
       37. A process as claimed in claim 1, 3 or 4, wherein said moiety comprises iron and said iron accumulates on the catalyst at a rate equal to 1 to 5 times the rate of accumulation of nickel plus vanadium. 
     
     
       38. A process as claimed in claim 1, 2, 3, 4, 10, or 5, whereby older high iron containing catalysts low in catalytic activity are separated from younger low iron containing catalysts high in activity. 
     
     
       39. A process as claimed in claim 1, 2, 3, 4, 11, or 5, whereby the magnetic separation is by means of a high gradient electro magnetic separator. 
     
     
       40. A process as claimed in claim 1, or 5, whereby a non-magnetic stainless steel belt is employed. 
     
     
       41. A process as claimed in claim 1, 2, 3, 4, 11, or 5, whereby the magnetic separation is by means of a superconducting high gradient electro magnetic separator whereby the SCHGMS operates up to 20,000 Gauss magnetic field. 
     
     
       42. A process as claimed in claim 17, whereby the SCHGMS operates up to 50,000 Gauss. 
     
     
       43. A process as claimed in claim 1, 2, 3, 4, 11, or 5, whereby the feedstock has an API gravity between 5 and 35. 
     
     
       44. A process as claimed in claims 1, 2 or 11, whereby the magnetically active moiety is an additive consisting of an element or compound having a one gram formula (atomic) magnetic susceptibility of 1,000×10 -6  cgs or greater at or about 293° K. 
     
     
       45. A process as claimed in claims 1, 2 or 11, whereby the magnetically active moiety is an additive consisting of an element or compound having a one gram formula (atomic) magnetic susceptibility of 3,500×10 -6  cgs or greater at or about 293° K. 
     
     
       46. A process as claimed in claims 1, 2, or 11, whereby the magnetically active moiety is an additive consisting of an element or compound having a one gram formula (atomic) magnetic susceptibility of 500×10 -6  cgs or greater at or about 293° K. 
     
     
       47. A process as claimed in claim 1, 2, or 11, whereby the magnetically active moiety is an additive consisting of two or more magnetically active moieties. 
     
     
       48. A process as claimed in claims 1, 2 or 11, whereby the magnetically active moiety is an additive consisting of two or more elements or compounds each having a one gram formula (atomic) magnetically susceptibility of 1,000×10 -6  cgs or greater at or about 293° K. 
     
     
       49. A process as claimed in claim 1 or 11, wherein said moiety comprises iron and said iron forms a vanadate which reduces mobility of the vanadium contaminant on the particles. 
     
     
       50. A process as claimed in claim 1, or 5, whereby a belt is utilized which reduces electrostatic charge. 
     
     
       51. In a process for cracking gas oil and heavier hydrocarbon fractions in the presence of recycled circulating catalytic cracking catalyst particles, the improvement comprising: A. intentionally adding iron over time to said circulating catalyst particles so that the concentration of iron on a particle increases in proportion to the time that the catalyst particle has remained in the system,   B. separation of old catalyst from new catalyst by magnetic separation.   
     
     
       52. In a process for cracking residual carbo-metallic feedstock in the presence of recycled circulating cracking catalyst particles, the improvement comprising: A. intentionally adding iron continuously .Iadd.or periodically .Iaddend.to said circulating catalyst particles containing more than 200 ppm of nickel and vanadium so that the concentration of iron and the resulting magnetic susceptibility of said catalyst particles increases proportional to the time the particles has been recycled;   B. separating old catalyst, high in concentration of metals, from new catalyst, lower in concentration of metals, by magnetic separation.   
     
     
       53. In a process for cracking residual carbo-metallic feedstocks containing more than 2 ppm of nickel and vanadium in the presence of recycled circulating cracking catalyst particles containing more than 1000 ppm of nickel and vanadium the improvement comprising: A. intentionally adding iron to said circulating particles so that the concentration of iron and the resulting magnetic susceptibility of said catalyst particles are directly related to the length of time said particles have been circulating;   B. separating older catalyst high in iron concentration, from newer catalyst, low in iron, by magnetic separation.   
     
     
       54. A process as claimed in claim 1, 2, 3 or 4, whereby said moiety is added .[.continuously.]. to the catalyst by adding an iron-containing compound said feedstock.