Compositions and processes for reducing NOemissions during fluid catalytic cracking
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-011/05
C10G-047/16
C10G-047/18
C10G-047/20
B01J-029/90
출원번호
UP-0291379
(2008-11-07)
등록번호
US-7641787
(2010-02-11)
발명자
/ 주소
Yaluris, George
Ziebarth, Michael Scott
Zhao, Xinjin
출원인 / 주소
W.R. Grace & Co.-Conn.
대리인 / 주소
Cross, Charles A.
인용정보
피인용 횟수 :
4인용 특허 :
145
초록▼
Compositions for reduction of NOx generated during a catalytic cracking process, preferably, a fluid catalytic cracking process, are disclosed. The compositions comprise a fluid catalytic cracking catalyst composition, preferably containing a Y-type zeolite, and a particulate NOx composition contain
Compositions for reduction of NOx generated during a catalytic cracking process, preferably, a fluid catalytic cracking process, are disclosed. The compositions comprise a fluid catalytic cracking catalyst composition, preferably containing a Y-type zeolite, and a particulate NOx composition containing particles of a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a SiO2 to Al2O3 molar ratio of less than about 500. Preferably, the NOx reduction composition contains NOx reduction zeolite particles bound with an inorganic binder. In the alternative, the NOx reduction zeolite particles are incorporated into the cracking catalyst as an integral component of the catalyst. Compositions in accordance with the invention are very effective for the reduction of NOx emissions released from the regenerator of a fluid catalytic cracking unit operating under FCC process conditions without a substantial change in conversion or yield of cracked products. Processes for the use of the compositions are also disclosed.
대표청구항▼
What is claimed is: 1. A process of reducing NOx emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process comprising a) contacting a hydrocarbon feedstock during a fluid catalytic cracking (FCC) process wher
What is claimed is: 1. A process of reducing NOx emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process comprising a) contacting a hydrocarbon feedstock during a fluid catalytic cracking (FCC) process wherein NOx emissions are released from a regeneration zone of a fluid catalytic cracking unit (FCCU) operating under FCC conditions with a circulating inventory of an FCC cracking catalyst and a particulate NOx reduction catalyst/additive composition having a mean particle size of greater than 45 μm and comprising (i) at least 10 weight percent of a NOx reduction zeolite component selected from the group consisting of ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NO, Nu-87, Cit-1, SSZ-35, SSZ48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Gooseereekite, Natrolite, omega or mixtures thereof, and (ii) from about 5 to about 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, alumina phosphate and mixtures thereof; and b) reducing the amount of NOx emissions released from the regeneration zone of the FCCU by at least 10% as compared to the amount of NOx emissions released in the absence of the particulate NOx reduction composition. 2. The process of claim 1 wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone. 3. The process of claim 1 or 2 wherein the NOx reduction zeolite component is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof. 4. The process of claim 1 or 2 wherein the catalyst/additive composition further comprises a matrix material selected from the group consisting of alumina, silica, silica alumina, titania, zirconia, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, praseodymia, and mixtures thereof. 5. The process of claim 4 wherein the matrix material is present in an amount less than 70 weight percent. 6. The process of claim 1 or 2 further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst. 7. The process of claim 6 wherein the cracking catalyst and the particulate catalyst/additive composition are fluidized during contacting said hydrocarbon feedstock. 8. The process of claim 1 or 2 further comprising contacting the hydrocarbon feed with at least one additional NOx reduction composition. 9. The process of claim 8 wherein the additional NOx reduction composition is a non-zeolitic composition. 10. The process of claim 9 wherein the additional NOx reduction composition comprises (1) an acidic metal oxide containing substantially no zeolite; (2) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (3) an oxygen storage metal oxide component; and (4) at least one noble metal component. 11. The process of claim 8 wherein the additional NOx reduction composition is a low NOx CO combustion promoter composition which comprises (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) palladium. 12. The process of claim 8 wherein the additional NOx reduction composition comprises (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) a transition metal selected from Groups 1B and IIB of the Periodic Table, and mixtures thereof. 13. The process of claim 8 wherein the additional NOx reduction composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof. 14. The process of claim 13 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal. 15. The process of claim 13 wherein the third metal component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof. 16. The process of claim 13 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal. 17. The process of claim 13 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal. 18. The process of claim 8 wherein the additional NOx reduction composition is a zinc based catalyst. 19. The process of claim 8 wherein the additional NOx reduction composition is an antimony based NOx reduction additive. 20. The process of claim 8 wherein the additional NOx reduction composition is a perovskite-spinel NOx reduction additive. 21. The process of claim 8 wherein the additional NOx reduction composition is a hydrotalcite containing composition. 22. The process of claim 8 wherein the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof. 23. The process of claim 1 or 2 wherein the particulate NOx reduction catalyst/additive composition has a Davison attrition index (DI) value of less than 50. 24. The process of claim 23 wherein the particulate NOx reduction catalyst/additive composition has a DI value of less than 20. 25. The process of claim 24 wherein the particulate NOx reduction catalyst/additive composition has a DI value of less than 15. 26. The process of claim 1 wherein the FCC cracking catalyst comprises a Y-type zeolite. 27. The process of claim 26 wherein the amount of the catalyst/additive composition in the catalyst inventory is that amount sufficient to provide a ratio of NOx reduction zeolite component to Y-type zeolite in the total catalyst inventory of less than 2. 28. The process of claim 27 wherein the ratio of NOx reduction zeolite component to Y-type zeolite in the total catalyst inventory is less than 1. 29. The process of claim 26 wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone. 30. The process of claim 1 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition is at least 30 weight percent of the composition. 31. The process of claim 30 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition is at least 40 weight percent of the composition. 32. The process of claim 31 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition is at least 50 weight percent of the composition. 33. The process of claim 1 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition ranges from about 10 to about 85 weight percent of the composition. 34. The process of claim 33 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition ranges from about 30 to about 80 weight percent of the composition. 35. The process of claim 34 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition ranges from about 40 to about 75 weight percent of the composition. 36. The process of claim 1 wherein the NOx reduction zeolite component further comprises at least one stabilizing metal. 37. The process of claim 36 wherein the stabilizing metal is a metal selected from the group consisting of Groups 2A, 3B, 4B, 5B, 6B, 7B, 8B, 2B, 3A, 4A, 5A, and the Lanthanide Series of The Periodic Table, Ag and mixtures thereof. 38. The process of claim 37 wherein the stabilizing metal is selected from the group consisting of Groups 3B, 2A, 2B, 3A and the Lanthanide Series of the Periodic Table, and mixtures thereof. 39. The process of claim 38 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium, zinc, and mixtures thereof. 40. The process of claim 36 wherein the stabilizing metal is incorporated into the pores of the NOx reduction zeolite component. 41. The process of claim 1 wherein the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof. 42. The process of claim 41 wherein the inorganic binder is alumina. 43. The process of claim 42 wherein the alumina is an acid or base peptized alumina. 44. The process of claim 42 wherein the alumina is aluminum chlorohydrol. 45. The process of claim 1 wherein the amount of inorganic binder present in the particulate catalyst/additive composition ranges from about 10 to about 30 weight percent of the composition. 46. The process of claim 45 wherein the amount of inorganic binder present in the particulate catalyst/additive composition ranges from about 15 to about 25 weight percent of the composition. 47. The process of claim 1 wherein the NOx reduction zeolite component has a SiO2 to Al2O3 molar ratio of less than 500. 48. The process of claim 1 wherein the NOx reduction zeolite component is a zeolite selected from the group consisting of beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, Offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof. 49. The process of claim 1 wherein the particulate catalyst/additive composition further comprises an additional zeolite other than the NOx reduction zeolite. 50. The process of claim 49 wherein the additional zeolite is selected from the group consisting of ferrierite, ZSM-5, ZSM-35 and mixtures thereof. 51. The process of claim 49 or 50 wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition. 52. The process of claim 51 wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition. 53. The process of claim 1 wherein the particulate NOx reduction catalyst/additive composition has a mean particle size from about 50 to about 200 μm. 54. The process of claim 53 wherein the particulate NOx reduction catalyst/additive composition has a mean particle size from about 55 to about 150 μm.
연구과제 타임라인
LOADING...
LOADING...
LOADING...
LOADING...
LOADING...
이 특허에 인용된 특허 (145)
Chin Arthur A. (Cherry Hill NJ) Johnson Ivy D. (Medford NJ) Kresge Charles T. (Westchester PA) Sarli Michael S. (Haddonfield NJ), Additive for vanadium capture in catalytic cracking.
Ogawa Hiroshi,JPX ; Ito Yukio,JPX ; Nakano Masao,JPX ; Itabashi Keiji,JPX, Adsorbent for ethylene, method for adsorbing and removing ethylene and method for purifying an exhaust gas.
Bhattacharyya Alakanada (Columbia MD) Cormier ; Jr. William E. (Ellicott City MD) Woltermann Gerald M. (Westminster MD), Alkaline earth metal spinels and processes for making.
Nicolaides Christakis P. (Pretoria ZAX), Aluminosilicate catalyst, a process for the manufacture thereof and a process for the skeletal isomerization of linear o.
Hall W. Keith ; Feng Xiaobing, Catalyst for purifying the exhaust gas from the combustion in an engine or gas turbines and method of making and using the same.
Chin Arthur A. (Cherry Hill NJ) Child Jonathan E. (Cherry Hill NJ) Schipper Paul H. (Wilmington DE), Catalytic cracking process with isolated catalyst for conversion of NOx in FCC regenerator.
Dwyer Francis G. (West Chester PA) Schwartz Albert B. (Philadelphia PA), Continuous process for manufacturing crystalline zeolites in continuously stirred backmixed crystallizers.
Hansen Allen R. (Glassboro NJ) Johnson David L. (Glen Mills PA) Stevenson Scott A. (Newtown PA) Schipper Paul H. (Doylestown PA) Harandi Mohsen N. (Langhorne PA), Conversion of NOxin FCC bubbling bed regenerator.
Marler David O. (Deptford NJ) Sapre Ajit V. (W. Berlin NJ) Shihabi David S. (Pennington NJ) Socha Richard F. (Newtown PA) Stevenson Scott A. (Newtown PA), Denitrification of flue gas from catalytic cracking.
Kennedy James V. (Greenbrae CA) Jossens Lawrence W. (Albany CA), Dual component cracking catalyst with vanadium passivation and improved sulfur tolerance.
Avidan Amos A. (Yardley PA) Mathias Mark F. (Turnersville NJ) Menon Raghu K. (Medford NJ) Sodomin ; III Joseph F. (Centerville VA) Stevenson Scott A. (Newton PA) Teitman Gerald J. (Vienna VA), FCC of nitrogen containing hydrocarbons and catalyst regeneration.
Mohr Gary David ; Chen Tan Jen ; Clem Kenneth Ray ; Janssen Mechilium Johannes Geradus,BEX ; Ruziska Phillip Andrew ; Verduijn Johannes Petrus,BEX ; van den Berge Jannetje Maatje,NLX ITX executor of , Hydrocarbon conversion process using a zeolite bound zeolite catalyst.
Cormier William E. (Ellicott City MD) Woltermann Gerald M. (Westminister MD) Magee John S. (Ellicott City MD) Baars Fred J. (Leiden IL NLX) Upson Lawrence L. (Barrington IL), Increasing metal-tolerance of FCC catalyst by sulfur oxide removal.
Pinnavaia Thomas J. (East Lansing MI) Amarasekera Jayantha (East Lansing MI) Polansky Christine A. (Ithaca MI), Layered double hydroxide sorbents for the removal of SOx from flue gas and other gas streams.
Yoo Jin S. (Flossmoor IL) Radlowski Cecelia A. (Riverside IL) Karch John A. (Marriottsville MD) Bhattacharyya Alakananda (Columbia MD), Metal-containing spinel composition and process of using same.
Yoo Jin S. (Flossmoor IL) Radlowski Cecelia A. (Riverside IL) Karch John A. (Marriottsville MD) Bhattacharyya Alakananda (Columbia MD), Metal-containing spinel composition and process of using same.
Farris Thomas S. (Bethlehem PA) Li Yuejin (Wescosville PA) Armor John N. (Orefield PA) Braymer Thomas A. (Allentown PA), Method for decomposing N2O utilizing catalysts comprising calcined anionic clay minerals.
Park, Sang Eon; Park, Yong Ki; Lee, Jin Woo; Lee, Chul Wee; Chang, Jong San; Cho, Jung Kuk, Method for preparing noble metal-supported zeolite catalyst for catalytic reduction of nitrogen oxide.
Park Sang-Eon,KRX ; Kim Gyung-Mi,KRX ; Lee Yun-Jo,KRX ; Chang Jong-San,KRX ; Han Seong-Hee,KRX, Method for removing nitrogen oxides in exhaust gas by selective catalytic reduction and catalyst for reduction of nitrog.
Peters Alan W. ; Rudesill John A. ; Weatherbee Gordon Dean ; Rakiewicz Edward F. ; Barbato-Grauso Mary Jane A., NO.sub.x reduction compositions for use in FCC processes.
Peters Alan W. ; Rudesill John A. ; Weatherbee Gordon Dean ; Rakiewicz Edward F. ; Barbato-Grauso Mary Jane A. ; Zhao Xinjin, NO.sub.x reduction compositions for use in FCC processes.
Grasselli Robert K. (12 Black Rock Rd. Chadds Ford PA 19317-9270) Lago Rudolph M. (633 Kings Rd. Yardley PA 19067) Socha Richard F. (42 Teaberry La. Newtown PA 18940) Tsikoyiannis John G. (191 Snowde, NOx abatement process.
Alan W. Peters ; John A. Rudesill ; Gordon Dean Weatherbee ; Edward F. Rakiewicz ; Mary Jane A. Barbato-Grauso, NOx reduction compositions for use in FCC processes.
Peters Alan W. ; Rudesill John A. ; Weatherbee Gordon Dean ; Rakiewicz Edward F. ; Barbato-Grauso Mary Jane A. ; Zhao Xinjin, NOx reduction compositions for use in FCC processes.
Siefert Kristine S. (Dolton IL) Yoo Jin S. (Flossmoor IL) Burk ; Jr. Emmett H. (Glenwood IL), Preparative process for alkaline earth metal, aluminum-containing spinels.
Yoo Jin S. (Flossmoor IL) Karch John A. (Homewood IL) Poss Richard F. (Flossmoor IL) Burk ; Jr. Emmett H. (Mountain Home AR), Preparative process for alkaline earth metal, aluminum-containing spinels.
Edwards Michael S. (West Deptford NJ) Land David A. (Marlton NJ) Markham Catherine L. (Glen Mills PA) Misiewicz Joseph R. (Aston PA) Schields John P. (Voorhees NJ), Process and apparatus for reducing NOx emissions from high-efficiency FFC regenerators.
David A. Morgenstern ; Juan P. Arhancet ; Howard C. Berk ; William L. Moench, Jr. ; James C. Peterson, Process and catalyst for dehydrogenating primary alcohols to make carboxylic acid salts.
Ebner Jerry R. (St. Peters MO) Franczyk Thaddeus S. (Maryland Heights MO), Process for preparing carboxylic acid salts and methods for making such catalysts and catalysts useful in such process.
Yoo Jin S. (Flossmoor IL) Karch John A. (Marriottsville MD) Bhattacharyya Alakananda A. (Columbia MD) Radlowski Cecelia A. (Riverside IL), Process for reducing emissions of sulfur oxides and composition useful in same.
Biswas Jaydeep (Amsterdam NLX) Maxwell Ian E. (Amsterdam NLX) Van Der Eijk Johan M. (Amsterdam NLX), Process for the conversion of a hydrocarbonaceous feedstock.
Guthrie Charles F. (El Sobrante CA) Jossens Lawrence W. (Albany CA) Kennedy James V. (Greenbrae CA) Paraskos John A. (San Rafael CA), Process for the demetallization of FCC catalyst.
Gosselink Johan Willem,NLX ; Van Veen Johannes Anthonius Robert,NLX ; Van Welsenes Arend-Jan,NLX, Process for the preparation of a catalyst composition.
Ozin, Geoffrey A.; Kuperman, Alex; Nadimi, Susan, Process of growing crystalline microporous solids in a fluoride-containing, substantially non-aqueous growth medium.
Pinnavaia Thomas J. (East Lansing MI) Amarasekera Jayantha (East Lansing MI) Polansky Christine A. (Ithaca MI), Process using sorbents for the removal of SOx from flue gas.
Kasahara Senshi (Shinnanyo JPX) Okazaki Shuji (Yamaguchi JPX) Sekizawa Kazuhiko (Shinnanyo JPX), Purifying gases with an alkali metal and transition metal containing zeolite.
Buchanan John S. (Trenton NJ) Mathias Mark F. (Turnersville NJ) Sodomin ; III Joseph F. (Landenberg PA) Teitman Gerald J. (Vienna VA), Removing SOx, NOX and CO from flue gases.
Dimpfl William L. (Oakland CA) Blanton William A. (Woodacre CA), Simultaneous sulfur oxide and nitrogen oxide control in FCC units using cracking catalyst fines with ammonia injection.
Garces Juan M. (1106 W. Sugnet Midland MI 48640) Millar Dean M. (1101 Adams Dr. Midland MI 48642) Howard Kevin E. (1015 Whispering Oak Dr. Midland MI 48642), Synthesis of crystalline porous solids in ammonia.
Swan George A. ; Bedell Michael W. ; Ladwig Paul K. ; Asplin John E.,GBX ; Stuntz Gordon F. ; Wachter William A. ; Henry Brian Erik, Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C.sub.4 olefins.
※ AI-Helper는 부적절한 답변을 할 수 있습니다.